JPH09218508A - Photosensitive paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inhibit the gelation of photosensitive paste and to contrive stable use and high precision patterning by incorporating a compd. having a benzotriazole structure into the photosensitive paste contg. inorg. fine particles and an org. component contg. a photosensitive compd. as essential components. SOLUTION: A photosensitive org. component and a compd. having a benzotriazole structure are dissolved under heating to 80 deg.C, inorg. fine particles are added and they are kneaded to prepare the objective photosensitive paste. The inorg. fine particles are previously coated with a gelation inhibitor. The top of a soda glass substrate is coated three times with the paste by screen printing so that 100μm thickness is attained. After drying at 80 deg.C for 30min, the resultant coating film is exposed through a mask and developed by immersion in a 1% aq. soln. of monoethanolamine. The glass substrate is then dried and fired at 580 deg.C for 1hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel photosensitive paste.

The photosensitive paste of the present invention is used for patterning displays, circuit materials and the like.

[0003]

2. Description of the Related Art In recent years, miniaturization and high definition of circuit materials and displays have been progressing, and accordingly, there has been a demand for an improvement in pattern processing technology. In particular, for forming a green sheet used for a CPU or the like of a computer or a partition wall of a plasma display panel, a material which has high accuracy and is capable of pattern processing with a high aspect ratio is desired.

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 highly accurate pattern cannot be formed.

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

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

[0007]

The present inventors have intensively studied a photosensitive paste which enables high aspect ratio and high-precision pattern workability. However, depending on the type of inorganic fine particles used, the paste may react with an organic component. As a result, gelation may progress and the paste may become unusable due to thickening.

An object of the present invention is to obtain a photosensitive paste which suppresses gelation of such a photosensitive paste and can be stably used, and which enables pattern workability with a high aspect ratio and high accuracy.

[0009]

An object of the present invention is to introduce a compound having a benzotriazole structure into a photosensitive paste containing an inorganic component and an organic component containing a photosensitive compound as essential components. Achieved with a sex paste.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compound having an azole structure used in the present invention is a compound having an azole structure such as a pyrrole structure, an imidazole structure, a pyrazole structure and a triazole structure, and specifically, benzotriazole, naphthotriazole, Indazole, imidazole, benzimidazole, indole, or a compound having a substituent such as a methyl group, a carboxyl group or a chloro group in the benzene ring portion thereof, or 1,2,4-triazole, etc., but especially benzotriazole is used It is preferable.

When using these compounds, it is preferable to use about 0.01 to 5% by weight of the glass fine particles. More preferably, it is 0.05 to 1% by weight of the glass fine particles.

Further, regarding the way of mixing the gelling inhibitor, it is effective even if it is added at the time of forming the paste, but if it is coated on the surface of the glass fine particles in advance, the further effect is recognized. The coating can be obtained by immersing the glass particles in a gelling agent solution and removing the solvent. Methyl acetate, ethyl acetate, methanol, and ethanol are used as the solvent, and it is desirable to air-dry at 20 to 30 ° C. After that, it is more preferable to perform heat treatment at 70 to 90 ° C. for 12 hours or more.

The photosensitive paste for forming barrier ribs of the present invention contains 50% by weight of glass powder surface-treated with the above gelling inhibitor.
It is preferable to include the above.

The inorganic fine particles used in the present invention include glass and metals (gold, platinum, silver, etc.) commonly used in electronic materials.
Fine particles of copper, nickel, aluminum, palladium, tungsten, ruthenium oxide, etc.), and glass particles are particularly useful in the present invention. 5 of inorganic fine particles
It is preferable to use glass fine particles at 0% by weight or more.

The fine glass particles are not particularly limited as long as they are publicly known, but fine glass particles containing 5 to 50% by weight of bismuth oxide or lead oxide are excellent in workability.

As a glass composition containing bismuth oxide, in terms of oxide, SiO ₂ 3 to 60% by weight BaO 0 to 25% by weight Al ₂ O ₃ 0 to 10% by weight B ₂ O ₃ 5 to 40% by weight Bi ₂ O ₃ made of 5-50 wt% ZnO 2 to 40% by weight of the composition range preferably contains 90 wt% or more.

Further, in the glass powder, Li ₂ O, Ca
O, TiO ₂ , ZrO _{2 and the} like can be contained, but the amount thereof is preferably 0 to 20% by weight. Further, it is preferable that the oxide metal such as Na ₂ O, K ₂ O and Y ₂ O ₃ is not included so much. 5 even if a small amount is contained
It is preferable that the content be not more than weight%.

As a composition in the glass powder, it is preferable to mix SiO ₂ in the range of 3 to 60% by weight, and if it is less than 3% by weight, the denseness, strength and stability of the glass layer are deteriorated. A mismatch between the glass substrate and the coefficient of thermal expansion occurs and deviates from the desired value. Further, when the content is set to 60% by weight or less, there is an advantage that the heat softening point is lowered and baking on a glass substrate becomes possible.

By blending B ₂ O ₃ in the range of 5 to 40% by weight, electrical, mechanical and thermal characteristics such as electric insulation, strength, coefficient of thermal expansion and denseness of the insulating layer can be improved. it can. On the other hand, if it exceeds 40% by weight, the stability of the glass is reduced.

Bi ₂ O ₃ or PbO is preferably added in an amount of 5 to 50% by weight, more preferably 10 to 50% by weight. If it is less than 10% by weight, it is less effective in controlling the baking temperature when baking the glass paste on the glass substrate. If it exceeds 50% by weight, the heat-resistant temperature of the glass becomes too low, and it is difficult to bake the glass on a glass substrate.

ZnO is preferably blended in the range of 2 to 40% by weight. If it exceeds 40% by weight, the temperature for baking on the glass substrate becomes too low to control.
In addition, the insulation resistance is undesirably low.

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

Further, the inventors of the present invention, as glass fine particles,
By using glass particles that are spherical in shape,
It has been found that patterning with a high aspect ratio is possible.

As the glass fine particles used in this case,
50% by weight particle size is 1.0 to 7 μm, 10% by weight particle size is 0.4 to 2 μm, 90% by weight particle size is 4 to 10 μm,
Glass fine particles having a specific surface area of 0.2 to 3.0 m ² / g are suitable. Further, it is preferable to use 50% by weight or more of glass fine particles having a sphericity of 80% by number or more.

The glass transition temperature (Tg) of fine glass particles used when patterning a glass substrate is 35.
It is preferably 0 to 470 ° C.

The photosensitive organic component used in the present invention is an organic component (a portion excluding an inorganic component from the paste) containing a photosensitive compound in the paste.

The photosensitive organic component includes a reactive component selected from at least one of a photosensitive monomer, a photosensitive oligomer and a photosensitive polymer, a binder, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, Sensitization aid, polymerization inhibitor, plasticizer, thickener, organic solvent, antioxidant, dispersant,
Additive components such as organic or inorganic suspending agents may be added.

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

The reactive component includes a photo-insolubilizing type and a photo-solubilizing type, and the photo-insolubilizing type includes (1) a functional monomer having one or more unsaturated groups in the molecule. , Containing oligomers and polymers (2) containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds and organic halogen compounds (3) so-called diazo resins such as condensation products of diazo amines and formaldehyde There are things that are called. Further, as the photo-soluble type, (1) a complex containing an inorganic salt of a diazo compound or an organic acid, a quinone diazo compound is contained (2) a quinone diazo compound bound to an appropriate polymer binder, for example, phenol, Examples include naphthoquinone 1,2-diazide-5-sulfonic acid ester of novolac resin.

As the reactive component used in the present invention, all of the above can be used, but (1) is the simplest photosensitive paste.

As the reactive monomer used in this case,
A compound having a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, and n.
-Propyl acrylate, isopropyl acrylate,
n-butyl acrylate, sec-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, Cyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2
-Hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allyl Cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, diacrylate Pentaerythrito Monohydroxy pentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, Examples thereof include aminoethyl acrylate and those obtained by partially or entirely replacing the acrylate in the molecule of the above compound with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like.

In the present invention, one or more of these can be used. In addition, by adding an unsaturated carboxylic acid, the developability after exposure can be improved. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof are exemplified.

On the other hand, as the photosensitive oligomer or photosensitive polymer, the above-mentioned reactive monomer or methacrylate monomer or acrylate monomer having an aromatic ring such as benzene ring or naphthalene ring, specifically, phenyl (meth) acrylate, Phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A-ethylene oxide adduct di (meth) acrylate , Bisphenol A-propylene oxide adduct di (meth) acrylate, thiophenol (meth) acrylate, benzyl mercaptan (meth) acrylate, and 1 to 5 of the hydrogen atoms of these aromatic rings are chlorine. Monomers other was replaced by a bromine atom or, styrene, p- methyl styrene, o- methyl styrene, m- methyl styrene, chlorinated styrene,
An oligomer or polymer obtained by polymerizing at least one of brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, and hydroxymethylstyrene can be used. .

At the time of polymerization, other reactive monomers can be copolymerized so that the content of these monomers is at least 10% by weight, more preferably at least 35% by weight. As the monomer to be copolymerized, the above-mentioned compound having a carbon-carbon unsaturated bond can be used.

Further, by copolymerizing an unsaturated carboxylic acid, the developability after exposure can be improved. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid,
Examples thereof include fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The acid value (AV) of the thus obtained polymer or oligomer having a carboxyl group in the side chain is 5
The range is preferably from 0 to 180, and more preferably from 70 to 140.
When the acid value is less than 50 or more than 180, the development allowance is narrowed and it is difficult to obtain a high-definition pattern.

Photosensitivity can be imparted to the above-described polymer or oligomer by adding a photoreactive group to the side chain or the molecular end. Preferred photoreactive groups are those 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 method of adding such a side chain to an oligomer or polymer is carried out by a method such as an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or acrylic acid with respect to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer. There is a method in which chloride, methacrylic acid chloride or allyl chloride is subjected to 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, crotonic acid glycidyl ether, and isocrotonic acid glycidyl ether. .

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

In the photosensitive paste used in the present invention, a binder, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, a sensitization aid, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, and an antioxidant are added. Additive components such as agents, dispersants, and organic or inorganic suspending agents can also be added.

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

As a specific example of the photopolymerization initiator,
Benzophenone, methyl o-benzoylbenzoate, 4,
4-bis (dimethylamine) benzophenone, 4,4-
Bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,
2-diethoxyacetophenone, 2,2-dimethoxy-
2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl dimethyl ketanol, benzyl-2-
Methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone,
Benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,
6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2
-(O-Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2-
(O-ethoxycarbonyl) oxime, 1-phenyl-
3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone,
4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide and eosin, photoreducible dyes such as methylene blue And a reducing agent such as ascorbic acid or triethanolamine. In the present invention, these may be used alone or in combination of two or more. The photopolymerization initiator is added to the reactive component in a range of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight. If the amount of the polymerization initiator is too small, the photosensitivity becomes poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small.

It is also effective to add an ultraviolet absorber composed of an organic dye. A high aspect ratio, high definition, and high resolution can be obtained by adding a light absorber having a high ultraviolet absorption effect. As the ultraviolet light absorber, an organic dye is used, and among them, an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinones, benzophenones, diphenylcyanoacrylates, triazines, p-aminobenzoic acid dyes and the like can be used. . Even when the organic dye is added as a light absorbing agent, it is preferable because deterioration of the insulating film characteristics due to the light absorbing agent can be reduced without remaining in the insulating film after firing. Among these, azo dyes and benzophenone dyes are preferred. The addition amount of the organic dye is preferably 0.05 to 5 parts by weight. If it is less than 0.05% by weight, the effect of adding the ultraviolet absorber will be reduced, and if it exceeds 5% by weight, the characteristics of the insulating film after firing are deteriorated, which is not preferable. More preferably 0.1
It is 5 to 1% by weight. As an example of a method of adding an ultraviolet light absorber composed of an organic pigment, it can be prepared by preparing a solution in which the organic pigment is dissolved in an organic solvent in advance, and then mixing glass powder in the organic solvent and drying. By this method, a so-called capsule-like powder in which an organic film is coated on the surface of each glass powder can be produced.

The sensitizer is added to improve high sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,3-diethylthioxanthone.
Bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) 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-dimethylamino Benzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine , N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthio-tetrazole, 1-phenyl-5-ethoxycarbonylthio-tetrazole and the like. It is below. In the present invention, these may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste of the present invention,
The addition amount is usually 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, based on the reactive component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

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

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

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

An organic solvent may be added to the photosensitive paste of the present invention when the viscosity of the solution is desired to be adjusted. Examples of the organic solvent used at this time include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and bromobenzene. , Chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and an organic solvent mixture containing at least one of these are used.

The photosensitive paste is usually prepared by mixing various components such as inorganic fine particles, ultraviolet light absorber, photosensitive polymer, photosensitive monomer, photopolymerization initiator, glass frit and solvent so as to have a predetermined composition. It is prepared by uniformly mixing and dispersing with three rollers or a kneader. 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.
It is 0-200,000 cps (centipoise). For example, when applying to a glass substrate by a spin coating method other than the screen printing method, 2000 to 5000 cps is preferable. Coated once by screen printing method, film thickness 10-20μ
In order to obtain m, 50,000 to 200,000 cps is preferable.

Next, an example of performing pattern processing using a photosensitive paste will be described, but the present invention is not limited to this.

A photosensitive paste is applied to the entire surface or a part of the surface of a glass substrate or a ceramic substrate. As a coating method, a known method such as screen printing, bar coater, roll 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 the paste is applied on the glass substrate, the surface treatment of the substrate can be performed in order 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, and γ- (methacryloxy). Propyl) 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. Next, the surface treatment liquid is uniformly applied onto a substrate by a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes for surface treatment, and then, mask exposure is performed using a photomask. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. The active light source used at this time includes, for example, near-ultraviolet light, ultraviolet light, an electron beam, and X-ray. Among them, ultraviolet light is preferable, and examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, Halogen lamps, germicidal lamps and the like can be used. Among these, an ultra-high pressure mercury lamp is preferred. Exposure conditions vary depending on the coating thickness, but exposure is performed for 1 to 30 minutes using an ultra-high pressure mercury lamp having an output of 5 to 100 mW / cm ² .

The pattern shape can be improved by applying an oxygen shielding film on the surface after applying the photosensitive paste. As an example of the oxygen shielding film, PV
A film. The method for forming the PVA film has a concentration of 0.
After uniformly applying an aqueous solution of 5 to 5% by weight on a substrate by a method such as a spinner, the preferred PVA solution concentration is 1 to 3% by weight at 70 to 90 ° C for 10 to 60 minutes. Within this range, the sensitivity is further improved. It is estimated that the reason why the PVA coating improves the sensitivity is as follows. That is, when the reactive component undergoes a photoreaction, it is considered that the presence of oxygen in the air interferes with the photocuring sensitivity. However, the presence of a PVA film can block excess oxygen, so that the sensitivity is improved during exposure, which is preferable. . In addition to PVA, a water-soluble and transparent polymer such as cellulosic methylcellulose can also be used.

After exposure, development is performed using a developing solution. In this case, dipping or spraying is used. As the developing solution, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. Water may be added to the organic solvent as long as the solvent does not lose its solubility. When a compound having a carboxyl group is present in the photosensitive paste, it can be developed with an aqueous alkali solution. As the alkali aqueous solution, a metal alkali aqueous solution such as a sodium hydroxide or calcium hydroxide aqueous solution can be used, but it is preferable to use an organic alkali aqueous solution since the alkali component can be easily removed at the time of firing. As the organic alkali, a known amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the unexposed portions are not removed, and if the alkali concentration is too high, the pattern portions may be peeled off and the exposed portions may be corroded, which is not good.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste or substrate, but usually firing is performed in air or a nitrogen atmosphere. Firing temperature is 4
Perform at 00-1000 ° C. 520 when pattern processing is performed on a glass substrate or when silver is used as inorganic fine particles.
Baking is performed by holding at a temperature of ˜610 ° C. for 10 to 60 minutes.

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

[0058]

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

In the example, a photosensitive paste containing inorganic fine particles and a photosensitive organic component was prepared. In the preparation procedure, first, each component of the photosensitive organic component was dissolved while being heated to 80 ° C., and then inorganic fine particles were added and kneaded with a kneader to prepare a paste. The inorganic fine particles were previously coated with an antigelling agent.

Next, a soda glass substrate of 30 cm square was applied three times by a screen printing method to obtain 100 μm.
After applying the coating to the coating thickness of
And dried. However, some pastes were gelled and printing became impossible. Therefore, it was evaluated whether or not the printing was possible in one day, three days, and seven days.
The printable product was exposed and developed by the following methods.

Next, exposure was performed using a mask. The mask is a chrome mask designed to be capable of forming a striped pattern with a pitch of 220 μm and a line width of 60 μm. Exposure was performed using an ultra-high pressure mercury lamp with an output of 50 mW / cm ² for ultraviolet exposure.

Then, it was developed by immersing it in a 1% aqueous solution of monoethanolamine. Further, the obtained glass substrate was dried at 120 ° C. for 1 hour and then baked at 580 ° C. for 1 hour.

The pattern formability was evaluated by observing the pattern shape (line width 50 μm × height 80 μm, pitch 220 μm target) with an electron microscope.

The composition of the photosensitive paste of this example is shown below.

The abbreviations in the table are shown below. (The numbers in the polymer structure indicate the constituent molar ratios of the respective monomers.) TMPTA: trimethylolpropane triacrylate Polymer 1:

Embedded image MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 sudan: azo dye, C ₂₄ H ₂₀ N ₄ O DET: 2,4-diethylthioxanthone EPA: p-dimethylamino Benzoic acid ethyl ester DBP: dibutyl phthalate γ-BL: γ-butyrolactone BEEA: 2- (2-butoxyethoxy) ethyl acetate However, the weight of the glass fine particles includes the weight of the gelling inhibitor. The coating amount of the antigelling agent was 0.01 to 0.5% by weight based on the glass powder, and the comparison is shown in Examples 1 to 6 in Table 1. In Table 1, benzotriazole is shown.

Further, in Table 2, the coating amount is 0.4% by weight, and comparison is made with organic compounds having various triazole structures, and the results are shown in Examples 7 to 14.

The composition of the glass particles of this example is as follows. Bi ₂ O ₃ : 37% by weight B ₂ O ₃ : 14% by weight SiO ₂ : 17% by weight ZnO: 16% by weight BaO: 8% by weight Al ₂ O ₃ : 4% by weight Na ₂ O: 4% by weight

[Table 1]

[Table 2]

[0068]

According to the anti-gelling agent of the present invention, a photosensitive paste capable of high-aspect ratio and high-precision pattern processing can be used stably. As a result, a thick film such as a display or a circuit material, and a high-precision pattern processing can be performed, and the definition can be improved and the process can be simplified.

Particularly, it is possible to easily and easily form the partition wall of the plasma display panel with high accuracy.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area H05K 1/09 H05K 1/09 D

Claims (11)

[Claims] 1. A photosensitive paste comprising inorganic fine particles, a photosensitive organic component and a compound having an azole structure. 2. The photosensitive paste according to claim 1, wherein glass fine particles are used for 50% by weight or more of the inorganic fine particles. 3. A glass transition temperature (T
The photosensitive paste according to claim 2, wherein g) is glass fine particles having a temperature of 400 to 550 ° C. 4. The photosensitive paste according to claim 2, wherein glass fine particles containing 5 to 50% by weight of bismuth oxide or lead oxide are used as the glass fine particles. 5. The glass fine particles are, in oxide conversion notation, SiO ₂ 3 to 60% by weight BaO 0 to 25% by weight B ₂ O ₃ 5 to 40% by weight Bi ₂ O ₃ 5 to 50% by weight ZnO 2 to 40% by weight. %. The fine glass particles containing 0 to 10% by weight of Al ₂ O ₃ are used as the photosensitive paste. 6. The photosensitive paste according to claim 2, wherein glass fine particles having a sphericity of 80% by number or more are used in an amount of 50% by weight or more. 7. The photosensitive paste according to claim 1, wherein inorganic fine particles treated with a compound having an azole structure are used. 8. The photosensitive paste according to claim 1, wherein benzotriazole is used as the compound having an azole structure. 9. The photosensitive paste according to claim 1, which is used for forming partition walls of a plasma display or a plasma addressed liquid crystal display. 10. The photosensitive paste according to claim 1, which contains an ultraviolet absorber in an amount of 0.05 to 5% by weight. 11. A photosensitive paste for forming barrier ribs of a plasma display, comprising 50% by weight or more of glass powder surface-treated with benzotriazole.