JPH1053433A - Photosensitive paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive paste containing a specific compound, a photosensitive organic component and inorganic particles as essential components, suppressed in gelation, capable of being thereby stably used, and enabling a pattern processing having high aspect ratio and high precision. SOLUTION: This photosensitive paste contains an amine compound preferably having a primary or secondary amino group (e.g. 2-aminoethanol), a photosensitive organic component (e.g. a composition comprising trimethylolpropane triacrylate, a polymer of the formula, a photopolymerization initiator, and a photosensitizer), and inorganic particles containing glass particles in an amount of >=50wt.%. The amine compound is preferably contained in an amount of 0.01-10wt.% in the paste, and the inorganic particles are preferably coated with the amine compound. The glass particles preferably have a thermal softening temperature of 350-600 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel photosensitive paste. The photosensitive paste of the present invention is used for pattern processing of various displays including plasma displays and plasma addressed liquid crystal displays, circuit materials, and the like.

[0002]

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 of a plasma display panel, a material which has high precision and which can be patterned 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 pattern with high precision cannot be formed.

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

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. . Also, JP-A-4-109
No. 536 proposes a method of forming a partition using a photosensitive organic film. However, these methods have a problem that the number of steps 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.

[0008]

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 provide a photosensitive paste which suppresses gelation of such a photosensitive paste, can be used stably, and has a high aspect ratio and a high pattern workability with high precision.

[0010]

The object of the present invention is attained by a photosensitive paste characterized in that an amine compound is introduced into a photosensitive paste containing, as essential components, an organic component containing inorganic fine particles and a photosensitive compound. Is done.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The amine compound used in the present invention is a compound containing 3 to 60% by weight of a nitrogen atom in a molecule.

As the amine compound, a compound having one or more primary amino groups or secondary amino groups in the molecule has a high effect. Generally, the compounds represented by (A), (B), (C), and (D) are exemplified.

[0013]

Embedded image (R, R ': hydrocarbon group) Specific examples include C1 such as propylamine, butylamine, hexylamine, octylamine, and decylamine.
C1 to C10 monoalkylamine, dimethylamine, diethylamine, C1 to C10 dialkylamine such as dipropylamine, aniline, aromatic amines such as diphenylamine, piperidine, pyrrolidine, secondary amine having a cyclic structure such as indole, ethylenediamine,
1,3-diaminopropane, C1-C10 alkyl diamines such as 1,4-diaminobutane, diaminotoluene, aromatic diamines such as diaminobenzophenone,
Use of a compound such as triamine such as 4,4 ', 4 "-triaminotriphenylmethane is effective.

Further, an aliphatic group and an aromatic group of the substituent R include:
As a further substituent, a compound substituted with an unsaturated group such as a vinyl group, vinyl ether, acrylate, or methacrylate may be used.

A compound having a nitrogen content of 3% by weight or more in the molecule is desirable because the larger the proportion of primary amino groups or secondary amino groups in the molecule of the amine compound used, the higher the effect of suppressing gelation. . That is, 2
An amine compound having a secondary amino group and having a small molecular weight per secondary amino group and being liquid at ordinary temperature is more preferred.

The amount of the amine compound to be added is preferably 0.01 to 5% by weight, more preferably 0.5 to 2% by weight in the paste to affect the photosensitivity, developability and adhesion to the substrate. And a good paste which does not affect the above can be obtained. When the addition amount is 0.01% by weight or less, the gelation preventing effect is lost, and when the addition amount is 5% by weight or more, the exposed portion is dissolved in the developing solution.

As the addition method, a method of dissolving in a paste, a method of dissolving in a solvent and mixing with a paste, a method of treating the surface of inorganic fine particles such as glass fine particles, and the like can be used. As a specific method for treating the surface, a method of dissolving an amine compound in a liquid such as an organic solvent or water and then distilling off the solvent can be used.

As the solvent, it is preferable to use methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol and acetone. After distilling off the solvent, it is more preferable to carry out a heat treatment at 50 to 200 ° C. for 12 hours or more.

The photosensitive paste of the present invention preferably contains 50% by weight or more of inorganic fine particles surface-treated with the above amine compound.

In the present invention, the inorganic fine particles include glass and metals (gold, platinum, silver, and the like) generally used for 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 glass fine particles are not particularly limited, but have a composition range of _{3 to} 60 parts by weight of SiO _2, 3 to 60 parts by weight of B ₂ O _3, 1 to 25 parts by weight of BaO, and 1 to 10 parts by weight of Al ₂ O _3. It is preferable to use

As a composition in the glass powder, SiO ₂ is preferably blended in a range of 3 to 60% by weight, and if less than 3% by weight, the denseness, strength and stability of the glass layer are reduced, and A mismatch between the glass substrate and the thermal expansion coefficient occurs, deviating from a 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 mixing B ₂ O ₃ in the range of ₃ to 60% by weight, it is possible to improve electric, mechanical and thermal properties such as electric insulation, strength, coefficient of thermal expansion and denseness of the insulating layer. it can. On the other hand, if it exceeds 60% by weight, the stability of the glass will be reduced. By adding BaO or Al ₂ O ₃ , a stable glass powder can be obtained. It is preferable that ZnO is blended in a range of 30% by weight or less. If it exceeds 30% by weight, the temperature for baking on the glass substrate becomes too low to control, and the insulation resistance is undesirably low.

In addition, TiO ₂ , ZrO
₂ , Y ₂ O _{3 and the} like can be contained, but the amount is preferably 20% by weight or less.

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

Further, the present inventors have proposed that, 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.

The glass fine particles used in this case include:
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 sphericity of the glass fine particles is evaluated by observing the particles with an electron microscope or the like, and evaluating the ratio of the number of spherical particles (including an oval and an oval).

The thermal softening temperature (Ts) of the glass fine particles used when performing pattern processing on a glass substrate is 350 to 350.
Preferably it is 600 ° C. Glass powder having such temperature characteristics can be obtained by introducing lead oxide, bismuth oxide, and alkali metal oxide.

Bi ₂ O ₃ and PbO are added in a total amount of 10 to 50.
The content by weight has an advantage that the temperature characteristics can be easily controlled.

Further, an oxide metal such as Na ₂ O, Li ₂ O and K ₂ O may be added, but the content is preferably 20% by weight or less from the viewpoint of water resistance. However, by adding 3 to 15% by weight of these alkali metal oxides,
There is an advantage that the softening temperature, the refractive index, and the coefficient of thermal expansion can be easily controlled.

By containing Bi ₂ O ₃ in a total amount of 5 to 25% by weight and containing an alkali metal oxide in an amount of 3 to 10% by weight, the softening temperature, the refractive index, the thermal expansion coefficient, and the electrical stability are obtained. Excellent glass can be obtained. Conventionally, such a glass easily gelated and was not used for a photosensitive paste. However, the glass can be used according to the present invention.

As a glass powder, a mercury lamp g
By using one having a refractive index of 1.5 to 1.65 at a line (436 nm), it is possible to match the refractive index of the organic component, and it is possible to perform high-precision pattern processing by suppressing light scattering.

The photosensitive organic component used in the present invention is an organic component containing a compound having photosensitivity in the paste (a part obtained by removing the inorganic component from the paste).

The organic component contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer and a photosensitive polymer, and, if necessary, a binder, a photopolymerization initiator, a light absorber, Sensitizer, sensitization aid,
Polymerization inhibitor, plasticizer, thickener, organic solvent, antioxidant,
Additive components such as dispersants, organic or inorganic suspending agents and leveling agents are also added.

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

The reactive component includes a photo-insolubilizing type and a photo-solubilizing type. The photo-insolubilizing type includes: (1) a functional monomer having at least one unsaturated group in the molecule. (2) Those containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds. (3) So-called diazo resins such as condensates of diazo-based amines and formaldehyde. And others. Also,
Examples of the photo-soluble type include (4) a complex of a diazo compound with an inorganic salt or an organic acid, and a product containing a quinone diazo compound. (5) a quinone diazo compound combined with a suitable polymer binder, for example, a phenol or novolak resin. Naphthoquinone 1,2-diazido-5-sulfonic acid ester and the like.

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

The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and sec-butyl. Acrylate, sec-
Butyl acrylate, iso-butyl acrylate, te
rt-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate Heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-
Methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene Glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxide Shi of cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate,
Trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct,
Bisphenol A-propylene oxide adduct diacrylate, thiophenol acrylate, benzyl mercaptan acrylate, and monomers in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p -Methylstyrene,
o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α
-Methyl styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and part or all of the acrylate in the molecule of the above compound to methacrylate Modified ones include γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. In the present invention, one or more of these can be used.

In addition to the above, the developability after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

An oligomer or polymer obtained by polymerizing at least one of the compounds having a carbon-carbon double bond described above can be used.

At the time of polymerization, these monomers can be copolymerized with other photosensitive monomers such that the content of these monomers is at least 10% by weight, more preferably at least 35% by weight.

As a monomer to be copolymerized, the developability after exposure can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained has an acid value (AV) of preferably from 50 to 180, more preferably from 70 to 140. When the acid value is less than 50, the allowable development width becomes narrow. On the other hand, if the acid value exceeds 180, the solubility of the unexposed portion in the developing solution decreases, so that if the developing solution concentration is increased, peeling occurs up to the exposed portion, making it difficult to obtain a high-definition pattern.

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

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

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

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, and glycidyl ether isocrotonic acid. .

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

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

Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, and 4,4-dichlorobenzophenone. , 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, 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, benzyldimethyl Ketanol, benzylmethoxyethyl 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,
Combination of photoreducing dyes such as benzothiazole disulfide, triphenylphorphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, and methylene blue with reducing agents such as ascorbic acid and triethanolamine Is raised. In the present invention, one or more of these can be used. The photopolymerization initiator, for the photosensitive component,
It is added in the 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 light absorber composed of an organic dye. A high aspect ratio, high definition, and high resolution can be obtained by adding a light absorbing agent having a high ultraviolet absorbing 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 the content is less than 0.05% by weight, the effect of adding the ultraviolet absorber is reduced, and if it exceeds 5% by weight, the properties of the insulating film after firing are undesirably deteriorated. More preferably 0.1
5 to 1% by weight. An example of the method of adding the ultraviolet light absorber composed of an organic pigment is as follows. A solution is prepared by dissolving the organic pigment in an organic solvent in advance, and then a glass powder is mixed in the organic solvent, followed by drying. By this method, a so-called capsule-like powder in which an organic film is coated on the surface of each powder of glass powder can be produced.

A sensitizer is added to improve the sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone,
2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone,
4,4-bis (diethylamino) -benzophenone,
4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene)- Isonaphthothiazole, 1,3-bis (4-
Dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone,
3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N
-Phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. Can be In the present invention, 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 photosensitive component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

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

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

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.

To adjust the viscosity of the solution to the photosensitive paste of the present invention, an organic solvent may be added. The organic solvent used at this time includes 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 these are used.

The photosensitive paste is usually prepared by mixing various components such as inorganic fine particles, an ultraviolet absorber, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, a glass frit and a solvent so as to have a predetermined composition. The mixture is uniformly mixed and dispersed with three rollers or a kneading machine. The viscosity of the paste is appropriately adjusted by the addition ratio of the inorganic fine particles, the thickener, the organic solvent, the plasticizer, the suspending agent and the like.
２０200,000 cps (centipoise) 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 on the entire surface or on a glass substrate, a ceramic substrate, or a polymer film. As the application method,
Screen printing, a bar coater, a roll coater, a die coater, a blade coater and the like 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, and tris-silane.
(2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like, or organic metals such as organic titanium, organic aluminum and organic zirconium. The silane coupling agent or the organic metal is dissolved in an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc.
Use the one diluted to a concentration of 1 to 5%. Next, after applying this surface treatment liquid uniformly on the substrate with a spinner or the like, 8
Surface treatment can be performed by drying at 0 to 140 ° C. for 10 to 60 minutes.When applied on a film, after drying on the film, performing the next exposure step,
There is a method in which an exposure step is performed after the film is pasted on a glass or ceramic substrate.

After applying, using a photomask,
Perform mask exposure. 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 .

After applying the photosensitive paste, the pattern shape can be improved by providing an oxygen shielding film on the surface of 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.
A 5 to 5% by weight aqueous solution is uniformly applied on a substrate by a method such as a spinner and then dried at 70 to 90 ° C. for 10 to 60 minutes. The preferred PVA solution concentration is 1 to 3% by weight. Within this range, the sensitivity is further improved. The reason why the sensitivity is improved by the PVA application is presumed 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 the exposure, development is performed using a developing solution. In this case, the development is performed by an immersion method or a spray method. 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 general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 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.
The sintering is performed at a temperature of 温度 610 ° C. for 10 to 60 minutes.

In the above steps, a heating step at 50 to 300 ° C. may be introduced for the purpose of drying and preliminary reaction.

[0067]

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.

Example 1 A photosensitive paste comprising glass 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 gelling inhibitor was added when the paste was prepared.

Next, a 30 cm square soda glass substrate was coated with a doctor blade to a coating thickness of 130 μm, and then dried at 80 ° C. for 30 minutes.
However, some pastes gelled and could not be applied. Therefore, after 3 days, 7 days, and 14 days, it was evaluated whether or not the coating could be applied. For those that could be applied, a pattern was formed by the following method.

Exposure was performed using a stripe-shaped mask used for a partition for a plasma display. 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 immersed in a 1% aqueous solution of monoethanolamine to perform development. Furthermore, after drying the obtained glass substrate at 120 ° C. for 1 hour, 560 ° C.
Firing was performed for 15 minutes.

In the evaluation, the pattern shape (a target having a line width of 50 μm × height of 100 μm and a pitch of 220 μm) was observed with an electron microscope. Table 1 shows the results.

A sample having a good pattern was evaluated as ○, a sample which could be coated, but a good pattern was not obtained due to poor development was evaluated as △, and a sample which could not be coated was evaluated as ×.

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

Glass fine particles: Glass 1 80.0 parts by weight Photosensitive monomer: TMPTA 9.0 parts by weight Photopolymer: Polymer 1 13.3 parts by weight Photopolymerization initiator: MTPMP 2.0 parts by weight Ultraviolet light absorber: Sudan 0.1 parts by weight Sensitizer: 2.0 parts by weight DET Sensitization aid: 1.0 part by weight EPA Organic solvent: 21.7 parts by weight γ-BL The following shows the abbreviations.

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

Embedded image (Weight average molecular weight: 43000, acid value: 90) MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 Sudan: azo dye, C ₂₄ H ₂₀ N ₄ O DET : 2,4-diethylthioxanthone EPA: p-dimethylaminobenzoic acid ethyl ester DBP: dibutyl phthalate γ-BL: γ-butyrolactone Spherical rate 85 number%, refractive index 1.73, 50% by weight average particle size 3.2 μm Spherical ratio 88 number%, refractive index 1.58, 50% by weight Average particle size 3.3 μm Examples 2 to 14 Except that the type of gelling inhibitor, the amount added, the method of addition, and the type of glass fine particles were changed, In the same manner as in Example 1,
A paste was created and a pattern was formed. Table 1 shows the results
Shown in

The anti-gelling agent may be added at the time of preparing the paste, or may be previously coated on the glass fine particles. For coating, glass particles were immersed in an isopropanol solution of a gelling inhibitor, distilled off at 50 ° C. under reduced pressure, and then heated at 80 ° C. for 1 hour.

Comparative Example 1 A paste was prepared and a pattern was formed in the same manner as in Example 1 except that no gelling inhibitor was added. Table 1 shows the results.

Comparative Example 2 A paste was prepared and a pattern was formed in the same manner as in Example 1 except that the type of the glass fine particles was changed without adding the gelling inhibitor. Table 1 shows the results.

[0079]

[Table 1] Abbreviations in the table are shown below.

AE: 2-aminoethanol ED: ethylenediamine DA: diethylamine

[0081]

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. In particular, a highly accurate partition wall of a plasma display panel can be formed easily.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01J 17/16 H01J 17/16

Claims (16)

[Claims] 1. A photosensitive paste comprising an amine compound, a photosensitive organic component and inorganic fine particles as essential components. 2. The method according to claim 1, wherein the amine compound is contained in the paste in an amount of 0.01 to 1%.
2. The photosensitive paste according to claim 1, which contains 0% by weight. 3. The photosensitive paste according to claim 1, wherein a compound containing a primary amine or a secondary amine is used as the amine compound. 4. The photosensitive paste according to claim 1, wherein inorganic fine particles coated with an amine-containing compound are used. 5. The photosensitive paste according to claim 1, wherein glass fine particles are used in 50% by weight or more of the inorganic fine particles. 6. A glass fine particle having a heat softening temperature of 350.
6. The photosensitive paste according to claim 5, wherein glass fine particles having a temperature of up to 600 [deg.] C. are used. 7. The glass fine particles have an average refractive index of 1.5 to 1.5.
6. The photosensitive paste according to claim 5, wherein 1.65 glass particles are used. 8. The photosensitive paste according to claim 5, wherein glass fine particles containing 10 to 50% by weight of bismuth oxide or lead oxide are used as the glass fine particles. 9. The photosensitive paste according to claim 5, wherein glass fine particles containing 3 to 20% by weight of an alkali metal oxide are used as the glass fine particles. 10. The glass fine particles contain a component of _{3 to} 60 parts by weight of SiO _2, 3 to 60 parts by weight of B ₂ O _3, 1 to 25 parts by weight of BaO, and 1 to 10 parts by weight of Al ₂ O _{3 in} terms of oxide. 6. The photosensitive paste according to claim 5, wherein glass paste is used. 11. The glass fine particles having an average particle size of 1 to 1
6. The photosensitive paste according to claim 5, wherein 0 μm glass fine particles are used. 12. The photosensitive paste according to claim 1, wherein a polymer containing a carboxyl group and having a weight average molecular weight of 300 to 100,000 is used as the photosensitive organic component. 13. The photosensitive paste according to claim 1, wherein a polymer having a weight average molecular weight of 300 to 100,000 containing a carbon-carbon double bond is used as the photosensitive organic component. 14. An ultraviolet light absorber comprising an organic dye is used in an amount of 0.0
2. The photosensitive paste according to claim 1, which contains 5 to 5% by weight. 15. A plasma display or a plasma addressed liquid crystal display for use in a plasma display.
Photosensitive paste. 16. The photosensitive paste according to claim 1, which is used for forming a partition of a plasma display or a plasma addressed liquid crystal display.