TW201042664A - Photosensitive conductive paste, method for producing display using the same and display - Google Patents

Abstract

The present invention provides a photosensitive conductive paste and a display, wherein forming a photosensitive conductive paste having low cost and a electrode with high electric conductivity by a photosensitive conductive paste comprising 30 to 45 wt% of Aluminum powder having an average particle size of 1 to 4 μ m, 5 to 15 wt% of glass powder having a softening point of 400 to 500 DEG C, 15 to 30 wt% of photosensitive organic component and 20 to 40 wt% of solvent, as well as a display is obtained by using the photosensitive conductive paste.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photosensitive conductive paste and a display, and more particularly to a photosensitive conductive paste containing an aluminum powder. [Prior Art] Since the plasma display panel (PDP) can be displayed at a higher speed than the liquid crystal panel and is easily enlarged, it is gradually applied to fields such as the A machine and the advertisement display device. In addition, it is also used in the field of high-quality TV.

The PDP is formed between the two glass substrates of the front plate and the back plate, and uses a minute gap as a discharge space to generate a plasma discharge between the anode electrode and the cathode electrode, and ultraviolet rays generated by the gas enclosed in the discharge space. The phosphor is irradiated to the phosphor provided in the discharge space to emit light, thereby performing display. In this case, the electrodes are arranged in strips on the front plate and the back plate, respectively, and a plurality of electrodes are parallel, and the electrodes of the front plate and the electrodes of the back plate are opposed to each other with only a slight gap therebetween. Formed in a vertical manner. Among the PDPs, a surface discharge type PDP having a three-electrode structure suitable for color display by a phosphor has a plurality of electrode pairs composed of display electrodes adjacent to each other in parallel, and is perpendicular to each electrode pair. Addressing electrodes. In addition, at the back panel *, the crosstalk of light is prevented, and the partition walls used for the discharge space are formed in the space between the electrodes. Further, a phosphor is formed in the discharge space. Among the above electrodes, the address electrodes formed on the back sheet need to have a uniform thickness or line width formed over a wide range. Furthermore, with the high refinement of the PDP, the addressing of the 201042664 electrode is continuing to evolve. Further, since the PDP is subjected to a step of firing at a temperature of 500 ° C or higher in air, it is necessary to use a material which does not oxidize even after the firing step. Due to such restrictions, it has been proposed to use a photosensitive paste using a noble metal such as silver or gold as an electrode material (for example, Patent Document 1). The electrode paste used in Patent Document 1 has a problem of high cost because it contains a precious metal. On the other hand, it is also considered to use a paste containing aluminum as a conductive paste which does not use a noble metal such as silver or gold, and apply a conductive paste containing an aluminum powder to dry it, and then, in air, at 500 ° C or higher. When the temperature is fired, the surface of the aluminum powder is oxidized, and sintering failure occurs, or the resistance enthalpy becomes high, and even the case where electricity cannot be supplied is caused. Further, in order to solve these problems, there has been proposed a conductive paste which contains aluminum and a material which prevents oxidation of aluminum (e.g., Patent Document 2). The metal or metal compound for oxidation inhibition used in this document may be reacted with a reactive organic component (polymer, oligomer, monomer, etc.) in the case where a photosensitive paste is added. Preservation 0 These problems are poor in stability, large change in paste viscosity with time, and inability to form a film uniformly. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open No. Hei 5-27 1 576 • [Patent Document 2] Japanese Patent Laid-Open No. Hei 5-2989 1 7 [Description of the Invention] [Problems to be Solved by the Invention] 201042664 SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive conductive paste capable of forming a high-definition pattern having a uniform thickness or a line width at a low cost, and a low-resistance conductive pattern can be obtained. [Means for Solving the Problem] That is, the present invention relates to a photosensitive conductive paste comprising: (A) 30 to 45 wt% of aluminum powder having an average particle diameter of 1 to 4/zm, (B) The softening point is 5 to 15% by weight of the glass powder of 00 to 550 ° C, (C) the photosensitive organic component is 15 to 30% by weight, and (D) the solvent is 20 to 40% by weight. The weight ratio of the above (A) aluminum powder to the above (B) glass powder is preferably in the range of 75:25 to 95:5. The spherical ratio of the aluminum powder (A) is preferably 60% or more. The average particle diameter Da of the aluminum powder (A) and the average particle diameter Dg of the glass powder (B) described above are preferably in the following formula. 0.3^ Dg^ Da^ \0 β m The specific surface area of the (A) aluminum powder is preferably 0.2 to 1.4 m 2 /g. Further, the present invention relates to a method of manufacturing a display comprising the steps of: applying a photosensitive conductive paste on a substrate and drying it to form a paste coating film; and exposing the paste coating film through a photomask; a step of developing a paste coating film after exposure; and a step of forming a pattern by firing. Further, the present invention relates to a display obtained by the aforementioned manufacturing method. [Effects of the Invention] The photosensitive conductive paste of the present invention can form a low-cost, high-definition, and thick pattern of 201042664 degrees or a uniform width, and a low-resistance conductive pattern can be obtained. Further, by using the photosensitive conductive paste, a high-performance display can be manufactured at low cost. [Embodiment] The present invention relates to a photosensitive conductive paste comprising: aluminum powder, glass powder, a photosensitive organic component, and a solvent. In addition to the aluminum powder as the conductive powder, the photosensitive conductive paste of the present invention further contains a photosensitive organic component for ensuring adhesion to the substrate, and a photosensitive organic component for forming a wiring pattern having a fine pitch and ensuring coating. The organic solvent used for stability. Among the conventional conductive pastes, it is considered to have low resistance or debonding at the time of firing. The binding property is such that the conductive powder is contained as much as possible, and the glass powder or the photosensitive organic component is preferably as small as possible. However, since the surface of the powder is easily oxidized when the aluminum powder is fired in the air, there is a case where sintering failure occurs, or the electric resistance enthalpy becomes high, and even the electric power cannot be supplied. In order to solve these problems, in the present invention, the photosensitive conductive paste is used in a photosensitive conductive paste containing a large amount of glass powder and a photosensitive organic component, that is, in the photosensitive conductive paste: aluminum 30 to 45 wt% of powder, 5 to 15 wt% of glass powder, 15 to 30 wt% of photosensitive organic component, and 20 to 40 wt% of solvent '' can prevent oxidation of aluminum powder during firing' to ensure adhesion to the substrate , and * can ensure power. Further, by applying a photosensitive conductive paste to a substrate and drying it, the dried film after evaporation of the solvent contains a photosensitive conductive paste of 40 to 65 wt% of aluminum powder and 20 to 50 wt% of photosensitive organic component of 201042664. It is possible to prevent oxidation of aluminum powder during firing and to ensure energization. First, regarding the aluminum powder, it must contain 30 to 45% by weight, preferably '35 to 40% by weight. When the amount is less than 30% by weight, the electric conduction of the electrode cannot be ensured. When the amount is more than 45% by weight, the pattern formation property is deteriorated, and the problem of the electrode pattern having a fine pitch cannot be obtained. The particle size of the aluminum powder is 50% (average particle diameter) in the weight distribution curve measured by a particle size distribution measuring device (for example, "MT3300" manufactured by Nikkiso Co., Ltd.) is 1 to 4; zm Preferably, 1.5 to 3//m is preferred. When it is less than l#m, the oxidation of the surface of the aluminum powder is promoted at the time of firing, and it is impossible to supply electricity. When the thickness exceeds 4/zm, the smoothness of the electrode pattern is deteriorated, and the electrode formed on the electrode is formed. The shape of the electric body or the partition pattern deteriorates. Further, the maximum particle diameter of the aluminum powder is preferably 20 // m or less, and preferably 10 β m or less. When the maximum particle diameter exceeds 20 μm, the pattern formability is lowered, and a large number of particles larger than the film thickness are present, which tends to adversely affect the electrode or the dielectric layer formed by lamination. The specific surface area of the aluminum powder is preferably 0.2 to 1.4 m 2 /g, and more preferably 0.5 to 1.2 m 2 /g. When the specific surface area is less than 0.2 m 2 /g, the smoothness of the electrode pattern is deteriorated, and the shape of the dielectric or the partition pattern formed on the electrode is deteriorated, and if it exceeds 1.4 m 2 /g, there may be In the case of firing, the oxidation of the surface of the aluminum powder is promoted, and the conductivity of the electrode is deteriorated. The glass powder is preferably contained in the photosensitive conductive paste in an amount of 5 to 15% by weight, preferably 7 to 12% by weight. When the amount is less than 5% by weight, the adhesion to the substrate 201042664 is poor, resulting in an electrode pattern. Broken line. If it exceeds 15% by weight, the probability of occurrence of a failure of power supply increases. The softening point of the glass powder is preferably 400 to 5 50 ° C, and more preferably 450 to 500 ° C. In the case of less than 400 ° C, the glass is softened by evaporation before the photosensitive organic component evaporates, so that the shape of the electrode after firing is deteriorated. When the temperature exceeds 550 °C, the softening of the glass may not proceed, and the adhesion to the substrate may not be secured. The average particle diameter of the glass powder may be appropriately selected according to the purpose, and it is preferably an average particle diameter of 0.3 to 2.0 / z m, more preferably 0.5 to 1.0 / z m. When the average particle diameter is less than 0.3 #m, aggregation tends to occur, so that pattern formation property is deteriorated. When it exceeds 2.0; / m, the sinterability at the time of baking tends to be insufficient. Further, the average particle diameter Dg of the glass powder and the average particle diameter Da of the aluminum powder are preferably OJiamSDgSDaSlO/zm, and preferably 0.1 SDg/Da S 0.9 is preferable. When Dg/Da is less than 0.1, the particle diameter of aluminum tends to be too small, and it tends to be very difficult to disperse. When it is more than 0.9, the pattern formability is lowered, and Q tends to adversely affect the sinterability at the time of firing. Further, the maximum particle diameter of the glass powder is preferably 20 M or less, and preferably 10 or less. When the maximum particle diameter exceeds 20 v m, the pattern formability is lowered, and many particles larger than the film thickness are present, which tends to adversely affect the electrode or dielectric layer formed by lamination. The specific surface area of the glass powder is preferably 1 to 15 cm 2 /g, and more preferably 2 to 10 cm 2 /g. When the specific surface area is less than 1 cm 2 /g, the pattern formability is lowered, and the sinterability at the time of firing tends to be insufficient. When the specific surface area is more than 15 cm 2 /g, the aggregation change 201042664 tends to occur. The content ratio of the aluminum powder to the glass powder is preferably in the range of 75:25 to 95:5 by weight. 80: 20 to 92: 8 is preferred. If it is less than '75:25, the amount of aluminum is too small, and if the power failure occurs, if the amount exceeds 95:5, the amount of the glass powder is too small, the adhesion to the substrate is deteriorated, and the electrode pattern is peeled off. After that. The spherical ratio of the aluminum powder is preferably 60% or more of the aluminum powder contained. More than 80% is preferred. If it is less than 60%, the degree of filling of the aluminum bismuth powder in the electrode after firing may be deteriorated, and as a result, unsuitable conditions such as poor electric current may occur. In the photosensitive organic component used in the photosensitive conductive paste of the present invention, at least one photosensitive organic component selected from the group consisting of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer is further included. It is necessary to add a photopolymerization initiator, a UV absorber, a sensitizer, a sensitizer, a polymerization inhibitor, a plasticizer, a tackifier, an organic solvent, an antioxidant, a dispersion Q agent, an organic or inorganic precipitation inhibitor, etc. Additive ingredients. In the case of a normal photosensitive conductive paste, in view of resistance or electrical conductivity, a paste is often produced with as little organic component content as possible, and the photosensitive paste of the present invention contains 15 to 30% by weight of the paste. Photosensitive organic components are preferred. This is because it suppresses the oxidation of aluminum powder during firing by containing a large amount of photosensitive organic components. In the case where the photosensitive organic component is less than 15% by weight, the effect of the oxidation suppression is small. When the amount is more than 30% by weight, there is a gap between the aluminum particles in the electrode pattern after the firing, and the electrical conductivity cannot be ensured. The -10-201042664 problem occurred. Hereinafter, it is described with respect to the photosensitive organic component of this invention. In the case of a photosensitive monomer, a compound containing a carbon-carbon unsaturated bond, and specific examples thereof may be a monofunctional or polyfunctional (meth) acrylate, an ethylenic compound, or an allyl group. Examples of the compound and the like include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, dibutyl acrylate, isobutyl acrylate, t-butyl acrylate, and n-butyl acrylate. Ester, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butylene triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glyceryl acrylate, glycidyl acrylate, acrylic acid 17. fluorodecyl ester, 2-hydroxyethyl acrylate, isodecyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, acrylic acid Isooctyl ester, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxy diethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, propylene Q acid Lipid ester, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, two Ethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, diquat 'pentaerythritol monohydroxypentaacrylate, bis(trimethylolpropane) tetraacrylate • Ester, glycerin diacrylate, methoxycyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglyceride diacrylate, trimethylolpropane triacrylate Ester, propylene 201042664 decylamine, urethane acrylate, phenyl acrylate, phenoxyethyl acrylate, decyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, bisphenol Acrylate such as diacrylate of A-ethylene oxide adduct, diacrylate of bisphenol A-epoxy 'propane adduct, thiophenolate acrylate, benzyl thiol alcohol ester, etc. 1 to 5 hydrogenogens in an aromatic ring a monomer substituted with a chlorine atom or a bromine atom, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, styrene chloride, styrene bromide, α-甲Styrene, α-methylstyrene chloride, α-methylstilbene bromide, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinyl anthracene, vinylcarbazole And a substance which changes part or all of the acrylate in the molecule of the above compound to a methacrylate, r--methacryloxypropyltrimethoxydecane, 1-vinyl-2-pyrrolidone, etc. . In the present invention, one type or two or more types may be used. In addition to these, an unsaturated acid such as an unsaturated carboxylic acid is further added, whereby the development after light exposure can be improved. As a specific example of the unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or the like may be mentioned. The content of the photosensitive monomers is preferably 7 to 15% by weight in the paste. In other cases, the formation of the pattern is deteriorated, and the phenomenon of insufficient hardness after hardening occurs, which is not preferable. In addition, as the photosensitive oligomer or the photosensitive polymer, an oligomer or a polymer obtained by polymerizing at least one of the above compounds containing a carbon-carbon unsaturated bond can be used. The content of the compound containing a carbon-carbon unsaturated bond -12-201042664 is preferably 10% by weight or more based on the total amount of the photosensitive oligomer and the photosensitive polymer, and preferably 35% by weight or more. In addition, the photosensitive oligomer is preferably obtained by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid with a photosensitive polymer to improve the developability after light exposure. Specific examples of the unsaturated citric acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or the like. The acid value (AV) of the oligomer or polymer having an acid group such as a carboxyl group in the side chain obtained in this manner is preferably 30 to 150, and more preferably 70 to 120. When the acid value is less than 30, the solubility of the unexposed portion in the developing solution is lowered, and if the concentration of the developing liquid is made thick, even the exposed portion may be peeled off, and it may be difficult to obtain a high-definition pattern. In addition, if the acid value exceeds 1,500, the image display tends to have a narrower width. In these photosensitive oligomers and photosensitive polymers, since a photoreactive group is added to a side chain or a molecular terminal, it can be used as a photosensitive photosensitive polymer or a photosensitive oligomer. use. A suitable photoreactive Q group having an ethylenically unsaturated group. The ethylenically unsaturated group may, for example, be a vinyl group, a propenyl group, an acrylic group or a methacryl group. A method of adding an oligomer or a polymer to such a side chain: an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or chlorine for a mercapto group, an amine group, a hydroxyl group or a carboxyl group in the polymer A method of adding an acrylic acid, a chlorinated 'methacrylic acid or an allyl chloride. Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl shrinkage-13-201042664 glyceryl ether, glycidyl ethacrylate, and crotonyl shrinkage. Glycerol ether, glycidyl crotonate, glycidyl isocyanate, and the like. Examples of the ethylenically unsaturated compound having an isocyanate group include (methionyl)acrylenyl isocyanate, (meth)acryloyl ethyl isocyanate, and the like. • In addition, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or a chlorinated acrylic acid, a chlorinated methacrylic acid or an allyl chloride is used for a mercapto group, an amine group, a hydroxyl group or a carboxyl group in the polymer. It is preferable to add 0.05 to 1 _ 当量 equivalent. The content of the photosensitive oligomer and/or the photosensitive polymer in the photosensitive conductive paste is preferably from 7 to 15% by weight in terms of pattern formation property and shrinkage ratio after firing. . Outside of this range, it is not good because the pattern cannot be formed, or the pattern becomes thick. Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzhydryl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4, 4 ·-Bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 4-benzylidene-4- Q-methylbenzophenone, dibenzyl ketone, anthrone, 2 ,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropionylbenzene, p-t-butyldichlorobenzene Ketone, thioxanthone, 2-methyl stilbone, 2-chlorothioxanthone, 2·isopropyl thioxanthone, diethyl thioxanthone, benzyl dimethyl ketal, benzyl methoxy Acetal, benzoin, benzoin methyl ether, benzoin butyric acid, onion, '2-tert-butyl fluorene, 2-pentyl hydrazine, /3-chloroindole, fluorenone , benzoxanthone, dibenzoxanone, methylene fluorenone, 4·azidobenzylidene acetophenone, 2,6-bis(p-azidobenzylidene)cyclohexanone, 2, 6-bis(p-azide subunit)-4- -14- 201042664 methylcyclohexanone, 2-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)anthracene, Im_phenyl-propanedione-2·(o-ethoxycarbonyl)anthracene, 1,3-two - glycerin, 2-(o-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxy-propanetrione-2-(o-benzylidene). Anthracene, mazinone, 2-methyl-[4-(methylthio)phenyl]-2-morpholin-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) ) butanone-1, chlorinated naphthalenesulfonyl, quinolinolsulfonyl chloride, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyl disulfide, benzene And thiazolyl disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylhydrazine, benzoin peroxide and eosin, methylene blue, etc.

A G-reducing dye, a reducing agent such as ascorbic acid or triethanolamine, or the like. In the present invention, one type or two or more types may be used. The photopolymerization initiator is preferably added in an amount of 0.05 to 20% by weight based on the photosensitive organic component, preferably 0.1 to 15% by weight. When the amount of the photopolymerization initiator exceeds 20% by weight, the residual ratio of the exposed portion tends to be too small. Q sensitizers are added to increase sensitivity. Specific examples of the sensitizer include 2,4·diethylthioxanthone, isopropylthioxanthone, and 2,3-bis(4-diethylaminobenzylidene)cyclopentane. Ketone, 2,6-bis(4-dimethylaminobenzylidene)cyclohexanone, 2,6-bis(4-dimethylaminobenzylidene)-4-methylcyclohexanone , Michelin, 4,4|-bis(diethylamino)-benzophenone, 4,4_-bis(dimethyl'amino) ketone (chalcone), 4,4'-double ( Diethylamino) chalcone, p-dimethylamino cinnamyl fluorenone, p-dimethylaminobenzylidene fluorenone, 2-(p-dimethylaminophenyl phenylene) -isonaphthylthiazole, 1,3-bis(4.dimethyl-15-201042664 aminobenzylidene)acetone, 1,3-carbonyl-bis(4-diethylaminobenzylidene) Acetone, 3,3, carbonyl-bis(7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenyl Ethanol* amine, isoamyl dimethylaminobenzoate, isoamyl ester of diethylaminobenzoate, 3-phenyl-5-benzhydrylthiotetrazole, 1-phenyl-5- Ethoxycarbonylthiotetrazole and the like. In the present invention, one type or two or more types may be used. Further, among the sensitizers, those which are photopolymerization initiators can also be used. When the sensitizer is added to the glass paste of the present invention, the amount of the sensitizer to be added is usually 0.05 to 30% by weight, preferably 0.1 to 20% by weight, based on the photosensitive organic component. When the amount is less than 0.05% by weight, the effect of improving the light sensitivity tends to be difficult to exert. When the amount is more than 30% by weight, the residual ratio of the exposed portion tends to be too small. The polymerization inhibitor is added for the purpose of improving the thermal stability during storage. Specific examples of the polymerization inhibiting agent include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenol thiophene, p-t-butylcatechol, and Q N-phenylnaphthalene. Alkylamine, 2,6-di(t-butyl)-p-cresol, chloranil, gallophenol, p-methoxyphenol, etc. In addition, by adding this substance, the threshold of photohardening reaction rises, and the pattern The line width is reduced, and the thick portion of the upper portion of the pattern with respect to the gap disappears. The amount of the polymerization inhibiting agent added is preferably 0.01 to 1 '% by weight in the photosensitive conductive paste. When the amount is less than 0.01% by weight, the effect of addition is less likely to be exhibited. When the amount is more than 1% by weight, the sensitivity is lowered. Therefore, the amount of exposure required for pattern formation tends to increase. -16- 201042664 Specific examples of the plasticizer include dibutyl phthalate 'dioctyl decanoate, polyethylene glycol, glycerin and the like. The antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of the antioxidant include 2,6-di(t-butyl)-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-B. Phenol, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) , 4,4'-bis(3-methyl-6-tert-butylphenol), 1,1,3-gin(2-methyl-4-hydroxy-6-t-butylphenyl) Alkane, bis[3,3-biguanide-(4-hydroxy-3-t-butylphenyl)butyric acid]ethylene glycol ester, dilauryl thiodipropionate, triphenyl phosphite, and the like. In the case where an antioxidant is added, the amount thereof is preferably 0.01 to 1% by weight in the glass paste. In the photosensitive conductive paste of the present invention, in the case where the viscosity of the solution is to be adjusted, it is preferred to add an organic solvent. The content of the organic solvent is preferably from 20 to 40% by weight in the paste. Outside of this range, the paste cannot be applied smoothly, and a film having a uniform thickness cannot be obtained. Further, as the organic Q solvent used at this time, cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, or the like can be used. Cyclopentanone, isobutanol, isopropanol, tetrahydrofuran, dimethyl hydrazine, T-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, 'products An alcohol, diethylene glycol monobutyl ether acetate, or the like, or a mixture of organic solvents containing one or more of the above. In the photosensitive conductive paste of the present invention, at least one of the photosensitive monomer, the photosensitive oligomer, and the photosensitive polymer is usually added, and a photopolymerization initiator, an ultraviolet absorber, and a photo-polymerization initiator are further added as necessary. Additives such as sensitizers, sensitizing and polymerization inhibiting agents, plasticizers, tackifiers, organic solvents, antioxidant powders, organic or inorganic precipitation inhibitors, etc., after blending and formulating, using a three-roller or a kneading machine The mixture is produced in a homogeneous manner. The viscosity of the photosensitive conductive paste is suitably adjusted, and its range is preferably ~200 Pa.s. For example, coating to a glass substrate by spin coating is preferably 0.2 to 5 Pa·s, and is applied by screen printing once to obtain a film thickness of 10 to 20 μm, which is 10 to 100 Pa·s. good. Further, the present invention relates to a method of producing a display, comprising the steps of: exposing a paste coating film by a photomask by drying the photosensitive conductive paste to form a paste coating film; and developing the paste after exposure. a step; and a step of forming a pattern by firing. Next, an example in which the paste coating film is formed by the photosensitive paste method will be described, but the present invention is not limited thereto. The photosensitive conductive paste is entirely or partially coated on a glass substrate or a ceramic substrate or a polymer film. As the coating method, a general method such as a screen printing method, a bar coater, a roll coater, or a die coater knife coater can be used. The coating thickness can be adjusted by selecting the coating number, the mesh of the screen, and the viscosity of the paste. In addition, a method such as a laminator for a photosensitive sheet coated with a photosensitive glass paste on a film such as a polyester film, or a method of transferring a photosensitive conductive paste on a substrate may be used after applying the photosensitive conductive paste. The exposure device is exposed to the agent, and is divided into two parts for coating, and the one side of the film is coated and scraped to make it. Exposure -18- 201042664 Light is generally a method of mask exposure using a photomask as is the case with conventional photolithography. The mask to be used is selected to be either a negative type or a positive type depending on the type of photosensitive organic component. Alternatively, a method of directly drawing a red or blue laser light without using a photomask may be employed. As the exposure device, a stepper exposure machine, a proximity exposure machine, or the like can be used. Further, when a large-area exposure is performed, a photosensitive glass paste is applied onto a substrate such as a glass substrate, and then exposed while being conveyed, whereby a large-area exposure can be performed with an exposure machine having a small exposure area. Examples of the active light source to be used include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet rays are preferred, and as the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a germicidal lamp, or the like can be used. Among these, ultra-high pressure mercury lamps are suitable. The exposure conditions vary depending on the coating thickness, and an ultrahigh pressure mercury lamp having an output of 1 to 100 mW/cm 2 is usually used for exposure for 0.1 to 10 minutes. After the exposure, development is performed by the difference in solubility between the exposed portion and the unexposed portion to the developing solution, and in this case, it can be carried out by a dipping method, a shower method, a spray method, or a brush method. The developing solution is a solution capable of dissolving an organic component to be dissolved in the photosensitive conductive paste. In addition, water can be added to the organic solvent without losing its solubility. In the case where a compound having an acidic group such as a carboxyl group is present in the photosensitive conductive paste, it can be developed with an aqueous alkali solution. In the case of an aqueous alkali solution, -19-201042664, an aqueous solution of sodium hydroxide, sodium carbonate, sodium carbonate, or calcium hydroxide can be used, and in the case of using an aqueous solution of an organic alkali, it is preferred to remove an alkali component during firing. . As the organic base, a general amine compound can be used. Specific examples thereof include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine, and the like. The concentration of the aqueous alkali solution is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. When the concentration of the aqueous alkali solution is less than 0.01% by weight, the soluble portion tends not to be removed, and if it exceeds 10% by weight, the pattern portion is peeled off and the non-soluble portion tends to be corroded. In addition, the development temperature at the time of development is suitable for step management at 20 to 50 °C. Next, it fires in a baking furnace. The firing environment or temperature is different depending on the type of paste or substrate, and is fired in an environment such as air, nitrogen or hydrogen. In the case of the firing furnace, a batch type firing furnace or a conveyor type continuous firing furnace can be used. The firing temperature ' is usually carried out at 400 to 1000 ° C. When pattern processing is performed on a glass substrate, it is usually baked at a temperature Q of 450 to 620 ° C for 10 to 60 minutes. Further, the firing temperature is determined in accordance with the glass powder to be used, and it is preferred to burn at a suitable temperature so that the shape does not collapse after pattern formation and the shape of the glass powder does not remain. Further, in the above steps of coating, exposure, development, and firing, the heating step of 50 to 300 °C may be introduced for the purpose of drying and preliminary reaction. - The display of the present invention obtained by the above-described production method does not contain a noble metal as a conductive powder, and the photosensitive conductive paste of the present invention containing an aluminum powder can be produced at a low cost. In addition, because there is no silver or copper, -20- 201042664, it is possible to manufacture a display that does not have problems such as migration or yellowing, and is electrically stable. Further, since it is rich in glass powder and a photosensitive organic component, it is possible to prevent problems such as poor sintering, high resistance enthalpy, and poor current due to oxidation of the surface of the aluminum powder during firing. [Examples] Next, the present invention will be specifically described by way of examples, and the present invention is not limited by the examples. 〇 In addition, the average particle diameter (d5.) and the maximum particle diameter (D-U) of the following inorganic powders were measured using "MT3 3 00" manufactured by Nikkiso Co., Ltd. Further, the softening point of the glass powder was measured by a differential thermal analyzer manufactured by Rigaku Corporation. _ Manufacturing Example 1 (Metal for forming a dielectric body)

Bi2〇3/Si〇2/Ah〇3/ZnO/B2〇3/BaO= 25/30/5/10/25/5 (% by weight) Q The glass powder (average particle size 2# m) 40 Parts by weight, titanium oxide 1 part by weight, cerium oxide 10 parts by weight, ethyl cellulose 3 parts by weight, monomer (trimethylolpropane triacrylate) 15 parts by weight, terpineol 25 parts by weight 'three The roller turbine is mixed and dispersed to obtain a paste for forming a dielectric body. 'Production Example 2 (partition forming paste)

Si〇2/Al2〇3/ZnO/B2〇3/BaO/LhO= 20/20/5/30/1 5/1 0 (% by weight) Glass powder (average particle size 2 # m) 67 weight , polymer-21 - 201042664 (made by Cyclomer P ACA250' DAICEL Chemical Industry Co., Ltd.) ι by weight, monomer (trimethylolpropane triacrylate), 1 part by weight, titanium oxide (average particle size 0.2 // m) 3 parts by weight, 4 parts by weight of benzyl alcohol, and 3 parts by weight of butyl carbitol acetate were mixed and dispersed in a three-roll mill to obtain a partition forming paste. <Measurement of specific resistance> The resistance 値, thickness, and line width of the in-plane 9-line electrode were measured for the back sheet on which the electrode was fabricated, and the specific resistance of each line was calculated. The average of the calculated enthalpy is determined as the measurement of the specific resistance 値" < L * 値, a * 値, b * 値 measurement> For the backing plate in which the partition walls have been formed, a spectrophotometer is used. (Minolta - Co., Ltd. CM-2002) b* 値 was measured from both sides of the partition film forming film surface. Three points were taken in the same substrate, and three different substrates were taken, and nine points were measured in total, and the average enthalpy was determined, and each measurement was performed. <Evaluation of adhesion strength> 〇For the back sheet in which the partition walls have been formed, peeling test (using Cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) with 1 920 pieces of cellophane tape is not peeled off Those who are determined to be excellent, only one peeling is determined to be good, and two or more peelings are determined to be bad. <Evaluation of Printability> In the substrate on which the photosensitive conductive paste was printed, the film thickness in the in-plane 36 was measured. 'The difference between the maximum 値 and the minimum 小于 is less than 2 m, and is preferably 2 or more. Less than 3# m is determined to be good, and 3ym or more is determined to be bad. -22- 201042664 <Evaluation of pattern shape> After the photosensitive conductive paste is applied and dried, the pattern is formed by exposure and development, and then baked, and the pattern is not defective, and one is made to one. 5 people were determined to be good, and 6 or more were classified as bad. Examples 1 to 17 and Comparative Examples 1 to 10 The aluminum powder of the characteristics disclosed in Table 1, the glass powder of the characteristics disclosed in Table 2, and the following additives are listed in Tables 3 to 5 and added. The amount ' 0 was mixed by a three-roll mill to prepare a photosensitive conductive paste. Photosensitive polymer: Photosensitive acrylic polymer having an acid value of 85 and Mw = 32,000 (APX-7 16 manufactured by Tore Co., Ltd.) Photosensitive monomer: trimethylolpropane triacrylate • Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 dispersant: polyether-ester type anionic surfactant (manufactured by Nanben Chemical Co., Ltd., "DISPARLON" 7004) Antimony polymerization inhibitor: p-methoxyphenol organic solvent: diethylene glycol monobutyl ether acetate forms a back sheet of an AC (alternating) type plasma display panel of size 42吋, and is evaluated. . The formation method will be described in order. As a glass substrate, a 42-inch size PD-200 (manufactured by Asahi Glass Co., Ltd.) of 590 x 964 x 2.8 mm was used. On this substrate, the photosensitive conductive paste obtained by the above method was applied by screen printing, and dried to serve as an address electrode. After a predetermined number of exposures through a predetermined mask, -23-201042664 is developed to form an unfired pattern. After the pattern is formed, at 590. (3) The substrate was fired for 15 minutes. The substrate was coated and dried with the paste for forming a dielectric material obtained in Production Example 1. In addition, the partition wall forming paste obtained in Production Example 2 was paste-coated by a die coater. After being formed into a predetermined thickness, it was dried in a dust-free oven at 100 ° C for 40 minutes to form a coating film. The gap with the predetermined mask was taken as 150 μm, and the formed coating film was exposed. 藉 By screen printing, The phosphor pastes of the respective colors were applied to the partition walls formed in this manner, and fired (500 ° C, 30 minutes) to form a phosphor layer on the side and bottom sides of the partition walls. - The obtained back sheet and the foregoing After the front plate is bonded and sealed, the sealing _ discharge gas is connected to the driving circuit to produce a plasma display (PDP). Evaluation of the photosensitive conductive pastes of Examples 1 to 18 and Comparative Examples 1 to 1

The results are disclosed in Table 6. Aluminum powder Average particle size (μ, m) Specific surface area (m2/s) Maximum particle size (am) Spherical ratio (Ψ〇) A 2.0 0.8 4.0 85 B 1.0 1.3 4.5 so . C 1.5 1.2 4.0 80 D 3.0 0.6 7.0 85 E 4.0 0.4 8.0 85 F 2.0 0.6 5.0 60 G 2.0 0.5 6.0 50 Η 2.0 1.9 3.5 55 I 2.0 0.7 15.0 80 J 0.8 2.0 4.0 80 K 5.0 0.3 15.0 80 -24- 201042664

[Table 2] Glass powder softening point CC) Average particle diameter (β m) Maximum particle diameter (β m) L 490 0.8 3.0 Μ 490 1.5 4.0 Ν 440 0.8 3.0 〇 530 0.8 3.0 Ρ 390 0.8 3.0 Q 570 0.8 3.0 -25 - 201042664

OD [ε漱] Example C<1 1 1 1 1 1 1 1 1 1 1 1 1 1 ο 1 1 ο ο IT IT) νη νη i 1 ο 1 1 1 1 1 1 1 1 1 1 1 1 ο τ < 1 1 1 2 ο 寸 CN 穿 wear 1 1 1 1 1 1 1 1 1 1 1 ο 1 1 1 1 ο ο ΙΤΪ ΙΤΪ un <Ν 1 1 1 1 1 1 1 ο 1 1 ο «111 Η 1 1 1 1 1 ο ο inch wn wn CN οο 1 1 1 1 1 1 1 ο 1 1 1 ο ι—Η 1 1 1 1 1 2 ο ννη Οί Γ- 1 1 1 1 1 1 ο 1 1 1 1 ο ι i 1 1 1 1 1 ο ο inch CS 1 1 1 1 1 ο 1 1 1 1 1 ο r__H 1 1 1 1 1 ο ο inch <Τ) νη CN ι〇1 1 1 1 ο 1 1 1 1 1 1 ο τ Η 1 1 1 1 1 ο ο 寸ν〇C<I inch 1 1 1 ο 1 1 1 1 1 1 1 ο 1 1 1 1 1 ο ο inch wn <Ν CO 1 1 ο 1 1 1 i 1 1 1 1 ο ι 1 1 i 1 1 1 2 ο 〇ν〇νη <Ν ο<ι 1 ο 1 1 1 1 1 1 1 1 ο ι"""Η 1 1 1 1 1 ο ο inch Ιη <Ν t < ο 1 1 1 1 1 1 1 1 1 1 ο ι—Η 1 1 1 1 1 ο ο ΙΟ ΙΟ νη CN < ΡΡ ο QW Ρ-. ο r-Ή Μ ζ ο 〇Η &<Π embedded aa ΉΠΒ nmL cnir 鏺蘅<Π dispersant 蘅Ή tear <Π organic Aluminum powder glass powder _φ side '-^ , 900- 201042664 ο ο [inch inch] Comparative example 1 1 1 1 1 1 1 1 1 VO 1 1 1 1 1 inch »〇v〇cs v〇1 1 1 1 1 1 1 1 1 o 1 1 1 1 1 VO inch ΙΟ 〇cs inch Ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ο ο ο 寸 m 〇in o \T) CsJ cn Ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1 o ”蜱1 ο ο 寸*〇<N CM 1 1 1 1 1 1 1 1 1 1 ο or~H 1 1 1 1 1 2 ο inch wo ο *〇 o <N 1 < 1 1 1 1 1 1 1 1 1 ο 1 o 1 1 1 1 1 2 ο 寸νη \n CS 翠oo 1 1 1 1 1 1 1 1 1 1 f" H 1 1 1 1 1 νο CO 0.75 1 0.25 csi rj 1 1 1 1 1 1 1 1 1 1 o 1 1 1 1 1 ιη ιη inch in vn cs 1 1 1 1 1 1 1 1 1 1 o 1 1 1 1 1 τ—< N (1⁄4 n 1 1 1 1 1 1 1 1 1 1 o 1 1 1 1 1 'Ο inch ίη v〇(N 1 1 1 1 1 1 1 1 1 1 o 1 1 1 1 1 CN rH cn f—寸 inch CO 1 1 1 1 1 1 1 1 1 1 υη 1 1 1 1 1 ο ο inch ίη v〇v〇cs < PQ UQ ω Ρ-, ϋ κ tH ;Zi o ο <□ embedded am photosensitive Monomer photopolymerization initiator 1 dispersant polymerization inhibitor organic solvent Aluminium powder glass powder blending amount (parts by weight) - Ll_ 201042664 [Table 5] Comparative Example 7 8 9 10 Blending amount (parts by weight) Aluminum powder A 40 40 48 35 B — One — — C — One — — DE — — — — F — — — — G — — — — Η — — — — I — — — — J — — — — K — — — — Glass powder L 20 2 11 7 Μ — — — ~ N — — — ~ 〇— — — ~ P — — — ~ Q — — — ~ Photosensitive polymer 8 12 5 13.5 Photosensitive monomer 7 13 5 13.5 Photopolymerization initiator 4 4 3 4 Dispersant 0.5 0.5 0.75 0.5 Polymerization inhibitor 0.5 0.5 0.25 0.5 organic solvent 20 28 27 28

-28- .201042664 [Table 6] Specific resistance (# Ω .cm) Adhesion strength b*値 Printability pattern shape Example 1 500 Excellent 2.2 Excellent example 2 960 Good 2.4 Excellent Example 3 860 Excellent 2.6 Excellent example 4 750 Excellent 2.1 Excellent Example 5 920 Good 2.5 Excellent Example 6 600 Excellent 2.6 Excellent Example 7 640 Excellent 2.6 Excellent Example 8 720 Excellent 3.0 Excellent Example 9 670 Excellent 2.4 Excellent Example 10 520 Excellent 2.5 Excellent Example 11 590 Excellent 2.4 Excellent Example 12 540 Good 2.6 Excellent Example 13 530 Good 2.9 Excellent Example 14 860 Excellent 3.0 Good Example 15 520 Excellent 2.5 Excellent Example 16 800 Excellent 2.6 Good Example 17 990 Good 2.5 Excellent Example 18 750 Excellent 2.6 Liangliang Comparative Example 1 2940 Bad 2.4 Good Bad Comparative Example 2 1300 Bad 2.6 Good Bad Comparative Example 3 850 Excellent 3.0 Good Bad Comparative Example 4 1450 Bad 2.5 Excellent Comparative Example 5 1050 Excellent 2.5 Excellent Comparative Example 6 1690 Good 3.4 Liangliang Comparative Example 7 1880 Excellent 2.9 Excellent Comparative Example 8 610 Bad 2.5 Good Excellent Comparative Example 9 1260 Excellent 2.6 Good Bad Comparison Example 10 1010 Good 2.5 Liangyou -29- 201042664 The back plate electrodes obtained in Examples 1 to 18 can form a good electrode pattern, and in the state in which the partition walls have been formed, the evaluation of the electrode adhesion and the yellowing of the back sheet Good results were obtained in terms of the degree of b*値. Any of Examples 1 to 18 was good. With respect to Comparative Examples 1 to 1 , all satisfactory results in terms of resistance 値, adhesion strength, and electrode pattern processability of the electrode could not be obtained. [Simple description of the diagram] None. [Main component symbol description] None. -30-

Claims (1)

201042664 VII. Patent application scope: 1. A photosensitive conductive paste containing: (A) 30 to 45 wt% of aluminum powder having an average particle diameter of 1 to 4 μm, and (B) a softening point of 400 to 550 ° C Glass • 5 to 15% by weight of the powder, (C) 15 to 30% by weight of the photosensitive organic component, » and (D) solvent 20 to 40% by weight. 2. The photosensitive conductive paste according to claim 1, wherein the weight ratio of the (A) aluminum powder to the (B) glass powder is in the range of 75: 25 to 95: 5. f) 3. The photosensitive conductive paste of claim 1 or 2 wherein the spherical ratio of the (A) aluminum powder is 60% or more. 4. The photosensitive conductive paste of claim 1, 2 or 3, wherein the average particle diameter Da of the (A) aluminum powder and the average particle diameter Dg of the (B) glass powder satisfy the following formula: 0.3# mS Dg Each DaS 10〆m. 5. For the photosensitive conductive paste of claim 1, 2, 3 or 4, the specific surface area of the (A) powder is 0.2 to 1.4 m2/g. 6. A method of manufacturing a display, comprising: a step of applying a photosensitive conductive paste according to claim 1, 2, 3, 4 or 5 to a substrate and drying it to form a paste coating film; a step of exposing the paste coating film through a photomask; a step of developing the paste coating film after exposure; and a step of forming a pattern by firing. 7. A display obtained by the method of manufacturing a display of claim 6 of the patent application. -31- .201042664 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: