JPWO2010113581A1 - Photosensitive conductive paste, display manufacturing method using the same, and display - Google Patents

Abstract

30 to 45% by weight of aluminum powder having an average particle size of 1 to 4 μm, 5 to 15% by weight of glass powder having a softening point of 400 to 550 ° C., 15 to 30% by weight of photosensitive organic component, and 20 to 20% of solvent Provided is a photosensitive conductive paste capable of forming a highly conductive electrode at a low cost by using a photosensitive conductive paste containing 40% by weight, and a display obtained using the photosensitive conductive paste.

Description

  The present invention relates to a photosensitive conductive paste and a method for manufacturing a display, and more particularly to a photosensitive conductive paste containing aluminum powder.

  A plasma display panel (PDP) can display at a higher speed than a liquid crystal panel and can be easily increased in size, and thus has penetrated into fields such as OA equipment and public information display devices. It is also used in the field of high-definition television.

  In the PDP, a slight gap formed between two glass substrates of a front plate and a back plate is used as a discharge space, and plasma discharge is generated between the anode electrode and the cathode electrode, and is enclosed in the discharge space. The display is performed by emitting ultraviolet light generated from the gas to a phosphor provided in the discharge space. In this case, the electrodes are arranged in stripes on the front plate and the back plate, respectively, a plurality of electrodes are parallel, the electrodes on the front plate and the electrodes on the back plate face each other with a slight gap and are orthogonal to each other. Formed as follows. Among the PDPs, a surface discharge type PDP having a three-electrode structure suitable for color display using a phosphor includes a plurality of electrode pairs composed of display electrodes adjacent in parallel to each other, and a plurality of address electrodes orthogonal to each electrode pair. Have. In addition, a barrier rib for preventing crosstalk of light and securing a discharge space is formed in the space between the electrodes on the back plate. Further, a phosphor is formed in the discharge space.

  Of the electrodes, the address electrodes formed on the back plate need to have a uniform thickness and line width over a wide range. Furthermore, with the higher definition of PDPs, the fine pitch of address electrodes is progressing. In addition, since PDP passed through the baking process at the temperature of 500 degreeC or more in air, it was necessary to use the material which does not oxidize even if it passes through a baking process. From these 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 noble metal. On the other hand, it is conceivable to use a paste containing aluminum as a conductive paste that does not use a noble metal such as silver or gold. However, when a conductive paste containing aluminum powder is applied and dried, it is fired in air at a temperature of 500 ° C. There is a problem that the surface of the aluminum powder is oxidized, resulting in poor sintering, a high resistance value, and further inability to conduct. Moreover, in order to solve such a problem, the electrically conductive paste containing the material which prevents the oxidation of aluminum and aluminum is proposed (for example, patent document 2). When added to a photosensitive paste, the metal or metal compound for inhibiting oxidation used in this document reacts with an organic component having reactivity (polymer, oligomer, monomer, etc.), There was a problem that the storage stability of the paste was poor, the change in paste viscosity with time was large, and a uniform film could not be formed.

JP-A-5-271576 JP-A-5-298997

  An object of the present invention is to provide a photosensitive conductive paste that can form a pattern with high definition and a uniform thickness and line width at low cost, and can obtain a conductive pattern with low resistance.

  That is, the present invention comprises (A) 30 to 45% by weight of aluminum powder having an average particle diameter of 1 to 4 μm, (B) 5 to 15% by weight of glass powder having a softening point of 400 to 550 ° C., and (C) photosensitivity. The present invention relates to a photosensitive conductive paste containing 15 to 30% by weight of a photosensitive organic component and 20 to 40% by weight of (D) a solvent.

  The weight ratio of the (A) aluminum powder and the (B) glass powder is preferably in the range of 75:25 to 95: 5.

  The sphericity of the (A) aluminum powder is preferably 60% or more.

It is preferable that 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 μm ≦ Dg ≦ Da ≦ 10 μm
The specific surface area of the (A) aluminum powder is preferably 0.2 to 1.4 m ² / g.

  The present invention also includes a step of applying and drying the above-described photosensitive conductive paste on a substrate to form a paste coating film, a step of exposing the paste coating film through a photomask, and developing the exposed paste coating film. The present invention relates to a display manufacturing method including a step and a step of forming a pattern by baking.

  Furthermore, this invention relates to the display obtained by the said manufacturing method.

  The photosensitive conductive paste of the present invention can form a high-definition, uniform thickness and width pattern at low cost, and a low-resistance conductive pattern can be obtained. Further, by using this, a high-performance display can be manufactured at a low cost.

  The present invention relates to a photosensitive conductive paste containing aluminum powder, glass powder, a photosensitive organic component, and a solvent.

  The photosensitive conductive paste of the present invention contains an aluminum powder as a conductive powder, a glass powder for ensuring adhesion with a substrate, and a photosensitive organic component for forming a fine pitch wiring pattern. And an organic solvent for ensuring coating stability.

  In the conventional conductive paste, it is appropriate to contain as much conductive powder as possible and to make glass powder and photosensitive organic components as small as possible in consideration of low resistance and debinderability during firing. However, since the powder surface of aluminum powder tends to oxidize when fired in air, sintering failure may occur, the resistance value may increase, and conduction may not be achieved. In order to solve this, in the present invention, the amount of the glass powder and the photosensitive organic component in the photosensitive conductive paste is relatively large, that is, 30 to 45% by weight of aluminum powder in the photosensitive conductive paste, glass By using a photosensitive conductive paste containing 5 to 15% by weight of powder, 15 to 30% by weight of photosensitive organic component, and 20 to 40% by weight of solvent, oxidation of aluminum powder during firing is prevented, and Adhesion can be ensured and conduction can be ensured.

  Furthermore, photosensitive conductive paste containing 40 to 65% by weight of aluminum powder and 20 to 50% by weight of photosensitive organic component in a dry film obtained by applying and drying a photosensitive conductive paste on a substrate and evaporating the solvent. By using the paste, it is possible to prevent the aluminum powder from being oxidized at the time of firing, and to ensure electrical conduction.

First, about aluminum powder, it is required to contain 30 to 45 weight%, Preferably 35 to 40 weight%. If it is less than 30% by weight, it is impossible to ensure the conduction of the electrode, and if it exceeds 45% by weight, the pattern formability deteriorates and a problem arises that a fine pitch electrode pattern cannot be obtained. Regarding the particle diameter of the aluminum powder, the 50% particle diameter (average particle diameter) in the weight distribution curve measured by a particle size distribution measuring apparatus (for example, “MT3300” manufactured by Nikkiso) is preferably 1 to 4 μm. More preferably, it is 5 to 3 μm. If the thickness is less than 1 μm, oxidation of the surface of the aluminum powder is promoted at the time of firing, and conduction may not be obtained. If the thickness exceeds 4 μm, the smoothness of the electrode pattern is deteriorated, and the dielectric or barrier rib pattern formed on the electrode There is a risk of worsening the shape. Further, the maximum particle diameter of the aluminum powder is preferably 20 μm or less, and more preferably 10 μm or less. If the maximum particle diameter exceeds 20 μm, pattern formation is degraded, or there are many particles larger than the film thickness, which tends to adversely affect electrodes and dielectric layers formed later. . The specific surface area of the aluminum powder is preferably 0.2~1.4m ² / g, more preferably 0.5~1.2m 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 and the partition pattern formed on the electrode may be deteriorated, and 1.4 m ² / g. In the case of exceeding, oxidation of the surface of the aluminum powder is promoted at the time of firing, and the conductivity of the electrode may be deteriorated.

  The glass powder is preferably contained in the photosensitive conductive paste in an amount of 5 to 15% by weight, and more preferably 7 to 12% by weight. If it is less than 5% by weight, the adhesion to the substrate is poor, leading to disconnection of the electrode pattern. If it exceeds 15% by weight, the probability of occurrence of poor conduction increases. The softening point of the glass powder is preferably 400 to 550 ° C, and more preferably 450 to 500 ° C. When the temperature is lower than 400 ° C., the glass is softened before the photosensitive organic component evaporates, so that the electrode shape after firing may be deteriorated. When it exceeds 550 ° C., the softening of the glass does not proceed, and the adhesion with the substrate tends to be not ensured.

  The average particle size of the glass powder may be appropriately selected according to the purpose, but the average particle size is preferably 0.3 to 2.0 μm, more preferably 0.5 to 1.0 μm. When the average particle diameter is less than 0.3 μm, aggregation tends to occur, and thus pattern formability may be deteriorated. If it exceeds 2.0 μm, the sinterability during firing tends to be insufficient.

The average particle diameter Dg of the glass powder and the average particle diameter Da of the aluminum powder are
0.3 μm ≦ Dg ≦ Da ≦ 10 μm
Preferably satisfying
0.1 ≦ Dg / Da ≦ 0.9
It is more preferable to satisfy. If Dg / Da is less than 0.1, the particle size of aluminum tends to be too small and dispersion tends to be very difficult. If it is more than 0.9, pattern formability is reduced, and sinterability during firing is reduced. There is a tendency to adversely affect.

  Further, the maximum particle diameter of the glass powder is preferably 20 μm or less, and more preferably 10 μm or less. If the maximum particle diameter exceeds 20 μm, pattern formation is degraded, or there are many particles larger than the film thickness, which tends to adversely affect electrodes and dielectric layers formed later. .

The specific surface area of the glass powder is preferably 1~15cm ² / g, and more preferably 2 to 10 cm ² / g. If the specific surface area is less than 1 cm ² / g, the pattern formability tends to decrease or the sinterability during firing tends to be insufficient, and if it exceeds 15 cm ² / g, aggregation tends to occur. .
The content ratio of the aluminum powder and the glass powder is preferably in the range of 75:25 to 95: 5 by weight. More preferably, it is 80: 20-92: 8. If the ratio is less than 75:25, the amount of aluminum may be too small and conduction failure may occur. If the ratio is more than 95: 5, the amount of glass powder will be too small and the adhesion to the substrate will deteriorate. There is a risk that problems such as peeling of the electrode pattern may occur.
The spherical ratio of the aluminum powder is preferably 60% or more of the aluminum powder contained. More preferably, it is 80% or more. If it is less than 60%, the degree of filling of the aluminum powder in the electrode after firing may deteriorate, resulting in problems such as poor conduction.
The photosensitive organic component used in the photosensitive conductive paste of the present invention contains a photosensitive organic component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and if necessary, Additives such as photopolymerization initiators, ultraviolet absorbers, sensitizers, sensitizers, polymerization inhibitors, plasticizers, thickeners, organic solvents, antioxidants, dispersants, organic or inorganic precipitation inhibitors The thing which added the ingredient is mention | raise | lifted. In the case of a normal photosensitive conductive paste, the organic component is often prepared with a content as low as possible in consideration of the resistance value and conductivity, but the photosensitive paste of the present invention is photosensitive. The organic component is preferably contained in an amount of 15 to 30% by weight in the paste. This is to prevent oxidation of the aluminum powder during firing by containing a relatively large amount of the photosensitive organic component. When the photosensitive organic component is less than 15% by weight, the effect of suppressing oxidation of aluminum is small, and when it exceeds 30% by weight, voids exist between the aluminum particles in the electrode pattern after firing, and the conductivity is low. The problem that it cannot be secured occurs.

  Hereinafter, the photosensitive organic component of the present invention will be described.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include monofunctional and polyfunctional (meth) acrylates, vinyl compounds, allyl compounds, and the like. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-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, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, Roll acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl 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, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol di Acrylate, 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, diacrylate of bisphenol A-propylene oxide adduct, acrylate such as thiophenol acrylate, benzyl mercaptan acrylate, and among these aromatic ring hydrogen atoms, Monomer substituted with 5 chlorine atoms 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 some acrylates in the molecule of the above compound Those changed hands methacrylate, .gamma.-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. In the present invention, one or more of these can be used.

  In addition to these, the development property 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.

  The content of these photosensitive monomers is preferably 7 to 15% by weight in the paste. In other ranges, the pattern formability is deteriorated and the hardness after curing is not preferable.

Moreover, as a photosensitive oligomer and a photosensitive polymer, the oligomer and polymer obtained by superposing | polymerizing at least 1 type of the compound containing the said carbon-carbon unsaturated bond can be used. The content of the compound containing a carbon-carbon unsaturated bond is preferably 10% by weight or more, and more preferably 35% by weight or more in the total amount of the photosensitive oligomer and the photosensitive polymer.
Furthermore, it is preferable to copolymerize a photosensitive oligomer or photosensitive polymer with an unsaturated acid such as an unsaturated carboxylic acid to improve developability after exposure. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. The acid value (AV) of the oligomer or polymer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 30 to 150, more preferably 70 to 120. If the acid value is less than 30, the solubility of the unexposed area in the developing solution is lowered. Therefore, when the developing solution concentration is increased, the exposed area is peeled off, and a high-definition pattern tends to be difficult to obtain. Further, when the acid value exceeds 150, the development allowable width tends to be narrowed.

  By adding a photoreactive group to the side chain or molecular end of these photosensitive oligomers and photosensitive polymers, they can be used as photosensitive polymers and photosensitive oligomers having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

  Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of addition reaction of acid chloride or allyl chloride.

  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 crotonic acid, glycidyl ether of isocrotonic acid, and the like.

  Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.

  In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add.

  The content of the photosensitive oligomer and / or the photosensitive polymer in the photosensitive conductive paste is preferably 7 to 15% by weight in the paste from the viewpoint of pattern formability and shrinkage after baking. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.

  Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoinmethi 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-butadion-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, Mihira -Ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, naphthalenesulfonyl chloride, quinoline Sulfonyl chloride, N-phenylthioacridone, 4,4′-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide and Examples include photoreductive dyes such as eosin and methylene blue, and reducing agents such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used.

  The photopolymerization initiator is preferably added in an amount of 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, based on the photosensitive organic component. When the photopolymerization initiator is less than 0.05% by weight, the photosensitivity tends to be poor, and when the photopolymerization initiator exceeds 20% by weight, the residual ratio of the exposed portion tends to be too small.

  A sensitizer is added in order to improve 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-dimethylaminoben) Colander) acetone, 1,3-carbonyl-bis (4-diethi) Aminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, dimethylaminobenzoic acid Examples thereof include isoamyl, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, and 1-phenyl-5-ethoxycarbonylthiotetrazole. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer to the glass paste of this invention, it is preferable that the addition amount is 0.05-30 weight% normally with respect to the photosensitive organic component, More preferably, it is 0.1-20 weight%. It is. If it is less than 0.05% by weight, the effect of improving the photosensitivity tends to be hardly exhibited, and if it exceeds 30% by weight, the residual ratio of the exposed portion tends to be too small.

  A polymerization inhibitor is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, pyrogallol and p-methoxyphenol. Further, by adding, the threshold of the photocuring reaction is increased, the pattern line width is reduced, and the pattern upper portion with respect to the gap is not increased.

  The addition amount of the polymerization inhibitor is preferably 0.01 to 1% by weight in the photosensitive conductive paste. If it is less than 0.01% by weight, the effect of addition tends to be difficult, and if it exceeds 1% by weight, the sensitivity tends to decrease, so that a large amount of exposure tends to be required for pattern formation.

  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 the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-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-4-hydroxy-6-tert-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-tert-butylphenyl) butyric Acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. When adding antioxidant, it is preferable that the addition amount is 0.01 to 1 weight% in a glass paste.

  In order to adjust the viscosity of the solution, an organic solvent is preferably added to the photosensitive conductive paste of the present invention. The content of the organic solvent is preferably 20 to 40% by weight in the paste. In other ranges, the paste cannot be applied successfully, and a film having a uniform thickness cannot be obtained. 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, bromo Benzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, terpineol, diethylene glycol monobutyl ether acetate and the like, and an organic solvent mixture containing one or more of these are used.

  The photosensitive conductive paste of the present invention is usually at least one of the photosensitive monomer, photosensitive oligomer, and photosensitive polymer, and if necessary, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, and a sensitizer. After preparing additive components such as an auxiliary agent, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, an antioxidant, a dispersant, an organic or inorganic suspending agent to have a predetermined composition, three It is mixed and dispersed homogeneously with a roller or kneader.

  The viscosity of the photosensitive conductive paste is appropriately adjusted, but the range is preferably 0.2 to 200 Pa · s. For example, when applying to a glass substrate by spin coating, 0.2 to 5 Pa · s is more preferable. To obtain a film thickness of 10 to 20 μm by applying it once by a screen printing method, 10 to 100 Pa · s. s is more preferable.

  The present invention also includes a step of applying and drying the above-described photosensitive conductive paste to form a paste coating film, a step of exposing the paste coating film through a photomask, a step of developing the exposed paste coating film, and The present invention relates to a display manufacturing method including a process of forming a pattern by baking.

  Next, an example of forming a paste coating film using a photosensitive paste method will be described, but the present invention is not limited to this.

  A photosensitive conductive paste is applied over the entire surface or partially on a glass substrate, a ceramic substrate, or a polymer film. As a coating method, a general method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, screen mesh, and paste viscosity. Alternatively, a method may be used in which a photosensitive sheet obtained by applying a photosensitive glass paste on a film such as a polyester film is prepared, and the photosensitive conductive paste is transferred onto the substrate using an apparatus such as a laminator.

  After applying the photosensitive conductive paste, exposure is performed using an exposure apparatus. As for exposure, a mask exposure method using a photomask is generally used, as in normal photolithography. 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. Alternatively, a method of directly drawing with a red or blue laser beam or the like without using a photomask may be used.

As the exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. In addition, when performing large area exposure, a photosensitive glass paste is applied on a substrate such as a glass substrate and then exposed while being conveyed, thereby exposing a large area with an exposure machine having a small exposure area. Can do. Examples of the active light source used include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet rays are most preferable, 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, or a germicidal lamp can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is usually performed for 0.1 to 10 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the unexposed portion in the developer.

  As the developer, a solution in which an organic component to be dissolved in the photosensitive conductive paste can be dissolved is used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive conductive paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, an aqueous solution of sodium hydroxide, sodium carbonate, sodium carbonate, calcium hydroxide, or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight. If the concentration of the aqueous alkali solution is less than 0.01% by weight, the soluble part tends to be removed, and if it exceeds 10% by weight, the pattern part tends to be peeled off and the insoluble part tends to corrode. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  Next, baking is performed in a baking furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. The firing temperature is usually 400 to 1000 ° C. When patterning on a glass substrate, firing is usually performed at a temperature of 450 to 620 ° C. for 10 to 60 minutes. The firing temperature is determined by the glass powder to be used, but it is preferable to fire at an appropriate temperature that does not break the shape after pattern formation and does not leave the shape of the glass powder.

  Moreover, you may introduce | transduce a 50-300 degreeC heating process for the purpose of drying and a preliminary reaction in each process of the above application | coating, exposure, image development, and baking.

  The display of the present invention obtained by the above manufacturing method can be manufactured at low cost because the photosensitive conductive paste of the present invention containing no aluminum and no aluminum is used as the conductive powder. In addition, since silver or copper is not contained, problems such as migration and yellowing do not occur, and an electrically stable display can be manufactured.

  Further, since the glass powder and the photosensitive organic component are contained in a large amount, problems such as poor sintering, high resistance, and poor conduction due to oxidation of the surface of the aluminum powder during firing can be prevented.

  Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to such examples.

In the following average particle diameter _{(D 50)} of the inorganic powder and the maximum particle diameter _{(D max)} is a value measured using "MT3300" manufactured by Nikkiso Co., Ltd.. Moreover, the softening point of the glass powder was measured with a differential thermal analyzer manufactured by Rigaku.

Production Example 1 (Dielectric Forming Paste)
Bi ₂ O ₃ / SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO = 25/30/5/10/25/5 (% by weight) glass powder (average particle size 2 μm) 40 parts by weight 10 parts by weight of titanium oxide, 10 parts by weight of silicon oxide, 3 parts by weight of ethyl cellulose, 15 parts by weight of monomer (trimethylolpropane triacrylate) and 25 parts by weight of terpineol were added and mixed and dispersed with three rollers to form a dielectric. A paste was obtained.

Production Example 2 (Partition Wall Forming Paste)
SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO / Li ₂ O = 20/20/5/30/15/10 (wt%) glass powder (average particle size 2 μm) 67 parts by weight, 10 parts by weight of polymer (Cyclomer P ACA250 manufactured by Daicel Chemical Industries, Ltd.), 10 parts by weight of monomer (trimethylolpropane triacrylate), 3 parts by weight of titanium oxide (average particle size 0.2 μm), 4 parts by weight of benzyl alcohol, 3 parts by weight of butyl carbitol acetate was added and mixed and dispersed with three rollers to obtain a partition wall forming paste.
<Measurement of specific resistance>
About the backplate produced to the electrode, the resistance value, thickness, and line width of the electrode of 9 lines in the surface were measured, and the specific resistance of each line was calculated. An average value of the calculated values was obtained and used as a measured value of specific resistance.
<Measurement of L ^* value, a ^* value, b ^* value>
About the backplate formed to the partition, b ^* value was measured from the both sides of the partition formation film surface using the spectrocolorimeter (Minolta Co., Ltd. CM-2002). A total of 9 points of 3 points on the same substrate and 3 different substrates were measured, and an average value was obtained as each measured value.
<Evaluation of adhesion strength>
The back plate formed up to the partition wall was subjected to a cellophane tape peeling test of 1920 electrode terminals (using Nichiban cello tape (registered trademark)). Those that were peeled off were considered defective.
<Evaluation of printability>
On the substrate printed with the photosensitive conductive paste, measure the film thickness at 36 locations in the surface, and the difference between the maximum and minimum values is excellent if it is less than 2 μm, good if it is 2 μm or more but less than 3 μm, if it is 3 μm or more Was regarded as defective.
<Evaluation of pattern shape>
After applying / drying the photosensitive conductive paste, patterning by exposure / development, baking is performed, the one with no pattern chip is excellent, the one from 1 to 5 is good, the one with 6 or more is bad It was.

Examples 1-17, Comparative Examples 1-10
A photosensitive conductive paste was prepared by mixing the aluminum powder having the characteristics shown in Table 1, the glass powder having the characteristics shown in Table 2, and the following additives in the types and addition amounts shown in Tables 3 to 5 with three rollers. .
Photosensitive polymer: photosensitive acrylic polymer having an acid value of 85 and Mw of 32,000 (APX-716, manufactured by Toray Industries, Inc.)
Photosensitive monomer: trimethylolpropane triacrylate photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
Dispersant: polyether ester type anionic surfactant (manufactured by Enomoto Kasei Co., Ltd., “Disparon” 7004)
Polymerization inhibitor: p-methoxyphenol Organic solvent: diethylene glycol monobutyl ether acetate A 42-inch size AC (alternating current) type plasma display panel back plate was formed and evaluated. The forming method will be described in order.

  As a glass substrate, PD-200 (manufactured by Asahi Glass Co., Ltd.) having a size of 590 × 964 × 2.8 mm and 42 inches was used. On this board | substrate, the photosensitive electrically conductive paste obtained by the said method was apply | coated and dried by screen printing as an address electrode. After exposing a predetermined number of times through a predetermined photomask, development was performed to form an unfired pattern. After pattern formation, baking was performed at 590 ° C. for 15 minutes.

  The substrate was coated and dried with the dielectric forming paste obtained in Production Example 1.

  Further, the partition wall forming paste obtained in Production Example 2 was applied to a predetermined thickness with a die coater, and then dried in a clean oven at 100 ° C. for 40 minutes to form a coating film. The formed coating film was exposed with a gap of 150 μm from a predetermined photomask.

  Each color phosphor paste was applied to the barrier ribs thus formed by screen printing and baked (500 ° C., 30 minutes) to form phosphor layers on the side and bottom portions of the barrier ribs.

  The obtained back plate was bonded to the front plate and sealed, and then a discharge gas was sealed, and a driving circuit was joined to produce a plasma display (PDP).

  Table 6 shows the evaluation results of the photosensitive conductive pastes of Examples 1 to 18 and Comparative Examples 1 to 10.

The back plate electrodes obtained in Examples 1 to 18 can form a good electrode pattern, and in the state where the partition walls are formed, the electrode adhesion evaluation and the back plate yellowness b ^* value measurement are good. Results were obtained. Examples 1 to 18 were all good. About Comparative Examples 1-10, what was satisfactory in all the points of the resistance value of an electrode, adhesive strength, and electrode pattern workability was not obtained.

  The present invention relates to a photosensitive conductive paste and a method for manufacturing a display, and more particularly to a photosensitive conductive paste containing aluminum powder.

  A plasma display panel (PDP) can display at a higher speed than a liquid crystal panel and can be easily increased in size, and thus has penetrated into fields such as OA equipment and public information display devices. It is also used in the field of high-definition television.

  In the PDP, a slight gap formed between two glass substrates of a front plate and a back plate is used as a discharge space, and plasma discharge is generated between the anode electrode and the cathode electrode, and is enclosed in the discharge space. The display is performed by emitting ultraviolet light generated from the gas to a phosphor provided in the discharge space. In this case, the electrodes are arranged in stripes on the front plate and the back plate, respectively, a plurality of electrodes are parallel, the electrodes on the front plate and the electrodes on the back plate face each other with a slight gap and are orthogonal to each other. Formed as follows. Among the PDPs, a surface discharge type PDP having a three-electrode structure suitable for color display using a phosphor includes a plurality of electrode pairs composed of display electrodes adjacent in parallel to each other, and a plurality of address electrodes orthogonal to each electrode pair. Have. In addition, a barrier rib for preventing crosstalk of light and securing a discharge space is formed in the space between the electrodes on the back plate. Further, a phosphor is formed in the discharge space.

  Of the electrodes, the address electrodes formed on the back plate need to have a uniform thickness and line width over a wide range. Furthermore, with the higher definition of PDPs, the fine pitch of address electrodes is progressing. In addition, since PDP passed through the baking process at the temperature of 500 degreeC or more in air, it was necessary to use the material which does not oxidize even if it passes through a baking process. From these 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 noble metal. On the other hand, it is conceivable to use a paste containing aluminum as a conductive paste that does not use a noble metal such as silver or gold. However, when a conductive paste containing aluminum powder is applied and dried, it is fired in air at a temperature of 500 ° C. There is a problem that the surface of the aluminum powder is oxidized, resulting in poor sintering, a high resistance value, and further inability to conduct. Moreover, in order to solve such a problem, the electrically conductive paste containing the material which prevents the oxidation of aluminum and aluminum is proposed (for example, patent document 2). When added to a photosensitive paste, the metal or metal compound for inhibiting oxidation used in this document reacts with an organic component having reactivity (polymer, oligomer, monomer, etc.), There was a problem that the storage stability of the paste was poor, the change in paste viscosity with time was large, and a uniform film could not be formed.

JP-A-5-271576 JP-A-5-298997

  An object of the present invention is to provide a photosensitive conductive paste that can form a pattern with high definition and a uniform thickness and line width at low cost, and can obtain a conductive pattern with low resistance.

That is, the present invention includes (A) 30 to 45 % by mass of aluminum powder having an average particle diameter of 1 to 4 μm, (B) 5 to 15 % by mass of glass powder having a softening point of 400 to 550 ° C., and (C) photosensitivity. It is related with the photosensitive electrically conductive paste which contains 15-30 mass% of a photosensitive organic component, and (D) 20-40 mass% of a solvent.

  The weight ratio of the (A) aluminum powder and the (B) glass powder is preferably in the range of 75:25 to 95: 5.

  The sphericity of the (A) aluminum powder is preferably 60% or more.

It is preferable that 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 μm ≦ Dg ≦ Da ≦ 10 μm
The specific surface area of the (A) aluminum powder is preferably 0.2 to 1.4 m ² / g.

  The present invention also includes a step of applying and drying the above-described photosensitive conductive paste on a substrate to form a paste coating film, a step of exposing the paste coating film through a photomask, and developing the exposed paste coating film. The present invention relates to a display manufacturing method including a step and a step of forming a pattern by baking.

  Furthermore, this invention relates to the display obtained by the said manufacturing method.

  The photosensitive conductive paste of the present invention can form a high-definition, uniform thickness and width pattern at low cost, and a low-resistance conductive pattern can be obtained. Further, by using this, a high-performance display can be manufactured at a low cost.

  The present invention relates to a photosensitive conductive paste containing aluminum powder, glass powder, a photosensitive organic component, and a solvent.

  The photosensitive conductive paste of the present invention contains an aluminum powder as a conductive powder, a glass powder for ensuring adhesion with a substrate, and a photosensitive organic component for forming a fine pitch wiring pattern. And an organic solvent for ensuring coating stability.

In the conventional conductive paste, it is appropriate to contain as much conductive powder as possible and to make glass powder and photosensitive organic components as small as possible in consideration of low resistance and debinderability during firing. However, since the powder surface of aluminum powder tends to oxidize when fired in air, sintering failure may occur, the resistance value may increase, and conduction may not be achieved. In order to solve this, in the present invention, the amount of the glass powder and the photosensitive organic component in the photosensitive conductive paste is relatively large, that is, 30 to 45 % by mass of aluminum powder in the photosensitive conductive paste, glass By using a photosensitive conductive paste containing 5 to 15 % by weight of powder, 15 to 30 % by weight of photosensitive organic component, and 20 to 40 % by weight of solvent, oxidation of aluminum powder during firing is prevented, and Adhesion can be ensured and conduction can be ensured.

Further, the photosensitive conductive paste containing 40 to 65 % by weight of aluminum powder and 20 to 50 % by weight of photosensitive organic component in a dry film obtained by applying and drying a photosensitive conductive paste on a substrate and evaporating the solvent. By using the paste, it is possible to prevent the aluminum powder from being oxidized at the time of firing, and to ensure electrical conduction.

First, about aluminum powder, it is required to contain 30-45 mass% , Preferably 35-40 mass% . If the amount is less than 30 % by mass, the conduction of the electrode cannot be ensured, and if it exceeds 45 % by mass , the pattern formability deteriorates and a fine pitch electrode pattern cannot be obtained. Regarding the particle diameter of the aluminum powder, the 50% particle diameter (average particle diameter) in the weight distribution curve measured by a particle size distribution measuring apparatus (for example, “MT3300” manufactured by Nikkiso) is preferably 1 to 4 μm. More preferably, it is 5 to 3 μm. If the thickness is less than 1 μm, oxidation of the surface of the aluminum powder is promoted at the time of firing, and conduction may not be obtained. If the thickness exceeds 4 μm, the smoothness of the electrode pattern is deteriorated, and the dielectric or barrier rib pattern formed on the electrode There is a risk of worsening the shape. Further, the maximum particle diameter of the aluminum powder is preferably 20 μm or less, and more preferably 10 μm or less. If the maximum particle diameter exceeds 20 μm, pattern formation is degraded, or there are many particles larger than the film thickness, which tends to adversely affect electrodes and dielectric layers formed later. . The specific surface area of the aluminum powder is preferably 0.2~1.4m ² / g, more preferably 0.5~1.2m 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 and the partition pattern formed on the electrode may be deteriorated, and 1.4 m ² / g. In the case of exceeding, oxidation of the surface of the aluminum powder is promoted at the time of firing, and the conductivity of the electrode may be deteriorated.

It is preferable to contain 5-15 mass% of glass powder in the photosensitive electrically conductive paste, and it is more preferable that it is 7-12 mass% . If it is less than 5 % by mass , the adhesion to the substrate is poor, leading to disconnection of the electrode pattern. If it exceeds 15 mass% , the probability of occurrence of poor conduction increases. The softening point of the glass powder is preferably 400 to 550 ° C, and more preferably 450 to 500 ° C. When the temperature is lower than 400 ° C., the glass is softened before the photosensitive organic component evaporates, so that the electrode shape after firing may be deteriorated. When it exceeds 550 ° C., the softening of the glass does not proceed, and the adhesion with the substrate tends to be not ensured.

  The average particle size of the glass powder may be appropriately selected according to the purpose, but the average particle size is preferably 0.3 to 2.0 μm, more preferably 0.5 to 1.0 μm. When the average particle diameter is less than 0.3 μm, aggregation tends to occur, and thus pattern formability may be deteriorated. If it exceeds 2.0 μm, the sinterability during firing tends to be insufficient.

The average particle diameter Dg of the glass powder and the average particle diameter Da of the aluminum powder are
0.3 μm ≦ Dg ≦ Da ≦ 10 μm
Preferably satisfying
0.1 ≦ Dg / Da ≦ 0.9
It is more preferable to satisfy. If Dg / Da is less than 0.1, the particle size of aluminum tends to be too small and dispersion tends to be very difficult. If it is more than 0.9, pattern formability is reduced, and sinterability during firing is reduced. There is a tendency to adversely affect.

  Further, the maximum particle diameter of the glass powder is preferably 20 μm or less, and more preferably 10 μm or less. If the maximum particle diameter exceeds 20 μm, pattern formation is degraded, or there are many particles larger than the film thickness, which tends to adversely affect electrodes and dielectric layers formed later. .

The specific surface area of the glass powder is preferably 1~15cm ² / g, and more preferably 2 to 10 cm ² / g. If the specific surface area is less than 1 cm ² / g, the pattern formability tends to decrease or the sinterability during firing tends to be insufficient, and if it exceeds 15 cm ² / g, aggregation tends to occur. .

  The content ratio of the aluminum powder and the glass powder is preferably in the range of 75:25 to 95: 5 by weight. More preferably, it is 80: 20-92: 8. If the ratio is less than 75:25, the amount of aluminum may be too small and conduction failure may occur. If the ratio is more than 95: 5, the amount of glass powder will be too small and the adhesion to the substrate will deteriorate. There is a risk that problems such as peeling of the electrode pattern may occur.

  The spherical ratio of the aluminum powder is preferably 60% or more of the aluminum powder contained. More preferably, it is 80% or more. If it is less than 60%, the degree of filling of the aluminum powder in the electrode after firing may deteriorate, resulting in problems such as poor conduction.

The photosensitive organic component used in the photosensitive conductive paste of the present invention contains a photosensitive organic component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and if necessary, Additives such as photopolymerization initiators, ultraviolet absorbers, sensitizers, sensitizers, polymerization inhibitors, plasticizers, thickeners, organic solvents, antioxidants, dispersants, organic or inorganic precipitation inhibitors The thing which added the ingredient is mention | raise | lifted. In the case of a normal photosensitive conductive paste, the organic component is often prepared with a content as low as possible in consideration of the resistance value and conductivity, but the photosensitive paste of the present invention is photosensitive. It is preferable to contain 15-30 mass% of organic components in the paste. This is to prevent oxidation of the aluminum powder during firing by containing a relatively large amount of the photosensitive organic component. When the photosensitive organic component is less than 15% by weight, less oxidation inhibiting effect of aluminum, when it exceeds 30 mass%, in the electrode pattern after the firing, there is a gap between the aluminum particles, conductivity is The problem that it cannot be secured occurs.

  Hereinafter, the photosensitive organic component of the present invention will be described.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include monofunctional and polyfunctional (meth) acrylates, vinyl compounds, allyl compounds, and the like. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-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, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, Roll acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl 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, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol di Acrylate, 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, diacrylate of bisphenol A-propylene oxide adduct, acrylate such as thiophenol acrylate, benzyl mercaptan acrylate, and among these aromatic ring hydrogen atoms, Monomer substituted with 5 chlorine atoms 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 some acrylates in the molecule of the above compound Those changed hands methacrylate, .gamma.-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. In the present invention, one or more of these can be used.

  In addition to these, the development property 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.

The content of these photosensitive monomers is preferably 7 to 15 % by mass in the paste. In other ranges, the pattern formability is deteriorated and the hardness after curing is not preferable.

Moreover, as a photosensitive oligomer and a photosensitive polymer, the oligomer and polymer obtained by superposing | polymerizing at least 1 type of the compound containing the said carbon-carbon unsaturated bond can be used. The content of the compound containing a carbon-carbon unsaturated bond is preferably 10 % by mass or more, and more preferably 35 % by mass or more, in the total amount of the photosensitive oligomer and the photosensitive polymer.

  Furthermore, it is preferable to copolymerize a photosensitive oligomer or photosensitive polymer with an unsaturated acid such as an unsaturated carboxylic acid to improve developability after exposure. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. The acid value (AV) of the oligomer or polymer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 30 to 150, more preferably 70 to 120. If the acid value is less than 30, the solubility of the unexposed area in the developing solution is lowered. Therefore, when the developing solution concentration is increased, the exposed area is peeled off, and a high-definition pattern tends to be difficult to obtain. Further, when the acid value exceeds 150, the development allowable width tends to be narrowed.

  By adding a photoreactive group to the side chain or molecular end of these photosensitive oligomers and photosensitive polymers, they can be used as photosensitive polymers and photosensitive oligomers having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

  Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of addition reaction of acid chloride or allyl chloride.

  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 crotonic acid, glycidyl ether of isocrotonic acid, and the like.

  Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.

  In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add.

The content of the photosensitive oligomer and / or the photosensitive polymer in the photosensitive conductive paste is preferably 7 to 15 % by mass in the paste from the viewpoint of pattern formability and shrinkage after baking. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.

  Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoinmethi 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-butadion-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, Mihira -Ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, naphthalenesulfonyl chloride, quinoline Sulfonyl chloride, N-phenylthioacridone, 4,4′-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide and Examples include photoreductive dyes such as eosin and methylene blue, and reducing agents such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used.

It is preferable that a photoinitiator is added in 0.05-20 mass% with respect to the photosensitive organic component, More preferably, it is 0.1-15 mass% . When the photopolymerization initiator is less than 0.05 % by mass , the photosensitivity tends to be poor, and when the photopolymerization initiator exceeds 20 % by mass , the residual ratio of the exposed portion tends to be too small.

A sensitizer is added in order to improve 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-dimethylaminoben) Colander) acetone, 1,3-carbonyl-bis (4-diethyla) Nobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, dimethylaminobenzoic acid Examples thereof include isoamyl, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, and 1-phenyl-5-ethoxycarbonylthiotetrazole. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer to the glass paste of this invention, it is preferable that the addition amount is 0.05-30 mass% normally with respect to the photosensitive organic component, More preferably, it is 0.1-20 mass%. It is. If it is less than 0.05 % by mass, the effect of improving the photosensitivity tends to be hardly exhibited, and if it exceeds 30 % by mass , the residual ratio of the exposed portion tends to be too small.

  A polymerization inhibitor is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, pyrogallol and p-methoxyphenol. Further, by adding, the threshold of the photocuring reaction is increased, the pattern line width is reduced, and the pattern upper portion with respect to the gap is not increased.

It is preferable that the addition amount of a polymerization inhibitor is 0.01-1 mass% in the photosensitive electrically conductive paste. If it is less than 0.01 % by mass, the effect of addition tends to be difficult, and if it exceeds 1 % by mass , the sensitivity tends to decrease, so that a large amount of exposure for pattern formation tends to be required.

  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 the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-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-4-hydroxy-6-tert-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-tert-butylphenyl) butyric Acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. When adding antioxidant, it is preferable that the addition amount is 0.01-1 mass% in a glass paste.

In order to adjust the viscosity of the solution, an organic solvent is preferably added to the photosensitive conductive paste of the present invention. The content of the organic solvent is preferably 20 to 40 % by mass in the paste. In other ranges, the paste cannot be applied successfully, and a film having a uniform thickness cannot be obtained. 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, bromo Benzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, terpineol, diethylene glycol monobutyl ether acetate and the like, and an organic solvent mixture containing one or more of these are used.

  The photosensitive conductive paste of the present invention is usually at least one of the photosensitive monomer, photosensitive oligomer, and photosensitive polymer, and if necessary, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, and a sensitizer. After preparing additive components such as an auxiliary agent, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, an antioxidant, a dispersant, an organic or inorganic suspending agent to have a predetermined composition, three It is mixed and dispersed homogeneously with a roller or kneader.

  The viscosity of the photosensitive conductive paste is appropriately adjusted, but the range is preferably 0.2 to 200 Pa · s. For example, when applying to a glass substrate by spin coating, 0.2 to 5 Pa · s is more preferable. To obtain a film thickness of 10 to 20 μm by applying it once by a screen printing method, 10 to 100 Pa · s. s is more preferable.

  The present invention also includes a step of applying and drying the above-described photosensitive conductive paste to form a paste coating film, a step of exposing the paste coating film through a photomask, a step of developing the exposed paste coating film, and The present invention relates to a display manufacturing method including a process of forming a pattern by baking.

  Next, an example of forming a paste coating film using a photosensitive paste method will be described, but the present invention is not limited to this.

  A photosensitive conductive paste is applied over the entire surface or partially on a glass substrate, a ceramic substrate, or a polymer film. As a coating method, a general method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, screen mesh, and paste viscosity. Alternatively, a method may be used in which a photosensitive sheet obtained by applying a photosensitive glass paste on a film such as a polyester film is prepared, and the photosensitive conductive paste is transferred onto the substrate using an apparatus such as a laminator.

  After applying the photosensitive conductive paste, exposure is performed using an exposure apparatus. As for exposure, a mask exposure method using a photomask is generally used, as in normal photolithography. 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. Alternatively, a method of directly drawing with a red or blue laser beam or the like without using a photomask may be used.

As the exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. In addition, when performing large area exposure, a photosensitive glass paste is applied on a substrate such as a glass substrate and then exposed while being conveyed, thereby exposing a large area with an exposure machine having a small exposure area. Can do. Examples of the active light source used include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet rays are most preferable, 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, or a germicidal lamp can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is usually performed for 0.1 to 10 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the unexposed portion in the developer.

As the developer, a solution in which an organic component to be dissolved in the photosensitive conductive paste can be dissolved is used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive conductive paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, an aqueous solution of sodium hydroxide, sodium carbonate, sodium carbonate, calcium hydroxide, or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is preferably 0.01 to 10 % by mass, and more preferably 0.1 to 5 % by mass . If the concentration of the alkaline aqueous solution is less than 0.01 % by mass, the soluble part tends not to be removed, and if it exceeds 10 % by mass , the pattern part tends to peel off and the insoluble part tends to corrode. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  Next, baking is performed in a baking furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. The firing temperature is usually 400 to 1000 ° C. When patterning on a glass substrate, firing is usually performed at a temperature of 450 to 620 ° C. for 10 to 60 minutes. The firing temperature is determined by the glass powder to be used, but it is preferable to fire at an appropriate temperature that does not break the shape after pattern formation and does not leave the shape of the glass powder.

  Moreover, you may introduce | transduce a 50-300 degreeC heating process for the purpose of drying and a preliminary reaction in each process of the above application | coating, exposure, image development, and baking.

  The display of the present invention obtained by the above manufacturing method can be manufactured at low cost because the photosensitive conductive paste of the present invention containing no aluminum and no aluminum is used as the conductive powder. In addition, since silver or copper is not contained, problems such as migration and yellowing do not occur, and an electrically stable display can be manufactured.

  Further, since the glass powder and the photosensitive organic component are contained in a large amount, problems such as poor sintering, high resistance, and poor conduction due to oxidation of the surface of the aluminum powder during firing can be prevented.

  Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to such examples.

In the following average particle diameter _{(D 50)} of the inorganic powder and the maximum particle diameter _{(D max)} is a value measured using "MT3300" manufactured by Nikkiso Co., Ltd.. Moreover, the softening point of the glass powder was measured with a differential thermal analyzer manufactured by Rigaku.

Production Example 1 (Dielectric Forming Paste)
Bi ₂ O ₃ / SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO = 25/30/5/10/25/5 ( mass% ) glass powder (average particle size 2 μm) 40 parts by weight 10 parts by weight of titanium oxide, 10 parts by weight of silicon oxide, 3 parts by weight of ethyl cellulose, 15 parts by weight of monomer (trimethylolpropane triacrylate) and 25 parts by weight of terpineol were added and mixed and dispersed with three rollers to form a dielectric. A paste was obtained.

Production Example 2 (Partition Wall Forming Paste)
SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO / Li ₂ O = 20/20/5/30/15/10 ( mass% ) glass powder (average particle size 2 μm) 67 parts by weight, 10 parts by weight of polymer (Cyclomer P ACA250 manufactured by Daicel Chemical Industries, Ltd.), 10 parts by weight of monomer (trimethylolpropane triacrylate), 3 parts by weight of titanium oxide (average particle size 0.2 μm), 4 parts by weight of benzyl alcohol, 3 parts by weight of butyl carbitol acetate was added and mixed and dispersed with three rollers to obtain a partition wall forming paste.
<Measurement of specific resistance>
About the backplate produced to the electrode, the resistance value, thickness, and line width of the electrode of 9 lines in the surface were measured, and the specific resistance of each line was calculated. An average value of the calculated values was obtained and used as a measured value of specific resistance.
<Measurement of L ^* value, a ^* value, b ^* value>
About the backplate formed to the partition, b ^* value was measured from the both sides of the partition formation film surface using the spectrocolorimeter (Minolta Co., Ltd. CM-2002). A total of 9 points of 3 points on the same substrate and 3 different substrates were measured, and an average value was obtained as each measured value.
<Evaluation of adhesion strength>
The back plate formed up to the partition wall was subjected to a cellophane tape peeling test of 1920 electrode terminals (using Nichiban cello tape (registered trademark)). Those that were peeled off were considered defective.
<Evaluation of printability>
On the substrate printed with the photosensitive conductive paste, measure the film thickness at 36 locations in the surface, and the difference between the maximum and minimum values is excellent if it is less than 2 μm, good if it is 2 μm or more but less than 3 μm, if it is 3 μm or more Was regarded as defective.
<Evaluation of pattern shape>
After applying / drying the photosensitive conductive paste, patterning by exposure / development, baking is performed, the one with no pattern chip is excellent, the one from 1 to 5 is good, the one with 6 or more is bad It was.

Examples 1-17, Comparative Examples 1-10
A photosensitive conductive paste was prepared by mixing the aluminum powder having the characteristics shown in Table 1, the glass powder having the characteristics shown in Table 2, and the following additives in the types and addition amounts shown in Tables 3 to 5 with three rollers. .
Photosensitive polymer: photosensitive acrylic polymer having an acid value of 85 and Mw of 32,000 (APX-716, manufactured by Toray Industries, Inc.)
Photosensitive monomer: trimethylolpropane triacrylate photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
Dispersant: polyether ester type anionic surfactant (manufactured by Enomoto Kasei Co., Ltd., “Disparon” 7004)
Polymerization inhibitor: p-methoxyphenol Organic solvent: diethylene glycol monobutyl ether acetate A 42-inch size AC (alternating current) type plasma display panel back plate was formed and evaluated. The forming method will be described in order.

  As a glass substrate, PD-200 (manufactured by Asahi Glass Co., Ltd.) having a size of 590 × 964 × 2.8 mm and 42 inches was used. On this board | substrate, the photosensitive electrically conductive paste obtained by the said method was apply | coated and dried by screen printing as an address electrode. After exposing a predetermined number of times through a predetermined photomask, development was performed to form an unfired pattern. After pattern formation, baking was performed at 590 ° C. for 15 minutes.

  The substrate was coated and dried with the dielectric forming paste obtained in Production Example 1.

  Further, the partition wall forming paste obtained in Production Example 2 was applied to a predetermined thickness with a die coater, and then dried in a clean oven at 100 ° C. for 40 minutes to form a coating film. The formed coating film was exposed with a gap of 150 μm from a predetermined photomask.

  Each color phosphor paste was applied to the barrier ribs thus formed by screen printing and baked (500 ° C., 30 minutes) to form phosphor layers on the side and bottom portions of the barrier ribs.

  The obtained back plate was bonded to the front plate and sealed, and then a discharge gas was sealed, and a driving circuit was joined to produce a plasma display (PDP).

Table 6 shows the evaluation results of the photosensitive conductive pastes of Examples 1 to 17 and Comparative Examples 1 to 10.

The back plate electrodes obtained in Examples 1 to 17 were able to form a good electrode pattern, and in the state where the partition walls were formed, the electrode adhesion evaluation and the back plate yellowing b ^* value measurement were good. Results were obtained. Examples 1 to 17 were all good. About Comparative Examples 1-10, what was satisfactory in all the points of the resistance value of an electrode, adhesive strength, and electrode pattern workability was not obtained.

Claims (7)

(A) 30 to 45% by weight of aluminum powder having an average particle diameter of 1 to 4 μm, (B) 5 to 15% by weight of glass powder having a softening point of 400 to 550 ° C., and (C) 15 to 15% of photosensitive organic component. A photosensitive conductive paste containing 30% by weight and (D) 20 to 40% by weight of a solvent. The photosensitive conductive paste according to claim 1, wherein a weight ratio of the (A) aluminum powder and the (B) glass powder is in a range of 75:25 to 95: 5. The photosensitive conductive paste according to claim 1 or 2, wherein the sphericity of the (A) aluminum powder is 60% or more. 4. The photosensitive conductive paste according to claim 1, 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. 5.
0.3 μm ≦ Dg ≦ Da ≦ 10 μm 5. The photosensitive conductive paste according to claim 1, wherein the (A) aluminum powder has a specific surface area of 0.2 to 1.4 m ² / g. A step of applying and drying the photosensitive conductive paste according to claim 1, 2, 3, 4 or 5 on a substrate to form a paste coating film, a step of exposing the paste coating film through a photomask, and an exposed paste A method for producing a display, comprising a step of developing a coating film and a step of forming a pattern by baking. A display obtained by the display manufacturing method according to claim 6.