JP2009203415A - Glass paste, production method therefor, and manufacturing method for display member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass paste of high performance restraining a rising-up width and height of the edge part of a coating film, in application onto a substrate, and hardly causing a film defect such as disconnection. <P>SOLUTION: This glass past contains glass powder, a binder resin, and an organic solvent, a content of the glass powder is 30-80 wt.%, and the glass paste contains 5-20 pts.wt. of urea urethane compound per 100 pts.wt. of binder resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a glass paste and a method for producing the same, and a method for producing a display member using the same.

  In recent years, large flat panel displays such as direct current (DC) and alternating current (AC) plasma displays, liquid crystal displays, and field emission displays have been developed, and some displays are already on the market and are forming a large market. A large flat panel display is formed with a structure having various functions such as pixel partitioning. For example, an AC type plasma display generates a plasma discharge between an anode and a cathode electrode facing each other in a discharge space provided between a front plate and a back plate, and a Xe-Ne mixed gas sealed in the discharge space. The display is performed by irradiating a phosphor provided in the discharge space with ultraviolet rays having a very short wavelength such as 147 nm and 172 nm generated from a discharge gas such as the above. The structure is provided mainly on the back plate in order to suppress the spread of the discharge to a certain area and perform display in a prescribed cell, and at the same time to ensure a uniform discharge space. Called ribs). The shape of the partition wall is generally a stripe shape or a lattice shape having a width of about 20 to 120 μm and a height of 50 to 150 μm, but the lattice shape is becoming the main force for high performance. The partition wall is generally formed by applying a paste made of a mixture of an organic material mainly composed of an organic binder and an inorganic material mainly composed of glass onto a glass substrate, patterning the material by a sandblasting method, a photolithography method, or the like, followed by firing. How to do is known.

  As a method for applying the glass paste used for forming these partition walls to the entire surface of the substrate at once, a doctor blade method, a slit die coating method, or the like is used. However, when applied using these methods, there is a problem that the edge portion of the coating film rises over a width of about 1 to 2 cm, and a coating layer having a uniform film thickness cannot be formed.

  In order to solve this problem, a method of adding a thixotropy imparting agent (thixotropic agent) to glass paste has been proposed. For this, an aliphatic amide compound is considered good (see, for example, Patent Document 1). . However, in order to develop thixotropy using this aliphatic amide compound, it is necessary to mix in a glass paste a paste or wax that has been swollen in a solvent in advance.

  In addition, a method containing a thixotropy imparting agent has been proposed for the purpose of improving the screen printing applicability of the conductive paste. From the viewpoint of easy removal in the firing step, fatty acid amide, hydrogenated castor oil, etc. (See, for example, Patent Documents 2 and 3).

However, when a paste-like or wax-like thixotropy-imparting agent is mixed into a glass paste, if the kneading is insufficient, an undispersed product (20-100 μm) of the thixotropy-imparting agent remains and is difficult to remove by filtration. As a result, there is a problem that it becomes a defect such as disconnection after being baked into the coating film. Moreover, when kneading | mixing too much, thixotropy property fell and there existed a problem that applicability | paintability and a coating-film shape became defective.
Japanese Patent No. 3832177 JP 2002-20570 A JP 2003-151351 A

  It is an object of the present invention to provide a high-performance glass paste that can realize a display that suppresses the rising width and height of the edge portion of a coating film and that does not easily cause film defects such as disconnection in application to a substrate. .

  That is, the present invention is a glass paste containing glass powder, a binder resin, and an organic solvent, wherein the glass powder content is 30 to 80% by weight, and the urea urethane compound is added to 100 parts by weight of the binder resin. 5 to 20 parts by weight of glass paste.

  Further, the present invention is a solution having a viscosity of 5,000 mPa · s or less in which a urea urethane compound is dissolved in an organic solvent, and 20 to 80 parts by weight of the solution is mixed with 100 parts by weight of the binder resin. It is a manufacturing method of this glass paste.

  Furthermore, this invention is a manufacturing method of the member for display panels characterized by including the process of apply | coating and drying the above-mentioned glass paste on a board | substrate.

  According to the present invention, it is possible to provide a high-performance glass paste that can realize a display that suppresses the rising width and height of an edge portion of a coating film and hardly causes film defects such as disconnection in application to a substrate.

  The glass paste of the present invention essentially comprises glass powder, a binder resin, an organic solvent, and a urea urethane compound.

  The glass powder content in the glass paste needs to be 30 to 80% by weight because the shrinkage rate during firing is small and the shape change due to firing is small. Preferably, it is 40 to 60% by weight.

The glass powder preferably has a thermal expansion coefficient of 50 × 10 ^{−7 to} 100 × 10 ⁻⁷ ° C. ⁻¹ at 50 to 400 ° C. Moreover, by blending silicon oxide in glass powder in the range of 3 to 60% by weight and boron oxide in the range of 5 to 50% by weight, partition walls such as electrical insulation, strength, thermal expansion coefficient, and denseness of the insulating layer can be obtained. The required electrical, mechanical and thermal properties can be improved. The glass powder in the present invention is preferably mainly composed of a low-melting glass powder. The glass transition temperature of the low-melting glass powder is preferably 430 to 500 ° C, and the glass softening point is preferably 470 to 620 ° C. When the glass transition temperature and the glass softening point are in this range, the distortion of the substrate is small during firing, and a dense partition layer is obtained. The volume average particle diameter of the low melting point glass powder is selected in consideration of the line width and height of the partition wall to be produced, but is preferably larger than 1.0 μm and smaller than 5.0 μm, and larger than 1.5 μm. More preferably, it is less than 4.0 μm. When the volume average particle size is 1.0 μm or less, the low melting point glass powders tend to aggregate in the paste and tend to hinder a uniform partition wall shape. When the thickness is 5.0 μm or more, there is a problem that a partition having a good shape cannot be obtained at the time of pattern formation, and disconnection or chipping is easily generated in the partition.

  Here, the volume average particle diameter refers to the volume average diameter of the powder measured using a laser diffraction / scattering particle size distribution meter.

The maximum particle size of the low melting glass powder is preferably 30 μm or less,
More preferably, it is 15 μm or less. If the maximum particle size exceeds 30 μm, disconnection or chipping is likely to occur during the formation of the barrier rib pattern, and huge particles remain as abnormal protrusions, which tends to cause disconnection or front plate failure due to contact with the front plate during panel production. is there. The specific surface area of the low melting point glass powder is preferably 1.0~4.0cm ² / g, more preferably 1.5~3cm ² / g. When the specific surface area of the low-melting glass powder satisfies this range, the low-melting glass powder can be prevented from aggregating in the paste, and the glass powder in the paste can be uniformly dispersed. This makes it possible to form partition walls with high accuracy.

  On the other hand, it is also preferable to contain a filler in the glass paste. In the present invention, the filler refers to inorganic particles having no softening temperature, melting point, or decomposition temperature at 620 ° C. or lower. The filler is not particularly limited, but from the viewpoint of firing stability and colorability, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, zinc oxide, cordierite, celsian, anorthite, steer It is preferable to include one or more fillers selected from the group consisting of tight, spodumene, forsterite, and high-melting glass powder, and more preferably high-melting glass powder.

  Here, the high melting point glass powder refers to a glass powder having a softening temperature higher than 620 ° C., and the softening temperature of the high melting point glass is preferably 1200 ° C. or less, more preferably 1000 ° C. or less.

  The binder resin used in the glass paste of the present invention is not particularly limited, but is preferably oxidized or / and decomposed or / and vaporized at the time of firing so that carbides do not remain in the partition walls. Cellulose compounds, acrylic polymers represented by polyisobutyl methacrylate, and the like can be used. Moreover, resins such as polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, α-methylstyrene polymer, and butyl methacrylate resin are exemplified.

  The content of the binder resin in the glass paste of the present invention is preferably 5 to 30% by weight, and the content ratio of the glass powder and the binder resin is preferably 10: 1 to 5: 5 by weight ratio.

  In the case of forming a high-precision partition wall, a method of forming a partition wall by a photosensitive paste method is preferable. In this case, as the organic component, at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer is used. A photosensitive glass paste containing a photosensitive organic component selected from various types, and if necessary, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, a sensitizer, a polymerization inhibitor, a plasticizer, a thickener And an additive component such as an organic solvent, an organic solvent, an antioxidant, a dispersant, and an organic or inorganic suspending agent.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond. 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, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxy Ethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycero 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, methoxy Diethylene 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, tri Tylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate , Polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, Diacrylate of bisphenol A-ethylene oxide adduct, acrylate of bisphenol A-propylene oxide adduct, acrylate such as thiophenol acrylate, benzyl mercaptan acrylate, and 1-5 of these aromatic ring hydrogen atoms Monomer substituted with chlorine atom or bromine atom, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, bromine Α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, and some or all of the acrylates in the molecule of the above compound Those changed to 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 3 to 20% by weight based on the sum of the inorganic powder and the photosensitive organic component.

  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 photosensitive oligomer or the photosensitive polymer. Furthermore, it is preferable because the developability after exposure in the case of using an aqueous developer such as an alkaline aqueous solution can be improved by copolymerizing a photosensitive oligomer or photosensitive polymer with 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 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.

  When the glass paste of the present invention is used as a photosensitive glass paste, the content of the photosensitive oligomer and / or the photosensitive polymer in the photosensitive glass paste is determined from the inorganic powder and the pattern forming property and the shrinkage ratio after firing. It is preferable that it is 5 to 30 weight% with respect to the sum of the photosensitive organic component.

  When the glass paste of the present invention is a photosensitive glass paste, it preferably contains a photopolymerization initiator. Specific examples thereof include benzophenone, methyl o-benzoylbenzoate, 4,4′-bis ( Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzy Dimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4 -Azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o -Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, -Phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butanone-1, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4′-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenyl Examples thereof include photoreducible dyes such as phosphine, camphorquinone, carbon tetrabrominated, tribromophenylsulfone, benzoin peroxide and 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.

  A photoinitiator is added in 0.1-30 weight% with respect to the photosensitive organic component, More preferably, it is 0.2-25 weight%.

  When the glass paste of the present invention is used as a photosensitive glass paste, a sensitizer can be used together with a photopolymerization initiator to improve sensitivity and to expand the effective wavelength range for the reaction.

  Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4 -Dimethylaminophenylvinylene) Isonaphtho Sol, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyl Diethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, diethylamino Isoamyl benzoate, (2-dimethylamino) ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 2-ethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazo Le, and a 1-phenyl-5-ethoxycarbonyl-thiotetrazole the like.

  When the glass paste of the present invention is a photosensitive glass paste, one or more of the above sensitizers can be used. When adding a sensitizer to a photosensitive glass paste, the addition amount is 0.1 to 30 weight% normally with respect to the photosensitive organic component, More preferably, it is 0.2 to 25 weight%.

  When the glass paste of the present invention is a photosensitive glass paste, it is also effective to add an ultraviolet absorber. In the glass paste of the present invention, low melting point glass powders and fillers having different properties are used as inorganic powders, so that exposure light scattering is large inside the photosensitive paste film, and the pattern tends to spread. By adding the ultraviolet absorber, the scattered light inside the photosensitive paste due to the exposure light is absorbed, the scattered light is weakened, and a sharp pattern can be obtained. Examples of the ultraviolet absorber include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, inorganic fine-particle metal oxides, and the like. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2 -Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -(2-hydroxy-3-methyl (Chryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl BONASORB UA-3901 (made by Orient Chemical Co., Ltd.) and BONASORB are acrylate and indole-based absorbents A-3902 (manufactured by Orient Chemical Industries, Ltd.), but such SOM-2-0008 (manufactured by Orient Chemical Co., Ltd.) without limitation. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  The addition amount of the ultraviolet absorber is 0.001 to 10% by weight, more preferably 0.005 to 5% by weight in the photosensitive glass paste.

  Furthermore, when the glass paste of the present invention is used as a photosensitive glass paste, it is also effective to add a polymerization inhibitor.

  Specifically, hydroquinone, phenothiazine, pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, N-phenylnaphthylamine, 2,6- Examples thereof include, but are not limited to, di-t-butyl-p-methylphenol, chloranil, hydroquinone monomethyl ether, and pyrogallol. In the present invention, one or more of these can be used.

  The addition amount of a polymerization inhibitor is 0.01 to 10 weight% in a photosensitive paste, More preferably, it is the range of 0.05 to 5 weight%.

  When the glass paste of the present invention is a photosensitive glass paste, the pattern shape can be controlled by controlling the ultraviolet absorber and the polymerization inhibitor.

  When the glass paste of the present invention contains an acrylic copolymer, it is preferable to contain an antioxidant in the glass paste in order 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.

  Examples of the organic solvent used in the glass paste of the present invention include cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, isopropyl alcohol, methyl alcohol, ethyl alcohol, butyl alcohol, normal propyl alcohol, benzyl alcohol, terpineol, and 3-methoxy. Alcohols such as -3-methyl-1-butanol, ketones such as methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, γ-butyrolactone, N-methyl-2-pyrrolidone, ethyl lactate, methyl acetate, ethyl acetate, Isopropyl acetate, normal propyl acetate, isobutyl acetate, normal pentyl acetate, 3-methoxy-3-methyl-1-butanol, 3-metho Ci-3-methyl-butyl acetate, propylene glycol-1-monomethyl ether-2-acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate , Esters such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and hydrocarbons such as hexane, cyclohexane, toluene and xylene.

  In the practice of the present invention, it is preferable to use two or more organic solvents having a difference in boiling point at normal pressure. When the coating film is one type, the edge portion may rise several to several tens of μm after the coating film is dried. When two or more kinds of organic solvents are used, the difference in boiling point between the low boiling point side organic solvent and the high boiling point side organic solvent at normal pressure is preferably 20 ° C. or more. More preferably, it is the range of 30-60 degreeC. When the difference in boiling points is smaller than 20 ° C., the edge of the coating film after drying may rise as in the case of using only one kind. If the difference in boiling points is too large, the temperature at which the organic solvent on the high boiling side is dried becomes high, which may affect the reaction components in the coating film.

  Furthermore, the weight ratio of the low-boiling organic solvent and the high-boiling organic solvent having a boiling point difference of 20 ° C. or higher is preferably 1: 9 to 9: 1. When the content of either organic solvent is small, the effect of adding the solvent cannot be obtained as a result, and the coating film edge portion after drying may be raised. When three or more kinds of organic solvents are used, it is preferable that each is divided into a low-boiling side group and a high-boiling side group having a boiling point difference of 20 ° C. or more, and each organic solvent group is in the above range.

  In the glass paste of the present invention, a urea urethane compound is used as a thixotropy imparting agent (thixotropic agent) for controlling thixotropy. The urea urethane compound has at least one urea group (—NHCONH— group) and one urethane group (—NHCOO— group) in the molecular structure, and is obtained by reacting an isocyanate compound with an amino compound and a hydroxy compound. .

  This urea urethane compound develops thixotropic properties by acting with the binder resin in the paste to form a three-dimensional network structure. It is necessary to contain 5 to 20 parts by weight of the urea urethane compound with respect to 100 parts by weight of the binder resin. If it is less than this range, the thixotropic property is low, so that there are problems such as dripping at the time of coating, swelling of the film edge portion cannot be suppressed, and sedimentation of the glass powder in the paste is likely to occur. On the other hand, if it exceeds the above range, the thixotropy becomes too large, which causes problems such as difficult application and handling of the paste.

The glass paste of the present invention has a thixotropy index defined by the following formula (1) of 1.2 to
It is preferable that the viscosity is 10 and the viscosity at a shear rate of 1.2 (s ⁻¹ ) is in the range of 5 to 100 (Pa · s 25 ° C.).

Thixotropic index = (viscosity at shear rate 1.2 (s ⁻¹ )) / (viscosity at shear rate 12 (s ⁻¹ )) (1)
The glass paste of the present invention is produced by weighing and mixing an organic vehicle in which a binder resin and other organic components are dissolved in an organic solvent and glass powder so as to obtain a desired paste composition. Pre-kneading is performed in order to mix the glass powder and the organic vehicle almost uniformly. The preliminary kneading may be carried out by hand stirring with a spatula made of silicon or fluororesin until it looks uniform, or may be carried out with a stirrer equipped with a blade, but it is preferable to use a preliminary kneader. As the pre-kneader, it is preferable to use a planetary mixer because the dispersibility of the inorganic particles in the paste becomes good. The planetary mixer is a kind of blade-type kneader, and two or more blades (blades) rotate and revolve in a container (tank) so that dead space does not occur as much as possible. This is a mechanism for kneading by a shearing force generated between container walls. In addition, since the planetary mixer has little dead space in the tank, a kneaded product having a relatively high viscosity can be preliminarily kneaded uniformly. If the preliminary kneading is sufficiently performed, the next kneading step can be completed in a short time. In this step, a preliminary kneaded material is produced. In order to loosen the secondary agglomerated particles of the inorganic powder in the pre-kneaded product prepared in the pre-kneading step to the primary particles, the main kneading is further performed. For the main kneading, a kneader such as a three-roll mill is used.

The urea urethane compound is a solution having a viscosity of 5,000 mPa · s or less dissolved in an organic solvent, and is mixed with an organic vehicle or glass paste. If the viscosity exceeds 5,000 mPa · s, it may take a long time to be uniform when mixed with an organic vehicle at room temperature, or uneven portions may remain.
The mixing ratio of the solution containing the urea urethane compound is 20 to 80 parts by weight with respect to 100 parts by weight of the binder resin contained in the organic vehicle. Mixing with an organic vehicle or glass paste as a solution facilitates dispersion and undispersed matter (20 to
100 μm) remains, and a gel-like material that is difficult to remove by filtration is mixed into the coating film, and there is no problem of defects such as disconnection after firing.
Furthermore, since thixotropic properties are exhibited after kneading, there is no problem that the thixotropic properties are lowered due to excessive kneading and the coating properties and the shape of the coating film are not good.

Further, the solution containing the urea urethane compound is mixed into the organic vehicle after other organic components are heated and dissolved, mixed with the pre-kneaded product immediately before and / or after the addition of the glass powder, Mix with the paste after the main kneading. If dissolved in advance in an organic vehicle together with other organic components, problems such as thixotropic properties appear in the organic vehicle and liquid feeding becomes difficult.

  Examples of commercially available solutions containing urea urethane compounds include BYK-410, 411, 420, and 425 (manufactured by BYK-Chemie).

Next, the manufacturing method of the member for display panels including the process of apply | coating and drying on a board | substrate using the said glass paste is demonstrated.

  A glass paste is applied on 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. After the application, the glass paste is dried using an optional oven such as a ventilating oven, a hot plate, or an infrared dryer to form a dry film of glass paste. The drying temperature is preferably in the range of 40 to 150 ° C., which does not affect the organic components in the paste.

  In the case of pattern formation, it is preferably a sand blast method, a photosensitive paste method, a screen printing method, or a mold transfer method, and it is a photosensitive paste method from the viewpoint of high definition and easy process. More preferred.

  Here, an example of performing the partition pattern processing for the plasma display panel using the photosensitive paste method will be described, but the present invention is not limited to this.

  After the photosensitive glass paste is applied and dried, exposure is performed using an exposure apparatus. As for the exposure, a mask exposure method using a photomask is generally used so as to be performed by a normal photolithography method. 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.

As the exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. 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 non-exposed portion in the developer. In this case, the immersion method, the shower method, the spray method, and the brush method can be used.

  As the developer, a solution in which an organic component to be dissolved in the photosensitive glass paste can be dissolved is used. When a compound having an acidic group such as a carboxyl group is present in the photosensitive glass paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium carbonate aqueous solution, a calcium hydroxide aqueous solution 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, and diethanolamine. 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 not to be removed, and if it exceeds 10% by weight, 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. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. The firing temperature is usually 500 to 600 ° C. 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. When the temperature is lower than the appropriate temperature, the porosity and the unevenness at the upper part of the partition wall are increased, so that the discharge life is shortened and erroneous discharge is easily caused. On the other hand, if the temperature is higher than the appropriate temperature, the shape at the time of pattern formation collapses, the upper part of the partition wall becomes round, and the height becomes extremely low, and a desired height cannot be obtained.

  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.

  After the barrier ribs are formed, phosphor layers that emit light of RGB colors are formed. A phosphor layer can be formed by forming a phosphor paste containing phosphor powder, an organic binder and an organic solvent as main components between predetermined partitions. As a method of forming the phosphor paste between the predetermined partition walls, a screen printing method for pattern printing using a screen printing plate, a dispenser method for pattern ejection of the phosphor paste from the tip of the ejection nozzle, and the organic binder described above By using an organic component having photosensitivity, a photosensitive phosphor paste can be prepared, and each color phosphor layer can be formed in a predetermined place by a photosensitive paste method.

  The substrate for the plasma display panel of the present invention can be produced by firing the substrate on which the phosphor layer is formed, if necessary, at 400 to 550 ° C.

  The plasma display panel substrate is used as a back plate, and after sealing with the front plate, a discharge gas composed of helium, neon, xenon, etc. is sealed in a space formed between the front and back substrates, and then a drive circuit A plasma display can be manufactured by mounting. The front plate is a substrate in which a transparent electrode, bus electrode, dielectric, and protective film (MgO) are formed in a predetermined pattern on the substrate, and the color corresponding to the RGB color phosphor layers formed on the back substrate is colored. A filter layer may be formed. Further, a black stripe may be formed in order to improve contrast.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.
(Example 1) Binder resin (styrene / acrylic acid copolymer, weight composition ratio 30/60, weight average molecular weight 34,000, acid value 105): 10 parts by weight, monomer (propylene oxide-modified trimethylolpropane triacrylate) : 5 parts by weight, photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1): 3 parts by weight, polymerization inhibitor (p-methoxyphenol): 0. 1 part by weight, organic dye (Sudan IV): 0.04 part by weight, dispersant (polyether / ester type anionic surfactant, “Disparon” 7004, manufactured by Enomoto Kasei Co., Ltd.): 0.5 part by weight, organic Solvent 1 (γ-butyrolactone boiling point 200-208 ° C.): 25 parts by weight, organic solvent 2 (3-methoxy-3-methyl-1-butanol boiling point 174 ° C.): 5-fold An amount of the solution was dissolved by heating and stirring at 50 ° C. for 60 minutes to prepare an organic vehicle solution. As a thixotropy-imparting agent, 3 parts by weight of urea urethane solution (N-methyl-2-pyrrolidone solution of urea urethane compound 25% by weight: BYK411 BYK-Chemie) was used as urea urethane solution with respect to 100 parts by weight of binder resin. 30 parts by weight and 7.5 parts by weight as a urea urethane compound) are added and stirred for 15 minutes with a planetary mixer. After that, glass powder (boron oxide, silicon oxide, aluminum oxide, barium oxide, lithium oxide, magnesium oxide is the main component) Powder obtained by pulverizing glass with an average particle diameter of 2 μm): 45 parts by weight was added and stirred for 30 minutes to obtain a pre-kneaded product. This was kneaded with a three-roll mill to obtain a glass paste.

When the viscosity of the obtained glass paste was measured with a B-type viscometer (DV-II manufactured by Brookfield), the viscosity at a shear rate of 1.2 (s ⁻¹ ) was 30 (Pa · s 25 ° C.), and the shear rate was 12 The viscosity at (s ⁻¹ ) was 10 (Pa · s 25 ° C.), and the thixotropy index was 3.

  Next, after applying a wet thickness of 300 μm on the substrate using a slit coater, the substrate was dried in a clean oven at 100 ° C. for 90 minutes. When the edge part shape of the dry film was measured using a surface roughness meter (Surfcom 1500A manufactured by Tokyo Seimitsu), the width was 0.5 mm and the height was 2 μm, which was good.

Next, mask exposure was performed. A striped chrome mask having a pitch of 220 μm and a line width of 50 μm was used. The exposure was performed at 0.5 mJ / cm ² with an ultrahigh pressure mercury lamp having an output of 30 mW / cm ² . Then, shower development was performed with a 2-aminoethanol 0.2% aqueous solution (35 ° C.). This substrate was baked at 590 ° C. to produce a stripe barrier rib forming substrate for plasma display.
As a result of observing the partition wall on the substrate with a microscope, a disconnection (disappeared completely by firing) caused by a gel-like material having a height of 120 μm, a bottom width of 70 μm, and an undispersed thixotropic agent (20 to 100 μm), There was no tunnel-like defect portion), and a well-shaped partition wall having no bulge at the end portion could be formed.
(Example 2) The same procedure as in Example 1 was carried out except that the organic solvent 2 of Example 1 was not used and the organic solvent 1 (γ-butyrolactone had a boiling point of 200 to 208 ° C): 30 parts by weight was changed.

The edge shape of the dried film was measured using a surface roughness meter (Surfcom 1500A manufactured by Tokyo Seimitsu). The width was 1 mm and the height was 10 μm, and the in-plane uniformity was slightly insufficient. As a result of observing the upper partition wall with a microscope, disconnection (disappeared completely by firing or tunneling) caused by a gel-like material having a height of 120 μm, a bottom width of 70 μm, and an undispersed thixotropic agent (20 to 100 μm) The defect portion became a good shape.
(Comparative Example 1) The same procedure as in Example 1 was repeated except that the urea urethane compound solution of Example 1 was changed to a paste-like fatty acid amide (polyN-vinylacetamide 20 wt% benzyl alcohol solution).

As a result of observing the partition wall on the substrate with a microscope, the height was 120 μm, the bottom width was 70 μm, and there was no bulge at the end, but due to the gel-like material that was undispersed (20 to 100 μm) There was some disconnection (defects that disappeared completely or became tunnel-like by firing).
(Comparative Example 2) The amount of the urea urethane compound solution of Example 1 was 1 part by weight (10 parts by weight as urea urethane solution and 2.5 parts by weight as urea urethane compound with respect to 100 parts by weight of the binder resin). The same operation as in Example 1 was performed.

When the viscosity of the obtained glass paste was measured with a B-type viscometer (DV-II manufactured by Brookfield), the viscosity at a shear rate of 1.2 (s ⁻¹ ) was 4.0 (Pa · s 25 ° C.), shear The viscosity at a speed of 12 (s ⁻¹ ) was 3.5 (Pa · s 25 ° C.), and the thixotropy index was 1.1.

Next, after applying a wet thickness of 300 μm on the substrate using a slit coater, the substrate was dried in a clean oven at 100 ° C. for 90 minutes. When the edge part shape of the dry film was measured using a surface roughness meter (Surfcom 1500A, manufactured by Tokyo Seimitsu), the width was 6 mm and the height was 10 μm. When this substrate was used as a plasma display, abnormal discharge derived from unevenness in the height of the barrier ribs occurred.
(Comparative Example 3) Example except that the amount of the urea urethane compound solution of Example 1 was 12 parts by weight (120 parts by weight as urea urethane solution and 30 parts by weight as urea urethane compound with respect to 100 parts by weight of the binder resin). 1 was carried out.

When the viscosity of the obtained glass paste was measured with a B-type viscometer (DV-II, manufactured by Brookfield), the viscosity at a shear rate of 1.2 (s ⁻¹ ) was 500 (Pa · s 25 ° C.), and the shear rate was 12 The viscosity at (s ⁻¹ ) was 40 (Pa · s 25 ° C.), and the thixotropy index was 12.

  Next, an attempt was made to apply on the substrate using a slit coater, but the application was difficult because the viscosity was too high.

Claims (7)

A glass paste containing glass powder, a binder resin, and an organic solvent, wherein the glass powder content is 30 to 80% by weight, and the urea urethane compound is 5 to 20 parts by weight with respect to 100 parts by weight of the binder resin. Glass paste characterized by containing. The glass paste according to claim 1, further comprising a photosensitive organic component. 2. The organic solvent contains two or more organic solvents having a boiling point difference of 20 ° C. or more, and the weight ratio of the low boiling organic solvent to the high boiling organic solvent is in the range of 1: 9 to 9: 1. Or the glass paste of 2. The glass paste according to claim 1, wherein the glass paste is used for forming a partition wall of a display. It is a manufacturing method of the glass paste in any one of Claims 1-4, Comprising: It is set as the solution of viscosity 5,000 mPa * s or less which melt | dissolved the urea urethane compound in the organic solvent, and this solution with respect to 100 weight part of binder resin A method for producing a glass paste, comprising mixing 20 to 80 parts by weight. 6. The method for producing a glass paste according to claim 5, wherein the solution containing the urea urethane compound is mixed with an organic vehicle in which other organic components are dissolved by heating. A method for producing a member for a display panel, comprising a step of applying and drying the glass paste according to any one of claims 1 to 4 on a substrate.