TW200813186A - Fluorescent substance paste and method for producing display - Google Patents

Abstract

The purpose of the present invention provides a fluorescent substance paste of which its fluorescent substance powder could be dispersed uniformity and stability, its variation with time of viscosity is small; further, the chromaticity variation of the fluorescent substance after calcning is small. The solution mean of the present invention is a fluorescent substance paste which is characterized in that comprises fluorescent substance paste, binder resin, primary or secondary amine compound containing hydroxyl group and/or alkoxy group and its molecular weight is 300 or less, and organic solvent.

Description

200813186 IX. Description of the Invention: [Technical Field] The present invention relates to a phosphor paste in which a phosphor powder is uniformly dispersed, and more particularly to a phosphor used in a plasma display panel (hereinafter referred to as PDP). Light paste, and the method of making the display. [Prior Art] Compared with liquid crystal panels, PDPs are entering the field of office automation (OA) machines and mass communication display devices due to their high-speed display and large size. Furthermore, it is very much expected to make progress in the field of high-quality TV sets. As this use is expanded, color PDPs having a fine and a large number of display cells are attracting attention. In the discharge space provided between the glass substrate and the rear substrate, the PDP generates plasma discharge between the electrodes, and emits ultraviolet light from the gas enclosed in the discharge space to cause the phosphor in the discharge space to emit light. This is used to display the person. When a phosphor layer is formed in a PDP, in order to achieve high luminance, the phosphor paste is applied not only to the bottom of the display unit but also to the side surface of the spacer unit, and it takes time and effort to prevent uneven brightness. Stable and uniform coating. Therefore, it is necessary to make the phosphor paste into a desired viscosity, and it is necessary to stably and uniformly disperse the phosphor powder contained in the phosphor paste. Further, the surface of the phosphor powder used for the phosphor paste is acidic when it is treated with the total composition and various surface treatments, and is alkaline or has a state in which acidic and alkaline inclusions are present. With the combination of such a phosphor powder and a binder resin, there is a problem that a gelation reaction occurs with a functional group of the binder to increase the viscosity of 200813186. Further, among the red, green, and blue phosphor particles used in the general PDP apparatus, the chargeability of the green phosphor particles is negative, and is opposite to the phosphor particles of other colors. Therefore, when the phosphor paste is continuously applied, depending on the choice of the binder resin, the binder resin may be difficult to adsorb on the surface of the negatively charged green phosphor particles, so that the green phosphor particles aggregate, causing nozzle clogging or coating. In all cases, the obtained PDP has problems such as deterioration in display characteristics. Therefore, it has been proposed to coat the surface of the fluorescent powder by using an oxide, a fluorine compound, a boron compound or the like of an element having a large electronegativity, to prevent deterioration of each phosphor layer, and to simultaneously irradiate each phosphor. A method in which the charging tendency of the fine particles is uniform (see Patent Documents 1 to 4). However, when the surface of the phosphor powder is coated with the above compound, there is a problem that aggregation tends to be easy and dispersion stability is lowered. Further, it is known that an anionic surfactant or a nonionic surfactant (see Patent Documents 5 to 7), an alkylamine (see Patent Documents 8 to 9), and a carboxylic acid amine salt are added to the phosphor paste. (Dispersion agent, such as patent document 10) can improve dispersion stability. However, when an anionic or nonionic surfactant is used as a dispersing agent, there is a problem that the dispersion effect with respect to the amount of addition is small because of the large molecular weight. In addition, when an amine compound such as an alkylamine or a carboxylic acid amine salt is used, it is difficult to obtain a sufficient dispersion stability effect, and when the addition amount is increased in order to obtain a dispersion stability effect, it remains on the surface of the phosphor after firing, and coloration occurs. Therefore, it is difficult to use as a dispersant. [Patent Document 1] JP-A-2004-323576 [Patent Document 2] JP-A-2005-100954, No. 200813186 [Patent Document 3] Japanese Patent Laid-Open No. 2 0 0 5 - 1 8 3 2 4 6 [Patent Japanese Patent Publication No. 2003-96443 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei No. Hei. [Patent Document 8] Japanese Laid-Open Patent Publication No. Hei. No. 7-188599 (Patent Document No. JP-A-2002-82432). The purpose of the present invention is to provide a phosphor powder which is uniformly and stably dispersed in a paste, and the viscosity changes little with time, and the luminescent color of the phosphor layer formed after firing is higher than that of the unfired powder. A phosphor paste with a small change in chromaticity. In the present invention, a phosphor powder, a binder resin, a primary or secondary amine compound having a hydroxyl group and/or an alkoxy group and having a molecular weight of 300 or less, and an organic solvent are contained. A phosphor paste is preferred. The boiling point of the amine compound is preferably from 80 to 350 °C. The blending amount of the amine compound is preferably from 2 to 5% by weight based on 5% by weight of the phosphor paste. The blending amount of the phosphor powder is 40 to 60% by weight in the phosphor paste, and the blending amount of the binder resin is preferably 5 to 20% by weight in the phosphor paste. 200813186 The organic solvent preferably has a hydroxyl group. Further, it is preferred to further contain an acid compound. Further, the present invention relates to a method of producing a display comprising the step of forming a phosphor layer by baking the above-mentioned phosphor paste on a substrate and baking it. EFFECTS OF THE INVENTION In the present invention, since an amine compound having a hydroxyl group and/or an alkoxy group is contained in the phosphor paste, the mutual affinity between the surface of the phosphor and the binder resin is increased, and the phosphor powder is dispersed and stabilized. Further, since the molecular weight of the amine compound is small, the amine compound does not remain when the phosphor paste is fired, and a phosphor layer having a small change in chromaticity can be formed, and as a result, the luminance deterioration of the obtained display becomes small. BEST MODE FOR CARRYING OUT THE INVENTION The paste of the present invention must include a phosphor paste including a phosphor powder, a binder resin, a first order having a hydroxyl group and/or an alkoxy group and a molecular weight of 300 or less. A secondary amine compound, as well as an organic solvent. Specific examples of such an amine compound, such as N-(2-methoxyethyl)-1-butylamine, 4,4-dimethyloxazolidine, N-(2-methoxyethyl)-1 · propylamine, 3-(methylamino)-1-propanol, 2-ethoxy-N-ethyl-ethylamine, N-ethyl-2-methoxyethylamine, N-(2- Ethoxyethyl)-1-butylamine, methyl N-ethylcarbamate, methyl N-benzylmethylcarbamate, 3-methoxypiperidine, methyl butylcarbamate, amine Carbamate, 2,2'-iminoindole-ethanol, 1,1'-iminoindole-2-propanol, morpholine, 2-(methylamino)ethanol, 2-(ethylamino group Ethanol, N-(2-methoxyethyl)methylamine, diethanolamine, hydrazine (2-methoxyethyl)amine, hydrazine (2-ethoxyethyl)amine, 2-

200813186 Aminocyclohexanol, 2-methoxy-2-methyl-1-propylamine, 3-amino-2-propanol, 1-amino-2·methyl-2·propanol, 5 -Amino-1-pentanol, propanol, 1-amino-2-propanol, 2-methoxyethylamine, 2-ethoxyethylethoxy)ethanol, 1,2-anthracene (amine) Ethyl ethoxy) ethane and the like. The amine compound used in the phosphor paste of the present invention has a high surface of the phosphor and a binder resin due to an alkoxy group. When an alkoxy group is present, it is preferred because the boiling point is easily easier to burn than the amine compound only when it has a hydroxyl group. Examples of the alkoxy group are a methoxy group, an ethoxy group, a butoxy group, a propoxy group, etc., but the amount is improved from the affinity, and the burning point of the phosphor paste is methoxy, B. An oxy group is preferred. The amine compound used in the phosphor paste of the present invention is preferably in the first stage. It is not clear that it is easy to produce a dispersion stabilization mechanism with a small addition amount by using a first- or second-stage amine compound, but it is presumed that compared with the third-stage, the first-stage amine compound Alkaline is highly correlated. For the first-order amine and the second-order amine, it is preferred to use a first-order amine such as 2-methyl-1-propylamine or 3-amino-2,2-dimethyl-1-propane. Alcohol, 1-aminopropanol, 5-amino-1,pentanol, 3-amino-1-propanol, 1-amino-: aminoethanol, 2-methoxyethylamine, 2- Ethoxyethylamine, oxy)ethanol, and the like. The amine compound used in the phosphor paste of the present invention is preferably 3 or less, and preferably 200 or less, and 100 or less. When the amount is more than 30,000, the amount of the amine group per unit weight is caused by the compound. The effect of dispersing and stabilizing is difficult to produce, and the chlorpyrifos, 2-dimethyl-3-amino-1, amine, 2-(amine has a hydroxyl affinity, and the alkyl group can be low molecular. - grade or second and third grade: effect. Its grade and second amine, large methoxy-2--2 -methyl-2-propanol, 2-2-(aminoethyl f molecular weight It is more preferable that I is small, and the amine is inferior, and the amine is deteriorated. The brightness of the phosphor layer is deteriorated after burning 200813186, which tends to cause chromaticity change, etc. The molecular weight lower limit of the amine compound is not particularly limited, but the molecular weight is as follows. When the viscosity is low, it is preferably 60 or more because it is easily volatilized during the paste production process. The molecular weight can be evaluated by using TOF-M AS S (time-of-flight mass spectrometer), etc. The specificity of the amine compound having a molecular weight of 60 or more and 100 or less. For example, 1-amino-2-methyl-2-propanol, 3-(methylamino)-1-propanol, morpholine, 2- (Methylamino)ethanol, 2-(ethylamino)ethanol, N-(2-methoxyethyl)methylamine, 3-amino-1-propanol, 1-amino-2- Propyl alcohol, 2-aminoethanol, 2-methoxyethylamine, 2-ethoxyethylamine, etc. The carbon chain in the skeleton is linear or branched alkyl chain, epoxy alkyl chain ratio A heterocyclic ring and a fat ring are preferred. The carbon number is preferably 2 to 10, more preferably 2 to 5. When the carbon number is more than 10, the burning property is liable to be deteriorated to use an ethylene oxide chain or a ring. An epoxyalkyl chain such as an oxypropane chain is preferred. In particular, when the carbon number is as small as about 2 to 5, it is more preferable from the viewpoint that a good burn-through property is easily obtained even if an epoxyalkyl chain is not introduced. Specific examples of the amine compound having a carbon number of 2 to 5, such as N-(2-methoxyethyl)-1-butylamine, N-(2-methoxyethyl)-1-propylamine, 3- ( Methylamino)-1-propanol, 2-ethoxy-N-ethyl-ethylamine, N-ethyl-2-methoxy-ethylamine, N-(2-ethoxyethyl) -1-butylamine, 2,2'-iminoguanidine _ ethanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, N-(2-methoxyethyl) A Base amine diethanolamine, hydrazine (2-methoxyethyl) Amine, bis(2-ethoxyethyl)amine, 2-methoxy-2-methyl-1-propylamine, 3-amino-2,2-dimethyl-propanol, 5-amino 1-pentanol, 2·(aminoethoxy)ethanol, 1-amino-2-methyl-2-propanol, 3-amino-1-propanol, 1-amino-2-propanol Alcohol, 2-aminoethanol, 2-methoxyethylamine, 2-ethoxyethylamine, etc. -10- 200813186 The amine compound used in the phosphor paste of the present invention has a boiling point of 80 to 3 50 ° C. Preferably, it is preferably 1 Torr to 200 ° C. When the boiling point is higher than 350 ° C or higher, the burn-through property at the time of firing is deteriorated, and the brightness is lowered and the chromaticity is changed (yellow). Propensity. On the other hand, if the boiling point is lower than 80. (:, there is a tendency that the odor is likely to occur when the phosphor paste is dried and the plastiness of the phosphor paste is dried, and the flammability of the paste becomes high, etc. Further, the boiling point is lower than 200. At ° C, the amine compound is easily volatilized during the drying process described below, and scorching of the amine compound during firing is less likely to occur, and it is preferable that the brightness of the phosphor is less likely to decrease and the chromaticity changes. Specific examples of the amine compound of i 00 to 2 0 ° C, such as 4,4-dimethylindole, N-(2-methoxyethyl)-1-propylamine, 2-ethoxy- Ethyl-ethylamine, N-ethyl-2-methoxy-ethylamine, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, N-(2-methoxyethyl) )-1 - butylamine, 3-(methylamino)-1-propanol, n-(2-ethoxyethyl)-1-butylamine, methyl N-ethylcarbamate, 3- Methoxypiperidine, methyl butyl carbamate, urethane, morpholine, 2-methoxy-2-methyl-1-propylamine, 1-amino-2-methyl-2-propanol , 2-ethoxyethylamine, 2-methoxyethylamine, 3-amino-2,2-dimethyl-1-propanol, 3-amino-1-propanol, 1- Amino-2-propanol, 2-aminoethanol, etc. In addition to the above-mentioned preferred requirements, from the viewpoint of the burn-up property at the time of firing, the effect of the viscosity stabilization effect, and the ease of handling, 2-A Oxyethylamine, 2-(methylamino)ethanol, and 2-(2-aminoethoxy)ethanol are particularly preferred. The blending amount of the amine compound used in the phosphor paste of the present invention is The weight of the phosphor paste is preferably 0.2 to 5% by weight, and more preferably 0.25 to 5% by weight, and more preferably 0. 5 to 1% by weight. /., 200813186, there is a tendency that it is difficult to produce a dispersion stabilization effect. Moreover, as the content increases, the dispersion stability effect is increased to a certain degree to reach saturation, and if the blending amount is more than 5% by weight, the amine compound in the firing step It does not burn and remains, and the brightness of the phosphor film deteriorates after firing, and chromaticity change tends to occur, etc. Further, by the combination of the phosphor powder and the binder resin in the phosphor paste, A reaction such as an acid-base reaction occurs, and a viscosity stability such as gelation or the like is lowered. The above amine compound is Since it is alkaline, the pH of the fluorescent paste can be adjusted, so that, for example, even if the phosphor powder reacted under acidic conditions is combined with the binder resin, it is possible to suppress an unnecessary reaction. The viscosity of the reaction between the bulk powder and the binder resin increases. The phosphor powder used in the present invention, for example, the red phosphor powder is Y2〇3·· Eu, YV04: Eu, (Y, Gd). B03 : Eu, Y203s · Eu, r -Zn3 (P04) 2 : Mn, (Zn, Cd) S · · Ag + In203, Y (P, V) 04 : Eu I or the like. The green phosphor powder is Zn2Ge02: Mn, BaAl12019: Mn, Zn2 S1Ο4* Mn, LaP〇4: Tb, ZnS: Cu, A1, ZnS: Au, Cu, A1, (Zn, Cd)S: Cu, A1 Zri2Si〇4 : Mn, As, Y3A15012 : Ce, CeMgAl"〇i9: Tb, Gd2〇2S: Tb, Y3Al5〇i2: Tb, ZnO: Zn, (Y, Gd) B03: Tb, (Ba, Sr, Mg )0· aAl203Mn and the like. The blue phosphor powders are Sr5(P04)3Cl:Eu, BaMgAl14023: Eu, BaMgAl16〇27: Eu, BaMg2Al14〇24: Eu, CaMgSi2〇6: Eu, t Y2Si03 : Ce, BaMgAl10〇i7 : Eu, and the like. Further, at least one element selected from the group consisting of Tm, Tb, and Eu (Eu) may be substituted for yttrium (Y), gadolinium (Gd), and radium ( At least one parent selected from the group consisting of rare earth elements and rare earth elements. Among them, the rare earth molybdenum-based phosphorescent system is preferably a ruthenium-activated bismuth molybdate phosphor represented by a composition formula of Yi-xEuxTaOd and X is about 0·005 to 0.1). In the red phosphor, it is preferable to use yttrium activated yttrium yttrium, and in the green phosphor, the rare acid rare earth phosphor is used in the composition formula Yi_xTbxTa04 (wherein, X is about 0.00 1 to 0·2). The ruthenium molybdate molybdate shown is preferred. Further, in the blue phosphor, the rare earth molybdate phosphor is activated by a table represented by a composition formula YuTmxTaC^ (wherein, X is about 〇·〇〇1 to 〇·2). Preferably. The phosphor powder used in the phosphor paste of the present invention is preferably a particle diameter of 0.2 to 5/m, and more preferably 1 to 3/zm. When the particle size is larger than 5 // m, when the paste is placed after the preparation, the phosphor powder is likely to settle, and the composition is coarse and dense, and there is a tendency that coating unevenness or uneven brightness is likely to occur, and the powder is too fine, because it is easy. Aggregation of the phosphor powder occurs and the surface is activated, and there is a tendency that it is likely to chemically react with other components such as a binder or the like. The evaluation of the particle size in the powder state can be evaluated by a laser refractive particle size distribution meter (for example, "Microtrac MT3 3 00" manufactured by Nikkiso Co., Ltd.). The state of the film after coating or the film after firing can be evaluated by a transmission electron microscope (for example, "JEM-4000EX" manufactured by JEOL Ltd.). When the image is observed through a transmission electron microscope, the phosphor powder and the organic component can be identified from the contrast. Therefore, the transmission electron microscope observation image of the area of the film cross section of 10 μm >< 50 /zm can be evaluated by image analysis. -13- 200813186 The phosphor powder used in the phosphor paste of the present invention preferably has a specific surface area of 200 to 1 200 m 2 /kg, more preferably 300 to 1 000 m 2 /kg. When the specific surface area is in this range, the dispersibility of the phosphor powder in the organic binder resin and the organic solvent is improved, and a phosphor paste excellent in coatability can be obtained. Further, by increasing the dispersibility, a dense phosphor layer can be formed, the luminous efficiency can be improved, and the life can be prolonged. Further, when the specific surface area is less than 200 m2/kg, it is difficult to form a phosphor layer having a desired thickness uniformly and smoothly, and when the paste is placed after the production, the phosphor powder is easily sedimented, and the composition is coarse and dense, so that coating is likely to occur. The tendency to be uneven or uneven in brightness. On the other hand, when the amount is more than 1,200 m2/kg, the powder is too fine, and aggregation of the phosphor powder is likely to occur, and the surface is activated, which tends to cause chemical reaction with other components such as a binder or the like. Furthermore, the specific surface area can be measured by using the Lee-Nas method (L ea · N ursemeth 〇d), the particle analyzer (Sub-sieve sizer) method, the Blaine method, and the constant pressure ventilation type. A method of air permeation by a specific surface area measuring device or the like, or an adsorption method in which molecules or ions of a known size are adsorbed on the surface of the powder, and the specific surface area of the powder is measured from the amount. The blending amount of the phosphor powder is preferably from 40 to 60% by weight in the phosphor paste, and more preferably from 40 to 55% by weight. When the blending amount of the phosphor powder is less than 40% by weight, the thickness of the wet film required to obtain a desired film thickness becomes large, and the film thickness tends to be uneven. Further, in particular, when a phosphor is formed in a groove of a stripe-like or lattice-shaped separator pattern, the wet film thickness is larger than the height of the separator, and it is easy to allow the phosphor paste to flow into the adjacent groove. Color mixing and tendency to produce uneven film thickness. On the other hand, when the blending amount of the phosphor-14-200813186 powder is more than 60% by weight, the phosphor powder in the phosphor paste is liable to settle, the viscosity of the paste is likely to change, and the viscosity of the paste tends to become high. . In addition, since the ratio of the solvent component is relatively reduced, the binder in the paste tends to have uneven thickness during coating, and the chargeability of the phosphor film after firing is remarkably lowered, and the brightness tends to decrease. . Further, for the purpose of uniformizing the chargeability of the red, blue, and green powders and suppressing the change in viscosity, the surface of the phosphor powder may be coated with a metal oxide. The metal oxide may be zinc oxide, cerium oxide, aluminum oxide, cerium oxide, magnesium oxide or the like. The binder resin is preferably oxidized or/and decomposed or/and vaporized at the time of firing so that no carbide remains in the inorganic material, specifically, ethyl cellulose, methyl cellulose, and nitro group are used. Cellulose resin such as cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, hydroxy cellulose, methyl hydroxy cellulose; methyl (meth) acrylate, ethyl (meth) acrylate, (a) Base) n-butyl acrylate, isobutyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethyl methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, polyacrylic acid Acrylic resin formed by a polymer or copolymer such as sodium, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polyethylene, polyoxymethylene polymer (for example, polymethyl siloxane, poly Methylphenyl siloxane, butadiene/styrene copolymer, polystyrene, polyvinylpyrrolidone, polyamine, high molecular weight polyether, copolymer of ethylene oxide and propylene oxide, Polyacrylamide, poly-methyl maple, polybutene or the like is preferred. In such a binder resin, from the viewpoint of the difficulty in causing a gelation reaction or the like due to the addition of an amine compound, and the viewpoint of forming a phosphor layer of -15-200813186 having a small amount of binder residue after firing, A plain resin is preferable, and specifically, methyl cellulose, ethyl cellulose, hydroxy cellulose, or methyl hydroxy cellulose is preferable. In addition, when an acrylic resin is used, there is a tendency that viscosity change does not occur due to the addition of an amine compound. However, compared with the case of using an ethyl cellulose resin, the burning property of the resin polymer during baking is poor. It is difficult to obtain uniformity of coating thickness and the like. Further, in the cellulose resin, a solvent mixture of toluene/ethanol (mixing ratio of 80/20) was used to form a 5% by weight solution, and the viscosity of the solution became 〇. 〇〇4 to 0 · 02 5 P a · s of cellulose A resin is preferred. If the viscosity of the solution is higher than 〇. 02 5 P a · s ', the viscosity of the entire phosphor paste is increased, which is not preferable from the viewpoint of coatability. On the other hand, in the case where the solution viscosity is less than 0.004 Pa·s, in order to obtain an appropriate viscosity to form a phosphor paste, it is necessary to increase the amount of the binder resin, and it is difficult to maintain the ratio of the phosphor powder to the binder resin which is necessary in the present invention. The viscosity can be evaluated using a B-type viscometer (for example, "DV-III" manufactured by Brookfield Corporation). Further, the blending amount of the binder resin is preferably from 5 to 20% by weight in the phosphor paste, more preferably from 5 to 15% by weight. When the amount of the binder resin added is less than 5% by weight, if the weight ratio of the phosphor powder to the binder resin is maintained, the ratio of the phosphor powder required for the phosphor paste of the present invention cannot be obtained, and If it is more than 20% by weight, the viscosity of the paste tends to be too high. Further, when the amount of the binder resin added is small, the burn-in property is good. Further, in general, there is a case where a dispersion stabilization effect is obtained by adding an acid compound. However, when an acid compound is used, the viscosity becomes easy to change with time depending on the characteristics of the surface of the phosphor powder. For example, when an alkaline component is exposed on the surface of the phosphor powder, a certain dispersion stabilization effect can be obtained by the acid compound at the time of preparation of the paste, but on the other hand, when the paste is left for several days, gelation occurs. Form a different viscosity from the paste immediately after production. In this case, by containing the amine compound of the present invention, chemical reactions such as gelation can be suppressed, and viscosity stability can be ensured. Specific examples of the acid compound include a fatty acid, a fatty acid salt, an alkyl sulfate salt, an alkylbenzenesulfonate, an alkylsulfonic acid succinate, a naphthalenesulfonic acid, a polycarboxylic acid polymer, and the like. In the acid compound, by forming the same carbon number and carbon chain type as the amine compound used in the phosphor paste of the present invention, the burn-in property and the dispersion stabilization effect can be obtained. Specific examples of such an acid compound include, for example, n-heptanoic acid, octanoic acid, n-decanoic acid, n-decanoic acid, n-dodecanoic acid, sodium n-heptanoate, sodium carboxydecanoate, and sodium lauryl sulfate. , sodium sulforaphane, sodium dodecyl benzene sulfonate, sodium dipropyl sulfosuccinate, sodium dibutyl sulfosuccinate, sodium propyl naphthalene sulfonate, sodium butyl naphthalene sulfonate However, from the viewpoint of burn-through property, a low molecular weight material such as n-heptanoic acid, octanoic acid or sodium n-heptanoic acid carboxylate is preferred. In the case of a combination of a phosphor powder which promotes a gelation reaction by an acid compound and a binder resin, the combination of the acid compound and the amine compound and the addition amount of both are preferably in a range. As a result of intensive review by the present inventors, it was found that the above-mentioned particularly preferred amine compound such as N-methoxyethylamine, or 2-(methylamino)ethanol, or 2-(2-aminoethoxy) When ethanol is selected as a fatty acid compound, a fatty acid salt type or a polycarboxylic acid polymer type material as an acid compound, if the blending amount of the amine compound is more than the acid compound, the gelation-17-200813186 reaction can be suppressed and used. Compared with the case of individual compounds, there is a tendency to ensure viscosity stability over a long period of time. The organic solvent may be appropriately selected depending on the viscosity finally obtained by the phosphor paste or the drying conditions of the phosphor coating. Specifically, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether alcohol, and the like may be used. Glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, 2,2,4-trimethyl-1,3 - pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2-ethyl-1,3·hexanediol, methylethyl Ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutanol, isopropanol, caprolol, benzyl alcohol, tetrahydrofuran, V-butyrolactone, propylene carbonate, ethyl lactate, hydrazine-methyl A pyrrolidone or the like, or a mixture of one or more organic solvents. The organic solvent is preferably a good solvent for the binder resin to be used. The choice of the organic solvent is mainly selected in consideration of the volatility of the organic solvent and the solubility of the binder resin used. When the solubility of the organic solvent to the binder resin is low, even if the solid content ratio is the same, the viscosity of the coating liquid becomes high, and the coating property tends to be deteriorated. Further, those having a hydroxyl group in these organic solvents are preferred because they have a large affinity with a hydroxyl group or an alkoxy group of the amine compound and are more likely to exhibit a dispersion stability effect. Further, when drying or baking, the organic solvent is easily volatilized together with the amine compound when it is volatilized, and the effect of promoting the burning of the amine compound can be obtained. Specific examples of the organic solvent having a hydroxyl group, such as an alcohol compound, specifically, isobutanol 'isopropanol, caprolol and benzyl alcohol are preferred among the above organic solvents. The blending amount of the organic solvent is preferably from 35 to 65 by weight -18 to 2008 13186% in the phosphor paste, and more preferably from 40 to 60% by weight. When the blending amount of the organic solvent is less than 35 wt%, the viscosity of the phosphor paste becomes too high, and the smoothness of the coated surface tends to be poor due to poor leveling. On the other hand, when the blending amount of the organic solvent is more than 65% by weight, the sedimentation of the dispersed particles becomes fast, and it is difficult to stabilize the composition of the phosphor paste, and a large amount of energy and time are required to cause drying. In the phosphor paste of the present invention, an antioxidant, an antifoaming agent, a tackifier, and a plasticizer (for example, dibutyl phthalate, dioctyl phthalate, polyethylene glycol) may be added as needed. Etc., etc., however, the amount of these organic components added is preferably 3% by weight or less. Since these components remain at the time of firing, they cause a change in chromaticity of the phosphor light emission and a cause of deterioration in luminance. A photosensitive component such as a photosensitive monomer, a photosensitive oligomer, or a photosensitive polymer, or a photopolymerization initiator, a sensitizer, an antioxidant, an ultraviolet absorber, or the like may be added to the phosphor paste of the present invention. An additive component such as a polymerization inhibitor is used as a photosensitive phosphor paste. The phosphor paste of the present invention is prepared by blending various components into a predetermined composition, and then kneading and dispersing them uniformly by kneading/dispersing means such as a three-roller or a kneader. The present invention also relates to a method of manufacturing a display comprising the step of applying the above-described phosphor paste to a substrate. An example of a method of manufacturing a plasma display is given to the display of the present invention. First, a method of manufacturing the front panel of the plasma display will be described. "PP8" (manufactured by Nippon Electric Glass Co., Ltd.) and "PD200" (manufactured by Asahi Glass Co., Ltd.), which are heat-resistant glass for sodium glass or plasma display, can be used as the substrate. The size of the glass substrate of -19-200813186 is not particularly limited, and a thickness of 1 to 5 mm can be used. First, indium-tin oxide (ITO) was sputtered on a glass substrate, and a pattern was formed by photolithography. Next, a black electrode paste for black electrodes was printed. The black electrode paste is mainly composed of an organic binder, a black pigment, a conductive powder, and a photosensitive component when photolithography is used. It is preferred to use a metal oxide for the black pigment. The metal oxide may be titanium black or an oxide of copper, iron or lanthanum or a composite oxide thereof, or a cobalt oxide. However, from the viewpoint of less discoloration when mixed with glass, cobalt is oxidized. The object is better. The conductive powder may be a metal powder or a metal oxide powder. As the metal powder, gold, silver, copper, nickel or the like which is usually used as an electrode material can be used, but it is not particularly limited. Since the black electrode has a large resistivity, a bus electrode is formed to form an electrode having a small resistivity, and a highly conductive electrode paste (for example, silver as a main component) is printed on the black electrode paste. On the surface. Next, a bus electrode pattern is produced by one exposure/image development. In order to surely ensure conductivity, an electrode paste having high conductivity is printed before development, and then developed after exposure. After the bus electrode pattern is formed, firing is performed. Thereafter, in order to improve the contrast, it is preferable to form a black stripe or a black matrix. The thickness of the black electrode paste after firing and the conductive paste after firing are preferably in the range of 1 to 5 /z m. Further, the line width after firing is preferably from 20 to 100 m. Next, a transparent dielectric layer is formed using a transparent dielectric paste. The transparent dielectric paste is mainly composed of an organic binder, an organic solvent, and glass, and may be added with an additive such as a suitable plasticizer. Although the method of forming a transparent dielectric layer is not particularly limited, it can be transparent by, for example, screen printing, a bar coater, a roll coater, a die coater, a knife coater, a spin coater, and the like. After the dielectric paste is completely coated or partially coated on the electrode-formed substrate, it is dried using any type such as a ventilating oven, a hot plate, an infrared drying oven, or vacuum drying to form a thick film. Further, the transparent dielectric paste may be formed into a green sheet and then laminated on the electrode forming substrate. The thickness is preferably 0.01 to 0.03 mm. Next, baking is performed in a baking furnace. The surrounding environment or temperature may vary depending on the type of paste or substrate, but it may be fired in the air, nitrogen, or hydrogen. As the baking furnace, a batch type firing furnace or a roll conveying type continuous type firing furnace can be used. The firing may be carried out at a temperature at which the resin to be used can be sufficiently debonded. Usually, in the case of using an acrylic resin, firing is carried out at 43 0 to 65 °C. When the baking temperature is too low, the resin component tends to remain, and if it is too high, the substrate is deformed and cracked. Furthermore, a protective film is formed. The protective film may be made of MgO, MgGd204, BaGd2〇4, Sr〇.6Ca〇.4Gd2〇4, Ba〇.6Sr〇4Gd2〇4, Si〇2, Ti〇2, Al2〇3, the above low softening point glass. At least one selected from the group, especially MgO is particularly preferred. A known technique such as electron beam evaporation or ion plating can be used as the method for producing the protective film. Next, a method of manufacturing the back panel of the plasma display will be described. The glass substrate can be made of soda glass, "PD200" or "PP8" in the same manner as the front panel. A line electrode pattern for an address is formed on a glass substrate by a metal such as silver, aluminum, chromium, or nickel. Regarding the formation method, a metal paste containing such a metal powder and an organic binder as a main component can be printed by screen printing.

200813186 Line pattern printing method. After applying a paste using a photosensitive organic component as an organic binder, the pattern exposure using a photomask is partially dissolved and removed by a developing step, usually again, at 350, hot, and burned. A photosensitive paste method for forming an electrode pattern. Further, after the chromium or aluminum is vapor-deposited on the glass substrate, the resist is applied, and after the anti-invasive image is formed, an etching method for removing unnecessary portions is performed by etching. The dielectric is placed on the address electrode. By providing the dielectric layer, the property can be improved, and the separator formed by the upper layer of the dielectric layer can be suppressed from peeling off. In addition, a method of forming a dielectric layer may be a method in which an inorganic powder such as a glass-melting glass powder or an organic binder is used as a main body paste by screen printing, a slit die coater or the like. Next, a method of forming a separator by photolithography will be described. The photosensitive paste separator paste of the present invention is preferably applied to a substrate on which a dielectric body is formed in a lattice shape, a honeycomb shape or the like, without particular limitation. As the coating method, a method such as a bar coater, a roll coater, a coater, a knife coater, or screen printing can be used. The height of the desired separator and the shrinkage ratio formed by the paste formation can be determined by the number of coatings, the mesh size of the screen, the viscosity of the paste, etc., and the coating thickness after drying is applied to 10.5. When zm is 15 〇vm or more, a sufficient discharge space of 5 bodies can be obtained and the brightness of the plasma display can be improved. The coated separator paste was exposed after drying. Exposure of a boat's light lithography method through a reticle exposure. In addition, you can also use photosensitive gold, which will not need / 600 〇C. Use: Expose the agent to make a discharge or a powder or a high-division dielectric printing or baffle pattern. First, the thickness of the formed slit die is visible. Coating thickness adjustment. This is preferred. Expanding the fluorescence 〖If you do not use the -22- 200813186 mask, use the direct method of laser light. As the exposure device, a stepper (stePPer) exposure machine or a proximity exposure machine or the like can be used. The active light source used at this time may be, for example, near ultraviolet rays, ultraviolet rays, rays, ray rays, X-rays, laser light, or the like. Among them, ultraviolet rays are preferred, and for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a germicidal lamp, or the like can be used. Among them, an ultrahigh pressure mercury lamp is preferred. The exposure conditions vary depending on the thickness of the coating. However, an ultrahigh pressure ice silver lamp having an output of 1 to 10 μm/cm 2 is usually used for exposure for 1 to 30 minutes. After the exposure, development is performed by the difference in solubility between the exposed portion and the non-exposed portion in the developing solution, but it is usually carried out by a dipping method, a spray method, a brush method, or the like. As the developing liquid, an organic solvent which can dissolve the organic component in the photosensitive paste can be used. However, when a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, it can be developed by an aqueous alkaline solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used. However, an organic alkaline aqueous solution is preferred because it is easy to remove an alkali component during firing. As the organic base, a general amine compound can be used. Specifically, it is tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine or the like. The concentration of the alkaline aqueous solution is usually 0.05 to 5% by mass, and more preferably 0.1 to 1% by mass. If the alkali concentration is too low, it is difficult to remove the soluble portion, and if the alkali concentration is too high, there is a fear that the pattern is peeled off or corroded, which is not preferable. Further, the development is carried out at a developing temperature of 20 to 50 ° C, which is preferable from the viewpoint of process management. -23- 200813186 Further, the separator may be composed of two or more layers. The structure of the separator shape can be expanded in a three-dimensional manner by two or more structures. For example, in the case of a two-layer structure, the first layer is coated and exposed to a line shape, and then the second layer is applied and exposed to the line in the direction perpendicular to the first layer, and the image is formed to have a high profile. The partition of the well-shaped structure. Next, it is baked in a baking furnace at a temperature of 520 to 620 ° C for 1 to 60 minutes to form a separator. In the separator thus formed, the above-described phosphor paste pattern is formed. The method for forming the phosphor paste pattern is not particularly limited, and may be, for example, a screen printing method in which a phosphor paste is discharged from a metal opening, and a photosensitive photoresist or a phosphor paste is provided with photosensitivity. A method of forming a photolithography method. However, since the method of performing the method of ejecting the phosphor paste from the metal opening and the screen printing method are simple, a low-cost PDP can be obtained, which is preferable. After the phosphor paste pattern is formed, it is dried and fired, and a phosphor layer is formed on the side and bottom of the separator. The thickness of the phosphor is not particularly limited, but the thickness of the surface of the dielectric layer when it is zero at the center position between the adjacent spacers is 10 to 30 // m, and is 1 5 to 2 5 # m is better. The drying of the phosphor paste is carried out for the purpose of removing the solvent or curing the resin component (thermal crosslinking by thermal polymerization of the unsaturated double bond component, etc.), and the temperature and time can be matched with the boiling point of the solvent. Although the curing temperature of the resin component is set, etc., it is usually carried out under the conditions of a temperature of 80 ° C to 200 ° C and a drying time of 10 to 30 minutes. Further, the firing is carried out mainly by removing the organic component such as the binder resin or the amine compound, and the organic component characteristics such as the volatility and the flammability of the organic component, or the heat resistance of the fluorescent powder, etc. -24- 200813186 The composition of the machine is set. However, it is usually carried out at a temperature of 400 to 550 ° C for a period of time 〇 3 〇 minutes. Both drying and baking can be carried out in a multi-stage heating mode. In particular, when the firing temperature is in multiple stages, it is easy to avoid the problem that the organic component is scorched on the surface of the phosphor and the luminescent properties of the phosphor change. It is also possible to continuously perform calcination without drying after drying, and this method is preferable from the viewpoint of ensuring uniformity of the thickness of the phosphor layer. Next, after the back plate of the vapor is sealed to the front plate, the space formed by the interval between the two substrates is heated, and after vacuum evacuation, the discharge gas composed of He, Ne, Xe or the like is sealed and sealed. From the viewpoint of discharge voltage and brightness, a Xe-Ne mixed gas having a Xe of 5 to 15% by volume is preferred. Since the efficiency of ultraviolet light generation is large, Xe can be increased to about 30% by volume. Finally, a driver circuit is mounted and a plasma display can be fabricated by performing a feed. [Embodiment] Next, an embodiment of the present invention will be described, but the present invention is not limited to the related embodiment. The concentration (%) in the examples is % by weight. Examples 1 to 1 9 A phosphor paste was prepared using the following materials. (A) Phosphor powder • (A-1) Blue phosphor powder: BaMgAl1() 017: Eu (hereinafter, referred to as BAM), average particle diameter 2·4 μ m ; (A-2) red Phosphor powder: (Y, Gd) B03 · Eu (hereinafter, referred to as YGB), average particle diameter 2.3 / zm; -25- 200813186 • (A-3) green phosphor powder: Zn2Si04: Μη (below , called ZSM), with an average particle size of 2.5 // m; • (A-4a) ZSM coated with a zinc oxide layer with an average thickness of 0.2/m; • (A-4b) surface with an average thickness of 0.2/ Zm oxide layer coated ZSM. Further, the method of coating the metal oxide on the surface of the phosphor in (A-4a) and (A-4b) is a coating of a metal oxide (zinc oxide or cerium oxide) chloride, nitrate, or the like. The ZSM powder was placed in an aqueous solution, stirred well, dried, and fired at 400 to 600 ° C to form. The thickness of the film can be adjusted by controlling the concentration of chloride or nitrate. (B) Amine compound having an amine group and a hydroxyl group and/or an alkoxy group as a dispersant: • (B-1) 2-(methylamino)ethanol, molecular weight: 75, boiling point: 156 ° C; • (B- 2) 2-methoxyethylamine, molecular weight: 88, boiling point: 90 ° C; • (B-3) N-ethyl-2-methoxy-ethylamine, molecular weight: 103, boiling point: 1 1 6 °C; • (B-4) triethanolamine, molecular weight: 1 4 9, boiling point: 3 3 5 °C; • (B-5) gin[2-(2-methoxyethoxy)ethyl]amine , molecular weight: 3 23, boiling point: 3 3 0 ° C; acid compound • (B-6) n-heptanoic acid, molecular weight: 130, boiling point: 223. (:. Amine compound without hydroxyl or alkoxy group: • (B-7) N-n-butylethylamine, molecular weight: 1〇1, boiling point: 11 (rc -26- 200813186 Carboxylic acid amine salt: • (B-8) Ammonium acetate, molecular weight: 77, melting point: 1 12 ° C (boiling point unknown) (C) Adhesive resin • (c_l) ethyl cellulose resin (ethoxyl group content 50%) (D) Organic solvent • (D-1) mixed solution of guar alcohol and ethylene glycol monobutyl ether acetate in a weight ratio of 30/70, each of which is a phosphor powder, a dispersant, a binder resin, and an organic solvent. The components were mixed at a ratio shown in Table 1, and kneaded by three rolls made of ceramics to obtain a phosphor paste. The components and blending amounts of the obtained phosphor paste are shown in Table i. As the photosensitive silver paste, a paste having the following composition was used: Silver particles (average particle diameter: 1.5/xm, specific surface area: 0.80 m 2 /g): 150 parts by weight; 1% by mass of acrylic acid, 50% by mass of methyl methacrylate, glycerin Acrylic copolymer resin composed of 40% by mass of monoacrylate (acid value: 30 mg KOH/g, hydroxyl value: 410 mg KOH/g, weight average molecular weight: 12,000): 12 parts by weight; Propane triacrylate ("TPA 3 30", trifunctional), manufactured by Nippon Kayaku Co., Ltd.: 6 parts by weight; 2-benzyl-dimethylamino-1-(4-morpholinylphenyl) - Butanone-1: 3 parts by weight; 7 - Butyrolactone: 18 parts by weight. -27- 200813186 (F) The dielectric paste is paste using the following composition: Glass transfer point 47 5 ° C, softening point 5 1 5 t of lanthanide glass: 40 parts by weight; ethyl cellulose resin (ethoxy group content: 50%): 5 parts by weight; capenol: 40 parts by weight. (G) Photosensitive glass paste using the following composition Paste ® Glass transfer temperature 491 ° C, softening point 52 8 ° C glass powder: 24 parts by weight; Glass transfer point 6 5 2 ° C 塡 剂 powder: 6 parts by weight from acrylic acid 10% by mass, methacrylic acid Acrylic copolymer resin composed of 50% by mass of methyl ester and 40% by mass of glycerin monoacrylate (acid value: 30 mg KOH/g, hydroxyl group: 410 mg KOH/g, weight average molecular weight: 12,000): 7 parts by weight, trishydroxyl Propane triacrylate (Nippon Chemical Co., Ltd. _ system, "TPA3 30", 3-functional) ···3 parts by weight of 2-benzyl-dimethyl -1- (4 - morpholinophenyl) - butanone-1: 1.5 parts by weight of the urethane compound UA-3 3 48PE :( Shin-Nakamura Chemical Co., Ltd.) 1.5 parts by weight of -28-200813186

[Table 1] Example Fluorescent powder Dispersant Binder Resin Organic solvent type Blending amount (parts by weight) Kind of blending amount (parts by weight) Molecular weight boiling point 种类 Kind of blending amount (parts by weight) Kind of blending amount (weight 1) 1 A-1 48.0 B-1 0.1 75 156 C-1 9.0 D-1 42.9 2 A-1 48.0 B-1 0.5 75 156 C-1 9.0 D-1 42.5 3 A-1 48.0 B-1 1.0 75 156 C-1 9.0 D-1 42.0 4 A-1 48.0 B-1 3.0 75 156 C-1 9.0 D-1 40.0 5 A-1 48,0 B-1 7.5 75 156 C-1 9.0 D-1 35.5 6 A-1 48.0 B-2 1.0 75 90 C-1 9.0 D-1 42.0 7 A-1 48.0 B-3 1.0 103 116 C-1 9.0 D-1 42.0 8 A-1 35.0 B-1 1.0 75 156 C- 1 9.0 D-1 55.0 9 A-1 45.0 B-1 1.0 75 156 C-1 9.0 D-1 45.0 10 A-1 48.0 B-1 1.0 75 156 C-1 3.0 D-1 48.0 11 A-1 48.0 B -1 1.0 75 156 C-1 8.0 D-1 43.0 12 A-1 48.0 B-1 1.0 75 156 C-1 15.0 D-1 36.0 13 A-1 48.0 B-1 1.0 75 156 C-1 22.0 D-1 29.0 14 A-1 48.0 B-1/B-6 1.0/0.5 75/130 156/223 C-1 9.0 D-1 41.5 15 A-1 48.0 B-1/B-6 1.0/1.5 75/130 156/ 223 C-1 9.0 D-1 40.5 16 A-2 48.0 B-1 1.0 75 156 C-1 9.0 D-1 42.0 17 A-4a 48.0 B-1 1.0 75 156 C -1 9.0 D-1 42.0 18 A-4b 48,0 B-1 1.0 75 156 C-1 9.0 D-1 42.0 19 A-3 48.0 B-1 1.0 75 156 C-1 9.0 D-1 42.0 -29- 200813186 Next, the viscosity stability and the film thickness precision of Examples 1 to 19, and the chromaticity change of the phosphor and the relative luminance of the phosphor were evaluated according to the following measurement methods. 1. Viscosity stability The viscosity (▽ 〇) after the paste was prepared and the viscosity after 20 days at a temperature of 22 to 25 ° C (7? 2 〇) were measured by the following conditions, and the viscosity was just after the production. The reference viscosity change rate D = ( 7 20 - β 〇) / β 〇 xl 〇〇 (%) is used as an indicator of viscosity stability. In the viscosity measurement, the viscosity meter is a B-type viscosity agent (type DV-III manufactured by Brookfield, Inc.), the shaft is SC4-14, and the container is a small connector (sample cup 3c〇, measuring temperature is 25 ° C, shear rate) It is 1 .2^1], and the time from the start of measurement to the reading of viscosity 値 is 5 minutes. Furthermore, although D is closer to 〇, the better, but as long as -2% g DS 8%, there is no problem in practical use. In particular, in the range of 0% g D ^ 5%, the viscosity stability can be said to be stable, and even if it is left for 20 days, the coating property deterioration described below is not preferable, and the film thickness is as follows. The back panel is produced by using the 340x260x2.8mm glass substrate ("PD-200" manufactured by Asahi Glass Co., Ltd.) to form the back panel of the AC (alternating) type plasma display panel. Silver paste (E), and by line photolithography, a line electrode having a pitch of 140/zm, a line width of 60/zm, and a thickness of 4/zm after firing is formed as an input electrode. After the dielectric paste (F) is applied by screen printing, it is fired at 55 ° C to form a thickness l.介#m dielectric layer. -30- 200813186 Furthermore, using the above-mentioned photosensitive glass paste (G) on the dielectric layer, the pattern is formed by photolithography, and then 57 (TC firing) In 15 minutes, a line-shaped separator having a pitch of 140 μm, a line width of 20 μm, and a height of 100 μm was formed. On the separator formed in this manner, the phosphor of the composition shown in Table 1 was pasted on the separator. The screen printing is performed on the groove between the patterns. The phosphor paste is used after being prepared into a paste and stored at a temperature of 22 to 25 ° C for 10 days under a seal. The screen is made with #200 mesh, and the spacing is 140 // m, a line-shaped opening pattern with a width of 50 // m. Printing is carried out. Then, drying (150 ° C, ^ 30 minutes), firing (500 ° C, 30 minutes), on the side and bottom of the separator The phosphor layer is formed, and the coating speed at the time of screen printing is adjusted such that the average thickness of the phosphor film after firing is 15 ± 0.5 μm. The glass substrate is visible in a direction perpendicular to the glass substrate. The profile is cut off by a scanning electron microscope (S2400, manufactured by Hitachi, Ltd.) The cross section was evaluated for the thickness of the phosphor film formed at the bottom of the groove between the separators (the thickness of the phosphor layer adjacent to the central portion between the separators). Further, 20-point fluorescence randomly selected from the same back panel was measured. The film thickness is thick, and the film thickness accuracy is evaluated in the following manner from the width of the film thickness. A : The difference between the maximum 値 and the minimum 20 of the 20-point phosphor film thickness is 0.8 μm or less; B: 20-point fluorescence The difference between the maximum 値 and the minimum 体 of the body thickness is greater than 〇.8/zm and less than 1.2 μm; .C : The difference between the maximum 値 and the minimum 20 of the 20-point phosphor film thickness is greater than 1.2/zm and is 1 · 5 /zm or less; D : The difference between the maximum 値 and the minimum 20 of the 20-point phosphor film thickness is greater than 1.5 // -31 - 200813186 The film thickness accuracy is deteriorated when the dispersion of the phosphor powder in the phosphor paste is deteriorated. Getting worse. When the blending amount of the phosphor powder is small, the thickness (wet film thickness) of the coating film having a necessary thickness after firing is required to be increased, and the film thickness accuracy is likely to be deteriorated. In order to obtain uniform display characteristics in the PDP, the difference between the maximum 値 and the minimum 必须 must be 1.2 // m or less. 3. The chromaticity change and relative brightness of the phosphor are formed on a glass substrate of 34 〇 x 26 〇 x 2.8 mm ("PD-200" manufactured by Asahi Glass Co., Ltd.) by screen printing to form an average film thickness - 15 ± 0.5 / X m, covering a phosphor paste of an area of 20 0mm X 200mm, then drying (150 ° C, 30 minutes), firing (500 ° C, 30 minutes), forming a phosphor layer. The glass substrate of the obtained additional phosphor was cut into an area of 5 cm x 5 cm, and placed in a vacuum chamber, and an excimer lamp (eximer lamp) (UER2 0H-made by Ushio Electric Co., Ltd.) was formed in the system to form a nitrogen atmosphere. 146V) As an excitation light source, a vacuum ultraviolet ray having a wavelength of 147 nm was irradiated, and a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., $MCPD2000) and a luminance meter (manufactured by Minolta Co., Ltd., LS-100), 'Measurement from fluorescence The chromaticity and brightness of the layer. The nitrogen atmosphere was obtained by depressurizing the vacuum chamber to 9 Pa by a vacuum pump and then introducing nitrogen gas at a pressure of 98.4 kPa. The irradiation of the excitation light is performed at an angle of 15° from the vertical direction of the film surface of the phosphor layer, and is irradiated from the upper side of the phosphor film to the phosphor layer. The luminosity and brightness of the phosphor layer were evaluated by measuring the illuminance on the upper side of the film surface of the phosphor layer by a spectrophotometer and a luminance meter. Further, when the measurement target is an untreated phosphor powder, a stainless steel container having a groove depth of 1 mm and an area of 30 mm 0 is filled with a powder, and -32-200813186 is measured in the same manner as above, and the color is evaluated. brightness. The chromaticity and brightness of the coated and fired phosphor film were compared with the untreated phosphor powder, and the effects of gelatinization treatment and firing on the light-emitting characteristics were evaluated. The change in chromaticity of the phosphor layer was evaluated in the following manner. A: in terms of chromaticity X and y, the change is within ±0.020 with respect to X and y of the untreated phosphor powder; B: any of chromaticity X and y, relative to The X and y of the treated phosphor powder varied by more than ±0.020. ® The relative brightness of the phosphor film after firing was evaluated based on the untreated phosphor powder. If the relative luminance is 95.0% or more, the effect of the gelatinization treatment on the brightness is small and is good. Table 2 shows viscosity changes, chromaticity changes, film thickness accuracy, and relative brightness.

-33- 200813186

[Table 2] Example Evaluation Results Viscosity Change Rate (23〇C, 20th) Film Thickness Accuracy//zm (20 Point Deviation) Fluorescence Change in Phosphor (Based on Untreated Powder) Fluorescence Relative brightness of the body (based on untreated powder) 1 +7.2% BA 100.0% 2 +5.3% AA 99.8% 3 +3.1% AA 99.5% 4 + 1.8% AA 98.2% 5 -1.0% BA 96.3% 6 +5.0% AA 98.0% 7 +8.0% AA 96.1% 8 + 1.5% BA 99.8% 9 +3.0% AA 99.4% 10 -3.0% BA 99.5% 11 +2.8% AA 99.2% 12 + 1.5% AA 95.8% 13 + 0.3% AA 95.7% 14 + 1.5% AA 99.4% 15 +2.5% AA 99.2% 16 +2.8% AA 99.5% 17 +0.5% AA 99.5% 18 +0.5% AA 99.2% 19 +2.8% AA 99.3% -34- 200813186 Comparative Example 1 A phosphor paste was prepared in the same manner as in Example 3 except that N-n-butylethylamine (B-7) was used as a dispersing agent, and physical properties were evaluated in the same manner as in Example 1. . The blending amounts and measurement results of the respective components in the phosphor paste are shown in Tables 3 and 4. Comparative Example 2 A phosphor paste was prepared in the same manner as in Comparative Example 1, except that the dispersing agent and the organic solvent were blended as shown in Table 2, and the physical properties were evaluated in the same manner as in Example 1. The blending amount of each component in the phosphor paste and the measurement results are shown in Tables 3 and 4. Comparative Example 3 A blending amount of the phosphor paste as shown in Table 2 was prepared without adding a dispersing agent, and the physical properties were evaluated in the same manner as in Example 1. The blending amount and measurement results of the respective components in the phosphor paste are shown in Tables 3 and 4. Comparative Example 4 A phosphor paste was prepared in the same manner as in Example 4 except that the reference [2-(2-methoxyethoxy)ethyl]amine (B-5) was used as a dispersing agent, and The physical properties were evaluated in the same manner as in Example 1. The blending amounts and measurement results of the respective components in the phosphor paste are shown in Tables 3 and 4. Comparative Example 5 Physical properties were evaluated in the same manner as in Example 1 except that ammonium acetate (B-8) was used as a dispersing agent. The blending amount of each component in the phosphor paste and the measurement results are shown in Tables 3 and 4. Comparative Example 6 - 35 - 200813186 Physical properties were evaluated in the same manner as in Example 5 except that ammonium acetate (B_8) was used as a dispersing agent. The blending amount of each component in the phosphor paste and the measurement results are shown in Tables 3 and 4. Comparative Example 7 Physical properties were evaluated in the same manner as in Example 3 except that triethanolamine (B-4) was used as a dispersing agent. The amounts of the components added to the phosphor paste and the measurement results are shown in Tables 3 and 4.

-36- 200813186

[Table 3 Comparative Example Phosphor Powder Dispersant Binder Resin Organic Solvent Type Blend Amount (Parts by Weight) Kind Blend (Parts by Weight) Molecular Weight Boiling Point (°c) Kind Blend Amount (Part by Weight) Kind Blend (parts by weight) 1 A-4 48.0 B-7 1.0 101 110 C-1 9.0 D-1 42.0 2 A-1 48.0 B-7 5.0 101 110 C-1 9.0 D-1 38.0 3 A-4a 48.0 C-1 9.0 D-1 43.0 4 A-1 48.0 B-5 1.0 323 330 C-1 9.0 D-1 42.0 5 A-1 48.0 B-8 1.0 77 C-1 9.0 D-1 42.0 6 A-1 48.0 B-8 7.5 77 C-1 9.0 D-1 35.5 7 A-1 48.0 B-4 1.0 149 335 C-1 9.0 D-1 42.0

[Table 4] Comparative Example Evaluation Results Viscosity Change Rate (23〇C, 20th) Film Thickness Accuracy//zm (20 Point Deviation) Fluorescence Change in Phosphor (Based on 'Untreated Powder) Relative brightness of light body (based on untreated powder) 1 + 15.5% DA 99.6% 2 + 11.5% CA 99.5% 3 + 17.5% DA 99.8% 4 +9.5% AB 93.5% 5 + 13.5% CA 98.0% 6 +9.5% BB 94.5% 7 +9.0% AA 95.8% -37 - 200813186 In Examples 1 to 5, the blending amount of the dispersing agent was 1. p part by weight of Example 3 and 3.0 parts by weight of Example 4 The viscosity change is small and the coating property is also good. In Example 5, since the amount of addition was large, the relative brightness of the phosphor was also lowered to some extent. The blending amount of the dispersing agent was 1.0 part by weight, and in Examples 6 and 7 in which the type of the dispersing agent was changed, the degree of deterioration of Example 6 was not more than that of Example 1, but Example 7 used a dispersing agent having a large molecular weight, The viscosity change rate becomes large, and the relative brightness of the phosphor decreases. Examples 8 to 1 3 are phosphor pastes having the same composition type but different blend amounts of phosphor powder, and the blend ratios of Example 9 and Example 13 are such that "the phosphor powder is not produced". As a result of sedimentation, the burn-up property at the time of firing was good, and the change in viscosity was small, and the coatability was also good. In Example 14 and Example 15, not only 2-(methylamino)ethanol (B-1) but also n-heptanoic acid (B-6) was contained as a dispersing agent. Therefore, by coexisting with the acid in the phosphor paste, the viscosity stability and the film thickness accuracy can be improved. For Examples 1 to 15, a phosphor paste was prepared using (Ba, Eii) MgAl1() 017 (Al) which is a blue phosphor powder, but a red phosphor powder (Example 16) and green fluorescent light were used. In the case of the bulk powder (Example 19), and the ZSM in which the surface of the phosphor powder is coated with a zinc oxide layer having an average thickness of 0.2 μm and the ZSM coated with a cerium oxide layer having an average thickness of 0.2/zm In Examples 1 7 and 18, dispersion stability and coating stability were also obtained. In particular, when a powder coated with a ruthenium oxide layer is used, the effect of suppressing the change in viscosity is increased. On the other hand, 'Comparative Examples 1 and 2 using hydrazine-methylethylamine as a dispersing agent without a hydroxyl group or an alkoxy group, and Comparative Example 3 containing no powder of -38-200813186 m in the case of an amine compound, Both the viscosity stability and the film thickness accuracy are inferior to the examples. Further, in Comparative Example 4, the effect of suppressing the change in viscosity by using the amine compound having a molecular weight of 300 or more was small. Further, since it remains in the film after firing, the chromaticity change and the decrease in brightness of the phosphor are outside the allowable range. Further, in Comparative Example 5, since the carboxylic acid amine salt compound was used, the effect of suppressing the viscosity change was small, and the film thickness precision was also somewhat lowered. In Comparative Example 6, since the addition amount of the carboxylic acid amine salt was increased, the dispersion effect was obtained, but the change in color degree and the change in brightness were outside the allowable range. Further, in Comparative Example 7, since triethanolamine which is a tertiary amine was used, the effect of suppressing the change in viscosity was not sufficiently obtained. [Simple description of the diagram] 4rrr withdrawal. [Main component symbol description] No 0

-39-

Claims (1)

200813186 I X. Patent application scope β· 1. A phosphor paste characterized by comprising: a phosphor powder, a binder resin, a primary or secondary having a hydroxyl group and/or an alkoxy group and having a molecular weight of 300 or less. An amine compound, and an organic solvent. 2. The phosphor paste according to claim 1, wherein the amine compound has a boiling point of from 80 to 350 °C. 3. The phosphor paste according to claim 1 or 2, wherein the amine compound is added in an amount of 0.2 to 5% by weight based on the phosphor paste. The phosphor paste according to any one of claims 1 to 3, wherein the phosphor powder is added in an amount of 40 to 60% by weight in the phosphor paste, and the binder resin is added. The amount accounts for 5 to 20% by weight in the phosphor paste. The phosphor paste according to any one of claims 1 to 4, wherein the organic solvent has a hydroxyl group. 6. The phosphor paste according to any one of claims 1 to 5, which further comprises an acid compound. A method of producing a display comprising the step of forming a phosphor layer by baking a phosphor paste according to any one of claims 1 to 6 onto a substrate. -40- 200813186 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 200813186 V. Summary of Chinese Abstract: Supplement (7)...ΤΓ: 71 祚年(丨月(四)丨 The object of the present invention is to provide a phosphor powder which is uniformly and stably dispersed in the paste, and the viscosity change is small over time, and then burned. A phosphor paste having a small change in chromaticity of the phosphor layer formed thereafter. The solution of the present invention is to use a phosphor paste characterized by comprising: a phosphor powder, a binder resin, having a hydroxyl group and/or A primary or secondary amine compound having an alkoxy group and a molecular weight of 300 or less, and an organic solvent. 6. The invention of the present invention provides a fluorescent substance paste of which its fluorescent substance powder could be dispersed uniformity and stability,its variation with time of viscosity is small; further, the chromaticity variation of the fluorescent substance after calcining Is small. The solution mean of the present invention is a fluorescent substance paste which is characterized in that the fluorescent substance paste, binder resin, primary or secondary amine compound containing hydroxyl group and/or alkoxy group and its molecular weight is 300 or less, and organic solvent .