JP2010015697A - Metal oxide paste for plasma display panel, and method of manufacturing plasma display panel - Google Patents

Abstract

An object of the present invention is to realize a plasma display panel having high-definition and high-luminance display performance and low power consumption.
In a plasma display panel, a protective layer includes a metal oxide paste containing a metal oxide, an organic resin component, and a diluting solvent after the base film is deposited on the dielectric layer. And then baking the metal oxide paste to form a plurality of metal oxide particles attached to the base film 91, and the metal oxide paste is formed of the metal oxide contained in the paste. The organic resin component has a molecular weight grade of 1.5 vol% or less, and the organic resin component contains two or more types of organic resin components and a viscosity stabilizer containing a hydroxyl group.
[Selection] Figure 3

Description

  The present invention relates to a metal oxide paste for a plasma display panel and a method for manufacturing the plasma display panel.

  Plasma display panels (hereinafter referred to as “FPDs”) called flat panel displays (hereinafter referred to as “FPDs”), FPDs represented by liquid crystal displays and organic ELs, etc., have recently been improved in definition, and the market has low cost and low consumption. There is a demand for a full HD (high definition) FPD with high power and high luminance (1920 × 1080 pixels: progressive display). Among them, since PDPs can achieve high definition and large screens, 65-inch class televisions have been commercialized.

  A PDP basically includes a front plate and a back plate. The front plate is a glass substrate made of sodium borosilicate glass by a float method, a display electrode composed of a striped transparent electrode and a bus electrode formed on one main surface of the glass substrate, and a display electrode A dielectric layer that covers and acts as a capacitor, and a protective layer made of magnesium oxide (MgO) formed on the dielectric layer. On the other hand, the back plate is a glass substrate, stripe-shaped address electrodes formed on one main surface thereof, a base dielectric layer covering the address electrodes, a partition formed on the base dielectric layer, It is comprised with the fluorescent substance layer which light-emits each of red, green, and blue formed between the partition walls.

The front plate and the back plate are hermetically sealed with their electrode forming surfaces facing each other, and Ne—Xe discharge gas is sealed at a pressure of 400 Torr to 600 Torr in a discharge space partitioned by a partition wall. PDP discharges by selectively applying a video signal voltage to the display electrode, and the ultraviolet rays generated by the discharge excite each color phosphor layer to emit red, green and blue light, thereby realizing color image display (See Patent Document 1).
JP 2007-48733 A

  In such a PDP, the protective layer formed on the dielectric layer of the front plate protects the dielectric layer from ion bombardment due to discharge, and emits initial electrons for generating address discharge. It is done. Protecting the dielectric layer from ion bombardment plays an important role in preventing an increase in discharge voltage, and emitting initial electrons for generating an address discharge is an address discharge error that causes image flickering. It is an important role to prevent.

  In order to increase the number of initial electrons emitted from the protective layer and reduce the flicker of the image, for example, an attempt has been made to add Si or Al to MgO.

  In recent years, high definition has been advanced in televisions, and a low-cost, low-power-consumption, high-brightness full HD (high definition) (1920 × 1080 pixels: progressive display) PDP is required in the market. Since the electron emission characteristics from the protective layer determine the image quality of the PDP, it is very important to control the electron emission characteristics.

  The present invention has been made in view of such problems, and an object of the present invention is to realize a PDP having high-definition and high-luminance display performance and low power consumption.

  In order to achieve the above object, a metal oxide paste of the present invention is a metal oxide paste for a plasma display panel containing metal oxide particles, an organic resin component, and a diluting solvent, and the metal contained in the paste The content of the oxide particles is 1.5 vol% or less, and the organic resin component includes two or more types of organic resin components having a molecular weight grade and a viscosity stabilizer containing a hydroxyl group.

  In addition, the manufacturing method of the present invention forms a dielectric layer so as to cover the display electrodes formed on the substrate and forms a protective layer on the dielectric layer, and forms a discharge space in the front plate. And a back plate having an address electrode formed in a direction intersecting with the display electrode and provided with a partition that partitions the discharge space, and the protective layer of the front plate is the dielectric layer After depositing a base film on the base film, a metal oxide paste containing a metal oxide, an organic resin component, and a diluting solvent is applied to the base film, and then the metal oxide paste is baked to form a metal on the base film. The metal oxide paste is formed by adhering a plurality of oxide particles, and the content of the metal oxide particles contained in the paste is 1.5 vol% or less, and the organic resin component has a molecular weight grade. But It includes more kinds of organic resin component, and is characterized in that comprising a viscosity stabilizer containing a hydroxyl group.

  In PDPs, attempts have been made to improve the electron emission characteristics by mixing impurities in the protective layer. However, if the impurities are mixed in the protective layer to improve the electron emission characteristics, the surface of the protective layer is simultaneously developed. The charge is accumulated in the memory, and the decay rate at which the charge is reduced over time when used as a memory function increases. Therefore, it is necessary to take measures such as increasing the applied voltage to suppress this. As described above, the protective layer must have a high electron emission ability and a low charge decay rate as a memory function, that is, a high charge retention characteristic. There was a problem.

  The present invention provides a PDP that improves electron emission characteristics, has charge retention characteristics, and can achieve both high image quality, low cost, and low voltage, thereby achieving low power consumption, high definition, and high brightness. A PDP having display performance can be realized.

  Further, according to the present invention, by providing a metal oxide paste excellent in dispersibility, printability, and flammability, metal oxide particles can be uniformly adhered to the panel surface, and have high definition and high brightness. A PDP having the display performance can be realized.

  Hereinafter, a PDP according to an embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a perspective view showing the structure of a PDP according to an embodiment of the present invention. The basic structure of the PDP is the same as that of a general AC surface discharge type PDP. As shown in FIG. 1, the PDP 1 has a front plate 2 made of a front glass substrate 3 and a back plate 10 made of a back glass substrate 11 facing each other, and its outer peripheral portion is sealed with a glass frit or the like. The material is hermetically sealed. The discharge space 16 inside the sealed PDP 1 is filled with a discharge gas such as Ne or Xe at a pressure of 400 Torr to 600 Torr. On the front glass substrate 3 of the front plate 2, a pair of strip-like display electrodes 6 made up of scanning electrodes 4 and sustain electrodes 5 and black stripes (light-shielding layers) 7 are arranged in a plurality of rows in parallel with each other. A dielectric layer 8 serving as a capacitor is formed on the front glass substrate 3 so as to cover the display electrode 6 and the light shielding layer 7, and a protective layer 9 made of magnesium oxide (MgO) is formed on the surface. Has been.

  On the back glass substrate 11 of the back plate 10, a plurality of strip-like address electrodes 12 are arranged in parallel to each other in a direction orthogonal to the scanning electrodes 4 and the sustain electrodes 5 of the front plate 2. Layer 13 is covering. Further, a partition wall 14 having a predetermined height is formed on the base dielectric layer 13 between the address electrodes 12 to divide the discharge space 16. For each address electrode 12, a phosphor layer 15 that emits red, green, and blue light by ultraviolet rays is sequentially applied to the grooves between the barrier ribs 14 and formed. A discharge cell is formed at a position where the scan electrode 4 and the sustain electrode 5 intersect with the address electrode 12, and the discharge cell having the red, green and blue phosphor layers 15 arranged in the direction of the display electrode 6 is used for color display. Become a pixel.

FIG. 2 is a cross-sectional view showing the configuration of the front plate 2 of the PDP 1 in one embodiment of the present invention, and FIG. 2 is shown upside down from FIG. As shown in FIG. 2, a display electrode 6 and a light shielding layer 7 including scanning electrodes 4 and sustaining electrodes 5 are formed in a pattern on a front glass substrate 3 manufactured by a float method or the like. Scan electrode 4 and sustain electrode 5 are transparent electrodes 4a and 5a made of indium tin oxide (ITO), tin oxide (SnO ₂ ), etc., and metal bus electrodes 4b and 5b formed on transparent electrodes 4a and 5a, respectively. It is comprised by. The metal bus electrodes 4b and 5b are used for the purpose of imparting conductivity in the longitudinal direction of the transparent electrodes 4a and 5a, and are formed of a conductive material mainly composed of a silver (Ag) material. The dielectric layer 8 includes a first dielectric layer 81 provided on the front glass substrate 3 so as to cover the transparent electrodes 4a and 5a, the metal bus electrodes 4b and 5b, and the light shielding layer 7, and a second dielectric. The protective layer 9 is formed on the dielectric layer 8.

  Next, the structure of the protective layer 9 that is a feature of the PDP according to the present invention will be described. As shown in FIG. 2, the protective layer 9 is formed with a base film 91 made of MgO containing Al as an impurity on the dielectric layer 8, and MgO that is a metal oxide is formed on the base film 91. The crystal particles 92 are dispersed discretely and formed so as to be distributed almost uniformly over the entire surface. Further, the MgO crystal particles 92 are adhered on the base film 91 so as to be distributed almost uniformly over the entire surface with a coverage of 2% to 12%.

  Here, the coverage is a ratio of the area a where the MgO crystal particles 92 are adhered in the area of one discharge cell as a ratio of the area b of one discharge cell. %) = A / b × 100. As an actual measurement method, for example, an image of a region corresponding to one discharge cell divided by the barrier ribs 14 is captured by a camera, trimmed to the size of one cell of x × y, and then trimmed. The later photographed image is binarized into black and white data, and thereafter the area a of the black area by the MgO crystal particles 92 is obtained based on the binarized data, and is calculated by the formula a / b × 100 as described above. It is obtained by this.

  Next, a method for manufacturing a PDP will be described. First, as shown in FIG. 2, scan electrode 4, sustain electrode 5, and light shielding layer 7 are formed on front glass substrate 3. The transparent electrodes 4a and 5a and the metal bus electrodes 4b and 5b are formed by patterning using a photolithography method or the like. The transparent electrodes 4a and 5a are formed using a thin film process or the like, and the metal bus electrodes 4b and 5b are solidified by baking a paste containing a silver (Ag) material at a desired temperature. Similarly, the light shielding layer 7 is also formed by screen printing a paste containing a black pigment or by forming a black pigment on the entire surface of the glass substrate and then patterning and baking using a photolithography method.

  Then, a dielectric paste is applied onto the front glass substrate 3 by a die coating method or the like so as to cover the scan electrode 4, the sustain electrode 5, and the light shielding layer 7, thereby forming a dielectric paste layer (dielectric material layer). Thereafter, the dielectric paste layer is baked and solidified to form the dielectric layer 8 that covers the scan electrode 4, the sustain electrode 5, and the light shielding layer 7. The dielectric paste is a paint containing a dielectric material such as glass powder, a binder and a solvent.

  Further, a protective layer 9 made of magnesium oxide (MgO) is formed on the dielectric layer 8 by a vacuum deposition method.

  Through the above steps, predetermined components (scanning electrode 4, sustaining electrode 5, light shielding layer 7, and dielectric layer 8) other than the protective layer 9 according to the present invention are formed on the front glass substrate 3.

  Next, the manufacturing process for forming the protective layer according to the present invention will be described with reference to FIG. As shown in FIG. 3, after performing the dielectric layer forming step A1 for forming the dielectric layer 8, in the next base film vapor deposition step A2, by a vacuum vapor deposition method using a sintered body of MgO containing Al as a raw material. A base film made of MgO is formed on the dielectric layer 8. Thereafter, a step of discretely forming MgO crystal particles 92 which are metal oxides is performed on the unfired base film formed in the base film deposition step A2. In the crystal particle paste film forming step A3, the crystal particle paste film is formed on the unfired base film by the screen printing method using the metal oxide paste for screen printing of the present invention. The details of the paste of the present invention will be described later. Further, as a method for forming a crystal particle paste film on an unfired base film, a spray method, a spin coating method, a die coating method, a slit coating method, or the like can be used in addition to the screen printing method.

  Next, a drying step A4 for drying the crystal particle paste film is performed. Thereafter, the unfired base film formed in the base film deposition step A2 and the crystal particle paste film formed in the crystal particle paste film formation step A3 and subjected to the drying step A4 are heated and fired at a temperature of several hundred degrees. In step A5, the protective layer 9 in which the MgO crystal particles 92 are attached to the base film 91 can be formed by simultaneously baking and removing the solvent and resin components remaining in the crystal particle paste film. .

In the above description, MgO is taken as an example of the protective layer. However, the performance required for the base is to have high anti-spattering performance for protecting the dielectric from ion bombardment, and has a high charge retention capability. That is, the electron emission performance may not be so high. In conventional PDPs, in order to achieve both the electron emission performance above a certain level and the sputter resistance performance, a protective layer mainly composed of MgO has been formed in many cases. Since the composition is controlled predominantly by the material single crystal particles, there is no need to use MgO, and other materials having excellent impact resistance such as Al ₂ O ₃ may be used. In the above description, MgO particles are used as the crystal particles. However, other single crystal particles are also oxides of metals such as Sr, Ca, Ba, and Al that have high electron emission performance like MgO. Since the same effect can be obtained even if crystal grains are used, the particle type is not limited to MgO.

  Through the above steps, scan electrode 4, sustain electrode 5, light shielding layer 7, dielectric layer 8, base film 91, and MgO crystal particles 92 are formed on front glass substrate 3.

  On the other hand, the back plate 10 is formed as follows. First, the structure for the address electrode 12 is formed by a method of screen printing a paste containing silver (Ag) material on the rear glass substrate 11 or a method of patterning using a photolithography method after forming a metal film on the entire surface. An address electrode 12 is formed by forming a material layer to be an object and firing it at a desired temperature. Next, a dielectric paste is applied on the rear glass substrate 11 on which the address electrodes 12 are formed by a die coating method so as to cover the address electrodes 12 to form a dielectric paste layer. Thereafter, the base dielectric layer 13 is formed by firing the dielectric paste layer. The dielectric paste is a paint containing a dielectric material such as glass powder, a binder and a solvent.

  Next, a partition wall forming paste including a partition wall material is applied on the base dielectric layer 13 and patterned into a predetermined shape to form a partition wall material layer and then fired to form the partition walls 14. Here, as a method of patterning the partition wall paste applied on the base dielectric layer 13, a photolithography method or a sand blast method can be used. Next, the phosphor layer 15 is formed by applying a phosphor paste containing a phosphor material on the base dielectric layer 13 between the adjacent barrier ribs 14 and on the side surfaces of the barrier ribs 14 and baking it. Through the above steps, the back plate 10 having predetermined components on the back glass substrate 11 is completed.

  In this way, the front plate 2 and the back plate 10 having predetermined constituent members are arranged to face each other so that the scanning electrodes 4 and the address electrodes 12 are orthogonal to each other, and the periphery thereof is sealed with a glass frit, so that a discharge space is obtained. 16 is filled with a discharge gas containing Ne, Xe or the like, thereby completing the PDP 1.

  Next, the results of experiments conducted to confirm the mass production stability effect of the metal oxide paste according to the present invention will be described. The numerical conditions such as the kind of chemical used and the amount thereof described in the following description are merely examples within the scope of the present invention, and the present invention is not limited to this.

  First, a metal oxide paste for forming a layer to which metal oxide crystal particles were adhered was prepared according to the composition shown in Table 1.

  In Table 1, composition 1 uses 0.2 vol% of powder of MgO crystal particles having a particle diameter of 1.2 μm as the metal oxide, and 68.4 vol% of butyl carbitol and 22.8 vol% of terpineol as the diluting solvent. It was. Further, ethyl cellulose (manufactured by Nisshin Kasei) is used as the organic resin component, and 10 cP ethyl cellulose (Lot a) having a different molecular weight grade is 3.44 vol%, and 100 cP ethyl cellulose (Lot A) is 5.16 vol%. What was dissolved and mixed was used. A powder of MgO crystal particles, butyl carbitol, terpineol, and ethyl cellulose are homogeneously dispersed with three rolls to prepare a metal oxide paste. This composition 1 had a paste viscosity of 19,920 mPa · s. Here, the paste viscosity indicates a viscosity value at a shear rate D = 1 (1 / s) using Rheostress RS600 (manufactured by Hakke).

  Composition 2 was prepared by preparing a paste with the same composition as Composition 1 described above except that 2.60 vol% of 10 cP ethyl cellulose (lot b) and 6.00 vol% of 100 cP ethyl cellulose (lot B) were used. The paste viscosity of composition 2 was 21050 mPa · s. Composition 3 was prepared by preparing a paste with the same composition as Composition 1 described above except that 2.60 vol% of 10 cP ethyl cellulose (lot c) and 6.00 vol% of 100 cP ethyl cellulose (lot C) were used. The paste viscosity of composition 3 was 19400 mPa · s. Composition 4 was prepared by preparing a paste with the same composition as Composition 1 described above, except that 1.72 vol% of 10 cP ethyl cellulose (lot d) and 6.88 vol% of 100 cP ethyl cellulose (lot D) were used. The paste viscosity of composition 4 was 2,070 mPa · s.

  In the above composition, ethyl cellulose is used as the organic resin component, but cellulose derivatives such as hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate, and hydroxypropyl methylcellulose acetate can also be used. In addition to the cellulose derivative, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, monomethyl fumarate, Monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, sorbic acid, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, hydroquinone monoacrylate , Hydroquinone monomethacrylate, hydroquinone diacrylate, hydroquinone di-2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate 2-hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl Acrylate, isobornyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate Trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, 1,6-hexanediol diacrylate, 1,6-hexane Diol dimethacrylate, cardo epoxy diacrylate, glycidyl methacrylate, glycidyl methacrylate ethylene glycol diacrylate, fumaric acid ester in which (meth) acrylate of these exemplary compounds is replaced with fumarate, maleic acid ester in place of maleate, crotonic acid in place of crotonate Itaconic acid ester instead of ester, itaconate, urethane methacrylate, An acrylic resin such as a polymer or copolymer such as tylene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc. may be used alone or in combination with a cellulose derivative.

  Diethylene glycol monobutyl ether (butyl carbitol) and terpineol are used as the dilution solvent, but other than that, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3 -Methoxybutyl acetate, -Methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, etc. alone or 2 It can be used by combining more than one species.

  If necessary, dioctyl phthalate, dibutyl phthalate, triphenyl phosphate, tributyl phosphate are added to the paste as needed, and glycerol monooleate, sorbitan sesquioleate, homogenol (Kao Corporation) as a dispersant. Product name), phosphoric esters of alkylallyl groups, and the like may be added.

  By applying the metal oxide paste prepared as described above onto the substrate on which the scan electrode 4, the sustain electrode 5, the light shielding layer 7, the dielectric layer 8, and the protective layer 9 are formed using a screen printing method, A layer to which crystal grains of MgO were adhered was formed, and the coverage and variation in each composition 1-4 were examined. The result is shown in FIG. Note that L380S mesh was used for the screen plate. The variation in coverage mentioned here is a value obtained by obtaining the standard deviation σ and the average value M for the coverage of 54 points in the plane obtained by the above-described method and dividing σ by the average. That is, the in-plane variation of the coverage ratio = σ / M × 100 (%).

  As can be seen from FIG. 4, by using a composition containing ethyl cellulose which is an organic resin component having two or more molecular weight grades, any ratio of the amount of metal oxide, the amount of solvent and the amount of organic resin component contained in the paste can be obtained. The viscosity can be stabilized without change, and as a result, the influence on the screen printability can be suppressed, and the average coverage and the in-plane variation in the coverage can be stabilized.

  In addition, although the example which uses 10 cP ethylcellulose and 100 cP ethylcellulose was shown as an example in which the molecular weight grades of ethylcellulose differ in the said composition, 4 cP, 45 cP, 200 cP, and 300 cP ethylcellulose can be used in addition to that. .

  As described above, a metal oxide paste containing metal oxide particles, an organic resin component, and a diluent solvent, wherein the content of the metal oxide particles contained in the paste is 1.5 vol% or less, By using an organic resin component containing two or more types of organic resin components with a molecular weight grade, a metal oxide layer can be uniformly formed in the panel surface by a screen printing method. Dispersibility, printability, and flammability In addition, a paste suitable for mass production stability can be provided.

  Next, the result of adding a viscosity stabilizer containing a hydroxyl group to the metal oxide paste will be described. In addition, numerical conditions, such as the chemical | medical agent used in the description and its quantity, are only examples within the scope of the present invention, and the present invention is not limited to this.

First, a paste for forming an MgO crystal layer was prepared by thoroughly kneading a material composed of the composition components based on Table 2 with three rolls. The viscosity measurement result after preparation of the paste prepared as described above is shown in FIG. In addition, FIG. 5 is a figure which shows the relationship between the storage period after adjustment, and viscosity (eta) (D = 1s < ^-1 >).

  As can be seen from FIG. 5, in the case of adding ethanol as a viscosity stabilizer, the viscosity is stabilized immediately after the preparation of the paste, compared to the case where no addition is made. After each day, the printability was confirmed, but no problem was found.

  On the other hand, in the case where the viscosity stabilizer is not added, the viscosity gradually increases after preparing the paste, so in the printability confirmation, the release of the plate gradually worsens after 1 day, 3 days, and 5 days after the paste preparation, It was found that the average coverage and the variation in the coverage varied greatly.

  In other words, those without added viscosity stabilizers form a three-dimensional network by ionic cross-linking with ions eluted from the metal oxide powder gradually after the paste is prepared due to the hydroxyl groups contained in the paste, such as solvents. In contrast to those with a viscosity stabilizer containing a hydroxyl group, the viscosity of the additive is increased by forcibly ionically crosslinking the hydroxyl group of the additive and the ions eluted from the metal oxide powder. As a result, the stability of the viscosity can be improved.

  From the above, a metal oxide paste containing a metal oxide, an organic resin component and a diluting solvent, wherein the content of the metal oxide particles contained in the paste is 1.5 vol% or less, and the organic resin Ingredients contain two or more organic resin components with molecular weight grades and a viscosity stabilizer containing a hydroxyl group, so that a metal oxide layer can be uniformly formed in the panel surface by screen printing, and dispersibility It is possible to provide a paste that is excellent in printability and flammability and suitable for mass production stability, has a high-definition and high-brightness display performance, and has low power consumption.

  Next, the results of experiments conducted to confirm the effect of a PDP having a protective layer formed using the metal oxide paste according to the present invention will be described.

  First, a PDP having a protective layer having a different configuration was made as a prototype. Prototype 1 is a PDP in which only a protective layer of MgO is formed, Prototype 2 is a PDP in which a protective layer of MgO doped with impurities such as Al and Si is formed, and Prototype 3 is a PDP according to the paste of the present invention. Thus, the PDP has crystal particles made of a metal oxide deposited on a protective layer made of MgO so as to be distributed almost uniformly over the entire surface. In Prototype 3, when the cathode luminescence was measured using single crystal particles of MgO as the metal oxide, it had the characteristics shown in FIG.

  The PDP having these three types of protective layer configurations was examined for its electron emission performance and charge retention performance.

  The electron emission performance is a numerical value indicating that the larger the electron emission amount, the greater the amount of electron emission. The initial electron emission amount can be measured by irradiating the surface with ions or an electron beam and measuring the amount of electron current emitted from the surface, but it is difficult to perform non-destructive evaluation of the front plate surface of the panel. Accompanied by. Therefore, as described in Japanese Patent Application Laid-Open No. 2007-48733, among the delay times at the time of discharge, a numerical value called a statistical delay time, which is a measure of the ease of occurrence of discharge, is measured, and the reciprocal thereof is integrated. Therefore, since the numerical value corresponds linearly to the amount of initial electron emission, evaluation is performed using this numerical value. This delay time at the time of discharge means the time of discharge delay that is delayed from the rise of the pulse, and the discharge delay is the time when the initial electrons that trigger when the discharge is started are discharged from the surface of the protective layer to the discharge space. It is considered as a main factor that it is difficult to be released into the inside.

  In addition, as an indicator of the charge retention performance, a voltage value of a voltage applied to the scan electrode (hereinafter referred to as a Vscn lighting voltage) necessary for suppressing the charge emission phenomenon when manufactured as a PDP was used. That is, the lower the Vscn lighting voltage, the higher the charge retention capability. Since this can be driven at a low voltage even in the panel design of the PDP, it is possible to use components having a small withstand voltage and capacity as the power source and each electrical component. In the current product, an element having a withstand voltage of about 150 V is used as a semiconductor switching element such as a MOSFET for sequentially applying a scanning voltage to the panel, and the Vscn lighting voltage is 120 V or less in consideration of variation due to temperature. It is desirable to keep it at a minimum.

  The results of examining these electron emission performance and charge retention performance are shown in FIG. As is apparent from FIG. 7, the prototype 3 formed by using the paste of the present invention on the base film made of MgO so that the single crystal particles of MgO are distributed almost uniformly over the entire surface has the charge retention performance. In the evaluation, the Vscn lighting voltage can be reduced to 120 V or lower, and the electron emission performance can be obtained as 6 or more.

  That is, generally, the electron emission capability and the charge retention capability of the protective layer of the PDP are contradictory. For example, it is possible to improve the electron emission performance by changing the film forming conditions of the protective layer and forming the film by doping impurities such as Al, Si, and Ba in the protective layer. As a result, the Vscn lighting voltage also rises. However, the prototype 3 formed using the paste of the present invention so that MgO single crystal particles are distributed almost uniformly over the entire surface has an electron emission capability of 6 or more, and the charge retention capability is as follows. A Vscn lighting voltage of 120V or less can be obtained, and the number of scanning lines increases and the cell size tends to decrease due to high definition. Both ability can be satisfied.

  Next, the particle size of the crystal particles used in the prototype 3 will be described. In the following description, the particle diameter means an average particle diameter, and the average particle diameter means a volume cumulative average diameter (D50).

  FIG. 8 shows the experimental results of examining the electron emission performance of the prototype 3 of the present invention described with reference to FIG. 7 by changing the particle diameter of MgO crystal particles. In FIG. 8, the particle diameter of MgO crystal particles indicates the average particle diameter when the particle size distribution is measured in a reagent grade 1 or higher ethanol solution using a Microtrac HRA particle size distribution meter. It is measured by SEM observation.

  As shown in FIG. 8, it can be seen that when the particle size is reduced to about 0.3 μm, the electron emission performance is lowered, and when it is approximately 0.9 μm or more, high electron emission performance is obtained.

  By the way, in order to increase the number of electrons emitted in the discharge cell, it is desirable that the number of crystal particles per unit area on the protective layer is larger. When the crystal particles are present in the part corresponding to the top of the partition wall of the back plate that is in close contact with the substrate, the top of the partition wall is damaged, and the corresponding material is placed on the phosphor. It has been found that a phenomenon that does not turn off occurs. The phenomenon of the partition wall breakage is unlikely to occur unless the crystal particles are present in the portion corresponding to the top of the partition wall. Therefore, if the number of attached crystal particles increases, the probability of the partition wall breakage increases.

  FIG. 9 is a diagram showing the results of experiments on the relationship between partition wall breakage in the prototype 3 according to the present invention described with reference to FIG. 7 by spraying the same number of crystal particles having different particle sizes per unit area. As is clear from FIG. 9, when the crystal particle diameter is increased to about 2.5 μm, the probability of partition wall breakage increases rapidly. However, if the crystal particle diameter is smaller than 2.5 μm, the probability of partition wall breakage is compared. It can be seen that it can be kept small.

  Based on the above results, in the protective layer in the PDP according to the present invention, it is considered desirable that the crystal particle has a particle size of 0.9 μm or more and 2.5 μm or less. Therefore, it is necessary to take into account variations in the production of crystal grains and variations in production when forming a protective layer.

  In order to take into account such factors as manufacturing variations, as a result of experiments using crystal particles having different particle size distributions, the average particle size is 0.9 μm to 2 μm as shown in FIG. It has been found that the use of the crystal grains in the range can provide the above-described effects of the present invention stably.

  As described above, in the PDP having the protective layer formed by using the metal oxide paste for screen printing according to the present invention, the electron emission capability has a characteristic of 6 or more, and the charge retention capability is Vscn lighting voltage of 120 V or less. As a protective layer of a PDP in which the number of scanning lines increases and the cell size tends to decrease due to high definition, both the electron emission capability and the charge retention capability can be satisfied, As a result, a high-definition, high-luminance display performance and low power consumption PDP can be realized.

  By the way, in the PDP according to the present invention, as described above, the MgO crystal particles 92 are attached so as to be distributed over the entire surface with a coverage of 2% to 12%. This is based on the results of the present inventors making samples with varying coverage of the MgO crystal particles 92 and examining the characteristics of these samples. That is, it has been found that the Vscn lighting voltage increases and deteriorates as the coverage of MgO crystal particles increases, and conversely, the Vscn lighting voltage decreases as the coverage decreases.

  As a result of repeating experiments and examinations based on these results, the MgO crystal particle coverage is 12% or less in order to sufficiently exhibit the effect of attaching the MgO crystal particles as described above. I knew that I should do it.

  On the other hand, MgO crystal particles need to be present in each discharge cell in order to reduce the variation in characteristics, and for that purpose, they adhere to the base film so as to be distributed almost uniformly over the entire surface. However, it was found that when the coverage is small, the in-plane variation tends to increase, and the variation in the adhesion state of the crystal particles between the discharge cells increases. As a result of experiments conducted by the present inventors, it was found that in-plane variation can be suppressed to about 4% or less when MgO crystal particles are deposited so that the coverage is 4% or more. Further, it was found that even when MgO crystal particles were adhered so that the coverage was 2% or more, the in-plane variation could be suppressed to about 6%, and there was no problem in practical use.

  From these results, in the present invention, it is desirable to deposit MgO crystal particles so that the coverage is in the range of 2% to 12%, and further, the coverage is in the range of 4% to 12%. It is desirable to attach MgO crystal particles to the substrate.

  As described above, the present invention is useful for realizing a PDP having high-definition and high-luminance display performance and low power consumption.

The perspective view which shows the structure of PDP in embodiment of this invention Sectional drawing which shows the structure of the front plate of the PDP Process drawing which shows the process of protective layer formation in the manufacturing method of PDP by this invention Characteristic diagram showing the results of experiments using the same paste The characteristic figure which shows the viscosity result measured using the paste in this invention Characteristic diagram showing the results of cathodoluminescence measurement of crystal particles FIG. 6 is a characteristic diagram showing the results of examination of electron emission characteristics and Vscn lighting voltage in a PDP in the results of experiments conducted to explain the effects of the present invention. Characteristic diagram showing the relationship between crystal grain size and electron emission characteristics Characteristic diagram showing the relationship between the grain size of crystal grains and the incidence of partition wall breakage The characteristic figure which shows an example of the particle size distribution of a crystal particle in PDP by this invention

Explanation of symbols

1 PDP
2 Front plate 3 Front glass substrate 4 Scan electrode 4a, 5a Transparent electrode 4b, 5b Metal bus electrode 5 Sustain electrode 6 Display electrode 7 Black stripe (light shielding layer)
8 Dielectric layer 9 Protective layer 10 Back plate 11 Back glass substrate 12 Address electrode 13 Base dielectric layer 14 Partition 15 Phosphor layer 16 Discharge space 91 Base film 92 MgO crystal particles

Claims (4)

A metal oxide paste for a plasma display panel comprising metal oxide particles, an organic resin component and a diluting solvent, wherein the content of the metal oxide particles contained in the paste is 1.5 vol% or less, and the organic A metal oxide paste for a plasma display panel, wherein the resin component contains an organic resin component having a molecular weight grade of 2 or more and a viscosity stabilizer containing a hydroxyl group. The metal oxide paste for a plasma display panel according to claim 1, wherein the organic resin component is ethyl cellulose. A front plate in which a dielectric layer is formed so as to cover the display electrode formed on the substrate and a protective layer is formed on the dielectric layer, and the front plate is disposed so as to face each other so as to form a discharge space. A back plate provided with barrier ribs for partitioning the discharge space and forming address electrodes in a direction intersecting with the electrodes, and the protective layer of the front plate is formed by depositing a base film on the dielectric layer, A metal oxide paste containing a metal oxide, an organic resin component, and a diluting solvent is applied to the base film, and then the metal oxide paste is baked to attach a plurality of metal oxide particles to the base film. And the metal oxide paste includes an organic resin component having a content of particles of the metal oxide contained in the paste of 1.5 vol% or less, and the organic resin component having two or more molecular weight grades. Seen, and method of manufacturing a plasma display panel, characterized in that those comprising a viscosity stabilizer containing a hydroxyl group. 4. The method of manufacturing a plasma display panel according to claim 3, wherein the metal oxide paste is applied by a screen printing method.

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