JP2008186749A - Method of forming display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a display member having a thin dielectric layer of high withstanding voltage over an electrode pattern formed on a substrate. <P>SOLUTION: The dielectric layer is formed by an aerosol deposition method using a raw material including aluminum oxide particles of a purity of 98% or more by weight as the principal ingredient. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for forming a dielectric layer used in a flat display such as a plasma display panel (hereinafter referred to as PDP) or a field emission display (hereinafter referred to as FED).

  In recent years, development of flat displays such as PDPs, FEDs, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes has been rapidly advanced. Among these, the PDP causes plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and from the gas sealed in the discharge space. Display is performed by irradiating the generated ultraviolet rays to a phosphor provided in the discharge space. In the FED, display is performed when electrons radiated by a voltage applied between a gate electrode and a cathode travel toward an anode and collide with a phosphor existing between the cathode and the anode. Gas discharge type displays such as PDPs and fluorescent display tubes require dielectric layers between the drive electrodes (sustain / discharge electrodes, address electrodes) and between the electrodes and the discharge space to maintain the discharge. To do. In addition, a field emission display such as an FED requires a dielectric layer for insulating the gate electrode and the cathode. These dielectric layers such as PDP and FED are required to have high withstand voltage characteristics in order to insulate the electrodes. In addition, the PDP front plate dielectric layer is required to prevent coloring (yellowing) due to reaction with the discharge electrode and to achieve high transparency in order to improve luminance.

Conventionally, as a method for forming such a dielectric layer, there is a method in which a dielectric glass paste mainly composed of glass powder and an organic binder is applied to a predetermined film thickness by a die coater, screen printing or the like and then baked. Are known. However, in this method, depending on the composition of the dielectric glass, there is a problem that the dielectric layer is likely to be colored (yellowing) due to reaction with the electrode, and defects due to bubbles generated during firing are likely to occur. In order to prevent this, a method of forming a dielectric layer having a two-layer structure in which a high softening point glass is a lower layer and a low softening point glass is an upper layer has been proposed (see Patent Document 1). In this method, since it is necessary to increase the film thickness to about 40 μm, there is a problem that the transparency is not sufficient for the PDP front plate and the material cost is increased. Furthermore, productivity is not good due to an increase in the number of coating / drying / firing processes. On the other hand, formation methods that do not use glass paste have been studied. For example, a method of forming a silica thin film as a dielectric layer by a plasma chemical vapor deposition (plasma CVD) method has been proposed (see Patent Document 2). However, this method has a problem that a sufficient withstand voltage cannot be obtained because it is difficult to increase the film thickness.
JP 2005-317247 A JP 2000-021304 A

  Accordingly, the present invention aims to realize and provide a high-performance display member by paying attention to the problems of the prior art. Specifically, it is an object of the present invention to provide a method for forming a dielectric layer for a display having a thin film thickness, a high withstand voltage, and no yellowing on an electrode pattern formed on a substrate.

In order to solve the above problems, the present invention has the following configuration.
(1) A method for producing a display member having an electrode pattern and a dielectric layer covering the electrode pattern on a substrate, wherein an aerosol is produced using a raw material containing 80 to 100% by volume of aluminum oxide particles having a purity of 98% by weight or more A method for producing a display member, comprising forming a dielectric layer by a deposition method.
(2) The method for manufacturing a display member according to (1), wherein the raw material used for forming the dielectric layer contains 5 to 20 vol% of zirconium oxide particles or strontium oxide particles.
(3) The method for producing a display member according to (1) or (2), wherein the raw material used for forming the dielectric layer contains 5 to 20% by volume of glass particles.
(4) A first dielectric layer is formed by the method described in any one of (1) to (3), and aluminum oxide particles having a purity of 98% by weight or more are further added on the first dielectric layer to 80%. A method for producing a display member, wherein a second dielectric layer is formed by an aerosol deposition method using a raw material containing ~ 100% by volume.
(5) The volume-based concentration of aluminum oxide particles in the raw material used for forming the second dielectric layer is greater than the volume-based concentration of aluminum oxide particles in the raw material used for forming the first dielectric layer. (4) The manufacturing method of the member for a display as described in (4).
(6) A first dielectric layer is formed by the method described in any one of (1) to (3), and aluminum oxide particles having a purity of 98% by weight or more are further added on the first dielectric layer. The second dielectric layer is formed by an aerosol deposition method using a raw material containing ~ 95% by volume and 5-20% by volume of glass particles, and the glass particles in the raw material used for forming the second dielectric layer A method for producing a display member, wherein a volume concentration is larger than a volume concentration of glass particles in a raw material used for forming the first dielectric layer.
(7) A first dielectric layer is formed by any one of the methods (1) to (3), and a glass paste further containing glass powder and an organic component is applied on the first dielectric layer, A method for manufacturing a display member, wherein the second dielectric layer is formed by firing.

  According to the present invention, by forming a dielectric layer by an aerosol deposition method using a specific raw material, a thin film thickness, high withstand voltage, and no yellowing are formed on an electrode pattern formed on a substrate. A dielectric layer can be formed. Therefore, a high-performance display member can be realized and provided.

  As the substrate used in the present invention, soda glass or heat-resistant glass “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) or “PD200” (manufactured by Asahi Glass Co., Ltd.) can be used. The size of the glass substrate is not particularly limited, and a glass substrate having a thickness of 1 to 5 mm can be used.

  In the present invention, it is essential to form a dielectric layer by an aerosol deposition method using specific particles on an electrode pattern formed on a substrate.

  The electrode pattern in the present invention will be described. The electrode pattern on the PDP front plate is, for example, a narrow silver or chromium-copper-chromium electrode on a wide transparent electrode made of a conductive metal oxide such as indium tin oxide (ITO), tin oxide, zinc oxide. It has a laminated structure. The electrode patterns in the PDP back plate and FED are, for example, silver, copper, gold, chromium, titanium, aluminum, molybdenum, tungsten, niobium, tin oxide, indium oxide, indium tin oxide (ITO), zinc oxide, antimony oxide, oxide It consists of metals or metal oxides such as antimony tin. The electrode pattern is formed using a film forming technique such as a printing method, a slurry method, a vapor deposition method, sputtering, a slit die coater, or a spin coating, and a desired pattern is formed by, for example, a photolithography method.

  The aerosol deposition method in the present invention is a technique for forming a film by agitating and mixing a carrier gas and particles to form an aerosol and then colliding and depositing the aerosol from a nozzle on a substrate at high speed. FIG. 1 is a schematic view of a dielectric layer forming apparatus used in the method for producing a display member of the present invention. This dielectric layer forming apparatus has a dielectric layer forming unit 1 and an aerosol generating unit 2. The aerosol generation unit 2 performs aerosolization of the particles as a raw material, and the particles formed by the aerosol in the dielectric layer forming unit 1 are collided and deposited at high speed to form a dielectric layer. The aerosol generating unit 2 includes an aerosol generator 3 having particles as raw materials therein, and a high-pressure gas cylinder for carrier gas used to generate the aerosol by stirring and mixing the particles and the carrier gas in the aerosol generator 3. 4, a gas transport pipe 5 that connects the high-pressure gas cylinder 4 and the aerosol generator 3, and an aerosol transport pipe 6 that connects the aerosol generator 3 and the nozzle 7. The injection port of the nozzle 7 is disposed in the dielectric layer forming chamber 8 so as to face the substrate. The nozzle 7 is fixed, and a predetermined range on the substrate can be formed by moving the stage 9 on which the substrate is placed. In this method, if the particles can be aerosolized, a dielectric layer having a dense and stable performance can be formed without firing.

  As the carrier gas, nitrogen, oxygen, dry air, or carbon dioxide gas is preferable. A rare gas such as helium is not preferable because discharge is likely to occur at the time of particle collision, and it may be difficult to obtain a highly transparent dielectric layer.

  The inside of the dielectric layer forming chamber 8 is preferably decompressed to 0.1 to 1000 Pa. If it is less than 0.1 Pa, it may take time to reach the set pressure reduction degree, and productivity may be reduced. When the pressure exceeds 1000 Pa, it may be difficult to maintain the activity of the surface until the new surface of the particle surface comes into contact with the surface of another fine particle or the new surface.

  In the present invention, metal oxide particles such as silicon oxide particles, aluminum oxide particles, strontium oxide particles, zirconium oxide particles, or glass particles can be used as a raw material used for forming the dielectric layer by the aerosol deposition method. However, it is necessary to use a raw material containing aluminum oxide particles having a purity of 98% by weight or more as a main component. By containing 80 to 100% by volume of aluminum oxide having a purity of 98% by weight or more as a raw material, a dielectric layer having a thin film thickness and a high withstand voltage can be realized. The reason why such an effect can be obtained is that the withstand voltage of the aluminum oxide particles themselves is high, and that it is easy to form a dense film with good compatibility between the aerosol deposition method and the aluminum oxide particles. Conceivable.

  Furthermore, the effect of improving the withstand voltage of the formed dielectric layer can be obtained by containing 5 to 20% by volume of at least one particle selected from strontium oxide particles and zirconium oxide particles as a subcomponent.

  Moreover, the effect which improves the transmittance | permeability of the formed dielectric material layer is acquired by containing 5-20 volume% or less of glass particles in all the particles as a subcomponent.

The particle diameters of the aluminum oxide, zirconium oxide, and strontium oxide particles used in the present invention are 50% particle diameter (average particle diameter) d ₅₀ in the weight distribution curve of 0.1 μm to 2.0 μm and the maximum particle diameter d _max. Is preferably 3.0 μm or less. If the average particle diameter is smaller than 0.1 μm, the kinetic energy at the time of substrate collision is small, and it is difficult to obtain a dense dielectric layer, which is not preferable. Moreover, when the average particle diameter is larger than 2.0 μm or the maximum particle diameter is larger than 3.0 μm, the formed dielectric layer is inferior in surface smoothness, which is not preferable. The average particle diameter d ₅₀ and the maximum particle diameter d _max of the particles can be measured by a measuring apparatus such as a laser diffraction / scattering particle size distribution measuring apparatus (for example, “MT3300” manufactured by Nikkiso).

As for the particle diameter of the glass particles used in the aerosol deposition method in the present invention, d ₅₀ is preferably 0.5 μm or more and 5.0 μm or less, and the maximum particle diameter d _max is preferably 10.0 μm or less. If the average particle diameter is smaller than 0.5 μm, the kinetic energy at the time of substrate collision is small, and it is difficult to obtain a dense dielectric layer, which is not preferable. On the other hand, when the average particle diameter is larger than 5.0 μm or the maximum particle diameter is larger than 10.0 μm, the formed dielectric layer is inferior in surface smoothness, which is not preferable.

  The purity of the aluminum oxide particles used in the present invention needs to be 98% by weight or more. If the purity is less than 98% by weight, a dense dielectric layer cannot be obtained due to the influence of impurities, so that the withstand voltage and the transmittance are lowered, which is not preferable particularly for the PDP front plate application. The purity of the particles can be analyzed by, for example, an inductively coupled plasma emission spectrometer.

  As another aspect of the present invention, it is also preferable to form a dielectric layer having a two-layer structure on an electrode pattern formed on a substrate. In the two-layer structure, first, a first dielectric layer is formed on an electrode pattern formed on a substrate by an aerosol deposition method, and then a second dielectric is formed on the first dielectric layer. It is a structure formed by forming a layer. By forming a dielectric layer having a two-layer structure, for example, a dielectric layer having an effect of suppressing yellowing is formed on the first dielectric layer, and the second dielectric layer has high transparency. By forming the dielectric layer, it is conceivable that both withstand voltage and transmittance can be improved.

  It is preferable that the first dielectric layer and the second dielectric layer are both formed by the above-described aerosol deposition method as the two-layered dielectric layer.

  In this case, the volume-based concentration of the aluminum oxide particles in the raw material used for forming the second dielectric layer is used for the formation of the first dielectric layer, particularly in order to suppress yellowing and prevent migration of the metal element constituting the electrode. The concentration may be larger than the volume-based concentration of aluminum oxide particles in the raw material to be used.

  In addition, the second dielectric layer is used to suppress yellowing and prevent migration of metal elements constituting the electrode with the first dielectric layer, and to achieve high transmittance and surface smoothness with the second dielectric layer. The volume concentration of the glass particles contained in the particles used for the formation may be larger than the volume concentration of the glass particles contained in the particles used for forming the first dielectric layer.

  In forming a dielectric layer having a two-layer structure, a combination with a conventional glass paste method is also possible. For example, the first dielectric layer may be formed by the above-described aerosol deposition method, and the second dielectric layer may be formed using a glass paste. Yellowing can be prevented by performing the first dielectric layer by the above-described aerosol deposition method, and the first dielectric layer is composed of the first dielectric layer by the aerosol deposition method and the second dielectric layer by the glass paste method. By using a dielectric layer having a layer structure, a dielectric layer having high withstand voltage and high transmittance can be obtained even when the first dielectric layer formed by the aerosol deposition method is relatively thin.

  The glass paste used in the present invention includes glass powder as an inorganic component, a binder polymer and an organic solvent as organic components, and further, filler powder, antioxidant, dispersant, plasticizer, organic or inorganic as necessary. Additional components such as suspending agents and leveling agents may be added.

  The glass powder is preferably a low softening point glass powder, and a known glass insulating material can be applied. For example, lead borosilicate glass, bismuth borosilicate glass, or glass showing high transparency such as zinc borosilicate should be used. Can do. In the present invention, the low softening point glass powder refers to a glass powder having a softening point in the range of 400 to 600 ° C. Specifically, the glass powder contains at least any one of lead oxide, bismuth oxide, and zinc oxide, and the total amount is 40 to 80% by weight in terms of oxide. The softening point of the glass powder can be measured by TMA (thermomechanical analysis).

  As the binder polymer, it is preferable that the binder polymer has a characteristic that it is oxidized or / and decomposed or / and vaporized at the time of firing so that the carbide does not remain in the inorganic substance. For example, cellulose compounds such as methyl cellulose and ethyl cellulose, high molecular weight polyethers, acrylic resins, and the like can be used as materials satisfying these characteristics. The cellulose compound refers to, for example, methyl cellulose, ethyl cellulose, and the acrylic resin refers to, for example, methyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, isobutyl acrylate, isobutyl methacrylate, etc. And a resin comprising a polymer or a copolymer.

  The organic solvent is used to adjust the viscosity when the glass paste is applied to the substrate according to the application method. Examples of the organic solvent used at this time include, for example, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, terpineol, tetrahydrofuran, dimethyl sulfoxide, and γ-butyrolactone. , Bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these.

  Filler powder can be added to the glass paste of the present invention. The filler powder in the present invention is added to improve the strength of the dielectric layer, and refers to inorganic particles that hardly melt and flow even at the firing temperature. Specifically, it refers to an inorganic particle that does not have a softening point, a melting point, or a decomposition temperature at 600 ° C. or less and exists as a solid at 600 ° C. As the filler powder, at least one selected from a high softening point glass powder having a softening point of 650 to 1200 ° C. and a metal oxide powder such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide is added. be able to. In this invention, it is preferable that the ratio of glass powder and filler powder is 70-100 volume% of glass powder and 0-30 volume% of filler powder. By containing the filler powder, shrinkage due to firing can be suppressed, and there can be formed a dielectric layer having no protruding foreign matter and excellent in strength after firing. When the filler powder is more than 30% by volume, sintering during firing becomes difficult, and the porosity of the dielectric layer after firing tends to increase, which is not preferable.

  The method for forming the dielectric layer using glass paste is not particularly limited. For example, the first dielectric formed by the aerosol deposition method using screen printing, bar coater, roll coater, die coater, blade coater, spin coater, or the like. After applying the glass paste on the layer, it varies depending on the organic solvent in the paste using an optional oven such as a ventilated oven, hot plate, infrared drying oven, vacuum drying, etc., but generally 70 to 250 ° C. Can be dried for 5 to 60 minutes to form a thick film. Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Generally, baking is performed at 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked. In the present invention, a dielectric layer formed by an aerosol deposition method may be fired.

  The PDP front plate is formed by forming a transparent dielectric layer covering the electrodes formed on the substrate by the above-described method, and forming a magnesium oxide layer thereon as a protective film.

  As described above, the PDP back plate is formed by forming a dielectric layer covering the electrode formed on the substrate as described above, and using a partition paste on the dielectric layer, by a method such as a screen printing method, a sand blast method, or a photosensitive paste method. Form a pattern. Further, a phosphor layer is formed between the formed barrier ribs by a method such as a screen printing method, a photosensitive paste method, or a dispenser method, thereby producing a PDP back plate.

  The FED forms a dielectric layer pattern that covers the electrode formed on the substrate by the above-described method, and forms a gate electrode and a gate hole thereon by vapor deposition and patterning of a metal material or screen printing of a metal paste. Further, a focusing electrode is formed on the gate electrode by the same formation method as the gate electrode, and a field emission source is formed in the gate hole by a screen printing method, a slurry method, a die coater method, etc. A substrate is produced.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this. The dielectric layer formation conditions in the aerosol deposition method, the glass paste preparation method, the substrate preparation method, and the evaluation method of the formed dielectric layer will be described.
(Conditions for forming the dielectric layer in the aerosol deposition method)
The dielectric layer formation conditions by the aerosol deposition method described in the examples are as follows.

Dielectric layer formation range: 30 mm x 30 mm
Used nozzle: width 30 mm x 0.3 mm slit nozzle Ultimate pressure: 11 Pa
Carrier gas: Nitrogen Nozzle gap: 13mm
Stage moving speed: 4mm / sec
Film thickness: adjusted by particle ejection time Raw material: Particles listed in Table 1

(Production method of glass paste)
A binder polymer and an organic solvent were mixed and dissolved, then glass particles were added, and kneaded with three rollers to prepare a paste composed of glass particles and organic components. The paste was defoamed with a centrifugal defoamer as a pretreatment for application. The following compositions were used for each component.

Binder polymer: Ethyl cellulose resin, 5.0% by weight
Organic solvent: Terpineol, 50.0% by weight
Glass particles: Zinc-boron glass (D2 in Table 1) having a glass transition point of 459 ° C and a softening point of 561 ° C, 45.0% by weight
(Manufacturing method of substrate)
A substrate with an ITO electrode was produced by sputtering ITO on a 5-inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.) for withstand voltage measurement and transmittance measurement.

  For yellowing evaluation, a silver electrode pattern was formed using a photosensitive silver paste. The composition of the photosensitive silver paste was as follows.

Silver particles: Mitsui Mining & Mining Co., Ltd. SPN10J, 73.0 wt%
Glass particles: bismuth borosilicate glass having a glass transition point of 460 ° C. and a softening point of 495 ° C., 2.5% by weight
Binder polymer: Addition reaction of 0.4 equivalent of glycidyl methacrylate to the carboxyl group of the styrene / methyl methacrylate / methacrylic acid copolymer, a polymer having a weight average molecular weight of 43,000 and an acid value of 95, 16.5% by weight
Monomer: Trimethylolpropane triacrylate, 3.9% by weight
Polymerization initiator: IC369 manufactured by Ciba Specialty Chemicals Co., Ltd., 1.6% by weight
Dispersant: Solsperse 20000, 0.5% by weight
Organic solvent: gamma butyrolactone, 2.0% by weight
A photosensitive silver paste was applied on a 5-inch square glass substrate by a screen printing method (printing plate: SUS # 325) and dried at 120 ° C. for 10 minutes. After forming an electrode pattern by exposure and development, a substrate with a silver electrode was prepared by firing at a maximum temperature of 590 ° C. (maximum temperature holding time of 18 minutes).
(Evaluation method of the formed dielectric layer)
(Measurement method of withstand voltage)
Four 5 mm × 9 mm rectangular silver electrode patterns were formed on the dielectric layers obtained in Examples 1 to 10 and Comparative Examples 1 to 3 using a silver paste (N-2051 manufactured by Shoei Chemical Industry Co., Ltd.). The withstand voltage evaluation sample was produced by applying by screen printing, drying and firing. Using a withstand voltage / insulation resistance tester (KOSUI ELECTRONICS CO., LTD., TOS9201), an AC voltage was applied between the ITO electrode and silver electrode of the sample for 2 seconds, and the current value flowing at that time was less than 0.5 μA. The applied voltage was gradually increased as much as possible, and the withstand voltage of the dielectric layer on which the voltage immediately before the current value reached 0.5 μA or more was defined. The measurement results are shown in Table 2. When the withstand voltage is 1.3 kV or more, the withstand voltage is sufficiently high, and when the withstand voltage is less than 1.3 kV, the withstand voltage is insufficient.
(Measurement method of total light transmittance)
The total light transmittance (hereinafter abbreviated as transmittance) of the dielectric layers obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was measured with a spectrophotometer (manufactured by Hitachi, Ltd., U-3410). The results are shown in Table 2. When the transmittance is 70% or more, the transmittance is high, and when the transmittance is less than 70%, the transmittance is insufficient.
(Evaluation of yellowing)
For dielectric layers obtained in Examples 1-10, and Comparative Examples 1 to 6, spectrophotometer (Minolta, CM-2002) ^{b *} values measured by, if the ^{b *} value is less than 5 ○ When the b ^* value is 5 or more, yellowing was evaluated as x. The evaluation results are shown in Table 2.

AD shown in the formation method in Table 2 represents an aerosol deposition method, and GP represents a glass paste method. A1, A2, B, C, D1, and D2 shown in the raw materials represent the particles shown in Table 1.
(Example 1)
By performing the aerosol deposition method using aluminum oxide particles (A1) as a dielectric material, a dielectric layer having a thickness of 15 μm made of aluminum oxide was obtained on the substrate with ITO electrode and the substrate with silver electrode. It showed a sufficiently high withstand voltage and a high transmittance.
(Comparative Example 1)
A dielectric layer was formed in the same manner as in Example 1 except that the aluminum oxide particles (A2) were used as the dielectric material. Since the purity of the particles was low, both withstand voltage and transmittance were insufficient.
(Comparative Example 2)
After applying the above glass paste on a substrate with an ITO electrode and a substrate with a silver electrode by a screen printing method (printing plate: SUS # 325) to a coating thickness of 52 μm and drying at 100 ° C. for 15 minutes, Firing was performed at a maximum temperature of 580 ° C. (maximum temperature holding time: 15 minutes) to obtain a dielectric layer made of glass and having a thickness of 15 μm. Although the transmittance was sufficiently high, the withstand voltage was insufficient. Furthermore, yellowing of the dielectric layer was observed.
(Example 2)
The same procedure as in Example 1 was performed except that a raw material containing 85% by volume of aluminum oxide particles (A1) in all particles and 15% by volume of zirconium oxide particles (B) in all particles was used as a dielectric raw material. Then, a dielectric layer was formed. Since the raw material contains zirconium oxide particles having a high withstand voltage, it showed a high transmittance and a withstand voltage higher than that of Example 1.
(Comparative Example 3)
The same procedure as in Example 1 was performed except that a raw material containing 70% by volume of aluminum oxide particles (A1) in all particles and 30% by volume of zirconium oxide particles (B) in all particles was used as a dielectric raw material. Then, a dielectric layer was formed. Since the volume concentration of the aluminum oxide particles was 80% by volume or less and a sufficiently dense dielectric layer could not be obtained, both the withstand voltage and the transmittance were insufficient.
(Example 3)
The same operation as in Example 1 was conducted except that a raw material containing 85% by volume of aluminum oxide particles (A1) in all particles and 15% by volume of strontium oxide particles (C) in all particles was used as a dielectric raw material. Then, a dielectric layer was formed. Since the strontium oxide particles having a high withstand voltage were contained in the raw material, the transmittance was high and the withstand voltage was higher than that of Example 1.
Example 4
The same procedure as in Example 1 was carried out except that a raw material containing 90% by volume of aluminum oxide particles (A1) in all particles and 10% by volume of glass particles (D1) in all particles was used as a dielectric raw material. A dielectric layer was formed. It showed a sufficiently high withstand voltage and a high transmittance.
(Example 5)
As a dielectric material, aluminum oxide particles (A1) are contained in 85% by volume in all particles, zirconium oxide particles (B) are contained in 10% by volume in all particles, and strontium oxide particles (C) are contained in 5% in all particles. A dielectric layer was formed in the same manner as in Example 1 except that the raw material containing volume% was used. Since the raw material contains zirconium oxide particles and strontium oxide particles having high withstand voltage, the raw material showed high transmittance and higher withstand voltage than Example 1.
(Example 6)
As a dielectric material, aluminum oxide particles (A1) are contained in 84% by volume in all particles, zirconium oxide particles (B) are contained in 8% by volume in all particles, and glass particles (D1) are contained in 8% by volume. A dielectric layer was formed in the same manner as in Example 1 except that a raw material containing% was used. A high transmittance was exhibited, and a withstand voltage higher than that of Example 1 was exhibited.
(Example 7)
By carrying out the aerosol deposition method using a raw material containing 85% by volume of aluminum oxide particles (A1) in all particles as a raw material of the dielectric and 15% by volume of zirconium oxide particles (B) in all particles, A first dielectric layer is formed on a substrate with an ITO electrode and a substrate with a silver electrode, and further contains 85% by volume of aluminum oxide particles (A1) as a dielectric raw material, and strontium oxide. A second dielectric layer was formed by performing an aerosol deposition method using a raw material containing 15% by volume of particles (C) in all particles, and a dielectric layer having a two-layer structure with a thickness of 15 μm was obtained. Since the raw material contains zirconium oxide particles and strontium oxide particles having high withstand voltage, the raw material showed high transmittance and higher withstand voltage than Example 1.
(Example 8)
By performing an aerosol deposition method using a raw material containing 82% by volume of aluminum oxide particles (A1) in all particles and 18% by volume of zirconium oxide particles (B) in all particles as a dielectric raw material, ITO is used. A first dielectric layer is formed on a substrate with an electrode and a substrate with a silver electrode, and further contains 95% by volume of aluminum oxide particles (A1) as a dielectric material on the total particles, and zirconium oxide particles A second dielectric layer was formed by performing an aerosol deposition method using a raw material containing 5% by volume of (B) in all particles, and a dielectric layer having a two-layer structure with a film thickness of 15 μm was obtained. Since the first dielectric layer material contains 18% by volume of zirconium oxide particles and the second dielectric layer material contains 5% by volume of zirconium oxide particles, a high withstand voltage is secured in the first dielectric layer. A high transmittance was ensured by the dielectric layer of Example 2, 3, 5 and 7, and the same dielectric strength was exhibited as compared with the dielectric layers of Examples 2, 3, 5, and 7.
Example 9
As a dielectric material, aluminum oxide particles (A1) are contained in 85% by volume in all particles, zirconium oxide particles (B) are contained in 10% by volume in all particles, and glass particles (D1) are contained in 5% by volume. The first dielectric layer is formed on the substrate with an ITO electrode and the substrate with a silver electrode by carrying out an aerosol deposition method using a raw material containing 1% of aluminum oxide particles (as a dielectric raw material) A second dielectric layer is formed by performing an aerosol deposition method using a raw material containing 85% by volume of A1) in all particles and 15% by volume of glass particles (D1) in all particles, A dielectric layer having a two-layer structure having a thickness of 15 μm was obtained. Since the first dielectric layer material contains 5% by volume of glass particles and the second dielectric layer material contains 15% by volume of glass particles, the transmittance was higher than those of Examples 1-3 and 5-8. .
(Example 10)
By performing an aerosol deposition method using aluminum oxide particles (A1) as a dielectric raw material, a first dielectric layer is formed on the substrate with the ITO electrode and the substrate with the silver electrode, and further, Using glass paste as a raw material for the dielectric, it is applied to a coating thickness of 40 μm by screen printing, dried at 100 ° C. for 15 minutes, and then fired at a maximum temperature of 580 ° C. (maximum temperature holding time of 15 minutes). As a result, a second dielectric layer was formed, and a dielectric layer having a thickness of 15 μm and a two-layer structure was obtained. Although the 2nd dielectric material layer is formed using the glass paste, since the 1st dielectric material layer is formed by the aerosol deposition method, from Examples 1-9, maintaining a high withstand voltage. Also showed high transmittance.

  The dielectric layers of Examples 1 to 10 had a withstand voltage of 1.3 kV or higher and a sufficiently high withstand voltage. On the other hand, the dielectric layers of Comparative Examples 1 to 3 had a withstand voltage of less than 1.3 kV, and the withstand voltage was insufficient.

  The dielectric layers of Examples 1 to 10 and Comparative Example 2 had a transmittance of 70% or more, and were excellent in the transmittance. On the other hand, the dielectric layers of Comparative Examples 1 and 3 had a transmittance of less than 70%, and the transmittance was insufficient for PDP front plate applications.

From the above results, the dielectric layers of Examples 1 to 10 can be used for display dielectric layers such as FED dielectric layers and PDP dielectric layers, and the dielectric layer forming method of the present invention is useful. It was shown that.
(Example 11)
PDP was manufactured and evaluated by the following manufacturing method.

1. Preparation of front plate and back plate The front plate was prepared as follows. First, on a 5-inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.), a transparent electrode pattern composed of a pair of a scan electrode stripe pattern and a sustain electrode stripe pattern was formed using ITO. The scan electrode and the sustain electrode each had a line width of 300 μm and a thickness of 100 nm. The gap between the scan electrode and the sustain electrode was 80 μm. The pitch of the transparent electrode pattern was 1080 μm. The transparent electrode pattern and the bus electrode pattern, dielectric layer, and MgO protective film described below are formed so that they can be lit under the same driving conditions as a panel in the central 8 cm square of the substrate. The drawer part was formed until.

  Next, a bus electrode pattern composed of a pair of bus electrode stripe patterns was formed on the transparent electrode pattern. The bus electrode stripe pattern had a thickness of 3 μm, a width of 100 μm, and a gap between adjacent stripe patterns of 440 μm. As shown in FIG. 1, the bus electrode was formed along the end of the transparent electrode pattern so as to be parallel to the transparent electrode pattern. The bus electrode paste was applied by a screen printing method (printing plate: SUS # 325) so as to have a thickness of 5 μm after drying, and dried at 90 ° C. for 10 minutes. After drying, a negative chrome mask having a stripe pattern with a pitch of 1080 μm and a line width of 105 μm was set and exposed. After exposure, development is performed in a 0.5% ethanolamine aqueous solution, followed by heating at 200 ° C. for 15 minutes using a hot air dryer, and then baking at 580 ° C. for 15 minutes to obtain a desired pattern. It was.

  Next, according to the method described in Example 1, a transparent dielectric layer was formed so as to cover the transparent electrode pattern and the bus electrode pattern.

  Next, an MgO protective film having a thickness of 0.8 μm was formed on the transparent dielectric layer by an electron beam evaporation method, thereby completing the front plate.

  The back plate was produced as follows. A stripe pattern of address electrodes having a pitch of 240 μm, a line width of 80 μm, and a thickness of 3 μm is formed on a 5-inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.) in the same manner as the electrode paste on the front plate. did. The address electrode pattern and the dielectric layer, barrier rib pattern, and phosphor pattern described below are formed so that they can be lit under the same driving conditions as a panel in the central 8 cm square of the substrate. A drawer portion was formed.

  Next, a dielectric layer having a thickness of 10 μm after firing was formed using the dielectric paste. The dielectric paste was applied by a screen printing method (printing plate: SUS # 325) so that the thickness after drying was 20 μm, and dried at 90 ° C. for 10 minutes. After drying, a dielectric layer was formed by baking at 580 ° C. for 15 minutes. In addition, the inorganic component used for the dielectric paste was used in combination with a glass powder exhibiting white color by light scattering after firing.

  Next, a stripe-shaped barrier rib pattern having a thickness of 120 μm, a line width (bottom width) of 100 μm, and a pitch of 240 μm was formed, and an address electrode was disposed between the adjacent barrier ribs. A photosensitive partition paste was used to form the partition. The barrier rib paste was dried and then die-coated to a thickness of 180 μm and dried at 100 ° C. for 30 minutes. After drying, the film was exposed using a negative chrome mask having a stripe shape with a line width of 70 μm and a pitch of 240 μm. After exposure, development was performed in a 0.5% ethanolamine aqueous solution, followed by baking at 590 ° C. for 30 minutes to obtain a desired partition wall pattern.

  Red, green, and blue phosphor layers were formed on the grooves and inner walls of the stripe pattern of the partition walls so that the thickness after firing was 10 to 15 μm, thereby completing the back plate. A phosphor paste was applied by a dispensing method, and then dried and baked to obtain a phosphor layer.

2. Lamination of the front plate and the back plate Positioning of the front plate and the back plate in a state where the sealing paste is placed on the peripheral portion of the back plate manufactured above and pre-baked at 390 ° C. for 10 minutes and then held at 150 ° C. Together. In alignment, the bus electrode and the address electrode are orthogonal to each other, and can be lit under the same driving conditions in an 8 cm square area in the center of the substrate. The holding temperature was kept until the main baking was performed. Then, main baking was performed for 30 minutes at 480 degreeC, and the front board and the back board were bonded together. As the sealing paste, a paste mainly composed of bismuth glass powder having a softening point of 398 ° C. was used.

3. Production and Evaluation of PDP After bonding and sealing the front plate and the back plate, Xe 5% -Nebal. Gas was sealed up to 66.5 kPa. Finally, a drive circuit was mounted and aging was performed for 24 hours to complete the PDP.

The PDP obtained by the above production method was evaluated. No yellowing of the front plate dielectric was observed, and a display with high brightness, no display defects, and a stable driving voltage could be obtained.
(Example 12)
A PDP was produced in the same manner as in Example 11 except that the transparent dielectric layer was formed so as to cover the transparent electrode pattern and the bus electrode pattern according to the method described in Example 10 in the front plate production process.

  The PDP obtained by the above production method was evaluated. No yellowing of the front plate dielectric was observed, and a display with high brightness, no display defects, and a stable driving voltage could be obtained.

It is a schematic diagram of the dielectric material layer forming apparatus used for the manufacturing method of the display member of this invention.

Explanation of symbols

1: Dielectric layer forming unit 2: Aerosol generating unit 3: Aerosol generator 4: High-pressure gas cylinder 5: Gas conveying pipe 6: Aerosol conveying pipe 7: Nozzle 8: Dielectric layer forming chamber 9: Stage 10: Substrate

Claims (7)

A method for producing a display member having an electrode pattern and a dielectric layer covering the electrode pattern on a substrate, wherein an aerosol deposition method using a raw material containing 80 to 100% by volume of aluminum oxide particles having a purity of 98% by weight or more A method for producing a display member, comprising: forming a dielectric layer by: The manufacturing method of the member for a display of Claim 1 with which the raw material used for formation of the said dielectric material layer contains 5-20 volume% of zirconium oxide particles or strontium oxide particles. The manufacturing method of the member for a display of Claim 1 or 2 with which the raw material used for formation of the said dielectric material layer contains 5-20 volume% of glass particles. A first dielectric layer is formed by the method according to claim 1, and aluminum oxide particles having a purity of 98% by weight or more are further contained on the first dielectric layer by 80 to 100% by volume. A method for manufacturing a display member, wherein a second dielectric layer is formed by an aerosol deposition method using a raw material. The volume-based concentration of aluminum oxide particles in the raw material used for forming the second dielectric layer is higher than the volume-based concentration of aluminum oxide particles in the raw material used for forming the first dielectric layer. Item 5. A method for producing a display member according to Item 4. A first dielectric layer is formed by the method according to any one of claims 1 to 3, and aluminum oxide particles having a purity of 98% by weight or more are further added on the first dielectric layer by 80 to 95% by volume, A second dielectric layer is formed by an aerosol deposition method using a raw material containing 5 to 20% by volume of glass particles, and the volume concentration of the glass particles in the raw material used for forming the second dielectric layer is The manufacturing method of the member for a display larger than the volume concentration of the glass particle in the raw material used for formation of a 1st dielectric material layer. A first dielectric layer is formed by the method according to any one of claims 1 to 3, and a glass paste further containing glass powder and an organic component is applied onto the first dielectric layer, followed by firing. A manufacturing method of a member for display which forms 2 dielectric layers.

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