JP2008159360A - Method for manufacturing plasma display panel - Google Patents

Abstract

A manufacturing method suitable for pattern formation using an offset printing method is provided. Even if the film is thinned, a pattern with a high shielding rate and no line disturbance can be formed.
A line-shaped black layer 16b is formed on a windshield substrate 11 using a black paste composition by an offset printing method, and a white conductive paste composition is formed on the unfired black layer by an offset printing method. The white layer 16a whose line width is narrower than that of the black layer is stacked using an object. A black paste composition used for forming a black film, which is a black layer, including the steps of forming the black electrode and the white layer by simultaneously firing the formed black layer and the white layer. However, the average particle size of the black oxide powder is 0.01 to 0.5 μm, including 10 to 50% by weight of the black oxide powder, 5 to 30% by weight of the glass powder, and the balance being an organic vehicle. The specific surface area of the black oxide powder is 5 to 50 m ² / g.
[Selection] Figure 1

Description

  The present invention relates to a method for manufacturing a plasma display panel (hereinafter referred to as PDP), and more specifically, a PDP suitable for manufacturing bus electrodes and black stripes on a windshield substrate by an offset printing method. It relates to a manufacturing method.

  PDP applies voltage to the electrode pair of the discharge cell, which is a sealed space filled with gas, generates plasma discharge, and irradiates the phosphor applied in the discharge cell with ultraviolet rays generated from the gas, thereby exciting the phosphor. It is a display device that displays information by causing it to emit light.

  As shown in FIG. 1, in the PDP 10, the spread of discharge is restricted to a certain area between the front glass substrate 11 and the rear glass substrate 12, and display is performed in a prescribed cell, and at the same time, a uniform discharge space is secured. In order to do so, partition walls (barriers, ribs) 13 are provided. A bus electrode 16 is provided on the inner surface of the front glass substrate 11, and an address electrode 17 is provided on the inner surface of the rear glass substrate 12 so as to face the bus electrode 16. Both substrates 11 and 12 are partitioned by a partition wall 13, and gas is sealed in the partitioned interior to form a discharge space 14. In the discharge space 14, phosphors 18G, 18B, 18R are provided. The PDP generates plasma discharge between the bus electrode 16 and the address electrode 17 that are opposed to each other in the discharge space 14, so that ultraviolet rays generated from the gas sealed in the discharge space 14 are generated in the discharge space 14. The display is performed by touching the phosphor 18 provided on the surface. In FIG. 1, reference numeral 19 denotes a protective film, reference numeral 21 denotes a transparent dielectric layer, reference numeral 22 denotes a color filter, and reference numeral 23 denotes a transparent electrode.

  In recent years, it has been required to produce a high-quality PDP. One measure for improving the image quality of PDP is to improve contrast. Conventionally, the contrast of a PDP has been lower than that of a CRT television. As a factor for reducing the contrast, the high reflection luminance of room light has been pointed out. Although the indoor light is visible light, the reflectance of the phosphor with respect to visible light is high. Therefore, when the indoor light enters the discharge cell constituting the PDP and hits the phosphor, the indoor light is reflected and the front surface of the PDP. This is because it is difficult for the viewer to visually recognize the light emitted by the phosphor.

  Therefore, in recent PDPs, as a measure for solving the decrease in contrast due to the reflected luminance of room light, there is a method of improving the shielding ratio of the front substrate and preventing the room light from entering the discharge cells constituting the PDP. It has been adopted. As shown in FIG. 1, the first method is to form a black stripe 24 at an undischarged portion of the panel, that is, at the partition wall 13 partitioning each discharge cell, thereby shielding the outside light reflectance. It is a method of lowering. In the second method, a black layer is first applied to a portion where a white layer is formed, instead of the conventional bus electrode 16 composed of a white layer 1a 16a composed of silver having a low electrical resistivity. This is a method of forming a bus electrode 16 composed of black and white two layers 16a and 16b by forming 16b and laminating a white layer 16a thereon.

  When forming a black film such as the black stripe 24 or the black layer 16b of the bus electrode 16, it is generally formed by a photolithography method. For example, in the case of forming a bus electrode by using a photolithography method, a photosensitive paste is applied to the entire surface of the substrate, exposed and developed through a mask having a predetermined pattern, and the remaining layer after development is fired. Was forming. Also, the black stripes are generally formed using a photolithography method.

  However, in the photolithography method, it is necessary to use a photosensitive paste containing a photopolymerizable monomer and a photopolymerization initiator. Therefore, by exposing the photopolymerizable monomer and photopolymerization initiator present in all thickness directions of the coating layer formed by applying such a photosensitive black paste, all of the exposed coating layer Therefore, even if you try to form a black film with a finer pattern by reducing the particle size of the black powder, such as the black pigment contained in the photosensitive black paste, In the following cases, the particles gather to form a dense state and block the exposure light, so that the light transmittance is insufficient and the coating layer does not cure, and the hardness sufficient for pattern formation Therefore, there is a problem that a black film with a fine pattern cannot be formed.

  Further, in the photolithography method, since the portions other than the exposed portion are removed, there is a problem that the utilization efficiency of the paste material is extremely poor and cannot be effectively used. Furthermore, depending on the type of element contained in the paste material to be removed, there has been a problem that the processing method, recycling, etc. are costly. Further, since exposure and development are necessary, there is a problem that the process becomes complicated.

Therefore, a technique for forming a pattern by an offset printing method instead of the photolithography method has been developed. Specifically, a pattern forming step of forming the first black layer pattern, the main electrode layer pattern, and the second black layer on the substrate on which the transparent electrode is formed by an offset printing method, and the first black layer pattern, the main electrode Disclosed is a method for manufacturing a display panel, comprising: simultaneously firing a layer pattern and a second black layer pattern to form a first black layer, a main electrode layer, and a second black layer. (For example, refer to Patent Document 1). In Patent Document 1, a black conductive paste (black Ag paste) in which an inorganic black pigment, silver powder, glass powder, resin, and solvent are mixed is used as a material for forming the first black layer pattern, and the main electrode layer pattern is formed. The material is a conductive paste (white Ag paste) mixed with silver powder, glass powder, resin, and solvent, and the second black layer (BS layer) pattern forming material is inorganic black pigment, glass powder, resin, A black paste mixed with a solvent is used.
JP 2004-185895 A (Claim 1, paragraph [0019])

However, the above-mentioned Patent Document 1 discloses components for preparing each pattern forming material, but does not mention various conditions of each component that are optimized for the offset printing method. An object is to provide a method of manufacturing a PDP suitable for pattern formation using an offset printing method.
An object of the present invention is to provide a method for manufacturing a PDP that can form a pattern having a high shielding rate and no line disturbance even when the film thickness is reduced.

As shown in FIG. 2, the invention according to claim 1 includes a step of forming a line-shaped black layer 16b on a windshield substrate 11 using a black paste composition by an offset printing method, and an unfired black color formed. On the layer 16b, a step of laminating a white layer 16a having a line width narrower than that of the black layer 16b using a white conductive paste composition by an offset printing method, and two layers of the formed black layer 16b and the white layer 16a This is an improvement of the PDP manufacturing method including the step of forming the bus electrode 16 composed of the black layer 16b and the white layer 16a by firing simultaneously. The characteristic structure is that the black paste composition used for forming the black film that is the black layer 16b is composed of 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance being an organic vehicle. The average particle size of the black oxide powder is 0.01 to 0.5 μm, and the specific surface area of the black oxide powder is 5 to 50 m ² / g.
In the invention according to claim 1, the offset printing method is used to form the line-shaped black layer 16b with the black paste composition in which the mixing ratio of each component is controlled to be optimal for use in the offset printing method. The black oxide powder constituting the black paste composition is controlled so as to have an average particle diameter and a specific surface area within the above ranges. The black layer 16b having a high pattern and no line disturbance can be formed. In addition, since the stacked two-layer coating films are fired at the same time, the process can be shortened.

  The invention according to claim 2 is the invention according to claim 1, wherein a white layer is formed on the formed unfired black layer after the step of forming the unfired black layer by an offset printing method. It is a manufacturing method of the plasma display panel further including the process of drying an unbaked black layer before the process of laminating | stacking.

  The invention according to claim 3 is the invention according to claim 2, wherein the step of drying the unfired black layer is a step of drying by blowing air at room temperature to the black layer or heating the black layer to dry It is the manufacturing method of the plasma display panel which is the process to perform.

  The invention according to claim 4 is the invention according to claim 1, wherein the organic vehicle constituting the black paste composition used for forming the black layer contains a thermosetting resin or a photocurable resin, and is offset printing. After the step of forming an unfired black layer, and before the step of laminating the white layer on the formed unfired black layer, the step of thermosetting or photocuring the unfired black layer A plasma display panel manufacturing method is further included.

  In the inventions according to claims 2 to 4, the adhesiveness of the black paste composition forming the black layer can be reduced by drying or curing the unfired black layer. Even if dust or the like adheres to the surface of the black layer in the meantime, it can be easily removed by blowing or the like. Moreover, the shape maintenance property of a black layer can be improved by drying or hardening | curing an unbaked black layer.

The invention according to claim 5 is the invention according to claim 1, wherein the white conductive paste composition used for forming the white layer 16a comprises 50 to 90% by weight of silver-containing powder and 1 to 10% by weight. The organic powder contained in the black paste composition used for forming the black layer 16b and the organic vehicle contained in the white conductive paste composition are the same type of components, including the glass powder and the balance being an organic vehicle. It is a manufacturing method of a certain PDP.
In the invention according to claim 5, in order to form the line-shaped white layer 16a with the white conductive paste composition in which the mixing ratio of each component is controlled to be optimal for use in offset printing, the offset printing method is used. Suitable for the pattern formation used. Further, the organic vehicle contained in the white conductive paste composition is the same type of component as the organic vehicle contained in the black paste composition used for forming the black layer 16b, so that Adhesion of the white layer 16a to be stacked is increased.

  The invention according to claim 6 is the invention according to claim 1, wherein the organic vehicle includes a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins. A display panel manufacturing method.

  The invention according to claim 7 is the invention according to claim 6, wherein the synthetic resin comprises an epoxy resin, a cellulose resin, a urethane resin, a butyral resin, an acrylic resin, a polyester resin, a styrene resin, a phenol resin, and these resins. This is a method for manufacturing a plasma display panel, which is a resin selected from the group consisting of a plurality of mixed and cross-linked resins.

  The invention according to claim 8 is the invention according to claim 6, wherein the organic solvent is an alcohol solvent, a ketone solvent, an ether solvent, a carbitol solvent, a hydrocarbon solvent, a diol solvent, or a glycol solvent. This is a method for producing a plasma display panel, which is one single solvent or two or more mixed solvents selected from the group consisting of a solvent and a glycol ether solvent.

  The invention according to claim 9 is the invention according to claim 1, wherein the offset printing method fills the paste composition into a printing plate having a concave pattern, and the filled paste composition has a silicone rubber sheet on the surface. A method for producing a plasma display panel in which, after transferring to a printing blanket, when the paste composition is transferred from the printing blanket onto the substrate, air of 5 to 30 ° C. is continuously blown on the printing blanket surface during printing It is.

As shown in FIG. 2, the invention according to claim 10 includes a step of forming a line-shaped black layer 16b on a windshield substrate 11 using a black paste composition by an offset printing method, and the formed black layer 16b. A step of firing, a step of laminating a white layer 16a having a narrower line width than the black layer 16b on the fired black layer 16b using a white conductive paste composition by an offset printing method; This is an improvement of the method for manufacturing a PDP including the step of forming the black electrode 16b and the bus electrode 16 composed of the white layer 16a by firing the white layer 16a. The characteristic configuration is that the black paste composition used for forming the black layer 16b includes 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance of the organic vehicle, The average particle diameter of the black oxide powder is 0.01 to 0.5 μm, and the specific surface area of the black oxide powder is 5 to 50 m ² / g.
In the invention according to claim 10, the offset printing method is used to form the line-shaped black layer 16b with the black paste composition in which the mixing ratio of each component is controlled to be optimal for use in the offset printing method. The black oxide powder constituting the black paste composition is controlled so as to have an average particle diameter and a specific surface area within the above ranges. The black layer 16b having a high pattern and no line disturbance can be formed.

The invention according to claim 11 is the invention according to claim 10, wherein the white conductive paste composition used for forming the white layer 16a comprises 50 to 90% by weight of silver-containing powder and 1 to 10% by weight. The organic powder contained in the black paste composition used for forming the black layer 16b and the organic vehicle contained in the white conductive paste composition are the same type of components, including the glass powder and the balance being the organic vehicle. It is a manufacturing method of a certain PDP.
In the invention according to claim 11, in order to form the line-shaped white layer 16a with the white conductive paste composition in which the blending ratio of each component is controlled to be optimal for use in offset printing, the offset printing method is used. Suitable for the pattern formation used. Further, the organic vehicle contained in the white conductive paste composition is the same type of component as the organic vehicle contained in the black paste composition used for forming the black layer 16b, so that Adhesion of the white layer 16a to be stacked is increased.

  The invention according to claim 12 is the invention according to claim 10, wherein the organic vehicle contains both a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins. A display panel manufacturing method.

  The invention according to claim 13 is the invention according to claim 12, wherein the synthetic resin comprises an epoxy resin, a cellulose resin, a urethane resin, a butyral resin, an acrylic resin, a polyester resin, a styrene resin, a phenol resin, and these resins. This is a method for manufacturing a plasma display panel, which is a resin selected from the group consisting of a plurality of mixed and cross-linked resins.

  The invention according to claim 14 is the invention according to claim 12, wherein the organic solvent is an alcohol solvent, ketone solvent, ether solvent, carbitol solvent, hydrocarbon solvent, diol solvent, glycol solvent. A method for producing a plasma display panel, which is one single solvent or two or more mixed solvents selected from the group consisting of a solvent and a glycol ether solvent.

  The invention according to claim 15 is the invention according to claim 10, wherein the offset printing method fills the paste composition into a printing plate having a concave pattern, and the filled paste composition has a silicone rubber sheet on the surface. A method for producing a plasma display panel in which, after transferring to a printing blanket, when the paste composition is transferred from the printing blanket onto the substrate, air of 5 to 30 ° C. is continuously blown on the printing blanket surface during printing It is.

As shown in FIG. 1, the invention according to claim 16 is formed on the front glass substrate 11 and on the dielectric layer 21 opposite to the partition wall 13 formed on the rear glass substrate 12 by an offset printing method. Forming a black stripe 24 using a black paste composition. The characteristic structure is that the black paste composition used for forming the black stripes 24 contains 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance is an organic vehicle. The average particle diameter of the black oxide powder is 0.01 to 0.5 μm, and the specific surface area of the black oxide powder is 5 to 50 m ² / g.
In the invention according to claim 16, in order to form the black stripe 24 with the black paste composition in which the blending ratio of each component is controlled to be optimal for use in the offset printing method, pattern formation using the offset printing method is performed. In addition, by controlling the black oxide powder constituting the black paste composition to have an average particle size and a specific surface area within the above range, it is fine and has a high shielding rate even if it is thinned. In addition, a black stripe 24 having a pattern with no line disturbance can be formed.

  The invention according to claim 17 is the invention according to claim 16, wherein the organic vehicle contains both a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins. A display panel manufacturing method.

  The invention according to claim 18 is the invention according to claim 17, wherein the synthetic resin comprises an epoxy resin, a cellulose resin, a urethane resin, a butyral resin, an acrylic resin, a polyester resin, a styrene resin, a phenol resin, and these resins. This is a method for manufacturing a plasma display panel, which is a resin selected from the group consisting of a plurality of mixed and cross-linked resins.

  The invention according to claim 19 is the invention according to claim 17, wherein the organic solvent is an alcohol solvent, a ketone solvent, an ether solvent, a carbitol solvent, a hydrocarbon solvent, a diol solvent, or a glycol solvent. This is a method for producing a plasma display panel, which is one single solvent or two or more mixed solvents selected from the group consisting of a solvent and a glycol ether solvent.

  The invention according to claim 20 is the invention according to claim 16, wherein the offset printing method fills the paste composition into a printing plate having a concave pattern, and the filled paste composition has a silicone rubber sheet on the surface. A method for producing a plasma display panel in which, after transferring to a printing blanket, when the paste composition is transferred from the printing blanket onto the substrate, air of 5 to 30 ° C. is continuously blown on the printing blanket surface during printing It is.

In the manufacturing method according to claim 1 or claim 10, since the line-shaped black layer is formed by the black paste composition in which the blending ratio of each component is controlled to be optimal for use in the offset printing method, Suitable for pattern formation using the printing method, and by controlling the black oxide powder constituting the black paste composition to have an average particle size and specific surface area within the above range, it is fine and thinned. However, it is possible to form a black layer having a pattern with a high shielding rate and no line disturbance.
In the manufacturing method according to claim 16, the offset printing method is used to form black stripes with the black paste composition in which the mixing ratio of each component is controlled to be optimal for use in the offset printing method. Suitable for pattern formation, and by controlling the black oxide powder constituting the black paste composition to have an average particle size and a specific surface area within the above ranges, it is fine and has a shielding rate even if it is thinned. It is possible to form a black stripe having a high pattern without line disturbance.

Next, the best mode for carrying out the present invention will be described with reference to the drawings.
First, a windshield substrate 11 as shown in FIG. 2A is prepared, and a transparent electrode 23 is formed on the windshield substrate 11 as shown in FIG. The transparent electrode 23 formed here is formed of a transparent material that is necessary for plasma discharge and does not hinder light emission. The transparent electrode 23 uses an oxide film such as ITO (Indium Tin Oxide) or SnO _2, and can be formed by a vacuum film formation method such as sputtering or vapor deposition or a CVD (Chemical Vapor Deposition) method.

Next, as shown in FIG. 2 (c), a black paste composition is applied on the transparent electrode 23 formed on the windshield substrate 11 by an offset printing method to form a line-shaped black layer 16b. . In the method of the present invention, the black paste composition used for forming the black layer 16b contains 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance containing an organic vehicle. Configured. A black oxide powder having a small average particle size and a large specific surface area with an average particle size in the range of 0.01 to 0.5 μm and a specific surface area of 5 to 50 m ² / g is used. Thus, in the method of the present invention, the line-shaped black layer 16b is formed by the black paste composition in which the mixing ratio of each component is controlled to be optimal for use in the offset printing method. Suitable for forming the pattern used, and by controlling the black oxide powder constituting the black paste composition to have an average particle size and a specific surface area within the above ranges, it is fine and can be shielded even if it is thinned. The black layer 16b having a pattern with a high rate and no line disturbance can be formed. Among these, the black oxide powder to be used is preferably a powder having an average particle size of 0.05 to 0.3 μm and a specific surface area of 15 to 45 m ² / g.

The black oxide powder constituting the black paste composition for forming the black layer 16b contains one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Fe and Ni. It is preferably a metal oxide or a composite oxide thereof. Among these, Co ₃ O ₄ , Fe, Mn, Cu composite oxide, and Cu, Cr, Mn composite oxide are particularly preferable.

The glass powder constituting the black paste composition for forming the black layer 16b is selected from the group consisting of lead oxide, bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide, phosphorus oxide, calcium oxide and titanium oxide. The frit glass having a softening point of 400 to 550 ° C. containing one or more oxides is preferable. The softening point is within the above range because, in the frit glass having a softening point less than the lower limit, the glass powder hinders the binder removal of the binder resin constituting the organic vehicle in the paste composition, and the residue is a black layer. This is because the frit glass having a softening point exceeding the upper limit value cannot provide a sufficient anchor between the glass substrate and the glass substrate. The softening point of the frit glass is particularly preferably 450 to 550 ° C. Specifically, PbO—B ₂ O ₃ —SiO ₂ , ZnO—B ₂ O ₃ —SiO ₂ , PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ , PbO—ZnO—B ₂ O ₃ —SiO ₂ , PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ —ZnO, PbO—B ₂ O ₃ —SiO ₂ —CaO, B ₂ O ₃ —ZnO—Bi ₂ O ₃ , B ₂ O ₃ —Bi ₂ O ₃ , B ₂ O ₃ —ZnO, Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ , ZnO—P ₂ O ₅ —SiO ₂ , P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ , ZnO— Combinations such as P ₂ O ₅ —TiO ₂ can be mentioned.

  The organic vehicle constituting the black paste composition for forming the black layer 16b includes both a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins. It is preferable to use those prepared by dissolving in an organic solvent. As the synthetic resin, a resin selected from the group consisting of epoxy resins, cellulose resins, urethane resins, butyral resins, acrylic resins, polyester resins, styrene resins, phenol resins, and resins obtained by mixing and crosslinking these resins. Is mentioned. As the organic solvent, one kind of single solvent selected from the group consisting of alcohol solvents, ketone solvents, ether solvents, carbitol solvents, hydrocarbon solvents, diol solvents, glycol solvents and glycol ether solvents. One solvent or a mixed solvent of two or more kinds may be mentioned. Moreover, you may add additives, such as a dispersing agent and a viscosity modifier, as needed. A dispersant is added to improve the dispersibility of the black oxide powder or glass powder, and a viscosity modifier is added to adjust the paste viscosity.

  In the offset printing method performed here, the paste composition is filled into a printing plate having a concave pattern, the filled paste composition is transferred to a printing blanket, and then the paste composition is transferred from the printing blanket onto the substrate. By doing so, a line-shaped black layer is formed on the substrate. In the offset printing method, in order to transfer the paste composition from the printing blanket to the substrate 100%, a silicone rubber sheet is used on the surface of the printing blanket, and the silicone rubber sheet on the surface of the printing blanket is used for the paste composition. By adding a solvent that is easy and difficult to penetrate and lowering the surface tension at the interface between the paste composition and the silicone rubber, the paste composition is easily peeled off from the silicone rubber, and the paste composition is removed from the printing blanket onto the substrate. Is being transcribed.

  In the manufacturing method of this invention, it is suitable to spray 5-30 degreeC air continuously during printing with respect to the printing blanket surface. After transferring the paste composition from the printing plate to the printing blanket by continuously blowing air at 5 to 30 ° C. on the silicone rubber sheet on the surface of the printing blanket during printing, the solvent component from the paste composition Is quickly volatilized, so that the cohesive force of the paste composition transferred to the printing blanket surface is improved. When the cohesive force of the paste composition is improved, the paste composition hardly remains on the printing blanket when printing from the printing blanket onto the substrate. In addition, after transferring the paste composition from the printing blanket onto the substrate and finishing one printing, the state of the printing blanket is changed in order to quickly remove the solvent component penetrating the printing blanket surface. It can be kept in the state before the solvent component penetration. With these effects, it is possible to reduce the occurrence of the pyring phenomenon in continuous printing and to increase the number of continuous printings until the pyring phenomenon occurs.

  Preferably, the method further includes a step of drying the unfired black layer after applying the step of laminating the white layer on the formed unfired black layer after forming the unfired black layer by the offset printing method. It is. Examples of the step of drying the unfired black layer include a step of blowing air at room temperature to the black layer and drying, and a step of heating and drying the black layer. In order to dry the surface layer of the black layer by blowing air at room temperature onto the black layer, for example, an unfired black layer formed on the substrate with air at room temperature at a speed in the range of 0.1 to 10 m / sec. For 1 to 30 minutes. Moreover, in order to dry the surface layer of a black layer by heating a black layer, it is performed by hold | maintaining the board | substrate in which the unbaked black layer was formed at the temperature of 100-220 degreeC for 1 to 30 minutes, for example.

  Also, after forming the unfired black layer by the offset printing method and before applying the step of laminating the white layer on the formed unfired black layer, the step of thermosetting or photocuring the unfired black layer It is preferable to further contain. In order to cure the surface layer of the black layer by thermally curing the unfired black layer, for example, an organic monomer is used with an unsaturated monomer such as an acrylic monomer or methacrylic monomer and a thermal radical compound such as butyl peroxide. The substrate on which the unfired black layer is formed is held at a temperature of 100 to 220 ° C. for 1 to 30 minutes. Moreover, in order to harden the surface layer of a black layer by photocuring an unbaked black layer, unsaturated monomer, such as an acrylic monomer and a methacryl monomer, and 2-methyl-1 [4- ( Using a compound that generates radicals by ultraviolet rays, such as methylthio) phenyl] -2-morpholinopropan-1-one, light having a wavelength of 200 to 380 nm is applied to an unfired black layer formed on the substrate. The irradiation is performed for 5 to 360 seconds.

  By drying or curing the unfired black layer, the adhesiveness of the black paste composition forming the black layer can be reduced. Even if dust adheres, it can be easily removed by blowing or the like. Moreover, the shape maintenance property of a black layer can be improved by drying or hardening | curing an unbaked black layer. If the shape retention of the black layer is increased in this way, even if a white layer is laminated on the black layer in a subsequent process, an effect is obtained that the shape of the underlying black layer is not easily broken. . In addition, if the shape retention of the black layer is increased by drying or curing, even if a white layer is laminated on the black layer in the subsequent process, it exists at the lamination interface between the black layer and the white layer. Since there are few solvent components compared with the case where drying and hardening are not performed, the laminated white layer will not be dripped.

  Subsequently, as shown in FIG. 2 (d), a white conductive paste composition is applied onto the formed unfired black layer 16b by an offset printing method so that the line width is narrower than that of the black layer 16b. The white layer 16a is laminated. The white conductive paste composition used for forming the white layer 16a is configured to contain 50 to 90% by weight of silver-containing powder, 1 to 10% by weight of glass powder, and the balance being an organic vehicle. Moreover, it is preferable that the organic vehicle contained in the black paste composition used for forming the black layer 16b and the organic vehicle contained in the white conductive paste composition are the same kind of components. Thus, in order to form the line-shaped white layer 16a with the white conductive paste composition in which the blending ratio of each component is controlled to be optimal for use in offset printing, pattern formation using the offset printing method is performed. Suitable for. The organic vehicle contained in the white conductive paste composition is laminated on the black layer 16b by using the same type of component as that of the organic vehicle contained in the black paste composition used for forming the black layer 16b. The adhesion of the white layer 16a is increased.

The silver-containing powder constituting the white conductive paste composition may be a conductive powder of Ag alone, or may be a conductive powder containing not only Ag but also Au, Al, Pt, Pd and the like.
The glass powder constituting the white conductive paste composition is the same as the frit glass used in the glass powder constituting the black paste composition for forming the black layer 16b. Since the adhesiveness of a layer improves, it is especially preferable. If the same type of frit glass is used, the coefficient of thermal expansion will be the same, so there will be no distortion when firing the two layers, and cracking, warping, and poor adhesion will not occur, contributing to improved adhesion. To do.
As described above, the organic vehicle constituting the white conductive paste composition is preferably the same type of component as that of the organic vehicle constituting the black paste composition for forming the black layer 16b.

  As for offset printing when laminating the white layer, it is preferable that air at 5 to 30 ° C. is continuously blown on the printing blanket surface during printing, similarly to the offset printing when forming the black layer. is there.

Next, the two layers of the black layer 16b and the white layer 16a thus formed are fired simultaneously, whereby the bus electrode 16 composed of the black layer 16b and the white layer 16a is formed. In the method of the present invention, since the two layers of the coating film are simultaneously fired, the process can be shortened. The firing temperature here is preferably 560 to 580 ° C.
In addition, after forming the line-shaped black layer 16b using the black paste composition by the offset printing method on the transparent electrode 23 formed on the windshield substrate 11, this black layer 16b is baked, By laminating a white layer 16a having a narrower line width than the black layer 16b on the fired black layer 16b using a white conductive paste composition by an offset printing method, and firing the line-shaped white layer 16a. The bus electrode 16 composed of the black layer 16b and the white layer 16a can also be formed.

  Next, as shown in FIG. 2E, a transparent dielectric layer 21 is formed on the entire surface of the windshield substrate 11 so as to cover the transparent electrode 23 and the bus electrode 16. The transparent dielectric layer 21 is formed in order to provide a memory function by forming wall charges on the surface of the dielectric layer during electrode protection and discharging. The transparent dielectric layer 21 is formed on the bus electrode 16 so as to have a thickness of 20 to 40 μm.

  Next, as shown in FIG. 3A, a black stripe 24 is formed by applying a black paste composition on the transparent dielectric layer 21 formed on the windshield substrate 11 by an offset printing method. . As shown in FIG. 1, the black stripe 24 is formed at a position facing the end of the partition wall 13 formed on the rear glass substrate 12. By forming the black stripe 24, the external light reflectance is reduced and the contrast is improved.

In the method of the present invention, the black paste composition used for forming the black stripes 24 contains 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance containing an organic vehicle. Configured. A black oxide powder having a small average particle size and a large specific surface area with an average particle size in the range of 0.01 to 0.5 μm and a specific surface area of 5 to 50 m ² / g is used. As described above, in the method of the present invention, the black stripe 24 is formed by the black paste composition in which the mixing ratio of each component is controlled to be optimal for use in the offset printing method. Suitable for formation, and by controlling the black oxide powder constituting the black paste composition to have an average particle diameter and a specific surface area within the above ranges, it is fine and has a high shielding rate even when thinned. In addition, a black stripe 24 having a pattern with no line disturbance can be formed. Among these, the black oxide powder to be used is preferably a powder having an average particle size of 0.05 to 0.3 μm and a specific surface area of 15 to 45 m ² / g.

The black oxide powder constituting the black paste composition for forming the black stripe 24 contains one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Fe and Ni. It is preferably a metal oxide or a composite oxide thereof. Among these, Co ₃ O ₄ , Fe, Mn, Cu composite oxide, and Cu, Cr, Mn composite oxide are particularly preferable.

The glass powder constituting the black paste composition for forming the black stripe 24 is selected from the group consisting of lead oxide, bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide, phosphorus oxide, calcium oxide and titanium oxide. The frit glass having a softening point of 400 to 550 ° C. containing one or more oxides is preferable. The softening point is within the above range because, in the frit glass having a softening point less than the lower limit, the glass powder hinders the binder removal of the binder resin constituting the organic vehicle in the paste composition, and the residue is a black layer. This is because the frit glass having a softening point exceeding the upper limit value cannot provide a sufficient anchor between the glass substrate and the glass substrate. The softening point of the frit glass is particularly preferably 450 to 550 ° C. Specifically, PbO—B ₂ O ₃ —SiO ₂ , ZnO—B ₂ O ₃ —SiO ₂ , PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ , PbO—ZnO—B ₂ O ₃ —SiO ₂ , PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ —ZnO, PbO—B ₂ O ₃ —SiO ₂ —CaO, B ₂ O ₃ —ZnO—Bi ₂ O ₃ , B ₂ O ₃ —Bi ₂ O ₃ , B ₂ O ₃ —ZnO, Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ , ZnO—P ₂ O ₅ —SiO ₂ , P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ , ZnO— Combinations such as P ₂ O ₅ —TiO ₂ can be mentioned.

  The organic vehicle constituting the black paste composition for forming the black stripe 24 includes both a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins. It is preferable to use those prepared by dissolving in an organic solvent. As the synthetic resin, a resin selected from the group consisting of epoxy resins, cellulose resins, urethane resins, butyral resins, acrylic resins, polyester resins, styrene resins, phenol resins, and resins obtained by mixing and crosslinking these resins. Is mentioned. As the organic solvent, one kind of single solvent selected from the group consisting of alcohol solvents, ketone solvents, ether solvents, carbitol solvents, hydrocarbon solvents, diol solvents, glycol solvents and glycol ether solvents. One solvent or a mixed solvent of two or more kinds may be mentioned. Moreover, you may add additives, such as a dispersing agent and a viscosity modifier, as needed. A dispersant is added to improve the dispersibility of the black oxide powder or glass powder, and a viscosity modifier is added to adjust the paste viscosity.

  As for the offset printing when laminating the black stripes, air of 5 to 30 ° C. is continuously applied to the printing blanket surface during printing, as in the offset printing when forming the black layer and the white layer described above. And spraying is preferred.

  Next, as shown in FIG. 3B, the color filter 22 is formed on the transparent dielectric layer 21 so as to have the same height as the black stripe 24. Subsequently, as shown in FIG. 3C, a transparent dielectric layer 21 is formed on the color filter 22 and the black stripe 24. Further, as shown in FIG. 3D, a protective film 19 is formed on the transparent dielectric layer 21. The protective film 19 is formed when the dielectric layer is damaged by ion bombardment due to discharge and the panel life is shortened, and the efficiency of secondary electron emission necessary for plasma discharge is low, and the discharge voltage becomes high. This is to prevent this. The protective film 19 is made of MgO and can be formed by electron beam evaporation, ion plating, or sputtering.

  As described above, the front substrate for PDP is obtained through the steps of FIGS. 2 (a) to 3 (d).

The figure which shows the discharge cell of PDP. The figure which shows the front | former stage of the manufacturing process of the front substrate for PDP. The figure which shows the back | latter stage of the manufacturing process of the front substrate for PDP.

Explanation of symbols

10 PDP
DESCRIPTION OF SYMBOLS 11 Front glass substrate 12 Rear glass substrate 13 Partition 16 Bus electrode 16a White layer of bus electrode 16b Black layer of bus electrode 21 Dielectric layer 24 Black stripe

Claims (20)

Forming a line-shaped black layer on the front glass substrate using a black paste composition by an offset printing method;
On the formed unfired black layer, a step of laminating a white layer having a narrower line width than the black layer using a white conductive paste composition by an offset printing method;
In the method of manufacturing a plasma display panel, comprising simultaneously baking the formed black layer and the white layer to form a bus electrode composed of a black layer and a white layer.
The black paste composition used for forming the black layer contains 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance includes an organic vehicle,
The black oxide powder has an average particle size of 0.01 to 0.5 μm,
The method for producing a plasma display panel, wherein the black oxide powder has a specific surface area of 5 to 50 m ² / g.   A step of drying the unfired black layer after the step of forming the unfired black layer by an offset printing method and before the step of laminating a white layer on the formed unfired black layer The method of manufacturing a plasma display panel according to claim 1, further comprising:   The method for producing a plasma display panel according to claim 2, wherein the step of drying the unfired black layer is a step of blowing air at room temperature to the black layer and drying or heating and drying the black layer. The organic vehicle constituting the black paste composition used for forming the black layer contains a thermosetting resin or a photocurable resin,
After the step of forming an unfired black layer by an offset printing method and before the step of laminating a white layer on the formed unfired black layer, the unfired black layer is thermally cured or The method of manufacturing a plasma display panel according to claim 1, further comprising a step of photocuring. The white conductive paste composition used for forming the white layer contains 50 to 90% by weight of silver-containing powder, 1 to 10% by weight of glass powder, and the balance is an organic vehicle.
2. The method for manufacturing a plasma display panel according to claim 1, wherein the organic vehicle contained in the black paste composition used for forming the black layer and the organic vehicle contained in the white conductive paste composition are the same kind of components.   The method for producing a plasma display panel according to claim 1, wherein the organic vehicle includes both a synthetic resin that disappears without being carbonized upon firing and an organic solvent that can dissolve these resins.   The synthetic resin is a resin selected from the group consisting of epoxy resins, cellulose resins, urethane resins, butyral resins, acrylic resins, polyester resins, styrene resins, phenol resins, and resins obtained by mixing and crosslinking these resins. A method for manufacturing a plasma display panel according to claim 6.   The organic solvent is one kind selected from the group consisting of alcohol solvents, ketone solvents, ether solvents, carbitol solvents, hydrocarbon solvents, diol solvents, glycol solvents, and glycol ether solvents. The method for producing a plasma display panel according to claim 6, which is a solvent or a mixed solvent of two or more kinds. In the offset printing method, the paste composition is filled into a printing plate having a concave pattern, and the filled paste composition is transferred to a printing blanket having a silicone rubber sheet on the surface, and then the printing blanket onto the substrate. When transferring the paste composition,
The method for manufacturing a plasma display panel according to claim 1, wherein air of 5 to 30 ° C is continuously blown onto the printing blanket surface during printing. Forming a line-shaped black layer on the front glass substrate using a black paste composition by an offset printing method;
Baking the formed black layer;
On the fired black layer, a step of laminating a white layer having a narrower line width than the black layer using a white conductive paste composition by an offset printing method;
In the method for manufacturing a plasma display panel, including the step of forming a bus electrode composed of a black layer and a white layer by firing the formed line-shaped white layer,
The black paste composition used for forming the black layer contains 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance includes an organic vehicle,
The black oxide powder has an average particle size of 0.01 to 0.5 μm,
A method for manufacturing a bus electrode of a plasma display panel, wherein the black oxide powder has a specific surface area of 5 to 50 m ² / g. The white conductive paste composition used for forming the white layer contains 50 to 90% by weight of silver-containing powder, 1 to 10% by weight of glass powder, and the balance is an organic vehicle.
11. The method for manufacturing a plasma display panel according to claim 10, wherein the organic vehicle contained in the black paste composition used for forming the black layer and the organic vehicle contained in the white conductive paste composition are the same kind of components.   The method for producing a plasma display panel according to claim 10, wherein the organic vehicle contains both a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins.   The synthetic resin is a resin selected from the group consisting of epoxy resins, cellulose resins, urethane resins, butyral resins, acrylic resins, polyester resins, styrene resins, phenol resins, and resins obtained by mixing and crosslinking these resins. The method for manufacturing a plasma display panel according to claim 12.   The organic solvent is one kind selected from the group consisting of alcohol solvents, ketone solvents, ether solvents, carbitol solvents, hydrocarbon solvents, diol solvents, glycol solvents, and glycol ether solvents. The method for producing a plasma display panel according to claim 12, which is a solvent or a mixed solvent of two or more kinds. In the offset printing method, the paste composition is filled into a printing plate having a concave pattern, and the filled paste composition is transferred to a printing blanket having a silicone rubber sheet on the surface, and then the printing blanket onto the substrate. When transferring the paste composition,
The manufacturing method of the plasma display panel of Claim 10 which sprays 5-30 degreeC air continuously on printing with respect to the said blanket surface for printing. Forming a black stripe on a dielectric layer formed on a front glass substrate and facing a partition wall end formed on the rear glass substrate by using a black paste composition by an offset printing method. In the manufacturing method of
The black paste composition used for forming the black stripe includes 10 to 50% by weight of black oxide powder, 5 to 30% by weight of glass powder, and the balance comprising an organic vehicle,
The black oxide powder has an average particle size of 0.01 to 0.5 μm,
The method for producing a plasma display panel, wherein the black oxide powder has a specific surface area of 5 to 50 m ² / g.   The method for producing a plasma display panel according to claim 16, wherein the organic vehicle contains both a synthetic resin that disappears without being carbonized during firing and an organic solvent that can dissolve these resins.   The synthetic resin is a resin selected from the group consisting of epoxy resins, cellulose resins, urethane resins, butyral resins, acrylic resins, polyester resins, styrene resins, phenol resins, and resins obtained by mixing and crosslinking these resins. The method for manufacturing a plasma display panel according to claim 17.   The organic solvent is one kind selected from the group consisting of alcohol solvents, ketone solvents, ether solvents, carbitol solvents, hydrocarbon solvents, diol solvents, glycol solvents, and glycol ether solvents. The method for producing a plasma display panel according to claim 17, which is a solvent or a mixed solvent of two or more kinds. In the offset printing method, the paste composition is filled into a printing plate having a concave pattern, and the filled paste composition is transferred to a printing blanket having a silicone rubber sheet on the surface, and then the printing blanket onto the substrate. When transferring the paste composition,
The manufacturing method of the plasma display panel of Claim 16 which sprays 5-30 degreeC air continuously with respect to the said printing blanket surface.

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