JP4877247B2 - Black film paste composition and method for producing black film using the composition - Google Patents

Description

  The present invention provides a black film paste composition suitable for producing black films for bus electrodes and black stripes on a windshield substrate of a plasma display panel (PDP) by an offset printing method. And a method for producing a black film using the composition.

  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.

The image display method of the PDP will be further described below with reference to FIG. In the PDP, a partition wall 13 is provided between the front glass substrate 11 and the rear glass substrate 12 to suppress the spread of the discharge to a certain region and to perform display in a prescribed cell, and to ensure a uniform discharge space. . 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,
12 is defined by a partition wall 13. Gas is sealed in the partitioned interior, and a discharge space 14 is formed. 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 being applied to the phosphors 18G, 18B, and 18R provided in.

  In recent years, there has been a demand for higher image quality of PDP, and one of the countermeasures is high contrast. Conventionally, the contrast of a PDP has been lower than that of a cathode ray tube television, but one of the causes for lowering the contrast is the high reflection luminance of room light.

  The room light is visible light, but the reflectance of the visible light to the phosphor in the discharge cell that constitutes the PDP is high, so that the room light reflected by the phosphor enters the viewer's eyes and the light emitted from the phosphor is visible. Cause the weakening.

  For this reason, in recent PDPs, as a measure for solving a decrease in contrast due to reflection of room light, the room light is prevented from entering the discharge cells constituting the PDP by improving the room light shielding rate on the front substrate. The method is adopted. The first method is a method of shielding and lowering the external light reflectance by forming the black stripes 24 at the positions of the barrier ribs 13 that create the discharge spaces, that is, the portions of the panel that are not discharged. In the second method, a black electrode 16b is first formed by applying a black paste to a bus electrode that has been conventionally composed of only one white layer mainly composed of silver or the like, and the white layer 16a is formed thereon. In this method, the bus electrode 16 is formed by stacking two layers of black and white 16a and 16b.

  A light comprising a heat-resistant black pigment, an organic binder, a photopolymerizable monomer, a photopolymerization initiator, and organic beads as a material for forming a black film such as the black stripe or the black layer of the bus electrode. A PDP front substrate is proposed in which a curable resin composition and a black layer and a black matrix (black stripe) are formed of the photocurable resin composition (see, for example, Patent Document 1). ). A photolithography method is used to form a black layer and a black matrix constituting a bus electrode made of the photocurable resin composition disclosed in Patent Document 1.

Specifically, first, a photocurable resin composition is applied to the entire surface of the front glass substrate on which the transparent electrode is formed, and dried to form a tack-free black layer. A photomask having a bus electrode and a black matrix pattern is superimposed on the formed black layer and exposed. Next, a highly conductive composition containing conductive powder such as Ag is applied to the entire surface of the black layer and dried to form a tack-free white layer (conductive layer). This is overlaid with a photomask having an exposure pattern of bus electrodes and exposed. Next, a non-exposed portion is removed by development with an aqueous alkali solution and baked to form a bus electrode composed of a black layer (lower layer) electrode and a white layer (upper layer) electrode on the transparent electrode of the windshield substrate. , A black matrix is formed. In the photolithography method, a so-called photosensitive black paste containing a photocurable monomer having a photocuring property or the like is used as a material for a black layer or a black matrix. Here, “tack” is a value indicating the degree of adhesive strength.
Japanese Patent Laying-Open No. 2005-8700 (Claims 1 and 4, specification [0052], FIG. 2)

  In the photolithography method, it is necessary to expose and cure the entire coating layer formed by applying a photosensitive black paste. However, when the particle size of a black powder such as a black pigment contained in the photosensitive black paste is reduced to form a black film with a finer pattern, if the particle size is set to a certain value or less, the particles become dense. In such a situation, the exposure light is blocked and the photocurable composition such as the photocurable monomer cannot be sufficiently cured, and a black film having a fine pattern cannot be formed. . On the other hand, when the particle size of the black powder is increased to obtain sufficient curing of the photocurable composition, the gap between the particles is increased, and the effect of shielding the visible light of the black layer is sufficiently obtained. The problem of not.

  In addition, since the portions other than the exposed portions are removed in a post process in the photolithography method, the use efficiency of the paste material is extremely poor, and depending on the type of element contained in the paste material to be removed, the cost for the processing method, recycling, etc. Such a problem has also occurred.

  Furthermore, when forming a black layer or a black matrix by the photolithography method as in Patent Document 1, complicated manufacturing processes such as coating, drying, exposure, development, and baking must be performed.

  Therefore, the present invention has been made to solve the problems of such conventional techniques.

  An object of the present invention is to provide a black film paste composition capable of producing a black film having a high density, a high shielding rate, and fine and free from line disturbance, and a method for producing a black film using the composition. is there.

  Another object of the present invention is to provide a method for producing a black film using a paste composition for black film, which can improve the utilization efficiency of the paste material.

  Still another object of the present invention is to provide a method for producing a black film using a black film paste composition, which can improve the complexity of a conventional production process using a photolithography method and simplify the production process. There is.

  The inventor initially used black oxide powder as a black component when preparing a paste composition for offset printing. Generally, an oxide is obtained by raising the temperature of a hydroxide to a certain temperature. The black oxide powder is also obtained by the same method. At this time, the hydroxide becomes an oxide by adding oxygen. The particle size of the oxide powder obtained by this method grows when changing from hydroxide to oxide, so that the particle size of the oxide powder becomes larger than the particle size of the hydroxide powder. It was difficult to use a black oxide powder having a small diameter. Therefore, as a result of investigation by the present inventor, black oxyhydroxide powder having a particle size smaller than that of black oxide powder is used instead of black oxide powder as a component constituting the paste composition. It has been found that a black film can be produced with finer and less line disturbance than when oxide powder is used.

As shown in FIG. 1, the invention according to claim 1 is an improvement of the black film paste composition for producing the black films 16 b and 24 on the windshield substrate 11 constituting the PDP 10 by the offset printing method. The characteristic composition is that the composition contains an oxyhydroxide powder of 10 to 50% by mass, a glass powder of 5 to 30% by mass, and the balance is an organic vehicle, and the average particle size of the oxyhydroxide powder Is 0.01 to 0.2 μm, and the specific surface area of the oxyhydroxide powder is 5 to 80 m ² / g.

  By making the content rate of the oxyhydroxide powder and glass powder in the paste composition for black films into the said range, it becomes the paste composition for black films suitable for offset printing. Moreover, if the average particle diameter and specific surface area of an oxyhydroxide powder are made into the said range, the black film of a fine pattern can be produced. The black film paste composition according to the present invention is blackened by oxidizing the oxyhydroxide powder in the composition at the firing stage.

  The invention according to claim 2 is the invention according to claim 1, wherein the oxyhydroxide powder contains one metal element selected from the group consisting of Co, Cr, Mn, Fe and Ni. A black film paste composition which is an oxide, a composite hydroxide containing two or more metal elements, or a mixture thereof.

  The invention according to claim 3 is the invention according to claim 1, wherein the glass powder is selected from the group consisting of lead oxide, bismuth oxide, zinc oxide, boron oxide, silicon oxide, phosphorus oxide, calcium oxide and titanium oxide. The paste composition for black film which is a frit glass which has the softening point of 450-550 degreeC containing the 1 or 2 or more oxide.

  As shown in FIGS. 2 and 3, the invention according to claim 4 is the black film 16b on the substrate 11 by the offset printing method using the black film paste composition according to any one of claims 1 to 3. , 24 is produced, a method for producing a black film.

  In the invention according to claim 4, since the paste composition using the oxyhydroxide powder having a particle diameter smaller than that of the black oxide powder is used, it is finer than using the black oxide powder as the black component. A black film without line disturbance can be produced. Compared with the photolithography method used in the conventional manufacturing process, the paste composition must be applied to the entire desired surface and then exposed, and unnecessary portions must be removed and discarded. When the black film is produced by the offset printing method, the paste composition only needs to be applied to a necessary portion, so that the material used is not wasted and the utilization efficiency of the paste material can be improved. Moreover, the complexity of the conventional manufacturing process using the photolithography method can be improved, and the manufacturing process can be simplified.

  In the present invention, a powder having a small particle diameter can be used for the paste composition for producing a black film by utilizing the offset printing method. In the present invention, the oxyhydroxide powder having a smaller particle diameter than the black oxide powder originally used by the present inventors is used as a component for exhibiting black color, so that there is no finer line disturbance. A black film with a pattern can be produced. In addition, by using the oxyhydroxide powder, the oxygen that the oxyhydroxide powder has in its structure can be used for the oxidation of the oxyhydroxide powder at the firing stage, so oxygen is not given from the outside. In addition, sufficient blackening of the oxyhydroxide powder is obtained.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

As shown in FIG. 1, the black film paste composition of the present invention is used to produce black films 16 b and 24 on a windshield substrate 11 constituting the PDP 10 by an offset printing method. The paste composition for black film of this invention is comprised so that 10-50 mass% oxyhydroxide powder, 5-30 mass% glass powder, and the remainder may contain an organic vehicle. The average particle size of the oxyhydroxide powder is in the range of 0.01 to 0.2 μm, and the specific surface area of the oxyhydroxide powder is in the range of 5 to 80 m ² / g. The average particle size of the oxyhydroxide powder used in the present invention was measured with a laser diffraction / scattering particle size distribution measuring device (LA-950, manufactured by Horiba, Ltd.), and the particle size reference was calculated as the number. 50% average particle diameter (D ₅₀ ). The number-based average particle diameter measured by the laser diffraction / scattering particle size distribution measuring apparatus is the value of any 50 particles in an image observed with a scanning electron microscope (S-4300SE and S-900 manufactured by Hitachi High-Technologies). It almost coincides with the average particle diameter when the particle diameter is actually measured. The specific surface area is a value measured by a BET three-point method with a specific surface area measuring device (AUTOSORB-1 manufactured by QUANTACHROME).

  In the conventional manufacturing process, the photosensitive paste is exposed and cured by a photolithography method. Therefore, in order to secure a gap for passing the exposure light, the black particle size is in the range of micron order to submicron order. It was necessary to use powder. However, since the offset printing method is used in the present invention, it is possible to use a powder having a smaller particle diameter than that used in the prior art. In the present invention, by using an oxyhydroxide powder having a smaller particle diameter than that of the black oxide powder originally used by the inventors, it is more than the case of using the black oxide powder than the prior art. However, it is possible to produce a black film that is fine and free from line disturbance.

  The reason why the content of the oxyhydroxide powder in the paste composition for black film in the present invention is 10 to 50% by mass is that the lower limit is less than 10% by mass, which is sufficient for the black film to be formed. Since blackness cannot be obtained, a black film having a high shielding rate cannot be produced, and when the upper limit of 50% by mass is exceeded, the proportion of the powder having a small particle size in the entire paste increases and printing This is because the line shape is sometimes disturbed. Moreover, the content ratio of the glass powder is set to 5 to 30% by mass, when the lower limit is less than 5% by mass, the adhesion with the substrate is deteriorated. This is because the blackness decreases and the shielding rate decreases. By making the content rate of the oxyhydroxide powder and glass powder in the paste composition for black films into the said range, the paste composition for black films suitable for offset printing is obtained. Among these, it is preferable that the content rate of oxyhydroxide powder is the range of 15-30 mass%, and it is preferable that the content rate of glass powder is the range of 8-20 mass%.

The average particle size of the oxyhydroxide powder is in the range of 0.01 to 0.2 μm, and the specific surface area is in the range of 5 to 80 m ² / g. When the oxyhydroxide powder has an average particle size and specific surface area within the above ranges, a black film paste composition suitable for offset printing and suitable for producing a fine pattern black film can be obtained. Among these, the average particle diameter is preferably in the range of 0.05 to 0.1 μm, and the specific surface area is preferably in the range of ²⁰ to 65 m ² / g.

  The oxyhydroxide powder is a metal oxyhydroxide containing one metal element selected from the group consisting of Co, Cr, Mn, Fe and Ni, or a composite oxyhydroxide containing two or more metal elements, or A mixture of these is preferable. Of these, Mn oxyhydroxide, Fe oxyhydroxide, Co oxyhydroxide, Ni oxyhydroxide, a composite oxyhydroxide of Co and Cr, or a mixture of Ni oxyhydroxide and Co oxyhydroxide is particularly preferable. .

  Here, the manufacturing method of an oxyhydroxide is demonstrated. First, one or more desired metal salts are selected from Co, Cr, Mn, Fe and Ni used for the paste composition for black film, and dissolved in water to obtain an aqueous solution. At this time, the metal salt is preferably a sulfide or chloride that is easily soluble in water. Next, oxyhydroxide is obtained by supplying sufficient oxygen of about 100 cc / min to the hydroxide generated in the aqueous solution. The produced oxyhydroxide in the aqueous solution is recovered by filtration and then dried to obtain a powdery oxyhydroxide. The particle size of the oxyhydroxide powder obtained at this time is 0.01 to 0.2 μm. Note that the color of the paste composition for black film produced using the obtained oxyhydroxide powder is not black because it depends on the color exhibited by the oxyhydroxide, but at the firing stage, Oxidation of the oxide results in a black color that can be applied to PDP shielding.

The glass powder contains one or more oxides 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, 400 to 400 A frit glass having a softening point of 550 ° C. is preferable. The softening point of the frit glass is preferably 450 to 550 ° C. The reason why the softening point is within the above range is that, in the frit glass having a softening point less than the lower limit, the glass powder hinders the binder resin from being removed from the binder resin constituting the organic vehicle in the paste composition. This is because the black film produced using the paste composition causes a problem that the resistance value increases. Moreover, in the frit glass whose softening point exceeds the upper limit value, the glass powder cannot provide a sufficient anchor between the glass substrate. The average particle size of the glass powder is preferably 0.05 to 0.7 μm. If it is less than 0.05 μm, a black film excellent in adhesion to the substrate can be produced, but at present, it takes too much cost and time to obtain a glass powder of 0.05 μm or less. On the other hand, when the thickness exceeds 0.7 μm, voids called pores are likely to be formed in the vicinity of the glass powder having a large particle size, and there is a tendency that a black film having a nonuniform composition and a low shielding rate is formed. 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.

  It is preferable to use an organic vehicle prepared by dissolving an alkali-soluble resin in an organic solvent. A dispersant for improving the dispersibility of the oxyhydroxide powder and the glass powder, a viscosity modifier for adjusting the paste viscosity, and the like are added as necessary.

  The method for producing a black film according to the present invention is characterized in that a black film is produced on a substrate by the offset printing method using the paste composition for black film. Since the offset printing method is used in the present invention, a paste composition using a powder having a particle size smaller than that of a paste composition used in the prior art such as a photolithography method can be used. In the present invention, a fine black film without line disturbance can be produced by using a paste composition using an oxyhydroxide powder having a small particle size. By using this oxyhydroxide powder, the oxygen required when the oxyhydroxide powder is oxidized into an oxide in the firing step is the oxygen that the oxyhydroxide has in its structure. Can be used. Therefore, even if oxygen is not given from the outside, the oxyhydroxide can be oxidized and becomes black enough to be applied to shielding with PDP. Further, in the photolithography method used in the conventional manufacturing process, the paste composition is applied to the entire desired surface and then exposed, and unnecessary portions are discarded and removed in a subsequent process. Since the black film is produced by the offset printing method, it is only necessary to apply the paste composition only to a necessary portion, so that an effect of improving the material utilization efficiency can be obtained. Further, the number of steps can be reduced instead of complicated steps such as coating, exposure, and development in the photolithography method. Furthermore, in the offset printing method, after forming the black layer, after forming the white layer on the formed unfired black layer, it is possible to simultaneously fire the two layers of the black layer and the white layer. It can be simplified.

  Next, a method for producing a front substrate for PDP using the method for producing a black film of the present invention will be described.

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. Specifically, the transparent electrode 23 uses an oxide film such as ITO (Indium Tin Oxide) or SnO _2, and is formed by a vacuum film forming method such as sputtering or vapor deposition or a CVD (Chemical Vapor Deposition) method.

  Next, as shown in FIG. 2C, the black layer 16b is formed on the formed transparent electrode 23 by applying and baking the paste composition for black film of the present invention by an offset printing method. In the method of the present invention, since the coating film is formed by the offset printing method, a powder having a smaller particle diameter can be used, and further, for a black film using an oxyhydroxide powder having a smaller particle diameter than the black oxide powder. Since the paste composition is used, it is possible to produce a black film having a higher density, a higher shielding rate, and a fine and free of line disturbance. In addition, the temperature required for the oxyhydroxide to be oxidized and sufficiently blackened compared to the firing temperature of the paste composition is about 400 to 500 ° C., which is lower than the firing temperature. At the same time, the oxyhydroxide powder can be blackened. Subsequently, as shown in FIG. 2D, a highly conductive white conductive paste containing conductive powder such as Ag, Au, Pt, or Pd is applied to the formed black layer 16b and baked. Thereby, the white layer 16a is formed. Thereby, the bus electrode 16 composed of the black layer 16b and the white layer 16a is formed.

  The black film paste composition of the present invention is applied by an offset printing method to form a black layer 16b, and then a white conductive paste is applied by an offset printing method to form a white layer on the black layer 16b. It is also possible to form the bus electrode 16 composed of the black layer 16b and the white layer 16a by forming 16a and firing the black layer 16b and the white layer 16a simultaneously. In such a method, the two layers of the coated film are simultaneously fired, so that the process can be shortened.

  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 and baking the paste composition for black film of the present invention on the formed transparent dielectric layer 21 by an offset printing method. To do. By forming the black stripe 24, the external light reflectance is reduced and the contrast is improved. In the method of the present invention, since the coating film is formed by the offset printing method, a powder having a smaller particle diameter can be used, and further, for a black film using an oxyhydroxide powder having a smaller particle diameter than the black oxide powder. Since the paste composition is used, it is possible to produce a black film having a high density, a high shielding rate, and a fine and free of line disturbance.

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).

  Next, examples of the present invention will be described in detail together with comparative examples.

<Examples 1-8 and Comparative Examples 1-4>
Prepare the oxyhydroxide powder, glass powder and organic vehicle shown in the following Table 1 and Table 2, and add the oxyhydroxide powder and organic vehicle to the organic vehicle so as to have the contents shown in the following Table 1 and Table 2. Glass powder was mixed to prepare a black film paste composition. The average particle diameter and specific surface area of the oxyhydroxide powders shown in Table 1 and Table 2 below are values measured by the method described above.

  The organic vehicle was prepared by dissolving an alkali-soluble resin in an organic solvent. Additives such as a dispersant and a viscosity modifier are appropriately added to the organic vehicle depending on the black film paste composition to be produced. The dispersant was appropriately added to improve the dispersibility of the black oxide powder and the glass powder, and the viscosity modifier was appropriately added to adjust the viscosity of the paste.

<Comparison test 1>
Using the black film paste compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4, the following offset printability, minimum line width, and storage stability were evaluated. The results are shown in Table 3 below.

  (1) Offset printability: Transferability when the black film paste composition was printed on a glass substrate with an offset printing machine (manufactured by JEOL Ltd.) was evaluated as offset printability. When the black film paste composition is transferred from the blanket onto the glass substrate, the line shape is not disturbed and 100% is transferred and the blanket has no residual paste. Although it was evaluated as “good” and some blurring and disturbance were confirmed in the line shape, there was no residual paste composition on the blanket and 100% transfer was possible. An evaluation of “impossible” was made when spots or defects were confirmed, or when paste that could not be transferred remained on the blanket.

  (2) Minimum line width: The line width capable of offset printing is represented by four line widths of 50 μm, 70 μm, 100 μm, and 150 μm, and this line width is defined as the minimum line width.

  (3) Storage stability: The black film paste composition is stored in a low-temperature storage kept at 15 ° C, and the time until deterioration or precipitation occurs in the stored black film paste composition is defined as the number of days that can be stored. The number of days that can be stored was used as an index of storage stability.

  Next, the black film paste compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were applied onto a glass substrate by a screen printing method, and the applied film was baked at 580 ° C. for 30 minutes to obtain a black film. Was made. About the produced black film, the following blackness and adhesiveness were evaluated. The results are shown in Table 3 below.

  (4) Blackness: The blackness of the produced black film was measured using a color computer (manufactured by Suga Test Instruments Co., Ltd.). Specifically, a Y value representing blackness when an XYZ color difference was measured was obtained. The smaller the Y value, the higher the blackness.

  (5) Adhesion: The black film was evaluated for adhesion by a cross-cut tape test method based on JIS-K5400. The specific evaluation of the adhesion is a “good” evaluation when the black film on the tape side is not transferred and the black film adheres to 100% on the glass substrate when the grid tape tape test is performed. When the black film adheres to both the tape and the glass substrate due to internal destruction, it was evaluated as “Yes”. Many black films adhered to the tape side, and the glass substrate was observed at the interface after thinning. The evaluation was “impossible”.

  As is clear from Table 3, when Examples 1 and 2 were compared with Comparative Examples 1 and 2, Examples 1 and 2 showed values superior to Comparative Examples 1 and 2 in all evaluation items. When Examples 3 and 4 are compared with Comparative Examples 1 and 2, in Example 3, the same results as in Comparative Examples 1 and 2 are obtained in adhesion, and in Example 4, the offset printability is equivalent to that in Comparative Example 2. Except for the results, the results of Examples 3 and 4 were superior to those of Comparative Examples 1 and 2 in all other items. From this, it was found that it is effective to use oxyhydroxide powder. Further, when Examples 5 and 6 were compared with Comparative Examples 1 and 2, in Examples 5 and 6, results superior to Comparative Examples 1 and 2 were obtained in all evaluation items. From this, as the oxyhydroxide powder used in the present invention, a composite oxyhydroxide containing two or more metal elements, a metal oxyhydroxide containing one metal element, or two or more metal elements It was confirmed that the effect was obtained even when a mixture of composite oxyhydroxides containing was used. Further, when Examples 7 and 8 are compared with Comparative Examples 3 and 4, Comparative Example 3 does not provide sufficient results in blackness as compared with Example 7, and Comparative Example 4 compared with Example 8. As a result, sufficient results were not obtained in the adhesion. From this, in the paste composition for black films of this invention, the content rate of an oxyhydroxide powder is the range of 10-50 mass%, and the content rate of a glass powder is the range of 5-30 mass%. Has been confirmed to be effective.

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.

Claims (4)

A black film paste composition for producing a black film by an offset printing method on a windshield substrate constituting a plasma display panel,
The composition contains 10-50 mass% oxyhydroxide powder, 5-30 mass% glass powder, and the balance is an organic vehicle, and the average particle diameter of the oxyhydroxide powder is 0.01. A paste composition for black film, characterized in that it is ˜0.2 μm and the specific surface area of the oxyhydroxide powder is 5 to 80 m ² / g.   A metal oxyhydroxide containing one metal element selected from the group consisting of Co, Cr, Mn, Fe and Ni, or a composite oxyhydroxide containing two or more metal elements, or The black film paste composition according to claim 1, which is a mixture thereof.   The glass powder has a softening point of 450 to 550 ° C. containing one or more oxides selected from the group consisting of lead oxide, bismuth oxide, zinc oxide, boron oxide, silicon oxide, phosphorus oxide, calcium oxide and titanium oxide. The black film paste composition according to claim 1, wherein the paste composition is a frit glass.   A method for producing a black film, comprising producing a black film on a substrate by an offset printing method using the paste composition for a black film according to any one of claims 1 to 3.

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