JP2005022962A - Glass composition, mixture, paste, green sheet and PDP - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass having high water resistance that is lead-free and capable of lowering the working temperature from 550 ° C. and having a desired coefficient of thermal expansion.
SOLUTION As glass components, 35 mol% or more and 45 mol% or less of P ₂ O ₅ , 45 mol% or more and 55 mol% or less of ZnO, and 5 mol% or more and 15 mol% or less of CaO, SrO. And an oxide of one or more alkaline earth metals selected from the group consisting of BaO.
[Selection] Figure 1

Description

  The present invention relates to a glass composition, a mixture, a paste, and a green sheet suitable for use in a plasma display panel (PDP) and the like.

  In a PDP, a large number of minute discharge cells are usually arranged vertically and horizontally (in a matrix), and characters and figures are displayed by causing discharge of the necessary portions of cells. This PDP is classified into an AC type in which a metal electrode is covered with a glass dielectric material in terms of an electrode structure, and a DC type in which the metal electrode is exposed in a discharge space.

For example, an AC-type PDP is configured by covering another glass substrate serving as a front glass through a plurality of barrier ribs (partitions) formed on a glass substrate at predetermined intervals. A display electrode and a dielectric layer covered with a protective film such as MgO (magnesium oxide) are formed on the surface of the front glass substrate facing the glass substrate, and the surface is finely divided by the glass substrate, the front glass substrate, and the barrier rib. In a space (hereinafter referred to as a discharge cell), an address electrode and a phosphor layer, which are anode discharge electrodes, are formed, and the address electrode is protected by an insulating layer (dielectric layer) as necessary. A discharge gas is injected into the discharge cell.
In the PDP configured as described above, characters and figures can be displayed by applying a voltage between the display electrode and the address electrode to selectively discharge the phosphor layer in the discharge cell. Yes.

Patent document 1 is disclosed as a glass composition of a barrier rib and an insulating layer (dielectric) formed on the glass substrate of the PDP. However, in the conventional glass composition such as Patent Document 1 described above, since it contains a lead component, the density of the glass composition is large, so that the glass substrate is increased in weight and the glass substrate is warped. In recent years, it has been necessary to consider the causes of environmental pollution, and there has been a great demand for using lead-free materials.
In order to eliminate these points, the glass which does not contain a lead component is disclosed by patent documents 2-4. These techniques include those containing lead-free glass such as phosphate glass and ceramic components such as alumina.

In addition, in the PDP, the properties required for the glass-ceramic composite material used for the barrier rib are not only excellent mechanical properties such as bending strength, but also light from the phosphor layer due to plasma generation to the front surface of the panel. In order to reflect well and improve luminance, it is required to have a high light reflection characteristic in visible light. Moreover, in order to cope with the temperature rise when using the PDP, it is necessary to keep the thermal expansion coefficient between the barrier rib and the glass substrate within a certain range.
From such a request, alumina is sometimes used as a ceramic component.
Japanese Patent Laid-Open No. 3-170346 Japanese Patent Laid-Open No. 8-301631 JP-A-11-322365

However, in the technique of Patent Documents 2 and 3, but includes a P ₂ O ₅ in a large amount to lower the sintering temperature, when containing a large amount of P ₂ O _5, the thermal expansion coefficient of the glass is the glass substrate It is necessary to add a large amount of ceramic filler to match the thermal expansion coefficient with that of the glass substrate. By adding a large amount of this filler, the structure after firing becomes porous, the strength is reduced, and the discharge is further reduced. There was a problem that the characteristics also deteriorated.
Further, there is a problem that the firing temperature becomes higher in the case of reducing the P ₂ O _5.

The glass composition used for PDP is required to have the following characteristics.
1. Thermal expansion coefficient α = (85 ± 5) × 10 ⁻⁷ / ° C.
2. Working temperature (firing temperature) Tw ≦ 550 ° C
Here, 1. Is because the thermal expansion coefficients of the glass composition and the glass substrate are not too different. This is because if the firing temperature is high, the glass substrate is likely to warp.

Further, in each of the above patent documents, P ₂ O ₄ , ZnO, MgO, CaO, BaO, SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , TiO, MoO, etc. are included as substances contained in the glass composition. Although described, the combination of such lead-free materials can lower the softening point for lowering the working temperature (firing temperature), and at the same time, becomes a crystalline material that cannot be used for the PDP front glass substrate. There has been no known composition that maintains vitreousness (amorphous).

  The present invention is lead-free, maintains water resistance, has a desired coefficient of thermal expansion, and has a working temperature (firing temperature) in order to reduce as much as possible the thermal strain generated in the glass substrate when used in a PDP. An object of the present invention is to provide a glass composition capable of lowering the temperature from 550 ° C. and maintaining the glass (amorphous) without being crystallized.

  Furthermore, the object of the present invention is to provide a barrier rib or dielectric, paste, mixture, which maintains lead-free water resistance, matches the coefficient of thermal expansion with the glass substrate, and prevents cracks from occurring with the glass substrate. And providing a PDP.

The present invention is a glass composition containing no lead,
In the present invention, as a glass component,
35 mol% or more and 45 mol% or less of P ₂ O ₅ ,
45 mol% or more and 55 mol% or less of ZnO;
One or more alkaline earth metal oxides selected from the group consisting of 5 mol% or more and 15 mol% or less of CaO, SrO, and BaO;
The above-mentioned problem was solved by including.
In the present invention, it is desirable that the ratio ZnO / P ₂ O ₅ between ZnO and P ₂ O ₅ is greater than 1.
The present invention also provides a glass component
ZnO, P ₂ O ₅ , SrO,
0 wt% or more and 1.5 wt% or less selected from the group consisting of Al ₂ O ₃ , SiO ₂ , CaO, K ₂ O, PbO, B ₂ O ₃ , CuO, Fe ₂ O ₃ , SO ₃ and NiO One or more oxides;
Can be included.
The mixture of the present invention comprises the above glass composition, alumina, titania, zircon, silica, cordierite, mullite, β-eucryptite, spodomen, anorsite, celsian, forsterite and titanic acid as ceramic fillers. It is preferable to mix one or more ceramics selected from the group consisting of aluminum.
The ceramic filler material may have a particle size in a range of 0.05 to 0.5 μm.
The paste of the present invention desirably contains the above glass composition or the above mixture, a resin, and a solvent.
The green sheet of this invention may contain said glass composition or said mixture, resin, and a solvent.
The barrier rib of the present invention can be obtained by firing the paste or the green sheet.
The dielectric of the present invention can employ means for firing the above paste or the above green sheet.
The PDP of the present invention has at least one of the barrier ribs or the dielectric.

The glass composition of the present invention is a glass composition containing, as a glass component, P, Zn, and one or more selected from Ca, Sr, and Ba in the above component ratio, or glass. As a component, P ₂ O ₅ , ZnO, and one or more alkaline earth metal oxides selected from the group consisting of CaO, SrO, and BaO are included in the above component ratio. Thus, in this glass composition, the working temperature Tw (firing temperature) is set lower than 550 ° C. while maintaining the water resistance of the dielectric (insulator) without containing a lead component, and glass (non-crystalline). Quality) can be maintained.
Therefore, the glass substrate is not distorted, and does not contain a lead component, so that the weight of the dielectric can be reduced, the environment is not polluted, and P ₂ O ₅ is relatively small. The water resistance of the dielectric can be improved. Furthermore, the coefficient of thermal expansion is α = (85 ± 5) × 10 ⁻⁷ / ° C.
In this range, the barrier rib and the dielectric do not crack.

Furthermore, the present invention provides ZnO, P ₂ O ₅ , SrO, and 0 wt% or more and 1.5 wt% or less of Al ₂ O ₃ , SiO ₂ , CaO, K ₂ O, PbO, By including one or more oxides selected from the group consisting of CuO, B ₂ O ₃ , Fe ₂ O ₃ , SO ₃ and NiO, without causing distortion in the glass substrate, Since the lead component is not contained, the weight of the dielectric can be reduced, the environment is not polluted, and the P ₂ O ₅ content is relatively small, so that the water resistance of the dielectric can be improved. Furthermore, the coefficient of thermal expansion is α = (85 ± 5) × 10 ⁻⁷ / ° C.
In this range, the barrier rib and the dielectric do not crack.

  The present invention also provides the above glass composition with alumina, titania, zircon, silica, cordierite, mullite, β-eucryptite, spodomen, anorsite, celsian, forsterite and aluminum titanate as ceramic fillers. It is a mixture in which one or more ceramics selected from the group consisting of: In this mixture, the strength of the barrier ribs and dielectric obtained after firing can be improved by mixing the ceramic filler with the glass composition.

  The glass composition or mixture is mixed with a resin (polymer resin) and a solvent to produce a barrier rib or dielectric paste, or the glass composition or mixture is mixed with a polymer resin and a solvent. It is preferable to produce a barrier rib or a dielectric green sheet by mixing. The glass composition or mixture is preferably fired to form a dielectric, or an FPD barrier rib or insulating layer (dielectric layer). Further, a paste containing a conductor powder, a resistor powder or a dielectric powder, a polymer resin, and a solvent is prepared on the glass or the mixture, applied to a substrate, dried and fired, and then a conductor. It is preferable to form a thick film for a resistor or a dielectric.

According to the present invention, as a glass component, 35 mol% or more and 45 mol% or less of P ₂ O ₅ , 45 mol% or more and 55 mol% or less of ZnO, and 5 mol% or more and 15 mol% or less of CaO. , SrO and BaO, and one or two or more alkaline earth metal oxides, thereby reducing the working temperature Tw (firing temperature) to less than 550 ° C. and glass ( Amorphous state can be maintained, the water resistance can be improved, and the coefficient of thermal expansion α can be set in the range of 8510 ^{−7 to} 90 × 10 ⁻⁷ / ° C.

  Hereinafter, an embodiment of a glass composition, a mixture, a paste, a green sheet, a barrier rib, and a PDP according to the present invention will be described with reference to the drawings.

In this embodiment, when each element is expressed in terms of oxide, as shown in the triangular composition diagram of FIG. 1 as a range surrounded by points A, B, C, D, E, and F, as a glass component, 35 mol. % And 45 mol% or less of P ₂ O ₅ , 45 mol% or more and 55 mol% or less of ZnO, and 5 mol% or more and 15 mol% or less of CaO, SrO and BaO 1 And an oxide of two or more alkaline earth metals.
In addition, in FIG. 1, the example of the vitrification formation range which selected SrO as an alkali metal oxide is shown.

The reason why P ₂ O ₅ is limited to 35 mol% or more and 45 mol% or less is that glass cannot be formed if it is 35 mol% or less, and if it exceeds 45 mol%, the water resistance of the fired product is poor and the thermal expansion of the fired product. This is because the rate becomes higher than the thermal expansion coefficient of the glass substrate. Incidentally, from the viewpoint of prevention of reduction and water resistance deterioration of the rise prevention and softening point of the thermal expansion coefficient, it is more preferable that the P ₂ O ₅ is less than 38 mol% or more and 42 mol%. Further, the reason why ZnO is limited to 45 mol% or more and 55 mol% or less is that if it is less than 45 mol%, the coefficient of thermal expansion becomes high, and if it exceeds 55 mol%, the softening point becomes high. More preferably, it is 52 mol%.

  The reason why the oxide of one or more alkaline earth metals selected from the group consisting of CaO, SrO and BaO is limited to 5 mol% or more and 15 mol% or less is that the softening point is less than 5 mol%. This is because there is a problem that it becomes high, and as shown in the triangular composition diagram of FIG. 1, if it exceeds 15 mol%, there is a problem that it does not become glass, and this oxide is more preferably 8 to 12 mol%. . Here, in FIG. 1, white circles indicate a glassy body, and black circles indicate a non-glass state, that is, a crystalline state. That is, the range above the solid line indicated by the symbol M in FIG.

  On the other hand, the ceramic filler is one or two selected from the group consisting of zircon, alumina, titania, cordierite, mullite, β-eucryptite, spodumene, anorthite, celsian, forsterite and aluminum titanate. Contains more than seed ceramics. The reason why the ceramic filler is mixed with the glass composition is to increase the strength of the barrier rib when, for example, a PDP barrier rib using the glass composition is formed on a glass substrate.

[1] Preparation Method of Glass Composition Powder In the preparation of the glass sample of this embodiment, (NH ₄ ) 3 PO ₄ .3H ₂ O (95%), ZnO (99.9%), and SrCO ₃ (99. 99%) was used. Each powder is selected from the group consisting of P ₂ O ₅ : 35 mol% or more and 45 mol% or less, ZnO: 45 mol% or more and 55 mol% or less, CaO, SrO and BaO in terms of oxides or Two or more alkaline earth metal oxides were weighed in a ratio of 5 mol% or more and less than 15 mol%. A batch of about 0.03 kg mixed at the above composition ratio and a predetermined composition ratio was melted at 1200 ° C. for 1 hour using an alumina crucible. About a part of these melts were poured out on a carbon plate and cooled, and then finely crushed in an alumina mortar for pulverization, and classified using a 325 # (mesh) sieve to obtain glass powder.

[1-2] Vitrification confirmation About the powder sample obtained by cooling the melt and subjecting it to pulverization classification, measurement was performed in the range of diffraction angle θ = 10 to 70 ° using an X-ray diffractometer (XRD). And the presence or absence of vitrification was confirmed.

[1-3] Measurement of coefficient of thermal expansion For the sample for measuring the coefficient of thermal expansion, the melt was poured into a carbon mold, and then annealed for 1 hour near the glass transition temperature Tg. The sample obtained after annealing was cut into a 3 mm × 3 mm × 15 mm rod shape, and each surface was polished and used as a measurement material.
The measurement is carried out using a thermomechanical analyzer with α-Al ₂ O ₃ having the same shape as the sample as a standard sample at a temperature rising rate of 5 ° C./min, and a coefficient of thermal expansion (α )

[1-4] Determination of working temperature Tw A powdery sample is formed into a 12 mmφ × 5 mm pellet, the molded body is placed on a PDP substrate glass, and the glass is inclined by 30 ° to a predetermined temperature. And baked for 30 minutes. The temperature at which the glass sample started to cause softening flow was taken as the working temperature (Tw).

[2] Method for preparing mixture From powder of the above glass composition and alumina, titania, zircon, silica, cordierite, mullite, β-eucryptite, spodomen, anorthite, celsian, forsterite and aluminum titanate One or two or more ceramic powders selected from the group consisting of (ceramic filler powder) are weighed so as to have a predetermined volume ratio, and mixed in the atmosphere using a ball mill or the like for 1 to 24 hours, A mixture is obtained.

[3] Method for Producing Glass Paste, Glass-Ceramic Mixed Paste and Green Sheet For the above glass composition powder or mixture, polymer resin such as ethyl cellulose (EC) or acrylic resin, pure water as a solvent, α- A paste is obtained by adding terpineol, butyl carbitol acetate, or the like so as to obtain a predetermined weight ratio and sufficiently kneading with a three roll or the like.
The ceramic filler powder in the mixture is preferably in the range of 5 to 30% by weight with respect to the weight of the glass composition powder, and 30% by volume or less with respect to the volume of the glass composition powder. It is preferable that This is because if the powder of the ceramic filler is 30% by weight or more and 30% by volume or more, the dielectric obtained by firing becomes porous, which is not preferable. Moreover, it is preferable that the compounding ratio of each component of a paste is 70 to 90 weight% of the powder of a glass composition and a ceramic filler material, 1 to 5 weight% of polymer resins, and 8 to 25 weight% of a solvent. Moreover, you may produce a green sheet using this paste.

[4] Dielectric production method The powder or mixture of the glass composition is formed into a predetermined shape by a press molding method, or the paste is formed into a predetermined shape by a screen printing method, an extrusion molding method, an injection molding method, or the like. Then, the molded body is allowed to stand in an oven at 120 ° C. to evaporate the solvent and baked at 550 ° C. or lower to obtain a dielectric.

[5] Method for Producing Conductor Paste or Resistor Paste Add the conductor powder or resistor powder, the polymer resin, and the solvent to the powder or mixture of the glass composition, By fully kneading, a paste is obtained.
As the conductive powder Ag, Ag-Pd, Ag- Pt, Au, Al, etc. are used, _{RuO 2,} as the resistive powder Pb ₂ Ru ₂ O 6.5, the Ag-Pd or the like is used Is preferred. In addition, it is preferable to use ethyl cellulose, acrylic resin or the like as the polymer resin, and α-terpineol, butyl carbitol acetate or the like as the solvent.

  In addition, the compounding ratio of each component in the paste is 5 to 45% by weight for the glass composition powder and ceramic filler, 50 to 90% by weight for the conductor powder or resistor powder, and 1 to 5% for the polymer resin. %, And the solvent is preferably 4 to 25% by weight. The paste is patterned into a predetermined shape by screen printing or the like, dried and baked to obtain a conductor thick film or a resistor thick film.

  Next, a method for producing PDP barrier ribs by the sand blasting method using the glass-ceramic mixed paste will be described.

As shown in FIG. 2, first, a paste film 11 is formed on a glass substrate 10 by the table coater method using the paste. Next, the glass substrate 10 having the paste film 11 is dried at a temperature of 100 to 200 ° C. for 10 to 30 minutes, and then pre-baked at a temperature of 300 to 400 ° C. for 0.5 to 3 hours. After laminating a photosensitive dry film resist 12 (hereinafter referred to as DFR) on the surface of the paste film 11 subjected to the pre-baking, a film mask 13 is placed on the DFR 12 and irradiated with ultraviolet rays having a central wavelength of 254 nm. Perform exposure. Next, a Na ₂ CO ₃ aqueous solution having a concentration of 0.1 to 5% is sprayed on the exposed glass substrate 10 to remove an unexposed portion, and development is performed. By performing this development, the glass substrate 10 having the DFR pattern layer 16 is subjected to sand blasting using abrasive grains such as alumina powder, and the portion where the DFR pattern layer 16 is not formed is removed. A rib-like object 18 is formed on the substrate. Furthermore, the barrier rib 14 is formed on the glass substrate 10 by baking at a temperature of 550 ° C. or less for 0.1 to 2 hours.

  FIG. 3 shows a second embodiment of the present invention (a method for producing a barrier rib for PDP by a thick film printing method).

  In this embodiment, the paste is aligned on the surface of the glass substrate 10 by a thick film printing method in a predetermined pattern and repeatedly applied, and then dried at 100 to 200 ° C. for 10 to 30 minutes. A paste film 31 is formed thereon. This process is repeated many times to form the paste film 31 at a predetermined height, followed by baking at 550 ° C. or lower, thereby forming the barrier ribs 34 on the glass substrate 10 with a predetermined interval. Although not shown, a solid film is formed on the glass substrate by screen printing using the paste, and the substrate is dried at a temperature of 100 to 200 ° C. for 10 to 30 minutes. A dielectric layer (white insulating layer) may be formed on the substrate by baking for 5 to 3 hours.

  FIG. 4 shows a third embodiment of the present invention (a method for manufacturing a back panel in an AC type PDP).

  First, a conductive paste such as Ag is formed on the glass substrate 10 by a screen printing method at a predetermined interval to form a band-like pattern having a width of 50 to 200 μm and dried at a temperature of 100 to 200 ° C. for 10 to 30 minutes. The address electrode 51 is formed on the glass substrate 10 by baking at 550 to 580 ° C. for 0.1 to 1 hour. A paste film is formed on the glass substrate 10 by the screen printing method using the paste produced in the first embodiment and dried at a temperature of 100 to 200 ° C. for 10 to 30 minutes, and then a temperature of 550 ° C. or less. The dielectric layer 52 is formed on the glass substrate 10 by baking at 0.5 to 3 hours.

  Next, a paste film 11 is formed on the glass substrate 10 by the table coater method using the paste prepared in the first embodiment, and dried at a temperature of 100 to 200 ° C. for 10 to 30 minutes. Pre-baking is performed at ˜400 ° C. for 0.5 to 3 hours. After laminating the DFR 12 on the surface of the temporarily fired paste film 11, the film mask 13 is placed on the DFR 12, and ultraviolet light having a central wavelength of 254 nm is irradiated for exposure. Next, the exposed glass substrate 10 is sprayed with an aqueous solution of Na2CO3 having a concentration of 0.1 to 5% to remove the unexposed portion and develop. By performing this development, the glass substrate 10 having the DFR pattern layer 16 is subjected to sand blasting using abrasive grains such as alumina powder, and the paste film 11 where the DFR pattern layer 16 is not formed is removed. Ribs 18 are formed on the glass substrate 10 via the dielectric layer 52.

  The glass substrate 10 is baked at a temperature of 550 ° C. or lower for 0.1 to 2 hours to form the barrier ribs 14 on the glass substrate 10 with the dielectric layer 52 interposed therebetween. Further, on the inner surface of the cell 17 between the barrier ribs 14, a paste made of phosphor powder that emits red, green, or blue light by ultraviolet rays is used, but printing is performed by screen printing, respectively, at a temperature of 100 to 200 ° C. After drying for ˜30 minutes, the AC type PDP back plate 50 is obtained by baking at a temperature of 450 to 550 ° C. for 0.1 to 2 hours.

  5 and 6 show a fourth embodiment of the present invention (a method for manufacturing a PDP barrier rib using a blade having comb teeth).

  The inventors adopted a blade deforming process (Blade deforming process) in which a barrier rib paste was applied over the entire surface of the glass substrate, and then the paste was scraped off using a blade having a fine irregular shape at the tip. In this method, barrier ribs having a desired shape can be obtained and the process can be shortened, and the paste can be reused even after the unnecessary paste is removed from the substrate. Therefore, in the most expensive process in the PDP manufacturing process, It is characterized in that barrier ribs can be formed at low cost. In FIG. 4, reference numeral 10 denotes a glass substrate, 71 denotes a paste film, 72 denotes a blade, 72a denotes an edge, 72b denotes a comb tooth, and 73 denotes a rib-like object.

  The blade 72 has a plurality of comb teeth 72b formed at equal intervals and in the same direction. The blade 72 is made of a metal, ceramic, plastic, or the like that does not react with the paste or dissolve in the paste, and in particular, a ceramic or an alloy of Fe, Ni, Co base is preferable from the viewpoint of dimensional accuracy and durability.

  Due to the movement of the blade 72 or the glass substrate 10, the portion of the paste applied to the surface of the glass substrate 10 corresponding to the comb teeth 72b of the blade 72 moves to or is swept away from the comb teeth 72b. Only the paste located in the gap between them remains on the glass substrate 10 and the ceramic capillary ribs 73 are formed on the surface of the glass substrate 10. When the depth of the comb-tooth groove is larger than the thickness of the paste film 71, the paste swept away when moving the blade 72 or the glass substrate 10 enters the groove, and the height of the paste film 71 or more is increased. The rib-like product 73 can be formed.

The rib-like material 73 formed in this manner is dried at 100 to 200 ° C. for 10 to 30 minutes and baked to form the barrier rib 74 shown in FIG.
Firing at this time is 550 ° C. or less for about 0.1 to 2 hours.

  7 and 8 show a fifth embodiment of the present invention (a method for producing a PDP barrier rib and a PDP dielectric layer using a blade having comb teeth).

  In this embodiment, the edge 72a of the blade 72 having comb teeth 72b is levitated to a predetermined height from the surface of the glass substrate 10 with respect to the paste film 71 formed by applying the paste to the surface of the glass substrate 10. By moving the blade 72 or the glass substrate 10 in a certain direction in the state, a rib foundation layer 91 is formed on the surface of the glass substrate 10, and a rib-like object 92 is formed on the rib foundation layer 91 (FIG. 7).

  The rib base layer 91 and the rib-like material 92 are formed on the glass substrate 10 shown in FIG. 8 by drying at 100 to 200 ° C. for 10 to 30 minutes and firing at 550 ° C. or less for 0.1 to 2 hours. The dielectric layer 93 and the barrier rib 94 formed on the dielectric layer 93 are formed.

A PDP can be manufactured using the barrier rib of each of the above embodiments.
As shown in FIGS. 9 and 10, the AC type PDP 20 is configured by covering a front glass substrate 23 via barrier ribs 14 formed on the rear glass substrate 10 at a predetermined interval. A protective film 24 a is formed on the surface of the front glass substrate 23 facing the back glass substrate 10 via the display electrode 26 and the transparent dielectric layer 27.
A large number of discharge cells 28 are defined by the rear glass substrate 10, the front glass substrate 23, and the barrier ribs 14, and address electrodes are located on the rear glass substrate 10 so as to be located in the discharge cells 28 and to face the display electrodes 26. 29 is formed. In the discharge cell 28, a phosphor layer 21 is formed from the side surface of the barrier rib 14 to the upper surface of the rear glass substrate 10. Further, a discharge gas is injected into the discharge cell 28.

  Next, examples of the barrier rib or dielectric layer paste of the present invention will be described in detail together with comparative examples.

<Example 1>
In mole% ratio,
SrO: ZnO: P ₂ O ₅ = 10: 50: 40
A glass powder (glass composition) was prepared.
Specifically, the glass powder is prepared by mixing (NH ₄ ) ₃ PO ₄ .3H ₂ O as P ₂ O _{5 and} SnCO ₃ as ZnO and SnO so as to be predetermined components, respectively, A glass composition was prepared according to the method for preparing a glass composition powder, and this was designated as Example 1.

<Examples 2 to 10>
Similarly, a glass powder (glass composition) containing the following ratio by mol% was prepared in the same manner as in Example 1 and used as each Example.

Example 2
SrO: ZnO: P ₂ O ₅ = 10: 55: 35
Example 3
SrO: ZnO: P ₂ O ₅ = 10: 60: 30
Example 4
CaO: ZnO: P ₂ O ₅ = 10: 50: 40
Example 5
CaO: ZnO: P ₂ O ₅ = 10: 45: 45
Example 6
CaO: ZnO: P ₂ O ₅ = 12: 45: 43
Example 7
BaO: ZnO: P ₂ O ₅ = 10: 50: 40
Example 8
BaO: ZnO: P ₂ O ₅ = 15: 45: 40
Example 9
BaO: ZnO: P ₂ O ₅ = 5: 55: 40
Example 10
SrO: CaO: BaO: ZnO: P ₂ O ₅ = 4: 3: 3: 50: 40

<Comparative example>
Similarly, in mole% ratio,
Comparative Example 1
SrO: ZnO: P ₂ O ₅ = 15: 55: 30
Comparative Example 2
SrO: ZnO: P ₂ O ₅ = 5: 55: 50
The glass powder (glass composition) containing was prepared in the same manner as in Example 1 and used as comparative examples.

In the comparative example of the above example, CaCO ₃ and BaCO ₃ were used as CaO and BaO, which are alkaline earth metal oxides, respectively.

<Comparison test and evaluation>
After firing each of the comparative examples of the above examples, whether or not the glass was vitrified according to the above [1-2] Vitrification confirmation was determined, and the working temperature was determined according to the determination of the above [1-4] working temperature Tw. The thermal expansion coefficient was measured according to the measurement of the above [1-3] thermal expansion coefficient. These results are shown in Table 1.

Water resistance test A powdered sample was molded into a 12 mmφ x 5 mm pellet, and the sample fired at the working temperature Tw of the above [1-4] was placed in water for 1 hour, and the water resistance was evaluated from its weight change. did. The results are also shown in Table 1.
Here, a sample having a weight change of less than 1% was evaluated as x when a sample was 0.1% or more.

  From the above results, if it deviates from the range surrounded by point A, point B, point C, point D, point E, and point F in FIG. 1, it does not vitrify, the working temperature becomes high, and the coefficient of thermal expansion is predetermined. It turns out that it falls outside the range and the water resistance deteriorates.

この分析結果によれば、ガラス成分として、ＺｎＯと、Ｐ_２Ｏ_５と、ＳｒＯと、０重量％以上かつ１．５重量％以下Ａｌ_２Ｏ_３，ＳｉＯ_２，ＣａＯ，Ｋ_２Ｏ，ＰｂＯ，ＣｕＯ，Ｂ_２Ｏ_３，Ｆｅ_２Ｏ_３，ＳＯ_３およびＮｉＯからなる群より選ばれた１種又は２種以上の酸化物と、を含むことがわかる。 <Other embodiments>
Moreover, the composition of the glass powder (glass composition) of this invention is described in Table 2, Table 3 as another Example.

According to this analysis result, ZnO, P ₂ O ₅ , SrO, 0 wt% or more and 1.5 wt% or less Al ₂ O ₃ , SiO ₂ , CaO, K ₂ O, PbO, 1 or 2 or more types of oxides selected from the group consisting of CuO, B ₂ O ₃ , Fe ₂ O ₃ , SO ₃ and NiO.

SrO in an embodiment of the glass composition according to the present invention, ZnO, is a triangular composition diagram indicating whether or not P 2 _{O 5,} the composition ratio of the vitrification. Sectional drawing which shows the process for producing the barrier rib for PDP of 1st Embodiment of this invention. Sectional drawing which shows the process for producing the barrier rib for PDP of 2nd Embodiment of this invention. Sectional drawing which shows the process for producing the barrier rib for PDP and the dielectric material layer for PDP of 3rd Embodiment of this invention. The perspective view which shows the molding state of the rib-shaped object of this invention 4th Embodiment. Sectional drawing which shows the barrier rib for PDP obtained by drying, heating, and baking the rib-like thing in the AA line cross section of FIG. The perspective view corresponding to FIG. 4 which shows the molding state of the rib rib with a rib foundation layer of 5th Embodiment of this invention. Sectional drawing corresponding to FIG. 6 which shows the barrier rib obtained by drying, heating, and baking the rib rib with a rib foundation layer in the BB line cross section of FIG. It is sectional drawing of the front glass substrate in PDP which concerns on embodiment of this invention. It is principal part sectional drawing of PDP which concerns on embodiment of this invention.

Explanation of symbols

10 Glass substrate 14, 34, 74, 94 Barrier rib 52, 93, 27 Dielectric layer

Claims (10)

As a glass component,
35 mol% or more and 45 mol% or less of P ₂ O ₅ ,
45 mol% or more and 55 mol% or less of ZnO;
One or more alkaline earth metal oxides selected from the group consisting of 5 mol% or more and 15 mol% or less of CaO, SrO, and BaO;
A glass composition comprising: Glass composition according to claim 1, wherein the component ratio ZnO _/ P 2 _{O 5} and ZnO and _P 2 _{O 5} being greater than 1. As a glass component,
ZnO, P ₂ O ₅ , SrO,
0 wt% or more and 1.5 wt% or less of _{Al 2 O 3, SiO 2,} CaO, K 2 O, PbO, B 2 O 3, CuO, selected from the group consisting of Fe ₂ O _3, SO 3 and NiO One or more oxides,
The glass composition of Claim 1 or 2 containing. The glass composition according to any one of claims 1 to 3, wherein alumina filler, titania, zircon, silica, cordierite, mullite, β-eucryptite, spodomen, anorsite, celsian, forsterite and titanium are used as ceramic fillers. A mixture obtained by mixing one or more ceramics selected from the group consisting of aluminum oxide. The mixture according to claim 4, wherein the ceramic filler has a particle size in the range of 0.05 to 0.5 μm. A paste comprising the glass composition according to any one of claims 1 to 3 or the mixture according to claim 4 or 5, a resin, and a solvent. A green sheet comprising the glass composition according to any one of claims 1 to 3 or the mixture according to claim 4 or 5, a resin, and a solvent. The barrier rib which baked the paste of Claim 6, or the green sheet of Claim 7. A dielectric obtained by firing the paste according to claim 6 or the green sheet according to claim 7. A PDP having at least one of a barrier rib according to claim 8 or a dielectric according to claim 9.

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