JP2005063835A - Glass composition for plasma display panel formation and plasma display panel using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass composition for PDP formation satisfying glass-baking conditions and excellent in electric PDP characteristics and a PDP using the glass composition. <P>SOLUTION: The glass composition for forming a dielectric layer constituting a plasma display panel, ribs, or a sealing layer for panel sealing contains glass frit, a vehicle and a filler, with a content of boron oxide of the glass frit of 8 mol% or less. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dielectric layer, a rib, and a glass composition for forming a panel sealing seal layer constituting a plasma display panel (hereinafter also referred to as PDP), and a PDP using the glass composition.

  In general, a PDP has a structure in which a front glass substrate and a back glass substrate are opposed to each other and sealed, and a rare gas such as Ne or Xe is sealed between the two substrates. Electrodes are formed on the surfaces of both substrates, these electrodes are covered with a dielectric layer, and gas discharge cells separated by partition walls (ribs) are provided in the space of both substrates. When an AC voltage is applied between adjacent transparent electrodes, a gas discharge is generated in the cell and plasma is formed. The ultraviolet rays generated here excite the phosphor to emit visible light, and display emission is obtained through the front plate.

  A glass material is generally used as a material for forming the sealing agent, the dielectric layer, and the partition wall for sealing both the substrates. This glass material is required to be able to be fired at 600 ° C. or lower in order to suppress deformation of the glass substrate. In addition, the material forming the dielectric and the partition is required to have material characteristics that lower the dielectric constant in order to suppress the power consumption of the PDP.

  In order to realize these required characteristics, glass materials include lead oxide glass consisting of lead oxide, boron oxide, silicon oxide, zinc oxide, calcium oxide, bismuth oxide, boron oxide, silicon oxide, zinc oxide, calcium oxide. A material having a relatively low softening temperature, such as bismuth oxide glass made of, is used. In the glass material, boron oxide is included as a constituent component for adjusting the softening point and adjusting the thermal expansion coefficient, and for reducing the dielectric constant and expanding the vitrification region.

  However, the PDP using a glass material containing boron oxide has a problem that the electrical characteristics of the PDP are not stable.

Summary of the Invention

  In general, when the boron oxide content in the glass is high, the present inventors diffuse boron alone or boron compounds from the glass during the heat treatment in the PDP panel manufacturing process, and adhere to the surface of the MgO layer or the phosphor surface. It has been found that it exists in the space and adversely affects the electrical characteristics of the PDP, and that the electrical characteristics of the PDP are improved by setting the composition amount of boron oxide to a predetermined value.

  Therefore, the present invention provides a glass composition for forming PDP that is excellent in PDP electrical characteristics while satisfying the glass firing conditions in a glass composition used for PDP, and a PDP using the glass composition. It is aimed.

  That is, a glass composition for forming a plasma display panel according to the present invention is a glass composition for forming a dielectric layer, a rib, or a panel sealing seal layer constituting a plasma display panel, and comprises a glass frit and a vehicle. And a filler, and the content of boron oxide in the glass frit is 8 mol% or less.

  As another aspect, the plasma display panel according to the present invention is a plasma display panel in which at least one of a dielectric layer, a rib, and a panel sealing seal layer is made of the above glass composition for forming a plasma display panel. The amount of boron present on the surface of the dielectric layer, rib, or panel sealing seal layer is 7 atomic% or less.

Furthermore, as another aspect, a method for producing a plasma display panel according to the present invention is a method for producing a plasma display panel using the glass composition for forming a plasma display panel, wherein the glass for forming a plasma display panel is formed on a substrate. Forming dielectric layers and ribs made of the composition to produce a back plate, firing the back plate, washing the back plate after firing, and firing the back plate after washing The process of
Is included.

  By using the glass composition according to the present invention, it is possible to obtain a PDP having excellent electrical characteristics while satisfying the glass firing conditions during production.

DETAILED DESCRIPTION OF THE INVENTION

  Hereinafter, the glass composition for PDP formation by this invention, PDP using the glass composition, and the manufacturing method of the PDP are demonstrated in detail.

1. PDP Forming Glass Composition The PDP forming glass composition according to the present invention comprises a glass frit, a vehicle, and a filler, and the content of boron oxide in the glass frit is 8 mol% or less. Here, the “boron oxide content” in the present specification is a numerical value representing the composition of the glass frit in the glass composition for PDP formation as a percentage of the number of moles of each oxide. By using a glass composition having such a composition, the amount of boron present on the surface of ribs and the like of the PDP can be reduced to 7 atomic% or less, and a PDP having excellent discharge characteristics can be obtained.

  The content of boron oxide in the glass composition is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 0 mol%.

  In general, when a dielectric layer or rib is formed using a glass composition for forming a PDP, the glass frit contained in the glass composition is used after being powdered. The powdered glass frit can be used in the form of a paste or a green sheet. For example, the glass paste is produced by kneading glass powder, ceramic powder, an organic vehicle, and the like. On the other hand, the green sheet is kneaded with glass powder, ceramic powder, and resin, and is produced by applying the kneaded material onto a film such as PET and drying it.

  The paste and the green sheet are applied to or pasted at predetermined positions on the glass substrate and baked to form a dielectric layer, ribs (partition walls), or a sealing layer.

  In general, PDP is baked at 600 ° C. or lower in order to prevent deformation of the glass substrate. Further, the glass composition is required not to be softened at about 400 ° C. or lower when the decomposition of the organic resin in the paste and the green sheet is completed. Therefore, it is desirable that the glass transition point (Tg) of the glass frit is equal to or higher than the temperature at which the resin used as the paste contained in the glass composition completely disappears upon firing. Furthermore, the softening point of the glass frit must be below the temperature at which the glass substrate is deformed. Specifically, Tg is appropriately selected between 350 to 500 ° C. and the softening point is 350 to 650 ° C., preferably 400 to 600 ° C.

  The glass frit constituting the PDP forming composition preferably has a particle size of 0.5 to 10.0 μm in D50 value. When the particle size of the glass frit is less than 0.5 μm, the dispersibility of the glass composition (paste) decreases due to aggregation of the glass frit. On the other hand, if the particle size of the glass frit exceeds 10 μm, the sinterability at the time of rib formation is deteriorated, or defects are generated in the rib.

  In the present invention, the glass frit is selected from the group consisting of lead oxide, silicon oxide, titanium oxide, aluminum oxide, bismuth oxide, copper oxide, cerium oxide, tin oxide, magnesium oxide, calcium oxide, barium oxide, and strontium oxide. It is preferable that the alkaline earth metal oxide selected or one or a mixture of two or more of these alkaline earth metal oxides is included. Moreover, you may mix alkali metal oxides, such as lithium oxide, sodium oxide, and potassium oxide, as needed.

  Furthermore, in the glass composition according to the present invention, the thermal expansion coefficient (α) of the glass frit is set so that the residual strain is minimized and the warpage of the glass substrate and the occurrence of cracks in the dielectric layer or rib are suppressed. It is preferable that the thermal expansion coefficient is close to that of the underlayer and the dielectric layer.

  Such a glass composition for forming a PDP is obtained by mixing the glass frit, filler, and colorant as required, adding an organic vehicle, and kneading and dispersing with a three roll, bead mill or the like. The composition preferably contains 40 to 95% by weight of the glass frit and 1 to 60% by weight of the filler.

2. The following plasma display panel, the glass composition according to the invention is further illustrated by way of example the case of forming a PDP by applying the rib material, can of course be applied to the dielectric layer or panel sealing sealing layer.

  In the plasma display according to the present invention, the amount of boron present on the rib surface is 7 atomic% or less, preferably 5 atomic% or less, and particularly preferably 0 atomic%. Here, “atomic%” in the specification of the present application means that the surface composition of the dielectric layer, rib, or seal layer constituting the PDP is measured with a photoelectron spectrometer, and atoms of all elements other than oxygen are measured. It means a value expressed as a percentage of the number. In this way, by setting the boron abundance on the rib surface of the PDP to 7 atomic% or less, diffusion of boron due to heat can be effectively suppressed, so that contamination of the phosphor or the protective film (MgO) by boron can be reduced.

  In the present invention, the boron contained in the ribs is transferred or diffused in the cells between the barrier ribs by the thermal energy or discharge energy at the time of drying, firing, cleaning, or PDP discharge in the PDP manufacturing process. It has been found that, due to diffusion, rare gas, phosphor or MgO is contaminated, and the display characteristics such as discharge characteristics are deteriorated. In order to suppress such boron transfer or diffusion, it is necessary to strictly control the amount of boron on the rib surface. This boron amount can be controlled by adjusting the boron oxide content of the glass composition forming the ribs. That is, by using the glass composition according to the present invention, a boron amount in the above range can be realized.

  In addition, in order to strictly control the amount of boron present on the rib surface so as to be in the above range, in addition to using the glass composition with controlled boron oxide content according to the present invention, the rib is formed after the rib is formed. The amount of boron on the rib surface can also be controlled within a predetermined range by performing heat treatment such as drying or firing, water or solvent cleaning, alkali treatment, acid treatment, UV treatment, ozone treatment, or plasma treatment. Further, after the rib is formed using a glass composition having a boron oxide content exceeding 8 mol%, the rib may be overcoated with a glass composition having a low boron content or an inorganic material not containing boron oxide. Good.

3. Manufacturing Method of Plasma Display Panel Next, the manufacturing method of the PDP of the present invention will be described with reference to FIG. 1 taking an AC type PDP as an example.

  In the method for producing a PDP according to the present invention, a step of forming a dielectric layer and ribs made of the above glass composition for forming a plasma display panel on a substrate to produce a back plate, and a step of firing the back plate The step of washing the back plate after firing and the step of firing the back plate after washing are further included. After the ribs and the like are baked and formed once in this manner, cleaning is performed and further calcination is performed, whereby the amount of boron oxide diffused by calcination or the like can be reduced.

  In general, as shown in FIG. 1, the PDP is fixed at regular intervals so as to form a cell in which a front plate 1 and a back plate 2 made of glass are sealed. On the back side of the front plate 1, a composite electrode composed of a sustain electrode 4 that is a transparent electrode and a bus electrode 5 that is a metal electrode is formed in parallel with each other, and a dielectric 6 and an MgO layer 7 are sequentially formed so as to cover this. Is formed. On the front side of the back plate 2, address electrodes 8 are formed in parallel to each other on the stripe so as to be perpendicular to the composite electrode and between the ribs, and the phosphor layer 9 is formed on the cell bottom surface on the address electrode 8. Is provided. Further, as shown in the sectional view of FIG. 2, the structure is such that the address electrode 8 is provided on the glass substrate 2, the dielectric layer 6 ′ is further laminated, and then the rib 3 and the phosphor layer 9 are provided. is there.

  In the manufacturing method of the present invention, first, the address electrode 8 is patterned on the glass substrate 2. The electrode 8 can be formed by (1) a method of combining a thin film formation process such as sputtering or vacuum deposition and a photo process, (2) a method of forming a pattern by screen printing, and (3) screen printing or blade coating. And a method of combining a photo process with a coating method such as die coating or roll coating.

  As a photo process, there are a method of applying a photoresist and drying it, and then patterning by an exposure and development process, or a method of patterning in the same manner using a dry film resist.

  The film thickness of the electrode is, for example, about 0.5 μm when the film is formed by sputtering using Cr as the electrode material, and the electrode is formed by patterning the formed Cr thin film using a photoresist. Is formed. The electrode material and the patterning method are not necessarily limited to these methods.

  The ribs 3 are formed after the address electrodes 8 having a predetermined pattern are formed by using any one of the above methods. The rib may be formed by a method of pattern printing in a partition shape by screen printing using the above-mentioned glass composition for PDP formation, or after a solid film is produced by screen printing, blade coating, die coating, etc. An example is a method in which a mask having samba resistance is formed on a pattern, and unnecessary portions of the partition wall forming material are removed by sand blasting to obtain a predetermined rib shape. The height of the rib 3 is preferably about 50 to 250 μm.

  Although a specific example is shown and this invention is demonstrated further in detail, this invention is not limited to these Examples.

1. Preparation of glass composition A glass frit was prepared in order to form ribs of the PDP back plate. As the glass frit, PbO, SiO ₂ and B ₂ O ₃ were used as main components, and the respective B ₂ O ₃ contents shown in Table 1 were used.

Next, after mixing the following components uniformly using said glass frit, the glass composition was adjusted by kneading | mixing with a three roll mill.
Glass frit 70 parts by weight Filler 30 parts by weight Alumina (D50 = 2.5 μm) 15 parts by weight Titania (D50 = 0.2 μm) 15 parts by weight Organic vehicle 22 parts by weight Ethosel STD-100FP 2 parts by weight Diethylene glycol butyl ether acetate 10 parts by weight 10 parts by weight of screen oil 759

2. Production of PDP A photosensitive Ag paste was printed on a glass substrate (PD200) by screen printing and dried at 80 ° C. Next, it exposed at 400 mJ / cm < ² > through the mask, developed with 0.4% sodium carbonate aqueous solution, and baked at 580 degreeC, and formed the electrode.

  On the electrode formed on the substrate, the glass composition obtained above was applied by screen printing, dried at 120 ° C. and baked at 570 ° C. to form a dielectric layer.

Next, a glass composition was applied on the dielectric and dried at 120 ° C. A dry film resist was laminated, exposed at 150 mJ / cm ² through a mask, and developed with 0.2% sodium carbonate to form a sandblast mask. After the dried coated surface was sandblasted, the dry film resist was peeled off with a 1.5% NaOH aqueous solution and baked at 560 ° C. to form ribs.

  Between the ribs, phosphors of R, G, and B were filled by screen printing, dried at 120 ° C., and fired at 470 ° C. The back plate thus obtained was bonded to the front plate to produce a PDP device.

3. Measurement of the amount of boron on the rib surface The front plate of the PDP device thus obtained was peeled off from the back plate, and the amount of boron present on the rib top surface of the back plate was measured by XPS. The measurement conditions are shown below.
X-ray source: Monochromatic AL-Kα ray (15 kV, 10 W)
X-ray beam diameter: 50 μmφ
Photoelectron detection angle: 45 °
The obtained results are shown in Table 1.

4). Evaluation of Boron Diffusion Amount The back plate obtained above was washed with water, and was fired at 550 ° C. after washing with water. For these cleaned and uncleaned back plates, a silicon wafer was placed on the ribs of the back plate, and a 1 kg weight was placed thereon and left at 400 ° C. for 10 hours. Thereafter, the silicon wafer was removed from the back plate, and the amount of boron present on the surface of the silicon wafer that was in contact with the ribs was measured using a time-of-flight secondary ion mass spectrometer.

The measurement conditions are shown below.
Primary ion beam: Ga (15 Kv)
Primary ion beam diameter: 2 μm
Degree of vacuum: 6.7 × 10 ⁻⁸ Pa or less Measurement area: 200 μm × 200 μm

  By the above measurement, the case where boron was detected on the surface of the silicon wafer was indicated as x, and the case where boron was not detected was indicated as ◯.

The evaluation results are shown in Table 1.

  In this example, only the rib constituting the PDP was evaluated, but it goes without saying that the same effect can be obtained for the dielectric layer and the seal layer.

It is the schematic of the AC type plasma display panel which is one embodiment of this invention. It is sectional drawing of the backplate of an AC type plasma display panel.

Claims (8)

  A glass composition for forming a dielectric layer, a rib, or a panel sealing seal layer constituting a plasma display panel, comprising a glass frit, a vehicle, and a filler, and the boron oxide of the glass frit The glass composition for plasma display panel formation whose content is 8 mol% or less.   The glass composition for forming a plasma display panel according to claim 1, wherein the boron oxide content is 0 mol%.   The composition for forming a plasma display panel according to claim 1, wherein PbO is substantially not contained.   The glass composition for plasma display panel formation of any one of Claims 1-3 whose softening point is 350-650 degreeC.   The glass composition for forming a plasma display panel according to any one of claims 1 to 4, further comprising a heat-resistant pigment.   A plasma display panel comprising the glass composition for forming a plasma display panel according to any one of claims 1 to 5, wherein at least one of a dielectric layer, a rib, and a panel sealing seal layer, wherein the dielectric The plasma display panel, wherein the amount of boron present on the surface of the body layer, rib, or panel sealing seal layer is 7 atomic% or less.   The plasma display panel according to claim 6, wherein the boron abundance is 0 atomic%. It is a manufacturing method of the plasma display panel using the glass composition for plasma display panel formation of any one of Claims 1-5,
Forming a dielectric layer and ribs made of a glass composition for forming a plasma display panel on a substrate to produce a back plate;
Firing the back plate,
Washing the back plate after firing, and
A step of firing the back plate after washing,
A method for producing a plasma display panel, comprising:

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