JP2007134221A - Phosphoric acid-based glass sealing ring, its manufacturing method, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel glass sealing ring with a complex shape corresponding to a tip shape of a ventilating pipe, excellent in sealability and stability despite reduction of a lead content through use of a phosphoric acid-based glass material. <P>SOLUTION: The phosphoric acid-based glass sealing ring 22, for sealing a ventilating pipe in a panel so that a ventilating hole of the panel and the ventilating pipe are communicated with each other, is provided with a stepped part 21 as a saucer for the ventilating pipe on the surface of an inner periphery wall face, and substantially contains no binders. The phosphoric acid-based glass sealing ring 22 is manufactured through processes including, for instance, that of obtaining a molded ring containing the stepped part by molding a frit binder mixture composed of phosphoric acid-based glass frit and a binder with a boiling point of 400°C or less and solid under an atmosphere of 25°C, and a binder removal process of removing the binder by heating the molded ring. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to phosphoric acid for sealing a vent pipe to a panel in which the vent hole is formed so that the vent hole and the vent pipe in a display device such as a plasma display panel or a field emission display communicate with each other. The present invention relates to a glass sealing ring. Moreover, it is related with the manufacturing method of this phosphate type glass sealing ring. The present invention also relates to a display device using this phosphate glass sealing ring.

  Display devices such as a plasma display panel (hereinafter referred to as PDP) and a field emission display (hereinafter referred to as FED) are attracting attention as thin display devices capable of realizing both large screens and thin and light weights. .

  In such a display device, a light emission excitation source space is formed between a pair of panels. The emission excitation source space corresponds to, for example, a discharge space filled with a discharge gas mainly composed of a rare gas in the case of PDP, and a vacuum space in which an electron beam emitted from the electron source can be taken out without being attenuated in the case of FED. Space that requires high airtightness.

  When manufacturing a display device, it is necessary to appropriately adjust the atmosphere in the light emission excitation source space. The adjustment of the atmosphere is performed through a vent pipe provided so as to communicate with a vent hole formed in the panel. As this vent pipe, in general, in order to improve the stability of joining to the panel, one having a tip shape having excellent stability, for example, one having an enlarged diameter portion 53 and a flange portion 52 as shown in FIG. 4A is used. ing. Further, for sealing the vent pipe and the panel, as shown in FIG. 4A, a glass having a shape in which a step portion serving as a receiving tray into which the tip opening of the vent pipe is fitted is provided on the inner peripheral wall surface of the ring. A sealing ring is used. This is for facilitating alignment of the vent hole, the vent pipe, and the through hole of the ring. Such a complicated ring shape is not easy to form without defects such as cracks, chips, and glass alteration, and the glass material that can realize this is limited to lead oxide glass.

Here, from the viewpoint of protecting the natural environment, it is required to replace the material used for a glass sealing ring material with a glass material that does not contain a lead component, instead of the conventional lead-based glass. As the candidate, for example, a phosphorus oxide-containing glass material (phosphate glass material) has been proposed (see, for example, Patent Document 1 or 2).
JP 2003-238199 A JP 2004-182584 A

  However, when the phosphoric acid glass material disclosed in Patent Document 1 or 2 is used, it has a complicated shape corresponding to the tip shape of the vent pipe having excellent stability, and cracks, alterations, etc. It is very difficult to mold a glass sealing ring with few defects. In addition, in the glass ring with a defect | deletion, the sealing force sufficient to maintain the airtightness of light emission excitation space cannot be obtained.

  In addition, a ring having a simple shape such as a cylindrical shape can be formed using a phosphate glass material. However, in the ring having a simple shape, the ventilation hole, the ventilation pipe, and the sealing of the display device panel are used. It is difficult to align the opening with the ring and it is difficult to improve the productivity of the display device.

  Therefore, the present invention provides a display device panel vent hole having a complicated shape corresponding to the tip shape of the vent pipe having excellent sealing properties and excellent stability while using a phosphate glass material. An object of the present invention is to provide a novel phosphoric acid-based glass sealing ring in which the opening position of the ventilation pipe and the sealing ring can be easily aligned, and there is no crack or chipping or glass alteration.

  Moreover, an object of this invention is to provide the manufacturing method of this novel phosphoric acid type glass sealing ring. In addition, this new phosphoric acid-based glass sealing ring is used, has an excellent glass sealing part that does not contain lead in consideration of environmental problems, maintains sufficient airtightness, and has good image display performance. It aims at providing the display device which exhibits.

  The phosphate glass sealing ring of the present invention is a phosphate glass sealing ring for sealing the vent tube to the panel so that the vent hole of the panel communicates with the vent tube, It includes an inner peripheral wall surface, a step portion serving as a tray for the vent pipe is provided on the surface of the inner peripheral wall surface, and substantially does not contain a binder.

  Further, according to another aspect of the present invention, as a method suitable for the production of the phosphate glass sealing ring, a phosphate glass frit and a binder that is solid in an atmosphere of 25 ° C. and has a boiling point of 400 ° C. or less. And a binder removing step of heating the molded body ring to remove the binder by molding a frit / binder mixture containing To do.

  In another aspect, the present invention includes a panel having a vent hole formed therein, a vent pipe communicating with the vent hole, and a phosphate glass sealing ring for sealing the vent pipe to the panel. Provided is a display device, wherein the phosphate glass sealing ring is bonded to an opening end surface and an outer wall surface of the vent pipe and the panel, and substantially does not contain a binder.

  In the present specification, the phrase “substantially not containing a binder” means that the content of a known organic substance used as a glass binder is less than 1 ppm, more specifically less than 1 ppb. In this specification, “ppm” means mass parts per million, and “ppb” means mass parts per billion. What is necessary is just to evaluate organic content using well-known methods, such as gas chromatograph mass spectrometry (GC-MS), for example.

  According to the present invention, the amount of lead, which is a harmful chemical substance, suitable for manufacturing display devices such as FEDs and PDPs is reduced to reduce adverse effects on the natural environment, as well as cracking and chipping, glass alteration, etc. Therefore, it is possible to provide a phosphoric acid-based glass sealing ring having a complicated shape corresponding to the tip shape of the vent pipe which has no sealing property and excellent sealing properties and excellent stability. With this phosphoric acid-based glass sealing ring, it is easy to align the opening positions of the ventilation holes of the panel, the sealing ring, and the ventilation pipe in the display device.

  Moreover, according to this invention, the method suitable for manufacture of this phosphate type glass sealing ring can be provided. Moreover, according to this invention, the display device using this phosphoric acid type glass sealing ring can be provided.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and can take various forms as long as the gist of the present invention is not changed.

<1-1. Composition of glass sealing ring>
Phosphate glass sealing ring according to a first embodiment of the present invention, P ₂ O ₅ -SnO-based, P ₂ O _{5 -SnO-ZnO-based, P 2 O 5 -SnO-SiO} 2 system, P ₂ O Phosphorus oxide (P ₂ O) as a main component (main component of a glass network former) that forms a glass network structure such as a _5- SnO—Al ₂ O ₃ system or a P ₂ O ₅ —SnO—B ₂ O ₃ system. ₅ ) a frit / binder mixture containing a phosphoric glass frit containing 2) and a sublimable binder that is solid in an atmosphere of 25 ° C. and has a boiling point of 400 ° C. or less, and is sintered. It is a lead-free (non-lead) ring. In addition, although mentioned later for details, the glass sealing ring of a finished product does not contain a binder substantially.

  The phosphate glass frit is a phosphate glass powder or a mixed powder of a phosphate glass powder and a refractory lead-free filler powder.

The phosphate glass powder preferably contains 20 mol% or more of P ₂ O ₅ in terms of mol% based on oxide (hereinafter the same). On the other hand, from the viewpoint of producing a high-quality glass sealing ring with few defects, the content of P ₂ O ₅ is preferably 50 mol% or less. This is because when the content exceeds 50 mol%, the water resistance decreases.

Moreover, when SnO is contained in the phosphoric acid glass powder in an amount of 15 mol% or more, the water resistance can be improved while maintaining the softening point of the glass low. On the other hand, when the content exceeds 60 mol%, the stability of the glass is lowered. ZnO, SiO ₂ , Al ₂ O ₃ , B ₂ O _3, etc. help to form glass and exhibit effects such as improved stability of glass, control of thermal properties, improved water resistance, etc. When the amount is excessive, the softening point is increased, the fluidity is decreased, the glass is crystallized, and the sealing property is decreased. Therefore, the content of each component system is set to ZnO: 0.5-10. mol%, SiO _2: 1 to 10 mol%, Al ₂ O _3: 1~10 mol%, B ₂ O _3: it is preferable that 0.5 to 5 mol% of the range.

For the phosphoric acid glass frit, if necessary, for example, Li ₂ O, Na ₂ O, K ₂ O, MgO, CaO, SrO, BaO, V ₂ O ₅ , TeO ₂ , CuO, Bi ₂ O _{3 are used.} TiO ₂ , MnO ₂ , ZrO ₂ , Nb ₂ O ₅ , MoO ₃ , WO ₃ , rare earth oxides, and the like can be included. When these components are added, it becomes easier to control the thermal characteristics of the glass composition and to improve the strength.

Examples of the refractory lead-free filler include cordierite, willemite, forsterite, anorthite, zircon, mullite, β-eucryptite, β-spodumene, cristobalite, barium titanate, aluminum titanate, titanium oxide, At least one selected from tin oxide, aluminum oxide, zirconium oxide, zirconium oxide, quartz glass, sialon, silicon nitride, silicon carbide, β-quartz solid solution, and a compound represented by the formula AD ₂ (MO ₄ ) ₃ is used. be able to. In the above formula, A is at least one element selected from Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni and Mn, and D is Zr, Ti, Sn, It is at least one element selected from Nb, Al, Sc and Y, and M is at least one element selected from P, Si, W and Mo.

  The amount of the refractory lead-free filler contained in the glass frit is not particularly limited, and is, for example, in the range of 0 to 70% by mass, and preferably in the range of 5 to 50% by mass. When manufacturing a display device, it is preferable to make the difference between the thermal expansion coefficient of the substrate (panel) and the thermal expansion coefficient of the glass sealing ring as small as possible. The refractory filler has a function of controlling the thermal expansion coefficient of the glass. Therefore, the difference between the glass sealing ring and the coefficient of thermal expansion of the substrate can be reduced by selecting the type and amount of the refractory filler contained in the glass sealing ring.

<1-2. Glass sealing ring shape>
As shown in FIG. 4A, the phosphoric acid-based glass sealing ring of the present invention includes an inner peripheral wall surface, and a stepped portion 21 serving as a receiving tray into which the tip opening of the glass vent tube 12 is fitted on the inner peripheral wall surface. Is provided.

  In general, as shown in FIG. 4A, the tip portion of the glass ventilation tube is provided with a flare portion (diameter-enlarged portion 53) whose diameter increases toward the tip, and an annular flange portion 52 is provided at the tip. Is provided. By providing the enlarged diameter portion at the tip of the glass vent tube, the diameter of the flange portion, that is, the tip opening can be increased, and the stability when the glass vent tube is held perpendicular to the display device is increased.

  The phosphate glass sealing ring is installed between the panel and the glass ventilation pipe so that the ventilation hole formed in the panel of the display device and the ventilation pipe are conducted, and the temperature is higher than the softening point of the glass frit. The display device and the glass vent pipe can be sealed by firing at. In this case, in order to maintain sufficient airtightness, it is necessary to make the outer diameter of the ring larger than the outer diameter of the flange portion and make the inner diameter of the ring smaller than the inner diameter of the flange portion. In addition, sufficient airtightness cannot be maintained unless the center axis of the through hole of the ring is aligned with the center axis of the flange portion. However, in the phosphoric acid-based glass sealing ring according to the present invention, as shown in FIG. 4A, a step portion is provided on the surface of the inner peripheral wall surface of the ring. The central axes of the trachea and the through-hole of the ring can be easily matched. As a result, the glass vent tube and the glass sealing ring can be easily moved together, so that they can be easily aligned with the vent of the display device. Therefore, incomplete sealing due to misalignment between the vent hole and the glass vent tube is unlikely to occur, and there is no possibility of causing a defect that the airtightness of the display device cannot be sufficiently maintained.

<1-3. Manufacturing method of glass sealing ring>
The phosphate glass sealing ring (stepped glass sealing ring) is an organic substance that is solid and has a boiling point of 400 ° C. or less in the atmosphere of normal temperature and normal pressure (25 ° C., 101325 Pa) with the phosphate glass frit. And a binder removing step of heating the molded body ring to remove the binder by molding a frit / binder mixture containing a binder to obtain a molded body ring including a stepped portion. To do.

  More specifically, a frit / binder mixture containing a phosphoric glass frit containing a sublimable organic substance as a binder is formed into a stepped ring shape, and then the glass transition point of the phosphoric glass frit is less than the softening point. It is produced by debinding and sintering at the firing temperature.

  Examples of the sublimable organic substance include camphor (boiling point 204 ° C.), naphthalene (boiling point 218 ° C.), anthracene (boiling point 354 ° C.), and the like. These can be used alone or in admixture of two or more. Such a sublimable organic substance completely disappears at a pre-baking temperature not lower than the glass transition point of the phosphoric acid glass frit and lower than the softening point, that is, 250 to 450 ° C., and does not cause a defect derived from the residual binder. Moreover, since such a sublimable organic substance is hydrophobic (has no hydrophilic group in the molecule) and has a strong binding force, a glass sealing ring can be formed from various low melting point glass frit. It is effective as a binder, but when using a phosphate glass frit with inferior water resistance, it protects it from moisture and does not change its quality, so it forms a stepped glass sealing ring that does not crack or chip. It is effective as a binder that can be used.

  The content of the sublimable organic substance is in the range of 1% by mass to 20% by mass, and preferably in the range of 5% by mass to 15% by mass with respect to the phosphate glass frit. When the content of the sublimable organic substance is less than 1% by mass, the phosphate glass frit cannot be sufficiently bound and held. On the other hand, if it exceeds 20% by mass, a small amount of sublimable organic matter may remain after calcination.

  In order to obtain a uniform frit / binder mixture of a sublimable organic substance and a phosphate glass frit, for example, 50 to 150 parts of an organic solvent is added to 100 parts by mass of a phosphate glass frit prepared by adding the sublimation organic substance to the above content. An example is a method in which after adding part by mass and stirring sufficiently, the organic solvent is evaporated to dryness at 30 ° C. or lower. Here, in order not to reduce the content of the sublimable organic substance in the frit / binder mixture, it is preferable to evaporate to dryness at as low a temperature as possible and in a short time. For this reason, as an organic solvent which melt | dissolves the said sublimable organic substance, a thing with a boiling point of 100 degrees C or less is preferable, and a thing with a boiling point of 85 degrees C or less is especially preferable. For example, ethanol, isopropanol, diethyl ether, isopropyl ether, acetone, methyl ethyl ketone, ethyl acetate, methylene chloride, chloroform, 1,2-dichloroethane and the like can be mentioned.

  Next, after filling the frit / binder mixture thus obtained in a step-shaped ring-shaped mold molding machine, this is press-molded to obtain a molded body ring including a stepped portion.

  Finally, the resulting molded ring is sealed with a step by debinding and sintering at a pre-baking temperature not lower than the glass transition point of the phosphate glass frit and lower than the softening point, that is, 250 to 450 ° C. A ring is manufactured.

  The completed phosphoric acid-based glass sealing ring contains 20 mol% or more of phosphorus oxide based on the oxide.

  Note that the organic binder can be almost completely removed by the binder removal step due to its sublimation property, so that it becomes easy to produce a glass sealing ring having no residual binder. The method for producing a glass sealing ring using such an organic binder is particularly effective when tin oxide (SnO) or phosphorus oxide is contained as a glass material. This is because the glass containing SnO has a relatively low strength and the adverse effect of the remaining binder is particularly serious. If the binder remains in the sealing ring, the glass may be deteriorated or cracks may occur during the sealing operation, and sufficient sealing properties may not be obtained. In addition, although glass containing phosphorus oxide has low water resistance and easily changes in quality, the organic binder has so-called sublimation properties, so that the organic binder is volatilized violently during manufacturing operations other than the binder removal step. Thus, since the air flow is generated in the direction away from the molded body ring, the approach of moisture that corrodes the glass can be prevented. That is, at the time of manufacturing the glass sealing ring, the phosphate glass can be protected from moisture and its alteration can be prevented, so that a phosphate glass sealing ring with few defects can be produced. In particular, when a glass sealing ring having a complicated outer wall surface shape is produced using a phosphorus oxide-tin oxide-containing glass material, the effect is high. This is because the more complicated the shape is, the more difficult the stress balance is made to be uniform, and the number of cases where defects occur due to the deterioration of the glass or the remaining binder.

  On the other hand, when a conventional binder that does not have sublimability is used, for example, when a polymer binder such as polyethylene carbonate, polyethylene glycol derivative, polymethylstyrene, etc. disclosed in Patent Document 2 is used, Although the polymer structure can be decomposed to a certain level by heating in the binder removing step, it is difficult to completely remove the polymer structure, and a certain amount or more of the binder remains. Moreover, a defect | deletion may generate | occur | produce in the glass sealing member resulting from the residue after decomposition | disassembly. Moreover, since it does not evaporate vigorously like a binder having a sublimation property, it is difficult to prevent moisture erosion, and the phosphate glass may be altered.

  The phosphate glass sealing ring of the present invention can be used, for example, in the production of display devices. In addition, below, the usage aspect of the said glass sealing ring is demonstrated in detail using PDP concerning Embodiment 2 of this invention as an example.

<2-1. Configuration of PDP>
FIG. 1 is a cross-sectional view showing the structure of a PDP produced using the phosphate glass sealing ring of the present invention. In the PDP 51, a front panel including a substrate 1a (front substrate) and a back panel including a substrate 1b (back substrate) are arranged to face each other, and a discharge space 2 (light emission excitation source space) is formed therebetween. ing. Although the material of the board | substrates 1a and 1b is not specifically limited, Usually, glass is used. As shown in detail in FIG. 4B, the substrate 1 b is provided with a vent hole 11. On the main surface of the substrate 1 b on the side opposite to the discharge space 2, a flare-equipped vent tube 12 communicating with the vent hole 11 is provided. Has been placed.

  The peripheral edges of the substrates 1 a and 1 b are sealed by a peripheral sealing wall 3. Moreover, the terminal (narrow tube part) on the opposite side to the vent hole side of the vent pipe 12 is sealed.

  The sealing between the ventilation pipe 12 and the back panel is performed by the glass sealing member 23 formed by the phosphate glass sealing ring 22 according to the first embodiment shown in FIG. ) And the opening end face on the vent hole side and the panel 1b.

  An electrode group 4 including a sustain electrode and a scan electrode, a dielectric layer 5 and a protective layer 6 are arranged on the substrate 1a, and a data electrode 7, a dielectric layer 8 and a partition wall 9 are arranged on the substrate 1b. Has been. The PDP 51 has a so-called three-electrode structure. In FIG. 1, the number of partition walls and data electrodes in an actual PDP is omitted.

  FIG. 2 shows a perspective view of the PDP 51 shown in FIG. 1 when the substrate 1a and the substrate 1b are separated from each other. In FIG. 2, the peripheral sealing wall 3 and the glass sealing member 23 are not shown, and only a part of the substrates 1a and 1b is shown.

  As shown in FIG. 2, stripe-shaped scan electrodes 41 and sustain electrodes 42 are arranged in parallel with each other as the electrode group 4 on the substrate 1 a, and the display electrodes 43 are formed by the scan electrodes 41 and the sustain electrodes 42. ing. Scan electrode 41 and sustain electrode 42 have a structure in which bus electrode (scan electrode) 41b and bus electrode (sustain electrode) 42b are laminated on transparent electrode (scan electrode) 41a and transparent electrode (sustain electrode) 42a, respectively. is doing. For the transparent electrodes 41a and 42a, ITO (Indium Tin Oxide), tin oxide or the like is used. Aluminum, copper, silver, or the like is used for the bus electrodes 41b and 42b. Between the scan electrode 41 and the sustain electrode 42, a black film 40 made of glass and black pigment, called black stripes, is arranged for improving the black display quality and increasing the contrast of the image. Each electrode and the black film 40 included in the electrode group 4 can be formed on the substrate 1a by a method such as screen printing, for example.

  A dielectric layer 5 is disposed on the substrate 1a so as to cover the display electrodes 43. On the dielectric layer 5 (on the discharge space 2 side of the dielectric layer 5), the dielectric layer 5 is disposed. The protective layer 6 for protecting the is disposed. The dielectric layer 5 serves as a capacitor for accumulating charges when the PDP 51 displays an image. The dielectric layer 5 and the protective layer 6 are made of low melting point glass, MgO, or the like.

  On the substrate 1b, a dielectric layer 8, partition walls 9, and stripe-shaped address electrodes 7 are arranged. The dielectric layer 8 is disposed so as to cover the address electrodes 7, and the partition walls 9 are disposed so as to be parallel to each other. A phosphor layer 10 is disposed between adjacent barrier ribs 9, and the discharge space 2 is divided into pixels by the barrier ribs 9. The phosphor layer 10 contains a phosphor that emits red, green, or blue light. The configuration of the address electrode 7 is the same as the configuration of the bus electrode, and the dielectric layer 8 is the same as the dielectric layer 5. The partition wall 9 is formed using a glass material and a pigment.

  Substrates 1a and 1b are arranged such that protective layer 6 and barrier rib 9 face discharge space 2, and striped electrode group 4 and address electrode 7 are orthogonal to each other when viewed from the main surfaces of substrates 1a and 1b. , Are arranged facing each other. The discharge space 2 is filled with a discharge gas containing a rare gas such as neon or xenon. The pressure of the discharge gas in the discharge space 2 may be in the range of 53329 to 79993 Pa (400 to 600 Torr), for example.

  In this PDP 51, a video signal voltage is selectively applied to the display electrode 43 to discharge a plasma of the discharge gas, and the phosphors contained in the phosphor layer 10 are excited by the generated ultraviolet rays, and the excited phosphors are red, green Alternatively, a color image is displayed by emitting blue light.

  In this PDP, since the ventilation pipe is sealed to the panel so as to communicate with the ventilation hole of the panel using the phosphate glass sealing ring according to the first embodiment of the present invention, the airtightness is high. Sex is demonstrated. As a result, it is possible to suppress the occurrence of problems such as a slow leak in the sealed portion, and to exhibit a good image display performance, while maintaining a good gas pressure in the discharge space and maintaining a normal discharge for a long time. The

<2-2. Manufacturing method of PDP>
The PDP 51 can be manufactured, for example, as follows.

(Preparation of front panel)
On the surface of the front substrate 1a made of soda-lime glass having a thickness of about 2.6 mm, a display electrode is produced as follows. Although an example in which the display electrode is formed by a printing method is shown here, it can be formed by a die coating method, a blade coating method, or the like.

  First, an ITO (transparent electrode) material is applied on a surface substrate in a predetermined pattern and dried. In parallel with this, a photosensitive paste is prepared by mixing a metal (Ag) powder and an organic vehicle with a photosensitive resin (photodegradable resin). Next, this photosensitive paste is applied over the ITO pattern, and then covered with a mask having a pattern of display electrodes to be formed. Then, it exposes from the said mask, and image development and baking (baking temperature of about 590-600 degreeC). Thereby, bus electrodes 41b and 42b are formed on the transparent electrodes 41a and 42a. Other metal materials for the bus electrode include Pt, Au, Cu, Al, Ni, Cr, tin oxide, indium oxide, and the like.

  In addition, when such a photomask method is used, the bus electrode can be thinned to a line width of about 30 μm as compared with the screen printing method in which the line width of 100 μm is conventionally limited. It does not exclude a known formation method in which an electrode material is formed by vacuum deposition, sputtering, or the like and then formed by etching.

Next, a paste containing a lead-free dielectric glass is applied on the formed display electrode by a screen printing method or the like. Subsequently, after drying for a certain period, the dielectric layer 5 is formed by firing at a predetermined temperature. Examples of lead-free dielectric glass materials used include P ₂ O ₅ —SnO, P ₂ O ₅ —SnO—ZnO, Bi ₂ O ₃ , and ZnO—B ₂ O ₃ —SiO ₂ . Examples include glass powder.

  Thereafter, a protective layer 6 made of magnesium oxide having a thickness of about 1 μm is formed on the surface of the dielectric layer 5 by sputtering or the like. Thus, the front panel is manufactured.

(Production of back panel)
On the surface of the back substrate 1b made of soda-lime glass having a thickness of about 2.6 mm, a conductive material mainly composed of metal (Ag) is applied in a stripe pattern at a predetermined interval by screen printing, and the thickness is about 5 μm. Address electrode 7 is formed.

  Subsequently, a paste containing a lead-free dielectric glass is applied on the formed address electrode with a thickness of about 20 to 30 μm using a screen printing method or the like. Subsequently, after performing a drying process for a certain period, the dielectric film 8 is formed by baking at a predetermined temperature.

  Next, a partition wall 9 having a height of about 60 to 100 μm is formed on the dielectric film 8 and between adjacent address electrodes. The partition wall 9 can be formed, for example, by using a paste containing a non-lead-based dielectric glass used for forming the dielectric film 8, and repeatedly firing the paste by screen printing.

Finally, either the red (R) phosphor, the green (G) phosphor, or the blue (B) phosphor is contacted with the side wall of the barrier rib and the dielectric film exposed between the adjacent barrier ribs. The phosphor ink (15 × 10 ⁻³ Pa · s) is applied by spraying it between adjacent partitions using a pump having a diameter of 60 μm. At this time, the panel is moved in the longitudinal direction of the partition wall 9 and the phosphor ink is applied in a stripe shape. Thereafter, the phosphor layer 10 is formed by baking at around 500 ° C. for 10 minutes. Through the above steps, a back panel can be manufactured.

For example, the following RGB phosphors can be used.
Red phosphor; Y ₂ O ₃ : Eu ³⁺
Green phosphor; Zn ₂ SiO ₄ : Mn ²⁺
Blue phosphor; BaMgAl ₁₀ O ₁₇ : Eu ²⁺

  The phosphor ink is, for example, a mixture of 50% by mass of each phosphor material having a volume average particle diameter of 2.0 μm, 1.0% by mass of ethyl cellulose, and 49% by mass of a solvent (α-terpineol) with a sand mill. Can be prepared.

(Production of PDP)
A glass paste containing a lead-free glass frit is applied on the main surface of at least one of the front panel and the back panel so as to go around the periphery of the main surface. Examples of the lead-free glass frit include low melting glass powders such as Bi ₂ O ₃ and ZnO—B ₂ O ₃ —SiO _2, or mixed powders of these low melting glass powders and refractory lead-free filler powders. can do.

  Then, after drying the apply | coated paste for a fixed time, the peripheral sealing member 14 of a glass panel is formed by carrying out temporary baking in the softening point vicinity of the lead-free glass in glass paste, for example, 350-450 degreeC. The firing time can be, for example, 30 minutes.

  Next, as shown in FIG. 3A, both panels are arranged to face each other so that the electrode group 4 on the front panel and the address electrode 7 on the back panel are orthogonal to each other. Further, for example, as shown in FIG. 4A, the flare portion-attached vent pipe 12 is connected to the glass sealing ring 22 so that the flange portion 52 contacts the stepped portion 21 so as to communicate with the vent hole 11 of the back panel. After the fitting, the pack panel vent hole and the vent pipe are arranged to communicate with each other.

  Subsequently, by firing for 30 minutes at a temperature 30 to 50 ° C. higher than the softening point of the lead-free glass contained in the glass sealing ring 22 and the peripheral sealing member 14, for example, 380 to 500 ° C. As shown by 3B, the peripheral sealing member 3 for sealing between the panels is formed. In addition, as shown in FIG. 4B, at least a part of the glass sealing ring 22 is melted to form a glass sealing member 23 by the firing, and a ventilation tube is welded to the panel. In addition, as a ventilation pipe, the ventilation pipe | tube 13 with a cylindrical part which has the cylindrical enlarged diameter part 53 as shown to FIG. 5A, or the ventilation pipe 14 with a bell part which has the enlarged diameter part 53 of a bell shape as shown to FIG. 6A. Similarly, the glass sealing member 23 shown in FIGS. 5B and 6B can be formed.

Then, after exhausting until the inside of the discharge space 2 is in a high vacuum state (about 1.0 × 10 ⁻⁴ Pa) through the vent tube 12, the inside is set to a predetermined pressure (here, about 66.5 to 101 kPa). The discharge gas such as Ne—Xe, He—Ne—Xe, He—Ne—Xe—Ar, etc. is sealed until). Next, the end of the vent tube 12 opposite to the vent hole side (the end opposite to the substrate 1b side (thin tube portion)) is heated, the tube wall of the end is fused, and the discharge space 2 is hermetically sealed. Hold. Thus, the PDP 51 is completed.

  Hereinafter, examples of the present invention will be described by using as an example a PDP produced using the phosphate glass sealing ring according to the first embodiment. In addition, this invention is not limited by these.

Example 1
Example 1 includes a flared vent pipe 12 shown in FIG. 4A and a phosphate glass sealing ring 22 in which a stepped portion 21 serving as a tray for the flared vent pipe is provided on the inner peripheral wall surface. It is a PDP produced by using it.

(1) Preparation phosphate frit binder mixture - as tin oxide glass frit, by mol% based on oxides, P ₂ O _5: 30 mol%, SnO: 60 mol%, ZnO: 10 mol% of the composition 90 mass% of a glass powder having a weight of 100% by mass of acetone as a solvent is added to 100 mass parts of a mixture of the glass frit and 10 mass% of camphor as a binder. Kneaded for a minute. Thereafter, the mixture was placed in an atmosphere of 30 ° C. or lower for 30 minutes, the added acetone was evaporated, and the mixture was dried to prepare a frit / binder mixture.

(2) Preparation of phosphate glass sealing ring After filling the above-mentioned frit / binder mixture into a step-shaped ring-shaped mold molding machine, press molding to form a molded body ring including a stepped portion, 360 While heating at 0 degreeC and removing a binder, the said molded object ring was baked and the phosphoric acid type glass sealing ring of the said shape was produced.

(3) Production of PDP The PDP shown in FIG. 1 was produced using the phosphate glass sealing ring. The specific procedure for producing the PDP followed the PDP manufacturing method according to the second embodiment. In addition, sealing of the peripheral part of a front panel and a back panel and sealing of a glass vent pipe and a back panel were performed simultaneously, and each sealing temperature was 450 degreeC. The discharge space was filled with Xe—Ne gas as a discharge gas so that the pressure was 0.53 atm (400 Torr).

(Example 2)
Example 2 used a frit / binder mixture prepared using a mixture of 80% by mass of the above glass powder, 20% by mass of cordierite as a refractory lead-free filler, and 10% by mass of camphor as a binder. Other than this, the PDP was produced in the same manner as in Example 1 above.

(Example 3)
Example 3 is a PDP produced in the same manner as in Example 1 except that naphthalene was used as a binder instead of camphor and a frit / binder mixture prepared using ethanol as a solvent instead of acetone was used. is there.

(Comparative Example 1)
In Comparative Example 1, frit / binder mixture prepared using polyethylene carbonate (mass average molecular weight: 50,000) as a binder instead of camphor and using 1,2-dichloroethane as a solvent instead of acetone was used. A PDP produced in the same manner as in Example 1 above.

(Conventional example 1)
In Conventional Example 1, instead of phosphoric acid glass frit, the composition of PbO: 66 mol%, B ₂ O ₃ : 30 mol%, SiO ₂ : 4 mol% is used instead of phosphoric glass frit. It was produced in the same manner as in Example 1 except that a lead oxide glass frit composed of a mixture of 60% by mass of lead oxide glass powder having an amount of 40% by weight and lead titanate as a refractory filler was used. PDP.

[Rating evaluation]
For the rings used in Examples 1 to 3, Comparative Example 1 and Conventional Example 1, the generated gas when heated from room temperature (25 ° C.) to 400 ° C. was measured by gas chromatograph mass spectrometry (GC-MS). The amount of the remaining binder was determined. The results are shown in Table 1.

[Evaluation of PDP]
The lighting test of PDP of Examples 1-3, the comparative example 1, and the prior art example 1 was done, and the brightness | luminance of the panel was evaluated. The luminance was evaluated using a luminance meter (display color analyzer) for a PDP immediately after production and a PDP 1000 hours after the start of lighting (after a long-term lighting test). The results are shown in Table 1. Table 1 shows the relative values of the measured luminance of each sample when the luminance obtained from the PDP of Conventional Example 1 immediately after manufacture is 100%.

  As shown in Table 1, it was confirmed that the glass sealing rings of Examples 1 to 3 and Conventional Example 1 did not substantially contain a binder. On the other hand, in Comparative Example 1, 40 ppm of residual binder was present.

  Moreover, when the crack and chip | tip in the glass sealing member used by Examples 1-3, the comparative example 1, and the prior art example 1 were observed by visual observation or microscopic observation, in Examples 1-3 and the prior art example 1, such a crack was observed. While no defect was observed, the defect was observed in Comparative Example 1. In addition, the glass frit and binder mixture used in Examples 1 to 3, Comparative Example 1 and Conventional Example 1 was formed into a cylindrical shape of 20 cmφ × 10 cm and then fired at 360 ° C. When the alteration of the glass in the ring was evaluated, no alteration was observed in Examples 1 to 3 and Conventional Example 1, whereas alteration was observed in Comparative Example 1.

  Moreover, in PDP of Examples 1-3, as shown in Table 1, even after a long-term lighting test, it is lit with a luminance equal to each initial value and the initial value of the conventional example, and exhibits excellent lighting performance. On the other hand, in the PDP of Comparative Example 1, only about 60% lighting luminance was obtained even at the initial value, and even lighting was not observed after the long-term lighting test, and it was found that the lighting performance was extremely inferior. . This is because the glass sealing ring used in Comparative Example 1 has a lot of initial defects and the binder remains, so that the sealing property between the vent hole and the vent tube is lowered, and the PDP discharge space is less airtight. This is thought to be due to the fact that it cannot be raised.

  The present invention reduces the adverse effect on the natural environment by reducing the amount of lead, which is a harmful chemical substance, suitable for manufacturing display devices such as FED and PDP, and has excellent sealing properties and stability. The present invention can be applied to providing a glass sealing ring having a complicated shape corresponding to the tip shape of an excellent vent pipe.

It is sectional drawing which shows typically an example of the display device produced using the phosphate type glass sealing ring of this invention. It is a schematic diagram for demonstrating an example of the structure of the display device produced using the phosphate type glass sealing ring of this invention. It is sectional drawing which shows typically an example of the manufacturing method of the display device shown in FIG. It is sectional drawing which shows typically an example of the manufacturing method of the display device shown in FIG. It is sectional drawing for demonstrating an example of the phosphate pipe | tube sealing ring of this invention, and the vent pipe fitted to the said ring. It is sectional drawing for demonstrating an example of the sealing aspect of a vent hole and a vent pipe by the phosphoric acid type glass sealing ring of this invention. It is sectional drawing for demonstrating another example of the phosphate glass sealing ring of this invention, and the vent pipe fitted to the said ring. It is sectional drawing for demonstrating another example of the sealing aspect of a vent hole and a vent pipe by the phosphoric acid type glass sealing ring of this invention. It is sectional drawing for demonstrating another example of the phosphate glass sealing ring of this invention, and the vent pipe fitted to the said ring. It is sectional drawing for demonstrating another example of the sealing aspect of a vent hole and a vent pipe by the phosphoric acid type glass sealing ring of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1b Board | substrate 2 Discharge space 3 Periphery sealing wall 4 Electrode group 5, 8 Dielectric layer 6 Protective layer 7 Address electrode 9 Partition 10 Phosphor layer 11 Vent hole 12 Flared part vent pipe 13 Cylindrical part vent pipe 14 Bell Vent tube with part 22 Glass sealing ring 23 Glass sealing member 40 Black film 41 Scan electrode 41a Transparent electrode (scan electrode)
41b Bus electrode (scanning electrode)
42 sustain electrode 42a transparent electrode (sustain electrode)
42b Bus electrode (sustain electrode)
43 Display electrode 51 PDP
52 Flange 53 Expanded Diameter

Claims (10)

A phosphate glass sealing ring for sealing the vent pipe to the panel so that the vent hole of the panel communicates with the vent pipe,
Including the inner wall,
On the surface of the inner peripheral wall surface, a stepped portion serving as a tray for the vent pipe is provided,
Contains substantially no binder,
Phosphoric glass sealing ring.   The phosphoric acid-based glass sealing ring according to claim 1, which contains 20 mol% or more of phosphorus oxide on an oxide basis.   The phosphate-based glass sealing ring according to claim 1 or 2, further comprising tin oxide. A method for manufacturing a phosphate glass sealing ring for sealing the vent pipe to the panel so that the vent hole of the panel communicates with the vent pipe,
The phosphoric acid-based glass sealing ring includes an inner peripheral wall surface, provided on the surface of the inner peripheral wall surface is a stepped portion serving as a tray for the vent pipe, and does not substantially contain a binder,
Molding a frit / binder mixture including a phosphate glass frit and a binder having a boiling point of 400 ° C. or lower in an atmosphere of 25 ° C. to obtain a molded body ring including a step portion;
A binder removing step of removing the binder by heating the molded body ring;
including,
A method for producing a phosphate glass sealing ring.   The method for producing a phosphate glass sealing ring according to claim 4, wherein the binder is at least one selected from the group consisting of camphor, naphthalene, and anthracene.   The phosphate glass sealing according to claim 4 or 5, wherein a content of the binder in the frit / binder mixture is in a range of 1% by mass to 20% by mass with respect to the phosphate glass frit. Ring manufacturing method.   The manufacturing method of the phosphoric acid type glass sealing ring in any one of Claims 4-6 which exists in the range whose heating temperature of the said binder removal process is 200 degreeC or more and 450 degrees C or less.   The manufacturing method of the phosphoric acid type glass sealing ring in any one of Claims 4-7 in which the said phosphoric acid type glass frit contains 20 mol% or more of phosphorus oxides on an oxide basis.   The method for producing a phosphate glass sealing ring according to any one of claims 4 to 8, wherein the phosphate glass frit further contains tin oxide. A display device comprising: a panel formed with a vent hole; a vent pipe communicating with the vent hole; and a phosphate glass sealing ring for sealing the vent pipe to the panel,
The phosphate glass sealing ring is bonded to the opening end surface and outer wall surface of the vent pipe and the panel, and substantially does not contain a binder.
Display device.

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