JP5171050B2 - Image display device and glass frit for sealing - Google Patents

Description

  The present invention relates to an image display device having a vacuum container, and relates to a glass frit or glass composition for sealing for producing the image display device.

Various types are known as so-called flat display devices in which a flat back substrate and a front substrate are bonded together. For example, a flat panel display device (flat panel display: FPD) having electron sources arranged in a matrix is attracting attention, and one of them is a field emission image display device using a small and accumulating cold cathode ( FED: Field
Emission display) and electron emission type image display devices are known.

  The FPD includes a rear substrate including the electron source as described above, and a phosphor layer and an anode that forms an electric field (acceleration voltage) for projecting electrons emitted from the electron source onto the phosphor layer. The front substrate is bonded, and the opposing internal space of both substrates is sealed in a predetermined vacuum state.

As a sealing method, Japanese Patent Application Laid-Open No. 2000-206905 (Patent Document 1) discloses a method of forming a container with a glass frame. And the lead-free low melting glass used for sealing of glass is disclosed by Unexamined-Japanese-Patent No. 2003-192378 (patent document 2). Patent Document 2 discloses the use of B ₂ O _3, V ₂ O ₅ , or BaO instead of PbO—B ₂ O ₃ glass that causes environmental pollution. Japanese Patent Laid-Open No. 2004-250276 (Patent Document 3) discloses a glass containing V ₂ O ₅ , ZnO, BaO, TeO ₂ as a glass for sealing.

JP 2000-206905 A JP 2003-192378 A JP 2004-250276 A

  As glass for sealing, one containing lead (particularly, one made of PbO as a raw material) has been generally used. However, the water resistance of low melting point glass for sealing applications is low. For example, the sealing part of glass containing lead is corroded in a few minutes in 85 ° C. × 85% wet air. Therefore, when a high vacuum container is sealed, the sealing portion may be eroded from a portion that is in contact with the atmosphere, and the degree of vacuum may be reduced. On the other hand, sealing glass that does not contain lead also has low water resistance like glass that contains lead. Further, for sealing, there is a problem that if it is kept at a high working temperature for a long time, it is easy to crystallize, the fluidity is deteriorated and uniform adhesion becomes difficult.

  Accordingly, an object of the present invention is to solve the above-mentioned problems, provide a glass for sealing that is substantially free of lead, has good water resistance and moisture resistance, and has a long life and reliability in which a decrease in the degree of vacuum is prevented. It is in providing an image display apparatus with high.

A feature of the present invention that solves the above problems is a sealing glass containing at least a transition metal, phosphorus, barium, and antimony, and BaO and Sb ₂ O ₃ in terms of oxides of each component 15 to 35 wt% in total, and the weight ratio of BaO / Sb ₂ O ₃ or Sb ₂ O ₃ /
The BaO weight ratio is to be 0.3 or less. Another feature of the present invention is that a rear substrate having a plurality of electron sources, a phosphor layer, and an electric field (acceleration voltage) for causing electrons emitted from the electron source to collide with the phosphor layer are formed. A flat-panel image display device having a front substrate provided with an anode, and the inside of the space where both substrates are opposed is decompressed and sealed, wherein the sealing glass is used for sealing. It is in having a sealing part. In particular, the glass for sealing preferably has V ₂ O ₅ of 45 to 60% by weight and P ₂ O ₅ of 15 to 30% by weight.

  Transition metals and phosphorus are components that form a glass skeleton, and Ba and Sb are effects that change the properties of glass (network-modified oxides). The inventors of the present invention have found that the effect of improving the water resistance and moisture resistance of glass containing phosphorus can be obtained by mixing predetermined amounts and ratios of Ba and Sb. Examples of the transition metal component include vanadium and tungsten. Moreover, you may add Ag, Cu, Cs, Hf, Na, K, or Te suitably to the said glass for sealing. By mixing these components, the sealing temperature can be lowered. The addition amount is preferably 10% by weight or less in terms of oxide.

  Moreover, since the glass of the present invention is excellent in water resistance and moisture resistance, it has little moisture absorption. Therefore, when the glass of the present invention is employed as a material for members disposed inside the vacuum vessel, moisture absorption in the production and storage stages of each member is small, and moisture released by evacuation is preferably reduced.

  By using the glass for sealing of the present invention, the water resistance and moisture resistance of the sealing portion can be improved. In addition, the display device of the present invention can prevent a decrease in the degree of vacuum and increase durability. Furthermore, environmental pollution by lead can be avoided.

  First, the configuration of the display device will be described. The flat display device is configured using a vacuum container in which a rear substrate and a front substrate are opposed to each other, and a space formed therebetween is sealed and integrated with a peripheral edge. The outer surface side of the front substrate is the display surface of the display device.

  Sealing of the back substrate and the front substrate is bonded by glass for sealing directly or via an edge frame (sealing frame) or the like. The edge frame is preferably made of glass (frame glass), and it is preferable to bond between the back substrate and the frame glass and between the front substrate and the frame glass. Further, in a display device having a flat back substrate and an integrated edge frame on the periphery of the front substrate, the end surface of the edge frame facing the back substrate and the back substrate are sealed with the sealing glass.

  As an electron source of the back substrate, a Spindt type electron source, a surface conduction type electron source, a carbon nanotube type electron source, a metal-insulator-metal laminated MIM (Metal-Insulator-Metal) type, and a metal-insulator-semiconductor are used. A laminated MIS (Metal-Insulator-Semiconductor) type or a thin film type electron source such as a metal-insulator-semiconductor-metal type can be used. A plurality of electron sources (electron source arrays) and a plurality of phosphors (phosphor arrays) corresponding to each electron source constitute a unit pixel. Usually, one pixel (color pixel, pixel) is composed of unit pixels of three colors of red (R), green (G), and blue (B). In the case of a color pixel, the unit pixel is also called a sub-pixel (sub-pixel).

  On the inner surface side of the rear substrate, a large number of wirings connected to the electron source array and for supplying selection signals and display data are formed of a metal thin film. In addition, there are wiring for feeding power to the acceleration electrode on the inner surface of the front substrate via a wiring formed on the rear substrate, or wiring for feeding acceleration electrodes on the inner edge of the front substrate. . At least one edge of each substrate has a wiring region provided with a wiring led out to the edge. The peripheral edges of both the substrates including the wiring region serve as a bonding region where the substrate and the other member are bonded with sealing glass through the wiring.

The wiring formed on the rear substrate or the front substrate is often made of aluminum, silver, copper, chromium, or an alloy containing any of them. Moreover, these laminated bodies (for example, Cr-
Al-Cr) is also used. Since Cr has good wettability with glass, it is suitable as a wiring material provided in the bonding region. The wiring is preferably a metal film formed by a film forming technique. Moreover, the glass for sealing of this invention does not have a component which corrodes the wiring containing Au and Ag. Therefore, it is possible to provide a highly reliable image display device from the viewpoint of wiring corrosion.

  In order to maintain a gap between the back substrate and the front substrate, a member called a partition (spacer) arranged to support both substrates may be used. The spacer is made of a plate-like member made of a material such as glass or ceramics having some conductivity, and is usually installed at a position where the operation of the pixel is not hindered for each of the plurality of pixels. When the spacer is fixed to the front substrate and the rear substrate, it is preferable to use the sealing glass. This is because the glass of the present invention hardly releases moisture into the vacuum as described above.

  The present invention is similar to the display device of this embodiment in that various other displays using a glass plate on which wiring is formed, such as an electron emission type or field emission type display device using a thin film electron source or a plasma display device. The same applies to the device. Also, structural materials such as substrates for flat panel display devices, not only for bonding and vacuum sealing thereof, but also glass structural members for electronic devices such as magnetic disk substrates, structures in various other technical fields It can also be applied to materials.

  When sealing to form a vacuum container for an image display device, it is desirable to use a glass frit in which the glass of the above components is flakes or powder. The glass frit is used as a glass paste by mixing a solvent such as ethanol and water with a binder such as an organic compound. The frit can be made liquid by mixing with a solvent. The binder maintains the applied shape when the paste is applied and dried. The ratio of the solvent / binder can be changed as appropriate, but usually the solvent is 20-30% and the binder is 10% or less of the entire paste. The glass frit can be used by mixing the above-mentioned glass flakes or powders with various particles (fillers and beads) made of a material having a higher melting point than the sealing glass.

The filler improves various properties such as the thermal expansion coefficient of the adhesive, the sealing temperature, the electrical resistance value, or the wettability with the members constituting each display. The ratio between the sealing glass and the filler contained in the glass frit can be adjusted according to the purpose, but 20 to 90 volume% of the sealing glass and 10 to 80 volume% of the filler are preferable in the entire glass frit. As the filler, a plurality of fillers having different properties such as a thermal expansion coefficient can be used in combination. The filler is preferably a granular metal or an inorganic oxide, and examples of the inorganic oxide include SiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZrSiO ₄ , cordierite, mullite, and eucryptite. The particle size of the filler is preferably in the range of 0.5 to 10 μm, particularly 1 to 5 μm. By mixing such a small filler or increasing the amount of filler, the viscosity of the adhesive is increased, and the adhesive is prevented from being sucked in due to the internal decompression condition when bonded by heating.

A plurality of types of fillers can be mixed and used according to the intended characteristics. SiO ₂ has a smaller thermal expansion coefficient than glass mainly composed of vanadium and phosphorus, and is effective in adjusting the thermal expansion coefficient. In addition, Al ₂ O ₃ has almost the same coefficient of thermal expansion as glass with vanadium and phosphorus as main components, so the viscosity can be adjusted by mixing or the amount of adhesive can be increased to reduce the cost. Can do. By mixing a filler having a higher thermal conductivity than the sealing glass, such as crystalline particles, the thermal conductivity of the adhesive is increased to facilitate adhesion.

  Further, by mixing substantially spherical beads in a glass frit and dispersing them in the adhesive portion, it is possible to make the thickness of the sealing portion within a certain range according to the beads. For example, when the front substrate and the back substrate are opposed to each other with a gap of 100 μm and the peripheral portion is bonded, the size of the beads is 90 to 100 μm (in the range of 90 to 100% of the width of the gap) and the particle size and shape are precise. The one controlled by can be used. The bead particles preferably have an average particle size of 100 to 300 μm and a minor axis / major axis ratio of 0.8 or more. The mixing amount is preferably 0.1 to 1.0% by volume in the entire glass frit. The beads are made of a material having a melting point higher than that of the sealing glass so that the particles are not deformed at the time of adhesion, and examples thereof include silica and alumina particles. When using beads, the accuracy of the height held by the beads can be maintained by sufficiently reducing the particle size dispersed in an adhesive such as another filler.

  Hereinafter, it will be described in detail with reference to the drawings. FIG. 1 is a schematic plan view mainly illustrating the configuration of a flat panel display device. In this display device, a structure using an MIM as an electron source is taken as an example. 2 is a perspective view more specifically showing an example of the overall structure of the flat panel display device shown in FIG. 1, and FIG. 3 is a cross-sectional view taken along line AA ′ of FIG.

1, FIG. 2 and FIG. 3, the image signal wiring d (d1, d1) is formed on the inner surface of the back substrate SUB1.
d2,... dn) are formed, and the scanning signal wiring s (s1, s2, s3,.
sm). The electron source ELS is connected to the scanning electrode wiring s by the connection electrode ELC.
Power is supplied from (s1, s2, s3,... Sm). Reference VS indicates the vertical scanning direction.

  The front substrate SUB2 is slightly smaller in size than the rear substrate SUB1, and wirings dT serving as lead terminals for the image signal wiring d and wirings serving as lead terminals for the scanning signal wiring s are provided on the end surface of the rear substrate SUB1 protruding from the front substrate SUB2. sT is formed. Further, phosphor layers PH (PH (R), PH (G), PH (B)) of three colors are formed on the inner surface of the front substrate SUB2, and an anode electrode AD is formed thereon. An aluminum layer is used for the anode AD. In operation, a voltage of about 2 kV to 10 kV is applied to the anode AD of the front substrate. In this configuration, the phosphor PH (PH (R), PH (G), PH (B)) is partitioned by a light shielding layer (black matrix) BM. Although the anode electrode AD is shown as a solid electrode, the anode electrode AD may be a striped electrode that is divided for each pixel column by crossing the scanning signal wiring s (s1, s2, s3,... Sm). Electrons radiated from the electron source ELS are accelerated and collided with the phosphor layer PH (PH (R), PH (G), PH (B)) constituting the corresponding subpixel. As a result, the phosphor layer PH emits light of a predetermined color and is mixed with the light emission color of the phosphors of other subpixels to form a color pixel of a predetermined color.

As shown in FIGS. 2 and 3, the rear substrate SUB1 and the front substrate SUB2 are integrated by a sealing frame MFL installed around the display area. The integration of the back substrate SUB1, the front substrate SUB2, and the sealing frame MFL is achieved by bonding with sealing glass. As described with reference to FIG. 1, the image signal wiring d (d1, d2, d3,... Dn) and the scanning signal wiring s (s1, s2, s3, and so on) are arranged on the inner side of the sealing region on the inner surface of the back substrate SUB1. ... having a plurality of electron sources in a display area constituted by a matrix of sm). The wiring dT and the wiring sT are drawn out beyond the sealing region where the sealing frame MFL is installed.

  The power supply of the anode AD reaches the rear substrate SUB1 side through an inter-substrate connecting conductor (not shown), and goes outside the sealing region which is the installation portion of the sealing frame MFL as an extraction terminal (wiring) at an appropriate portion of the rear substrate SUB1. Pulled out.

  In the present embodiment, an example in which the sealing frame MFL is positioned in the sealing region where the wiring is drawn out and bonded with the sealing glass F between the front substrate SUB2 and the rear substrate SUB1 is taken as an example. The inner surfaces of the front substrate SUB2 and the back substrate SUB1 are opposed to each other, and the peripheral edge is fixed using the above-described sealing glass F so that the internal space sandwiched between the two substrates is isolated from the outside. In this example, when glass was used for sealing, glass was used as a frit.

  At the time of fixing using the sealing glass, for example, heating at about 450 ° C. is performed. A glass paste is prepared, and the paste is applied to the periphery of the substrate with a dispenser device. The paste is dried, for example, at about 250 ° C. to remove the solvent. Next, pre-baking is performed at about 460 ° C., the binder is removed and the glass is melted, and then a sealing frame (edge frame) is placed and baked and fixed at 450 ° C. Thereafter, the inside of the display device is exhausted to about 1 μPa through the exhaust pipe 303 and then sealed.

  Note that the softening point of the sealing material on either the surface of the edge frame that adheres to the back substrate or the surface that adheres to the front substrate is set higher than the other, and the other side is bonded after the side with the higher softening point is bonded. Then, it is preferable that the positional deviation at the time of adhesion hardly occurs. The front substrate SUB2 is formed as an edged shallow dish with an edge that bends and protrudes toward the back substrate SUB1 on the periphery, and the two substrates are sealed by bonding to the contact portion between the edge and the back substrate with glass. It can also be set as the structure to do. In this case, the glass is applied only on the back substrate side.

Further, when a spacer SPC is provided in the sealed space to maintain a space between the back substrate and the front substrate, the sealing glass of the present invention is formed on the spacer SPC and the planted portion of the spacer SPC. Apply and fix. Usually, the spacer SPC is installed on the scanning signal wiring s.

An example of the sealing glass sample is shown in FIG. In FIG. 4, a plurality of glass names SPL-01 to SPL-30 are shown depending on the difference in content of each component. Each component is shown in weight% (wt%) in terms of oxide. Starting materials are V ₂ O ₅ (manufactured by High Purity Chemical Laboratory, purity 99.9%), BaCO ₃ (manufactured by High Purity Chemical Laboratory, purity 99.9%), P ₂ O ₅ (High Purity Chemical Laboratory) Manufactured, purity 99.9%), Sb ₂ O ₃ (Wako Reagent, purity 99.9%). Sample SPL-28 is
The composition is almost the same as that of SPL-27, the starting materials are V ₂ O ₅ , BaPO ₃ , and Sb ₂ O _3, and P is supplied using barium phosphate instead of P ₂ O ₅ .

  In order to produce the glass for sealing, first, each raw material is mixed by the weight ratio shown in FIG.

With regard to BaCO ₃ , taking into account that it can be decomposed into BaO + CO ₂ , it was converted into an equivalent amount of BaO and mixed. All raw materials except P ₂ O ₅ are mixed in advance. This is because P ₂ O ₅ is highly hygroscopic and is not left in the atmosphere for a long time. A mixed powder other than P ₂ O ₅ is put into a platinum crucible, and the platinum crucible is put on a balance, and a predetermined amount of P ₂ O ₅ is weighed, and simultaneously mixed with a metal spoon. At this time, in order to avoid moisture absorption from the atmosphere, it is preferable not to mix using a mortar or a ball mill.

The platinum crucible containing the above raw material mixed powder is placed in a glass melting furnace and heating is started. The temperature increase rate is set to 5 ° C./min, and the temperature is maintained for 1 hour from the time when the target temperature is reached. In this embodiment, the target temperature is fixed at 1000 ° C. The molten glass is held for 1 hour with stirring. After the holding, the platinum crucible is taken out of the melting furnace and cast into a graphite mold heated to 300 ° C. in advance. The glass cast into the graphite mold was transferred to a strain relief furnace that had been heated to a strain relief temperature in advance, and the strain was removed by holding for 1 hour, and then cooled to room temperature at a rate of 1 ° C./min. The obtained glass has a size of 30 mm × 40 mm × 80 mm. The obtained glass block was cut into a size of 4 mm × 4 mm × 15 mm, and the thermal expansion coefficient (α), glass transition point (Tg), and glass softening point were evaluated. Moreover, the water resistance test and the constant temperature and humidity test were done using the test piece of the same shape. As a result of sample preparation, SPL-16, 21, 26, 32, 33, 37, 38, 41,
In the glass No. 42, the ratio of phosphorus to vanadium deviated from the range in which vitrification tends to occur, and the workability when producing a glass suitable for bonding was not good. Accordingly, the V ₂ O ₅ content is preferably in the range of 45 to 60% by weight and P ₂ O ₅ in the range of ₁₅ to 30% by weight.

  The method of the water resistance test is as follows.

  Into a 200 cc beaker, 70 ° C., 100 cc of water is put, and one glass test piece of this example whose weight has been measured in advance is put therein. Further, the beaker is placed in a 70 ° C. water bath, and the test piece after 2 hours is taken out, and the weight after drying with a heater at 150 ° C. for 30 minutes is measured. The weight change rate of the test piece before and after the water resistance test was calculated as: (weight before water resistance test−weight after water resistance test) / weight before water resistance test × 100 (%).

  The method of the constant temperature and humidity test is as follows.

  Each glass was pulverized to prepare a 1 g compact, and the one placed on a soda glass substrate was baked in air at 450 ° C. for 30 minutes to prepare a sealing simulation sample. Next, the sample was placed in a thermostatic bath, and a test for 48 hours was performed in 85 ° C. × 85% humid air. The sample after the test was washed with an ultrasonic washing machine to completely remove the glass components that were actually decomposed and dissociated, and then dried at 150 ° C. for 30 minutes using a heater. Similar to the water resistance test described above, the weight change rate of the test piece before and after the constant temperature and humidity test = (weight after the constant temperature and humidity test−weight before the constant temperature and humidity test) / weight before the constant temperature and humidity test × 100 (%) Calculated. Moreover, it evaluated by the external appearance of the sample after a test, and classified into the following categories.

  The change in weight before and after the test was 0.1% or less, and the gloss before the test was kept as it was and the appearance was not distinguished at all. A change in weight before and after the test was 0.1% or less, and a change in gloss slightly duller than that before the test was indicated as “◯”. A weight change between before and after the test of 0.1% to 5.0% is indicated by Δ. The case where the weight change before and after the test was 5.0% or more was indicated as x.

In FIG. 4, the evaluation result by a water resistance test and a constant temperature and humidity test is shown. As a result of the water resistance test, SPL-01, 02, 03, 06, 09, 11, 14, 18, and 19 have a weight change rate of 1% or less by keeping 2 hours in 70 ° C. warm water. In particular, the glass SPL-07, 08, 12, 13, of the present invention.
The weight change rate of 22, 23, 24, 27, 28, 29, and 30 was not recognized. As a result of the water resistance test, when the total of Ba and Sb was 15% or less and 35% or more, the water resistance was not excellent.

As a result of the constant temperature and humidity test, (BaO + Sb ₂ O ₃ ) is 15 to 35 wt%, and BaO /
When the Sb ₂ O ₃ weight ratio or the Sb ₂ O ₃ / BaO weight ratio is outside the range of 0.3 or less, that is, SPL-2, 3, 4, 9, 14, 17, 18, 19 The water resistance was good as a sealing glass, but it deteriorated in a constant temperature and humidity atmosphere. Therefore, the constant temperature and humidity test evaluation results of the glass of the present invention are both ◎ or ○.

The test result of SPL-28 with different raw materials was almost the same as SPL-16, and the constant temperature and humidity test evaluation result was ◎. Also prepared HPL-1 containing TeO ₂ as a comparative example was evaluated in the same manner. In HPL-1 containing TeO ₂ , there was no gloss after the constant temperature and humidity test, the color tone became yellowish dark green, and it was shown to deteriorate with humidity.

  Therefore, if these glasses are used, it is possible to perform various types of sealing and bonding that are used under conditions that come in contact with high humidity air.

Various additives were studied for lowering the melting point of the glass of the present invention. The composition ratio of SPL-27 was selected as a representative sample in the above examples, and Ag ₂ O, Cu ₂ O, Cs ₂ O, HfO ₂ , Na ₂ O, K ₂ O were further added to the raw material powder of the glass. Alternatively, the state of change of the glass transition point when the addition amount of TeO ₂ was changed was examined. The result of the examination is as shown in FIG. 5, and it is confirmed that Ag ₂ O, Cu ₂ O, Cs ₂ O, HfO ₂ , Na ₂ O, K ₂ O or TeO ₂ has the effect of lowering the transition point of the glass of the present invention. It was done. In addition, when many of these additives were added, crystals were precipitated on the glass. Therefore, the addition amount of these additives is preferably in the range of 1 to 10%. The reason why crystals are likely to precipitate is thought to be that the vanadium and phosphorus content ratio is reduced, resulting in exceeding the vitrification range.

  FIG. 6 is a schematic diagram illustrating the configuration of the plasma display device. In the plasma display device of this example, the rear substrate SUB1 and the front substrate SUB2 are opposed to each other, and the peripheral portion is bonded by the bonding material F using the glass composition of the present invention. Discharge electrodes H are provided on the front substrate, and address electrodes A are provided on the back substrate, and a protective layer for protecting these electrodes is provided. The rib SPC is formed between the pixels and serves as a partition that holds a gap between the front substrate and the rear substrate. Each pixel is provided with phosphors PH of red, green and blue colors. In this example, this rib was also made of a glass composition having the composition range of the present invention. FIG. 7 shows a modified example in which the glass beads B and the filler f are mixed into the bonding material F. By dispersing glass beads having a substantially uniform particle diameter in the bonding material, the thickness of the bonding material in the entire apparatus can be made uniform.

  The plasma display device is formed by once depressurizing the inside of a vacuum vessel under heating and then enclosing a rare gas. Since the glass composition of the present invention has low hygroscopicity, it can be easily applied to a vacuuming process in which a vacuum container prepared for display is decompressed under heating. Even if the panel is temporarily stored before and after the evacuation process, there are few problems such as deterioration.

It is a schematic plan view which mainly demonstrates the structure of the flat type display apparatus of this invention. FIG. 2 is a perspective view more specifically showing an example of the overall structure of the flat panel display device shown in FIG. 1. It is a figure which shows the AA 'sectional drawing of FIG. It is a table | surface explaining the composition and characteristic of the glass for sealing of this invention. It is a figure which shows the effect which lowers the glass softening point of the glass for sealing of this invention. It is the figure which applied the glass of this invention to the rib of the plasma display. It is the figure which showed typically the glass bead and filler mixed with the glass for sealing of this invention.

Explanation of symbols

SUB1 Rear substrate SUB2 Front substrate s (s1, s2,... Sm) Scan signal wiring d (d1, d2, d3,...) Image signal wiring ELS Electron source ELC Connection electrode AD Anode BM Black matrix PH (PH ( R), PH (G), PH (B)) Phosphor layer SDR Scanning signal line drive circuit DDR Image signal line drive circuit

Claims (12)

A glass containing vanadium, phosphorus, barium, and antimony,
The barium oxide basis to BaO, and in terms oxides and antimony to _Sb 2 _{O 3,} containing 15 to 26 wt%, the total of BaO and _{Sb 2 O 3, BaO / Sb} 2 O 3 Is less than 0.24 in weight ratio, and
A glass comprising 45 to 60% by weight of vanadium in terms of oxide to V ₂ O ₅ and 15 to 30% by weight of phosphorus in terms of oxide to P ₂ O ₅ . The glass according to claim 1,
The glass contains an additive of at least one of Ag, Cu, Cs, Hf, Na, K, or Te, and the additive includes Ag ₂ O, Cu ₂ O, Cs ₂ O, HfO ₂ , Na ₂ O. , K ₂ O or TeO ₂ in terms of oxide, 1 to 10% by weight contained in glass. A display device in which a back substrate having a plurality of electron sources, a front substrate having a plurality of phosphors, and a space formed by facing the back substrate and the front substrate are decompressed and sealed with an adhesive,
The said adhesive material contains the glass of Claim 1 or 2, The display apparatus characterized by the above-mentioned.   4. The display device according to claim 3, further comprising an edge frame that forms the space between the front substrate and the rear substrate.   4. The display device according to claim 3, wherein the front substrate has a peripheral portion that is bent and protrudes toward the back substrate, and the peripheral portion and the back substrate are bonded to each other. Display device. A display device according to any one of claims 3 to 5,
The adhesive material contains 20 to 90% by volume of the glass and 10 to 80% by volume of a filler. A display device according to any one of claims 3 to 6,
The display device according to claim 1, wherein the adhesive contains 0.1 to 1.0% by volume of beads having a particle diameter of 90 to 100% of a gap between the front substrate and the rear substrate. The display device according to claim 4,
A display device, wherein a softening point of an adhesive that bonds the edge frame and the front substrate is different from a softening point of an adhesive that bonds the edge frame and the rear substrate. A plasma display device having a front substrate, a rear substrate facing the front substrate, and a partition wall provided on the rear substrate and holding a gap with the front substrate,
The plasma display device according to claim 1, wherein the partition wall is made of the glass according to claim 1. A glass frit for sealing, in which at least the glass according to claim 1 or 2 and a filler are mixed,
A glass frit for sealing, containing 20 to 90% by volume of the glass and 10 to 80% by volume of a filler. The glass frit for sealing according to claim 10, wherein the filler is at least one of SiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZrSiO ₄ , cordierite, mullite, and eucryptite. Glass frit for sealing.   12. The glass frit for sealing according to claim 10 or 11, wherein the filler has an average particle diameter of 0.5 to 10 [mu] m.

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