JP2002075170A - Gettering material, flat display panel and their manufacturing methods - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a FDP(a flat display panel) which can suppress the influence of an impurity gas accompanying manufacturing and realize high quality with a low cost. SOLUTION: A paste-like or a sheet-like gettering material, of which the main components are a mixture of at least either material of ceramics or glass, which is selected from among a group consisting of ceramics and glass, and an alloy having gas absorptivity is used for manufacturing of a FDP. This FDP manufactured by using the getter material has a front panel member 11f, a back-panel member 11r and barrier ribs 2a, 2b fixed between both the panel members, and the barrier ribs 2a, 2b are formed by a composite material, which is dispersed of an alloy having gas absorptivity into a matrix comprising at least either the ceramics or glass selected from among the group consisting of ceramics and glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a getter material for removing or inactivating impurities in a predetermined system, a flat display panel (FDP) using the same, and a method for manufacturing the same.

[0002]

2. Description of the Related Art A plasma display panel (PDP), which is a typical example of the FDP, has, for example, a structure in which a large number of partitions are sandwiched between two glass substrates. Are formed. An image is displayed by discharging and emitting light in this cell. FIG.
Shows an example of an AC type PDP. In the PDP 1, a display electrode 13, a dielectric layer 14, and a protective film 15 are provided on a front glass substrate 11f. The address electrode 16 and the dielectric layer 1 are provided on the rear glass substrate 11r.
7 are provided. Partition walls 2a and 2b are provided between the front glass substrate 11f and the rear glass substrate 11r, and a phosphor layer 8G for a specific color (for example, green) is provided in a space partitioned by these partition walls. Will be accommodated. A portion between the partition walls 2a and 2b and provided with the phosphor layer 8G, the display electrode 13, and the address electrode 16 constitutes a plasma discharge cell 10G for a specific color (for example, green). In the PDP 1, a large number of such plasma discharge cells are arranged via partition walls. For example, a plasma display cell 10R for displaying red that accommodates a phosphor layer 8R for a specific color (for example, red) is provided next to the plasma discharge 10G via the partition wall 2a. Partition wall 2b
The blue plasma discharge cell 10B that accommodates the blue phosphor layer 8B is provided next to the plasma discharge cell 10G via the.

For example, Japanese Patent Application Laid-Open No. 2-114430 discloses a method of manufacturing a partition wall of a PDP by forming a thick paste by screen printing a glass paste on a front glass plate and baking the glass paste.

Japanese Patent Application Laid-Open No. 6-36683 discloses a method in which a paste for partition walls and an anti-sandblasting paste are sequentially applied to a glass substrate, unnecessary portions are removed by sandblasting, and firing is performed. As a similar production method, a method of pasting a partition material in a sheet shape in advance to a glass substrate and then removing an unnecessary portion by sandblasting, or a method using a photosensitive resin is also known.

[0005] A screen printing method or a sandblasting method is used for forming the phosphor layer, similarly to the partition walls.

A rear glass substrate on which partition walls and a phosphor layer are formed by such a method and a front glass substrate on which a display electrode, a dielectric layer, a protective film and the like are formed are assembled with a low-melting glass interposed therebetween. Sealing is integrated by performing heat treatment. Thereafter, the inside of the panel is evacuated to a vacuum, and a discharge gas such as He-Xe or Ne-Xe
PD by sealing at a pressure of 00 to 500 Torr
P is obtained.

[0007]

The inside of the PDP manufactured by the above-described method contains impurity gas contained in the discharge gas, glass and residual resin components contained in the partition walls, etc.
There is a small amount of gas released from a dielectric layer, an electrode, or the like. Specific examples of these gases include water vapor, oxygen,
Nitrogen, carbon dioxide, etc., when present in the panel, absorb the energy of the discharge gas, or oxidize the electrodes, making the plasma discharge unstable or shortening the life of the discharge cell. There was a problem.
Furthermore, when the panel is not used for a long time after manufacturing, for example, when the panel storage period before assembling is long, the amount of impurity gas in the panel increases, so that plasma discharge does not occur and the discharge function itself is lost. It can happen.

Further, in the above-described panel exhaust process, since a large number of partitions are provided in a narrow space, exhaust resistance is large, and it takes a long time to reduce productivity. Since the exhaust cannot be performed completely, the above-described problem may occur.

As an FDP other than the PDP, for example, a plasma-addressed liquid crystal display (PALCD) uses plasma discharge for an address of the liquid crystal display, and is a display in which partitions and electrodes are formed similarly to the PDP. Therefore, if an impurity gas exists in the panel, there is a problem similar to that of the PDP.

[0010] A field emission display (FED) is a display utilizing the same electron-beam-excited phosphor emission as a CRT. A large number of electron sources and phosphors are arranged in a vacuum space between two substrates. You. In this display, it is necessary to maintain a vacuum in order to generate an electron beam, and it is necessary to remove an impurity gas inside the panel as in a PDP or the like.

An object of the present invention is to solve the above-mentioned problems, and more specifically, to provide a technique for suppressing the influence of an impurity gas accompanying a device such as an FDP.

It is a further object of the present invention to provide a high quality FDP at low cost.

[0013]

SUMMARY OF THE INVENTION The present inventor has provided a getter function which can improve the performance and extend the life of an apparatus by disposing the apparatus in an apparatus in which a reduced pressure or a rare gas atmosphere is sealed like FDP. The materials to have were studied. as a result,
A material obtained by combining a glass component and / or a ceramic component with a gas absorbing alloy having a gettering function is useful for easily and effectively forming a structure having a gettering function in an apparatus space. I found it.

Further, the present inventor has found that inside the FDP,
By forming the partition walls or spacers supporting the front panel and the rear panel with such a getter material, it becomes easy to absorb impurity gas inside the panel and to maintain a vacuum degree, thereby reducing the performance at a low cost. Stable FDP
Was obtained.

Thus, according to the present invention, there is provided a paste-like or sheet-like getter material containing as a main component a mixture of at least one material selected from the group consisting of ceramics and glass and an alloy having a gas absorbing ability. You. In this getter material, the content of the alloy in the mixture is preferably 1% by mass to 10% by mass. In particular, the getter material according to the invention can be for FDP production.

Further, according to the present invention, there is provided a flat display panel having a front panel material, a rear panel material and a partition or spacer provided therebetween, wherein the flat display panel has a partition or spacer made of ceramics and glass. It is formed of a composite material in which an alloy having a gas absorbing ability is dispersed in a matrix made of at least one material selected from the group. Typically, the composite is a sintered body.

Further, the present invention provides a method of manufacturing a flat display panel, comprising the steps of forming a pattern of partition walls or spacers on a back panel material using the getter material, forming the pattern on the back panel material. Baking the patterned pattern in an inert atmosphere, in the process of cooling the partition walls or spacers obtained by baking the pattern at the required maximum temperature, introducing oxygen into the inert atmosphere, and separating the partition walls or the spacers. A step of oxidizing, a step of joining the front panel material to the back panel material with the partition or spacer interposed therebetween, a step of making the space between them an inert atmosphere or vacuum, and heating the joined panel material to form the partition Alternatively, the method includes a step of activating the gettering function of the spacer.

In particular, the getter material according to the present invention is suitable for forming an internal structure of a display device or the like in which a vacuum or a rare gas atmosphere is sealed, and is particularly expected as a thin or large display replacing CRT. PD
Suitable for forming internal structures such as P, PALCD, FDP such as FED, and other devices such as high intensity lamps.

FD using getter material according to the present invention
Gettering of impurity gases such as hydrogen, water vapor, oxygen, carbon monoxide, carbon dioxide, and nitrogen that can adversely affect the operation of FDP if barriers and spacers that support the front and rear substrates of P are formed Or F
The degree of vacuum inside the DP can be maintained. Such an operation and effect leads to an improvement in the performance of the panel and a longer life.
Further, by using the getter material according to the present invention, it is possible to shorten the evacuation time in the panel manufacturing process. Hereinafter, the present invention will be described in more detail.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the case of a PDP, for example, a partition for separating discharge cells on a glass substrate can be formed by patterning and sintering the above paste or sheet getter material. In this case, PD
The discharge gas enclosed in the P contains impurity gas, the gas is released from the glass and residual resin components, the dielectric layer, the electrodes, etc. contained in the panel. Even if the gas remains, the partition walls contain the gas absorbing alloy, so that the impurity gas can be absorbed in the partition walls, the plasma discharge is stabilized, and the life of the discharge cells can be extended. Further, since the gas absorbing alloy is contained in the partition existing inside the discharge cell, the impurity gas can be uniformly removed over the entire panel. For example, when a material having a gettering function is arranged on the outer peripheral portion of the panel. Thus, the problem that the discharge becomes locally unstable in the panel is less likely to occur.

As the gas-absorbing alloy which can be used in the present invention, those having irreversible gas-absorbing properties for water vapor, oxygen, nitrogen and carbon dioxide and not absorbing inert gases such as He, Ne and Xe are suitable. ing. As such an alloy, for example, a zirconium alloy is preferable. Specific examples of the zirconium alloy include a Zr—Ni-based alloy such as Zr
₂ Ni, Zr-Al based alloys such as Zr ₂ Al, Zr-V
-Ni-based alloys such as _{Zr 30 V 50 Ni 20, Zr} -Ni-
Fe-based alloys such as _{Zr 25 Ni 15 Fe 60, Zr} -Fe-
V-based alloys such as _{Zr 70 Fe 5 V 25, Zr} -V-Fe-
And the like Ni-based alloys such as _{Zr 50 V 30 Fe 19 Ni 1} .

The glass and ceramics which are the main components of the getter material according to the present invention are not particularly limited. For example, general low-melting glass such as lead-based glass and zinc-based glass can be used for the glass, and the ceramic can be used for the ceramic. Relatively high-strength materials such as silica, alumina, and zirconia can be used. Further, by forming a composite composition of low melting point glass and high-strength ceramic, a dense structure having high mechanical strength can be obtained by sintering at a low temperature of about 500 ° C. The adverse effect that the glass substrate to be softened and deformed can be suppressed.

The getter material according to the invention can be used in addition to glass and / or ceramics and gas-absorbing alloys,
Components for maintaining the paste or sheet form, for example, a binder such as a resin, a solvent, a dispersant, and a thickener can be contained. In a preferred embodiment,
The getter material according to the present invention is characterized in that, for example, 5% by mass of an alloy having a gas absorbing ability is added to a powder obtained by mixing the above-mentioned glass and the above-mentioned ceramics at a weight ratio of, for example, about 1: 1. For example, about 10% by mass of a resin such as polyvinyl butyral is added as a resin, and a suitable amount of a solvent such as terpineol, and a dispersant or the like are added and mixed as necessary to obtain a paste. Also, a slurry is prepared by adding a resin such as polyvinyl butyral and a solvent such as toluene and butanol to the mixed powder of the ceramics and the glass in an amount of about 10% by mass and forming the slurry into a sheet shape by a doctor blade method or the like. can do.

As the resin contained in the getter material of the present invention, besides polyvinyl butyral, a thermoplastic resin such as an acrylic resin, a polyolefin resin, or a fluororesin which is burned off by a heat treatment at about 400 to 500 ° C. can be used. Acrylic resin having excellent thermal decomposability in an inert atmosphere is a more preferable material.

In the getter material of the present invention, if the compounding ratio of the alloy having the gas absorbing ability is too large, the mechanical strength of the structure may be lowered or the insulating property may be lowered. Also, if the alloying ratio is too small, a sufficient gas absorbing effect cannot be obtained. From such a viewpoint, a preferable addition amount is about 1% by mass to 10% by mass with respect to a mixture of glass and / or ceramics and the alloy. Further, in the getter material of the present invention, it is desirable that ceramics and / or glass and the gas absorbing alloy are mixed as uniformly as possible. Although the ratio of ceramics to glass is not impaired, the effect of the present invention is not impaired. However, from the viewpoint of securing the function as a partition wall of the FDP, ceramics: glass = 20: 80 to 6 by mass ratio.
0:40 is a preferable mixing ratio. Glass ratio is 80
%, The mechanical strength of the partition walls may be insufficient, and if the glass ratio is less than 40%, the densification at a general partition wall sintering temperature of 550 ° C. to 600 ° C. becomes insufficient. Insufficient strength and insulation may be insufficient.

In the method of manufacturing an FDP according to the present invention, for example, the above-mentioned getter material is patterned on the surface of a glass substrate constituting a back panel in order to form a partition or a spacer. The patterned getter material is then fired in an inert atmosphere, and oxygen is introduced into the inert atmosphere during at least a portion of its cooling process.
The introduction of oxygen oxidizes the surface of the partition or spacer formed by firing the getter material. Next, the back panel and the front panel may be joined, and the space therebetween may be sealed with an inert atmosphere or vacuum. Next, the partition or the spacer is heated to activate the gettering function of the partition or the spacer.

The manufacturing method will be described in more detail by taking PDP as an example. First, an address electrode and a dielectric layer are previously formed on the surface of the rear glass substrate of the PDP by a printing method, a vapor deposition method, or the like. Next, a paste or a sheet as the gettering material of the present invention is applied on a glass substrate. If it is a paste, it can be applied to a pattern corresponding to a partition or a spacer by a screen printing method or the like. If it is a sheet, it can be crimped to the glass substrate by a thermocompression bonding method or bonded with a general adhesive, and then unnecessary to form the shape of the partition wall or the spacer by a well-known sand blast method etc. What is necessary is just to remove a part. Further, after forming the phosphor materials for red, blue and green on the surface of the gettering material forming the partition walls or the spacers by a screen printing method or the like, the gettering material and the phosphor layer are formed in an inert atmosphere such as an Ar atmosphere. May be fired. By firing, a partition wall or a spacer made of a composite material in which a gas absorbing alloy is dispersed in a matrix made of ceramics and / or glass is obtained. Generally, the composite material is a sintered body. By the firing step, a structure in which the phosphor layer is formed on the partition wall or the spacer is obtained.

Here, the surface of the gas-absorbing alloy is usually covered with an inert surface coating such as an oxide or a nitride, but when heated in an inert atmosphere as described above, a surface inert layer is formed. Oxides and nitrides that have been diffused into the alloy start gas absorption. When the surface layer of the gas-absorbing alloy is activated in this way, it cannot be handled in the air or the like, which may hinder the panel manufacturing process.
In order to prevent this, in the cooling step after heating at the highest temperature in the baking step, a small amount of oxygen may be introduced into an inert atmosphere to form an oxide layer on the surface of the gas absorbing alloy. Since the gas-absorbing alloy whose surface is oxidized does not absorb gas even when exposed to the atmosphere, the subsequent panel manufacturing process can be performed in the atmosphere. The temperature at which the introduction of oxygen starts depends on the type of gas-absorbing alloy, but is 1
The temperature may be about 00 ° C., and the oxygen concentration may be, for example, 1000
It may be about ppm.

The rear glass substrate having the partition walls or spacers and the phosphor layer formed by the above method, and the front glass substrate on which the display electrodes, the dielectric layer and the protective film of a predetermined pattern are formed are formed using a glass paste or the like. After sealing, the space between the two glass substrates is evacuated and filled with a discharge gas.

After the discharge gas is filled between the sealed glass substrates, the gas absorbing alloy is not exposed to the atmosphere. Therefore, the surface of the gas absorbing alloy can be activated by heating to, for example, 400 ° C. or higher at the same time as or after the vacuum exhaust step or the discharge gas filling step to start gas absorption.

The activation treatment of the gas-absorbing alloy depends on the kind of the alloy, the atmosphere inside the panel, the atmospheric pressure, the heat treatment time, and the like.
The activation effect can be obtained by the treatment for about 10 minutes to 1 hour. The PDP having the structure as shown in FIG.
Can be obtained. In the obtained PDP, the partition walls or spacers provided between the front glass substrate and the rear glass substrate are made of a composite material in which a gas absorbing alloy is dispersed in a matrix made of ceramics and / or glass.

[0032]

EXAMPLE A PDP having a structure as shown in FIG. 1 was manufactured by the following process. First, a display electrode, a dielectric layer and a protective film were formed in a predetermined pattern on the surface of a commercially available soda glass substrate to obtain a front panel.

Next, Zr- ground to a particle size of 10 μm or less.
After mixing a V-Fe alloy (composition: Zr ₇₀ V ₂₅ Fe ₅ ), commercially available lead-based glass powder, silica powder, and alumina powder, a 20% by mass terpineol solution of acrylic resin was added to 1
5% by mass was added and mixed to prepare a partition wall paste shown in Table 1. In addition,% in Table 1 shows mass%. As a comparative example, after mixing a lead-based glass powder, a silica powder, and an alumina powder, an acrylic resin solution was added and mixed to prepare a paste for partition walls. An address electrode and a dielectric layer were previously formed on a soda glass substrate, and the paste was applied in a predetermined shape by a screen printing method, and then dried. After printing and drying are repeated several times to obtain a partition shape, baking is performed at 550 ° C. in an Ar atmosphere, and in the cooling step, oxygen is reduced to 1000 ppm from 100 ° C.
Introduced. After forming a phosphor layer by a screen printing method on the side wall and the bottom of the cell on the obtained glass substrate,
The back panel was obtained by firing in an Ar atmosphere and introducing oxygen during cooling in the same manner. The partition walls formed on the back panel were composed of a composite sintered body in which a Zr-V-Fe alloy was dispersed in a matrix composed of lead glass, silica, and alumina.

After the obtained front panel and rear panel were integrated and sealed with a commercially available glass paste with a partition wall interposed therebetween, a vacuum pump was connected to exhaust the gas to 10 ⁻³ Pa.
After the evacuation was stopped once, heating was performed at 400 ° C. for 30 minutes. Then, the chamber was evacuated again, and the time to reach 10 ^-4 Pa was measured. After reaching 10 ^-4 Pa, heating and evacuation were stopped, and then a change in the degree of vacuum caused by generation of impurity gas in the panel was measured.

As shown in Table 2, in the example according to the present invention, the evacuation time was shortened as compared with the comparative example which is a conventional PDP. Further, as shown in Table 3, in the example of the present invention, even if an impurity gas was generated in the panel, it was absorbed by the partition walls, so that a decrease in the degree of vacuum was hardly observed.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

As described above, according to the present invention,
With respect to a display device or the like in which a vacuum or a rare gas atmosphere is sealed, high performance and long life can be achieved. In particular, the getter material according to the present invention can provide a high-performance and long-life FDP at low cost in a manufacturing process equivalent to the conventional one, and its industrial utility value is great.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a structure of a PDP.

[Explanation of symbols]

Reference Signs List 1 PDP, 2a, 2b partition, 11f front glass substrate, 11r rear glass substrate, 13 display electrode, 14
Dielectric layer, 15 protective film, 16 address electrode, 17
Dielectric layer.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Yoshihisa Ohashi 1-8 Fuso-cho, Amagasaki City, Hyogo Prefecture Inside the Electronics Technology Research Laboratories, Sumitomo Metal Industries, Ltd. (72) Hideya Kaminaka 1st Fuso-cho, Amagasaki City, Hyogo Prefecture No. 8 Sumitomo Metal Industries, Ltd. Electronics Technology Laboratory F-term (reference) 5C012 AA09 5C027 AA09 5C035 JJ11 5C040 FA01 GF19 HA08 KA02 MA26 MA30 5C058 AA11 AB06 BA35

Claims (4)

[Claims] 1. A paste-like or sheet-like getter material mainly comprising a mixture of at least one material selected from the group consisting of ceramics and glass and an alloy having a gas absorbing ability. 2. The getter material according to claim 1, wherein the content of the alloy in the mixture is 1% by mass to 10% by mass. 3. A flat display panel having a front panel material, a rear panel material, and a partition or a spacer provided therebetween, wherein the partition or the spacer is at least one selected from the group consisting of ceramics and glass. A flat display panel formed of a composite material in which an alloy having a gas absorbing ability is dispersed in a matrix made of such a material. 4. A method of manufacturing a flat display panel according to claim 3, wherein a pattern of a partition or a spacer is formed on a back panel material using the getter material according to claim 1 or 2. Baking the pattern formed on the back panel material in an inert atmosphere, in a step of cooling a partition or a spacer obtained by baking the pattern at a required maximum temperature, Introducing oxygen to oxidize the partition walls or the spacers; bonding the front panel material to the back panel material with the partition walls or the spacers interposed therebetween to make the space therebetween an inert atmosphere or vacuum A step of heating the joined panel material to activate the gettering function of the partition wall or the spacer. Method of manufacturing a flat display panel having.