JP2009289425A - Gas discharge display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas discharge display panel having a longer life and highly reliable display quality while suppressing the deterioration and aging effects of discharge property and emission luminance/chromaticity resulting from impurity gas. <P>SOLUTION: The gas discharge display panel includes a gas adsorbing device 20 containing copper-exchanged ZSM-5 type zeolite and provided in a space to be aerated with a discharge space held between a first substrate and a second substrate. The copper-ion-exchanged ZSM-5 type zeolite is formed into the gas adsorbing device which can be stored without deterioration until used, to exhibit very low adsorption balancing pressure on impurity gas such as oxygen, nitrogen, carbon monoxide, carbon dioxide or hydrogen, and to exhibit chemically adsorptive strong force, therefore removing the impurity gas from the discharge space in a display region while keeping filled gas highly pure. This produces a longer life and highly reliable display quality while suppressing the deterioration and aging effects of discharge property and emission luminance/chromaticity resulting from the impurity gas. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a gas discharge display panel, and more particularly to a plasma display including a glass substrate, electrodes, a dielectric layer, a barrier layer, a light emitter layer, and a gas adsorbent.

  A plasma display panel (hereinafter referred to as PDP) is a display that displays a screen by exciting phosphors with ultraviolet rays generated by gas discharge.

  Conventionally, when a PDP is switched from one screen display to a different screen display, the operating voltage (discharge start voltage and discharge sustaining voltage) of the cells lit in the former screen display rises and lighting becomes unstable. (Discharge flickering phenomenon) was a problem. In addition, when the lighting is performed for a long time, the operating voltage fluctuates with time, so that the discharge flicker phenomenon of the cell occurs in a wide range of the panel. In other words, the cathode film is sputtered faster due to the influence of the impurity gas, and the problem of deterioration of lighting over time such as abnormal discharge due to a decrease in the amount of secondary electrons emitted from the cathode film in thousands of hours in continuous lighting. Had occurred.

  Therefore, in order for the screen display to be stable for tens of thousands of hours, the gas sealed in the panel needs to be kept highly purified. For this reason, in the gas filling process of PDP production, a method is generally adopted in which the inside of the panel is heated while being evacuated and the discharge gas is sealed after removing the impurity gas in the panel.

  However, in this method, since the discharge gas is introduced through the exhaust pipe that exhausts the inside of the panel, the impurity gas exhausted from the inside of the panel is adsorbed on the inner wall of the vacuum exhaust system, and the discharge gas is introduced into the panel again together with the discharge gas. I will enter. For this reason, it cannot be said that it is sufficient in terms of preventing the impurity gas from being mixed into the panel.

  Thus, a technique for improving the purity of the discharge gas in the panel by applying a gas adsorbent (getter) is disclosed.

  The front substrate and the rear substrate are combined, the periphery of the combination is sealed to form a panel body, a getter is provided in advance in an exhaust pipe attached to the panel body, the panel body is decompressed, and the getter is flushed ( The discharge gas is supplied after the mercury is supplied. Thereafter, the glass tube is heated and melted, sealed, and cut to obtain a plasma display panel (see, for example, Patent Document 1). According to this technique, since the impurity gas mixed in the discharge space is adsorbed and removed by the getter, there is a temporary effect in improving the purity of the discharge gas in the panel.

  Further, a technique characterized by providing an impurity gas adsorbing layer under a phosphor layer made of phosphor particles is disclosed, and any material of MgO, CaO, SrO, BaO can be used as a material having a getter action. A soil oxide material has been proposed (see Patent Document 2).

Similarly, for the purpose of adsorbing impurity gas discharged at the time of sealing, a technique characterized by applying an ion exchange zeolite such as lithium ion exchange mordenite around the inside of the frit or in the frit is disclosed. (For example, refer to Patent Document 3).
JP-A-4-269425 JP 2002-358892 A JP 2002-367520 A

  However, the non-evaporable getters exemplified in Patent Document 1 often include those that are harmful to the environment. As an example, HPTF getters commercially available from SAES Getters as PDP getters contain Zr, V, and Fe, but V is toxic in its oxidized form and is a deleterious substance subject to the Poisonous and Deleterious Substances Control Law. It is also a PRTR Law Class 1 Designated Chemical Substance. Since it is used inside the PDP, it does not directly affect the human body. However, considering future recycling, etc., it is preferable to use a harmless material as much as possible.

  In addition, in the case of using an alkali metal earth thin film exemplified in Patent Document 2 as a getter, there is no harmfulness to the environment, and a certain amount of impurity gas can be adsorbed. However, a slight residual impurity gas generates a gradient of impurity gas concentration in the panel, and this gradient of impurity gas may cause a problem of non-uniform drive voltage and light emission luminance as a panel characteristic. . In addition, there is a possibility that the same problem may occur due to the impurity gas that intrudes with time, so that higher purity gas purification is desired.

  Similarly, ion exchange zeolites such as lithium ion exchange type mordenite, sodium ion exchange type mordenite and calcium ion exchange type faujasite exemplified in Patent Document 2 are not harmful to the environment and can adsorb impurity gas. However, higher purity gas purification is desired.

  The object of the present invention is to provide a gas adsorbing material that is not harmful to the environment and can fix and remove a fixed amount of impurity gas in the discharge space of the display area of the gas discharge display panel even under a low pressure. By applying it in the form of a device that can fully demonstrate the characteristics, it is possible to suppress the deterioration of discharge characteristics, emission luminance and chromaticity due to impurity gas, and change over time, and to provide a long-life and reliable display quality. A discharge display panel is provided.

  In order to achieve the above object, according to the present invention, in a gas discharge display panel having a discharge space sandwiched between a first substrate and a second substrate, at least copper is exchanged in the space that can be vented to the discharge space. It is equipped with a gas adsorption device containing ZSM-5 type zeolite.

  By containing the ZSM-5 type zeolite exchanged with copper ions as the gas adsorbent in the gas discharge display panel, the impurity gas components that cannot be removed by the industrial vacuum exhaust process are efficiently adsorbed. It is possible to suppress discharge characteristics, light emission luminance and chromaticity deterioration, and change with time due to impurity gas in the space, and to obtain a long-life and highly reliable display quality.

  Here, the gas adsorption device includes at least a ZSM-5 type zeolite exchanged with copper ions, a container for storing the copper ion exchanged ZSM-5 type zeolite separated from the surrounding space until use, and the above-mentioned at the time of gas adsorption. It is a general term for mechanisms that enable gas adsorption by communicating inside and outside a container.

In the copper ion exchanged ZSM-5 type zeolite, copper is first ion exchanged as Cu ²⁺ . Next, by performing an appropriate heat treatment under low pressure, Cu ²⁺ is reduced to Cu ⁺ and exhibits gas adsorption activity.

Therefore, regarding the silica to alumina ratio of the ZSM-5 type zeolite, when the silica to alumina ratio is low, that is, when a large amount of −1 valent aluminum is present, Cu ²⁺ is more stable, and heat treatment makes Cu ⁺ become Cu ⁺ . Since the sites to be reduced are reduced, the nitrogen adsorption activity is also reduced.

On the other hand, when the silica to alumina ratio is large, i.e., when there is little −1 valent aluminum, less copper is introduced by ion exchange and thus less Cu ⁺ sites, which also reduces the nitrogen adsorption activity. Therefore, in order to express the nitrogen adsorption activity, it is desirable that the silica to alumina ratio is in an appropriate range, and in the present invention, it is determined that a range of 8 to 25 is appropriate.

  With this configuration, the ZSM-5 type zeolite exchanged with copper ions has a very low adsorption equilibrium pressure for impurity gases such as moisture, oxygen, nitrogen, carbon monoxide, carbon dioxide, and hydrogen, and is also chemisorbable. In order to exert a strong adsorption power, the impurity gas in the discharge space of the display area is removed, and the deterioration of discharge characteristics, emission luminance and chromaticity due to the impurity gas, and change over time are suppressed. High display quality can be obtained.

  Further, the copper ion exchange ZSM-5 type zeolite has no harmful information and is considered to have a low environmental load.

  The gas adsorbing device comprises at least a copper exchanged ZSM-5 type zeolite, a moisture adsorbing material, and a container made of a gas poorly permeable material, and the container has at least two or more by a partition capable of controlling air permeability. When the gas adsorbent and the moisture adsorbent are respectively stored in different spaces in the container, the copper-exchanged ZSM-5 type zeolite is not deteriorated by moisture, and more Gas can be adsorbed.

  According to the present invention, the ZSM-5 type zeolite subjected to copper ion exchange is converted into a gas adsorption device that can be stored without deterioration until the time of use, so that oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen, etc. In order to demonstrate a very low adsorption equilibrium pressure against impurity gas and to exhibit a strong adsorption force of chemisorption, it is possible to remove the impurity gas in the discharge space of the display area and keep the sealed gas in high purity. It is possible to suppress the deterioration of discharge characteristics, emission luminance and chromaticity, and change with time due to impurity gas, and to obtain a long-life and highly reliable display quality.

  Further, since the gas adsorption device comprises at least a copper exchanged ZSM-5 type zeolite, a moisture adsorbing material, and a container made of a gas permeable material, the copper exchanged ZSM-5 type zeolite is deteriorated by moisture. Therefore, more gas can be adsorbed.

  Furthermore, when the pressure is reduced by the vacuum pump, the time required for reducing the pressure to a high vacuum is significantly longer than the time required for roughing. By using the gas adsorption device, a high vacuum can be achieved only by roughing time, and productivity can be improved.

  The gas discharge display panel according to claim 1 of the present invention is a gas discharge display panel having a discharge space sandwiched between a first substrate and a second substrate. And a gas adsorption device containing at least a copper exchanged ZSM-5 type zeolite.

  Copper ion-exchanged ZSM-5 type zeolite is known for its high activity for nitrogen adsorption, presumably due to the shape selectivity due to the relative relationship between the pore diameter and the molecular diameter of nitrogen, and its three-dimensional structure. I think it depends on specificity. Furthermore, it also has adsorption activity to gas species other than nitrogen, that is, oxygen, moisture, carbon monoxide, carbon dioxide, hydrogen, etc., and ZSM-5 type zeolite exchanged with copper ions is contained in the gas discharge display panel. By including it as a gas adsorbent, it effectively adsorbs impurity gas components that cannot be removed by an industrial evacuation process, and as a result, discharge characteristics, emission luminance, and chromaticity caused by impurity gas in the discharge space of the display area Deterioration and change with time can be suppressed, and a long-life and highly reliable display quality can be obtained.

  The production of the ZSM-5 type zeolite subjected to the copper ion exchange is performed through a process of copper ion exchange, washing with water, drying and heat treatment of a commercially available ZSM-5 type zeolite.

Copper ion exchange can be performed by a known method, but a method of immersing in an aqueous solution of a soluble salt of copper, such as an aqueous solution of copper chloride or an aqueous solution of copper ammine, is generally used, particularly copper (II) propionate or acetic acid. Those prepared by a method using a Cu ²⁺ solution containing carboxylate such as copper (II) have high nitrogen adsorption activity.

  Wash with water thoroughly after ion exchange.

  Next, heat drying or drying under reduced pressure is performed to remove surface adhering water.

Thereafter, an appropriate heat treatment is performed under a low pressure. This is necessary to reduce Cu ²⁺ introduced by ion exchange to Cu ⁺ and develop nitrogen adsorption ability. The pressure during the heat treatment is 10 mPa or less, preferably 1 mPa or less, and the temperature is about 300 ° C. or more, preferably about 500 ° C. to 600 ° C. in order to promote the reduction to Cu ⁺ .

  Through the above process, the copper ion exchanged ZSM-5 type zeolite imparted with gas adsorption activity has gas adsorption activity of nitrogen, moisture, oxygen, carbon monoxide, carbon dioxide, hydrogen and the like.

  Further, when the copper ion exchanged ZSM-5 type zeolite having gas adsorption activity is handled in the atmosphere, the atmospheric components are adsorbed and deactivated. Therefore, after activation by heat treatment, it is usually necessary to handle under high vacuum or in an inert gas.

When applied to a gas discharge display panel, it is possible to perform heat treatment simultaneously with the process of heating while adhering water in the panel while evacuating, but the conditions of this process and the conditions of the reduction heat treatment to Cu ⁺ are also possible. Does not necessarily match. Therefore, in consideration of deactivation due to atmospheric contact and the development of sufficient adsorption activity after application to a gas discharge display panel, it should be sealed in a gas adsorption device that does not directly contact air and that optionally develops air permeability. is required.

  Here, the gas adsorption device includes at least a ZSM-5 type zeolite exchanged with copper ions, a container for storing the copper ion exchanged ZSM-5 type zeolite separated from the surrounding space until use, and the above-mentioned at the time of gas adsorption. It is a general term for mechanisms that enable gas adsorption by communicating inside and outside a container.

  Moreover, pelletization, shaping | molding, etc. may be given when handling copper ion exchange ZSM-5 type zeolite as a gas adsorbent.

In the copper ion exchanged ZSM-5 type zeolite, copper is first ion exchanged as Cu ²⁺ . Next, by performing an appropriate heat treatment under low pressure, Cu ²⁺ is reduced to Cu ⁺ and exhibits gas adsorption activity. Therefore, regarding the silica to alumina ratio of the ZSM-5 type zeolite, when the silica to alumina ratio is low, that is, when a large amount of −1 valent aluminum is present, Cu ²⁺ is more stable, and heat treatment makes Cu ⁺ become Cu ⁺ . Since the sites to be reduced are reduced, the nitrogen adsorption activity is also reduced. On the other hand, when the silica to alumina ratio is large, i.e., when there is little −1 valent aluminum, less copper is introduced by ion exchange and thus less Cu ⁺ sites, which also reduces the nitrogen adsorption activity. Therefore, in order to express the nitrogen adsorption activity, it is desirable that the silica to alumina ratio is in an appropriate range, and in the present invention, it is determined that a range of 8 to 25 is appropriate.

  With this configuration, the ZSM-5 type zeolite exchanged with copper ions has a very low adsorption equilibrium pressure for impurity gases such as moisture, oxygen, nitrogen, carbon monoxide, carbon dioxide, and hydrogen, and is also chemisorbable. In order to exert a strong adsorption power, the impurity gas in the discharge space of the display area is removed, and the deterioration of discharge characteristics, emission luminance and chromaticity due to the impurity gas, and change over time are suppressed. High display quality can be obtained.

  Further, the copper ion exchange ZSM-5 type zeolite has no harmful information and is considered to have a low environmental load.

  The gas discharge display panel according to claim 2 of the present invention is the gas discharge display panel according to claim 1, wherein the gas adsorption device is at least a copper exchanged ZSM-5 type zeolite, a moisture adsorbent, and a gas hardly permeable. The container is divided into at least two spaces by a partition capable of controlling air permeability, and the gas adsorbent and the moisture adsorbent are accommodated in different spaces of the container, respectively. It is characterized by being.

  In both cases of adsorbing air remaining in the discharge space and adsorbing and removing air entering the discharge space over time, the air contains moisture together with nitrogen, oxygen, and the like. Copper-exchanged ZSM-5 type zeolite is very active against moisture. If water is contained in the adsorbed gas, water is preferentially adsorbed. There is a risk of being deactivated.

  Therefore, by making both the copper exchanged ZSM-5 type zeolite and the moisture adsorbent into a device, the moisture adsorbs the moisture and adsorbs the copper exchanged ZSM-5 type zeolite more effectively. An adsorption device is provided. That is, the positional relationship between the copper-exchanged ZSM-5 type zeolite and the moisture adsorbent in the container is optimized as follows.

  Copper-exchanged ZSM-5 type zeolite and moisture adsorbent are accommodated in independent spaces. In addition, independent spaces ensure appropriate air permeability. Furthermore, when the gas outside the gas adsorption device is adsorbed, the gas passes through the space containing the moisture adsorbing material and the contained moisture is adsorbed, and then reaches the space containing the copper-exchanged ZSM-5 type zeolite.

  At this time, if the air permeability between the spaces is too large, the moisture adsorbing material cannot absorb moisture, and a gas containing a large amount of moisture reaches the ZSM-5 type zeolite in which copper is exchanged. On the other hand, when the air permeability between the spaces is too small, the amount of gas reaching the ZSM-5 type zeolite exchanged with copper is small, and the adsorption performance of the ZSM-5 type zeolite exchanged with copper cannot be sufficiently developed. Therefore, it is important to appropriately control the air permeability of the partition member that can control the air permeability.

  Furthermore, when installing ZSM-5 type zeolite in which copper is exchanged in a limited space as in the present invention, it is desirable to make it thin, but for example, it can be made thin as follows.

  In order to reduce the thickness of the gas adsorption device, it is effective to accommodate the gas adsorbent and the moisture adsorbent in parallel. Since the copper-exchanged ZSM-5 zeolite and the moisture adsorbent are housed in independent spaces, the maximum thickness of the gas adsorption device depends on the maximum thickness of the copper-exchanged ZSM-5 zeolite or moisture adsorbent To do. Therefore, the thickness of the gas adsorption device can be controlled by controlling the maximum thickness of the copper exchanged ZSM-5 type zeolite or moisture adsorbent.

  Here, the moisture adsorbent is capable of adsorbing moisture contained in the gas, and includes activated carbon, silica gel, calcium oxide and the like.

Further, the gas hardly permeable material is a material having a gas permeability of 10 ⁴ [cm ³ / m ² · day · atm] or less, and more desirably 10 ³ [cm ³ / m ² · day · atm] or less. It will be. Moreover, a container divides space inside and outside like a spherical shell, for example.

  With the above configuration, the ZSM-5 type zeolite subjected to copper ion exchange has a very low adsorption equilibrium pressure for impurity gases such as moisture, oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen, and chemisorption. In order to exert a strong adsorbing power, the impurity gas in the discharge space of the display area is removed, and the discharge characteristics, emission luminance and chromaticity deterioration due to the impurity gas, and deterioration with time are suppressed, and long life and reliability High display quality can be obtained.

  In addition, even when moisture is contained in the gas, it is possible to maintain excellent adsorption performance for a long time without reducing the gas adsorption capacity, and a highly reliable gas discharge display panel can be obtained.

  Moreover, it is possible to reduce the space required for installation by applying the thinned gas adsorption device.

  According to a third aspect of the present invention, there is provided a gas discharge display panel according to the second aspect, wherein the partition is a continuous porous body.

  If the air permeability of the partition between the space containing the copper ion-exchanged ZSM-5 type zeolite and the space containing the water adsorbent is too large, the water adsorbent cannot fully absorb the water, and the copper ion-exchanged ZSM-5 type Zeolite adsorbs excess water and deteriorates. On the other hand, if the air permeability of the partition between the space containing the copper ion exchanged ZSM-5 type zeolite and the space containing the water adsorbent is too small, the amount of gas reaching the copper ion exchanged ZSM-5 type zeolite is small, Adsorption characteristics of ZSM-5 type zeolite subjected to copper ion exchange cannot be sufficiently exhibited. Accordingly, it is important to appropriately control the air permeability of the partition material, and this air permeability depends on the gas permeability, the cross-sectional area, and the length of the partition material.

  In order to appropriately control the gas permeability so as to meet the requirements, a continuous porous structure is suitable, and it can be appropriately selected depending on the amount of remaining air and the speed of air entering over time.

  Here, the continuous porous body is composed of a solid portion and a void portion, and the voids communicate with each other. Although it may be an aggregate of particles made of an inorganic material such as ceramics or an organic material such as a continuous urethane foam, it is more desirable to generate less gas under reduced pressure.

  When the gas adsorbing device is installed in a limited closed space such as the inside of a member constituting the gas discharge display panel, the degree of freedom of shape of the partition is limited, and a reduction in thickness is required. Even in such a case, necessary air permeability can be obtained by optimizing the gas permeability of the partition.

  With the above configuration, the ZSM-5 type zeolite subjected to copper ion exchange has a very low adsorption equilibrium pressure for impurity gases such as moisture, oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen, and chemisorption. In order to exert a strong adsorbing power, the impurity gas in the discharge space of the display area is removed, and the discharge characteristics, emission luminance and chromaticity deterioration due to the impurity gas, and deterioration with time are suppressed, and long life and reliability High display quality can be obtained.

  In addition, even when moisture is contained in the gas, it is possible to maintain excellent adsorption performance for a long time without reducing the gas adsorption capacity, and a highly reliable gas discharge display panel can be obtained.

  A gas discharge display panel according to a fourth aspect of the present invention is the gas discharge display panel according to the second or third aspect, wherein the container is opened by remote control and a space in which the gas adsorbent and the moisture adsorbent are accommodated. It is characterized in that it has a closed space and a mechanism that allows ventilation.

  In order to suppress the deterioration of ZSM-5 type zeolite that has exchanged copper ions with high gas adsorption activity until the time of use, the gas adsorption device can be installed inside the components of the gas discharge display panel and the inside can be vented to the closed space after decompression Is desirable.

  The parts constituting the gas discharge display panel are not easily deformed by an external force. For this reason, it is difficult to apply force indirectly to the container of the gas adsorption device by applying force to the gas discharge display panel.

  Therefore, as a mechanism for applying a force to the container of the gas adsorption device without applying an external force to the components of the gas discharge display panel, that is, a remote operation mechanism, a method based on a temperature change will be described as an example.

  Installed inside the gas discharge display panel is a gas adsorption device in which the container is made of a thermoplastic material, and a protruding member that applies a certain stress to the container.After sealing under reduced pressure, heat is applied from the outside of the gas discharge display panel. Addition increases the temperature of the gas adsorption device. In this case, although the hardness of the container is superior to the stress at normal temperature and does not deform, the container made of a thermoplastic material is softened above a certain temperature, and the protruding member can cause a through hole in the container.

  By using a thermoplastic resin as a thermoplastic material, a through-hole can be formed in the container at a relatively low temperature, for example, a low temperature of about 70 ° C., without deteriorating the material constituting the gas discharge display panel, It is possible to obtain a gas discharge display panel having excellent quality at low cost and with little thermal history of components.

  With the above configuration, the ZSM-5 type zeolite subjected to copper ion exchange has a very low adsorption equilibrium pressure for impurity gases such as moisture, oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen, and chemisorption. In order to exert a strong adsorbing power, the impurity gas in the discharge space of the display area is removed, and the discharge characteristics, emission luminance and chromaticity deterioration due to the impurity gas, and deterioration with time are suppressed, and long life and reliability High display quality can be obtained.

  The invention of a gas discharge display panel according to claim 5 of the present invention is characterized in that, in the invention according to any one of claims 2 to 4, the moisture adsorbing material is in a powder form.

  When the adsorbed gas contains a large amount of moisture, the moisture adsorption of the ZSM-5 type zeolite that has been exchanged with copper ions is suppressed, so that moisture adsorption by the moisture adsorbent is ensured and the ZSM-5 type zeolite with exchanged copper ions is reached. In order to reliably reduce the amount of moisture contained in the gas, the relationship between the air permeability of the partition and the moisture adsorption rate of the moisture adsorbing material may be optimized.

  When there is a large amount of moisture that enters the space containing the moisture adsorbing material, the moisture adsorbing property by the moisture adsorbing material is improved by reducing the air permeability of the partition. However, since the gas adsorption rate of the ZSM-5 type zeolite exchanged with copper ions decreases due to the decrease in air permeability, if there is a large amount of gas entering the gas discharge panel, the gas entering is sufficiently adsorbed. Can not do it.

  Therefore, when it is necessary to improve the moisture adsorption characteristics of the moisture adsorbing material in a state where the air permeability of the partition is ensured, a powdery moisture adsorbing material may be used to improve the specific surface area.

  With this configuration, it is possible to obtain a gas adsorption device that is excellent in the gas adsorption rate and the moisture adsorption characteristics of the moisture adsorbent. By using this gas adsorption device, it is possible to obtain a gas discharge display panel that is thin and capable of exhibiting sufficient performance even when the adsorbed gas is in a humid condition.

  Here, the powder form has an average particle diameter of 100 μm or less, and more preferably 50 μm or less.

  With the above configuration, the ZSM-5 type zeolite subjected to copper ion exchange has a very low adsorption equilibrium pressure for impurity gases such as moisture, oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen, and chemisorption. In order to exert a strong adsorbing power, the impurity gas in the discharge space of the display area is removed, and the discharge characteristics, emission luminance and chromaticity deterioration due to the impurity gas, and deterioration with time are suppressed, and long life and reliability High display quality can be obtained.

  The invention of the gas discharge display panel according to claim 6 of the present invention is the invention according to any one of claims 1 to 5, wherein roughing is performed by a vacuum pump and the pressure is reduced to a high vacuum by a gas adsorption device. It is produced by reducing the pressure.

In general, when the closed space is depressurized with a vacuum pump, the time required to depressurize to a high vacuum of 10 ⁻³ Pa or less, which is required for a gas discharge display panel, compared to the time required for roughing up to about 130 Pa. Will be significantly longer. By using the gas adsorption device, a high vacuum can be achieved only by roughing with a vacuum pump. Thereby, the time required for production can be greatly shortened and productivity can be improved by reducing only the rough pressure by the vacuum pump. Therefore, a glass gas discharge display panel can be obtained at a lower cost.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 1 is a flowchart showing a method for producing a gas adsorbent made of ZSM-5 type zeolite subjected to copper ion exchange in Embodiment 1 of the present invention.

  In the embodiment of the present invention, the production of the adsorbent comprising ZSM-5 type zeolite subjected to copper ion exchange is performed by an ion exchange step (STEP 1) using an ion exchange solution containing copper ions and ions having a buffer action. The washing step (STEP 2) for washing the ZSM-5 type zeolite exchanged with copper ions, the drying step (STEP 3), and the heat treatment step (STEP 4) for reducing copper ions.

  In the ion exchange step (STEP 1), aqueous solutions of existing compounds such as copper acetate, copper propionate, and copper chloride can be used as a solution containing copper ions. For this purpose, copper acetate is desirable.

The number of ion exchanges, the concentration of the copper ion solution, the ion exchange time, the temperature and the like are not particularly limited, but the ion exchange rate exhibits excellent adsorption performance in the range of 100% to 180%. More preferably, it is in the range of 110% to 170%. The ion exchange rate shown here is a calculated value based on the premise that Cu ²⁺ is exchanged per two Na ^{+ s} . When copper is exchanged as Cu ⁺ , the calculation exceeds 100%. Is done.

  In the washing step (STEP 2), it is desirable to wash with distilled water. In the drying step (STEP 3), it is desirable to dry under conditions of less than 100 ° C., and vacuum drying at room temperature may be used.

In the heat treatment step (STEP 4), it is desirable to perform heat treatment at a temperature of 300 ° C. or higher and 800 ° C. or lower under reduced pressure, preferably under a condition of less than 10 ⁻² Pa. The heat treatment time depends on the amount of ZSM-5 type zeolite exchanged with copper ions, but sufficient time is required to reduce the copper ions from divalent to monovalent. Moreover, if it is 300 degrees C or less, there exists a possibility that the reduction | restoration to monovalence may become inadequate, and if it is 800 degrees C or more, there exists a possibility that the structure of a zeolite may be destroyed. More preferably, it is about 500 ° C to 600 ° C.

  The adsorbent made of ZSM-5 type zeolite exchanged with copper ions thus produced is directly applied to the air in consideration of deactivation due to atmospheric contact and expression of sufficient adsorption activity after application to a gas discharge display panel. By sealing the gas adsorbing device in a gas-absorbing device that can develop air permeability without touching it, the impurity gas in the discharge space of the display area is fixed and removed, and the discharge characteristics, emission luminance, and chromaticity caused by the impurity gas are reduced. Since deterioration and change with time can be suppressed, a long-life and highly reliable display quality can be obtained.

(Embodiment 2)
2 (a) and 2 (b) are cross-sectional views of the gas adsorption device before heating in Embodiment 2 of the present invention.

  As shown in FIG. 2, the gas adsorption device 5 includes a cylindrical container 6 made of thermoplastic plastic in which a powdery moisture adsorbent 7 and ZSM-5 type zeolite 8 exchanged with copper ions are enclosed.

  Further, the moisture adsorbent 7 and the ZSM-5 type zeolite 8 exchanged with copper ions are partitioned by a partition 9 made of continuous urethane foam. Stress is applied to the container 6 by a member 10 that applies stress. In addition, a support 11 is provided in the vicinity of the member 10 that applies stress inside the container 6. Here, the tip of the member 10 to which stress is applied is sharp. Furthermore, a fine hole is opened in the support 11 and is near the tip of the member 10 to which stress is applied.

  3A and 3B are cross-sectional views of the gas adsorption device after heating in the second embodiment of the present invention.

  The ZSM-5 type zeolite 8 exchanged with the water adsorbent 7 of the gas adsorbing device 5 and the copper ion is enclosed in the cylindrical container 6, so that deterioration during storage is small. The gas adsorption device 5 is installed in a discharge space sandwiched between the first substrate and the second substrate in the PDP and a space that can be vented, exhausted by a vacuum pump, sealed after reaching a predetermined pressure. Thereafter, the gas adsorbing device 5 can adsorb the gas remaining in the space, the air entering from between the members constituting the PDP, and the like, which is realized as follows.

  The temperature of the container 6 rises by heating the gas adsorption device 5 site | part installed in PDP from the outside. Since the container 6 is a thermoplastic resin, it softens as the temperature rises.

  Here, as the thermoplastic resin, it is desirable to select a material whose softening temperature does not affect the members constituting the PDP. Since stress is applied to the container 6 in advance by the member 10 that applies stress, the strength of the container 6 exceeds the strength of the container 6 when the temperature reaches a predetermined temperature. Since the container 6 is softened, the through hole is not easily formed to follow the shape of the member 10 to which stress is applied, but there is a hole in the support 11 near the tip of the member 10 to which stress is applied. The deformation rate is significantly increased, and a through hole 12 is formed in the container 6.

  The copper ion-exchanged ZSM-5 type zeolite 8 can adsorb the gas inside the space through the through hole 12. Here, the part which produces the through-hole 12 is a side including the moisture adsorbent 7 in the space in the container 6 divided by the partition 9, and is preferably a part farther away from the partition 9. .

  When there is a gas containing moisture in the space, the gas containing moisture enters the container 6 through the through hole 12. When a gas containing moisture enters the container 6, it stays in the vicinity of the powdery moisture adsorbing material 7 for a predetermined time. The ZSM-5 type zeolite 8 that has passed through the copper ion exchange and has passed through the copper ion exchange can efficiently adsorb gas.

(Embodiment 3)
FIG. 4 is a schematic cross-sectional view of a main part showing a main configuration of a PDP including a gas adsorbent containing ZSM-5 type zeolite exchanged with copper ions in a discharge space and a space that can be ventilated in Embodiment 3 of the present invention. It is.

  As shown in FIG. 4, the structure of the PDP is roughly divided into a first substrate and a second substrate that are disposed with their main surfaces facing each other.

  A front glass substrate 13 serving as a first substrate has a plurality of strip-like display electrodes 14 (sustain electrodes and scanning electrodes) formed on one main surface thereof.

  On the front glass substrate 13 provided with the display electrodes 14, a dielectric layer 15 and a protective layer 16 made of magnesium oxide are sequentially formed over the entire main surface of the glass.

  A plurality of address electrodes 18 are arranged in stripes at regular intervals on one main surface of the rear glass substrate 17 serving as a second substrate, and the rear glass substrate 17 includes the address electrodes 18. A dielectric layer 19 is formed over the entire surface. On the dielectric layer 19, a gas adsorption device 20 containing copper-exchanged ZSM-5 type zeolite is installed in order to adsorb impurity gas, and a partition wall 21 is arranged in accordance with the gap between adjacent address electrodes 18. The phosphor layers 22 to 24 corresponding to red (R), green (G), and blue (B) are respectively provided on the side surfaces of the two adjacent partition walls 21 and the surface of the gas adsorption device 20 therebetween. Is formed.

  The first substrate and the second substrate having such a configuration are sealed with glass frit on the outer peripheral edge of both substrates while facing the address electrodes 18 and the display electrodes 14 so that their longitudinal directions are orthogonal to each other. Has been. A discharge gas (filled gas) made of a rare gas component such as He, Xe, or Ne is sealed between the substrates at a predetermined pressure (usually about 500 to 600 Torr (66.5 to 79.8 kPa)).

  When driving the PDP, a panel driving unit (not shown) applies pulses to the address electrodes 18 and the display electrodes 14 to perform write discharge (address discharge), and then applies pulses to the display electrodes 14 of each pair. As a result, the discharge is started in the gap between the display electrodes 14 where the address discharge has been performed. Then, sustain discharge is performed in the discharge space, and screen display is performed.

  During the operation of the PDP, the impurity gas generated from the panel member reaches the gas adsorption device 20 containing the ZSM-5 type zeolite exchanged with copper through the gaps between the phosphor layers 22 to 24 formed of phosphor particles. Adsorbed. As a result, an increase in impurity gas in the discharge space due to discharge is suppressed, and a stable operation can be realized.

  As described above, in the present embodiment, it is possible to stably realize excellent gas discharge display panel performance over a long period of time.

(Example 1)
A container made of polyethylene terephthalate was used as the gas permeable container 6. The shape of the container 6 is a cylindrical shape having a thickness of 1 mm, an inner diameter of 8 mm, and a length of 100 mm. The support 11 is made of stainless steel, has a length of 10 mm, an inner diameter of 7 mm, an outer diameter of 8 mm, has a hole with a diameter of 2 mm, and is inscribed in the container 6. The member 10 that applies stress to the container 6 is a clip made of stainless steel, and a portion in contact with the container 6 is sharp, and the sharp portion is attached so as to overlap the hole of the support 11.

  The partition is a continuous urethane foam.

The gas adsorption device having the above configuration was applied to the PDP for evaluation. The gas adsorbing device 20 is installed in the discharge space of the PDP and a space that can be vented, and after being evacuated to about 130 Pa by a vacuum pump, it is sealed. It can be confirmed that the internal pressure of the space after a lapse of a certain time is 1 × 10 ⁻⁴ Pa, and the gas adsorption device 20 adsorbs the gas remaining in the space, the air entering from between the members constituting the PDP, and the like. I was able to confirm.

Moreover, the space internal pressure after one-year progress was 0.8 * 1 * 10 < ^-5 > Pa, and it has confirmed that the gas adsorption | suction device 20 was acting also with time.

  Next, a comparative example for the gas discharge display panel of the present invention will be shown.

(Comparative Example 1)
When MgO, which is disclosed as a material having a getter action in existing literature, is applied to the PDP in the same manner as in Example 1, it can be confirmed that the internal pressure of the space after a certain period of time is 140 Pa. It was revealed that the residual gas was not adsorbed.

(Comparative Example 2)
When applied to a PDP and evaluated in the same manner as in Example 1 of lithium ion exchange type mordenite, which is disclosed as a material having a getter action in existing literature, the space internal pressure after a lapse of a certain time may be 80 Pa. It was confirmed that not all the gas remaining in the space was adsorbed.

  As described above, ZSM-5 type zeolite exchanged with copper ions is converted into a gas adsorption device that can be stored without deterioration until it is used, so that impurities such as oxygen, nitrogen, carbon monoxide, carbon dioxide, and hydrogen can be stored. Exhibits a very low adsorption equilibrium pressure for gas and exhibits a strong adsorption force with chemisorption, so that the impurity gas in the discharge space of the display area can be removed and the sealed gas can be kept at high purity. Therefore, it is possible to suppress the deterioration of discharge characteristics, emission luminance and chromaticity, and change with time due to the impurity gas, and to obtain a long-life and highly reliable display quality.

  Further, since the gas adsorption device comprises at least a copper exchanged ZSM-5 type zeolite, a moisture adsorbing material, and a container made of a gas permeable material, the copper exchanged ZSM-5 type zeolite is deteriorated by moisture. Therefore, more gas can be adsorbed.

  Furthermore, when the pressure is reduced by the vacuum pump, the time required for reducing the pressure to a high vacuum is significantly longer than the time required for roughing. By using the gas adsorption device, a high vacuum can be achieved only by roughing time, and productivity can be improved.

  This configuration can be used for a gas discharge display panel that requires a high purity inert gas atmosphere, such as a PDP or an organic EL display.

The flowchart which shows the manufacturing method of the gas adsorbent which consists of ZSM-5 type zeolite which carried out the copper ion exchange in Embodiment 1 of this invention. (A) Sectional view cut along a plane parallel to the longitudinal direction of the gas adsorption device before heating in Embodiment 2 of the present invention (b) In the longitudinal direction of the gas adsorption device before heating in Embodiment 2 of the present invention Sectional view cut along a vertical plane (A) Sectional drawing cut | disconnected by the plane parallel to the longitudinal direction of the gas adsorption device after the heating in Embodiment 2 of this invention (b) In the longitudinal direction of the gas adsorption device after the heating in Embodiment 2 of this invention Sectional view cut along a vertical plane Main part schematic sectional drawing of PDP in Embodiment 3 of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 5 Gas adsorption device 6 Container 7 Moisture adsorption material 8 Copper ion exchanged ZSM-5 type zeolite 9 Partition 10 Stress applying member 11 Support body 12 Through-hole 20 Gas adsorption device

Claims (6)

In a gas discharge display panel having a discharge space sandwiched between a first substrate and a second substrate, a gas adsorbing device including at least copper-exchanged ZSM-5 type zeolite is provided in the space that can be vented to the discharge space. A gas discharge display panel characterized by that. The gas adsorbing device comprises at least a copper-exchanged ZSM-5 type zeolite, a moisture adsorbing material, and a container made of a gas-impermeable material, and the container has at least two spaces by a partition capable of controlling air permeability. The gas discharge display panel according to claim 1, wherein the gas adsorbent and the moisture adsorbent are accommodated in different spaces of the container. The gas discharge display panel according to claim 2, wherein the partition is a continuous porous body. The gas discharge display panel according to claim 2 or 3, further comprising a mechanism in which the container is opened by remote operation so that the space in which the gas adsorbent and the moisture adsorbent are accommodated can be vented to the closed space. The gas discharge display panel according to any one of claims 2 to 4, wherein the moisture adsorbent is in a powder form. The gas discharge display panel according to any one of claims 1 to 5, wherein the gas discharge display panel is manufactured by performing roughing with a vacuum pump and reducing the pressure to high vacuum with a gas adsorption device.