JP5287663B2 - Gas discharge display panel and gas recycling method - Google Patents

Description

  The present invention relates to a gas discharge display panel and a gas recycling method, and more particularly to a technique for directly recovering xenon gas with high efficiency at normal temperature and pressure from a discharge display panel in which at least xenon is sealed.

  In recent years, xenon has been widely used as a process for manufacturing semiconductors and as a luminescent gas for plasma displays.

  On the other hand, since xenon contains only a very small amount in the air, the method of separating and producing from air is manufactured through a complicated separation and purification process that takes in a large amount of air, so purified high-purity xenon gas Is very expensive.

  For this reason, it is considered very important to establish a system for collecting, purifying, and reusing used xenon.

  For example, a method for purifying and recovering xenon gas in a detector of an X-ray inspection apparatus by removing moisture and carbon dioxide gas by a zeolite adsorption tank and removing other impurity gases by a getter layer is proposed. (For example, refer to Patent Document 1).

  Also, moisture is adsorbed and removed by silica gel etc. from the oxygen-containing gas obtained from the liquid oxygen building low in the low temperature air separation plant, and xenon is selectively adsorbed and desorbed by Li-Ag exchanged X-type zeolite. Thus, a method of collecting is proposed (for example, see Patent Document 2).

  In addition, as a method for efficiently removing impurities contained in exhaust gases of various processes that use rare gases such as xenon, trace impurities such as hydrogen, water vapor, and nitrogen oxides from a mixed gas composed mainly of rare gas and nitrogen Has been proposed (see, for example, Patent Documents 3 and 4).

  In addition, in order to effectively utilize discharged xenon containing a small amount of radioactive krypton, a technique for purifying recovered xenon using the PSA / purge method has been proposed. In this technique, Na-X type or Ca-X type zeolite is used as a xenon selective adsorbent from a xenon-krypton mixed gas (see, for example, Non-Patent Document 1).

JP-A-4-145921 Japanese Patent Laid-Open No. 2003-221212 JP 2003-342010 A JP 2004-161503 A

“Matsugi Technical Report”, No. 15, June 2002, P113-129

  However, the configurations of Patent Documents 1 to 4 and Non-Patent Document 1 are not applicable to the direct recovery from a used gas discharge display panel in which at least xenon is sealed as a discharge gas, which is an application required by us.

  Currently, xenon-enclosed plasma displays, etc., are disposed of after being disposed of in a recycle disposal site or disposed of in landfills, but xenon is mostly released into the atmosphere during the decomposition process. The current situation is that it has not been recovered.

  In addition, xenon released into the atmosphere is controlled to a reference concentration or lower, but it is not preferable because a decomposition worker may inhale a small amount.

  Therefore, it is desirable to be able to adsorb and remove xenon at normal temperature and normal pressure from the inside of the gas discharge display panel in the previous process until the gas discharge display panel is disassembled or buried, There is a need for technology that can recover adsorbed xenon again.

  In the conventional configuration described in Patent Document 1, it is possible to remove impurities, cool and solidify highly purified xenon below the melting point, and recycle and reuse it again in this apparatus, but this is not a technique for adsorbing and recovering xenon. It is completed by increasing the purity in the apparatus and is different from the object of the present invention.

  In addition, the configurations described in Patent Documents 2 to 4 are techniques for purifying xenon gas containing impurities discharged from a plant or the like, but are intended for direct recovery from a gas discharge display panel enclosing xenon. It is not what I did.

  The configuration of Non-Patent Document 1 is also a technique for purifying xenon gas containing impurities discharged from a plant or the like, but it is intended for direct recovery from a gas discharge display panel enclosing xenon. It is not a thing. In addition, since the technology uses the PSA / purge method, it is not suitable for direct recovery at normal temperature and normal pressure from a gas discharge display panel in which xenon is encapsulated, which is the application required by us.

  The present invention solves the above-described conventional problems, and can efficiently recover xenon from a used gas discharge display panel in which xenon is sealed, so that an operator who separates and separates equipment does not inhale xenon. An object of the present invention is to provide a gas discharge display panel and a gas recycling method.

  In order to achieve the above object, a gas discharge display panel according to 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 adsorbing device in which a discharge gas adsorbing material containing a zeolite having a pore diameter of at least 4.5 to 7.3 mm is made of a hardly gas permeable material and hermetically confined in a container that can be opened by a predetermined operation. It is characterized by.

  As a result, if the gas discharge display panel in which the xenon is sealed in the discharge space is discarded, and the container of the gas adsorption device is opened, the discharge gas xenon will be discharged into the discharge gas adsorbent zeolite at room temperature and normal pressure Therefore, xenon is efficiently recovered without being released into the atmosphere, and after disposal, the worker who decomposes and separates does not inhale xenon. Therefore, a highly efficient and highly safe xenon recovery technique can be provided.

  Further, the gas recycling method of the present invention opens the container of the gas adsorbing device when the gas discharge display panel of the present invention is disposed of, and converts the xenon that is the discharge gas of the discharge space into the discharge gas adsorbent. The xenon is recovered by being adsorbed on the surface of the gas, and is newly reused in the manufacture of a gas discharge display panel. As a result, xenon is recovered without being released into the atmosphere, and compared. Inexpensive xenon can be used for manufacturing new gas discharge display panels.

  The gas discharge display panel of the present invention can adsorb and immobilize xenon, which is a discharge gas, at room temperature and normal pressure by opening a container containing a discharge gas adsorbent, if necessary. Can be recovered without being released into the atmosphere, and the decomposition / separation operator of the gas discharge display panel does not inhale xenon, thereby providing a highly efficient and safe xenon recovery technique.

  In addition, since the gas recycling method of the present invention can recover xenon without releasing it into the atmosphere, it provides a highly efficient and highly safe xenon recovery method without inhaling xenon by an operator who separates and separates equipment. In addition, a relatively inexpensive reuse xenon can be used for manufacturing a new gas discharge display panel.

Sectional drawing of the gas adsorption device used for the gas discharge display panel in Embodiment 1 of this invention Sectional drawing which shows the state after the heating of the gas adsorption device used for the gas discharge display panel of the embodiment (A) Sectional drawing which cut | disconnected the gas adsorption device used for the plasma display panel (gas discharge display panel) in Embodiment 2 of this invention in the longitudinal direction (b) Cut | disconnected the gas adsorption device in the plane perpendicular | vertical to a longitudinal direction Cross section (A) Sectional drawing cut | disconnected in the longitudinal direction which shows the state after the heating of the gas adsorption device used for the plasma display panel (gas discharge display panel) of the embodiment (b) The state after the heating of the gas adsorption device Sectional view cut along a plane perpendicular to the longitudinal direction shown

  A first aspect of the present invention is a gas discharge display panel having a discharge space sandwiched between a first substrate and a second substrate, wherein at least 4.5 to 7.3 mm in the space that can be vented to the discharge space. A gas discharge display panel comprising a gas adsorbing device in which a discharge gas adsorbing material containing zeolite having a pore diameter is hermetically confined in a container that is made of a hardly gas permeable material and can be opened by a predetermined operation.

  In the present invention, by using a zeolite having a pore diameter of 4.5 to 7.3 mm as a discharge gas adsorbent, it is possible to adsorb a large volume of atmospheric xenon at a rate of 30 cc / g or more. Xenon sealed in the display panel can be efficiently adsorbed and recovered.

  In addition, since the discharge gas adsorbing material is accommodated in a container made of a gas hardly permeable material, it is possible to suppress the discharge gas adsorbing material from adsorbing and deteriorating an unintended gas before adsorbing xenon.

  With the above configuration, when xenon adsorption becomes necessary, for example, in the step of recovering xenon after discarding the gas discharge display panel, xenon can be easily recovered. As a result, the disassembly operator can disassemble the device after the xenon adsorption and removal, and can eliminate the possibility of sucking xenon, thereby improving work safety.

  In addition, the adsorbed xenon can be desorbed by suction or heating in the next step, and xenon can be easily recovered for each gas discharge display panel, and the recovered xenon can be purified as necessary. And can be reused.

  According to a second invention, the zeolite in the first invention includes at least MFI type, BETA type, and MOR type zeolite, and although details are not clear, it is presumably xenon due to pore diameter and pore shape. By using these zeolites, it is possible to adsorb atmospheric xenon in a large volume of 40 cc / g or more and efficiently adsorb xenon enclosed in a gas discharge display panel. Can be stored.

  In the third invention, the zeolite in the first invention contains at least a ZSM-5 type zeolite, and although details are not clear, the interaction with xenon probably due to the pore diameter and the pore shape is present. By becoming the strongest, it becomes possible to adsorb a large volume of 55 cc / g or more of atmospheric xenon, and the xenon enclosed in the gas discharge display panel can be efficiently adsorbed and stored.

  In a fourth invention, the zeolite in the first invention contains at least a ZSM-5 type zeolite subjected to copper ion exchange, and the copper ion introduced by ion exchange exhibits a behavior similar to chemical adsorption, and more Since the amount of xenon adsorption at a low partial pressure increases, xenon enclosed in the gas discharge display panel can be more efficiently adsorbed and stored.

  According to a fifth invention, there is provided a mechanism according to the first to fourth inventions, wherein the container is opened by remote control and the storage space for the discharge gas adsorbent is communicated with the discharge space and a space that allows ventilation. Since the discharge space in which xenon is sealed and the storage space for the discharge gas adsorbent can be communicated arbitrarily, the discharge gas adsorbent is adsorbed and saturated by adsorbing gas other than the adsorption purpose until use. An operation for preventing inactivation and collecting xenon can be arbitrarily and simply performed.

  According to a sixth aspect of the present invention, when the mechanism in the fifth aspect of the present invention heats the gas adsorption device to a predetermined temperature, the container is opened, for example, between a discharge gas adsorbent accommodating space and a discharge space. Is sealed with a material that melts by heating, the material is melted by appropriate heating, and communication between the space in which xenon is sealed and the accommodation space for the discharge gas adsorbent can be easily achieved. Is.

  In a seventh aspect of the invention, when the gas discharge display panel according to the first to sixth aspects of the invention is disposed of, the container of the gas adsorption device is opened, and the discharge gas adsorbs xenon as the discharge gas in the discharge space. The gas recycling method is characterized in that the xenon is recovered by being adsorbed on a material and is newly reused for manufacturing a gas discharge display panel.

  According to this gas recycling method, a large volume of xenon at or below normal pressure can be easily adsorbed and recovered. In addition, the disassembly operator in the waste recycling process can disassemble the gas discharge display panel after xenon adsorption and removal, and can eliminate the possibility of sucking xenon, so that the work safety can be improved. Further, the adsorbed xenon can be sucked and desorbed in the next step, and a technique can be provided in which xenon can be easily recovered and reused for each gas discharge display panel.

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

(Embodiment 1)
FIG. 1 shows a cross-sectional view of a gas adsorption device used in a gas discharge display panel according to Embodiment 1 of the present invention.

  As shown in FIG. 1, the gas adsorption device 1 of Embodiment 1 of the present invention is a ZSM-5 type zeolite 3 having a pore diameter of 4.5 to 7.3 mm as a discharge gas adsorbent and having a pore diameter of 4.5 to 7.3 mm. And a gas adsorption device 1 comprising a bottomed cylindrical container 2 made of Pyrex (registered trademark) glass, which is a gas-impermeable material containing the ZSM-5 type zeolite 3 exchanged with copper ions, A space capable of communicating with the storage space of the ZSM-5 type zeolite 3 exchanged with copper ions and the discharge space (xenon enclosed space) sandwiched between the first substrate and the second substrate of the gas discharge display panel (not shown). And a joint 4 for installing the gas adsorbing device 1 on a gas discharge display panel (not shown) and a ZSM-5 type in which the communication path is closed and a copper ion exchange is performed until a predetermined operation is performed. With zeolite 2 When the container 2 is sealed without coming into contact with senone and a predetermined operation is performed, the storage space for the ZSM-5 type zeolite 3 exchanged with copper ions, the first substrate of the gas discharge display panel (not shown), and the first substrate And an arbitrarily openable mechanism made of low-melting-point glass 5 that allows a discharge space (xenon enclosed space) sandwiched between two substrates to communicate with a communicable space.

  FIG. 2 shows a cross-sectional view of the gas adsorption device after heating in the present embodiment.

  Storage space for the ZSM-5 type zeolite 3 exchanged with copper ions, a space capable of communicating with the first substrate of the gas discharge display panel (not shown) and the discharge space (xenon enclosed space) sandwiched between the second substrate, The communication path is substantially horizontal and is farther from the storage space for the ZSM-5 type zeolite 3 (discharge gas adsorbent) exchanged with copper ions than the low-melting glass 5 serving as a mechanism for arbitrarily opening the gas adsorption device 1. Gas discharge by connecting the joint 4 located on the side to a discharge space (xenon enclosed space) sandwiched between a first substrate and a second substrate of a gas discharge display panel (not shown). A portion of the gas adsorption device 1 installed on a display panel (not shown), which can be opened arbitrarily, is a part where the low melting glass 5 is installed from above the container 2, and the low melting glass 5 is made of Pyrex (registered trademark). Melting point of glass Low, by heating to be a temperature higher than the melting point of the low melting glass 5, the low-melting glass 5 is melted deformed so as not to block the communication passage, the sealing of the housing space of the discharge gas adsorbent can be solved. As a result, it is possible to communicate with the storage space of the ZSM-5 type zeolite 3 exchanged with copper ions and the discharge space (xenon enclosed space) sandwiched between the first substrate and the second substrate of the gas discharge display panel (not shown). In the discharge space (xenon enclosed space) sandwiched between the first substrate and the second substrate of the gas discharge display panel (not shown). It comes into contact with the xenon sealed in and exhibits excellent adsorption characteristics and can be efficiently adsorbed and stored.

  According to the configuration of the gas adsorption device 1 of the present embodiment, a discharge gas adsorbent (copper ion exchanged ZSM-5 type zeolite 3) is enclosed in a Pyrex (registered trademark) glass container 2 made of a gas-impermeable material. Therefore, deterioration of the discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions) until xenon is adsorbed can be suppressed.

  According to this configuration, the discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions) is hermetically confined in the container 2 made of a gas hardly permeable material. Deterioration of (copper ion exchanged ZSM-5 type zeolite 3) can be suppressed.

  Further, a discharge space of a gas discharge display panel (not shown) filled with xenon and a space in which a discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions) is accommodated by remote control, When xenon adsorption is necessary due to the provision of a low melting point glass 5 that can be optionally ventilated, for example, in the step of recovering xenon after discarding a discharge gas display panel (not shown). In addition, it is possible to communicate with the accommodation space of the discharge gas adsorbent (copper ion exchanged ZSM-5 type zeolite 3) arbitrarily, and xenon can be easily recovered. As a result, the disassembly operator can disassemble the device after the xenon adsorption and removal, and can eliminate the possibility of sucking xenon, thereby improving work safety.

  Here, the gas adsorption device 1 is a discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions) and a discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions). Xenon enclosed space in a container 2 that is separated from the space, and a storage space for a discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions) and a device enclosing xenon when xenon adsorption is developed. Is a generic term for an arbitrarily openable mechanism (low melting point glass 5) that enables adsorption of gas by communicating with each other.

  The mechanism that can be opened arbitrarily is to connect the storage space of the discharge gas adsorbent (ZSM-5 type zeolite 3 exchanged with copper ions) arbitrarily and the xenon enclosed space in the device enclosing xenon when xenon adsorption is developed. Any mechanism that can be contacted by the discharge gas adsorbent (copper ion-exchanged ZSM-5 type zeolite 3) with xenon by mechanical, chemical, or mechanical change may be used. A means for melting and communicating the closed mechanism (low-melting glass 5) by heating is simple and desirable.

  In the first embodiment, low melting point glass 5 is used as a mechanism that can be arbitrarily opened, and Pyrex (registered trademark) glass is used as a gas-permeable material container 2, but the former is made of an aluminum brazing material and the latter is made of an aluminum container. Combinations such as use are also possible. In addition, a mechanism or the like in which the discharge gas adsorbing material enclosed in the capsule opened in the container 2 is opened by an external stimulus such as heat and automatically communicated can be used.

  The zeolite that can be used in the present invention is a zeolite having a pore size of 4.5 to 7.3 mm because the xenon van der Waals diameter is 4.32 mm for the purpose of adsorbing xenon. Therefore, in order to express the adsorption ability by interaction with the xenon molecule, 4.5 mm or more is necessary, and if the pore diameter is too large, the interaction force between the pore wall and the xenon molecule is reduced. 7.3cm or less is desirable. In fact, we show good xenon adsorption characteristics for BETA-type zeolite with a pore size of 7.1 や and AFI-type zeolite with 7.3Å, whereas X-type zeolite with a pore size of 7.4７ has xenon. It was confirmed that the amount of adsorption was low.

  Desirably, it includes MFI type, BETA type, and MOR type zeolite, more preferably ZSM-5 type zeolite, and more preferably ZSM-5 type zeolite exchanged with copper ions. . Moreover, even if it is a mixture of these, the discharge gas adsorbent which can adsorb | suck another xenon may be contained. Further, the discharge gas adsorbing material may be a powder or may be pelletized or molded.

Further, the gas permeable material is a material having a gas permeability of 10 ⁴ [cm ³ / m ² · day · atm] or less, more preferably 10 ³ [cm ³ / m ² · day · atm] or less. It will be. For example, a laminated film in which glass, metal, or metal foil is laminated can be used. In particular, when glass containing silicate as a main component is used as a container, gas permeability is low, and communication between the space in which xenon is sealed and the storage space for the discharge gas adsorbent is visually observed from the outside. Since it can be confirmed, xenon recovery work can be performed more reliably.

  The joint 4 with the device in which xenon is sealed is not particularly specified, but in order to prevent the outside air from entering from the joint 4, the device and the gas adsorption device 1 are melted using a gas permeable material or the like. It is desirable to join by bonding, welding or the like.

  Further, the xenon adsorbed and recovered by the gas adsorption device 1 can be desorbed by suction or heating in the next step, and xenon can be easily recovered and reused for each device. The process at the time of reuse is not particularly limited. However, since xenon is directly recovered from equipment using high-purity xenon, there is relatively little impurity gas other than air components that may be mixed during recovery. Since it is small, it can be easily recovered by the existing impurity separation and recovery process.

  Hereinafter, with respect to Embodiment 1 of the present invention, Examples 1 to 5 show the xenon adsorption evaluation results of the gas adsorption device 1 when various types of zeolite used as the discharge gas adsorbent are changed. The xenon adsorption characteristic is less than 10 Pa in order to compare the xenon adsorption amount at atmospheric pressure, the xenon adsorption amount from a device enclosed at a space volume of 50 cc and a xenon partial pressure of 30000 Pa, and particularly the xenon adsorption at a low pressure. The amount of xenon adsorption saturation was evaluated. The evaluation was also performed on the residual xenon partial pressure (corresponding to the limit pressure capable of adsorbing xenon) after the adsorbent and xenon passed continuously. Moreover, the zeolite used for the conventional example was evaluated as a comparative example.

Example 1
In Example 1, when the gas adsorption device was evaluated using the AFI zeolite commercial product having a pore diameter of 7.3 mm as the gas adsorbent in the gas adsorption device 1 of Embodiment 1, the xenon adsorption amount was It was 30 cc / g at atmospheric pressure, 10 cc / g at 30000 Pa, and almost 0 cc / g at 10 Pa. The residual xenon partial pressure was 40 Pa.

  Since the pore diameter is in the range of 4.5 to 7.3 mm, compared with Comparative Example 1 and Comparative Example 2, the xenon adsorption amount is excellent and the residual xenon partial pressure is low, which is suitable for xenon adsorption in the discharge space. It can be said that it is an adsorbent.

(Example 2)
In Example 2, when the gas adsorption device was evaluated using a commercial product of BETA type zeolite having a pore diameter of 7.1 mm as the gas adsorbent in the gas adsorption device 1 of Embodiment 1, the xenon adsorption amount was It was 40 cc / g at atmospheric pressure, 18 cc / g at 30000 Pa, and almost 0 cc / g at 10 Pa. The residual xenon partial pressure was 20 Pa.

  As a result of using a BETA type zeolite as a discharge gas adsorbent, the pore diameter is in the range of 4.5 to 7.3 mm, and compared with Comparative Example 1 and Comparative Example 2, the xenon adsorption amount is excellent. The residual xenon partial pressure is also low, which can be said to be a gas adsorption device suitable for xenon adsorption in the discharge space.

(Example 3)
In Example 3, the gas adsorption device was evaluated using a commercial product of MOR type zeolite having a pore diameter of 6.8 mm as the gas adsorbent in the gas adsorption device 1 of Embodiment 1, and the xenon adsorption amount was It was 50 cc / g at atmospheric pressure, 40 cc / g at 30000 Pa, and almost 0 cc / g at 10 Pa. The residual xenon partial pressure was 10 Pa.

  As a result of using the MOR type zeolite as a discharge gas adsorbent as the pore diameter is in the range of 4.5 to 7.3 mm, compared with Comparative Example 1 and Comparative Example 2, the xenon adsorption amount is excellent. The residual xenon partial pressure is also low, which can be said to be a gas adsorption device suitable for xenon adsorption in the discharge space.

Example 4
In Example 4, the gas adsorption device was evaluated using the ZSM-5 commercial product, which is an MFI type zeolite having a pore diameter of 5.5 mm, as the gas adsorbent in the gas adsorption device 1 of the first embodiment. The xenon adsorption amount was 55 c / g at atmospheric pressure, 35 cc / g at 30000 Pa, and 0.1 cc / g at 10 Pa. The residual xenon partial pressure was 3 Pa.

  As a result of using ZSM-5, which is a MFI type zeolite, as a discharge gas adsorbent, having a pore diameter in the range of 4.5 to 7.3 mm, compared with Comparative Example 1 and Comparative Example 2, xenon It can be said that it is a gas adsorption device suitable for adsorption of xenon in the discharge space because of its excellent adsorption amount and low residual xenon partial pressure.

(Example 5)
In Example 5, the gas adsorption device was evaluated by using the gas adsorption device 1 of Embodiment 1 as a gas adsorbent and a ZSM-5 commercial product, which is a MFI type zeolite having a pore diameter of 5.5 mm, subjected to copper ion exchange. As a result, the xenon adsorption amount was 55 c / g at atmospheric pressure, 35 cc / g at 30000 Pa, and 3 cc / g at 10 Pa. The residual xenon partial pressure was 0.005 Pa.

  As a result of using a zeolite in which the pore diameter is in the range of 4.5 to 7.3 mm and the copper ion exchange of ZSM-5, which is an MFI type zeolite, is compared with Comparative Example 1 and Comparative Example 2, xenon adsorption The gas adsorption device is excellent in quantity and has a low residual xenon partial pressure, and is suitable for adsorption of xenon in the discharge space. Furthermore, the xenon adsorption characteristics in the low-pressure region are superior to those in Examples 1 to 3, and the residual xenon partial pressure is three orders of magnitude lower, so that it can be said that efficient xenon recovery is possible.

  Here, 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. Those prepared by a method using a Cu ²⁺ solution containing carboxylate such as copper (II) have high chemisorption 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 in order to reduce the Cu ²⁺ introduced by ion exchange to Cu ⁺ and develop chemical adsorption ability. The pressure at the time of 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 ⁺ .

  After the above process, the ZSM-5 type zeolite exchanged with copper ion exchanged with reduced-pressure xenon adsorption activity adsorbs atmospheric components and becomes inactive when handled in the atmosphere. These are sealed in a gas adsorbing device that does not directly contact air and optionally develops air permeability.

(Comparative Example 1)
In Comparative Example 1, the gas adsorption device was evaluated by using a commercial product of Na-X zeolite having a pore diameter of 7.4 mm as the gas adsorbent for the gas adsorption device of Embodiment 1, and the xenon adsorption amount was The pressure was 18 c / g at atmospheric pressure, 9 cc / g at 30000 Pa, and 0 cc / g at 10 Pa. The residual xenon partial pressure was 800 Pa.

  This is probably due to the fact that the pore size is probably larger than the van der Waals diameter of xenon, so that the interaction force with the xenon molecule is smaller than that of the zeolite limited in the present invention. As a result, the residual partial pressure of xenon is relatively large, and X-type zeolite is applied as a xenon adsorbent in Patent Document 2 and Non-Patent Document 1, but is inappropriate for application to the present invention. I think. In addition to the Na-X type, evaluation of Li-X type, Ag-X type, and Ca-X type was also performed, but almost the same result was obtained.

(Comparative Example 2)
In Comparative Example 2, the gas adsorption device was evaluated using the gas adsorption device of Embodiment 1 using a commercially available A-type zeolite having a pore diameter of 4.1 mm as the gas adsorbent, and the xenon adsorption amount was large. It was 3 cc / g at atmospheric pressure, almost 1 cc / g at 30000 Pa, and 0 cc / g at 10 Pa. The residual xenon partial pressure was 28000 Pa.

  This is probably because the pore diameter is smaller than the van der Waals diameter of xenon and is not suitable for adsorption of xenon molecules. As a result, the residual xenon partial pressure is also large, and A-type zeolite is applied as a xenon adsorbent in Patent Documents 3 and 4, but is considered inappropriate for application to the present invention.

(Embodiment 2)
FIG. 3 shows a cross-sectional view of a gas adsorption device used for a plasma display panel (gas discharge display panel) in Embodiment 2 of the present invention.

  As shown in FIG. 3, the gas adsorption device 6 according to the second embodiment of the present invention encloses a ZSM-5 type zeolite 8 exchanged with copper ions as a discharge gas adsorbent in a cylindrical container 7 made of thermoplastic plastic. Has been.

  Stress is applied to the outer peripheral surface of the container 7 from the outside by a member 9 that applies stress from the outside. A support 10 having a C-shaped cross section is provided on the inner side (inner surface) of the portion to which stress is applied by the member 9 for applying stress in the container 7. Here, the tip of the member 10 to which stress is applied comes into contact with the container 7 is sharp. Further, a hole is opened in the vicinity of the tip of the member 9 that applies stress to the support 10.

  FIG. 4 is a cross-sectional view of the gas adsorption device 6 after heating in the present embodiment.

  Since the ZSM-5 type zeolite 8 subjected to the copper ion exchange is sealed in the cylindrical container 7, there is almost no deterioration during storage. A step of installing the gas adsorption device 6 in a discharge space sandwiched between the first substrate and the second substrate in the plasma display panel and a space where ventilation is possible, and adsorbing xenon as a discharge gas after disposal, It is realized as follows.

  The temperature of the container 7 rises by heating the gas adsorption device 6 part installed in the plasma display panel from the outside. Since the container 7 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 plasma display panel. Since stress is applied to the container 7 in advance by the member 9 that applies stress, the strength of the container 7 exceeds the strength of the container 7 when the temperature reaches a predetermined temperature. Since the container 7 is soft, it follows the shape of the member 9 to which stress is applied, and if it is normal, a through-hole is not easily generated. The deformation rate in the vicinity thereof is remarkably increased, and the through hole 11 is generated in the container 7.

  As a result, the ZSM-5 type zeolite 8 exchanged with copper ions can adsorb the gas in the external space, that is, the discharge gas containing at least xenon, through the through-hole 11.

  Here, although the installation site | part of the gas adsorption device 6 is not specifically limited, It does not affect a display screen and needs to be in the space which can ventilate with discharge space. Further, if a method for heating the gas adsorption device 6 is selected so that the discharge space and the accommodation space for the discharge gas adsorbent can be easily ventilated, the gas adsorption device 6 can be easily heated. desirable. Therefore, it is preferable to design a gas adsorption device 6 installation site that can vent the discharge space on the peripheral edge of the panel and the back surface.

  Hereinafter, an example in which the gas adsorption device 6 is applied to a plasma display panel according to the second embodiment of the present invention will be described in Example 6.

(Example 6)
A container made of polyethylene terephthalate was used as the container 7 made of a gas permeable material. The support 10 is made of stainless steel, has a hole, and is inscribed in the container 7. The member 9 for applying stress to the container 7 is a clip made of stainless steel, and a portion in contact with the container 7 is sharp, and the sharp portion is attached so as to overlap the hole of the support 10.

Evaluation was performed by applying the gas adsorption device 6 having the above configuration to a discharge space in the plasma display panel and a space in which ventilation is possible. Assuming the time of disposal, the gas adsorption device 6 is heated from the outside, and the container 7 is softened. As a result, through holes are formed, and the ZSM-5 type zeolite 8 exchanged with copper ions can be vented to the discharge space. It became possible to adsorb. It was confirmed that the internal pressure of the space after a lapse of a certain time was 1 × 10 ⁻² Pa, and it was confirmed that the gas adsorption device 6 adsorbed the discharge gas remaining in the space.

  The gas adsorption device and the gas recycling method used in the gas discharge display panel according to the present invention are capable of adsorbing xenon enclosed in equipment at room temperature and normal pressure when the equipment is disposed of and recovering it without releasing it into the atmosphere. This makes it possible to provide highly efficient and safe xenon removal / recovery technology without inhaling xenon, so that it can be used for recycling and recycling equipment that encloses xenon. It can also be applied to applications where it is desired to remove xenon safely temporarily for maintenance.

DESCRIPTION OF SYMBOLS 1 Gas adsorption device 2 Container 3 Copper ion exchanged ZSM-5 type zeolite 4 Junction part 5 Low melting glass 6 Gas adsorption device 7 Container 8 Copper ion exchanged ZSM-5 type zeolite 9 Stress applying member 10 Support body 11 Through-hole

Claims (6)

In a gas discharge display panel having a discharge space sandwiched between a first substrate and a second substrate, a zeolite having a pore diameter of at least 4.5 to 7.3 mm in the space that can be vented to the discharge space. and a gas adsorbing device of the discharge gas adsorbent confined hermetically openable container made from a gas impermeable material comprising, the gas discharge display panel Ultimate disposal, the container of the gas adsorbing device is opened Then, xenon, which is a discharge gas in the discharge space, is adsorbed on the discharge gas adsorbent, whereby the xenon is recovered and reused for manufacturing a gas discharge display panel. The gas recycling method according to claim 1, wherein the container of the gas adsorption device is opened by heating from the outside. The gas recycling according to claim 2, wherein the container of the gas adsorption device is sealed with a low-melting glass, and the container is opened by melting the low-melting glass by the heating. Method. The member which applies a stress to the part softened by heating of the container of the gas adsorption device is provided, and the container is opened by applying a stress to the member which applies the stress. Gas recycling method. 5. The gas recycling method according to claim 1, wherein the gas adsorption device is disposed on a peripheral portion of a gas discharge display panel. 5. The gas recycling method according to claim 1, wherein the gas adsorption device is disposed on a rear surface of the gas discharge display panel so as to be able to ventilate the discharge space. 6.