JP4862569B2 - Glass panel - Google Patents

Description

  The present invention is a glass panel that requires heat insulation, or a glass panel that requires changing heat insulation performance, for example, a building such as a house, a heat-retaining device such as a refrigerator, a showcase, an automobile, a railway vehicle It is related with the glass panel which can be used for a vehicle body / airframe etc.

  In recent years, energy saving is strongly desired from the viewpoint of preventing global warming, and glass that improves thermal insulation performance by reducing the space formed by double-glazed glass having excellent heat insulation performance in the housing field, or facing glass, and reducing pressure. Panels are used.

  Glass materials, organic polymer materials, and the like have been proposed as bonding materials for bonding the peripheral portions of the pair of glasses.

For example, when a glass material is used, a polymer material is proposed because a heating process at 400 to 500 ° C. is necessary to perform sealing (see, for example, Patent Document 1). In the case of a polymer material, since there is a problem in long-term reliability due to gas intrusion from the outside, it has been proposed to provide an activated getter material in a low-pressure space.
JP 2001-206740 A

  However, in the conventional configuration described in Patent Document 1, heating is performed at about 800 ° C. under vacuum in order to activate the getter material, and a heating device is necessary.

  Also, when the getter material is heated, the peripheral part is also hot, so it is necessary to dispose a metal container in contact with the opening of the gap of the double-glazed glass or to cut the corner part diagonally. Or may adversely affect the glass.

  Further, when the joining member is particularly a polymer material, increasing the temperature at the time of activating the getter material leads to deterioration of the polymer material itself, and the durability of the glass panel may be deteriorated.

  This invention solves the said conventional subject, and aims at providing the glass panel excellent in productivity and heat insulation performance.

  Furthermore, it is providing the glass panel which can change a heat insulation performance according to a season and necessity.

  In order to achieve the above object, the present invention provides a pair of plate crows arranged at intervals via spacers, a joining member that joins the peripheral portions of the pair of plate crows, and the pair of plate glasses. And an adsorbent that adsorbs nitrogen or oxygen at least under a reduced pressure at room temperature and disposed in a space surrounded by the joining member.

  Since nitrogen or oxygen is adsorbed at room temperature and reduced pressure, it is possible to adsorb gas generated from the internal residual gas, the joining member, etc., and invading gas over time without heating at a high temperature in the glass panel.

  Furthermore, for example, the interior space of the glass panel is evacuated with a vacuum pump to a vacuum level that is easily reachable industrially, and the remaining gas is adsorbed by the adsorbent material without heating, so that the joining member becomes a polymer material, glass material, metal Regardless of the material, the evacuation time can be shortened and a glass panel can be produced efficiently.

  Further, as an adsorbent, at least an adsorbent comprising a solid substance having a hardness of 5 or more mixed with Li or a hardness mixed by mechanical milling or an adsorbent composed of ZSM-5 type zeolite subjected to copper ion exchange is used. Nitrogen or oxygen can be adsorbed under reduced pressure and kept at a low pressure.

  Moreover, this invention consists of a pair of plate glass arrange | positioned through the spacer at intervals, and the joining member which joins the peripheral part of a pair of said plate glass, and is enclosed by the said pair of plate glass and the said joining member. It is characterized in that the pressure inside the created space changes arbitrarily.

  For example, when air is enclosed inside, the thermal conductivity of still air is about 0.025 W / mK. On the other hand, by evacuating it, heat conduction by air can be eliminated and the heat insulation performance can be improved. By performing this arbitrarily, it is possible to obtain a glass panel capable of changing the heat insulation performance so as to suit the environment at that time.

  The glass panel is characterized in that the pressure inside the space is arbitrarily changed by adsorbing and desorbing at least a part of the gas present in the space.

  When high heat insulation is required, heat conduction by gas is eliminated by adsorbing gas existing in the space, and heat insulation performance is improved. On the other hand, when high heat insulation is not desirable, the heat-insulating performance is lowered by releasing the adsorbed gas into the space inside the glass panel and providing heat conduction by the gas. Thus, the glass panel which can change heat insulation performance so that it may be suitable for the environment at that time can be obtained.

  At this time, the adsorbent adsorbs and desorbs the gas by controlling the temperature, that is, adsorbs the gas near normal temperature, releases the gas by heating, and adsorbs the gas by cooling to near normal temperature, It can have variable heat insulation with excellent responsiveness.

  Further, by using at least copper ion exchanged ZSM-5 type zeolite as the adsorbent, for example, nitrogen can be adsorbed at room temperature and nitrogen can be desorbed by heating. The performance can be changed.

  The glass panel of the present invention provides a glass panel excellent in productivity and heat insulation performance by applying an adsorbent capable of adsorbing a low activity gas such as nitrogen without the need for high temperature heating in the glass panel. Can do.

  In addition, for example, when a high degree of heat insulation is required in a house, for example during winter heating, the inside of the glass panel is evacuated to improve the heat insulation performance, while when heat insulation is not necessary, for example, when it is desired to make the temperature close to the outside temperature, for example Etc. can provide a glass panel that can change the heat insulation performance according to the season or necessity, such as increasing the pressure inside the glass panel to deteriorate the heat insulation performance.

  The invention of the glass panel according to claim 1 of the present invention includes a pair of plate crows arranged at intervals via a spacer, a joining member for joining the peripheral portions of the pair of plate crows, and the pair And an adsorbent that adsorbs nitrogen or oxygen at least under a reduced pressure at room temperature.

  The adsorbent may be disposed as it is in a space surrounded by a pair of plate glasses and a bonding member, or a portion communicating with the space, or may be disposed in a container or bag material. .

  At this time, after evacuating to a predetermined pressure, it is desirable to allow the adsorbent or a container enclosing the adsorbent to communicate with the space. For example, after reaching a predetermined pressure, an air hole is provided in a container in which an adsorbent is sealed by an external physical stimulus, and the adsorbent is communicated with the space. There is a method of filling the bag, placing the container / bag inside the space and reducing the pressure, and forming an opening with a pressure difference by the pressure reduction, but it is not particularly specified.

  Further, in the present invention, the adsorption includes absorption to the inside, sorption, or occlusion in addition to adsorption to the surface.

  The predetermined pressure may be a pressure at which the glass panel exhibits performance, that is, 10 Pa or 1 Pa or less, or the glass panel and the container may be communicated at a higher pressure.

  Further, the container or the adsorbent can be disposed in a place where it cannot be seen from the outside, or can be used as a spacer.

  Moreover, a plate glass, a joining member, and a spacer are not particularly specified, and known ones can be used.

  Further, the inside of the space may be filled with a core material that can transmit light, for example, airgel.

  The invention of the glass panel according to claim 2 of the present invention comprises a pair of plate glasses arranged at intervals via spacers, and a joining member for joining the peripheral portions of the pair of plate glasses. The pressure inside the space surrounded by the plate glass and the joining member is arbitrarily changed.

  The gas to be sealed inside is not particularly specified such as air, nitrogen, moisture, carbon dioxide and the like.

  For example, in the case of air, if the distance between a pair of plate glasses is about 0.5 mm, the heat conduction of air can be almost eliminated by setting the internal pressure to 10 Pa or 1 Pa. Further, by setting the internal pressure to 10000 Pa or 1000 Pa, the heat conduction of air can be made substantially the same as the normal pressure.

  Thereby, the heat conduction of a glass panel can be made variable according to an internal pressure.

  The invention of the glass panel according to claim 3 of the present invention is the glass panel according to claim 2, wherein the adsorbent adsorbs and desorbs at least a part of the gas present in the space, whereby the pressure in the space is reduced. It is characterized by changing arbitrarily.

  The adsorbent is not particularly specified as long as it can adsorb and desorb the gas present inside.

  The invention of the glass panel according to claim 4 of the present invention is characterized in that the adsorbent in the invention according to claim 3 performs gas adsorption / desorption by temperature control.

  Gas adsorption / desorption by temperature control means that the gas adsorption temperature is desirably 50 ° C. or less, preferably near normal temperature, and the gas desorption temperature is desirably 200 ° C. or less, more desirably 150 ° C. or less. Desirably, it is preferably performed at 100 ° C. or lower.

  The invention of the glass panel according to claim 5 of the present invention is such that the adsorbent in the invention according to claim 1 or claim 3 or claim 4 is mixed by at least mechanical milling and has a hardness of 5 or more. It is characterized by including the solid substance of this.

The solid material is hardness of 5 or more, Si, B, c-C ( _{diamond), SiO 2, SiC, c} -BN ( cubic boron _{nitride), Al 2 O 3, MgO} , TiO 2 and the like .

  It is also possible to add other components.

  Mixing by mechanical milling means mixing mechanically and is not particularly specified. In order to produce a highly active gas adsorbing substance, it is preferable to perform mechanical milling in an inert gas, for example, in an atmosphere of Ar, He, or the like, or in a vacuum.

  Moreover, when performing mechanical milling, you may prevent adhesion to a container by adding C separately, performing under cooling, or dripping a small amount of alcohol etc. dripping.

  By using an adsorbent mixed with mechanical milling and containing a solid substance with a hardness of 5 or more, it is possible to adsorb nitrogen molecules, which are nonpolar molecules having a large binding energy of about 940 kJ / mol, for example, and oxygen molecules Can adsorb gas that intrudes over time, or gas remaining from manufacturing or gas generated from materials, etc., and obtains a glass panel that is excellent in durability and productivity. Can do.

  Further, the adsorbent is capable of adsorbing at least nitrogen or oxygen, but it does not specify any gas that adsorbs in addition to nitrogen or oxygen. In particular, by adsorbing nitrogen and oxygen, it is effective because it can adsorb gas that enters with time or gas that remains during production.

  Further, it is only necessary to be able to adsorb at least under normal temperature and reduced pressure, and of course, adsorption under normal pressure and increased pressure in an atmosphere below normal temperature or the melting point of Li is also possible.

  In addition, examples of the use form of the adsorbent include powder, compression molding, pelletization, sheet form, thin film form, storage in a separate container, and vapor deposition on other substances, but those specified in particular Absent.

  It is also possible to use a general-purpose adsorbent in addition to the adsorbent.

  Other adsorbents include those that can adsorb moisture, oxygen, etc., such as calcium oxide, magnesium oxide, zeolite, silica gel, unsaturated fatty acids, iron and iron compounds, but are not particularly specified. Multiple use is also possible.

  In the invention of the glass panel according to claim 6 of the present invention, the adsorbent in the invention according to claim 1 or claim 3 or claim 4 contains at least a copper ion exchanged ZSM-5 type zeolite. It is characterized by that.

  Thereby, chemically stable nitrogen can be chemically adsorbed, and nitrogen or oxygen can be adsorbed even under reduced pressure.

  Moreover, it is preferable that at least 60% or more of the copper sites of the ZSM-5 type zeolite exchanged with copper ions are copper monovalent sites. Thereby, it is possible to further increase the gas adsorption amount.

  Furthermore, it has been clarified that, among the copper monovalent sites, the oxygen tricoordinate copper monovalent site has a stronger interaction with gas molecules and can chemisorb gas. Therefore, it is preferable that at least 70% or more of the copper monovalent sites be oxygen tricoordinate copper monovalent sites. As a result, the gas adsorption capacity increases, and the chemical adsorption capacity for adsorbing gas more firmly can be increased.

  Further, the ZSM-5 type zeolite subjected to the copper ion exchange can desorb nitrogen and the like by heating, and then adsorbs again by cooling. Therefore, it is possible to easily increase the pressure by heating to deteriorate the heat insulation performance and to reduce the pressure by cooling to improve the heat insulation performance.

  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 is a cross-sectional view showing an example of a glass panel according to Embodiment 1 of the present invention.

  As shown in FIG. 1, a glass panel 1 is composed of a plate glass 2 with a Low-E film, a plate glass 3 disposed at a distance of about 0.2 mm on the Low-E film side of the plate glass 2, and a plate glass 2. A bonding member 4 made of a polymer material that is disposed between the peripheral edge portion and the peripheral edge portion of the plate glass 3 and joins the peripheral edge portions of the plate glasses 2 and 3, and disposed between the plate glass 2 and the plate glass 3 on the inner peripheral side of the bonding member 4. The spacer 5 that keeps the distance between the plate glass 2 and the plate glass 3, the space 6 surrounded by the plate glasses 2 and 3 and the bonding member 4, and the decompressed space 6, and the exhaust hole 7 provided in the plate glass 2 on the inner peripheral side of the bonding member 4. And an adsorbent 8 disposed in the exhaust hole 7 and a lid 9 that covers the exhaust hole 7 from the outside.

  The adsorbent 8 was made of a material (Li-MgO) in which 1 mol of Li and 2 mol of MgO were mixed by mechanical alloying using a vibrating ball mill using a stainless steel container / ball.

  Moreover, in order to measure the adsorption amount of the adsorbent 8, the nitrogen adsorption amount evaluation of the adsorbent 8 (Li-MgO) was performed.

By evaluating the amount of nitrogen adsorbed from the low pressure side in order, 0.5 cm ³ / g STP at about 10 Pa, about 100Pa at 6.1 cm ³ / g STP, it was confirmed 12.3 cm ³ / g STP to adsorb at about 1000 Pa.

  When the glass panel 1 is manufactured, an adsorbent 8 enclosed in a container is arranged in a space 6 connected via a vacuum pump and an exhaust hole 7. After reducing the pressure of the space 6 through the exhaust hole 7, the container in which the adsorbent 8 is enclosed is communicated with the space 6, and then the outside of the vent hole (exhaust hole 7) between the space 6 and the vacuum pump is covered with the cover material. 9 and sealed.

  Then, predetermined performance was obtained by leaving the glass panel 1 for a predetermined time.

  Compared to a glass panel that does not use the adsorbent 8, the vacuum pumping time by the vacuum pump for obtaining a predetermined performance was reduced. Moreover, compared with the glass panel which does not use the adsorbent 8, the predetermined pressure could be maintained for a long time without the adsorbent high-temperature treatment in the glass panel.

(Embodiment 2)
FIG. 2 is a cross-sectional view showing an example of a glass panel according to Embodiment 2 of the present invention.

  As shown in FIG. 2, the glass panel 1 includes a plate glass 2 with a Low-E film, a plate glass 3 disposed at an interval of about 0.2 mm on the Low-E film side of the plate glass 2, and a plate glass 2. It arrange | positions between the plate glass 2 and the plate glass 3 on the inner peripheral side of the joining member 4, and the joining member 4 which consists of the low melting glass which is arrange | positioned between a peripheral part and the peripheral part of the plate glass 3, and joins the peripheral part of the plate glass 2 and 3. The spacer 5 that keeps the distance between the plate glass 2 and the plate glass 3, the space 6 surrounded by the plate glasses 2 and 3 and the bonding member 4, and the decompressed space 6, and the exhaust hole 7 provided in the plate glass 2 on the inner peripheral side of the bonding member 4. And an adsorbent 8 disposed in a recess formed in a portion of the plate glass 3 facing the space 6, a lid member 9 that covers the exhaust hole 7 from the outside, and a surface of the plate glass 3 opposite to the space 6. And a heater 10 attached close to the adsorbent 8 To.

  The adsorbent 8 is made of a copper ion-exchanged ZSM-5 type zeolite in which at least 60% of the contained copper sites are made of copper monovalent sites. Note that the nitrogen adsorption amount of the ZSM-5 type zeolite subjected to the copper ion exchange has a nitrogen gas adsorption capacity of 6.6 cc / g at a standard state of 10 Pa and 11.3 cc / g at 13200 Pa. Similarly, oxygen has an adsorption capacity of 2.8 cc / g at 10 Pa.

  In addition, the adsorbent 8 enclosed in the container was disposed in a sealed space, and after introducing nitrogen into the sealed space to be about 1500 Pa, the container enclosing the adsorbent 8 was opened. This confirmed that the inside of the sealed space was 1 Pa. In this case, it was confirmed that when the adsorbent 8 was heated to 80 to 150 ° C., the adsorbed nitrogen was desorbed to about 1500 Pa, and further cooled to room temperature to 1 Pa. Thus, it was confirmed that the pressure in the sealed space can be controlled by temperature control.

  Such an adsorbent 8 was sealed in a vacuum container and disposed in the space 6. The space 6 was depressurized, and when the pressure reached about 1500 Pa, the lid member 9 was sealed and sealed so as to cover the exhaust hole 7 from the outside. After that, when the container containing the adsorbent 8 and the space 6 were passed through, the inside of the glass panel 1 became 1 Pa, and it was confirmed that the heat insulation performance of the glass panel 1 was improved as compared with about 1500 Pa.

  Compared with the glass panel 1 not using the adsorbent 8, the evacuation time by the vacuum pump for obtaining a predetermined performance was reduced. Moreover, compared with the glass panel which does not use the adsorbent 8, the predetermined pressure could be maintained for a long time without the adsorbent high-temperature treatment in the glass panel.

  Furthermore, by heating 8 parts of the adsorbent to about 80 ° C. with the heater 10 attached to the glass panel 1, it is confirmed that the air adsorbed by the adsorbent 8 is released and the heat insulation performance deteriorates to about 1500 Pa. did.

  Further, it was confirmed that when the heater 10 is turned off, the adsorbent 8 again adsorbs air components, the pressure inside the space 6 is reduced, and the heat insulation performance of the glass panel 1 is improved.

  Thus, adsorption / desorption of the adsorbent 8 can be repeated by temperature control, and the pressure inside the sealed space 6 can be easily changed. Thereby, the heat insulation performance can be made variable, and the glass panel 1 which can change heat insulation performance according to an environment or a situation can be obtained.

  As described above, the present invention can obtain a glass panel that requires heat insulation, or a glass panel that requires changing heat insulation performance, for example, heat insulation of a building such as a house, a refrigerator, a showcase, etc. It can be used in various fields such as glass panels that can be used for cold bodies, automobiles, railway vehicles, and other car bodies and aircraft.

Sectional drawing which shows an example of the glass panel in Embodiment 1 of this invention Sectional drawing which shows an example of the glass panel in Embodiment 2 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass panel 2 Sheet glass 3 Sheet glass 4 Joining member 5 Spacer 6 Space 8 Adsorbent

Claims (2)

A pair of plate glass disposed at intervals via spacers, the joining member for joining the peripheral edge portions of the pair of plate glass, the enclosed pair of plate glass and the bonding member space And an adsorbent that adsorbs nitrogen or oxygen at least at room temperature under reduced pressure , wherein the adsorbent contains at least Li and a solid substance having a hardness of 5 or more mixed by mechanical milling. panel. A pair of plate glasses disposed at intervals via a spacer; a joining member for joining the peripheral portions of the pair of plate glasses; and a space surrounded by the pair of plate glasses and the joining member. A glass panel comprising: an adsorbent that adsorbs nitrogen or oxygen under reduced pressure at room temperature, wherein the adsorbent contains at least ZSM-5 type zeolite exchanged with copper ions.

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