JP2019147720A - Getter material for insulation member and insulation member using same - Google Patents

Abstract

To provide a getter material that can be activated at 300°C or lower and can maintain the high gas capture characteristics even after gas release in the air atmosphere or in the sealing process.SOLUTION: The getter material for insulation member according to the present invention is characterized by having a metal phase composed of a metal or an alloy that melts at 300°C or less, and particles that are contained in the metal phase and composed of a metal or a metal oxide.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a getter material for a heat insulating member and a heat insulating member using the same.

Getter materials for heat insulation members are used for building material window glass, commercial refrigerators, freezer doors, water bottles and electric kettle insulation layers, and window materials for transportation equipment such as automobiles and ships that require high heat insulation performance. The member getter material is used to maintain these heat insulation properties. In recent years, improvement in heat insulation and durability of a heat insulation layer has been demanded by the global trend of energy saving and CO ₂ emission reduction. Among them, the energy saving of buildings due to laws and regulations is rapidly progressing, and the demand for vacuum double glazing, which is a window glass with excellent heat insulation performance, is increasing. The vacuum double-glazed glass has a structure in which heat transfer by gas is suppressed by evacuating a space (hereinafter referred to as a gap) formed by opposing plate glasses to a vacuum, thereby improving heat insulation. On the other hand, due to the long-term use of the vacuum double-layer glass, the degree of vacuum in the gap portion is reduced due to the gas being released from the sealing material that seals the glass plate and the opposing glass plate, and the heat insulation is reduced. There's a problem. Therefore, a getter material is installed in the gap for the purpose of capturing gas released from the glass plate and the sealing material and maintaining heat insulation.

  Patent Document 1 discloses a vacuum double-glazed glass having a getter material that adsorbs a gas in a decompression space. As the getter material, a general non-evaporable getter material is used. Specifically, Ti, Zr, Hf, V, Fe, Al, Cr, Nb, Ta, W, Mo, Ni, Mn, Y A porous sintered body made of one or more of these metals or alloys is used.

International Publication No. 2016/017709

  The getter material disclosed in Patent Document 1 needs to be activated by local heating or the like, and the activation temperature is 350 ° C. or higher.

  From the viewpoint of manufacturing efficiency, it is desired that the getter material can be activated simultaneously with the sealing of the glass panel. However, in order to prevent breakage due to high vacuum, safety, crime prevention, etc., it is required to apply tempered glass that is subjected to air-cooling tempering treatment and the like and is hard to break. In the tempered glass that has been strengthened by forming a compression-strengthened layer on the surface, the tempered layer gradually decreases at a heating temperature of about 320 ° C. or higher. For this reason, the sealing temperature of a glass panel is desirably 300 ° C. or lower, and a getter material that can be activated at 300 ° C. or lower in accordance with the sealing temperature of glass is desired.

  In addition, the vacuum multilayer glass panel is sealed while being evacuated in two stages of pre-baking and main baking. From the viewpoint of manufacturing efficiency, it is desirable from the viewpoint of improving manufacturing efficiency that the preliminary firing is performed in an air atmosphere. However, with the current getter material, when pre-baked in the air atmosphere, it is activated as the temperature rises and traps gas components in the air, making it difficult to trap the released gas in the panel after sealing. There is a fear. Therefore, a getter material that can maintain activity even after a firing process in an air atmosphere is expected.

  Therefore, an object of the present invention is to provide a getter material that can be activated at 300 ° C. or less and can maintain high gas trapping characteristics even after gas discharge in an atmospheric atmosphere or a sealing process.

In order to solve the above problems, the gist of the present invention is as follows.
(1) a metal phase made of a metal or alloy that melts at 300 ° C. or lower;
A getter material for a heat insulating member, comprising: particles contained in the metal phase and made of metal or metal oxide.
(2) The getter material for a heat insulating member according to (1),
The getter material for a heat insulating member, wherein the particles are dispersed in the metal phase.
(3) The getter material for a heat insulating member according to (1) or (2),
The getter material for a heat insulating member, wherein the particles contain an alkali metal oxide or an alkaline earth metal oxide.
(4) The getter material for a heat insulating member according to (3),
The particles heat insulating member for a getter material which comprises a Li 2 _O.
(5) The getter material for a heat insulating member according to any one of (1) to (4),
The getter material for a heat insulating member, wherein the metal phase contains Sn.
(6) The getter material for a heat insulating member according to any one of (1) to (5),
Content of the said particle | grains in the said getter material is 10 volume% or more and 90 volume% or less, The getter material for heat insulation members characterized by the above-mentioned.
(7) The getter material for a heat insulating member according to any one of (1) to (6),
A getter material for a heat insulating member, characterized by being in the form of a thin film.
(8) A heat insulation comprising: a first substrate; a second substrate facing the first substrate; and a gap formed by an internal space between the first substrate and the second substrate. A member,
A heat insulating member comprising the getter material for a heat insulating member according to any one of (1) to (7) in the gap portion.

  ADVANTAGE OF THE INVENTION According to this invention, the getter material which can be activated at 300 degrees C or less and can maintain a high gas capture characteristic even if it passes through the gas discharge | release in air | atmosphere atmosphere or a sealing process can be provided. Problems, configurations, and effects other than those described above will be clarified by the following description of the embodiments.

It is a perspective view of the multilayer glass panel which concerns on one Embodiment of this invention. It is sectional drawing of the multilayer glass panel which concerns on FIG. It is sectional drawing which shows typically an example of a structure of the getter material which concerns on this embodiment. It is a figure which shows an example of activation of the getter material which concerns on this embodiment. It is a DTA curve of a general glass composition. It is a figure which shows the crystal structure before and behind the air baking of the getter material which concerns on this embodiment. It is a figure which shows the gas capture | acquisition characteristic of the getter material which concerns on an Example.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Hereinafter, a vacuum heat insulating multilayer glass panel will be described as an example of a heat insulating member, but the following description shows specific examples of the contents of the present invention, and the present invention is not limited to these descriptions. Various changes and modifications can be made by those skilled in the art within the scope of the technical idea disclosed in this specification. In all the drawings for explaining the present invention, components having the same function are denoted by the same reference numerals, and repeated description thereof may be omitted.

  Getter materials are usually covered with oxides or nitrides in the atmosphere, so gas trapping properties do not occur at room temperature, but oxides and nitrides formed on the surface when the getter material is heated It is known that gas molecules in a vacuum can be taken into the surface by decomposing the surface of the getter material and exposing a clean surface not exposed to the atmosphere to the surface of the getter material, resulting in gas trapping characteristics. On the other hand, from the viewpoint of improving the manufacturing tact of the glass panel, in the case of simultaneously activating the getter material in the glass panel sealing step, the gas component discharged from the glass paste and the glass plate used for the sealing material during heating, or the atmosphere When the firing process is performed, the getter material captures the gas component in the atmosphere, and thus there is a problem that the gas trapping characteristic cannot be exhibited during vacuum sealing.

As a result of investigating and investigating the types of gas released from each material inside the multilayer glass panel and the amount of the gas released, the present inventors have found CO released from the sealing material that seals the peripheral edge of the multilayer glass panel. ₂ and the moisture released from the sealing material and other materials was found to be the main cause of the high vacuum inside the panel. CO ₂ and moisture are also released in the firing process when sealing, and since they are present in large amounts in the atmosphere, the getter material has already been activated in the sealing process, and gas components immediately after activation It was found that the reaction and trapping state is unfavorable. That is, it has been found that a high vacuum inside the multilayer glass panel can be maintained by installing a getter material that can capture at least CO ₂ and moisture and can maintain activity even after a sealing process.

  FIG. 1 is a perspective view of a multilayer glass panel according to an embodiment of the present invention, and FIG. 2 is a sectional view of the multilayer glass panel of FIG. The multi-layer glass panel includes a first substrate 101, a second substrate 102 arranged to face the first substrate 101 with a space therebetween, and between the first substrate 101 and the second substrate 102. The sealing part 104 provided in the periphery of the gap | interval part 105 comprised by this interior space, and the getter material 107 arrange | positioned at the gap | interval part 105 are provided. The gap 105 formed by the first substrate 101, the second substrate 102, and the sealing portion 104 is in a vacuum state. In this specification, the vacuum state refers to a state where the pressure is reduced from the atmospheric pressure. A plurality of spacers 103 are arranged in the gap portion 105. Since the gap portion 105 of the multilayer glass panel is in a vacuum state, a pressure difference between the atmospheric pressure and the gap portion is generated, but the gap portion 105 can be maintained by arranging the spacer 103.

By disposing the getter material 107 in the gap portion 105, CO ₂ gas and moisture released from various members can be captured. As a result, a high vacuum in the gap can be maintained, and the heat insulation of the multilayer glass panel can be maintained.

<First substrate and second substrate>
As the first substrate 101 and the second substrate 102 of the multilayer glass panel, float plate glass, mold plate glass, rubbing glass, tempered glass, netted plate glass, lined plate glass, or the like can be used. These may be subjected to air cooling strengthening treatment or chemical strengthening treatment. The number of spacers can be reduced by using tempered glass that has been air-cooled or chemically strengthened. In the case of using a spacer made of a material having a high thermal conductivity, heat insulation is improved by reducing the number of spacers. Moreover, it is preferable that the kind of these glass is cheap soda-lime glass.

  In the multilayer glass panel of FIG. 2, a heat ray reflective film 106 is laminated on the surface of the second substrate 102. As shown in FIG. 2, a plate glass having a heat ray reflective film laminated on its surface can be used.

<Spacer>
The spacer 103 is used to maintain the space between the two glass substrates. The spacer is not particularly limited as long as the spacer has a lower hardness than the double-glazed plate glass and has a suitable compressive strength. For example, glass, metal, alloy, steel, ceramics, plastic, etc. can be used. From the viewpoint of heat insulation, it is preferable to use a material having low thermal conductivity.

  The spacer shape is not particularly limited. For example, a cylindrical, spherical, linear, or net-like spacer can be used.

  The size of the spacer can be selected according to the thickness of the space between the two glass substrates. For example, when it is desired to set the distance between two glass substrates to 200 μm, a spacer having a diameter of about 200 μm may be used. The interval at which the spherical, linear, and reticulated spacers are disposed is 200 mm or less, preferably 100 mm or less, and 10 mm or more. The spacers can be arranged regularly or irregularly as long as the distance is within the above-mentioned range.

  In addition, in order to obtain a space portion having an appropriate thickness in a vacuum state, it is effective to introduce spherical beads having a uniform particle diameter in the spacer or the sealing portion.

<Sealing part>
The sealing portion 104 is preferably formed of a sealing material containing low melting point glass. The sealing material may contain low thermal expansion filler particles, metal particles and the like in addition to the low melting point glass. A paste-like material in which these materials and a solvent are mixed can be applied to the periphery of the first substrate 101 or the second substrate 102 with a dispenser or the like, dried, and temporarily fired. Alternatively, the paste-like material may be applied to both sides of a ribbon-like foil, dried, and then temporarily fired, as a sealing material.

As the low melting point glass, lead-free low melting point glass containing oxide glass (V ₂ O ₅ ) and tellurium oxide (TeO ₂ ) can be used. This is because a glass containing vanadium oxide and tellurium oxide has a low softening point and can be hermetically sealed at a low temperature. In addition, since lead-based low melting glass contains a lot of lead specified as a prohibited substance of the RoHS Directive, it is not preferable to apply it to a vacuum heat insulating double-glazed glass panel or the like from an environmental viewpoint. The lead-free low-melting glass preferably further contains silver oxide (Ag ₂ O). Lead-free glass containing silver oxide in addition to vanadium oxide and tellurium oxide has a lower softening point. Therefore, it can be hermetically sealed at a lower temperature. Lowering the sealing temperature has the advantage that it can be manufactured at low cost because it is possible to shorten the manufacturing tact and reduce the investment cost for introducing mass production equipment for a vacuum heat insulating double-glazed glass panel or the like that is difficult to rapidly heat and cool. There is also an advantage that tempered glass can be applied to the first substrate and the second substrate. In the present specification, the low melting point glass means a glass having a softening point of 400 ° C. or lower.

The total amount of V ₂ O ₅ and TeO _{2 in} the low-melting glass is preferably 50 mol% or more and 80 mol% or less. Further, when Ag ₂ O is contained, the total amount of V ₂ O ₅ , TeO ₂ and Ag ₂ O is preferably 70 mol% or more, and more preferably 80 mol% or more and 98 mol% or less. . The content of V ₂ O ₅ is preferably 15 mol% or more and 45 mol% or less, the content of TeO ₂ is preferably 15 mol% or more and 45 mol% or less, and the content of Ag ₂ O is 10 mol%. It is preferable that it is 50 mol% or less. Further, the content of TeO ₂ is from 1 to 2 times molar ratio to _V 2 _{O 5,} the content of Ag ₂ O is 2 times or less in molar ratio with respect to _V 2 _{O 5} It is preferable.

The low melting point glass may contain 30 mol% or less of any one or more of K ₂ O, BaO, WO ₃ , MoO ₃ and P ₂ O ₅ . Any one or more of K ₂ O, BaO, WO ₃ , MoO _3, and P ₂ O ₅ are preferably included at 20 mol% or less. The low melting point glass further includes Fe ₂ O ₃ , Al ₂ O ₃ , Ga ₂ O ₃ , In ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Er ₂ O ₃ and Yb as additional components. Any one or more of ₂ O ₃ may be included. The content of these additional components is preferably 5 mol% or less, and preferably 0.1 or more and 3.0 mol% or less.

  The content of the lead-free low melting point glass in the sealing material is preferably 40% by volume or more. The low melting point glass does not need to be kept amorphous after sealing, and may be crystallized.

As the low thermal expansion filler, those having a negative thermal expansion coefficient are preferable. By including the low thermal expansion filler particles, a difference in thermal expansion between the first substrate, the sealing portion, and the second substrate can be reduced, and a sealing portion with higher bonding strength can be obtained. Examples of the low thermal expansion filler particles having a negative thermal expansion coefficient include zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ), niobium oxide (Nb ₂ O ₅ ), β-eucryptite (LiAlSiO _4). ), Quartz glass (SiO ₂ ), and the like. Among these low thermal expansion fillers, zirconium tungstate phosphate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ) is preferable. This is because zirconium tungstate phosphate has good wettability with lead-free low-melting glass containing vanadium oxide and tellurium oxide. From the viewpoint of achieving both airtightness and bonding strength, the content of the low thermal expansion filler particles in the sealing material is preferably 10% by volume or more and 45% by volume or less.

  The metal particles are preferably a low melting point metal having a melting point of 300 ° C. or lower. As the low melting point metal, for example, tin or a tin-based alloy can be used. As the tin-based alloy, an alloy containing any of silver, copper, zinc, and antimony can be preferably used. From the viewpoint of heat insulation and bonding strength, the ratio of the metal particles in the sealing material is preferably 10% by volume or more and 70% by volume or less.

  As a sealing material, when using the material which apply | coated the paste containing a low melting glass on both surfaces of a ribbon-shaped foil, and used the temporary baking, metal foil can be used as a ribbon-shaped foil. By using a material in which a paste containing low-melting glass is applied on both sides of a ribbon-like foil as a sealing material, the amount of low-melting glass used for the sealing material can be reduced. As a result, the amount of gas released from the low melting glass can be reduced and the degree of vacuum can be improved.

  As the ribbon-like metal foil, for example, an iron-nickel alloy, an iron-nickel-chromium alloy, an aluminum metal, an aluminum alloy, and a clad material thereof can be used.

<Getter material>
FIG. 3 is a cross-sectional view schematically showing an example of the configuration of the getter material according to this embodiment. The getter material according to the present embodiment includes a metal phase 301 made of a metal or an alloy that melts at 300 ° C. or less, and particles 302 that are contained in the metal phase and made of a metal or a metal oxide. The particles 302 are dispersed in the metal phase 301.

  The metal phase 301 is made of a metal or alloy having a melting point of 300 ° C. or lower. Specifically, Sn (tin), Bi (bismuth), In (indium), Sn (tin) -In (indium) alloy, Sn (tin) -Bi (bismuth) alloy, Sn (tin) -Zn (zinc) ) Alloy, Sn (tin) -Ag (silver) alloy, Sn (tin) -Ag (silver) -Cu (copper) alloy, Sn (tin) -Zn (zinc) -Bi (bismuth) alloy, Sn (tin) -Bi (bismuth) -Ag (silver) alloy, etc. can be used. This metal phase covers particles made of a metal or metal oxide that exhibits gas trapping properties in particular, thereby suppressing excessive reaction with excess gas released in the sealing process and atmospheric gas components in the atmospheric process. It has a function of maintaining gas trapping characteristics after stopping. In addition, the same effect can be acquired even if it is a metal and alloy whose melting | fusing point is 300 degrees C or less other than the said material.

The particle 302 made of a metal or metal oxide is a particle that exhibits gas trapping properties, and is one or more metal oxides selected from the group consisting of alkali metal oxides and alkaline earth metal oxides. Is preferred. Specifically, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, MgO, CaO, SrO, BaO, or the like can be used. These particles are effective components for capturing released CO ₂ and moisture. For example, the emitted gas is captured by the following reaction formulas (1) and (2).
Li ₂ O + CO ₂ → Li ₂ CO ₃ (1)
_{Li 2 O + H 2 O →} 2LiOH (2)
By covering these particles with the above-described metal phase 301, it is possible to suppress gas release during sealing and unnecessary gas trapping in the sealing process in the atmosphere, and maintain gas trapping characteristics after sealing. it can.

  FIG. 4 is a cross-sectional view schematically showing the getter material after the heat treatment. The getter material is a metal or metal that is a getter component by heat treatment from the state in which the particles 302 shown in FIG. 3 are dispersed in the metal phase 301 and by melting the metal or alloy constituting the metal phase 301 as shown in FIG. It is considered that the gas trapping property is exhibited when the particles 302 made of an oxide are selectively exposed on at least one surface of the metal phase 301.

  The shape of the getter material is not particularly limited, but is preferably a thin film from the viewpoint of installation on the heat insulating member. The shape of the thin film is not particularly limited, such as a disc shape, a strip shape, or a bellows shape. Further, the thickness and size of the getter material are not particularly limited as long as the thickness and size of the getter material are within the gap formed by the opposing glass plates, but are preferably large enough to be hidden by the sash because of the characteristics of the window glass. At that time, it is necessary to install an amount of getter material that can sufficiently capture the gas released from various members used in the multilayer glass panel.

  The content of particles made of a metal or metal oxide contained in the getter material is preferably 10% by volume to 90% by volume, and more preferably 20% by volume to 80% by volume. By setting it as 10 volume% or more, a desired gas capture characteristic can be obtained. Moreover, the particle | grains which consist of a metal or a metal oxide can be protected from an unnecessary emitted gas and an atmospheric gas component by setting it as 90 volume% or less.

  The particle diameter of the particles made of metal or metal oxide is preferably 10 nm to 200 μm, more preferably 100 nm to 100 μm. When the particle diameter of the particles is 10 nm or more, the particles are easily exposed on the surface of the metal phase during the heat treatment, and high gas trapping characteristics can be obtained. When the particle diameter of the particles is 200 μm or less, the metal phase can cover the particles, and can be protected from unnecessary emitted gas and atmospheric gas components.

The getter material is mainly intended to capture CO ₂ and moisture. For example, when capturing released gases such as O ₂ , CO, N ₂ , H ₂ , NO, NO ₂ , etc., as appropriate. Can be installed together with getter material tailored to the released gas. Examples of the getter material that can be installed together with the getter material of the present invention include alloys containing Zr (zirconium) and V (vanadium), Fe (iron), Ag (silver), Zn (zinc), Li (lithium), and the like. ), Mg (magnesium), Na (sodium), K (potassium), Ti (titanium), zeolite, Na ₂ TiO ₃ , Li ₂ TiO ₃ , Na ₂ ZrO ₃ , Li ₂ ZrO ₃ , CeO _{2 and the} like. . There are no restrictions on the type of installation, and two or more types may be installed together.

  In order to maintain the structure of the getter material or to facilitate installation in the gap, the getter material may be laminated and molded on the base material. The base material is not particularly limited, but a material that does not melt at 300 ° C. or lower is preferable. For example, Al (aluminum), Cu (copper), Au (gold), Ag (silver), Zn (zinc), Ti (titanium) Fe (iron), Co (cobalt), Ni (nickel), and the like.

  The getter material needs to be activated before use. An example of the activation method is heat treatment. The heat treatment temperature is not particularly limited as long as it is equal to or higher than the melting point of the metal phase. In addition, a clean metal surface is exposed when the metal used for the metal phase is melted at the melting point, and gas trapping characteristics can be expressed for various gas components. There is no restriction | limiting in particular also in the atmosphere in the case of activation, You may activate in an air atmosphere, an inert atmosphere, a reducing atmosphere, a reduced pressure atmosphere, etc. By activating simultaneously with the heat treatment at the time of sealing the multilayer glass panel, the production efficiency can be increased.

  The structure and composition of the getter material can be confirmed by Auger electron spectroscopy, X-ray photoelectron spectroscopy, fluorescent X-ray analysis, X-ray diffraction analysis, and electron microscope observation.

<Manufacturing method of multi-layer glass panel>
A multilayer glass panel according to an embodiment of the present invention seals the first substrate and the peripheral portion of the second substrate, which are arranged to face each other at a predetermined interval, with a sealing material. It can be manufactured by forming a sealable gap between the first substrate and the second substrate and exhausting the gap into a vacuum state. Specifically, a step of disposing a sealing material and a getter material on the first substrate, a stacking step of stacking and fixing the first substrate and the second substrate, and sealing the first substrate and the second substrate. A sealing step of sealing with a stopping material, and a vacuum exhausting step of exhausting the internal space of the first substrate and the second substrate.

  When a paste-like sealing material is used, the sealing material is disposed on the first substrate by applying the sealing material to the first substrate and then pre-baking. In the case where a ribbon-shaped sealing material is used, the sealing material may be disposed on the first substrate.

  When a thin-film getter material is used, it may be installed on the first substrate. Although the installation location is not particularly limited, it is preferably installed at a location that does not block the view from the viewpoint of the window glass.

  In the stacking step, the first substrate and the second substrate may be stacked and then fixed with a plurality of clips or the like. In consideration of the heat resistance of the spring, the clip may be made of stainless steel or inconel. As the second substrate, a surface on which a heat ray reflective film is laminated may be used.

When either the first substrate or the second substrate has an exhaust port, a vacuum exhaust process is performed after the sealing process. In the sealing process, the laminated and fixed pair of substrates are hermetically sealed by heating to a temperature near or above the softening point of the sealing material, and then the internal space is exhausted from the exhaust port by a vacuum pump or the like in the vacuum exhaust process. Evacuate. An exhaust pipe is connected to the exhaust port, and after exhausting through the exhaust pipe, the inside of the internal space can be maintained in a vacuum state by sealing the exhaust pipe. The sealing temperature is preferably the temperature between the vicinity of the softening point T _{s of the} glass contained in the sealing material and the working point T _w .

Here, the characteristic temperature of the low-melting glass will be described. FIG. 5 shows an example of a differential thermal analysis (DTA) graph of the glass composition. In general, DTA of glass uses glass particles having a particle size of about several tens of μm, and further uses high-purity alumina (α-Al ₂ O ₃ ) particles as a standard sample. Measured at temperature rate. As shown in FIG. 5, the starting temperature of the first endothermic peak or the temperature at which the glass transitions from the supercooled liquid is the transition point T _g , the endothermic peak temperature, or the point at which the expansion of the glass stops is the yield point M. _g , second endothermic peak temperature, or temperature at which softening starts, softening point T _s , temperature at which the glass becomes a sintered body, sintering point T _sint , temperature at which the glass melts pour point T _f , molding of molten glass The temperature suitable for is called the working point T _w , and the exothermic peak start temperature due to crystallization is called the crystallization start temperature T _cry . In addition, each characteristic temperature is calculated | required by the tangent method.

Also, the characteristic temperatures such as T _g , M _g and T _s are defined by the viscosity of the glass, T _g is 1013.3 poise, M _g is 1011.0 poise, T _s is 107.65 poise, T _sint is 106 poise, T _f is 105 poise, and T _w is a temperature corresponding to 104 poise.

  When neither the first substrate nor the second substrate has an exhaust port, the sealing step and the vacuum exhaust step are performed simultaneously. Before the stacking step, a column member having a height higher than the sealing portion may be installed on the first substrate. The column member is made of a metal or an alloy, and the melting point thereof is preferably the pour point of the low melting point glass contained in the sealing material + 20 ° C. or less, and more preferably 320 ° C. or less. Specifically, Bi, Sn, gold-tin alloy, zinc-tin alloy, tin-silver eutectic solder can be used as the metal or alloy constituting the column member. A pair of substrates fixed by a laminating process is placed in a vacuum apparatus, and the substrate is evacuated while being heated to a temperature that is higher than the softening point of the low melting point glass and 20 ° C. higher than the pour point of the glass composition. In the present specification, the temperature near the softening point is defined as the temperature at the softening point ± 10 ° C, and the temperature near the pour point is defined as the temperature at the pour point ± 10 ° C. In the temperature process, the temperature is raised to the first temperature which is not less than the softening point of the low-melting glass and less than the melting point of the column member, and after holding at the first temperature, the pour point of the glass composition above the melting point of the column member +10 It is preferable that the temperature is raised to a second temperature which is a temperature equal to or lower than ° C. and held at the second temperature. By setting it as the temperature profile as mentioned above, a sealing material and a column member are crushed simultaneously, and a favorable sealing state can be obtained. According to the above method, the process of providing an exhaust port on the substrate and the process of closing the exhaust port after evacuation can be reduced, and the manufacturing process can be simplified.

  Next, examples of the present invention will be described in detail, but the technical scope of the present invention is not limited thereto.

Example 1
<Getter material>
Li ₂ O powder and Sn powder were weighed so that Li ₂ O was 30% by volume and Sn was 70% by volume, and mixed in an agate mortar until visually uniform to obtain a mixed powder. Thereafter, 0.04 g of the mixed powder was put into a 10 mmφ die and held for 1 minute under a pressure of 60 MPa to produce a thin-film getter material. The gas trapping properties of this getter material were evaluated by thermogravimetry.

<Evaluation of gas trapping characteristics of getter materials>
The getter material is used in the gap between the multi-layer glass panel and the sealed layer isolated from the outside. It is difficult to clearly evaluate the characteristics. Therefore, in order to clarify the gas trapping characteristics of the getter material of the present invention and the effect thereof, the above-described thermogravimetry using a TG / DTA thermal analyzer (TG / DTA 6200, manufactured by Seiko Instruments Inc.) The heat treatment conditions at the time of sealing at the time of producing a multi-layer glass panel using the low melting point glass were simulated, and the effect was confirmed by taking the weight change at that time as gas capture and desorption. At that time, an alumina cell (φ5.0 mm, Epolide Service, P / N SSC515D001) was used as a sample cell. Measurement conditions were as follows. After holding at room temperature for 30 minutes in a CO ₂ atmosphere, the temperature was once increased from room temperature to 300 ° C. at 5 ° C./minute, held for 30 minutes, and then naturally cooled to room temperature.

(Example 2)
The same procedure as in Example 1 was performed except that the measurement atmosphere at the time of thermogravimetry was changed to an air atmosphere.

(Example 3)
The same procedure as in Example 1 was performed except that the composition of the getter material was changed to 20% by volume of Li ₂ O and 80% by volume of Sn.

(Example 4)
The procedure of Example 1 was followed except that the composition of the getter material was changed to 10% by volume of Li ₂ O and 90% by volume of Sn.

(Example 5)
The procedure of Example 1 was followed except that the composition of the getter material was changed to 50% by volume of Li ₂ O and 50% by volume of Sn.

(Example 6)
The same procedure as in Example 1 was performed except that the composition of the getter material was changed to 70% by volume of Li ₂ O and 30% by volume of Sn.

(Example 7)
The procedure of Example 1 was followed except that the composition of the getter material was changed to 80% by volume of Li ₂ O and 20% by volume of Sn.

(Example 8)
The procedure of Example 1 was followed except that the composition of the getter material was changed to 90% by volume of Li ₂ O and 10% by volume of Sn.

(Comparative Example 1)
The procedure was the same as in Example 1 except that the type of getter material was changed to a Zr-based alloy getter.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that the type of getter material was changed to Li ₂ O only.

In FIG. 6, the crystal structure change before and after the thermogravimetric measurement of Example 1 by X-ray diffraction measurement is shown. The measurement conditions for the X-ray diffraction measurement were a measurement range: 2θ = 10 to 80 °, a measurement width: 0.02 °, a tube voltage: 48 kV, and a tube current: 25 mA. The X-ray diffraction pattern before thermogravimetric measurement has a sharp peak especially at 2θ = 30.7 °, near 32.1 ° derived from Sn, whereas the X-ray diffraction pattern after thermogravimetric measurement shows Sn. Since 2θ = 30.7 ° derived from 23.2 ° substantially disappears and a peak of 2θ = 33.7 ° derived from Li ₂ O appears prominently, heat treatment simulating the glass sealing step It was proved that Li ₂ O inside the getter material was exposed on the surface.

In FIG. 7, the thermogravimetric measurement result of Example 1 and Example 2 is shown. In the first temperature rising process up to 300 ° C., the weight of Example 1 was rapidly increased from around 240 ° C. as compared with Example 2. This is because measurement was performed in a CO ₂ atmosphere in Example 1, so that gas capture by Sn did not occur, only an increase in the weight of CO ₂ gas capture by Li ₂ O was detected, and Sn melts. This is because Li ₂ O is exposed on the surface of the getter material and captures the CO ₂ gas. From this result, in Example 1 and Example 2, at a low temperature below the melting point of Sn, Li ₂ O is not activated and unnecessary gas trapping is suppressed, activated at a high temperature, and maintained active thereafter. Proved to be.

Table 1 shows the thermogravimetric measurement results of Examples 1 to 8 and Comparative Examples 1 and 2. The effect of the present invention can be confirmed from the reaction rate of the getter material calculated from the weight change at the following three points. That is, (1) room temperature holding in the first atmospheric atmosphere, (2) subsequent temperature raising process up to 300 ° C., and (3) holding at 300 ° C. for 30 minutes. Incidentally, the reaction rate is a weight increase a reaction amount between CO _2, and the ratio of the molar amount of Li 2 _O of the molar quantity. Further, the reaction rate of Comparative Example 1 was a ratio of the reaction rate in advance and the temperature was raised to 300 ° C. under a CO ₂ atmosphere. It shows that the trapping of unnecessary gas can be suppressed and the gas trapping property can be maintained after sealing in the actual sealing step of the multilayer glass as the total value of the reaction rate is lower.

In Comparative Example 1, almost no reaction was observed in the CO ₂ atmosphere at room temperature of (1), but after a 99% reaction rate increase was observed in the temperature raising process (2), the temperature was maintained at 300 ° C. (3 ) Showed almost no increase in response rate. That is, it is considered that gas trapping is saturated by activating and trapping gas in the temperature rising process, and then the gas trapping effect is lost, and the released gas and CO ₂ emitted during the sealing process of the multilayer glass panel are reduced. It was found that the activated state could not be maintained through the sealing step in the air atmosphere. Further, in Comparative Example 2, it has already reacted in the first CO ₂ atmosphere, and after that, the reaction rate is increased, and it is clear that unnecessary gas components are trapped and gas trapping characteristics are deteriorated. It was. On the other hand, in Examples 1 to 8, the increase in the reaction rate under the CO ₂ atmosphere (1) is almost not reacted with 0.01%, and the trapping of unnecessary gas is suppressed. I understood. Moreover, also in the 300 degreeC holding | maintenance process (3) which passed through the temperature rising process (2), the reaction rate was 1.0% or less, and it became clear that the fall of the gas capture characteristic by gas capture could be suppressed. From these results, it was proved by the present invention that the gas trapping characteristics can be maintained even after the gas emitted during the sealing process of the multi-layer glass panel and the heat treatment process in the atmosphere.

101 First substrate 102 Second substrate 103 Spacer 104 Sealing material (sealing part)
105 gap portion 106 heat ray reflective film 107 getter material 301 metal layer 302 metal oxide layer

Claims (8)

A metal phase composed of a metal or an alloy that melts at 300 ° C. or lower;
A getter material for a heat insulating member, comprising: particles contained in the metal phase and made of metal or metal oxide. The getter material for a heat insulating member according to claim 1,
The getter material for a heat insulating member, wherein the particles are dispersed in the metal phase. A getter material for a heat insulating member according to claim 1 or 2,
The getter material for a heat insulating member, wherein the particles contain an alkali metal oxide or an alkaline earth metal oxide. The getter material for a heat insulating member according to claim 3,
The particles heat insulating member for a getter material which comprises a Li 2 _O. A getter material for a heat insulating member according to any one of claims 1 to 4,
The getter material for a heat insulating member, wherein the metal phase contains Sn. A getter material for a heat insulating member according to any one of claims 1 to 5,
Content of the said particle | grains in the said getter material is 10 volume% or more and 90 volume% or less, The getter material for heat insulation members characterized by the above-mentioned. A getter material for a heat insulating member according to any one of claims 1 to 6,
A getter material for a heat insulating member, characterized by being in the form of a thin film. A heat insulating member comprising: a first substrate; a second substrate facing the first substrate; and a gap formed by an internal space between the first substrate and the second substrate. And
The heat insulation member provided with the getter material for heat insulation members as described in any one of Claims 1-7 in the said gap | interval part.

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