Getter material composition and method for manufacturing glass panel unit

Abstract

To provide a getter material composition that exhibits adsorption performance in a low-pressure range even if the manufacturing process of a glass panel unit is performed at lower temperatures.SOLUTION: A getter material composition includes a getter material and a solvent. The getter material includes a plurality of particles composed of crystals of copper ion-exchanged zeolite. The particles accounting for half or more of the total weight of the plurality of particles have a particle size of 200 nm or more. The solvent includes an organic solvent as the main ingredient.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a getter material composition and a method for manufacturing a glass panel unit, and more particularly to a method for manufacturing a heat insulating glass panel unit and a getter material composition used therein. [Background technology]

[0002] Patent Document 1 discloses a glass panel unit having a gas adsorbent therein, and also discloses that a zeolite-based material is used as the gas adsorbent. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 004135 Summary of the Invention [Problem to be solved by the invention]

[0004] However, Patent Document 1 does not disclose anything about the size of the zeolite that constitutes the gas adsorbent, and there is room for improvement.

[0005] An object of the present disclosure is to provide a getter material composition and a method for manufacturing a glass panel unit that exhibit adsorption performance in a low-pressure range even when the manufacturing process of the glass panel unit is performed at a low temperature. [Means for solving the problem]

[0006] A getter material composition according to one embodiment of the present disclosure comprises a getter material and a solvent, the getter material comprising a plurality of particles formed of copper ion-exchanged zeolite crystals, the particles accounting for more than half of the total weight of the plurality of particles having a diameter of 200 nm or more, and the solvent comprising an organic solvent as a main component.

[0007] A method for manufacturing a glass panel unit according to one embodiment of the present disclosure includes a processing step of preparing the getter material composition, an assembly step of preparing an assembly including a first glass plate, a second glass plate, a frame-shaped peripheral wall, an internal space, a gas adsorbent obtained from the getter material composition, and an exhaust port, a bonding step of melting the peripheral wall to airtightly bond the first glass plate and the second glass plate, and an exhaust step of evacuating the internal space through the exhaust port to create a reduced-pressure space. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a getter material composition and a method for manufacturing a glass panel unit that exhibit adsorption performance in a low-pressure region even when the manufacturing process of the glass panel unit is performed at a low temperature. [Brief explanation of the drawings]

[0009] [Figure 1] Fig. 1A is a plan view showing an assembly that is an intermediate product of a glass panel unit according to a first embodiment, and Fig. 1B is a cross-sectional view taken along line AA in Fig. 1A. [Figure 2] FIG. 2 is a plan view showing the glass panel unit of the same. [Figure 3] FIG. 3 is an explanatory diagram of a method for manufacturing a glass panel unit according to the first embodiment. [Figure 4] FIG. 4 is an explanatory diagram of a method for manufacturing a glass panel unit according to the first embodiment. [Figure 5] FIG. 5 is an explanatory diagram of a method for manufacturing a glass panel unit according to the first embodiment. [Figure 6] FIG. 6 is an explanatory diagram of a method for manufacturing a glass panel unit according to the first embodiment. [Figure 7] FIG. 7 is an explanatory diagram of a method for manufacturing a glass panel unit according to the first embodiment. [Figure 8] FIG. 8 is an explanatory diagram of a method for manufacturing a glass panel unit according to the first embodiment. [Figure 9] FIG. 9 is a diagram showing the relationship between equilibrium pressure and adsorption amount. [Figure 10] FIG. 10 is a graph (logarithmic axis) showing the relationship between equilibrium pressure and adsorption amount. [Figure 11] FIG. 11 is a graph showing the relationship between the adsorption amount ratio and the activation temperature. [Figure 12] FIG. 12 is a diagram showing the relationship between the amount of residual gas and the diameter of crystals (particles). [Figure 13] Fig. 13A is a graph showing the relationship between the residual gas amount and the crystal (particle) diameter for water and an organic solvent, respectively. Fig. 13B is a graph showing the relationship between the residual gas amount ratio and the crystal (particle) diameter. DETAILED DESCRIPTION OF THE INVENTION

[0010] First, the background to the present disclosure will be described.

[0011] A glass panel unit has thermal insulation properties due to the presence of a reduced pressure space (or vacuum space) between the two glass plates. It is believed that the thermal insulation properties of such a glass panel unit are reduced if gas remains in the reduced pressure space, even if there is a reduced pressure space between the two glass plates. Therefore, a gas adsorbent is provided in the reduced pressure space to reduce the amount of gas remaining in the reduced pressure space. Gas adsorbents containing a getter material made of zeolite have conventionally been used (see Patent Document 1).

[0012] Zeolite placed in the atmosphere or in a solution has adsorbed a large amount of gas. Therefore, in order to use zeolite as a gas adsorbent with sufficient adsorption capacity in a reduced-pressure space, it is necessary to desorb (activate) the adsorbed gases by heating it in a vacuum and reveal adsorption sites. In particular, copper ion-exchanged zeolite reveals strong nitrogen adsorption sites when copper oxide is reduced (oxygen is desorbed). If the zeolite is not activated at a sufficiently high temperature, oxygen or other gases such as moisture will not be desorbed, and sufficient adsorption capacity will not be achieved.

[0013] Zeolite activation in the manufacturing process of glass panel units can be carried out, for example, during the evacuation process, which is started during or at the end of the first melting process (bonding process). In this case, if the zeolite can be sufficiently heated during the evacuation process, sufficient adsorption performance can be obtained. On the other hand, to improve production takt time, simplify manufacturing equipment, and accommodate tempered glass, it is desirable to lower the temperature of the manufacturing process of glass panel units. For this reason, it is desirable for zeolite to fully exhibit its adsorption ability even in a low-temperature evacuation process (low-temperature activation).

[0014] Nitrogen, which is generally difficult to adsorb in low-pressure regions, is also released during the manufacturing process of glass panel units and after manufacturing when exposed to ultraviolet light while the glass panel units are in use. For this reason, copper ion-exchanged zeolite, which can also adsorb nitrogen, is particularly desirable. However, if copper ion-exchanged zeolite cannot be sufficiently activated in low-temperature processes (low-temperature evacuation process, low-temperature activation process), it becomes difficult to develop strong adsorption sites for nitrogen, and sufficient adsorption performance cannot be achieved.

[0015] Particles made of zeolite crystals have numerous pores formed on their surfaces, through which the gas to be adsorbed is absorbed and retained (adsorbed) in the complex internal space. The gas adsorption capacity of such zeolite particles is generally considered to be proportional to the surface area. Regarding the surface area of ​​zeolite particles, assuming that the total weight of a large number of zeolite particles is constant, in other words, per unit weight, the smaller the diameter of the zeolite particles and the greater the number of zeolite particles, the greater the total surface area of ​​the zeolite particles. Therefore, the smaller the diameter of the zeolite particles, the higher the gas adsorption capacity per unit weight. Note that in this disclosure, the diameter of zeolite particles and the crystal size (crystal size) of zeolite are described as synonymous. Furthermore, in this disclosure, zeolite particles are described as primary particles. That is, zeolite particles are not aggregates (secondary particles) but zeolite crystals.

[0016] However, as a result of extensive research, the inventors have found that in a low-pressure region (especially a region close to vacuum) where the pressure is reduced by a predetermined amount below atmospheric pressure, zeolite particles with larger diameters have a higher gas adsorption capacity than zeolite particles with smaller diameters, even if the total volume of the zeolite particles is constant. Furthermore, they have found that this tendency is particularly pronounced when the zeolite is activated at low temperatures. The present disclosure was developed to utilize these properties of zeolite particles to achieve high gas adsorption capacity in low-pressure regions. That is, this embodiment provides a getter material and a getter material composition for insulating a vacuum or reduced-pressure space, which are used to obtain a gas adsorbent with high gas adsorption capacity in low-pressure regions.

[0017] First Embodiment Next, an outline of the glass panel unit 10 according to this embodiment and a method for manufacturing the same will be described.

[0018] As shown in Fig. 2, the glass panel unit 10 includes a first glass plate 20, a second glass plate 30 facing the first glass plate 20, a frame 40, a reduced pressure space 50, and a gas adsorbent 60. The frame 40 airtightly joins the first glass plate 20 and the second glass plate 30 together. The reduced pressure space 50 is surrounded by the first glass plate 20, the second glass plate 30, and the frame 40. The gas adsorbent 60 is disposed within the reduced pressure space 50. The gas adsorbent 60 contains a getter material.

[0019] The manufacturing method of the glass panel unit 10 includes a processing step, an assembling step (see FIGS. 3 to 5), a joining step (first melting step, see FIG. 6), and an evacuation step (see FIG. 6). The processing step includes a getter material preparation step for obtaining a getter material containing a plurality of particles formed of zeolite crystals. The assembling step is a step for preparing an assembly 100. The assembly 100 includes a first glass plate 200, a second glass plate 300, a frame-shaped peripheral wall 410, an internal space 500, a gas adsorbent 60, and an exhaust port 700 (see FIGS. 1A and 1B). The second glass plate 300 faces the first glass plate 200. The peripheral wall 410 is located between the first glass plate 200 and the second glass plate 300. The internal space 500 is surrounded by the first glass plate 200, the second glass plate 300, and the peripheral wall 410. The gas adsorbent 60 is disposed within the internal space 500 and contains the getter material. The exhaust port 700 connects the internal space 500 to the external space. The bonding process is a process of melting the peripheral wall 410 to airtightly bond the first glass plate 200 and the second glass plate 300. The exhaust process is a process of evacuating the internal space 500 through the exhaust port 700 to create a reduced-pressure space 50. A manufacturing method for the glass panel unit 10 (hereinafter sometimes referred to as the manufacturing method) will be described in detail with reference to FIGS. 1 to 8. This manufacturing method is a method for manufacturing the glass panel unit 10 as shown in FIG. 2. In this embodiment, the direction D1 is parallel to the thickness direction of the first glass plate 200, the direction D2 is perpendicular to the direction D1, and the direction D3 is perpendicular to the directions D1 and D2. The direction D1 may be the first direction, the direction D2 may be the second direction, and the direction D3 may be the third direction.

[0020] The manufacturing method includes a preparation step and a removal step.

[0021] The preparation step is a step of preparing a work-in-progress 110 shown in Fig. 7. The work-in-progress 110 is formed from the assembly 100 shown in Figs. 1A and 1B. In other words, the work-in-progress 110 is an intermediate product for producing the glass panel unit 10 (see Fig. 2), and the assembly 100 is an intermediate product for producing the work-in-progress 110.

[0022] The preparation process includes a processing process, an assembly process (see FIGS. 3 to 5), a joining process (first melting process, see FIG. 6), an exhaust process (see FIG. 6), and a sealing process (second melting process, see FIGS. 6 and 7).

[0023] The processing step is a step of preparing a getter material composition. This getter material composition contains at least zeolite and a solvent (e.g., at least one of water and an organic solvent). The gas adsorbent 60 is a dried product of the getter material composition. The processing step includes a heating step, a getter material preparation step, and a mixing step. The getter material composition is preferably fluid, such as a liquid, paste, ink, or slurry, and is preferably in a form that can be supplied by coating or printing.

[0024] The heating step is a step of heating the zeolite contained in the gas adsorbent 60. The temperature of the heating step is preferably higher than the temperature of the evacuation step (the evacuation temperature Te described below), more preferably higher than the temperature of the first melting step (the first melting temperature Tm1 described below), and particularly preferably higher than the temperature of the second melting step (the second melting temperature Tm2 described below). In this case, gas components adsorbed by the zeolite can be desorbed before the assembly 100 is produced. Furthermore, by heating the zeolite in the heating step, oxygen adsorbed by the zeolite can be desorbed by the heating step. This reduces the amount of oxygen desorbed in the bonding step and subsequent steps, allowing the evacuation step to be performed at a lower temperature, and as a result, the first and second melting steps can be performed at lower temperatures. This reduces the manufacturing cost of the glass panel unit 10. Note that this heating step is an optional step and does not necessarily have to be performed.

[0025] Zeolites are small particles (microparticles) made of porous crystals with numerous pores formed on the surface. Gases to be adsorbed are drawn into the pores of zeolites and are retained (adsorbed) in the complex internal spaces. Examples of gases that can be adsorbed by zeolites include water vapor, carbon dioxide, oxygen, nitrogen, and hydrocarbons such as methane. In particular, zeolites can adsorb gases such as nitrogen and hydrocarbons (especially nitrogen) in a reduced pressure space, which are difficult to adsorb with other common adsorbents. The zeolite structure has a composition represented by the following general formula (1):

[0026] Me2 / XO・Al2O3・mSiO2・nH2O…(1) Here, Me is an x-valent cation present in the pores. m is the silica / alumina ratio and is an integer of 2 or more. n is an integer of 0 or more. In the composition of formula (1), each Al generates a monovalent negative charge. Therefore, when Me is a divalent or higher cation, a positive charge is generated within the zeolite pores. Also, when Me is a monovalent cation, the interior of the pores becomes electrically neutral.

[0027] In the zeolite structure, Me may be a monovalent cation. Me may be a divalent or higher cation. Me may be a combination of a monovalent cation and a divalent or higher cation. Examples of monovalent cations include Li + , Na + , and alkali metal ions such as K+; protons; and ammonium ions (NH 4+ ), Ag+, etc. Examples of divalent or higher cations include Ca 2+ , Mg 2+ , and Ba 2+ alkaline earth metal ions such as Cu 2+ , Au 2+ , Fe 2+ , Zn 2+ and Ni 2+ and other transition metal ions.

[0028] Examples of zeolite structures include A-type zeolite structure, X-type zeolite structure, Y-type zeolite structure, L-type zeolite structure, β-type zeolite structure, mordenite structure, ferrierite structure, USY zeolite structure, CHA-type zeolite structure, SAPO-type zeolite structure, and ZSM-5 structure (MFI), etc. The zeolite may contain any zeolite structure other than the above structures.

[0029] The water (HO) in general formula (1) is contained in zeolite as water of crystallization. This water is contained, for example, in the pores. When zeolite is heated, not only the water of crystallization but also gas components such as oxygen that were adsorbed before heating can be desorbed from the zeolite. This improves the gas adsorption ability of the zeolite. Note that when the water of crystallization is completely desorbed, n in general formula (1) becomes 0.

[0030] The zeolite obtained in the heating step preferably has desorbed oxygen and has adsorbed at least one component selected from nitrogen, methane, moisture, etc. (hereinafter, sometimes referred to as the adsorbed component). That is, the adsorption capacity of the zeolite obtained in the heating step is preferably saturated with the adsorbed component. In this case, the adsorbed component is desorbed from the zeolite during heating in the evacuation step, etc., thereby restoring the gas adsorption ability of the zeolite. Note that when the zeolite after the heating step is mixed with water, even if nitrogen or methane is adsorbed on the zeolite, it is believed that a portion of it is replaced with moisture.

[0031] The zeolite preferably contains copper ion-exchanged zeolite. This copper ion-exchanged zeolite is a component in which Me in general formula (1) is a copper ion. Here, copper ion-exchanged zeolite is a component in which copper ions are retained in the zeolite structure. Therefore, the term "copper ion-exchanged zeolite" does not limit the component before copper ions are retained in the zeolite structure. Furthermore, the zeolite preferably has a ZSM-5 crystal structure. Copper ion-exchanged ZSM-5 zeolite (Cu-ZSM-5) can strongly adsorb nitrogen, methane, and the like even at room temperature under low pressure. The silica / alumina molar ratio of ZSM-5 is preferably 100 or less, more preferably 20 to 45, but is not particularly limited thereto. The copper content is preferably 1 to 10 wt %, but is not limited thereto. The zeolite crystals contained in the gas adsorbent 60 according to the present disclosure satisfy certain conditions, which will be described in detail later.

[0032] The getter material preparation process is a process for obtaining a getter material using zeolite after the heating process or unheated. For example, the getter material preparation process includes a process for mixing particles (crystals) made of zeolite with particles made of a compound other than zeolite to obtain a composite getter material. The getter material preparation process also includes a process for preparing a plurality of particles having a predetermined particle size distribution (particles made of zeolite and particles made of a different type of zeolite or particles made of a compound other than zeolite). The getter material may contain a plurality of types of zeolite with different compositions, crystal structures, particle size distributions, etc., or may contain particles other than zeolite. After the getter material preparation process, a mixing process is performed.

[0033] The mixing step is a step of mixing a getter material with a solvent to obtain a getter material composition. The getter material contains a plurality of particles made of zeolite crystals as described above. The getter material may also contain particles made of compounds other than zeolite. The solvent may be water, an organic solvent, or a mixture of water and an organic solvent.

[0034] When water is used as the solvent, the water is present in the getter material composition so as to cover the getter material. This makes it difficult for the getter material to come into contact with air while in the getter material composition state. In other words, the getter material is less likely to adsorb air (particularly oxygen in the air). This makes it easier to store the getter material composition, reducing the complexity involved in manufacturing the glass panel unit 10. The water content in the getter material composition can be selected as desired. Water can be used as the solvent. Alternatively, a solution containing water as the main component can be used as the solvent. For example, the solvent may be water mixed with organic impurities or components such as calcium and sodium.

[0035] The solvent may also be a mixture of water and an organic solvent. In this case, the solvent may be a mixed solvent of water and 50% by mass or less of an organic solvent such as ethanol. The organic solvent may also be an organic solvent such as ethanol, butyl carbitol acetate, or terpineol, or a mixture thereof. When using water as a solvent, it is desirable to use pure water, ultrapure water, ion-exchanged water, distilled water, etc., whenever possible.

[0036] When an organic solvent is used as the solvent, the molecular size of the organic solvent is preferably equal to or larger than the pore size of the zeolite (especially ZSM-5 type). For example, when the pore size of the zeolite is 5.5 Å, the molecular size (maximum width of the molecule) of the organic solvent is preferably 5.5 Å or larger.

[0037] When the molecular size of the organic solvent is comparable to the pore size of the zeolite, fewer solvent molecules will enter the zeolite pores. This means that the diffusion rate of the organic solvent molecules into the zeolite is slow, and fewer organic solvent molecules will diffuse into the interior of the zeolite crystals. Therefore, the organic solvent molecules remain near the surface of the zeolite particles, and it does not require much energy to desorb the organic solvent molecules.

[0038] Furthermore, if the molecular size of the organic solvent is larger than the pore size of the zeolite, many of the organic solvent molecules cannot enter the pores of the zeolite, so the organic solvent molecules remain on the surface of the zeolite particles, and no additional energy is required to desorb the organic solvent molecules.

[0039] Therefore, when the molecular size of the organic solvent is equal to or larger than the pore size of the zeolite, the amount of organic solvent diffused inside the zeolite is small when removing the solvent from the getter material composition to form the gas adsorbent 60, so the solvent can be removed without requiring a large amount of energy. In addition, the organic solvent is less likely to remain inside the zeolite, making it easier to achieve the effects of increasing the particle size of the zeolite.

[0040] On the other hand, if the molecular size of the organic solvent is smaller than the pore size of the zeolite, the organic solvent molecules will diffuse inside the zeolite crystals, and a great deal of energy will be required to desorb the organic solvent molecules.

[0041] The organic solvent has a molecular size larger than the pore size (5.5 Å) of zeolite (ZSM-5), and examples of aromatic compounds include trimethylbenzene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, and m-xylene.

[0042] Examples of non-aromatic organic solvents having a molecular size larger than the pore size (5.5 Å) of zeolite (ZSM-5) include cyclic compounds containing a cyclic structure, such as cyclooctane, cycloheptane, dimethylquinoline, α-pinene, β-pinene, pinane, α-pinene oxide, pinocarveol, caryophyllene, verbenone, and isobornylcyclohexanol.

[0043] Examples of organic solvents with a molecular size similar to the pore size (5.5 Å) of zeolite (ZSM-5) include cyclic compounds containing a cyclic structure such as p-xylene, p-menthane, d-limonene, l-limonene, α-terpineol, β-terpineol, γ-terpineol, terpinene, menthol, myrtenal, myrtenol, p-menthene, benzyl benzoate, dihydroterpineol, and dihydroterpinyl acetate.

[0044] Thus, in the present disclosure, it is preferable to use a cyclic compound having a ring structure, including an aromatic compound or a non-aromatic compound, as the organic solvent. The molecules of organic solvents with a linear structure are not preferable because they easily enter the pores of zeolite even if they are large in molecular size. Furthermore, among cyclic compounds, aromatic compounds are often harmful to the human body, so it is desirable to avoid their use as much as possible, and it is preferable to use a non-aromatic compound as the organic solvent.

[0045] In addition, it is generally believed that organic solvents with highly polar molecules, such as those containing OH groups, tend to be less likely to desorb from zeolites due to their polarity. However, when copper ion-exchanged zeolite (Cu-ZSM-5) was mixed with various organic solvents and the desorption of solvent components upon heating was examined using GCMS, it was found that among organic solvents with molecular sizes similar to the pore diameter of zeolite (ZSM-5) (5.5 Å), organic solvents with low polarity, consisting only of carbon and hydrogen, such as p-xylene, p-menthene, and d-limonene, were less likely to desorb upon heating and tended to remain within Cu-ZSM-5. This is thought to be because, when zeolite and solvent are mixed, non-polar molecules diffuse into the zeolite over time during storage. However, relatively polar solvent molecules, such as those containing OH groups or elements such as O, F, and N, adsorb near the entrances of zeolite pores, blocking the pores and preventing the intrusion of other molecules, resulting in a lower diffusion rate of the solvent molecules. This effect is more pronounced as the zeolite crystal size increases. For example, a zeolite crystal size of 200 nm or more is advantageous, preferably 300 nm or more, more preferably 400 nm or more, even more preferably 500 nm or more, and even more preferably 600 nm or more. Furthermore, a zeolite crystal size of 750 nm or more, 1000 nm or more, 1500 nm or more, or 2000 nm or more is even more preferable.

[0046] In addition, organic solvents with molecular sizes larger than the pore diameter (5.5 Å) of zeolite (ZSM-5) and low polarity solvents composed only of carbon and hydrogen, such as α-pinene and β-pinene, did not show any tendency for the solvent to be difficult to desorb from Cu-ZSM-5. Therefore, it is more desirable to use organic solvents with molecular sizes larger than the pore diameter (5.5 Å) of zeolite (ZSM-5), or solvents with molecular sizes similar to the pore diameter (5.5 Å) of zeolite (ZSM-5) and containing OH groups or elements such as O, N, and F in their molecular structure. That is, the organic solvent to be mixed with Cu-ZSM-5 zeolite having a crystal size of 200 nm or more preferably contains at least one of cyclooctane, cycloheptane, dimethylquinoline, α-pinene, β-pinene, pinane, α-pinene oxide, pinocarveol, caryophyllene, verbenone, isobornylcyclohexanol, α-terpineol, β-terpineol, γ-terpineol, menthol, myrtenal, myrtenol, benzyl benzoate, dihydroterpineol, and dihydroterpineol acetate. Furthermore, this effect is particularly pronounced when the process temperature of the glass panel unit (double-glazed glass) is 350°C or below, at which point the solvent is less likely to desorb from the zeolite; in other words, it is more effective when one of the softening point, melting point, or adhesive temperature (the minimum temperature required to seal the glass panel unit with the sealing material) of the sealing material (of at least one of the first sealing material or the second sealing material) is 350°C or below, and is even more effective when one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 300°C or below.

[0047] Furthermore, the organic solvent to be mixed with Cu-ZSM-5 zeolite having a crystal size of 400 nm or more is more preferably one containing at least one of cyclooctane, cycloheptane, dimethylquinoline, α-pinene, β-pinene, pinane, α-pinene oxide, pinocarveol, caryophyllene, verbenone, isobornylcyclohexanol, α-terpineol, β-terpineol, γ-terpineol, menthol, myrtenal, myrtenol, benzyl benzoate, dihydroterpineol, and dihydroterpineol acetate. Furthermore, this effect is particularly pronounced when the process temperature of the glass panel unit (double glazing) is 350°C or below, at which point the solvent is less likely to desorb from the zeolite; in other words, it is more effective when any one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 350°C or below, and even more effective when any one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 300°C or below.

[0048] Alternatively, it is more desirable that the organic solvent to be mixed with Cu-ZSM-5 zeolite having a crystal size of 600 nm or more contains at least one of cyclooctane, cycloheptane, dimethylquinoline, α-pinene, β-pinene, pinane, α-pinene oxide, pinocarveol, caryophyllene, verbenone, isobornylcyclohexanol, α-terpineol, β-terpineol, γ-terpineol, menthol, myrtenal, myrtenol, benzyl benzoate, dihydroterpineol, and dihydroterpineol acetate. Furthermore, this effect is particularly pronounced when the process temperature of the glass panel unit is 350°C or below, at which point the solvent is less likely to desorb from the zeolite; in other words, this effect is more effective when any one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 350°C or below, and is even more effective when any one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 300°C or below.

[0049] Furthermore, it is more desirable that the organic solvent to be mixed with Cu-ZSM5 zeolite having a crystal size of 750 nm or more contains at least one of cyclooctane, cycloheptane, dimethylquinoline, α-pinene, β-pinene, pinane, α-pinene oxide, pinocarveol, caryophyllene, verbenone, isobornylcyclohexanol, α-terpineol, β-terpineol, γ-terpineol, menthol, myrtenal, myrtenol, benzyl benzoate, dihydroterpineol, and dihydroterpineol acetate. Furthermore, this effect is particularly pronounced when the process temperature of the glass panel unit is 350°C or below, at which point the solvent is less likely to desorb from the zeolite, and is more effective when any one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 350°C or below, and is even more effective when any one of the softening point, melting point, or adhesive temperature of the sealing material (of at least one of the first sealing material or the second sealing material) is 300°C or below.

[0050] The solvent of the getter material composition preferably contains an organic solvent having a boiling point of 300° C. or less. This makes it easier to remove the organic solvent from the getter material composition even at low temperatures, and makes it easier to form the gas adsorbent 60.

[0051] Thus, at least one of the softening point, melting point, and adhesive temperature of the sealing material is 300°C or lower, and the zeolite crystal size is advantageously 200 nm or larger, preferably 300 nm or larger, more preferably 400 nm or larger, even more preferably 500 nm or larger, and even more preferably 600 nm or larger. Furthermore, the zeolite crystal size is preferably 750 nm or larger, 1000 nm or larger, 1500 nm or larger, or 2000 nm or larger.

[0052] The getter material may contain multiple particles of a carbon dioxide adsorbent in addition to multiple particles of zeolite crystals. In this case, a composite getter material with high carbon dioxide adsorption performance is obtained. Examples of particles of a carbon dioxide adsorbent include particles of alumina such as γ-Al2O3, zinc oxide, silica, titania, platinum group metals such as platinum, lithium silicate, activated carbon, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, sodium hydroxide, yttrium oxide, metal complexes such as cobalt complexes, and cerium compounds such as cerium oxide and cerium hydroxide. Particles of these carbon dioxide adsorbents function as CO2 adsorbents. Therefore, CO2 released from organic solvents can be adsorbed by the carbon dioxide adsorbent, making it difficult for carbon dioxide to be adsorbed by the zeolite particles. This reduces the reduction in the function of the zeolite crystal particles due to carbon dioxide. In addition, similar effects can be expected from getter materials that are mixtures of Cu-ZSM-5 with particles of zeolite that has a higher carbon dioxide adsorption capacity than Cu-ZSM-5 and that has been ion-exchanged with a metal different from Cu-ZSM-5 (e.g., Ba, Sr, Pt, Pd, Ru, etc.), or particles of zeolite with a different crystal structure than Cu-ZSM-5, such as zeolite 13X or A-type zeolite.

[0053] The getter material preferably contains a hydrogenation catalyst. The hydrogenation catalyst is a catalyst for the hydrogenation reaction. The hydrogenation reaction is a reaction in which hydrogen atoms are added to multiple bond sites, such as carbon-carbon bonds, of compounds (e.g., hydrocarbons) such as organic solvents using hydrogen gas as a reducing agent. Such reactions are likely to occur when the compound comes into contact with a metal catalyst.

[0054] In this embodiment, the hydrogenation catalyst can be a commonly known metal, such as a platinum group metal (e.g., ruthenium, rhodium, platinum, or palladium), or a metal such as nickel, cobalt, molybdenum, tungsten, iron, copper, titanium, zirconium, or aluminum, or a compound such as an oxide of any of these metals. The inclusion of these metals in the getter material can promote the volatilization of organic solvents, facilitating their removal during the sealing process, or decompose hydrocarbons into H2, CO2, HO, or other highly reactive hydrocarbons. The resulting molecules can then be volatilized and removed, or adsorbed and removed by the getter material. Mixing the getter material with an organic solvent can be particularly effective in facilitating the removal of unwanted hydrocarbons. Furthermore, the hydrogenation catalyst can be supported on or added to another substance, or a metal powder of a platinum group metal, such as platinum black or palladium black, can be mixed as a porous metal or a powder of a size of less than a single micron.

[0055] The carrier on which the hydrogenation catalyst is supported is preferably a porous body. The specific surface area of ​​the porous body is 20 m 2 / g or more, and more preferably 50m 2 / g or more is more preferable. It may also be supported on the aforementioned carbon dioxide adsorbent. However, when copper ion-exchanged zeolite is used as the zeolite, copper ion-exchanged zeolite is activated by copper reduction in a vacuum and exhibits strong adsorption power, so it is more preferable to use a carbon dioxide adsorbent other than cerium oxide. While cerium oxide can be used to achieve high efficiency, mixing copper ion-exchanged zeolite with a substance that has oxygen storage properties, such as cerium oxide or a ceria-zirconia solid solution, can inhibit the activation of the copper ion-exchanged zeolite and cause performance degradation. Furthermore, cerium can react with the silica portion of the zeolite, degrading the copper ion-exchanged zeolite. Furthermore, it is desirable to minimize the amount of cerium used, a rare earth metal, from the perspective of cost and production stability. For this reason, the support for the hydrogenation catalyst is preferably at least one selected from the group consisting of alumina, silica, activated carbon, barium sulfate, etc., and more preferably an Al compound such as alumina or a Si compound such as silica, which has the same metal component as zeolite. The average particle size of the support for the hydrogenation catalyst is preferably 1 nm or more and 50 μm or less. The average particle size of the support for the hydrogenation catalyst can be confirmed by SEM observation. From the viewpoint of utilization efficiency of the hydrogenation catalyst, it is preferable that the mass ratio of the hydrogenation catalyst to the support be 0.01 wt % or more and 30 wt % or less.

[0056] The support for the hydrogenation catalyst can be at least one porous material selected from the group consisting of alumina, silica, activated carbon, barium sulfate, calcium carbonate, silicon carbide, titanium oxide, and zirconium oxide. Among these, porous alumina is particularly desirable because it has the ability to adsorb carbon dioxide. If the hydrogenation catalyst is supported on cerium oxide or cerium oxide is mixed into the getter material as a carbon dioxide adsorbent, the content of cerium oxide is preferably 30 wt% or less of the total getter material. It is more desirable to have a content of 15 wt% or less, even more desirable to have a content of 5 wt% or less, and even more desirable to have a content of 1 wt% or less.

[0057] Examples of combinations of hydrogenation catalysts and supports include the following. The following examples are shown in the format of A / B: hydrogenation catalyst / support: Ru / Al2O3, Rh / Al2O3, Pt / Al2O3, Pd / Al2O3, Ir / Al2O3, Os / Al2O3, Au / Al2O3, Ni / Al2O3, Co / Al2O3, Mo / Al2O3, W / Al2O3, Fe / Al2O3, Cu / Al2O3, Ti / Al2O3, Zr / Al2O3, Al / Al2O3, Ru / SiO2, Rh / SiO2, Pt / SiO2, Pd / SiO2, Ir / SiO2, Os / SiO2, Preferred combinations of hydrogenation catalyst and support include Au / SiO2, Ni / SiO2, Co / SiO2, Mo / SiO2, W / SiO2, Fe / SiO2, Cu / SiO2, Ti / SiO2, Zr / SiO2, Al / SiO2, Ru / C, Rh / C, Pt / C, Pd / C, Ir / C, Os / C, Au / C, Ni / C, Co / C, Mo / C, W / C, Fe / C, Cu / C, Ti / C, Zr / C, and Al / C (C stands for activated carbon).

[0058] Furthermore, among these, combinations of hydrogenation catalysts and supports such as Ru / Al2O3, Rh / Al2O3, Pt / Al2O3, Pd / Al2O3, Au / Al2O3, Ru / SiO2, Rh / SiO2, Pt / SiO2, Pd / SiO2, and Au / SiO2, in which a substance containing platinum group metals, gold, or a compound thereof is supported on porous ceramics such as alumina or silica, have high oxidation / reduction stability and exhibit particularly excellent properties when combined with copper ion-exchanged zeolite.

[0059] On the other hand, catalysts such as silver and silver oxide, which oxidize in air at temperatures below 350°C and release large amounts of oxygen when reduced in a vacuum at temperatures below 350°C, inhibit the activation of copper ion-exchanged zeolite, so it is desirable to avoid mixing substances with such properties with copper ion-exchanged zeolite as much as possible. For example, the content of substances with such properties is desirably at least less than 5 wt % of the total getter material, more desirably 1 wt % or less, and even more desirably 0.1 wt % or less.

[0060] The hydrogenation catalyst supported on the carrier is preferably a powder having a particle size smaller than that of the zeolite particles and the carbon dioxide adsorbent particles. Examples of hydrogenation catalyst powders include 5 wt% ruthenium-alumina powder (product code: JAN4987481323469), 5 wt% platinum-alumina powder (product code: JAN4987481317161), and 5 wt% palladium-alumina powder (product code: JAN4987481317109) manufactured by Wako Pure Chemical Industries, and 5 wt% Pd-alumina powder (ID Code: AA-2501), 5 wt% Pd-barium sulfate (ID Code: OP-2505), Pd black (BL-2901), 5 wt% Pt-alumina powder (ID Code: AA-1501), Pt black (ID Code: BL-1901), and 5 wt% Ru-alumina powder (ID Code: AA-4501) manufactured by N·E·Chemcat.

[0061] A specific example is shown below. A getter composition was created by mixing 10 wt% hydrogenation catalyst powder and 90 wt% Cu-ZSM5 powder with a crystal size of 400 nm, and using α-terpineol as a solvent. A glass panel unit was prototyped using this, and the thermal conductance of Cu-ZSM-5 alone was found to be 12 W / m 2 K, whereas the thermal conductance of a getter material composition made by mixing 10 wt% ruthenium 5 wt%-alumina powder with 90 wt% Cu-ZSM-5 powder with a crystal size of 400 nm and using α-terpineol as a solvent was 0.87 W / m 2 It was K.

[0062] In addition, in the case of a getter material composition in which 5 wt% platinum-alumina powder is mixed with 10 wt% Cu-ZSM-5 powder with a crystal size of 400 nm and 90 wt% Cu-ZSM-5 powder is mixed, and α-terpineol is used as a solvent, the thermal conductance is 0.78 W / m 2 K. In addition, the thermal conductance of the getter material composition, which was made by mixing 10 wt% palladium 5 wt%-alumina powder with 90 wt% Cu-ZSM-5 powder with a crystal size of 400 nm and using α-terpineol as a solvent, was 0.76 W / m 2In addition, the thermal conductance of a glass panel using a getter material made of a mixture of 10 wt% alumina without a hydrogenation catalyst and 90 wt% Cu-ZSM-5 powder with a crystal size of 400 nm was 2 W / m 2 When the residual gas in the glass panel using a getter material mixed with alumina that does not contain a hydrogenation catalyst was analyzed, a large amount of hydrocarbon gas was detected.

[0063] Furthermore, the thermal conductance of a glass panel using a getter material made of a mixture of 10 wt% cerium oxide without a hydrogenation catalyst and 90 wt% Cu-ZSM-5 powder with a crystal size of 400 nm was 2.6 W / m 2 In addition, when a similar experiment was carried out using a mixture of 50 wt% α-terpineol (boiling point 219°C) and 50 wt% high boiling point solvent (β-caryophyllene) (boiling point 260°C) as the solvent, the thermal conductance was 2.3 W / m when ruthenium 5 wt%-alumina powder was used. 2 When using K, platinum 5wt%-alumina powder, the thermal conductance is 0.78W / m 2 K, and when palladium 5 wt%-alumina powder is used, the thermal conductance is 0.76 W / m 2 K, and when alumina powder without hydrogenation catalyst was used, the thermal conductance was 8.3 W / m 2 K, and when the solvent contained a high-boiling point solvent with a boiling point of 250°C or higher, a greater difference was observed depending on whether or not the hydrogenation catalyst was present.

[0064] Furthermore, when platinum group metals such as ruthenium, palladium, or platinum are used as hydrogenation catalysts, relatively good thermal conductance is maintained even when high-boiling solvents with boiling points above 250°C are used. In particular, for palladium and platinum, the thermal conductance remains almost unchanged regardless of the presence or absence of high-boiling solvents with boiling points above 250°C. Therefore, hydrogenation catalysts such as platinum group metals are considered to be particularly advantageous when the solvent contains high-boiling solvents with boiling points above 250°C or components that are difficult to volatilize, such as resin components. Furthermore, palladium or platinum is considered to be even more advantageous when the solvent is mixed with high-boiling solvents with boiling points above 250°C or resin components. On the other hand, for getter materials that do not contain platinum group metals, it is preferable that the solvent mixed with the getter material be primarily composed of solvents with boiling points below 250°C (greater than 50 wt%).

[0065] These thermal conductance values ​​were compared assuming the total amount of each getter powder was constant. Therefore, carbon dioxide adsorbents such as alumina, especially when mixed with an organic solvent, are effective in keeping the internal pressure of the glass panel low by adsorbing the carbon dioxide released by the decomposition of the organic solvent. Furthermore, hydrogenation catalysts can promote the volatilization of the organic solvent, making it easier to remove during the sealing process, and can decompose the hydrocarbon gases gasified by the organic solvent and adsorb them onto zeolite, the carbon dioxide adsorbent, or the hydrogenation catalyst itself, thereby suppressing an increase in the internal pressure of the glass panel.

[0066] Furthermore, the effect of the hydrogenation catalyst is more likely to be greater when a high-boiling solvent or resin component is used than when a low-boiling solvent is used. Organic solvents with a cyclic structure tend to have a high boiling point due to their relatively large molecular weight. Therefore, by mixing an organic solvent with a cyclic structure, zeolite, and a hydrogenation catalyst to form a getter material composition, damage to the zeolite caused by the organic solvent can be suppressed while the organic solvent can be appropriately removed after application. This tendency is more pronounced when the zeolite crystal size is 200 nm or more, preferably 300 nm or more, more preferably 400 nm or more, more preferably 500 nm or more, and particularly preferably 600 nm or more.

[0067] Furthermore, the crystal size (diameter) of the zeolite is more preferably 750 nm or more, even more preferably 1000 nm or more, and even better still, 1500 nm or more, 2000 nm or more. High-boiling-point solvents and resins with boiling points of 250°C or more generally have high viscosity, and mixing these can more effectively suppress sedimentation of the getter material composition and improve coating stability. Examples of high-boiling-point solvents include β-caryophyllene, benzyl benzoate, and isobornylcyclohexanol. Examples of resin components include polycarbonate, acrylic resin, polyester, polyurethane, and phenolic resin. Solvents and resin binders commonly used in screen printing, etc., can be used, and at least one of these can be used.

[0068] In this way, by combining zeolite, a carbon dioxide adsorbent, and a hydrogenation catalyst, performance degradation is suppressed even when mixed with an organic solvent, and a high-performance getter composition and getter material can be obtained. On the other hand, since carbon dioxide adsorbents and hydrogenation catalysts are not suitable for nitrogen adsorption, copper ion-exchanged zeolites are particularly preferred, and ZSM-5 type zeolites are even more preferred. However, certain effects can be achieved with combinations containing only zeolite and a carbon dioxide adsorbent, or zeolite and a hydrogenation catalyst. Furthermore, combining zeolite, a carbon dioxide adsorbent, and a hydrogenation catalyst is also effective for adsorbing hydrocarbon gases and carbon dioxide released from sealing materials, glass substrates, pillars, etc.

[0069] In this embodiment, the getter material may be composed of zeolite particles alone, in which case 100% by weight of the particles constituting the getter material are zeolite particles.

[0070] In this embodiment, the getter material may be a mixture of zeolite particles and carbon dioxide adsorbent particles. In this case, the getter material preferably contains zeolite particles in a weight ratio of 1 to 0.01 to 0.99.

[0071] In this embodiment, the getter material may be a mixture of zeolite particles and hydrogenation catalyst powder. In this case, the getter material preferably contains zeolite particles in a weight ratio of 1 to 0.0001 to 0.3.

[0072] In this embodiment, the getter material may be a mixture of zeolite particles, carbon dioxide adsorbent particles, and hydrogenation catalyst powder. In this case, the getter material preferably contains zeolite particles in a weight ratio of 1:0.01 to 0.99, carbon dioxide adsorbent particles in a weight ratio of 0.0001 to 0.3, and hydrogenation catalyst powder in a weight ratio of 0.0001 to 0.3.

[0073] In this embodiment, the getter material composition preferably contains a getter material and a solvent in a predetermined ratio. For example, the getter material composition preferably contains 1 part getter material to 0.1 to 100 parts solvent by weight.

[0074] In this embodiment, the getter material composition preferably contains a getter material, a solvent, and a resin component in a predetermined ratio. For example, the getter material composition preferably contains 1 part getter material, 0.1 to 100 parts solvent, and 0.01 to 2 parts resin component by weight.

[0075] In this embodiment, the getter material composition preferably contains a getter material, a solvent having a boiling point of less than 250° C., and a high-boiling solvent having a boiling point of 250° C. or more in a predetermined ratio. For example, the getter material composition preferably contains, by weight ratio, 0.1 to 100 of the solvent having a boiling point of less than 250° C. and 0.01 to 2 of the high-boiling solvent having a boiling point of 250° C. or more to 1 part of the getter material.

[0076] Here, the effects of the hydrogenation catalyst on the getter material and getter material composition will be summarized again.

[0077] In order to form a getter material in a thin gap of a decompressed glass panel unit (double glazing), it is desirable to mix the getter material with a solvent and apply it to a glass substrate. The application method at this time is not particularly limited, and may be dispensing, screen printing, slit coating, spray coating, spin coating, or the like.

[0078] The advantages of mixing powdered getter material with a solvent and applying it include: (1) the ability to form a thin film (for example, one that is thinner than the thickness of the sealing material); (2) the powdered getter material aggregates after drying, reducing its apparent volume compared to when the powdered getter material is applied directly to the glass substrate; (3) the ability to accommodate any glass substrate shape during mass production; and (4) the getter material is electrostatically adsorbed to the substrate after drying, eliminating the need for any fixing members for the getter material.

[0079] On the other hand, there are some issues: (1) if a solvent with a low boiling point is used, the solvent will dry out during storage of the getter material composition or during the application process, causing poor application; (2) if a solvent with a certain degree of viscosity is not used, the getter material powder will settle and application stability will not be maintained; (3) solvents with high viscosity generally also have high boiling points, and when mixed with a getter material that has the property of adsorbing gases, the getter material will adsorb the solvent molecules, requiring a great deal of energy to desorb them; and (4) if the solvent is not sufficiently desorbed after application, the adsorption performance of the getter material will deteriorate (and in some cases the solvent molecules will be released as gas from the getter material, which may actually increase the amount of residual gas in the glass panel unit).

[0080] Specifically, using a high-boiling-point solvent for stable application makes it difficult to fully remove the solvent, resulting in a decrease in the adsorption performance of the getter material. In particular, the lower the process temperature of the glass panel unit, the more likely it is that the solvent cannot be fully removed after application of the getter material composition, leading to performance degradation. Furthermore, even if a certain organic solvent is heated to its boiling point, the solvent does not actually volatilize completely. In particular, when mixed with Cu-ZSM5, the solvent molecules do not completely volatilize unless the solvent is heated at a temperature 100–150°C higher than the boiling point. Because few organic solvents can be completely volatilized at temperatures below 350°C, this problem is particularly likely to occur when the process temperature is below 350°C or when the softening or melting point of the sealing material (at least one of the first and second sealing materials) is below 350°C.

[0081] The applied getter material composition undergoes the following steps: (A) it is heated in the subsequent drying and sealing steps (e.g., the first melting step) to remove the organic solvent, (B) the getter material is heated in a vacuum to be activated, and (C) after the assembly 100 is isolated from the vacuum pump, when gases such as carbon dioxide (most abundant), nitrogen, and methane are released from inside the assembly 100, the gases are adsorbed by the getter material (e.g., after the second melting step). By mixing the copper ion-exchanged zeolite with a hydrogenation catalyst, its effects can be exerted in both steps (A) and (C).

[0082] First, in step (A), the hydrogenation catalyst promotes the decomposition and reaction of the organic solvent, volatilizing it and preventing it from remaining in the copper ion-exchanged zeolite, which would cause performance degradation. Furthermore, in step (C), the hydrogenation catalyst (especially platinum group catalysts) also function as a strong carbon dioxide adsorbent or hydrocarbon gas adsorbent with chemical adsorption properties. This prevents the adsorption sites of the copper ion-exchanged zeolite, which can also adsorb nitrogen and methane, from becoming filled with carbon dioxide. Therefore, compared to getter materials consisting solely of copper ion-exchanged zeolite or hydrogenation catalyst, getter materials consisting solely of copper ion-exchanged zeolite adsorb more carbon dioxide, as well as nitrogen and methane. As a result, the residual gas pressure in the glass panel unit can be kept low.

[0083] This effect is particularly pronounced when the process temperature is 350°C or lower, under conditions where the organic solvent is difficult to desorb and the copper ion-exchanged zeolite is difficult to activate sufficiently. That is, this effect is particularly pronounced when the softening point or melting point of the sealing material (at least one of the first and second sealing materials) is 350°C or lower. Furthermore, when combined with Cu-ZSM-5, it is desirable for the organic solvent to contain a cyclic compound, but cyclic compounds generally have high boiling points. By combining Cu-ZSM5 with a solvent containing an organic solvent and a hydrogenation catalyst, a getter material composition that combines adsorption performance and coating stability can be realized.

[0084] Combining Cu-ZSM-5 with an organic solvent and a hydrogenation catalyst allows for the realization of a getter material composition that combines both adsorption performance and coating stability. Furthermore, when combined with Cu-ZSM-5, it is desirable for the organic solvent to have a cyclic compound, but cyclic compounds generally have high boiling points. Using a cyclic compound as the organic solvent reduces the penetration of the organic solvent into the Cu-ZSM-5, facilitating the reaction between the hydrogenation catalyst and the organic solvent, thereby enhancing the effectiveness of the hydrogenation catalyst. Furthermore, by maintaining the crystal size of Cu-ZSM-5 at 400 nm or more, more preferably 600 nm or more, and even more preferably 750 nm or more, degradation by the organic solvent can be further suppressed, resulting in a getter material composition with higher adsorption performance in the low-pressure range. Furthermore, mixing this with a hydrogenation catalyst and an organic solvent containing a cyclic compound reduces the proportion of organic solvent inside the Cu-ZSM-5 crystal, promoting the reaction with the hydrogenation catalyst and facilitating solvent desorption, resulting in greater effectiveness.

[0085] Examples of getter materials include 51 wt% to 99 wt% copper ion-exchanged zeolite with a crystal size of 400 nm to 5000 nm and 1 wt% to 49 wt% porous powder carrying a hydrogenation catalyst (the weight ratio of the hydrogenation catalyst to the total porous powder is 0.1 wt% to 20 wt%). Even better, the getter material may be 51 wt% to 99 wt% Cu-ZSM-5 with a crystal size of 400 nm to 5000 nm and 1 wt% to 49 wt% porous powder carrying a hydrogenation catalyst (the weight ratio of the hydrogenation catalyst to the total porous powder is 0.1 wt% to 20 wt%). Alternatively, the getter material may be 51 wt% to 99 wt% copper ion-exchanged zeolite with a crystal size of 400 nm to 5000 nm and 1 wt% to 49 wt% hydrogenation catalyst powder.

[0086] An example of a getter material composition could be 20 wt% to 60 wt% copper ion-exchanged zeolite with a crystal size of 400 nm to 5000 nm, 0.5 wt% to 40 wt% porous powder carrying a hydrogenation catalyst (the weight ratio of the hydrogenation catalyst to the entire porous powder is 0.1 wt% to 20 wt%), and 30 wt% to 95 wt% organic solvent. Alternatively, a more desirable composition would be 20 wt% to 60 wt% Cu-ZSM-5 with a crystal size of 400 nm to 5000 nm, 0.5 wt% to 40 wt% porous powder carrying a hydrogenation catalyst (the weight ratio of the hydrogenation catalyst to the entire porous powder is 0.1 wt% to 20 wt%), and 30 wt% to 95 wt% organic solvent whose main component is a cyclic compound (in this case, at least 50 wt% of the organic solvent is a cyclic compound). The content may be 20 wt % to 60 wt % of copper ion-exchanged zeolite with a crystal size of 400 nm to 5000 nm, 0.1 wt % to 40 wt % of hydrogenation catalyst powder, and 30 wt % to 95 wt % of organic solvent.

[0087] After the mixing step, the assembly step is carried out.

[0088] The assembly process is a process for preparing the assembly 100.

[0089] 1A and 1B, the assembly 100 includes a first glass plate 200, a second glass plate 300, a peripheral wall 410, and a partition 420. The assembly 100 also has an internal space 500 surrounded by the first and second glass plates 200, 300 and the peripheral wall 410. The assembly 100 also includes a gas adsorbent 60 and a plurality of pillars (spacers) 70 within the internal space 500. The assembly 100 also includes an exhaust port 700.

[0090] The first glass plate (first glass substrate) 200 is a base member for the first glass plate 20 described below, and is made of the same material as the first glass plate 20. The second glass plate (second glass substrate) 300 is a base member for the second glass plate 30 described below, and is made of the same material as the second glass plate 30. The first and second glass plates 200, 300 have the same planar shape. In this embodiment, the first glass plate 200 has a size that allows at least one first glass plate 20 described below to be formed, and the second glass plate 300 has a size that allows at least one second glass plate 30 described below to be formed.

[0091] The first and second glass plates 200, 300 are both polygonal (rectangular in this embodiment) flat plates.

[0092] The first glass plate 200 includes a body 210 and a low-emissivity coating 220 .

[0093] The low-emissivity film 220 is located within the interior space 500 and covers the main body 210. The low-emissivity film 220 is in contact with the main body 210. The low-emissivity film 220 is also called an infrared reflective film, and although it is translucent, it reflects infrared rays. Therefore, the low-emissivity film 220 can improve the thermal insulation of the glass panel unit 10. The low-emissivity film 220 is, for example, a thin metal film. The low-emissivity film 220 contains, for example, silver. One example of the low-emissivity film 220 is a Low-E film.

[0094] As described above, the first glass plate 200 includes the main body 210. The main body 210 has a first surface 211 and a second surface 212. The first surface 211 is a flat surface and is covered with a low-emissivity film 220. The second surface 212 is a flat surface parallel to the first surface 211 and is located on the opposite side of the internal space 500 in the direction D1. The main body 210 is a rectangular flat plate, which constitutes the main shape of the first glass plate 200. The main body 210 may be made of, for example, soda-lime glass, high-strain-point glass, chemically strengthened glass, alkali-free glass, quartz glass, Neoceram, or physically strengthened glass. The thickness of the first glass plate 200 may be 0.1 mm to 20 mm.

[0095] The second glass plate 300 includes a main body 310. The main body 310 has a first surface 311 and a second surface 312. The first surface 311 is a flat surface facing the low-emissivity film 220. The second surface 312 is a flat surface parallel to the first surface 311 and located on the opposite side of the interior space 500 in direction D1. The main body 310 is a rectangular flat plate, constituting the main shape of the second glass plate 300. The main body 310 has the same shape as the main body 210. In this embodiment, the second glass plate 300 is composed only of the main body 310; however, the second glass plate 300 may also include a low-emissivity film similar to the low-emissivity film 220 in addition to the main body 310. If the second glass plate 300 includes a low-emissivity film, the low-emissivity film covers the main body 310 and contacts the main body 310 within the interior space 500. The material of the main body 310 is, for example, soda lime glass, high strain point glass, chemically strengthened glass, alkali-free glass, quartz glass, neoceram, or physically strengthened glass. The thickness of the second glass plate 300 may be 0.1 mm to 20 mm.

[0096] The peripheral wall 410 includes a first sealing material (first thermal adhesive). The peripheral wall 410 is disposed between the first glass plate 200 and the second glass plate 300. As shown in FIG. 1A , the peripheral wall 410 is frame-shaped. In particular, the peripheral wall 410 is rectangular frame-shaped. The peripheral wall 410 is formed along the outer peripheries of the first and second glass plates 200, 300. As a result, in the assembly 100, an internal space 500 is formed that is surrounded by the peripheral wall 410, the first glass plate 200, and the second glass plate 300.

[0097] The first thermal adhesive includes, for example, glass frit. Examples of glass frit include low-melting-point glass frit. Examples of low-melting-point glass frit include bismuth-based glass frit, lead-based glass frit, and vanadium-based glass frit. In this embodiment, the first thermal adhesive is made of vanadium-based glass frit. The first thermal adhesive is not limited to glass frit and may include, for example, a low-melting-point metal or a hot-melt adhesive. The first thermal adhesive may further include one or both of an organic binder and an organic solvent. In this case, even if gas derived from one or both of the organic binder and the organic solvent is released into the reduced pressure space 50 after the sealing step (second melting step), the gas is adsorbed by the gas adsorbent 60, making it less likely for the gas to remain in the reduced pressure space 50.

[0098] The organic binder includes, for example, a resin. Examples of this resin include polyisobutyl methacrylate, ethyl cellulose, aliphatic polycarbonate, acrylic resin, and butyral resin. The organic binder is not limited to the above resins and may include any other component. The resin constituting the organic binder is preferably a low-molecular-weight resin that is easily decomposed.

[0099] Examples of the organic solvent include esters such as butyl carbitol acetate and ethyl carbitol acetate. However, the organic solvent is not limited to the above components and may include at least one of solvents used in general screen printing, such as terpene-based solvents, and solvents used in dispense coating.

[0100] When peripheral wall 410 further contains a resin, even if gas derived from this resin is released into internal space 500 after the assembly step, the gas derived from the resin is exhausted by the exhaust step. Even if gas derived from the resin remains in reduced pressure space 50 after the exhaust step, gas adsorbent 60 can adsorb this residual gas.

[0101] The partition 420 is disposed within the internal space 500. The partition 420 divides the internal space 500 into a first space 510 and a second space (ventilation space) 520. Therefore, the first space 510 is a space that is evacuated during the evacuation process, and the second space 520 is a space that is used to evacuate the first space 510. The partition 420 is formed closer to a first end (right end in FIG. 1A ) in the length direction (left-right direction in FIG. 1A ) of the second glass plate 300 than the center of the second glass plate 300 so that the first space 510 is larger than the second space 520. The partition 420 is disposed within the internal space 500 along the width direction (up-down direction in FIG. 1A ) of the second glass plate 300. However, both ends of the partition 420 in the length direction do not contact the peripheral wall 410. In this embodiment, the width direction of the second glass plate 300 is parallel to the direction D2, and the length direction of the second glass plate 300 is parallel to the direction D3.

[0102] The partition 420 includes a main body portion (partition main body portion) 421 that constitutes its main body, and a blocking portion 422. The blocking portion 422 includes a first blocking portion 4221 and a second blocking portion 4222. The main body portion 421 is linear and extends along direction D2. This direction D2 is, for example, the width direction of the second glass plate 300. In addition, in direction D2, both ends of the main body portion 421 do not contact the peripheral wall 410. Of both ends of the main body portion 421, the first blocking portion 4221 is formed so as to extend from one end toward the second space 520, and the second blocking portion 4222 is formed so as to extend from the other end toward the second space 520. One end of the main body portion 421 may be a first end, and the other end may be a second end.

[0103] The partition 420 includes a second sealing material (second thermal adhesive). The second thermal adhesive is, for example, glass frit. An example of the glass frit is low-melting point glass frit. Examples of the low-melting point glass frit are bismuth-based glass frit, lead-based glass frit, and vanadium-based glass frit. In this embodiment, the second thermal adhesive is made of vanadium-based glass frit. Furthermore, the second thermal adhesive is not limited to glass frit, and may be, for example, a low-melting point metal or a hot-melt adhesive. In this embodiment, the first thermal adhesive and the second thermal adhesive are the same. In other words, the first sealing material and the second sealing material are made of the same material.

[0104] 1A, the air passage 600 connects the first space 510 and the second space 520 within the internal space 500. The air passage 600 includes a first air passage 610 and a second air passage 620. The first air passage 610 is a gap between the first end (upper end in FIG. 1A) of the partition 420 and the peripheral wall 410. The second air passage 620 is a gap between the second end (lower end in FIG. 1A) of the partition 420 and the peripheral wall 410.

[0105] The exhaust port 700 is a hole that connects the second space 520 with the external space. The exhaust port 700 is used to exhaust air from the first space 510 via the second space 520 and the ventilation path 600 (the first ventilation path 610 and the second ventilation path 620). Therefore, the ventilation path 600, the second space 520, and the exhaust port 700 form an exhaust path for exhausting air from the first space 510. The exhaust port 700 is formed in the second glass plate 300 so as to connect the second space 520 with the external space. Specifically, the exhaust port 700 is located at a corner of the second glass plate 300.

[0106] The gas adsorbent 60 and the plurality of spacers 70 are disposed in the first space 510. In particular, the gas adsorbent 60 is formed along the width direction of the second glass plate 300 at the second end side in the length direction of the second glass plate 300 (the left end side in FIG. 1A ). In other words, the gas adsorbent 60 is disposed at the end of the first space 510 (decompression space 50). In this manner, the gas adsorbent 60 can be made inconspicuous. Furthermore, the gas adsorbent 60 is located away from the partition 420 and the ventilation path 600. This reduces the possibility that the gas adsorbent 60 will interfere with evacuation when the first space 510 is evacuated.

[0107] The assembly process is a process for forming the first glass plate 200, the second glass plate 300, the peripheral wall 410, the partition 420, the internal space 500, the ventilation channel 600, the exhaust port 700, the gas adsorbent 60, and the plurality of spacers 70 to obtain the assembly 100. The assembly process includes steps 1 to 6. The order of steps 2 to 5 may be changed as appropriate.

[0108] The first step is a step (substrate formation step) of forming the first glass plate 200 and the second glass plate 300. For example, in the first step, the first glass plate 200 and the second glass plate 300 are produced, and the first glass plate 200 and the second glass plate 300 are cleaned as necessary.

[0109] The second step is a step of forming the exhaust port 700. In the second step, the exhaust port 700 is formed in the second glass plate 300. Also, in the second step, the second glass plate 300 is cleaned as necessary.

[0110] The third step is a step of forming spacers 70 (spacer formation step) (see FIG. 3). In the third step, a plurality of spacers 70 are formed in advance, and then the plurality of spacers 70 are placed at predetermined positions on the second glass plate 300 using a chip mounter or the like. The plurality of spacers 70 are used to maintain a predetermined distance between the first and second glass plates 200, 300 when the assembly 100 has become the work-in-progress 110. Examples of materials that can be used to form such spacers 70 include metal, glass, and resin. The spacers 70 can contain one or more of these materials.

[0111] In the third step of this embodiment, as described above, the spacers 70 are formed in advance and placed on the second glass plate 300. However, a plurality of spacers 70 may be formed on the second glass plate 300 using a well-known pattern forming technique. Furthermore, when the spacers 70 contain resin, the plurality of spacers 70 may be formed using a photolithography technique and an etching technique, which is a method different from the above-described formation method. In this case, the plurality of spacers 70 may be formed using a photocurable material or the like.

[0112] The size of the spacers 70, the number of spacers 70, the spacing between the spacers 70, and the arrangement pattern of the spacers 70 can be selected as appropriate. Each spacer 70 is cylindrical with a height approximately equal to the predetermined spacing. For example, the spacers 70 have a diameter of 0.5 mm, a height of 100 μm, and a distance between the spacers of 20 mm. Each spacer 70 may have a desired shape, such as a prism or a sphere. For example, the spacers 70 may have a diameter of 0.1 mm to 5 mm, a height of 10 μm to 3000 μm, and a distance between the spacers of 2 mm to 100 mm.

[0113] The fourth step is a step of forming the gas adsorbent 60 (gas adsorbent formation step) (see FIG. 3). In the fourth step, the getter material composition from the processing step is applied to the second glass plate 300 using a dispenser or the like. The applied getter material composition is then dried to form the gas adsorbent 60. That is, the fifth step includes a drying step of drying the getter material composition. Drying the getter material composition can restore the gas adsorption properties of the getter material. Furthermore, applying the getter material composition can make the gas adsorbent 60 smaller. Therefore, the gas adsorbent 60 can be placed even if the first space 510 is narrow.

[0114] An example of the application process of the getter material composition will be described below, but the application process is not necessarily limited to the following.

[0115] First, a hydrogenation catalyst or a porous powder carrying the hydrogenation catalyst is prepared. The particle size of the hydrogenation catalyst powder or porous powder is preferably adjusted, as necessary, by pulverization or other methods, so that D50 is 20 μm or less. Then, 0.01 to 49 parts by mass of the hydrogenation catalyst or porous powder carrying the hydrogenation catalyst is mixed with 50 to 99.99 parts by mass of Cu-ZSM-5 powder with a crystal size of 400 to 5000 nm, and the resulting mixture serves as the getter material.

[0116] Next, 5 to 70 parts by weight of getter material and 30 to 95 parts by weight of organic solvent are mixed to obtain a getter material composition. The organic solvent preferably contains a cyclic compound. Furthermore, mixing a high-boiling-point solvent with a boiling point of 250°C or higher as the organic solvent can prevent nozzle clogging caused by the solvent drying in the coating head of the coating device.

[0117] The getter material composition is, for example, injected into a syringe such as a dispenser and applied along the periphery of the first or second glass plate on which the sealing material and spacers have been formed. It is preferable to apply the composition within 15 mm from the edge of the glass substrate, as this will hide the getter material when the glass panel unit is assembled into the sash, making it less noticeable. There is no particular restriction on the order in which the sealing material, spacers, and getter material composition are applied to the substrate. For example, the getter material composition may be applied after the spacers have been formed, and then the sealing material may be formed, or the getter material composition, spacers, and sealing material may be applied in this order.

[0118] Next, the glass substrate is subjected to a drying process, which dries out part of the solvent in the getter material composition and allows the powder to adhere to the glass substrate. After this, the first glass substrate and the second glass substrate are stacked together, and a sealing process, as described below, is carried out. Alternatively, the sealing material may be applied to the first or second glass plate and then subjected to a drying process, after which the getter material composition may be applied to the first or second glass plate and then subjected to another drying process. This may prevent the getter material from adsorbing the volatile components of the sealing material solvent, thereby suppressing deterioration of the getter material. However, simultaneous drying of the sealing material and getter material results in higher productivity.

[0119] The first melting step, described below, is performed in the atmosphere. This step removes the solvent residue from the getter material composition. The hydrogenation catalyst has the effect of promoting the removal of the solvent during the first melting step. Furthermore, by setting the crystal size of Cu-ZSM-5 to 400 nm or more, preferably 600 nm or more, and more preferably 750 nm or more, the influence of the solvent can be further suppressed. Furthermore, by including a cyclic compound in the solvent, the influence of the solvent can be further suppressed. It is desirable that as much of the solvent as possible be removed from the getter material composition at this stage. By sufficiently removing the solvent component from the getter material composition, the getter material composition returns to its getter material state. After the first and second glass substrates are bonded in the first melting step, the next step is the evacuation step. During this step, the getter material is activated and acquires adsorption capabilities.

[0120] Next, in the second melting process described below, the glass panel unit 10 is sealed and isolated from the vacuum pump. The gases released into the reduced pressure space 50 of the glass panel unit 10 are then adsorbed by the getter material. At this time, the hydrogenation catalyst preferentially adsorbs carbon dioxide and hydrocarbon gases, leaving the adsorption sites of the Cu-ZSM-5 available for adsorption of nitrogen and methane. Furthermore, by ensuring that the crystal size of the Cu-ZSM-5 is 400 nm or larger, and more preferably 600 nm or larger, a better degree of vacuum can be maintained in the low-pressure region.

[0121] The fifth step is a step of arranging the peripheral wall 410 and the partition 420 (sealing material arranging step) (see FIG. 3). In the fifth step, a first sealing material is applied to the second glass plate 300 using a dispenser or the like, and then the first sealing material is dried to form the peripheral wall 410. Also, a second sealing material is applied to the second glass plate 300 using a dispenser or the like, and then the second sealing material is dried to form the partition 420.

[0122] By completing the first to fifth steps, a second glass plate 300 is obtained as shown in Fig. 3. The second glass plate 300 is formed with a peripheral wall 410, a partition 420, an air passage 600, an exhaust port 700, a gas adsorbent 60, and a plurality of spacers 70.

[0123] The sixth step is a step (arrangement step) of arranging the first glass plate 200 and the second glass plate 300. In the sixth step, as shown in Fig. 4, the first glass plate 200 and the second glass plate 300 are arranged so as to be parallel to and face each other.

[0124] The assembly process described above results in the assembly 100 shown in Fig. 5. After the assembly process, a first melting process (joining process), an exhaust process, and a second melting process (sealing process) are performed as shown in Fig. 6.

[0125] The first melting step is a step of temporarily melting the peripheral wall 410 to airtightly bond the first glass sheet 200 and the second glass sheet 300 together at the peripheral wall 410. Specifically, the first glass sheet 200 and the second glass sheet 300 are placed in a melting furnace and heated at a first melting temperature Tm1 for a predetermined time (first melting time) tm1 (see FIG. 6 ). In this embodiment, the first sealing material and the second sealing material are made of the same material as described above, and therefore the softening point of the first sealing material (first softening point) is the same as the softening point of the second sealing material (second softening point). Therefore, the first melting temperature Tm1 is set to be equal to or higher than the first and second softening points. Even if the first melting temperature Tm1 is equal to or higher than the first and second softening points, the exhaust step is started after the first melting step (see FIG. 6 ). Therefore, the partition 420 does not block the ventilation path 600 during the first melting step. That is, in the first melting step, the ventilation path 600 is secured. In the first melting step, for example, the first and second softening points are set to 265° C., and the first melting temperature Tm1 is set to 290° C. In addition, the first melting time tm1 is, for example, 15 minutes.

[0126] In this embodiment, the embodiment in which the first softening point is the same as the second softening point includes not only an embodiment in which the first softening point is exactly the same as the second softening point, but also an embodiment in which the first softening point is approximately the same as the second softening point.

[0127] Heating the peripheral wall 410 to the first melting temperature Tm1 makes it possible to soften the peripheral wall 410 while suppressing deformation of the partition 420. This makes it easier for the peripheral wall 410 to airtightly bond the first glass plate 200 and the second glass plate 300 together.

[0128] The exhaust process is a process of exhausting the first space 510 through the ventilation path 600, the second space 520, and the exhaust port 700 to turn the first space 510 into a reduced-pressure space 50. The exhaust process is performed using, for example, a vacuum pump. As shown in FIG. 5 , the vacuum pump is connected to the assembly 100 by an exhaust pipe 810 and a seal head 820. The exhaust pipe 810 is joined to the second glass sheet 300 so that the interior of the exhaust pipe 810 communicates with the exhaust port 700. The seal head 820 is then attached to the exhaust pipe 810, thereby connecting the intake port of the vacuum pump to the exhaust port 700. The first melting process, the exhaust process, and the second melting process are performed while the assembly 100 remains in the melting furnace. Therefore, the exhaust pipe 810 is joined to the second glass sheet 300 at least before the first melting process.

[0129] In the evacuation process, the first space 510 is evacuated through the ventilation path 600, the second space 520, and the exhaust port 700 at an evacuation temperature Te or higher for a predetermined time (evacuation time) te or longer before the second melting process begins (see FIG. 6). The evacuation temperature Te is set lower than the second softening point of the second sealing material (e.g., 265°C). For example, the evacuation temperature Te is 250°C. In this manner, the partition 420 does not deform even during the evacuation process. During the evacuation process, at least the moisture in the gas adsorbent 60 is vaporized and released into the first space 510, which is then exhausted through the ventilation path 600, the second space 520, and the exhaust port 700. By exhausting the moisture and other substances released from the gas adsorbent 60, the gas adsorption properties of the getter material can be further restored. The evacuation time te is set so that the reduced pressure space 50 is reduced to a desired degree (e.g., a vacuum of 0.1 Pa or less). For example, the exhaust time te is set to 30 minutes. At this time, the activation temperature of the gas adsorbent 60 is the exhaust temperature Te. That is, the gas adsorbent 60 contains a powdered getter material, and the activation temperature of this getter material is equal to or lower than the exhaust temperature Te.

[0130] The second melting step is a step of forming the partition wall 42 by deforming the partition 420 to block at least the ventilation path 600, thereby obtaining the work-in-progress 110. That is, in the second melting step, the partition 420 is deformed to block the ventilation path 600. In other words, the deformed partition 420 blocks the first space 510, separating the first space 510 and the second space 520. As a result, a frame 40 that surrounds the reduced pressure space 50 is formed (see FIG. 7). In this embodiment, the partition 420 is deformed so that both ends in the length direction of the partition 420 (first and second blocking portions 4221, 4222) contact and become integrated with the peripheral wall 410. As a result, as shown in FIG. 7, the partition wall 42 that airtightly separates the internal space 500 into the first space 510 (reduced pressure space 50) and the second space 520 is formed. More specifically, the partition 420 is deformed by being melted at a predetermined temperature (second melting temperature) Tm2 equal to or higher than the second softening point of the second sealing material. Specifically, the first glass plate 200 and the second glass plate 300 are heated in a melting furnace at the second melting temperature Tm2 for a predetermined time (second melting time) tm2 (see FIG. 6 ). The second melting temperature Tm2 and the second melting time tm2 are set so that the partition 420 softens and the air passage 600 is blocked. The lower limit of the second melting temperature Tm2 is the second softening point (e.g., 265°C). The second melting temperature Tm2 is set to, for example, 300°C. The second melting time tm2 is, for example, 30 minutes. The sealing process of this embodiment is a second melting process, but the sealing process is essentially a process of spatially separating the reduced pressure space 50 from spaces other than the reduced pressure space 50. In this embodiment, the space other than the reduced pressure space 50 corresponds to a second space 520 .

[0131] In this embodiment, as shown in Fig. 6, the evacuation process is initiated after the first melting process and terminates upon completion of the second melting process. Therefore, during the second melting process, the first space 510 is evacuated via the ventilation path 600, the second space 520, and the exhaust port 700. This generates a pressure difference between the inside and outside of the assembly 100, and this pressure difference causes the first and second glass sheets 200, 300 to move closer to each other. Thus, during the second melting process, at the second melting temperature Tm2, ​​the first space 510 is evacuated via the ventilation path 600, the second space 520, and the exhaust port 700, while the partition 420 is deformed to form the partition wall 42 that closes the ventilation path 600.

[0132] 6, after the second melting time tm2 has elapsed, the temperature inside the melting furnace is cooled to room temperature at a constant rate. Then, the seal head 820 is removed, thereby completing the second melting step and the exhaust step.

[0133] The above-described preparation steps result in a work-in-progress 110 shown in Fig. 7. As shown in Fig. 7, the work-in-progress 110 includes a first glass plate 200, a second glass plate 300, a peripheral wall 41, and a partition wall 42. The work-in-progress 110 also includes a reduced pressure space 50 and a second space 520. The work-in-progress 110 further includes a gas adsorbent 60 and a plurality of pillars (spacers) 70 within the reduced pressure space 50. The work-in-progress 110 also includes an exhaust port 700.

[0134] The first and second glass plates 200 and 300 are both rectangular flat plates. The first and second glass plates 200 and 300 have the same planar shape.

[0135] The partition wall 42 (spatially) separates the reduced pressure space 50 from the second space 520. In other words, since the second space 520 of the work-in-process 110 is (spatially) connected to the external space via the exhaust port 700, the partition wall 42 separates the reduced pressure space 50 from the external space. The partition wall 42 and the peripheral wall 410 are integrated to form the frame body 40 that surrounds the reduced pressure space 50. The frame body 40 completely surrounds the reduced pressure space 50 and airtightly joins the first glass plate 200 and the second glass plate 300 together.

[0136] The gas adsorbent 60 is disposed within the reduced pressure space 50. Specifically, the gas adsorbent 60 is a long, flat plate and is disposed on the second glass plate 300. The gas adsorbent 60 is used to adsorb unnecessary gases (residual gases, etc.). The unnecessary gases are, for example, gases released from the thermal adhesives (first thermal adhesive and second thermal adhesive) that form the frame 40 when the thermal adhesives are heated.

[0137] A plurality of spacers 70 are disposed within the reduced pressure space 50. The plurality of spacers 70 are used to maintain the distance between the first and second glass plates 200, 300 at a desired value.

[0138] As described above, the reduced pressure space 50 is formed by evacuating the first space 510 through the second space 520 and the exhaust port 700. In other words, the reduced pressure space 50 is the first space 510 in which the degree of vacuum is equal to or less than a predetermined value. The predetermined value is, for example, 0.1 Pa. The reduced pressure space 50 is completely sealed by the first glass plate 200, the second glass plate 300, and the frame 40, and is therefore separated from the second space 520 and the exhaust port 700.

[0139] The removal process is performed after the preparation process. As shown in Fig. 8, the removal process is a process of obtaining the glass panel unit 10, which is the portion having the reduced pressure space 50, by removing the portion 11 having the second space 520 from the work-in-progress 110.

[0140] The glass panel unit 10 includes a first glass plate 20 and a second glass plate 30. The first glass plate 20 is a portion of the first glass plate 200 that corresponds to the first space 510 (decompression space 50), and the second glass plate 30 is a portion of the second glass plate 300 that corresponds to the first space 510 (decompression space 50).

[0141] On the other hand, the unnecessary portion 11 includes a portion 230 of the first glass plate 200 that corresponds to the second space 520, and a portion 320 of the second glass plate 300 that corresponds to the second space 520. In consideration of the manufacturing cost of the glass panel unit 10, it is preferable that the unnecessary portion 11 is small.

[0142] Specifically, in the removal process, the work-in-progress 110 removed from the melting furnace is cut along the partition wall 42 and divided into a portion (glass panel unit) 10 having the reduced pressure space 50 and a portion (unnecessary portion) 11 having the second space 520. The shape of the portion (cutting line) along which the work-in-progress 110 is cut is determined by the shape of the glass panel unit 10. Because the glass panel unit 10 is rectangular, the cutting line is a straight line along the length direction of the partition wall 42.

[0143] Through the above-described preparation step and removal step, the glass panel unit 10 shown in FIG. 2 is obtained.

[0144] FIG. 2 shows a glass panel unit (finished glass panel unit) 10 of this embodiment. The glass panel unit 10 includes a first glass plate 20, a second glass plate 30, and a frame body 40. The glass panel unit 10 also has a reduced pressure space 50 surrounded by the first and second glass plates 20, 30 and the frame body 40. The glass panel unit 10 also includes a gas adsorbent 60 and a plurality of pillars (spacers) 70 within the reduced pressure space 50. The glass panel unit 10 does not include an exhaust port 700 in the first and second glass plates 20, 30.

[0145] The first and second glass plates 20 and 30 are both rectangular flat plates. The first and second glass plates 20 and 30 have the same planar shape.

[0146] The first glass plate 20 of this embodiment is obtained by removing an unnecessary portion 230 of the first glass plate 200 through a removal process. Therefore, the first glass plate 20 has the same configuration as the first glass plate 200. That is, the first glass plate 20 includes a main body that forms the main shape of the first glass plate 20, and a low-emissivity film 220. This main body is covered by the low-emissivity film 220 within the reduced-pressure space 50. The first glass plate 20 has a rectangular flat plate shape.

[0147] The second glass plate 30 in this embodiment is obtained by removing the unnecessary portion 320 of the second glass plate 300 through a removal process. Therefore, the second glass plate 30 has the same configuration as the second glass plate 300. That is, the second glass plate 30 has a main body that constitutes its main shape. In this embodiment, the second glass plate 30 consists only of the main body, but the second glass plate 30 may also be provided with a low-emissivity film similar to the low-emissivity film 220 in addition to the main body. If the second glass plate 30 is provided with a low-emissivity film, the low-emissivity film covers the main body of the second glass plate 30 and is in contact with the main body within the reduced pressure space 50.

[0148] The frame body 40 is located between the first glass plate 20 and the second glass plate 30 and airtightly bonds the first glass plate 20 and the second glass plate 30 together. As a result, the reduced pressure space 50 is surrounded by the first glass plate 20, the second glass plate 30, and the frame body 40. The frame body 40 has a polygonal frame shape (quadrilateral in this embodiment) similar to the first and second glass plates 20, 30. The frame body 40 is formed along the outer peripheries of the first and second glass plates 20, 30.

[0149] A plurality of spacers 70 are disposed within the reduced pressure space 50. The plurality of spacers 70 are used to maintain the distance between the first and second glass plates 20, 30 at a desired value.

[0150] <Gas adsorption by gas adsorbents> The gas adsorbent 60 is disposed in the reduced pressure space 50 of the glass panel unit 10. The getter material contained in the gas adsorbent 60 contains multiple particles, and the activation temperature of these particles is 400°C or lower. In the present disclosure, the "activation temperature" refers to the temperature required to activate the multiple particles contained in the gas adsorbent 60. That is, the multiple particles contained in the gas adsorbent 60 are activated at the activation temperature or higher. The multiple particles in the activated gas adsorbent 60 have increased gas adsorption capacity. In other words, when the activation temperature is reached, the multiple particles in the gas adsorbent 60 are activated by releasing the adsorbed gas, and the gas adsorption capacity increases. For example, the activation temperature is set at a predetermined heating temperature in a vacuum of 0.001 Pa or lower for a sufficient period of time, and then the amount of nitrogen gas adsorption is measured in a 20°C environment at a nitrogen equilibrium pressure of 0.1 Pa. In this case, the nitrogen adsorption amount is 4×10 -11 This nitrogen adsorption amount is measured by, for example, using a Microtrackbell Belsorp-Max, heating 0.5 g of pre-treated adsorbent at a specified temperature (activation temperature) for 12 hours or more while evacuating with a turbo pump, then lowering the temperature to 20°C, using nitrogen gas with a purity of 6N or higher as the adsorbate, and measuring the nitrogen adsorption amount at an equilibrium pressure of 0.1 Pa. The adsorption amount is 4 × 10 -11 If the value is mol / g or more, it can be confirmed that the predetermined temperature (activation temperature) is equal to or higher than the activation temperature.

[0151] The particles made of zeolite crystals contained in the gas adsorbent 60 will be described below.

[0152] The getter material contained in the gas adsorbent 60 has zeolite particles with diameters of 200 nm or more that account for more than half of the total weight of the numerous (plural) zeolite particles. In other words, the weight of the zeolite particles with diameters of 200 nm or more accounts for more than half of the total weight of the zeolite particles that make up the getter material. Note that the weight of the zeolite particles with diameters of 200 nm or more may be the total weight of the zeolite particles contained in the getter material and the gas adsorbent 60, in which case all of the zeolite particles contained in the getter material and the gas adsorbent 60 have diameters of 200 nm or more.

[0153] As mentioned above, generally (for example, under pressures of 100 Pa or greater), the smaller the diameter of zeolite particles and the greater the number of zeolite particles, the greater the surface area of ​​the zeolite particles and the higher the gas adsorption capacity of the zeolite. When zeolite particles have a small diameter, the depth of the internal space (path length from the surface) through which gas molecules penetrate the interior through the surface pores is short. As a result, gas molecules cannot penetrate deep into the particle's internal space and are instead retained (adsorbed) near the surface. The gas retained near the surface desorbs from the particle after a certain period of time (which varies depending on the particle). However, since some gas molecules are newly adsorbed, equilibrium is reached between the desorbing and adsorbing gas molecules in the particle. From the perspective of this equilibrium, the lower the pressure, the smaller the amount of newly adsorbed gas and the smaller the equilibrium point between desorption and adsorption, resulting in a lower gas adsorption capacity per unit weight. Furthermore, at a given pressure, the smaller the diameter and the greater the total surface area, the greater the gas adsorption capacity per unit weight.

[0154] However, in low-pressure regions (for example, 100 Pa or less, particularly 30 Pa or less), it is thought that gas desorption from large particles is reduced from a perspective other than equilibrium. That is, in large particles, although the surface area per unit weight is small, the depth of the internal space that penetrates into the interior through the pores on the surface is longer, and gas penetrates deeper into the internal space than in small particles. Gas that penetrates deep into the internal space is less likely to desorb from the particle. For this reason, in low-pressure regions, it is thought that larger particles have a greater gas adsorption capacity per unit weight.

[0155] Here, the diameter of zeolite particles will be explained. When the shape of zeolite particles is spherical, the diameter of the sphere is the particle diameter. When the shape of zeolite particles is not spherical, the shape of zeolite particles is often ellipsoid or rectangular. In this case, the shortest width of the zeolite particle is considered to have the greatest effect on the gas adsorption capacity. The shortest width is the length of the shortest line segment passing through the center of a cross section including the center of the particle. For example, when the shape of the zeolite particle is ellipsoid, the shortest width is the length of the shortest side of the rectangular parallelepiped. When the shape of the zeolite particle is neither rectangular parallelepiped nor ellipsoid, the shortest width is the smallest particle width among the set of maximum particle widths perpendicular to the line indicating the longest width in any cross section including the line indicating the longest width of the particle. When the shape of the zeolite particle is spherical, the shortest width is the diameter of the sphere.

[0156] The reason why the shortest width of the particle is used as an index here is that the surface area of ​​the part corresponding to the shortest width tends to be large, and the shorter the depth of the internal space of the part corresponding to the shortest width, the easier it is for gas that has entered the internal space to escape, and therefore it is thought that this has the greatest impact on the gas adsorption capacity per unit weight of the zeolite particle.

[0157] The particle diameter can be determined by observing the particle with a scanning electron microscope (SEM) and measuring the minor axis width of the particle. For example, if the particle has a plate-like shape, the plate thickness can be measured as the minor axis width.

[0158] The weight ratio of each particle can be calculated by calculating the volume ratio from the particle shape obtained from SEM observation. However, if particles other than zeolite are mixed, the volume ratio is calculated excluding the particles other than zeolite.

[0159] 9 and 10 show the results of a comparative experiment on the gas adsorption capacities of copper ion-exchanged ZSM-5 particles with a diameter of 50 nm and copper ion-exchanged ZSM-5 particles with a diameter of 400 nm. In the equilibrium pressure-adsorption capacity diagrams shown in FIGS. 9 and 10, the horizontal axis represents equilibrium pressure (Pa), and the vertical axis represents the nitrogen adsorption capacity (arbitrary units) at 20°C. Note that the vertical and horizontal axes in FIG. 9 are normal axes, while the vertical and horizontal axes in FIG. 10 are logarithmic axes. FIG. 10 reveals that the gas adsorption capacities of the copper ion-exchanged ZSM-5 particles with a diameter of 50 nm and those of the copper ion-exchanged ZSM-5 particles with a diameter of 400 nm are reversed when the equilibrium pressure reaches approximately 30 Pa.

[0160] In this embodiment, it is sufficient that the diameters of the particles that account for more than half of the total weight of the multiple (large number) particles contained in the gas adsorbent 60 are 200 nm or more, but it is more preferable that the diameters of the particles that account for more than half of the total weight of the multiple particles contained in the gas adsorbent 60 are 300 nm or more. Furthermore, it is more preferable that the diameters of the particles that account for more than half of the total weight of the multiple particles contained in the gas adsorbent 60 are 400 nm or more. In other words, it is preferable that the weight of the multiple particles with diameters of 400 nm or more accounts for more than half of the total weight of the multiple particles contained in the gas adsorbent 60.

[0161] Figure 11 shows the results of an experiment comparing the activation temperature of gas adsorption capacity between 50 nm and 400 nm particles. The horizontal axis of the adsorption ratio-activation temperature diagram in Figure 11 represents activation temperature (°C), and the vertical axis represents the ratio of the nitrogen adsorption amount of 400 nm particles to that of 50 nm particles at an equilibrium pressure of 0.1 Pa under a 20°C environment. Figure 11 shows that the adsorption ratio is greater when the activation temperature is 350°C than when it is 400°C, and significantly greater when the activation temperature is 250°C than when it is 350°C. This is thought to be because, in the case of copper ion-exchanged zeolite, the development of strong nitrogen adsorption sites through copper oxide reduction becomes rapidly less likely when the activation temperature (the temperature during the evacuation process) is set below 350°C, resulting in a greater proportion of the crystal size effect.

[0162] For this reason, in this embodiment, the exhaust temperature (equivalent to the activation temperature) in the manufacturing process of glass panel unit 10 is more effective at 400°C or less, an even greater effect is obtained at 350°C or less, and even more effective at 300°C or less. Also, since the exhaust process is usually performed at a temperature close to or lower than the melting temperature of the sealing material (first sealing material and second sealing material), glass panel unit 10 in the present invention is more effective when the melting temperature of the sealing material (at least one of the first sealing material and second sealing material) is 400°C or less, even more significantly effective at 350°C or less, and even more effective at 300°C or less.

[0163] FIG. 12 shows a relationship diagram between the residual gas amount and the crystal diameter (crystal size) of the glass panel unit 10. The activation of the gas adsorbent 60 was performed under the same conditions as those in the exhaust process (exhaust temperature Te = 250°C) between the first and second melting processes shown in FIG. 6. The horizontal axis of the relationship diagram shown in FIG. 12 is the crystal size, which is the crystal diameter (nm), and the vertical axis is the residual gas amount (arbitrary unit). It can be seen from FIG. 12 that the residual gas amount is smaller when the crystal diameter is 400 nm and 2000 nm compared to when the crystal diameter is 50 nm.

[0164] Therefore, it is preferable that the getter material of glass panel unit 10 contains copper ion-exchanged zeolite with a crystal size of 400 nm or more, and the softening point or melting point of the sealing material (at least one of the first sealing material and the second sealing material) is 350° C. or less.

[0165] The partial pressure of nitrogen in the reduced pressure space 50 of the glass panel unit 10 can be easily kept at 0.1 Pa or less. This means that even if nitrogen, which is difficult to adsorb with ordinary adsorbents, remains in or is released from the reduced pressure space of the glass panel unit 10, a sufficient degree of vacuum can be achieved, and good heat insulating properties can easily be obtained.

[0166] Furthermore, the volume of the decompression space 50 is V (m 3 ), the total amount of nitrogen adsorption is 0.1V(Pa m 3 This means that even if the pressure in the reduced pressure space 50 would normally be 0.1 Pa or higher due to nitrogen remaining in or released from the reduced pressure space 50, the nitrogen partial pressure can be reduced to 0.1 Pa or lower due to nitrogen adsorption by the gas adsorbent 60.

[0167] Furthermore, the diameter of the particles that account for half or more of the total weight of the plurality of particles is 30 μm or less, and more preferably 10 μm or less.

[0168] 13A shows a relationship diagram between the residual gas amount and the crystal diameter (crystal size) of the glass panel unit 10. This diagram shows that the residual gas amount of the glass panel unit 10 differs depending on whether the solvent for the getter material composition is water or an organic solvent. That is, whether the solvent for the getter material composition is water or an organic solvent, the amount of solvent remaining in the particles made of zeolite crystals differs, and the gas adsorption capacity of the gas adsorbent 60 differs.

[0169] As is clear from Figure 13A, when the zeolite crystal size is very small, the gas adsorbent using an organic solvent as the solvent for the getter material composition has a larger residual gas amount (i.e., the gas adsorbent performance is somewhat lower). However, when the zeolite crystal size is 400 nm, the residual gas amounts of the gas adsorbent using an organic solvent as the solvent for the getter material composition and the gas adsorbent using water are almost the same (residual gas amount ratio is around 1). Furthermore, when the zeolite crystal size is larger than 400 nm, the gas adsorbent characteristics (gas adsorption capacity) are better when an organic solvent is used as the solvent for the getter material composition than when water is used. For example, when the zeolite crystal size is 600 nm or larger, the residual gas amount ratio is 1 or less.

[0170] As shown in Figure 13B, when the diameter of the zeolite crystal particles is 500 nm or more, the residual gas amount ratio becomes 1 or less, so that organic solvents are more advantageous than water as a solvent for the getter material composition (the gas adsorption capacity of the gas adsorbent becomes higher). The residual gas amount ratio is expressed by the following formula (2). Residual gas amount ratio = [residual gas amount when using organic solvent] ÷ [residual gas amount when using aqueous solvent] ... (2) Therefore, when an organic solvent is used as the solvent for the getter material composition, the diameter (crystal size) of the zeolite crystal particles is advantageously 200 nm or more, more preferably 300 nm or more, even more preferably 400 nm or more, even more preferably 500 nm or more, and even more preferably 600 nm or more. Furthermore, the diameter of the zeolite crystal particles is preferably 750 nm or more, 1000 nm or more, 1500 nm or more, or even more preferably 2000 nm or more. In other words, the getter composition preferably contains copper ion-exchanged zeolite with a crystal size of 400 nm or more (or 600 nm or more) and an organic solvent with a cyclic structure.

[0171] For example, it is preferable that the getter material composition contains a plurality of particles made of zeolite crystals, the diameter of which accounts for more than half of the total weight of the particles, and the average diameter of the particles is 200 nm or more. This results in a gas adsorbent 60 that is likely to exhibit adsorption performance in low-pressure regions. The average diameter (average size) of the plurality of particles made of zeolite crystals can be determined by measuring the minor axis widths of the plurality of particles by SEM observation and averaging the measurements, as described above.

[0172] For example, if a similar experiment were performed by mixing 0.5 parts by mass of zeolite particles with a crystal size of less than 200 nm (crystal size 50 nm) and 0.5 parts by mass of zeolite particles with a crystal size of 200 nm or more (crystal size 400 nm) with an organic solvent, the residual gas volume would be similar to that obtained when a total amount of zeolite with a crystal size of 400 nm was mixed with an organic solvent (1 to 1.5 times that when the total amount of crystal size was 400 nm). However, if 0.75 parts by mass of zeolite particles with a crystal size of less than 200 nm (crystal size 50 nm) and 0.25 parts by mass of zeolite particles with a crystal size of 200 nm or more (crystal size 400 nm) were mixed with an organic solvent, the residual gas volume would be approximately the same as that obtained when a total amount of zeolite particles with a crystal size of 50 nm was mixed with an organic solvent (0.8 to 1 times that when the total amount of crystal size was 50 nm). This is thought to be because, under the low-pressure conditions that would be achieved if large-crystal zeolite particles were used, the small-crystal zeolite actually releases gas, and when the proportion of small-crystal zeolite increases, the getter material as a whole releases more gas than it adsorbs in the low-pressure region, making it difficult to obtain the effect of large-crystal zeolite particles. For this reason, it is desirable that the amount of zeolite particles with a crystal size of less than 200 nm be less than half of the total weight of the multiple particles made of zeolite crystals.

[0173] Furthermore, of the total weight of the zeolite particles, the weight of the zeolite particles with a crystal size of less than 300 nm is more preferably less than half of the total weight of the zeolite particles, the weight of the zeolite particles with a crystal size of less than 400 nm is more preferably less than half of the total weight of the zeolite particles, the weight of the zeolite particles with a crystal size of less than 500 nm is more preferably less than half of the total weight of the zeolite particles, and even more preferably the weight of the zeolite particles with a crystal size of less than 600 nm is less than half of the total weight of the zeolite particles.Furthermore, of the total weight of the zeolite particles, the weight of the zeolite particles with a crystal size of less than 750 nm is more preferably less than half, the weight of the zeolite particles with a crystal size of less than 1000 nm is more preferably less than half, the weight of the zeolite particles with a crystal size of less than 1500 nm is more preferably less than half, and even more preferably the weight of the zeolite particles with a crystal size of less than 2000 nm is less than half. Alternatively, the weight of particles having a crystal size of less than 200 nm may be less than half of the total weight of the plurality of particles made of zeolite crystals, and the weight ratio of particles having a crystal size of 400 nm or more may be greater than 25%, thereby suppressing the influence of particles with small crystal sizes.

[0174] Although the ratio of zeolite crystal sizes is shown above as a weight ratio of particles, the same tendency is observed when comparing the ratio of particle numbers (number of pieces) or particle volume ratios. That is, it is desirable that particles with a crystal size of less than 200 nm account for less than half of the total number of particles made of zeolite crystals. Alternatively, it is desirable that particles with a crystal size of less than 200 nm account for less than half of the total volume occupied by particles made of zeolite crystals.

[0175] Furthermore, of the total volume of the zeolite particles, the volume of zeolite particles with a crystal size of less than 300 nm is more preferably less than half of the total volume of the zeolite particles, the volume of zeolite particles with a crystal size of less than 400 nm is more preferably less than half of the total volume of the zeolite particles, the volume of zeolite particles with a crystal size of less than 500 nm is more preferably less than half of the total volume of the zeolite particles, and even more preferably less than half of the total volume of the zeolite particles with a crystal size of less than 600 nm.Furthermore, of the total volume of the zeolite particles, the volume of zeolite particles with a crystal size of less than 750 nm is more preferably less than half, more preferably less than half, more preferably less than half, more preferably less than half, and even more preferably less than half, of the total volume of the zeolite particles with a crystal size of less than 1000 nm.

[0176] Furthermore, of the total number of zeolite crystal particles, the number of zeolite particles with a crystal size of less than 300 nm is more preferably less than half of the total number of zeolite crystal particles, the number of zeolite particles with a crystal size of less than 400 nm is more preferably less than half of the total number of zeolite crystal particles, the number of zeolite particles with a crystal size of less than 500 nm is more preferably less than half of the total number of zeolite crystal particles, and even more preferably less than half of the total number of zeolite crystal particles with a crystal size of less than 600 nm. Furthermore, of the total number of zeolite crystal particles, the number of zeolite particles with a crystal size of less than 750 nm is more preferably less than half, the number of zeolite particles with a crystal size of less than 1000 nm is more preferably less than half, the number of zeolite particles with a crystal size of less than 1500 nm is more preferably less than half, and even more preferably less than half of the total number of zeolite crystal particles with a crystal size of less than 2000 nm is more preferably less than half.

[0177] Alternatively, the volume of particles having a crystal size of less than 200 nm may be less than half of the total volume of the plurality of particles made of zeolite crystals, and the volume ratio of particles having a crystal size of 400 nm or more may be greater than 25%. This can suppress the influence of particles with small crystal sizes. Alternatively, for example, the number of particles having a crystal size of less than 200 nm may be less than half of the total number of particles made of zeolite crystals, and the number of particles having a crystal size of 400 nm or more may be greater than 25%.

[0178] The glass panel unit 10 used in FIGS. 13A and 13B is as follows. Getter material that makes up the gas adsorbent: Cu-ZSM-5 (copper ion-exchanged zeolite) Gas adsorbent amount: 100mg Solvent for getter material composition: α-pinene or water (note that the getter composition was applied after mixing the getter material and the solvent and leaving it for one week). Decompression space volume: 9000mm 3 First melting temperature: 290℃ Exhaust temperature and time: 250℃, 30min Second melting temperature: 300℃ · Sealing material: Vanadium frit (softening point 270℃, the same material was used for the first and second sealing materials).

[0179] (Variation) The embodiments of the present disclosure are not limited to the above-described embodiments. The above-described embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. Modifications of the above-described embodiments are listed below. In the following description, the above-described embodiments are used as basic examples.

[0180] In the basic example, of the first and second glass sheets 200, 300, only the first glass sheet 200 is provided with the low-emissivity coating 220, but in a modified example, the second glass sheet 300 may also be provided with a low-emissivity coating. That is, both the first and second glass sheets 200, 300 may be provided with a low-emissivity coating. Therefore, both the first and second glass sheets 20, 30 may also be provided with a low-emissivity coating. Also, neither the first nor second glass sheets 20, 30 may be provided with a low-emissivity coating.

[0181] In the basic example, of the first and second glass plates 200, 300, the first glass plate 200 is provided with a low-emissivity coating 220, and the second glass plate 300 is not provided with a low-emissivity coating. However, in a modified example, the second glass plate 300 may be provided with a low-emissivity coating, and the first glass plate 200 may not be provided with a low-emissivity coating 220. Therefore, in the glass panel unit 10 of the modified example, the second glass plate 30 may also be provided with a low-emissivity coating, and the first glass plate 20 may not be provided with a low-emissivity coating 220.

[0182] In the basic example, the exhaust process starts after the first melting process, but in a modified example, the exhaust process may start in the middle of the first melting process after the first melting time tm1 has elapsed and if the temperature inside the melting furnace is lower than the first softening point.

[0183] In the basic example, the evacuation step is completed when the second melting step is completed, but in a modified example, the evacuation step may start after the first melting step and end before the second melting step.

[0184] In the basic example, the glass panel unit 10 is rectangular, but in a modified example, the glass panel unit 10 may have a desired shape such as a circular shape or a polygonal shape. In other words, the first glass plate 20 and the second glass plate 30 may have a desired shape such as a circular shape or a polygonal shape instead of a rectangular shape.

[0185] The first and second glass plates 20 and 30 do not have to have the same planar shape and planar size. Furthermore, the first glass plate 20 does not have to have the same thickness as the second glass plate 30. These points also apply to the first and second glass plates 200 and 300.

[0186] The peripheral wall 410 does not have to have the same planar shape as the first and second glass plates 200 and 300 .

[0187] The peripheral wall 410 may further comprise other elements such as a core.

[0188] Furthermore, in the assembly 100, the peripheral wall 410 is simply between the first and second glass plates 200, 300 and does not join them together. However, the peripheral wall 410 may join the first and second glass plates 200, 300 together at the stage of the assembly 100. In short, in the assembly 100, it is sufficient that the peripheral wall 410 is between the first and second glass plates 200, 300, and it is not essential that the peripheral wall 410 joins them together.

[0189] In the basic example, the partition 420 is not in contact with the peripheral wall 410. As a result, gaps between both ends of the partition 420 and the peripheral wall 410 form the air passages 610, 620. However, only one of the ends of the partition 420 may be connected to the peripheral wall 410, in which case, one air passage 600 may be formed between the partition 420 and the peripheral wall 410. Alternatively, both ends of the partition 420 may be connected to the peripheral wall 410. In this case, the air passage 600 may be a through-hole formed in the partition 420. Alternatively, the air passage 600 may be a gap between the partition 420 and the first glass plate 200. Alternatively, the partition 420 may be formed by two or more partitions arranged at an interval. In this case, the air passage 600 may be a gap between two or more partitions.

[0190] In the basic example, the ventilation path 600 includes two ventilation paths 610 and 620, but the ventilation path 600 may be configured with only one ventilation path, or may be configured with three or more ventilation paths. In addition, the shape of the ventilation path 600 is not particularly limited.

[0191] In addition, in the basic example, the internal space 500 is partitioned into one first space 510 and one second space 520. However, the internal space 500 may be partitioned into one or more first spaces 510 and one or more second spaces 520 by a partition 420. When the internal space 500 has two or more first spaces 510, two or more glass panel units 10 can be obtained from one work-in-progress 110.

[0192] In the basic example, the first space 510 is the reduced pressure space 50, but a reduced pressure space may be used instead of the reduced pressure space 50. The reduced pressure space is the first space 510 in a reduced pressure state. The reduced pressure state may be a state in which the pressure is lower than atmospheric pressure.

[0193] In the basic example, the partition wall 42 spatially separates the reduced pressure space 50 from the external space. However, in a modified example, only the inside or outer periphery of the exhaust port 700 may be sealed with a sealing material. Also, instead of closing the ventilation path 600 in the second melting step, only the periphery of the exhaust port 700 may be locally heated to melt the sealing material, thereby achieving sealing. Alternatively, without forming the exhaust port 700, the entire furnace may be evacuated to a vacuum, thereby reducing the pressure inside the glass panel unit 10, and then the glass panel unit 10 may be heated in the vacuum to melt the sealing material on the periphery and thereby achieve sealing.

[0194] In the basic example, the decompression space 50 is spatially separated from the external space by the partition wall 42. However, in a modified example, the decompression space 50 may be spatially separated from the external space by a sealing portion formed by melting and cutting a portion of the exhaust pipe connected to the exhaust port 700. In other words, the partition wall 42 is not essential as a member that spatially separates the decompression space 50 from the external space.

[0195] (summary) As is clear from the above-described embodiment and modified examples, a glass panel unit (10) of a first aspect includes a first glass plate (20), a second glass plate (30) facing the first glass plate (20), a frame (40), a reduced-pressure space (50), and a gas adsorbent (60). The frame (40) airtightly joins the first glass plate (20) and the second glass plate (30). The reduced-pressure space (50) is surrounded by the first glass plate (20), the second glass plate (30), and the frame (40). The gas adsorbent (60) is disposed within the reduced-pressure space (50). The gas adsorbent (60) contains a getter material. The getter material contains a plurality of particles made of zeolite crystals. The particles, which account for more than half of the total weight of the plurality of particles, have a diameter of 200 nm or more. The particle activation temperature is 400°C or less.

[0196] The glass panel unit (10) of the first aspect is likely to exhibit adsorption performance in a low pressure region.

[0197] The glass panel unit (10) of the second aspect is realized by combining with the first aspect. In the glass panel unit (10) of the second aspect, the weight of particles having a diameter of less than 200 nm is less than half of the total weight of the plurality of particles.

[0198] The glass panel unit (10) of the second aspect is likely to exhibit adsorption performance in a low pressure region.

[0199] The glass panel unit (10) of the third aspect is realized by combining with the first or second aspect. In the glass panel unit (10) of the third aspect, the diameter of the particles that account for half or more of the total weight of the plurality of particles is 400 nm or more.

[0200] According to the third aspect, the adsorption performance is likely to be exhibited in a low pressure region.

[0201] The glass panel unit (10) of the fourth aspect is realized by combining it with any one of the aspects 1 to 3. In the glass panel unit (10) of the fourth aspect, the partial pressure of nitrogen in the reduced pressure space (50) is 0.1 Pa or less.

[0202] According to the fourth aspect, it is easy to provide a glass panel unit (10) with high heat insulating performance.

[0203] The glass panel unit (10) of the fifth aspect is realized by combining it with any one of the aspects 1 to 4. In the glass panel unit (10) of the fifth aspect, the total amount of nitrogen adsorbed by the particles at 20°C is set to a value equal to or larger than V (m 3 ), 0.1V(Pa·m 3 )That's all.

[0204] According to the fifth aspect, it is easy to provide a glass panel unit (10) with high heat insulating performance.

[0205] The glass panel unit (10) of the sixth aspect is realized by combining it with any one of the aspects 1 to 5. In the glass panel unit (10) of the sixth aspect, the zeolite is copper ion-exchanged zeolite.

[0206] According to the sixth aspect, the gas adsorbent (60) is more likely to exhibit its adsorption performance.

[0207] The glass panel unit (10) of the seventh aspect is realized by combining it with any one of the aspects 1 to 6. In the glass panel unit (10) of the seventh aspect, the particles are primary particles, and the diameter is the shortest width of the particles.

[0208] According to the glass panel unit (10) of the seventh aspect, the adsorption performance is likely to be exhibited in a low pressure region.

[0209] The glass panel unit (10) of an eighth aspect includes a first glass plate (20), a second glass plate (30) facing the first glass plate (20), a frame (40), a reduced-pressure space (50), and a gas adsorbent (60). The frame (40) airtightly joins the first glass plate (20) and the second glass plate (30). The reduced-pressure space (50) is surrounded by the first glass plate (20), the second glass plate (30), and the frame (40). The gas adsorbent (60) is disposed within the reduced-pressure space (50). The gas adsorbent (60) contains a getter material. The getter material contains a plurality of particles made of zeolite crystals. The particles, accounting for more than half of the total number of the plurality of particles, have a diameter of 200 nm or more. The activation temperature of the particles is 400°C or less.

[0210] The glass panel unit (10) of the eighth aspect is likely to exhibit adsorption performance in a low pressure region.

[0211] A glass panel unit (10) of a ninth aspect includes a first glass plate (20), a second glass plate (30) facing the first glass plate (20), a frame (40), a reduced-pressure space (50), and a gas adsorbent (60). The frame (40) airtightly joins the first glass plate (20) and the second glass plate (30). The reduced-pressure space (50) is surrounded by the first glass plate (20), the second glass plate (30), and the frame (40). The gas adsorbent (60) is disposed within the reduced-pressure space (50). The gas adsorbent (60) contains a getter material. The getter material contains a plurality of particles made of zeolite crystals. The particles, which occupy more than half of the total volume occupied by the plurality of particles, have a diameter of 200 nm or more. The particles have an activation temperature of 400°C or less.

[0212] According to the glass panel unit (10) of the ninth aspect, the adsorption performance is likely to be exhibited in a low pressure region.

[0213] A glass panel unit (10) of a tenth aspect includes a first glass plate (20), a second glass plate (30) facing the first glass plate (20), a frame (40), a reduced-pressure space (50), and a gas adsorbent (60). The frame (40) airtightly joins the first glass plate (20) and the second glass plate (30). The reduced-pressure space (50) is surrounded by the first glass plate (20), the second glass plate (30), and the frame (40). The gas adsorbent (60) is disposed within the reduced-pressure space (50). The gas adsorbent (60) contains a getter material. The getter material contains a plurality of particles made of zeolite crystals and a hydrogenation catalyst.

[0214] According to the glass panel unit (10) of the tenth aspect, the adsorption performance is likely to be exhibited in a low pressure region.

[0215] The getter material of an eleventh aspect contains a plurality of particles made of zeolite crystals, the diameter of the particles that accounts for half or more of the total weight of the plurality of particles is 200 nm or more, and the activation temperature of the particles is 400°C or less.

[0216] The getter material of the eleventh aspect is likely to exhibit adsorption performance in a low pressure region.

[0217] A getter material of a twelfth aspect is realized by combining with the getter material of the eleventh aspect. In the getter material of the twelfth aspect, the diameter of the particles that accounts for half or more of the total weight of the plurality of particles is 400 nm or more.

[0218] The getter material of the twelfth aspect can exhibit adsorption performance in a low pressure region.

[0219] The getter material of the thirteenth aspect is realized by combining with the getter material of the eleventh or twelfth aspect. In the getter material of the thirteenth aspect, the diameter of the particles that accounts for half or more of the total weight of the plurality of particles is 600 nm or more.

[0220] The getter material of the thirteenth aspect is likely to exhibit adsorption performance in a low pressure region.

[0221] The getter material of the fourteenth aspect is realized by combining it with any one of the aspects 11 to 13. In the getter material of the fourteenth aspect, each of the plurality of particles has a diameter of 1000 nm or more.

[0222] The getter material of the fourteenth aspect is likely to exhibit adsorption performance in a low pressure region.

[0223] A getter material of a fifteenth aspect is realized by combining it with any one of the eleventh to fourteenth aspects. In the getter material of the fifteenth aspect, the particles are primary particles, and the diameter is the shortest width of the particles.

[0224] The getter material of the fifteenth aspect is likely to exhibit adsorption performance in a low pressure region.

[0225] The getter material of the 16th aspect is realized by combining with any one of the aspects 11 to 15. The getter material of the 16th aspect further contains a carbon dioxide adsorbent (excluding cerium oxide).

[0226] The getter material of the sixteenth aspect is more likely to adsorb carbon dioxide and is more likely to exhibit adsorption performance in a low pressure region.

[0227] A getter material of a seventeenth aspect is realized by combining with the getter material of the sixteenth aspect. In the getter material of the seventeenth aspect, the carbon dioxide adsorbent includes at least one selected from the group consisting of silica, alumina, and activated carbon.

[0228] The getter material of the seventeenth aspect is more likely to adsorb carbon dioxide and is more likely to exhibit adsorption performance in a low pressure region.

[0229] The getter material of the 18th aspect is realized by combining with any one of the aspects 11 to 17. The getter material of the 18th aspect further contains a hydrogenation catalyst.

[0230] The getter material of the eighteenth aspect is easy to hydrogenate compounds and is easy to exhibit adsorption performance in a low pressure region.

[0231] The getter material of the 19th aspect is realized by combining with the getter material of the 18th aspect. In the getter material of the 19th aspect, the hydrogenation catalyst is a powder.

[0232] The getter material of the nineteenth aspect is easy to hydrogenate compounds and is easy to exhibit adsorption performance in a low pressure region.

[0233] The getter material of the 20th aspect is realized by combining with the getter material of the 18th or 19th aspect. In the getter material of the 18th aspect, the hydrogenation catalyst is supported on a support containing at least one selected from the group consisting of silica, alumina, and activated carbon.

[0234] In the getter material of the twentieth aspect, the hydrogenation catalyst is supported on a support, making it difficult for the hydrogenation catalyst to be desorbed.

[0235] The getter material of the 21st aspect is realized by combining with any one of the aspects 11 to 20. In the getter material of the 21st aspect, the zeolite is copper ion-exchanged zeolite.

[0236] The getter material of the 21st aspect is likely to exhibit adsorption performance.

[0237] A twenty-second aspect of the getter material composition includes a getter material and a solvent. The getter material includes a plurality of particles of zeolite crystals. The activation temperature of the particles is 400°C or less.

[0238] According to the getter material composition of the 22nd aspect, a gas adsorbent (60) that is likely to exhibit adsorption performance in a low pressure region can be obtained.

[0239] A getter material composition according to a twenty-third aspect of the present invention includes a getter material and a solvent. The getter material includes a plurality of particles made of zeolite crystals. The plurality of particles includes particles having a diameter of 200 nm or more.

[0240] According to the getter material composition of the 23rd aspect, a gas adsorbent (60) that is likely to exhibit adsorption performance in a low pressure region can be obtained.

[0241] The getter material composition of the 24th aspect is realized by combining with the getter material composition of the 22nd or 23rd aspect. In the getter material composition of the 24th aspect, the diameter of the particles that accounts for half or more of the total weight of the plurality of particles is 200 nm or more, and the average diameter of the plurality of particles is 200 nm or more.

[0242] According to the getter material composition of the 24th aspect, a gas adsorbent (60) that is likely to exhibit adsorption performance in a low pressure region can be obtained.

[0243] The getter material composition of the 25th aspect is realized by combining with any one of the aspects 22 to 24. In the getter material composition of the 25th aspect, the solvent contains an organic solvent having a boiling point of 300° C. or less.

[0244] According to the getter material composition of the 25th aspect, the energy required to desorb the organic solvent can be reduced, and the gas adsorbent (60) can be easily obtained.

[0245] The getter material composition of the 26th aspect is realized by combining with any one of the aspects 22 to 25. In the getter material composition of the 26th aspect, the solvent includes an organic solvent having a cyclic structure.

[0246] According to the getter material composition of the 26th aspect, the energy required to desorb the organic solvent can be reduced, and the gas adsorbent (60) can be easily obtained.

[0247] The getter material composition of the 27th aspect is realized by combining with any one of the aspects 22 to 26. In the getter material composition of the 27th aspect, the solvent includes an organic solvent having a non-aromatic group.

[0248] According to the getter material composition of the 27th aspect, the energy required to desorb the organic solvent can be reduced, and the gas adsorbent (60) can be easily obtained.

[0249] The getter material composition of the 28th aspect is realized by combining it with any one of the aspects 22 to 27. The getter material further contains a carbon dioxide adsorbent.

[0250] According to the getter material composition of the 28th aspect, it becomes easier to obtain a gas adsorbent (60) having excellent gas adsorption capacity.

[0251] The getter material composition of the 29th aspect is realized by combining it with any one of the aspects 22 to 28. The getter material further contains a hydrogenation catalyst.

[0252] According to the getter material composition of the 29th aspect, it becomes easier to obtain a gas adsorbent (60) having excellent gas adsorption capacity.

[0253] A manufacturing method for a glass panel unit (10) according to a 30th aspect includes a processing step, an assembling step, a bonding step, and an evacuation step. The processing step involves preparing the getter material composition according to any one of the 22nd to 29th aspects. The assembling step involves preparing an assembly (100) including a first glass plate (20), a second glass plate (30), a frame-shaped peripheral wall (410), an internal space (500), a gas adsorbent (60) obtained from the getter material composition, and an exhaust port (700). The bonding step involves melting the peripheral wall (410) to airtightly bond the first glass plate (20) and the second glass plate (20). The evacuation step involves evacuating the internal space (500) through the exhaust port (700) to form a reduced-pressure space (50).

[0254] According to the thirtieth aspect, a glass panel unit (10) that is likely to exhibit adsorption performance in a low pressure region is obtained.

[0255] A glass panel unit (10) of a thirty-first aspect includes a first glass plate (20), a second glass plate (30) facing the first glass plate (20), a frame (40), a reduced-pressure space (50), and a gas adsorbent (60). The frame (40) airtightly joins the first glass plate (20) and the second glass plate (30). The reduced-pressure space (50) is surrounded by the first glass plate (20), the second glass plate (30), and the frame (40). The gas adsorbent (60) is disposed within the reduced-pressure space (50). The gas adsorbent (60) contains a getter material. The getter material contains a plurality of particles made of zeolite crystals. The particles, which account for more than half of the total weight of the plurality of particles, have a diameter of 200 nm or more. At least one of the softening point, melting point, and adhesive temperature of the sealing material is 350°C or lower.

[0256] According to the glass panel unit (10) of the thirty-first aspect, the adsorption performance is likely to be exhibited in a low pressure region. [Explanation of symbols]

[0257] 10 glass panel units 20 First Glass Panel 30 Second glass pane 40 frames 50 Decompression Space 60 Gas Adsorbent

Claims

1. Contains a getter material and a solvent, the getter material contains a plurality of particles made of copper ion-exchanged zeolite crystals; the diameter of the particles occupying half or more of the total weight of the plurality of particles is 200 nm or more; The solvent contains an organic solvent as a main component, The getter material further contains a carbon dioxide adsorbent. Getter material composition.

2. Contains a getter material and a solvent, the getter material contains a plurality of particles made of copper ion-exchanged zeolite crystals; the diameter of the particles occupying half or more of the total weight of the plurality of particles is 200 nm or more; The solvent contains an organic solvent as a main component, the solvent contains, as a main component, an organic solvent whose molecular size is equal to or larger than the pore size of the copper ion-exchanged zeolite; Getter material composition.

3. Contains a getter material and a solvent, the getter material contains a plurality of particles made of copper ion-exchanged zeolite crystals; the diameter of the particles occupying half or more of the total weight of the plurality of particles is 200 nm or more; The solvent contains an organic solvent as a main component, The getter material further contains a hydrogenation catalyst. Getter material composition.

4. The average diameter of the plurality of particles is 200 nm or more. The getter material composition according to any one of claims 1 to 3.

5. The solvent contains an organic solvent having a boiling point of 300°C or less as a main component. The getter material composition according to any one of claims 1 to 3.

6. The solvent contains an organic solvent having a cyclic structure as a main component. The getter material composition according to any one of claims 1 to 3.

7. The solvent contains an organic solvent having a non-aromatic cyclic structure as a main component. The getter material composition according to any one of claims 1 to 3.

8. A processing step of preparing a getter material composition according to any one of claims 1 to 3; an assembling step of preparing an assembly including a first glass plate, a second glass plate, a frame-shaped peripheral wall, an internal space, a gas adsorbent obtained from the getter material composition, and an exhaust port; a joining step of airtightly joining the first glass plate and the second glass plate by melting the peripheral wall; an exhaust step of exhausting the internal space through the exhaust port to form a reduced pressure space; Including, A method for manufacturing a glass panel unit.

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