WO2013008724A1 - Double vitrage et son procédé de fabrication - Google Patents

Double vitrage et son procédé de fabrication Download PDF

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Publication number
WO2013008724A1
WO2013008724A1 PCT/JP2012/067231 JP2012067231W WO2013008724A1 WO 2013008724 A1 WO2013008724 A1 WO 2013008724A1 JP 2012067231 W JP2012067231 W JP 2012067231W WO 2013008724 A1 WO2013008724 A1 WO 2013008724A1
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WIPO (PCT)
Prior art keywords
glass
sealing
glass plate
layer
plate
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PCT/JP2012/067231
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English (en)
Japanese (ja)
Inventor
諭司 竹田
亮太 村上
暢子 満居
山田　和夫
元司 小野
篤人 ▲橋▼本
平松　徹也
みか 横山
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旭硝子株式会社
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Publication of WO2013008724A1 publication Critical patent/WO2013008724A1/fr

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    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/6612—Evacuated glazing units
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/24—Structural elements or technologies for improving thermal insulation
    • Y02A30/249—Glazing, e.g. vacuum glazing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
    • Y02B80/22—Glazing, e.g. vaccum glazing

Definitions

  • the present invention relates to a multilayer glass and a method for producing the same.
  • a double-layer glass in which a gap between two glass plates is hermetically sealed and a double-layer glass in which a gap between two glass plates is hermetically sealed (vacuum sealed) in a vacuum state (vacuum) Also known as double-glazed glass).
  • the vacuum-sealed multi-layer glass has a structure in which, for example, two glass plates are arranged opposite to each other, and a space between these two glass plates is sealed with a low-melting glass (see Patent Documents 1 and 2).
  • Patent Document 1 two glass plates laminated through a low melting point glass are heated using a firing furnace to melt the low melting point glass, and then cooled to room temperature to solidify the low melting point glass. It describes that a sealing layer (seal part) is formed.
  • Patent Document 2 after laminating two glass plates through a low-melting glass layer, the low-melting glass layer is locally heated and melted by irradiating laser light along the low-melting glass layer. The formation of a sealing layer is described.
  • Patent Document 3 after the low melting point glass layer is irradiated with laser light in an air atmosphere to form a sealing layer, it is evacuated through a through hole provided in one glass plate. The internal space between the two glass plates is in a vacuum state. The through hole is sealed after the internal space is evacuated.
  • the sealing process using local heating by laser light has advantages such as less energy consumption and reduced manufacturing steps and costs compared to heating by a firing furnace, but the low melting point glass is locally and rapidly applied. Since this is a process of heating and quenching, there is a problem that residual stress is likely to occur at or near the bonding interface between the sealing layer made of a melt-solidified layer of low-melting glass and the glass plate.
  • a window glass of a building such as a house or a building
  • an indoor and outdoor temperature difference is added to the double-glazed glass.
  • the adhesive interface between the glass plate and the sealing layer or the sealing layer may be caused by a temperature difference between the inside or outside of the room or warpage of the multilayer glass based on the difference. Cracks and cracks are likely to occur.
  • An object of the present invention is to provide a double-glazed glass and a method for producing the same capable of improving long-term reliability by reducing stress based on a temperature difference between indoors and outdoors.
  • stress based on a temperature difference between the inside and outside of the room is related to the amount of warpage of the double-glazed glass after sealing, and have completed the present invention.
  • the multilayer glass according to an aspect of the present invention has a first surface including a first sealing region, a first glass plate made of low expansion glass, and a first glass plate corresponding to the first sealing region.
  • a second surface having two sealing regions, and disposed on the first glass plate with a predetermined gap so that the second surface faces the first surface;
  • the first sealing region and the second glass plate are vacuum-sealed so that a gap between the second glass plate made of low expansion glass and the first glass plate and the second glass plate is vacuum-sealed.
  • a sealing layer made of a material obtained by melting and solidifying a sealing glass material having a laser absorption ability, which is formed between the sealing region and the sealing region.
  • the multilayer glass according to another aspect of the present invention has a first surface including a first sealing region, and corresponds to the first glass plate made of low expansion glass and the first sealing region.
  • the first sealing region and the first glass plate are vacuum-sealed so that the second glass plate made of low expansion glass and the gap between the first glass plate and the second glass plate are vacuum-sealed.
  • a sealing layer formed between two sealing regions, and the thickness of the first glass plate disposed on the high temperature side is T1
  • the second glass plate is disposed on the low temperature side.
  • the method for producing a multilayer glass includes a step of preparing a first glass plate having a first surface including a first sealing region and made of low expansion glass; A second sealing region comprising a second sealing region corresponding to the sealing region, and a sealing material layer formed on the second sealing region and made of a material obtained by baking a sealing glass material having laser absorption ability.
  • a second glass plate made of low-expansion glass, and the first surface and the second surface facing each other while the first material and the second surface are opposed to each other.
  • the gap between the first glass plate and the second glass plate is vacuum sealed by melting and solidifying. It is characterized by comprising a step of forming a sealing layer.
  • the method for producing a multilayer glass includes a step of preparing a first glass plate having a first surface including a first sealing region and made of low expansion glass, A second sealing region corresponding to one sealing region, a first sealing material layer formed on the second sealing region and made of a sealing resin material, and the second sealing region.
  • a second surface comprising a second sealing material layer formed of a material obtained by baking a sealing glass material having a laser absorption ability, which is formed on the inner peripheral side from the first sealing material layer above;
  • the double-glazed glass of the present invention low-expansion glass is applied to the first and second glass plates, and therefore stress based on the temperature difference between the inside and outside of the double-glazed glass, such as the temperature difference between the inside and outside, can be reduced. . Therefore, a multilayer glass excellent in long-term reliability can be provided.
  • FIG. 1 is a cross-sectional view showing the structure of a multilayer glass according to the first embodiment.
  • FIG. 2 is a cross-sectional view showing a process for producing a multilayer glass according to the first embodiment.
  • FIG. 3 to FIG. 6 are diagrams showing the configuration of the first and second glass plates used in the manufacturing process of the multilayer glass.
  • the multilayer glass 1 shown in these drawings includes a first glass plate 2 having a first surface 2a and a second glass plate 3 having a second surface 3a.
  • the first glass plate 2 and the second glass plate 3 are laminated with a predetermined gap so that the first surface 2a and the second surface 3a face each other.
  • the gap between the first glass plate 2 and the second glass plate 3 is hermetically sealed (vacuum) in a vacuum state by the sealing layer 4 provided in the outer peripheral region (sealing region) of the glass plates 2 and 3. Sealed). That is, the internal space 5 of the multilayer glass 1 is maintained in a predetermined vacuum state.
  • the sealing layer 4 is made of a material obtained by melting and solidifying a sealing glass material. It is preferable that the glass material for sealing has a laser absorption ability so that it may mention later.
  • the sealing layer 4 may be a material layer formed by locally irradiating a laser beam to a layer obtained by baking such a sealing glass material having laser absorption ability, and melting and solidifying the sealing glass material. preferable.
  • a plurality of spacers 6 are arranged for maintaining a desired gap. The spacer 6 is fixed to the surface 2a of the first glass plate 2, for example.
  • a low emissivity film 7 is formed on the surface 3 a of the second glass plate 3.
  • a first sealing region 8 is provided in the outer peripheral region of the surface 2 a of the first glass plate 2.
  • a second sealing region 9 corresponding to the first sealing region 8 is provided in the outer peripheral region of the surface 3 a of the second glass plate 3.
  • the first and second sealing regions 8 and 9 are regions for forming the sealing layer 4 (that is, the region for forming the sealing material layer for the first sealing region 8).
  • the sealing layer 4 is a melt in which the sealing material layer 10 formed in the sealing region 8 of the first glass plate 2 is melted with a laser beam and fixed to the sealing region 9 of the second glass plate 3. It consists of a solidified layer.
  • a frame-shaped sealing material layer 10 is formed in the sealing region 8 of the first glass plate 2 used for producing the multilayer glass 1.
  • the sealing material layer 10 formed in the sealing region 8 of the first glass plate 2 is melted and fixed to the sealing region 9 of the second glass plate 3 by the heat of the laser beam, so that the first A sealing layer 4 for vacuum-sealing the gap between the glass plate 2 and the second glass plate 3 (that is, the interval between the internal spaces 5) is formed.
  • the sealing material layer 10 is made of a material layer formed by baking a sealing glass material.
  • the glass material for sealing contains a sealing glass (glass frit) made of a low melting point glass as an essential component, and an inorganic filler such as a laser absorber or a low expansion filler as an optional component.
  • the glass material for sealing may contain other additives other than these as required.
  • Other additives include inorganic fillers other than laser absorbers and low expansion fillers. However, other additives shall exclude components that disappear during firing.
  • the combination and blending amount of the glass materials for sealing are selected in consideration of compatibility with the glass plates 2 and 3.
  • the content of the sealing glass in the sealing glass material is preferably 50 to 100% by volume.
  • the content of the inorganic filler as an optional component is preferably 0 to 50% by volume.
  • content of sealing glass 60 volume% or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 97% by volume or less, and more preferably 90% by volume or less in consideration of the adjustment of the thermal expansion coefficient with respect to the glass plates 2 and 3.
  • sealing glass for example, low-melting glass such as bismuth glass, tin-phosphate glass, vanadium glass, lead glass, and silica borate alkali glass is used.
  • sealing property adheresiveness
  • tin-phosphate glass vanadium glass
  • lead glass silica borate alkali glass
  • the bismuth glass as the sealing glass is a composition containing 70 to 90% Bi 2 O 3 , 1 to 20% ZnO, and 2 to 12% B 2 O 3 in terms of the following oxide-based mass ratio ( Basically, the total amount is preferably 100%). Since the glass formed of the three components Bi 2 O 3 , ZnO, and B 2 O 3 has properties such as transparency and low glass transition point, it serves as a main component (essential component) of the glass material for sealing. Suitable for sealing glass.
  • Bi 2 O 3 is a component that forms a glass network, and is preferably contained in the sealing glass in a range of 70 to 90% by mass.
  • the content of Bi 2 O 3 is less than 70% by mass, the softening temperature of the sealing glass is increased.
  • the content of Bi 2 O 3 exceeds 90% by mass, it becomes difficult to vitrify, it becomes difficult to produce glass, and the thermal expansion coefficient tends to be too high.
  • the Bi 2 O 3 content is more preferably in the range of 78 to 87% by mass.
  • ZnO is a component that lowers the thermal expansion coefficient and softening temperature, and is preferably contained in the range of 1 to 20% by mass in the sealing glass. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. If the content of ZnO exceeds 20% by mass, stability during molding of the sealed glass is lowered, devitrification is likely to occur, and glass may not be obtained. Considering the stability of glass production, the ZnO content is more preferably in the range of 7 to 12% by mass.
  • B 2 O 3 is a component that increases the range in which vitrification is possible by forming a glass skeleton, and is preferably contained in the sealing glass in the range of 2 to 12% by mass. If the content of B 2 O 3 is less than 2% by mass, vitrification becomes difficult. The content of B 2 O 3 is higher softening point exceeds 12 mass%. In consideration of the stability of the glass and the sealing temperature, the content of B 2 O 3 is more preferably in the range of 5 to 10% by mass.
  • the bismuth-based glass formed by the three components described above has a low glass transition point and is suitable for sealing glass, but Al 2 O 3 , CeO 2 , SiO 2 , Ag 2 O, WO 3 , MoO 3 , Nb 2 O 3 , Ta 2 O 5 , Ga 2 O 3 , Sb 2 O 3 , Li 2 O, Na 2 O, K 2 O, Cs 2 O, CaO, SrO, BaO, P 2 O 5 , SnO x ( x may be 1 or 2).
  • the content of any component is too large, the glass becomes unstable and devitrification may occur, or the glass transition point and softening point may increase, so the total content of any component is 10% by mass or less. Is preferred.
  • the lower limit of the total content of arbitrary components is not particularly limited, and an effective amount of optional components can be blended based on the content of addition.
  • Al 2 O 3 , SiO 2 , CaO, SrO, BaO and the like are components that contribute to glass stabilization, and the content is preferably in the range of 0 to 7% by mass.
  • Al 2 O 3 and BaO are excellent, and can be contained as the fourth component in the range of 0.1 to 7% by mass.
  • Li 2 O, Na 2 O, K 2 O, Cs 2 O and the like have an effect of lowering the softening temperature of the glass, and CeO 2 has an effect of stabilizing the fluidity of the glass.
  • the low expansion filler approximates the thermal expansion coefficient between the glass plates 2 and 3 and the sealing layer 4.
  • a low expansion filler is used to adjust the thermal expansion coefficient.
  • the low expansion filler is selected from the group consisting of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compounds, tin oxide compounds, and quartz solid solutions. It is preferable to use at least one selected from the above.
  • zirconium phosphate-based compound examples include (ZrO) 2 P 2 O 7 , NaZr 2 (PO 4 ) 3 , KZr 2 (PO 4 ) 3 , Ca 0.5 Zr 2 (PO 4 ) 3 , and NbZr (PO 4 ). 3 , Zr 2 (WO 3 ) (PO 4 ) 2 , and composite compounds thereof.
  • the content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing layer 4 which is a melt-solidified layer of the sealing glass material approaches the thermal expansion coefficient of the glass plates 2 and 3.
  • the low expansion filler is preferably contained in the range of 0 to 50% by volume with respect to the sealing glass material, although it depends on the thermal expansion coefficient of the sealing glass and the glass plates 2 and 3.
  • content of a low expansion filler exceeds 50 volume%, there exists a possibility that the fluidity
  • the lower limit of the content of the low expansion filler is not particularly limited, and is appropriately set according to the thermal expansion coefficients of the sealing glass and the glass plates 2 and 3.
  • the preferable lower limit of the content of the low expansion filler is 3% by volume or more, more preferably 10% by volume or more.
  • the laser absorbing material is a filler that enhances the ability of the sealing glass material to absorb laser light when the sealing glass material is heated by irradiating the laser beam.
  • a laser absorber at least one metal (including an alloy) selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu, or an oxide containing at least one metal of the metal, Ni At least one compound such as —Mn—Fe—Co—O, Co—Cr—Fe—O, and Cu—Cr—Mn—O is used.
  • the laser absorbing material may be a pigment other than these.
  • the content of the laser absorber in the sealing glass material is preferably in the range of 0.1 to 40% by volume.
  • content of the laser absorber exceeds 40% by volume, the fluidity at the time of melting of the glass material for sealing is lowered, and there is a possibility that the sealing cannot be performed satisfactorily.
  • content of a laser absorber 25 volume% or less is more preferable, More preferably, it is 20 volume% or less.
  • the first and second glass plates 2 and 3 are made of low expansion glass.
  • the low expansion glass constituting the first and second glass plates 2 and 3 has a thermal expansion coefficient of 55 ⁇ 10 ⁇ 7 / ° C. or less (thermal expansion coefficient in a temperature range of 0 to 300 ° C., and so on). Is preferred.
  • Examples of such low expansion glass include one selected from the group consisting of borosilicate glass, aluminoborosilicate glass, alkali-free aluminoborosilicate glass, alkali-free aluminosilicate glass, quartz glass, and crystallized glass. .
  • the 1st glass plate 2 and the 2nd glass plate 3 consist of the same kind or different kind of low expansion glass.
  • first and second glass plates 2 and 3 By constructing the first and second glass plates 2 and 3 with low expansion glass, a multilayer such as a temperature difference between the interior and the exterior when the multilayer glass 1 is applied to a window glass of a building such as a house or a building. The stress generated based on the temperature difference between the inside and outside of the glass 1 can be reduced.
  • the first glass plate 2 is disposed on the high temperature side (for example, the indoor side in a cold region and the outdoor side in a warm region where the temperature rises in summer), and the second glass plate 3 is disposed on the low temperature side (for example, a cold region).
  • the double-glazed glass 1 is based on the temperature difference between the inside and outside (temperature difference between the inside and outside), etc. A difference arises in the expansion amount of the plate 2 and the second glass plate 3. For this reason, although the curvature which the 2nd glass plate 3 becomes concave shape arises in the multilayer glass 1, the 1st and 2nd glass plates 2 and 3 are comprised by low expansion glass. The amount of warpage of the multi-layer glass 1, and further the warpage and stress due to repetition thereof can be reduced.
  • the multilayer glass 1 having the first and second glass plates 2 and 3 made of low expansion glass the adhesion between the glass plates 2 and 3 and the sealing layer 4 due to repeated warping and stress described above.
  • production of a crack, a crack, etc. of an interface and the sealing layer 4 can be suppressed over a long period of time. That is, it becomes possible to provide the multilayer glass 1 having excellent long-term reliability.
  • permit can be expanded by reducing the stress which generate
  • the allowable range for the temperature difference between the inside and outside of the double-glazed glass 1 is Can be spread.
  • the long-term reliability of the multi-layer glass 1 can be maintained even when the multi-layer glass 1 is installed in an environment where the temperature difference between the room and outside is, for example, 50 ° C. or more.
  • the first and second glass plates 2 and 3 have a coefficient of thermal expansion of 55 ⁇ 10 ⁇ 7 / ° C. or less in order to reduce stress due to the above-described temperature difference between the inside and outside of the room and the warp of the multilayer glass 1. It is preferable to comprise with the low expansion glass which has. By applying the low expansion glass having such a thermal expansion coefficient, it is possible to reduce stress based on the temperature difference between inside and outside of the multilayer glass 1 and warpage with good reproducibility. However, if the thermal expansion coefficient of the glass plates 2 and 3 becomes too small, the difference in thermal expansion from the glass material for sealing increases, and conversely, the stress generated in the vicinity of the sealing layer 4 may increase.
  • the thermal expansion coefficients of the glass plates 2 and 3 are preferably 20 ⁇ 10 ⁇ 7 / ° C. or more.
  • board thickness of the 1st and 2nd glass plates 2 and 3 is adjusted so that it may mention later, it is not this limitation.
  • the thicknesses of the first and second glass plates 2 and 3 are preferably in the range of 0.5 mm to 6 mm, respectively. If the thickness of the glass plates 2 and 3 is less than 0.5 mm, the strength and reliability of the multilayer glass 1 may be insufficient. On the other hand, when the thickness of the glass plates 2 and 3 exceeds 6 mm, not only the multi-layer glass 1 becomes heavy, but also warpage and stress based on the temperature difference between the inside and outside may increase. Considering the weight and reliability of the multilayer glass 1, the thickness of the glass plates 2 and 3 is more preferably 1 mm to 5 mm, still more preferably 2 mm to 5 mm.
  • the thickness T2 of the second glass plate 3 is the thickness T1 of the first glass plate 2.
  • Thinner (T2 ⁇ T1) is preferred.
  • the thickness T1 of the first glass plate 1 is in the range of 2 mm to 5 mm
  • the thickness T2 of the second glass plate 3 is different from the thickness T1 of the first glass plate 2 (T1 -T2) is preferably 1 mm to 4 mm.
  • the difference (T1 ⁇ T2) between the thickness T1 of the first glass plate 2 and the thickness T2 of the second glass plate 3 is more preferably 2 mm or more.
  • the thickness difference (T1 ⁇ T2) between the two glass plates 3 is preferably 4 mm or less.
  • board thickness ratio (T2 / T1) of the 1st glass plate 2 and the 2nd glass plate 3 0.2 or more and 0.8 or less are preferable.
  • the thermal expansion coefficient of the glass plates 2 and 3 is preferably 20 ⁇ 10 ⁇ 7 / ° C. or more.
  • the pressure of the internal space 5 of the multilayer glass 1, that is, the internal space 5 formed in the gap between the first glass plate 2 and the second glass plate 3 is appropriately determined according to the characteristics required for the multilayer glass 1. Although set, it is preferable that the vacuum state of 1.0 Pa or less is maintained. Thereby, the favorable heat insulation characteristic by the multilayer glass 1 can be obtained.
  • the pressure in the internal space 5 is more preferably 0.1 Pa or less. According to the double-glazed glass 1 according to the first embodiment, the inner space 5 in a higher vacuum state can be obtained as is apparent from the manufacturing process described later. That is, it becomes possible to provide the double-glazed glass 1 having excellent heat insulating properties.
  • the spacer 6 described above is preferably disposed, although it depends on the size of the multilayer glass 1 and the like. Thereby, the shape of the internal space 5 which is in a vacuum state such as 1.0 Pa or less can be stably maintained.
  • the spacer 6 is formed of, for example, a glass column, a resin column, or the like having a columnar shape, a prismatic shape, a ball shape, or the like. As will be described later, the spacer 6 is preferably formed of a glass column in consideration of the firing conditions at the time of forming the sealing material layer 10.
  • the spacer 6 made of a glass column can be formed, for example, by applying and baking glass frit paste. For example, as shown in FIG.
  • the spacers 6 are preferably provided so as to be scattered in a predetermined pattern in the internal space 5 of the multilayer glass 1.
  • the number and arrangement interval of the spacers 6 are appropriately set depending on the size of the multilayer glass 1, the pressure in the internal space 5, and the like.
  • the spacer 6 is not fixed to the surface 3a of the second glass plate 3, It is preferable that the first glass plate 2 is fixed only to the surface 2a.
  • the spacer 6 by fixing the spacer 6 only to the surface 2 a of the first glass plate 2, it is possible to further reduce the stress based on the temperature difference between inside and outside of the multilayer glass 1, warpage, and the like. That is, tensile stress is generated in the second glass plate 3 arranged on the low temperature side, but it can be freely deformed by not being fixed to the spacer 6. The stress based on it can be made still smaller. Therefore, the long-term reliability of the multilayer glass 1 can be further improved.
  • the gap between the first glass plate 2 and the second glass plate 3 (that is, the gap of the internal space 5) takes into consideration the thermal conductivity of the multi-layer glass 1, the formability of the sealing layer 4, and the like. It is preferably 30 ⁇ m or less, and more preferably 15 ⁇ m or less. That is, by narrowing the gap between the first glass plate 2 and the second glass plate 3, the sealing material layer 10 can be easily melted uniformly with the laser beam. Accordingly, it becomes possible to improve the formability of the sealing layer 4, the adhesiveness with the glass plates 2 and 3, and the reliability thereof. Further, the lower limit of the gap between the first glass plate 2 and the second glass plate 3 is not particularly limited, but is preferably 5 ⁇ m or more from the viewpoint of ensuring the heat insulating property of the multilayer glass.
  • the low emissivity film 7 is formed on the surface 3a of the second glass plate 3 disposed on the low temperature side, for example.
  • Various known materials can be used for the low emissivity film (Low-E film) 7.
  • the Low-E film is formed by laminating a dielectric layer and a metal layer on a base material (for example, a glass plate). (For example, see Japanese Patent Application Laid-Open No. 2000-229378 and Japanese Patent Publication No. 08-032436).
  • base material / dielectric layer / metal layer / dielectric layer “base material / dielectric layer / dielectric layer / metal layer / dielectric layer”, “base material / dielectric layer / metal layer / dielectric” Body layer / metal layer / dielectric layer ”,“ substrate / dielectric layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ substrate / dielectric layer / metal layer / dielectric ” Body layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ substrate / dielectric layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ” Or the like.
  • the dielectric layer present between the base material and the metal layer closest to the base material may be one layer or two or more layers.
  • the dielectric layer on the metal layer may be one layer or two or more layers.
  • a metal oxide layer is generally used, and tin oxide, zinc oxide, titanium oxide and the like are typical.
  • Typical examples of the metal layer are gold and silver.
  • the metal layer is silver, it may be 100% silver, or may be added with 3 atomic% or less of palladium.
  • the low emissivity film 7 is preferably formed inside the sealing region 9 so as not to impair the formability of the sealing layer 4.
  • the gap between the first glass plate 2 and the second glass plate 3 is the same as the surface of the low emissivity film and the first glass plate.
  • the distance from the glass plate surface In the above example, an example in which a low emissivity film is formed on the surface of the second glass plate (the surface on the gap side of the multilayer glass) is shown, but depending on the specification mode of the multilayer glass, the first A low emissivity film may be formed on the surface of the glass plate (the surface on the gap side of the multi-layer glass), or on both surfaces of the surface on the gap side of the multi-layer glass of the first and second glass plates May be.
  • the second glass plate is arranged on the low temperature side.
  • the above-described low emissivity film may be formed on either the first glass plate or the second glass plate, or may be formed on both in some cases.
  • the multi-layer glass 1 of the first embodiment is produced, for example, as follows. First, as shown in FIG. 2A, the sealing material layer 10 is formed in the sealing region of the surface 2 a of the first glass plate 2.
  • the sealing material layer 10 is made of a sealing glass material paste prepared by mixing a sealing glass, which is an essential component of a sealing glass material, and an inorganic filler, which is an optional component, with a vehicle. After being applied to the surface 2a of the film, it is formed by drying and baking.
  • a spacer glass paste prepared by mixing sealing glass with a vehicle is applied to the surface 2a of the first glass plate 2 with a predetermined coating pattern. After that, the spacer 6 is formed by drying and baking.
  • the vehicle is obtained by dissolving a resin as a binder component in a solvent.
  • resins for vehicles include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, An organic resin such as an acrylic resin obtained by polymerizing at least one acrylic monomer such as 2-hydroxyethyl acrylate is used.
  • terpineol, butyl carbitol acetate, ethyl carbitol acetate or the like is used in the case of a cellulose resin, and methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate or the like is used in the case of an acrylic resin.
  • the viscosity of the glass material paste for sealing and the glass paste for spacers may be adjusted to the viscosity corresponding to the device applied to the first glass plate 2, the ratio of the resin and solvent, the ratio of the glass material for sealing and the vehicle, It can be adjusted according to the type of sealing glass and the type of vehicle.
  • the resin is a component that disappears upon firing. You may add a well-known additive with a glass paste like a defoamer and a dispersing agent to the glass material paste for sealing, or the glass paste for spacers. These additives are also components that usually disappear during firing. A known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of each paste.
  • the glass material paste for sealing is apply
  • the glass material paste for sealing is applied by applying a printing method such as screen printing or gravure printing, or is applied using a dispenser or the like.
  • the width of the coating film is preferably 0.5 mm to 20 mm in order to maintain strength.
  • the thickness of the coating film is set according to the distance between the first glass plate 2 and the second glass plate 3 and can be set in consideration of the shrinkage of the film in the subsequent drying process or pre-baking process. preferable.
  • a coating film of the glass paste for spacers is formed on the surface 2 a of the first glass plate 2.
  • the coating film of the glass material paste for sealing and the glass paste for spacers is preferably dried at a temperature of 60 to 150 ° C. for 30 seconds to 10 minutes, for example, to remove the solvent in the coating film. Subsequently, after heating to a temperature 30 ° C. or more lower than the glass transition point of the sealing glass in a baking furnace to remove the binder component and the like in the coating film, the temperature above the softening point of the sealing glass (for example, the temperature of the softening point).
  • the glass material for sealing and the glass frit for spacers are baked on the first glass plate 2 by heating to a surface 2a of the first glass plate 2 to a frame-like sealing material layer. 10 and spacer 6 are formed.
  • the formation process of the sealing material layer 10 and the spacer 6 may be performed simultaneously or separately.
  • the glass transition point is defined by the temperature of the first inflection point of differential thermal analysis (DTA)
  • the glass softening point is defined by the temperature of the fourth inflection point of differential thermal analysis (DTA).
  • a low emissivity film 7 is formed on the surface 3a of the second glass plate 3 as necessary.
  • the low emissivity film 7 may be formed in a desired shape excluding the region where the sealing layer 4 is formed, or a low emissivity film is formed on the entire surface 3a of the second glass plate 3 in advance. Thereafter, a region where the sealing layer 4 is formed may be trimmed to have a desired shape.
  • the first glass plate 2 and the second glass plate 3 are placed in the vacuum chamber 11, and the inside of the vacuum chamber 11 is exhausted to a desired vacuum state.
  • the first glass plate 2 and the second glass plate 3 are laminated so that the first surface 2a having the sealing material layer 10 and the spacer 6 and the surface 3a having the low emissivity film 7 face each other.
  • the sealing material layer 10 is irradiated with the laser beam 12 through the second glass plate 3 (or the first glass plate 2).
  • the laser beam 12 is irradiated while scanning along the sealing material layer 10.
  • the laser light is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used.
  • the sealing material layer 10 is melted in order from the portion irradiated with the laser beam 12 scanned along the sealing material layer 10, and is rapidly solidified at the end of the irradiation of the laser beam 12 to be fixed to the second glass plate 3. Then, by irradiating the entire circumference of the sealing material layer 10 with the laser beam 12, the space between the first glass plate 2 and the second glass plate 3 is hermetically sealed as shown in FIG.
  • the sealing layer 4 is formed. Since the laser beam 12 is irradiated in the vacuum chamber 11 in a desired vacuum state, the gap between the first glass plate 2 and the second glass plate 3 is kept in the vacuum state in the vacuum chamber 11. Hermetic sealing is performed in a state where the pressure is maintained (for example, 1 Pa or less).
  • the multi-layer glass 1 having the internal space 5 maintained in a desired vacuum state can be obtained. Since the sealing layer 4 made of a material obtained by melting and solidifying the sealing material layer 10 with the laser beam 12 is excellent in airtightness, the internal space 5 having a vacuum state corresponding to the vacuum pressure of the vacuum chamber 11 can be obtained with good reproducibility. The internal space 5 having such a vacuum state can be maintained for a long period of time.
  • the internal space 5 of the multilayer glass 1 according to the first embodiment can be in a vacuum state such as 1.0 Pa or less, and further 0.1 Pa or less. Furthermore, since the laser beam 12 is irradiated in the vacuum chamber 11, there is no need for a through hole or the like for evacuating the internal space later. Since the through-hole and the suction part attached to the through-hole cause a reduction in the strength of the double-glazed glass, the reliability of the double-glazed glass 1 can be improved.
  • the heating temperature of the sealing material layer 10 by the laser beam 12 is set to be equal to or higher than the softening point of the sealing glass.
  • the heating temperature is preferably (T + 200 ° C.) or more and (T + 800 ° C.) or less, for example, with respect to the softening point temperature T (° C.) of the sealing glass.
  • T softening point temperature
  • low expansion glass such as borosilicate glass, alumino borosilicate glass, quartz glass, and crystallized glass has a smaller distortion than soda lime glass.
  • the formability of the sealing layer 4 can be improved by increasing the uniform meltability of the glass. It is also effective to reduce the thickness of the sealing material layer 10.
  • FIG. 7 is a cross-sectional view showing the structure of the multilayer glass according to the second embodiment.
  • FIG. 8 is a cross-sectional view showing a process for producing a multilayer glass according to the second embodiment.
  • the double-layer glass 21 shown in these drawings is similar to the first sealing layer (sealing resin layer) 22 made of a material obtained by solidifying the sealing resin material and the sealing layer 4 in the first embodiment.
  • a second sealing layer (sealing glass layer) 23 made of a material obtained by melting and solidifying a sealing glass material.
  • the first sealing layer (sealing resin layer) 22 is provided on the outer peripheral side of the second sealing layer (sealing glass layer) 23.
  • Other configurations are the same as those in the first embodiment.
  • the multi-layer glass 21 of the second embodiment is produced as follows, for example. First, as shown to Fig.8 (a), in the sealing area
  • the 2nd sealing material layer 25 is formed in the sealing area
  • the spacer 6 is formed in the same manner as in the first embodiment simultaneously with the formation of the second sealing material layer 25 or separately from the formation of the second sealing material layer 25.
  • the first sealing material layer 24 is applied by applying a resin composition paste containing an ultraviolet curable resin such as an acrylate resin or an epoxy resin by applying a printing method such as screen printing or gravure printing, or a dispenser. Etc. are applied and formed.
  • the resin composition paste is applied to the outer peripheral side of the second sealing material layer 25 and subjected to ultraviolet treatment as necessary.
  • an ultraviolet curable resin composition is used as the material for forming the first sealing material layer 24, an ultraviolet treatment or the like may be performed before the sealing treatment to make it semi-cured.
  • an ultraviolet treatment or the like may be performed before the sealing treatment to make it semi-cured.
  • the 1st sealing material layer 24 which consists of resin materials for sealing on the outer peripheral side of the sealing area
  • the sealing material layer 25 is formed.
  • a low emissivity film 7 is formed on the surface 3a of the second glass plate 3 as necessary (FIG. 8B).
  • the low emissivity film 7 may be formed in a desired region excluding the region where the sealing layer 4 of the second glass plate 3 is formed, or may be formed on the entire surface of the second glass plate 3 in advance.
  • An emissivity film may be formed, and a region where the sealing layer 4 is formed may be trimmed to form a low emissivity film 7 having a desired shape.
  • FIG. 8C the first glass plate 2 and the second glass plate 3 are disposed in the vacuum chamber 11, and the inside of the vacuum chamber 11 is evacuated to a desired vacuum state.
  • the first glass plate 2 and the second glass plate 3 are laminated so that the first surface 2a having the sealing material layers 24 and 25 and the spacer 6 and the surface 3a having the low emissivity film 7 face each other. To do. Then, in the vacuum chamber 11 in a predetermined vacuum state, the first sealing material layer 24 is cured by ultraviolet treatment to form the first sealing layer 22.
  • the laminate of the first glass plate 2 and the second glass plate 3 on which the first sealing layer (sealing resin layer) 22 is formed is placed in an air atmosphere.
  • the second sealing material layer (sealing glass material layer) 25 is irradiated with the laser beam 12 through the second glass plate 3 (or the first glass plate 2).
  • the laser beam 12 is irradiated in the same manner as in the first embodiment except that the laser beam 12 is irradiated in an air atmosphere.
  • the laser beam 12 is irradiated over the entire circumference of the second sealing material layer 25 to hermetically seal between the first glass plate 2 and the second glass plate 3 as shown in FIG. 2 sealing layers (sealing glass layers) 23 are formed.
  • the inside of the first sealing layer 22 is the vacuum in the vacuum chamber 11.
  • the pressure is maintained according to the state. Therefore, even if the laser beam 12 is irradiated to the second sealing material layer 25 disposed inside the first sealing layer 22 in the air atmosphere, the inner side of the second sealing layer 23 is not affected.
  • the space, that is, the internal space 5 of the multilayer glass 21 can be maintained in a desired vacuum state (for example, 10 Pa or less).
  • the 2nd sealing layer 23 is excellent in airtightness, the internal space 5 which has a desired vacuum state can be obtained with sufficient reproducibility, and also the internal space 5 which has such a vacuum state is maintained over a long period of time. it can.
  • Example 1 It has a composition of Bi 2 O 3 83.2%, B 2 O 3 5.6%, ZnO 10.7%, Al 2 O 3 0.5% in terms of mass ratio in terms of oxide, and further 150 ppm in mass ratio by weight of Na 2 O, an average particle diameter (D 50) 1.0 ⁇ m bismuth-based glass (softening point: 410 ° C.) and an average particle diameter (D 50) is cordierite of 4.3 ⁇ m as a low expansion Hama material A powder and a laser absorber having a composition of Fe 2 O 3 —CuO—MnO—Al 2 O 3 and an average particle diameter (D 50 ) of 1.2 ⁇ m were prepared.
  • Particle size distribution was measured using a particle size analyzer (Nikkiso Co., Ltd., Microtrac HRA) using a laser diffraction / scattering method.
  • the measurement conditions were as follows: measurement mode: HRA-FRA mode, Particle Transparency: yes, Special Particles: no, Particle Refractive index: 1.75, Fluid Refractive index: 1.33.
  • a glass material for sealing and a glass material for spacer were prepared by mixing 66.8% by volume of the bismuth-based glass, 32.2% by volume of cordierite powder, and 1.0% by volume of the laser absorber. 83% by mass of this glass material was mixed with 17% by mass of a vehicle prepared by dissolving 5% by mass of ethyl cellulose as a resin binder component in 95% by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. Thus, a glass paste for sealing and spacers was prepared.
  • a first glass plate (dimensions: 370 mm ⁇ 370 mm ⁇ 3 mm) made of borosilicate glass having a thermal expansion coefficient (0 to 300 ° C.) of 32.5 ⁇ 10 ⁇ 7 / ° C. is prepared.
  • the spacer glass paste was applied to the inner region of the sealing region with a desired printing pattern by a screen printing method to form a spacer coating layer, and then dried under conditions of 120 ° C. ⁇ 10 minutes.
  • the printing pattern of the spacers was arranged such that dots having a diameter of 0.25 mm were arranged in a range of 340 mm ⁇ 340 mm at intervals of 20 mm according to the spacer arrangement pattern.
  • this coating film is heated under conditions of 300 ° C. ⁇ 30 minutes to remove the resin binder component, and then baked under conditions of 480 ° C. ⁇ 10 minutes in an air atmosphere, whereby a spacer having a height of 12 ⁇ m. Formed.
  • the condition is 120 ° C. ⁇ 10 minutes. And dried.
  • This print pattern was a frame-like pattern of 340 mm ⁇ 340 mm with a line width of 0.5 mm.
  • the coating film is heated at 300 ° C. for 30 minutes to remove the resin binder component, and then fired in an air atmosphere at 480 ° C. for 10 minutes to seal the film thickness to 15 ⁇ m.
  • a material layer (sealing glass material layer) was formed.
  • “ZnO / Ag / ZnO / Ag / ZnO as a low emissivity film is formed on the surface of the second glass plate (a plate made of borosilicate glass having the same composition, shape, and dimensions as the first glass plate).
  • the film formation by the sputtering method was performed by masking so that the film did not adhere to the sealing region.
  • the masking tape was peeled off after film formation. Moreover, only the sealing area
  • the inside of the vacuum chamber was evacuated.
  • the first glass plate and the second glass plate were laminated.
  • the sealing material layer is irradiated with a laser beam (CW semiconductor laser) having a wavelength of 808 nm and an output of 16 W through the second glass plate at a scanning speed of 4 mm / second to melt and rapidly solidify the sealing material layer.
  • a sealing layer for vacuum-sealing the gap between the first glass plate and the second glass plate was formed.
  • the characteristics of the multilayer glass thus obtained were evaluated as follows.
  • Example 2 A multilayer glass was produced in the same manner as in Example 1 except that glass plates having a thermal expansion coefficient and a thickness as shown in Table 1 were used as the first and second glass plates. The characteristics and the like of these multilayer glasses were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.
  • Example 1 Comparative Example 1 Except for using glass plates (dimensions: 370 mm ⁇ 370 mm ⁇ 3 mm) made of soda lime glass having a thermal expansion coefficient (0 to 300 ° C.) of 85 ⁇ 10 ⁇ 7 / ° C. as the first and second glass plates.
  • a multilayer glass was produced in the same manner as in Example 1. The characteristics and the like of this multilayer glass were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.
  • Example 1 A multilayer glass was produced in the same manner as in Example 1 except that the distance (that is, the gap) between the first glass plate and the second glass plate was 200 ⁇ m. The characteristics and the like of this multilayer glass were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.
  • Comparative Example 2 A multilayer glass was produced in the same manner as in Comparative Example 1 except that the distance between the first glass plate and the second glass plate was 200 ⁇ m. The characteristics and the like of this multilayer glass were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.
  • the expression “low temperature side / vacuum layer / high temperature side” means “low temperature side (second glass plate) / vacuum layer / high temperature side (first glass plate)”.
  • the distance between the glass plates means “the gap between the first glass plate and the second glass plate”.
  • Example 7 A first glass plate (dimensions: 370 mm ⁇ 370 mm ⁇ 3 mm) made of borosilicate glass having a thermal expansion coefficient (0 to 300 ° C.) of 32.5 ⁇ 10 ⁇ 7 / ° C. is prepared.
  • a spacer and a second sealing material layer made of a sealing glass material were formed.
  • the 1st sealing material layer which consists of a resin material for sealing was formed by apply
  • Example 2 borosilicate glass having the same composition, shape, and dimensions as the first glass plate
  • the glass plate is disposed in the vacuum chamber so that the first surface 2a having the sealing material layer, the spacer, and the sealing resin material, and the surface 3a having the low emissivity film are opposed to each other.
  • the inside of the vacuum chamber was evacuated. After the pressure in the vacuum chamber reached 0.1 Pa, the first glass plate and the second glass plate were laminated. And the 1st sealing layer (sealing resin layer) was formed by performing an ultraviolet curing process in a vacuum chamber.
  • a laser beam (CW semiconductor laser having a wavelength of 808 nm and an output of 18 W is applied to the second sealing material layer through the second glass plate. )
  • the second sealing material layer is melted and rapidly cooled and solidified to vacuum seal the gap between the first glass plate and the second glass plate.
  • a sealing layer (sealing glass layer) was formed.
  • the characteristics of the multilayer glass thus obtained were evaluated in the same manner as in Example 1. As a result, the amount of warpage of the glass plate when it was made into a multilayer glass was not deteriorated.
  • the spacer is formed with the glass material paste, but a spherical spacer such as silica particles may be used. More specifically, silica particles having a particle diameter of about 10 ⁇ m that are widely used for liquid crystal displays can be used.
  • the low expansion glass is applied to the first and second glass plates, it is possible to reduce stress based on the temperature difference between the inside and outside of the multilayer glass, such as the temperature difference between the inside and outside, and therefore It is possible to provide a multilayer glass having excellent long-term reliability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention porte sur un double vitrage qui a une fiabilité à long terme améliorée par réduction de la contrainte sur la base de la différence de température entre l'intérieur et l'extérieur d'une pièce. Le double vitrage (1) comprend une première plaque de verre (2) et une seconde plaque de verre (3) qui sont disposées à une distance prédéterminée l'une de l'autre. L'espace entre la première plaque de verre (2) et la seconde plaque de verre (3) est scellé sous vide par une couche de scellement (4) qui est formée d'une matière obtenue par fusion et solidification d'une matière de verre de scellement qui a une aptitude à l'absorption laser. Les première et seconde plaques de verre (2, 3) sont formées de verre à faible dilatation.
PCT/JP2012/067231 2011-07-08 2012-07-05 Double vitrage et son procédé de fabrication WO2013008724A1 (fr)

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JP2016088775A (ja) * 2014-10-30 2016-05-23 パナソニックＩｐマネジメント株式会社 ガラスパネルユニットの製造方法
WO2017095784A1 (fr) * 2015-11-30 2017-06-08 Corning Incorporated Soudage au laser de vitres transparentes à l'aide d'un revêtement à faible émissivité
WO2017170379A1 (fr) * 2016-03-31 2017-10-05 パナソニックＩｐマネジメント株式会社 Procédé de production d'unités de panneaux de verre, procédé de production de monture, dispositif de production d'unités de panneaux de verre et unité de panneau de verre
WO2018211176A1 (fr) 2017-05-19 2018-11-22 Primoceler Oy Procédé et appareil de production d'un joint hermétique sous vide à basse température
WO2019145332A1 (fr) * 2018-01-23 2019-08-01 Agc Glass Europe Unité de vitrage isolant sous vide asymétrique
WO2019207971A1 (fr) * 2018-04-26 2019-10-31 パナソニックＩｐマネジメント株式会社 Unité de panneau en verre, produit semi-fini d'unité de panneau en verre, produit assemblé d'unité de panneau en verre, et procédé de fabrication d'unité de panneau en verre
WO2019219590A1 (fr) * 2018-05-14 2019-11-21 Agc Glass Europe Unité de vitrage isolant sous vide asymétrique
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WO2020002134A1 (fr) * 2018-06-29 2020-01-02 Vkr Holding A/S Unité de vitrage isolée sous vide présentant une distance de séparation entre un joint latéral et un revêtement à faible émissivité, et procédés de fabrication associés de cette dernière
JP2020507544A (ja) * 2017-02-06 2020-03-12 ショット ジェムトロン コーポレイションＳＣＨＯＴＴ Ｇｅｍｔｒｏｎ Ｃｏｒｐｏｒａｔｉｏｎ 不均一なコーティング層およびガス分子の封止されたキャビティを有する断熱ガラス積層体
CN111688303A (zh) * 2020-05-11 2020-09-22 湖南盾神科技有限公司 一种非对称型真空玻璃组成的复合安全玻璃结构
WO2020203012A1 (fr) * 2019-03-29 2020-10-08 パナソニックＩｐマネジメント株式会社 Unité panneau de verre et fenêtre vitrée
JPWO2020209371A1 (fr) * 2019-04-10 2020-10-15
CN112513399A (zh) * 2018-05-14 2021-03-16 旭硝子欧洲玻璃公司 非对称真空隔热玻璃窗单元
US10988973B2 (en) 2015-09-29 2021-04-27 Panasonic Intellectual Property Management Co., Ltd. Glass panel unit, glass window provided with same, and method for manufacturing glass panel unit
JP2022525784A (ja) * 2019-03-19 2022-05-19 エージーシー グラス ユーロップ 非対称真空断熱グレージングユニット

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JP2016088775A (ja) * 2014-10-30 2016-05-23 パナソニックＩｐマネジメント株式会社 ガラスパネルユニットの製造方法
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