WO2021038907A1 - Panneau de verre multicouche isolé sous vide - Google Patents

Panneau de verre multicouche isolé sous vide Download PDF

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Publication number
WO2021038907A1
WO2021038907A1 PCT/JP2020/003919 JP2020003919W WO2021038907A1 WO 2021038907 A1 WO2021038907 A1 WO 2021038907A1 JP 2020003919 W JP2020003919 W JP 2020003919W WO 2021038907 A1 WO2021038907 A1 WO 2021038907A1
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WO
WIPO (PCT)
Prior art keywords
glass
glass substrate
vacuum
double glazing
insulated double
Prior art date
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PCT/JP2020/003919
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English (en)
Japanese (ja)
Inventor
孝 内藤
信一 立薗
裕司 橋場
貴弘 五十幡
恵太 湧口
功幹 阿部
竜也 三宅
大剛 小野寺
拓也 青柳
Original Assignee
昭和電工マテリアルズ株式会社
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Publication of WO2021038907A1 publication Critical patent/WO2021038907A1/fr

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    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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
    • 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
    • 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
    • E06B3/663—Elements for spacing panes
    • 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
    • E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
    • 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
    • E06B3/677—Evacuating or filling the gap between the panes ; Equilibration of inside and outside pressure; Preventing condensation in the gap between the panes; Cleaning the gap between the panes
    • 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 vacuum insulated double glazing panel.
  • a space is provided by installing a large number of spacers between two glass substrates, and the space is made into a vacuum state and the vacuum state is made.
  • the edges of the two glass substrates are hermetically sealed for long-term retention.
  • a sealing material containing low melting point glass and low thermal expansion filler particles is applied to the airtight sealing of the peripheral portion.
  • windowpanes having significantly higher heat insulating properties than conventional double glazing panel windows are required.
  • the inside of the panel has a high heat insulating property in the order of an air layer, an argon layer, and a vacuum layer, and these thermal transmission rates are in the range of 3.0 to 1.4 W / m 2 ⁇ K.
  • the window glass ZEH and ZEB 0.7W / m 2 ⁇ K or less, depending on the country or region has been required following 0.4W / m 2 ⁇ K.
  • Tempered glass is hard to deform and break, so it is suitable for high vacuum inside the double glazing window.
  • it is necessary to increase the number of spacers in order to maintain the internal space of the double glazing panel with increasing vacuum, but it is not necessary to increase it with tempered glass, and it can be expected that it can be reduced. ..
  • a metal such as stainless steel is used as the material of the spacer, but increasing the number of spacers may increase the thermal transmission coefficient of the panel due to heat transfer by the spacer.
  • the use of tempered glass is effective for preventing damage due to high vacuum and for safety and security against crime.
  • Tempered glass is intended to have high strength by forming a compression strengthening layer on the glass surface, but when heated to 320 ° C. or higher, the strengthening layer is reduced, resulting in a large decrease in strength. Further, even if the temperature is less than 320 ° C., the strength may decrease depending on the heating conditions such as the holding time. Therefore, it is preferable to heat-treat at a temperature as low as possible. Therefore, when tempered glass is used for panel glass (glass substrate), it is necessary to seal it at least below 320 ° C.
  • the sealing temperature is as high as 400 ° C or higher, so it is difficult to apply it to vacuum-insulated double glazing panels using tempered glass.
  • lead-based low melting point glass contains a large amount of lead designated as a prohibited substance under the RoHS Directive, so it is environmentally friendly. , It is not preferable to apply it to a vacuum insulated double glazing panel.
  • such a decrease in the sealing temperature may change the material of the spacer from the conventional metal to the resin having low thermal conductivity. If the number of resin spacers is increased, the increase in thermal transmission rate is very small.
  • the spacer since the resin spacer is softer than the metal spacer, even if the inside of the panel is evacuated, the spacer prevents damage due to friction of the panel glass (glass substrate), resulting in higher reliability and safety. It has the potential to provide vacuum insulated double glazing panels. If the resin spacer is crushed by high vacuum and is greatly deformed, filler particles of glass or ceramics may be mixed in the resin.
  • the sealing temperature can be lowered, it is considered that the manufacturing tact of the vacuum-insulated double glazing panel, which is difficult to rapidly heat and quench, can be shortened, and the investment amount for introducing mass production equipment can be reduced. As a result, there is a possibility that a vacuum-insulated double glazing panel can be manufactured at low cost, and it is considered that it will be easily spread all over the world.
  • the vacuum-insulated double glazing panel has a great merit if it can be manufactured at a low temperature of less than 320 ° C., that is, if the peripheral portion of the panel can be airtightly sealed at a low temperature of less than 320 ° C. , A lead-free encapsulating material capable of realizing this and a lead-free low melting point glass used for the material are strongly desired.
  • Patent Document 1 contains an Ag 2 O and V 2 O 5 and TeO 2 as the main component, and the total content of 75 mass% or more, the balance being P 2 O 5, BaO, K 2 O, WO
  • a lead-free glass composition containing at least one of 3 , Fe 2 O 3 , MnO 2 , Sb 2 O 3, and ZnO is disclosed. From Patent Document 1, this lead-free glass composition has a softening point of 320 ° C. or less obtained from the second endothermic peak temperature of differential thermal analysis (DTA), and a sample obtained as an example in which a desired result can be obtained has a softening point. It can be read that the temperature is 268 ° C or higher. Further, Patent Document 1 describes a glass frit containing this lead-free glass composition, a sealing glass paste, a conductive glass paste, and electrical and electronic parts using these.
  • DTA differential thermal analysis
  • the sealing temperature should be less than 320 ° C in order to improve heat insulation by increasing vacuum, reduce manufacturing costs by improving mass productivity and capital investment costs, and improve safety. It is necessary to keep the temperature as low as possible.
  • the lead-free glass composition disclosed in Patent Document 1 can be applied as the glass phase of the sealing portion of the vacuum-insulated double glazing panel, sealing at less than 320 ° C. is possible.
  • this lead-free low-melting point glass has high airtightness and reliability due to insufficient adhesiveness and adhesion to a pair of glass substrates (panel glass) used for a vacuum-insulated double glazing panel.
  • a sealing part could not be obtained, and improvement was required.
  • An object of the present invention is that highly reliable airtight sealing is possible at a low temperature of less than 320 ° C., and the manufacturing cost is improved by improving the heat insulating property by increasing the vacuum of the internal space, improving mass productivity, and reducing the capital investment cost. It is an object of the present invention to provide a vacuum-insulated double glazing panel which realizes reduction of the amount of glass and improvement of safety.
  • the vacuum-insulated multilayer glass panel of the present invention includes a first glass substrate and a second glass substrate, and a spacer and a sealing portion are sandwiched between the first glass substrate and the second glass substrate.
  • the sealing portion is provided on the peripheral portion of the first glass substrate and the second glass substrate, the spacer is arranged in the space surrounded by the first glass substrate, the second glass substrate and the sealing portion, and the space is depressurized.
  • the sealed portion contains a low melting point glass phase, the low melting point glass phase contains vanadium oxide, tellurium oxide and lithium oxide, and the second heat absorption peak temperature by differential thermal analysis is 300 ° C. or less. ..
  • FIG. 1A It is a schematic perspective view which shows the typical vacuum insulation double glazing panel. It is sectional drawing of FIG. 1A and the enlarged sectional view of the airtight sealing part which is a part thereof. It is a schematic perspective view which shows a part of the manufacturing method of a vacuum insulation double glazing panel. It is an enlarged cross-sectional view which shows the peripheral part of FIG. 2A. It is a schematic perspective view which shows a part of the manufacturing method of a vacuum insulation double glazing panel. It is sectional drawing of FIG. 3A. It is the schematic sectional drawing which shows a part of the manufacturing method of the vacuum insulation double glazing panel. It is the schematic sectional drawing which shows a part of the manufacturing method of the vacuum insulation double glazing panel.
  • FIG. 5 is an enlarged cross-sectional view showing the vicinity of the sealing portion of FIG. 5A. It is the schematic sectional drawing which shows a part of the manufacturing method of the vacuum insulation double glazing panel.
  • FIG. 6 is an enlarged cross-sectional view showing the vicinity of the sealing portion of FIG. 6A. It is a graph which shows the temperature profile in the process of heating a sealing material paste applied to a glass substrate. It is a graph which shows the temperature profile in a vacuum exhaust sealing process. It is a graph which shows the result of the typical differential thermal analysis (DTA) peculiar to glass. It is a graph which shows the typical thermal expansion curve peculiar to glass.
  • DTA differential thermal analysis
  • the vacuum-insulated double glazing panel is applied to window glass for building materials and the like, and has a structure in which a large number of spacers are sandwiched between two glass substrates (panel glass). This maintains a gap between the two glass substrates (panel glass). Further, a sealing portion is provided on the peripheral edge of the two glass substrates. As a result, an internal space is formed inside the sealing portion as a sealed gap. This internal space is in a vacuum state, and is hermetically sealed by a sealing portion so that the vacuum state can be maintained for a long period of time.
  • the sealing portion is formed by using a sealing material containing a low melting point glass composition.
  • the distance between the two glass substrates (panel glass), that is, the height of the spacer and the thickness of the sealing portion is usually in the range of 100 to 300 ⁇ m.
  • soda lime glass SiO 2- Na 2 O-CaO-based glass having a coefficient of thermal expansion in the range of 85 ⁇ 10 -7 / ° C. to 90 ⁇ 10 -7 / ° C. is generally used.
  • the “vacuum state” refers to a state in which the pressure is reduced from the atmospheric pressure, preferably 10 -1 Pa or less, and more preferably 10 -2 Pa or less.
  • FIG. 1A shows the overall configuration of a typical vacuum-insulated double glazing panel.
  • the vacuum-insulated double glazing panel includes a first glass substrate 1, a second glass substrate 2, a spacer 3 sandwiched between them, and a sealing portion 4.
  • FIG. 1B is a cross-sectional view of FIG. 1A and an enlarged cross-sectional view of an airtight sealing portion that is a part thereof.
  • a space 5 (internal space) is formed between the first glass substrate 1 and the second glass substrate 2.
  • the space 5 is inside the sealing portion 4 formed on the peripheral edge of the panel, and its height is maintained by a large number of spacers 3.
  • a heat ray reflecting film 6 is formed on the inner surface of the second glass substrate 2.
  • the heat ray reflecting film 6 contributes to the improvement of heat insulating property.
  • the heat ray reflecting film 6 may also be provided on the inner surface of the first glass substrate 1.
  • the sealing portion 4 contains a low melting point glass phase 7.
  • the sealing portion 4 may have a structure in which the low thermal expansion filler particles 8 are dispersed in the low melting point glass phase 7.
  • the space 5 can be hermetically sealed and the vacuum state can be maintained for a long period of time.
  • the number of spacers 3 is affected by the degree of vacuum in the space 5, the thickness of the first glass substrate 1 and the second glass substrate 2, and the like. The higher the degree of vacuum and the thinner the plate, the more it is necessary to increase the number of spacers 3. Normally, the spacers 3 are installed at intervals of approximately 20 mm.
  • the low thermal expansion filler particles 8 have a function of adjusting so that the difference between the thermal expansion of the sealing portion 4 and the thermal expansion of the first glass substrate 1 and the second glass substrate 2 does not become large.
  • the coefficient of thermal expansion of the sealing portion 4 is about 15 to 20% smaller than the coefficient of thermal expansion of the first glass substrate 1 and the second glass substrate 2 so that the sealing portion 4 is not subjected to tensile stress. That is, about 70 ⁇ 10 -7 / ° C. is effective for a soda lime glass (SiO 2- Na 2 O-CaO based glass) substrate.
  • the sealing temperature for forming the sealing portion 4 airtightly is substantially determined by the softening flow characteristics of the low melting point glass phase 7 contained in the sealing portion 4 due to the heating temperature. That is, the lower the softening point of the low melting point glass phase 7 contained in the sealing portion 4, the lower the sealing temperature can be.
  • the low melting point glass phase 7 contains vanadium oxide (V 2 O 5 ), tellurium oxide (TeO 2 ) and lithium oxide (Li 2 O), and the difference of the low melting point glass phase 7 is
  • the second endothermic peak temperature by thermal analysis is 300 ° C. or lower.
  • the adhesiveness and adhesion of the low melting point glass phase 7 to the first glass substrate 1 and the second glass substrate 2 are remarkably improved, and the temperature is lower than 320 ° C., which is a desirable temperature when a tempered glass substrate is used. Airtight sealing is possible.
  • a tempered glass substrate can also contribute to the safety and security of vacuum-insulated double glazing panels because it can prevent damage and prevent crime due to high vacuum.
  • a resin having a low thermal conductivity can be adopted by lowering the sealing temperature.
  • a resin having high heat resistance that is, a resin that is not easily deformed at a temperature of less than 320 ° C. such as a polyimide resin is effective.
  • the spacer 3 When the spacer 3 is crushed and deformed by further increasing the vacuum of the space 5, it can be dealt with by dispersing inorganic filler particles, preferably spherical glass particles having low thermal conductivity, in the spacer 3 made of resin. ..
  • resin of the spacer 3 a fluororesin having high heat resistance and ultraviolet resistance, low moisture absorption and water absorption, and good slipperiness is particularly effective.
  • fluororesin polytetrafluoroethylene (PTFE) or the like is suitable.
  • lowering the sealing temperature can significantly improve the mass productivity of the vacuum-insulated double glazing panel and reduce the mass production capital investment, which can greatly contribute to the reduction of the manufacturing cost.
  • CO 2 emissions can be reduced, which can greatly contribute to global warming countermeasures.
  • the low melting point glass phase 7 of the sealing portion 4 has a tellurium oxide (TeO 2 ) content of 25 mol% or more and 42 mol% or less, and lithium oxide (Li 2).
  • the content of O) is preferably 3 mol% or more and 20 mol% or less.
  • the low melting point glass phase 7 satisfies the following two relational expressions (1) and (2) in terms of oxide.
  • the low melting point glass phase 7 further contains silver oxide as a glass component, and the second endothermic peak temperature by differential thermal analysis is 280 ° C. or lower.
  • the sealing portion 4 can be formed at a lower temperature of less than 300 ° C.
  • the content (mol%) of vanadium oxide, lithium oxide and silver oxide contained in the low melting point glass phase 7 preferably satisfies the following relational expression (3).
  • the low thermal expansion filler particles 8 are dispersed in the low melting point glass phase 7.
  • the low thermal expansion filler particles 8 are mixed to match the thermal expansion of the sealing portion 4 with the thermal expansion of the first glass substrate 1 and the second glass substrate 2. It is effective to use zirconium tungrate phosphate (Zr 2 (WO 4 ) (PO 4 ) 2 ) for the low thermal expansion filler particles 8.
  • Zirconium tungrate phosphate has a large negative coefficient of thermal expansion (-38 x 10-7 / ° C.) and a relatively high density (3.8 g / cm 3 ).
  • zirconium tungrate phosphate has good wettability and adhesion with the low melting point glass phase 7, it is easy to disperse in the low melting point glass phase 7, and the effect of low thermal expansion is large, and the sealing portion.
  • the effect that the thermal expansion of 4 can be easily matched with the thermal expansion of the first glass substrate 1 and the second glass substrate 2 can be obtained.
  • the present invention realizes highly reliable airtight sealing at a low temperature of less than 320 ° C., preferably less than 300 ° C., thereby improving heat insulation by increasing vacuum, improving mass productivity, and reducing capital investment costs. It is possible to provide a vacuum-insulated double glazing panel with reduced manufacturing cost and improved safety.
  • the sealing portion of the vacuum insulated double glazing panel according to the present invention contains low thermal expansion filler particles, and the low thermal expansion filler particles are zirconium tungrate phosphate (Zr 2 (WO 4 ) (PO 4). ) It is effective to include 2).
  • the vacuum-insulated double glazing panel according to the present invention is characterized in that at least one of the first glass substrate and the second glass substrate is tempered glass that has been subjected to air cooling tempering treatment or chemical strengthening treatment.
  • the material of the first glass substrate and the second glass substrate is soda lime glass (SiO 2- Na 2 O-CaO based glass).
  • the spacer that maintains the space between the first glass substrate and the second glass substrate is characterized by being made of resin. Inorganic filler particles are preferably dispersed in the resin spacer, and spherical glass particles are desirable as the inorganic filler particles. Further, as the spacer resin, a fluororesin is effective.
  • the sealing portion 4 shown in FIG. 1B is usually made by using a sealing material paste.
  • the sealing material paste contains lead-free low melting point glass powder constituting the low melting point glass phase 7 and low thermal expansion filler particles as solid content, and is a mixture of a binder resin and a solvent.
  • any one or more of aliphatic polycarbonate, ethyl cellulose and nitrocellulose is preferably used in consideration of the softening flow characteristics of lead-free low melting point glass and the influence on crystallization and the like.
  • any one or more of carbitol acetate, terpene solvent and propylene carbonate is preferably used.
  • a vacuum-insulated double glazing panel can be produced at a low temperature of less than 320 ° C., preferably less than 300 ° C.
  • the present inventor compares the results of differential thermal analysis (DTA) with the temperature based on the definition by viscosity for the transition point, yield point and softening point of the glass. It was confirmed that the second heat absorption peak temperature by DTA was substantially equal to the softening point measured as the temperature corresponding to the viscosity. Therefore, in the present specification, the second endothermic peak temperature by DTA is defined as "softening point T s".
  • DTA differential thermal analysis
  • FIG. 2A is a schematic perspective view showing a part of the manufacturing method of the vacuum-insulated double glazing panel, and shows the processing of the first glass substrate 1.
  • FIG. 2B is an enlarged cross-sectional view showing a peripheral portion of FIG. 2A.
  • FIG. 3A is a schematic perspective view showing a part of the manufacturing method of the vacuum insulated double glazing panel, and shows the processing of the second glass substrate 2.
  • FIG. 3B is a cross-sectional view of FIG. 3A.
  • FIG. 4A is a schematic cross-sectional view showing a part of a method for manufacturing a vacuum-insulated double glazing panel.
  • FIG. 4B is a schematic cross-sectional view showing a part of the manufacturing method of the vacuum insulated double glazing panel.
  • FIG. 5A is a schematic cross-sectional view showing a part of a method for manufacturing a vacuum insulated double glazing panel.
  • FIG. 5B is an enlarged cross-sectional view showing the vicinity of the sealing portion of FIG. 5A.
  • FIG. 6A is a schematic cross-sectional view showing a part of the manufacturing method of the vacuum insulated double glazing panel.
  • FIG. 6B is an enlarged cross-sectional view showing the vicinity of the sealing portion of FIG. 6A.
  • FIG. 7A is a graph showing a temperature profile in the step of heating the sealing material paste applied to the glass substrate.
  • FIG. 7B is a graph showing a temperature profile in the vacuum exhaust sealing process.
  • the sealing material paste 12 is applied to the peripheral edge of the first glass substrate 1 provided with the exhaust hole 9 and the exhaust pipe 10 using the dispenser 11. Then, it is dried on a hot plate at about 150 ° C. for 30 minutes to volatilize the solvent contained in the sealing material paste 12.
  • the binder is removed according to the temperature profile shown in FIG. 7A, and the lead-free low melting point glass powder contained in the sealing material paste 12 is softened and flowed. Then, the temperature is lowered to solidify the lead-free low melting point glass. As a result, the sealing material 13 fired on the first glass substrate 1 is formed.
  • the firing conditions are as follows.
  • the heating rate and cooling rate of about 2 ° C. / min and, first, as the temperature T 1 of the yield point M g ⁇ softening point T s of the lead-free low-melting glass contained in the sealing material paste 12 Hold for about 30 minutes to volatilize the binder resin. Then, it is further heated and held at a temperature T 2 higher than the softening point T s by about 10 to 20 ° C. for about 30 minutes, and then the temperature is lowered.
  • a heat ray reflecting film 6 is formed on the second glass substrate 2 by a vapor deposition method. Then, a large number of spacers 3 are arranged on the surface of the heat ray reflecting film 6.
  • the first glass substrate 1 and the second glass substrate 2 processed as described above are aligned so as to face each other as shown in FIG. 4A.
  • first glass substrate 1 and the second glass substrate 2 are fixed with a heat-resistant clip 14 or the like as shown in FIG. 4B.
  • this is installed inside the vacuum exhaust furnace 15, an electric heater 16 is attached to the exhaust pipe 10, and the exhaust pipe 10 is connected to the vacuum pump 17.
  • the vacuum pump 17 a dry pump, a turbo molecular pump, or the like is used.
  • This is first heated to a temperature T 3 near the softening point T s of the lead-free low melting point glass contained in the sealing material 13 at atmospheric pressure according to the sealing temperature profile shown in FIG. 7B, and held for about 30 minutes.
  • the space 5 is exhausted through the exhaust holes 9 and the exhaust pipe 10 shown in FIGS. 5A and 5B, and the space 5 is heated to a temperature T 4 higher than the softening point T s by about 10 to 20 ° C.
  • the sealing material 13 forms the sealing portion 4 on the peripheral edge portion, and the space 5 is evacuated.
  • the exhaust pipe 10 is burnt off by the electric heater 16 during or after cooling, and the space 5 is sealed in a vacuum state. In this way, the vacuum insulated double glazing panel is produced.
  • Table 1 shows the composition of lead-free low melting point glass of Examples and Comparative Examples.
  • Examples are GA-01 to GA-20, and comparative examples are GB-01 to GB-11. These lead-free low-melting-point glasses are substantially free of harmful lead and are environmentally and safety-friendly.
  • V 2 O 5 and TeO 2 which are essential in Examples and Comparative Examples, are manufactured by Shinko Kagaku Kogyo Co., Ltd., and Li 2 CO 3, which is essential in Examples, are manufactured by High Purity Chemical Laboratory Co., Ltd. Powder was used.
  • Ag 2 O a powder manufactured by Tanaka Kikinzoku Kogyo Co., Ltd. was used.
  • glass raw materials having a predetermined ratio were weighed so as to have a total weight of about 200 to 300 g, mixed, mixed, and put into a quartz crucible. It is installed in a glass melting furnace (electric furnace), heated to 700 to 800 ° C at a heating rate of about 10 ° C / min, and stirred with an alumina rod to make the melt in the quartz crucible uniform. It was held for 1 hour. Then, the quartz crucible was taken out from the glass melting furnace, and the melt in the crucible was poured into a stainless steel plate to obtain lead-free low melting point glass of Examples and Comparative Examples.
  • a glass melting furnace electric furnace
  • the melt in the crucible was poured into a stainless steel plate to obtain lead-free low melting point glass of Examples and Comparative Examples.
  • the characteristic temperature of each lead-free low melting point glass was determined by performing DTA at a heating rate of 5 ° C./min in the air using the same glass powder used for the density measurement.
  • an alumina ( ⁇ -Al 2 O 3 ) powder was used as a standard sample using a macrocell type DTA device so that the characteristic points of the DTA curve peculiar to glass could be clearly detected.
  • FIG. 8 is an example of a typical glass-specific DTA curve.
  • the horizontal axis represents the temperature of the standard sample, and the vertical axis represents the temperature difference (potential difference) between the glass sample to be measured and the standard sample.
  • transition point T g yield point M g and a softening point T s is defined by the viscosity of the glass.
  • the T g 10 13.3 poise
  • M g is 10 11.0 poise
  • the T s is the temperature corresponding to 10 7.65 poise.
  • the crystallization tendency is determined from the difference (absolute value) between the softening point T s and the crystallization temperature T cry, and the height of the exothermic peak due to crystallization, that is, the calorific value thereof.
  • the difference (absolute value) between the softening point T s and the crystallization temperature T cry is large, even if the glass reaches a temperature exceeding the softening point T s , the glass is softened and flowed in a temperature range that does not reach T cry. It becomes easy. Further, if the calorific value at the time of crystallization is small, when the temperature reaches T cry by heating at a constant temperature rise rate, an uncontrollable temperature rise due to the heat generation is unlikely to occur, so that the progress of crystallization Can be suppressed.
  • FIG. 9 is a graph showing a thermal expansion curve of a typical lead-free glass composition.
  • the amount of elongation on the vertical axis in the figure is a value obtained by subtracting the amount of elongation of quartz glass, which is a standard sample.
  • the lead-free glass composition stretches with heating, and remarkable elongation begins at the transition temperature TG.
  • This transition temperature TG substantially coincides with the transition point T g obtained from DTA.
  • the coefficient of thermal expansion of glass is generally measured from a gradient in the temperature range from room temperature to less than TG. Therefore, for the lead-free glass compositions of Examples GA-01 to GA-08 and Comparative Examples GB-01 to GB-04, the coefficient of thermal expansion was calculated from the gradient in the temperature range of 30 to 200 ° C. Further, the lead-free low melting point glasses of Examples GA-09 to GA-20 and Comparative Examples GB-05 to GB-11 having a lower transition point T g than these have a coefficient of thermal expansion from a gradient in a temperature range of 30 to 150 ° C. It was measured.
  • Table 2 shows the measurement results of density, characteristic temperature and coefficient of thermal expansion.
  • the low thermal expansion filler particles zirconium tungstate phosphate (Zr 2 (WO 4 ) (PO 4 ) 2 ) was used as the low thermal expansion filler particles.
  • the low thermal expansion filler particles were under 45 ⁇ m and had an average particle size (D 50 ) of about 15 ⁇ m.
  • the mixing ratio of the lead-free low melting point glass, which is the solid content of the sealing material paste, and the low thermal expansion filler particles takes into consideration the thermal expansion of the first glass substrate and the second glass substrate used in the vacuum-insulated double glazing panel. Decided.
  • Table 2 also shows the blending ratio.
  • the compounding ratio is based on the assumption that a soda lime glass (SiO 2- Na 2 O-CaO-based glass) substrate is used for the first glass substrate and the second glass substrate, and the coefficient of thermal expansion of the sealing portion is approximately 70 ⁇ .
  • the temperature was adjusted to 10-7 / ° C.
  • binder resin any one or more of aliphatic polycarbonate, ethyl cellulose and nitrocellulose was used.
  • solvent any one or more of carbitol acetate, terpene solvent and propylene carbonate was used.
  • the solid content was set to 80 to 85% by mass.
  • Example 1 Lead-free low melting point glass of Examples GA-01 to GA-20 and Comparative Examples GB-01 to GB-11 shown in Table 1 and zirconium tungate phosphate (Zr 2 (WO 4 )) (PO) which is a low thermal expansion filler particle. 4 ) Using the sealing material paste containing 2 ), the vacuum-insulated double glazing panel shown in FIG. 1 was produced, and its heat insulating property and reliability were evaluated.
  • the first glass substrate 1 and the second glass substrate 2 are provided with soda lime glass (SiO 2- Na 2 O-CaO-based glass) substrate (tempered glass substrate) having a size of 300 ⁇ 300 ⁇ 3 mm and subjected to a chemical strengthening treatment.
  • soda lime glass SiO 2- Na 2 O-CaO-based glass
  • tempered glass substrate tempered glass substrate
  • spacer 3 a polyimide resin spacer having a height of 200 ⁇ m and an outer diameter of 500 ⁇ m was used.
  • a vacuum pump 17 was exhausted using both a dry pump and a turbo molecular pump, aiming at a thermal transmission rate of 0.4 W / m 2 ⁇ K or less by the above-mentioned production method.
  • a vacuum-insulated double glazing panel was produced by airtight sealing at a low temperature of less than 320 ° C.
  • the thermal insulation property achieved a thermal transmission rate of 0.4 W / m 2 ⁇ K or less.
  • FIG. 10 is a schematic cross-sectional view showing a reliability test device for a vacuum insulated double glazing panel.
  • the manufactured vacuum-insulated double glazing panel 100 is sandwiched between the containers 18 and 19 via the silicon rubber packings 20 and 21, and the temperature is controlled by the cold air conditioner 51 and the hot air machine 52. It has a possible configuration.
  • the containers 18 and 19 are made of fluororesin (PTFE: polytetrafluoroethylene).
  • the vacuum-insulated double glazing panel 100 has a first glass substrate 1, a second glass substrate 2, a spacer 3, a sealing portion 4, and a heat ray reflecting film 6. A space 5 is formed between the first glass substrate 1 and the second glass substrate 2.
  • the cold air conditioner 51 can generate cold air at ⁇ 50 ° C.
  • the hot air conditioner 52 can generate hot air at 80 ° C.
  • cold air or hot air is introduced into the outer surface of the vacuum-insulated double glazing panel 100 arranged inside the containers 18 and 19 at a flow velocity of 30 L / min. Can be done.
  • the thermal transmission rate of the initial vacuum insulated double glazing panel 100 was measured.
  • the on-off valves 56, 57, 58, and 59 are switched, hot air is introduced into one surface of the vacuum-insulated double glazing panel 100, and cold air is introduced into the other surface, and the hot air and cold air are exchanged every 60 minutes. The process was repeated 100 times. Then, the thermal transmission rate of the vacuum insulated double glazing panel 100 was measured again.
  • the initial thermal transmissivity was substantially maintained and high.
  • the heat insulation was maintained. This indicates that the sealing portion 4 was maintained in a state of being strongly adhered to the first glass substrate 1 and the second glass substrate 2.
  • airtight sealing is possible at less than 300 ° C. This is a particularly desirable configuration.
  • Example 2 the vacuum-insulated double glazing panels of FIGS. 1A and 1B were produced in the same manner as in Example 1, and their heat insulating properties and reliability were evaluated.
  • the low melting point glass phase 7 of the sealing portion lead-free low melting point glasses of Examples GA-12 to GA-20 and Comparative Examples GB-07 to GB-11 shown in Table 1 were used.
  • the spacer 3 a fluororesin in which spherical glass particles were dispersed was used for the spacer 3.
  • Example 2 Regarding the reliability of the manufactured vacuum-insulated double glazing panel, the same results as in Example 1 were obtained. However, the initial thermal transmission rate in both Examples and Comparative Examples was slightly lower in Example 2 than in this Example 2. It is considered that this is due to the difference in the material of the spacer 3. A polyimide resin was used in the spacer 3 of Example 1, but in this Example 2, since a fluororesin having lower hygroscopicity and water absorption than the polyimide resin was used, the degree of vacuum in the space 5 was higher than that of Example 1. It is considered to be.
  • the fluororesin has a smaller coefficient of friction than the polyimide resin, it is considered that damage due to friction between the first glass substrate 1, the second glass substrate 2 and the heat ray reflecting film 6 can be prevented. Further, since it is also excellent in weather resistance such as ultraviolet resistance, it is considered that a fluororesin is suitable for the spacer 3.
  • Example 3 In Example 3, in order to further clarify the effect of Example 1, a joint body simulating the sealing portion of the vacuum-insulated double glazing panel was prepared using the same sealing material paste as in Example 1. , The reliability of the joint was evaluated. Specifically, a seal containing lead-free low melting point glass of Examples GA-01 to GA-20 and Comparative Examples GB-01 to GB-11 shown in Table 1 and zirconium tungate phosphate which is a low thermal expansion filler particle. Two glass substrates were joined using a stop material paste, and the joining strength of the joined body was evaluated by shear stress.
  • Example 3 The method for producing the bonded body in Example 3 is as follows.
  • FIG. 11A is a schematic perspective view showing a part of a manufacturing method of a joint body simulating a sealing portion of a vacuum insulated double glazing panel.
  • FIG. 11B is a schematic perspective view showing a part of a manufacturing method of a joint body simulating a sealing portion of a vacuum insulated double glazing panel.
  • FIG. 12A is a schematic cross-sectional view showing a part of a manufacturing method of a joint body simulating a sealing portion of a vacuum-insulated double glazing panel.
  • FIG. 12B is a schematic cross-sectional view showing a part of a manufacturing method of a joint body simulating a sealing portion of a vacuum insulated double glazing panel.
  • soda lime glass (SiO 2- Na 2 O-CaO-based glass) substrates without strengthening treatment having a thickness of 3 mm were used.
  • the first glass substrate 1 was 20 ⁇ 20 mm
  • the second glass substrate 2 was 10 ⁇ 10 mm.
  • the sealing material paste 12 was applied to the upper surface of the first glass substrate 1 with a diameter of 5 mm and a thickness of about 500 ⁇ m. Then, four spacers 3 made of polyimide resin having a height of 200 ⁇ m and an outer diameter of 500 ⁇ m were installed. Further, this was dried at 150 ° C. for 30 minutes.
  • the second glass substrate 2 was installed on the upper surface of the first glass substrate 1 with the spacer 3 sandwiched between them.
  • FIG. 13 is a schematic cross-sectional view showing a main part of the joint strength test apparatus for the joint body produced as described above.
  • the joint strength was measured by installing the joint body on the fixing jig 61 and applying a force to the side surface portion of the second glass substrate 2 by the shear jig 62.
  • the shearing jig 62 was arranged so that the lower end portion thereof was located 500 ⁇ m above the upper surface of the first glass substrate 1.
  • the shear jig 62 was moved at 34 ⁇ m / sec.
  • the joint strength was measured by taking the value of shear stress.
  • the average bonding strength was about 15 to 20 MPa in shear stress.
  • the bonding interface of the first glass substrate 1 or the second glass substrate 2, that is, the soda lime glass (SiO 2- Na 2 O-CaO based glass) substrate is observed in any of the bonded bodies. It was damaged in a state where it was peeled off in the vicinity.
  • the sealing material 13 shown in FIG. 13 was broken up and down, that is, in most cases, it was broken at the substantially central portion of the joint thickness of 200 ⁇ m.
  • the difference between the bonded body of the example and the bonded body of the comparative example is the composition of the low melting point glass phase contained in the joint portion (sealing portion), that is, the lead-free low melting point glass.
  • Glass structure of V 2 O 5 -TeO 2 -Li 2 O system lead-free low-melting-point glass has a layered structure consisting of V 2 O 5 and TeO 2, Li 2 O is a monovalent cation (Li + ), It is considered that they exist between the layers of the layered structure. Since Li + has a smaller ionic radius than other monovalent cations, it is considered that it easily moves in the glass structure. Further, it is considered that Li + easily diffuses into the glass substrate which is the material to be bonded. From this, it is considered that the adhesiveness and adhesion to the glass substrate are improved and the bonding strength is improved even in the case of low-temperature glass bonding or low-temperature glass sealing at a temperature of less than 320 ° C.
  • V 2 O 5 -TeO 2 -Li 2 O system lead-free low-melting-point glass can be effectively applied to a low temperature hermetic seal of the vacuum heat insulating double glazing.
  • Example 3 the basic effectiveness of the present invention could be confirmed.
  • Example 4 In Example 4, the lead-free low melting point glass of Examples GA-06, GA-11, GA-14, GA-20 and Comparative Example GB-08 shown in Table 1 and tungsten phosphate which is a low thermal expansion filler particle are used. Using a sealing material paste containing zirconium tungate (Zr 2 (WO 4 ) (PO 4 ) 2 ), vacuum insulated double glazing panels shown in FIGS. 1A and 1B were produced in the same manner as in Example 1. The heat insulating property and reliability were evaluated.
  • Zr 2 (WO 4 ) (PO 4 ) 2 zirconium tungate
  • a soda lime glass substrate (tempered glass substrate) having a size of 900 ⁇ 900 ⁇ 5 mm, which is larger and heavier than that of the first embodiment and has been subjected to air cooling strengthening treatment, is used.
  • the spacer 3 a resin spacer having the same shape and size as that of Example 1 and in which spherical glass particles were dispersed was used.
  • the spacer made of spherical glass particle dispersed polyimide resin and the low melting point glass phase 7 of the sealing portion 4 are In the case of the low melting point glass of Examples GA-14, GA-20 and Comparative Example GB-08, a spacer made of spherical glass particle dispersed fluororesin was used.
  • the vacuum pump 17 is dried with the target of thermal transmission rate of 0.4 W / m 2 ⁇ K or less by the above-mentioned manufacturing method of the vacuum-insulated double glazing panel. Evacuation was performed using both a pump and a turbo molecular pump and hermetically sealed below 320 ° C.
  • the thermal transmissivity achieved a thermal transmission rate of 0.4 W / m 2 ⁇ K or less in both Examples and Comparative Examples.
  • the reliability of the vacuum-insulated double glazing panels of the manufactured examples and comparative examples was evaluated by conducting a temperature cycle test of -50 ° C to + 80 ° C 1500 times and measuring the thermal transmission rate to determine the change in heat insulation. evaluated.
  • Example 4 From the above, it was found that the same effect as in Example 1 can be obtained even if the size of the vacuum-insulated double glazing panel is increased as in Example 4.
  • a vacuum-insulated double glazing panel in a vacuum-insulated double glazing panel, highly reliable airtight sealing can be realized at a low temperature of less than 320 ° C., improved heat insulating properties due to high vacuum, and mass production. It is possible to reduce manufacturing costs and improve safety by improving performance and reducing capital investment costs.
  • This vacuum-insulated double glazing panel can be effectively applied to window glass for building materials, etc., and by spreading it widely in the residential and building fields around the world, CO 2 emissions due to reduction of energy consumption will be reduced. , Can greatly contribute to measures against global warming. It can also be widely applied to parts and products that require heat insulation, such as window glass for vehicles, doors of commercial refrigerators and freezers.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (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)
  • Ceramic Engineering (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Securing Of Glass Panes Or The Like (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un panneau de verre multicouche isolé sous vide comprenant un premier substrat en verre et un second substrat en verre : un élément d'espacement et une partie d'étanchéité étant pris en sandwich entre le premier substrat en verre et le second substrat en verre ; la partie d'étanchéité étant disposée au niveau de sections de bord du premier substrat en verre et du second substrat en verre ; l'élément d'espacement étant disposé dans un espace entouré par le premier substrat en verre, le second substrat en verre et la partie d'étanchéité ; l'espace étant à l'état décomprimé ; la partie d'étanchéité contenant une phase vitreuse à bas point de fusion ; la phase vitreuse à bas point de fusion contenant un oxyde de vanadium, un oxyde de tellure et un oxyde de lithium ; et la seconde température de pic endothermique dans l'analyse thermique différentielle étant égale ou inférieure à 300 °C. Par conséquent, il est possible de fournir un panneau de verre multicouche isolé sous vide : avec lequel il est possible d'obtenir une étanchéité à l'air hautement fiable à une basse température inférieure à 320 °C ; et qui réalise une isolation thermique améliorée en raison de la création d'un environnement sous vide poussé dans l'espace intérieur, un coût de fabrication réduit grâce à une productivité améliorée et un coût d'investissement d'installation réduit, et une sécurité améliorée.
PCT/JP2020/003919 2019-08-30 2020-02-03 Panneau de verre multicouche isolé sous vide WO2021038907A1 (fr)

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WO2024116632A1 (fr) * 2022-11-30 2024-06-06 パナソニックＩｐマネジメント株式会社 Appareil de refroidissement/chauffage

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0986974A (ja) * 1995-09-22 1997-03-31 Nippon Sheet Glass Co Ltd 複層ガラス及びその製造方法
JP2006282741A (ja) * 2005-03-31 2006-10-19 Yokohama Rubber Co Ltd:The 硬化性樹脂組成物
JP2016050136A (ja) * 2014-08-29 2016-04-11 日立化成株式会社 無鉛低融点ガラス組成物並びにこれを含む低温封止用ガラスフリット、低温封止用ガラスペースト、導電性材料及び導電性ガラスペースト並びにこれらを利用したガラス封止部品及び電気電子部品
WO2016092849A1 (fr) * 2014-12-10 2016-06-16 パナソニックＩｐマネジメント株式会社 Unité de panneau de verre
JP2016135733A (ja) * 2015-01-15 2016-07-28 セントラル硝子株式会社 無鉛ガラス及び封着材料
WO2017126378A1 (fr) * 2016-01-18 2017-07-27 株式会社日立製作所 Composition de verre sans plomb, matériau composite en verre, pâte de verre, structure d'étanchéité, composant électrique/électronique et composant revêtu
CN108298822A (zh) * 2018-04-08 2018-07-20 武汉理工大学 一种真空玻璃封接用低熔点玻璃粉及其阳极键合增强封装方法
JP2019206458A (ja) * 2018-05-30 2019-12-05 日立化成株式会社 無鉛ガラス組成物ならびにそれを含むガラス複合材料、ガラスペーストおよび封止構造体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0986974A (ja) * 1995-09-22 1997-03-31 Nippon Sheet Glass Co Ltd 複層ガラス及びその製造方法
JP2006282741A (ja) * 2005-03-31 2006-10-19 Yokohama Rubber Co Ltd:The 硬化性樹脂組成物
JP2016050136A (ja) * 2014-08-29 2016-04-11 日立化成株式会社 無鉛低融点ガラス組成物並びにこれを含む低温封止用ガラスフリット、低温封止用ガラスペースト、導電性材料及び導電性ガラスペースト並びにこれらを利用したガラス封止部品及び電気電子部品
WO2016092849A1 (fr) * 2014-12-10 2016-06-16 パナソニックＩｐマネジメント株式会社 Unité de panneau de verre
JP2016135733A (ja) * 2015-01-15 2016-07-28 セントラル硝子株式会社 無鉛ガラス及び封着材料
WO2017126378A1 (fr) * 2016-01-18 2017-07-27 株式会社日立製作所 Composition de verre sans plomb, matériau composite en verre, pâte de verre, structure d'étanchéité, composant électrique/électronique et composant revêtu
CN108298822A (zh) * 2018-04-08 2018-07-20 武汉理工大学 一种真空玻璃封接用低熔点玻璃粉及其阳极键合增强封装方法
JP2019206458A (ja) * 2018-05-30 2019-12-05 日立化成株式会社 無鉛ガラス組成物ならびにそれを含むガラス複合材料、ガラスペーストおよび封止構造体

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