WO2012077771A1 - Miroir réfléchissant et son procédé de fabrication - Google Patents

Miroir réfléchissant et son procédé de fabrication Download PDF

Info

Publication number
WO2012077771A1
WO2012077771A1 PCT/JP2011/078489 JP2011078489W WO2012077771A1 WO 2012077771 A1 WO2012077771 A1 WO 2012077771A1 JP 2011078489 W JP2011078489 W JP 2011078489W WO 2012077771 A1 WO2012077771 A1 WO 2012077771A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
glass substrate
sealing
layer
reflecting mirror
Prior art date
Application number
PCT/JP2011/078489
Other languages
English (en)
Japanese (ja)
Inventor
壮平 川浪
山田　和夫
暢子 満居
幸紀 森谷
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Publication of WO2012077771A1 publication Critical patent/WO2012077771A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

  • the present invention relates to a reflector used for collecting sunlight, and more particularly to a reflector excellent in water resistance.
  • a reflecting mirror is manufactured by coating a metal thin film such as aluminum or silver on a transparent substrate such as glass.
  • a metal thin film such as aluminum or silver
  • the reflecting mirror coated with such a metal thin film has a problem that the metal thin film on the surface deteriorates due to moisture, oxygen, etc. in the environmental atmosphere.
  • reflectors with a protective film made of acrylic resin or epoxy resin on the metal thin film coating are the mainstream, but since these resins are inferior in water resistance, they deteriorate over a long period of time. It is difficult to prevent.
  • Patent Document 1 proposes a reflecting mirror covered with an elastic sealant made of silicon sealant along the entire circumference of a laminated glass mirror.
  • an elastic sealant made of silicon sealant along the entire circumference of a laminated glass mirror.
  • the water barrier property is not perfect and is inferior in water resistance.
  • Patent Document 2 proposes a reflecting mirror in which the entire surface is protected with an inorganic film.
  • the inorganic protective film is very thin, cracks are gradually formed due to thermal expansion or the like, resulting in poor reliability.
  • the present invention is to provide a reflector that is particularly excellent in water resistance.
  • the reflecting mirror of the present invention includes a first glass substrate having a reflecting film, a second glass substrate disposed opposite to the reflecting film side of the first glass substrate, the first glass substrate, and the second glass substrate. It is comprised from the sealing glass layer which seals a glass substrate in the peripheral part. Moreover, you may form a reflecting film also in the opposing surface with the reflecting film surface of said 1st glass substrate of a 2nd glass substrate. Furthermore, a reaction layer generated by sealing at the interface between the first glass substrate and the sealing glass layer and the interface between the second glass substrate and the sealing glass layer, that is, the glass substrate and the sealing glass material layer. It is preferable that a reaction layer generated by a reaction during the sealing process with the low melting point glass is formed.
  • the reflecting mirror manufacturing method of the present invention includes a step of preparing a first glass substrate having a reflecting film, a step of forming a sealing glass material layer on a peripheral portion on the second glass substrate surface, The step of placing the reflective film surface of the glass substrate and the surface on which the sealing glass material layer of the second glass substrate is formed to be an overlapping substrate, and heating and melting the sealing glass material layer of the overlapping substrate, Sealing the first glass substrate and the second glass substrate and forming a sealing glass layer.
  • the glass material layer for sealing is heated and melted by partial heating by electromagnetic wave irradiation or whole heating in which an overlapping substrate is placed in a baking furnace.
  • the peripheral portions of the first and second glass substrates are sealed with the sealing glass layer over the entire circumference, it is possible to prevent moisture and the like from entering the reflecting mirror. Therefore, it is possible to prevent deterioration of the characteristics of the reflective film and maintain the reflection characteristics for a long period of time.
  • a method of using an electromagnetic wave to heat and melt and seal a sealing glass material layer to form a sealing glass layer local heating is possible, so the characteristics of the reflective film due to heat during sealing Deterioration can also be prevented.
  • FIG. 1 to 3 are sectional views showing a typical structure of the reflecting mirror of the present invention.
  • a first glass substrate 2 having a reflecting film 5 and a second glass substrate 4 disposed to face the reflecting film 5 are provided by a sealing glass layer 3.
  • the outer periphery of the 1st glass substrate 2 and the 2nd glass substrate 4 is sealed over the perimeter. Further, the interface between the first glass substrate 2 and the sealing glass layer 3 and the interface between the second glass substrate and the sealing glass layer 3 are low in the glass substrate and the sealing glass material layer at the time of sealing.
  • a reaction layer 7 generated by the reaction during the sealing process with the melting point glass is formed.
  • the first and second glass substrates 2 and 4 are made of, for example, alkali-free glass or soda lime glass having various known compositions.
  • the alkali-free glass has a thermal expansion coefficient of about 35 to 40 ( ⁇ 10 ⁇ 7 / ° C.).
  • Soda lime glass has a thermal expansion coefficient of about 80 to 90 ( ⁇ 10 ⁇ 7 / ° C.).
  • the soda lime glass is preferably white plate glass (high transmission glass) having high transparency.
  • the so-called white glass (high transmittance glass) is a glass having a visible light transmittance higher than that of ordinary soda lime glass and 90% or more, such as iron content compared to ordinary soda lime glass.
  • the soda lime glass is desirably tempered glass.
  • the strengthening method may be either chemical strengthening or air cooling strengthening. Further, chemically strengthened glass other than soda lime glass may be used. Unless otherwise specified, “to” indicating the numerical range described above is used to mean that the numerical values described before and after it are used as a lower limit value and an upper limit value, and hereinafter “to” Used with meaning.
  • the thickness of the first and second glass substrates 2 and 4 is preferably 0.03 to 5 mm. Considering the reflectance, the thickness of the first and second glass substrates 2 and 4 is desirably thinner, more desirably 0.03 to 2.8 mm, and further desirably 0.03 to 1.1 mm. In consideration of the mass of the structure, the thickness of the first and second glass substrates 2 and 4 is desirably thinner, more desirably 0.03 to 2.8 mm, and further desirably 0.03 to 1.1 mm. It is. Considering the strength, the thickness of the first and second glass substrates 2 and 4 is desirably thicker, more desirably 0.7 mm to 5 mm, and further desirably 1.1 mm to 5 mm.
  • the thickness of the first glass substrate 2 is 0.03.
  • the thickness of the second glass substrate 4 is desirably 0.7 to 5 mm.
  • the reflective film 5 can be made of aluminum, silver, or a silver alloy (silver-platinum alloy, silver-palladium alloy).
  • the reflective film 5 is formed by any one of a vapor deposition method, a sputtering method, a CVD method, an ion plating method, an ion beam irradiation method, and a spray coating method.
  • acrylic resin or epoxy is formed on the reflective film 5 formed by the various methods described above. It is also possible to reduce the process of forming a protective film made of resin or the like.
  • the sealing glass layer 3 is obtained by melting and solidifying a sealing glass material containing a low melting point glass as an essential component and ceramic fillers and electromagnetic wave absorbing materials as optional components.
  • the main purpose of containing the ceramic filler is to adjust the difference in thermal expansion coefficient between the low melting point glass and the glass substrate, and the main purpose of containing the electromagnetic wave absorbing material is to improve the absorption of electromagnetic waves in the sealing glass material and to improve the heating efficiency. Is up. In this way, by performing sealing entirely with an inorganic material, it is possible to obtain higher airtightness than before, and to prevent deterioration of the reflective film 5, preventing intrusion of moisture and the like and having excellent environmental resistance. A mirror 1 can be obtained.
  • the combination and blending amount of the sealing glass material are selected in consideration of the heating method for forming the sealing glass layer 3, compatibility with the first and second glass substrates 2 and 4, and the respective characteristics.
  • a heating method there are a method in which the entire reflecting mirror 1 is heated using a baking furnace, or only a sealing portion of the reflecting mirror 1 is heated using a laser beam which is a kind of electromagnetic waves.
  • the composition of the sealing glass material is preferably 60 to 100% by volume of low-melting glass, 0 to 40% by volume of ceramic filler, and 0 to 40% by volume of electromagnetic wave absorber.
  • the sealing glass material only needs to contain at least a low-melting glass, and the content of the ceramic filler and the electromagnetic wave absorbing material may be zero.
  • the low melting point glass for example, a low melting point glass such as tin-phosphate glass, bismuth glass, vanadium glass, lead glass, silica alkali borate glass or the like is used.
  • a low melting point glass such as tin-phosphate glass, bismuth glass, vanadium glass, lead glass, silica alkali borate glass or the like.
  • the low melting point glass is less than 60% by volume, the fluidity of the sealing glass material at the time of sealing may be lowered, and good sealing may not be possible.
  • the ratio of the low melting point glass in the sealing glass material is preferably 60% by volume or more, more preferably 65% by volume or more.
  • the upper limit is 97% by volume or less, preferably 90% by volume or less in consideration of adjustment of thermal expansion with the glass substrate.
  • the ceramic filler it is preferable to use at least one selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass, and borosilicate glass.
  • 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 minimum with a preferable ceramic filler is 3 volume% or more, More preferably, it is 10 volume% or more.
  • it exceeds 40% by volume, the fluidity of the sealing glass material at the time of sealing is lowered, and good sealing becomes difficult.
  • it is 40 volume% or less, More preferably, it is 35 volume% or less.
  • the electromagnetic wave absorber at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu or at least one compound such as an oxide containing the metal is used. Moreover, electromagnetic wave absorbing materials other than these may be used.
  • the minimum with a preferable electromagnetic wave absorber is 0.1 volume% or more, More preferably, it is 1 volume% or more.
  • it exceeds 40% by volume the fluidity of the sealing glass material at the time of sealing decreases, and good sealing cannot be achieved.
  • it is 25 volume% or less, More preferably, it is 20 volume% or less.
  • the composition of Na 2 O As a specific low melting point glass, when bismuth-based glass is applied, 70 to 90% Bi 2 O 3 , 1 to 20% ZnO, 2 to 12% B 2 O 3 , and 10 to 1000 ppm by mass ratio are used. It is preferable to apply the composition of Na 2 O. Glass formed of three components of Bi 2 O 3 , ZnO, and B 2 O 3 is suitable for a sealing glass material because it has characteristics such as being transparent and having a low glass transition point. However, in the low melting point glass by the above three components, there is a possibility that a sufficient reaction layer 7 cannot be generated between the glass substrates 2 and 4 and the sealing glass layer 3. Therefore, it is preferable to contain a trace amount of Na 2 O.
  • an element that easily diffuses into the glass substrate specifically a monovalent light metal, is used in the low-melting glass. It is effective to contain. In particular, it is effective to contain Na 2 O in bismuth-based glass.
  • a glass substrate 2 is used. 4 and the sealing glass layer 3 are likely to generate the reaction layer 7 at the bonding interface.
  • Bi 2 O 3 is a component that forms a glass network, and is preferably contained in the sealing glass in the 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 low-melting glass becomes high.
  • 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, the stability at the time of molding a low-melting 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 to widen the range of possible vitrification by forming a glass skeleton, be contained in a range of 2 to 12 mass% in the low-melting glass is preferable. 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, the sealing temperature, etc., the content of B 2 O 3 is more preferably in the range of 5 to 10% by mass.
  • Na 2 O is a component that enhances the reactivity of the low-melting glass of the glass material layer for sealing to the glass substrates 2 and 4, and is preferably contained in the low-melting glass in a range of 10 to 1000 ppm by mass.
  • the content of Na 2 O is less than 10 ppm, the generation efficiency of the reaction layer 7 cannot be sufficiently increased.
  • the content of Na 2 O exceeds 1000 ppm, the stability of the glass is impaired and devitrification tends to occur.
  • the content of Na 2 O is in the range of 100 to 1000 ppm by mass. More preferably.
  • Li 2 O and K 2 O also function as components for forming the reaction layer 7 at the adhesive interface between the glass substrates 2 and 4 and the sealing glass layer 3.
  • Na 2 O which is particularly excellent in reactivity with the glass substrates 2 and 3 is effective, so that the bismuth glass used as the low melting point glass may contain Na 2 O.
  • a part of the Na 2 O may be substituted with at least one selected from the group consisting of Li 2 O and K 2 O.
  • the amount of substitution of Na 2 O by Li 2 O or K 2 O is preferably 50% by mass or less of the amount of Na 2 O in consideration of the formability of the reaction layer 7 at the adhesion interface.
  • Bismuth glass formed by 4 components described above has a low glass transition point, but is suitable for sealing material, Al 2 O 3, CeO 2 , SiO 2, Ag 2 O, WO 3, MoO 3,
  • Optional components such as Nb 2 O 3 , Ta 2 O 5 , Ga 2 O 3 , Sb 2 O 3 , Cs 2 O, CaO, SrO, BaO, P 2 O 5 , SnO x (x is 1 or 2) May be contained.
  • 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. Therefore, the total content of any component is 10 mass. % Or less is preferable.
  • the lower limit of the total content of arbitrary components is not particularly limited.
  • An effective amount of an optional component can be blended with the bismuth glass based on the purpose of addition.
  • Al 2 O 3 , SiO 2 , CaO, SrO, BaO and the like are components that contribute to glass stabilization, and the content thereof is preferably in the range of 0 to 5% by mass.
  • Cs 2 O has an effect of lowering the softening temperature of the glass
  • CeO 2 has an effect of stabilizing the fluidity of the glass.
  • Ag 2 O, WO 3 , MoO 3 , Nb 2 O 3 , Ta 2 O 5 , Ga 2 O 3 , Sb 2 O 3 , P 2 O 5 , SnO X and the like adjust the viscosity and thermal expansion coefficient of the glass. It can be contained as a component.
  • the content of each of these components can be appropriately set within a range where the total content of arbitrary components does not exceed 10% by mass (including 0% by mass).
  • the reaction layer 7 is a mixed layer of the constituent elements of the first and second glass substrates 2 and 4 and the constituent element of the sealing glass layer 3. Such a reaction layer 7 is generated on the surface layer of the glass substrates 2 and 4 and the maximum depth is set to 30 nm or more, thereby strengthening the bonding state between the glass substrates 2 and 4 and the sealing glass layer 3. it can. Moreover, the space 6 between the glass substrates 2 and 4 sealed with the sealing glass layer 3 can also be made into a favorable airtight structure. When the maximum depth of the reaction layer 7 is less than 30 nm, it is difficult to sufficiently obtain the effect of increasing the adhesive strength or forming an airtight structure.
  • the maximum depth of the reaction layer 7 is more preferably 30 nm or more, and further preferably 150 nm or more.
  • the upper limit value of the maximum depth of the reaction layer 7 is not particularly limited, but is preferably 3000 nm or less, more preferably 2000 nm or less, and further preferably 500 nm or less.
  • the reaction layer 7 has a shape in which the vicinity of the center portion protrudes in a convex shape toward the inside of the first and second glass substrates 2 and 4 from the vicinity of both end portions of the sealing glass layer 3 in the cross section in the width direction. It is preferable to have.
  • the reaction layer 7 preferably has a concave shape in which the depth to the inside of the first and second glass substrates 2 and 4 is deeper in the vicinity of the center than at both ends of the sealing glass layer 3. . According to such a reaction layer 7, stress generated at the interface between the first and second glass substrates 2, 4 and the reaction layer 7 can be dispersed throughout the reaction layer 7. The adhesive strength between the glass substrates 2 and 4 and the sealing glass layer 3 can be further increased.
  • the shape of the reaction layer 7 is not limited to a shape having a substantially circular cross section as shown in FIG. 4 but may be a shape having a plurality of protruding portions.
  • the maximum depth D1 of the reaction layer 7 is 1.1 times or more than the depth D2 in the vicinity of the end of the sealing glass layer 3. It is preferable that the protruding shape is (ie, D1 / D2 ⁇ 1.1).
  • the depth D2 near the end of the reaction layer 7 is a distance of 1/10 of the distance L1 from the end when the distance from the end of the reaction layer 7 to the position having the maximum depth D1 is L1.
  • D1 / D2 is obtained based on the depth D2.
  • L1 represents the width direction of the reaction layer 7, that is, the length in the A direction in FIG. If the value of D1 / D2 exceeds 500, stress concentration is likely to occur as in the case where the depth of the reaction layer is uniform. Therefore, the value of D1 / D2 is preferably 500 or less.
  • the reaction layer 7 in which the ratio (D1 / D2) of the maximum depth D1 to the depth D2 in the vicinity of the end portion of the sealing layer 3 is 1.1 or more the first and second glass substrates 2 and 4 are sealed. It is possible to further increase the adhesive strength with the glass-attached glass layer 3 and to obtain a stress dispersion effect at the interface between the first and second glass substrates 2 and 4 and the reaction layer 7 with good reproducibility. . That is, by setting the ratio of D1 / D2 to 1.1 or more, it is possible to increase the amount of reaction layer 7 to be formed and to make the shape of the reaction layer 7 protrude from the glass substrates 2 and 4.
  • the ratio of D1 / D2 is more preferably 2.0 or more.
  • the cross-sectional area of the width direction is 50 micrometers 2 or more.
  • the cross-sectional area of the reaction layer 7 is more preferably 100 ⁇ m 2 or more.
  • the cross-sectional area of the reaction layer 7 can be increased by, for example, the shape of the reaction layer 7 (for example, increasing the depth). Note that the cross-sectional area of the reaction layer 7 can be increased even if the width (line width) of the sealing glass layer 3 is increased, and this is also the first and second glass substrates 2 and 4 and the sealing glass layer 3. As a means for increasing the adhesive strength.
  • reaction layer 7 can be confirmed by FE-EPMA line composition analysis in the vicinity of the adhesive interface between the first and second glass substrates 2 and 4 and the sealing glass layer 3, but the following method is a practical method. Is mentioned. Here, regarding the shape (depth, cross-sectional area, D1 / D2 ratio, etc.) of the reaction layer 7, values measured by the following method are shown.
  • the sealing glass layer 3 is removed by immersing the sample from which one glass substrate has been removed in an etching solution.
  • an acid solution that does not dissolve the glass of the glass substrate but can dissolve the constituent elements of the sealing glass layer is used.
  • a 30% nitric acid aqueous solution is used. Since the reaction layer 7 is a mixed layer of the constituent elements of the first and second glass substrates 2 and 4 and the constituent elements of the sealing glass layer, the reaction layer 7 is also removed simultaneously with the removal of the sealing glass layer 3.
  • FIG. 6 is a diagram showing the results of measuring the surface shape of the reaction layer 7 of the glass substrate in the reflecting mirror 1 produced in Example 1 described later. As shown in this figure, after the reaction layer 7 is dissolved and removed from the first and second glass substrates 2 and 4, the surface shapes of the first and second glass substrates 2 and 4 are measured with a surface roughness meter. Thus, the shape of the reaction layer 7 can be evaluated.
  • the reflective film 5 in the sealing region where the sealing glass layer is formed, or a part of the reflective film 5 is trimmed directly to the sealing glass material layer and the first The glass substrate 2 may be brought into close contact with the sealing process.
  • a trimming method after forming the reflective film 5, a method of immersing the sealing region in an etching solution such as nitric acid, a spraying method, or a reflection that becomes a sealing region before the reflective film 5 is formed.
  • an etching solution such as nitric acid, a spraying method, or a reflection that becomes a sealing region before the reflective film 5 is formed.
  • the atmosphere in the space 6 surrounded and sealed by the first glass substrate 2, the second glass substrate 4, and the sealing glass layer 3 may be an air atmosphere, but oxygen in the air, the reflective film 5 and In view of this reaction, it is desirable that the atmosphere be a vacuum or an inert gas such as nitrogen gas or argon gas. In view of the strength, it is also preferable to fill the space 6 with resin or insert a spacer.
  • the distance between the first glass substrate 2 and the second glass substrate 4 is the reaction between the oxygen in the filler in the space 6 and the reflective film 5 or thermal expansion. Shorter is better to reduce the effect.
  • the distance between the first glass substrate 2 and the second glass substrate 4 is desirably 500 ⁇ m or less, more desirably 100 ⁇ m or less, and still more desirably 10 ⁇ m or less.
  • the manufacturing method of the reflecting mirror 1 basically includes a step of preparing a first glass substrate having a reflective film, and a step of forming a sealing glass material layer on the second glass substrate (the sealing glass described below).
  • a step of forming a material layer) and a step of arranging the reflective film surface of the first glass substrate and the surface of the second glass substrate on which the sealing glass material layer is formed to be an overlapping substrate (the following first and Step of superimposing the second glass substrate) and the glass material layer for sealing the superposed substrate are heated and melted to seal the first glass substrate and the second glass substrate to form a sealed glass layer (Steps for sealing the first and second glass substrates described below).
  • the step of preparing the first glass substrate having the reflection film described above and the step of forming the sealing glass material layer on the second glass substrate may be in this order or in the reverse order. However, they may be performed simultaneously.
  • a sealing glass paste is prepared in advance as follows.
  • the glass paste for sealing is prepared by mixing each component of the glass material for sealing and a vehicle.
  • the vehicle is obtained by dissolving a resin as a binder component in a solvent.
  • the resin for the vehicle include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate.
  • Organic resins such as acrylic resins obtained by polymerizing one or more acrylic monomers such as 2-hydroxyethyl acrylate are used.
  • Solvents such as terpineol, butyl carbitol acetate, and ethyl carbitol acetate are used in the case of a cellulose resin, and solvents such as methyl ethyl ketone, terpineol, butyl carbitol acetate, and ethyl carbitol acetate are used in the case of an acrylic resin. .
  • the viscosity of the glass paste for sealing may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 4, and can be adjusted by the ratio of the resin (binder component) and the solvent and the ratio of the glass material for sealing and the vehicle.
  • You may add a well-known additive with a glass paste like an antifoamer and a dispersing agent to the glass paste for sealing. 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.
  • a glass paste for sealing is applied to a sealing region on the outer periphery of the second glass substrate 4 by screen printing or a dispenser.
  • the width of the coating film is preferably 0.5 mm to 20 mm in order to maintain the strength of the reflecting mirror.
  • the thickness of the coating film is set to the target thickness of the sealing glass layer 3 after sealing (for example, 10 ⁇ m to 2000 ⁇ m). Should be adjusted.
  • the second glass substrate 4 coated with the sealing glass paste is put into a dryer at 60 to 150 ° C. for 30 seconds to 10 minutes and dried to fly away the organic solvent component. Subsequently, the resin binder component is blown off at a temperature lower by 30 ° C. from the glass transition point of the sealing glass material in a baking furnace, and the temperature at which the sealing glass material is temporarily fired (that is, from the glass softening point of the sealing glass material). The sealing glass material is baked on the second glass substrate 4 to form a sealing glass material layer.
  • a glass material layer for sealing is also referred to as a glass material layer for sealing.
  • the glass material layer for sealing is a layer obtained by drying and pre-baking the paste layer applied to the glass substrate in obtaining the sealing glass layer, or a layer obtained by further baking, and the first and second glass substrates. Are laminated through a sealing glass material layer formed over one or both of these glass substrates, and the sealing glass material layer is heated and melted to heat the first and second glasses. It is used separately from the sealing glass layer formed on the periphery of the substrate.
  • the glass transition point is defined by the temperature of the first inflection point of the suggested thermal analysis (DTA), and the glass softening point is defined by the temperature of the fourth inflection point of the suggested thermal analysis (DTA). is there.
  • the second glass substrate 4 having the glass material layer for sealing and the first glass substrate 2 having the reflective film 5 are arranged so as to face each other so that the glass material layer for sealing is inside and the reflective film 5 is inside.
  • the stacked substrates are heated and melted in a baking furnace to form a fired sealing glass layer.
  • the component of the composition in the low melting glass in the glass material layer for sealing penetrates the reflective film 5, and the reaction layer 7 is formed on the first glass substrate 2.
  • the spacer can be inserted at the time of superposition.
  • a ceramic spacer such as granular alumina or silica having heat resistance is desirable.
  • the atmosphere of the firing furnace is preferably an inert atmosphere such as nitrogen gas or argon gas or a vacuum state in order to prevent the reflection film 5 from deteriorating.
  • the component of the low melting point glass composition of the glass material layer for sealing penetrates the reflective film 5, and the reaction layer 7 is formed on the first glass substrate 2, whereby strong adhesion is obtained.
  • reaction layer 7 If the reaction layer 7 is thin, the adhesive force is weak, and it peels off in a heat cycle test or a peel test, making it difficult to make a long-life reflector 1.
  • Ease of formation of the reaction layer 7 depends on the composition of the low-melting glass in the glass material layer for sealing, the firing temperature, and the adhesion between the glass material layer for sealing and the reflective film 5 on the first glass substrate. .
  • bismuth-based, lead-based, and alkali silica borate are suitable as the composition of the low melting point glass in the sealing glass material layer. Based glass is preferred.
  • the adhesiveness between the sealing glass material layer and the reflective film on the first glass substrate is determined by firing the first and second glass substrates with a heat-resistant clip when the first and second glass substrates stacked are fired. This is improved by sandwiching or applying a load to the first and second glass substrates stacked during firing by weight or the like.
  • the manufacturing method of the reflecting mirror 1 is also basically a step of preparing a first glass substrate having a reflective film and a step of forming a sealing glass material layer on the second glass substrate. (Step of forming a sealing glass material layer described below), and a step of forming a laminated substrate by opposingly arranging the reflective film surface of the first glass substrate and the surface of the second glass substrate on which the sealing glass material layer is formed. (The first and second glass substrate overlapping steps described below) and the glass material layer for sealing the overlapping substrate are heated and melted, and the first glass substrate and the second glass substrate are sealed and sealed.
  • a step of forming a glass-attached glass layer (step of sealing the first and second glass substrates described below).
  • the step of preparing the first glass substrate having the reflection film described above and the step of forming the sealing glass material layer on the second glass substrate may be in this order or in the reverse order. However, they may be performed simultaneously.
  • a sealing glass paste is prepared in advance as described below.
  • the production method of the sealing glass paste is the same as the production method of the reflecting mirror 1 using a firing furnace except that an electromagnetic wave absorbing material is included.
  • a sealing glass paste is applied to a sealing region in the peripheral portion of the entire outer periphery of the second glass substrate 4 by screen printing or a dispenser.
  • the width of the coating film is preferably 0.5 mm to 20 mm in order to maintain the strength. Further, the thickness of the coating film should be adjusted in consideration of shrinkage in the next step such as drying and pre-baking so as to be the target thickness of the sealing glass layer 3 after sealing.
  • the second glass substrate 4 to which the sealing glass paste is applied is dried at 60 to 150 ° C. for 30 seconds to 10 minutes, and the organic solvent component is removed. Subsequently, the resin binder component is blown off in a firing furnace under a temperature condition 30 to 50 ° C. lower than the glass transition point of the sealing glass material. Further, the sealing glass material is fired at a temperature at which the sealing glass is temporarily fired (more specifically, a temperature condition higher by 10 to 50 ° C. than the glass softening point of the sealing glass material). The glass material layer for baking and sealing is formed.
  • the step of blowing the resin binder component and the step of baking the sealing glass material on the second glass substrate 4 can also be performed by an electromagnetic wave such as a laser. Since the area other than the sealing area is not heated by local heating by an electromagnetic wave such as a laser, when the second glass substrate 4 has the reflective film 5, the reflective film 5 other than the sealed area is sealed without deterioration. A glass material can be baked onto the second glass substrate 4.
  • the second glass substrate 4 having the sealing glass material layer and the first glass substrate 2 having the reflective film 5 are arranged such that the sealing glass material layer is on the inner side and the reflective film 5 is on the inner side. Are placed facing each other and superposed to assemble the superposed substrate.
  • An electromagnetic wave such as a laser is irradiated from the second glass substrate 4 side of the laminated substrate, and the sealing glass layer fired is formed by heating and melting the sealing glass material layer.
  • the component of the composition in the low melting glass in the glass material layer for sealing penetrates the reflective film 5, and the reaction layer 7 is formed on the first glass substrate 2.
  • the sealing glass material layer is locally heated by an electromagnetic wave such as a laser, the temperature of the glass substrate is not heated more than the sealing glass material layer. That is, the glass material layer for sealing may be heated at a higher temperature than when it is entirely heated in the firing furnace.
  • the reaction layer 7 can be formed deeper by heating at a higher temperature.
  • the intensity of the center of the laser spot is made strongest and weakened as it goes to the outside, so that the temperature distribution is given to the sealing glass material layer to be irradiated, and the shape of the reaction layer 7 is changed.
  • the shape of the reaction layer 7 is changed.
  • the glass material layer for sealing is locally heated by an electromagnetic wave such as a laser, it is difficult to heat except for the sealing region, so that the reflecting film 5 is not deteriorated by heat and the reflecting mirror 1 having a high reflectance can be obtained. .
  • the space 6 between the first glass substrate 2 and the second glass substrate 4 may be filled with air, but considering the reaction between oxygen in the air and the reflective film, nitrogen gas, argon gas, etc. It is desirable to be filled with an inert gas or in a vacuum state. In that case, sealing with an electromagnetic wave such as a laser is performed in an inert gas or in a vacuum.
  • the space 6 can be filled with resin, or a spacer as described above can be inserted.
  • a spacer such as granular alumina or silica having heat resistance may be used.
  • the spacer may be a resin or plastic having no heat resistance.
  • a granular spacer may be put in the sealing material.
  • Resin is applied to the inside of the region where the sealing glass material layer is formed, and the second glass substrate 4 and the first glass substrate 2 having the reflective film 5 are connected to the sealing glass material layer and the reflective film 5.
  • resins include epoxy resins, acrylic resins, polyester resins, urethane resins, melamine resins, phenol resins, polyesters, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl oxide, ABS resins, and fluorine resins. .
  • the second glass substrate 4 also has the reflecting film 5 as shown in FIG. 2, but the reflecting film is formed on the space 6 side surface of both the first and second glass substrates. May be.
  • a reflective film is formed on both the first and second glass substrates, if the first glass substrate 2 is used as a reflective surface, the outer surface is damaged, and the reflectance decreases due to irregular reflection or absorption.
  • the reflecting mirror 1 is inverted and the second glass substrate 4 side is used as a reflecting surface. By this operation, the life as the reflecting mirror 1 can be further extended.
  • both the first glass substrate 2 and the second glass substrate 4 use the reflecting mirror 1 having the reflecting film 5, and both sides of the first glass substrate 2 and the second glass substrate 4 are used as reflecting surfaces.
  • the thickness of the first glass substrate 2 and the second glass substrate 4 is preferably 0.55 to 2.8 mm in consideration of the balance between the strength and the reflectance of the reflecting mirror 1.
  • the shape of the reflecting mirror 1 may be a curved structure using a curved glass substrate as shown in FIG. It can be applied to trough solar power generators that require curved reflectors.
  • Example 1 As the low-melting glass, in terms of oxide of the following, Bi 2 O 3 83.2 wt%, B 2 O 3 5.6 wt%, ZnO10.7 wt%, Al 2 O 3 0.5 wt%, NaO 2 A bismuth-based glass frit (softening point: 410 ° C.) having a composition of 100 ppm and an average particle diameter (D 50 ) of 1.0 ⁇ m and cordierite powder as a ceramic filler were prepared. The cordierite powder has an average particle size (D 50 ) of 2.0 ⁇ m.
  • 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.
  • the vehicle is obtained by dissolving ethyl cellulose (2.5% by mass) as a binder component in a solvent (97.5% by mass) made of terpineol.
  • a second glass substrate 4 (dimensions: 100 mm ⁇ 100 mm ⁇ 1.1 mm) made of soda lime glass is prepared, and a sealing glass paste is applied to the sealing region in the peripheral portion of the entire four sides of the glass substrate. After applying by screen printing, it was dried at 120 ° C. for 10 minutes.
  • the printing pattern of the coating layer is a frame-like pattern with a line width of 1.0 mm, the dimension of the glass substrate area inside the coating layer (the area where the coating layer is not formed) is 80 mm ⁇ 80 mm, and the curvature of the corner portion The radius R was 2 mm.
  • the coating layer was heated under conditions of 300 ° C. ⁇ 30 minutes, and the resin binder component was skipped.
  • the glass material layer for sealing whose film thickness is 15 micrometers was formed by baking an application layer on the conditions for 480 degreeC x 10 minutes.
  • a silver thin film was formed on the first glass substrate 2 (a substrate made of soda lime glass having the same composition and shape as the second glass substrate 4) by a spray coating method.
  • the second glass substrate 4 having the sealing glass material layer and the first glass substrate 2 having a silver thin film as the reflective film 5 are laminated so that the sealing glass material layer and the reflective film 5 are inside. Then, the first glass substrate 2 and the second glass substrate 4 are sandwiched with heat-resistant clips, the two glass plates are brought into close contact, put into a firing furnace, and baked under a nitrogen atmosphere at 480 ° C. for 10 minutes. By doing so, the 1st glass substrate 2 and the 2nd glass substrate 4 were sealed, and the sealing glass layer 3 was obtained. In this way, the sealed reflecting mirror 1 was subjected to the characteristic evaluation described later.
  • the sealing region did not look like the reflective film 5, and the color of the sealing glass layer 3 was It was seen that the low melting point glass component in the sealing glass layer 3 penetrated through the silver thin film and reacted firmly with the first glass substrate 2. Further, no adhesion failure such as unbonded portions and cracks was observed, and it was confirmed that sufficient adhesion was obtained.
  • the produced reflector was put into a high-temperature and high-humidity test (temperature 60 ° C., relative humidity 90%) for 1000 hours, and the change in reflectance was confirmed, but there was almost no change.
  • reaction layer 7 was measured with the above-mentioned surface roughness meter, it was confirmed that a convex reaction layer was formed below about 50 to 60 nm as shown in FIG.
  • Example 2 As the low-melting glass, in terms of oxide of the following, Bi 2 O 3 83.2 wt%, B 2 O 3 5.6 wt%, ZnO10.7 wt%, Al 2 O 3 0.5 wt%, NaO 2 A bismuth glass frit (softening point: 410 ° C.) having a composition of 150 ppm and an average particle diameter (D 50 ) of 1.0 ⁇ m, cordierite powder as a ceramic filler, Fe 2 O 3 —CuO—MnO—Al An electromagnetic wave absorbing material having a 2 O 3 composition was prepared. Cordierite powder has an average particle size (D 50) is 2.0 .mu.m. The electromagnetic wave absorbing material has an average particle diameter (D 50 ) of 0.9 ⁇ m.
  • a glass material for sealing was mixed with 20% by mass of a vehicle to prepare a glass paste for sealing.
  • the vehicle is obtained by dissolving ethyl cellulose (2.5% by mass) as a binder component in a solvent (97.5% by mass) made of terpineol.
  • the 2nd glass substrate 4 (dimensions: 90 mm x 90 mm x 0.7 mm) which consists of an alkali free glass is prepared, and the glass paste for sealing is put on the sealing area
  • the printing pattern of the coating layer is a frame-like pattern with a line width of 0.75 mm, the size of the glass substrate area inside the coating layer (the area where the coating layer is not formed) is 80 mm ⁇ 80 mm, and the curvature of the corner portion The radius R was 2 mm.
  • the coating layer was heated under conditions of 300 ° C. ⁇ 30 minutes, and the resin binder component was skipped.
  • the glass material layer for sealing with a film thickness of 7 micrometers was formed by baking a coating layer on the conditions for 480 degreeC x 10 minutes.
  • an aluminum thin film was deposited on the first glass substrate 2 (a substrate made of non-alkali glass having the same composition and shape as the second glass substrate 4) by a vapor deposition method.
  • the second glass substrate 4 having the sealing glass material layer described above and the first glass substrate 2 having an aluminum thin film as the reflective film 5 are laminated so that the sealing glass material layer and the reflective film 5 are inside. did.
  • a laser having a wavelength of 940 nm, an output of 30 W, and a spot diameter of 1.6 mm is applied to the sealing glass material layer through the second glass substrate 4 with a pressure of 0.1 MPa applied from the second glass substrate 4.
  • the first glass substrate 2 and the second glass substrate 4 are sealed by irradiating light (semiconductor laser) at a scanning speed of 10 mm / s, melting the glass material layer for sealing, and then rapidly cooling and solidifying.
  • the sealing glass layer 3 was obtained.
  • the processing temperature during laser irradiation was 720 ° C. In this way, the sealed reflecting mirror 1 was subjected to the characteristic evaluation described later.
  • the sealing region did not look like the reflective film 5, and the sealing glass layer 3 was black. It was seen that the low melting point glass component in the sealing glass layer penetrated through the aluminum thin film and reacted firmly with the first glass substrate 2. Further, no adhesion failure such as unbonded portions and cracks was observed, and it was confirmed that sufficient adhesion was obtained.
  • the produced reflector 1 was put into a high-temperature and high-humidity test (temperature 60 ° C., relative humidity 90%) for 1000 hours, and the change in reflectance was confirmed, but there was almost no change.
  • reaction layer 7 was measured with the above-mentioned surface roughness meter, it was confirmed that the convex reaction layer 7 was formed below about 100 to 150 nm as shown in FIG.
  • Example 3 As the low-melting glass, in terms of oxide of the following, Bi 2 O 3 83.2 wt%, B 2 O 3 5.6 wt%, ZnO10.7 wt%, Al 2 O 3 0.5 wt%, NaO 2 A bismuth glass frit (softening point: 410 ° C.) having a composition of 150 ppm and an average particle diameter (D 50 ) of 1.0 ⁇ m, cordierite powder as a ceramic filler, Fe 2 O 3 —CuO—MnO—Al An electromagnetic wave absorbing material having a 2 O 3 composition was prepared. The cordierite powder has an average particle size (D 50 ) of 4.3 ⁇ m. The electromagnetic wave absorbing material has an average particle diameter (D 50 ) of 1.2 ⁇ m.
  • a second glass substrate 4 made of soda lime glass (dimensions: 100 mm ⁇ 100 mm ⁇ 0.7 mm) is prepared, and a glass paste for sealing is provided in the sealing region in the peripheral portion of the entire circumference of the four sides of the glass substrate 4.
  • the printing pattern of the coating layer is a frame-like pattern with a line width of 1.0 mm, the dimension of the glass substrate area inside the coating layer (the area where the coating layer is not formed) is 80 mm ⁇ 80 mm, and the curvature of the corner portion The radius R was 2 mm.
  • the coating layer was heated under conditions of 300 ° C. ⁇ 30 minutes, and the resin binder component was skipped.
  • the glass material layer for sealing whose film thickness is 15 micrometers was formed by baking an application layer on the conditions for 480 degreeC x 10 minutes.
  • a silver thin film was formed as a reflective film 5 on the first glass substrate 2 (a glass substrate made of soda lime glass having the same composition and shape as the second glass substrate 4) by a spray coating method.
  • An area other than the sealing area of the first glass substrate 2 is covered with a masking film, and the sealing area of the first glass substrate 2 is immersed in a 30% nitric acid aqueous solution for 30 seconds to 1 minute.
  • the silver thin film was peeled off and trimmed.
  • the aqueous nitric acid solution was washed away with distilled water, moisture was blown off with an air knife, the film cover was removed, and the solution was put into a 60 ° C. dryer and dried for 10 minutes.
  • the second glass substrate 4 having the sealing glass material layer and the first glass substrate 2 having a silver thin film as the reflective film 5 are laminated so that the sealing glass material layer and the reflective film 5 are inside. did.
  • a laser having a wavelength of 808 nm, an output of 70 W, and a spot diameter of 3.0 mm is applied to the glass material layer to be sealed through the second glass substrate 4 with a pressure of 0.25 MPa applied from the second glass substrate 4.
  • the first glass substrate 2 and the second glass substrate 4 are sealed by irradiating light (semiconductor laser) at a scanning speed of 2 mm / s, melting the glass material layer for sealing, and then rapidly solidifying it.
  • the sealing glass layer 3 was obtained.
  • the processing temperature during laser irradiation was 620 ° C. In this way, the sealed reflecting mirror 1 was subjected to the characteristic evaluation described later.
  • the produced reflector was put into a high-temperature and high-humidity test (temperature 60 ° C., relative humidity 90%) for 240 hours, and the change in reflectance was confirmed, but there was almost no change. Furthermore, the reflector described above was put in a high-temperature and high-humidity test (temperature 85 ° C. and relative humidity 85%) 2000 hours, which is a severe condition, and the change in reflectance was confirmed, but there was almost no change.
  • the heating source is a laser beam, but it is also possible to use electromagnetic waves such as infrared rays.
  • a silver thin film was formed as a reflective film on a glass substrate (size: 100 mm ⁇ 100 mm ⁇ 4 mm) made of soda lime glass by a spray coating method. Subsequently, a 0.03 ⁇ m copper thin film was spray-coated on the silver thin film, and an epoxy resin protective film was further coated by 45 ⁇ m to produce a reflecting mirror.
  • the prepared reflector was put in a high-temperature and high-humidity test (temperature 60 ° C., relative humidity 90%) for 240 hours and the change in reflectivity was confirmed. As a result, the reflectivity decrease was about 10 to 15% and the wavelength was 350 to 1000 nm. It was confirmed in the belt.
  • a silver thin film was formed as a reflective film on a glass substrate (size: 100 mm ⁇ 100 mm ⁇ 4 mm) made of soda lime glass by a spray coating method.
  • a polyvinyl butyral film having a thickness of 0.38 mm is sandwiched between a glass substrate on which the silver thin film has been formed and a glass substrate made of soda lime glass (dimensions: 100 mm ⁇ 100 mm ⁇ 4 mm), and heated at 120 ° C. for 40 minutes.
  • a laminated glass-type reflecting mirror was obtained.
  • the prepared reflector was put in a high-temperature and high-humidity test (temperature 60 ° C., relative humidity 90%) for 240 hours, and when the change in reflectance was confirmed, a decrease in reflectance of about 10 to 20% was observed at a wavelength of 350 to 1000 nm. It was confirmed in the belt.
  • the configuration of the reflecting mirror of the present invention has been described using the expressions of the first glass substrate and the second glass substrate.
  • the first glass substrate is used as the second glass substrate.
  • the second glass substrate may be replaced with the first glass substrate, and the present invention is the same.
  • the reflecting mirror of the present invention since the first and second glass substrates are sealed with the sealing glass layer over the entire circumference in the peripheral portion, the reflecting mirror is formed in the reflecting mirror. It is possible to prevent moisture and the like from entering the space. As a result, it is possible to provide a reflecting mirror that can prevent deterioration of the characteristics of the reflective film and maintain the reflection characteristics for a long period of time.
  • the method of sealing the glass material layer for sealing by using electromagnetic waves to form the sealing glass layer local heating can be performed, so that the characteristic deterioration of the reflective film due to heat at the time of sealing can be prevented. it can.
  • the reflecting mirror of the present invention is useful as a reflecting mirror for a solar condensing system and a solar thermal power generation system that are required to have long-term durability and no characteristic deterioration.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Sustainable Energy (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Mounting And Adjusting Of Optical Elements (AREA)
  • Non-Portable Lighting Devices Or Systems Thereof (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention a trait à un miroir réfléchissant qui est particulièrement résistant à l'eau. Le miroir réfléchissant comprend un premier substrat de verre comportant un film réfléchissant, un second substrat de verre disposé en regard du côté film réfléchissant du premier substrat de verre, et une couche de verre d'étanchéité conçue pour rendre étanches le premier substrat de verre ainsi que le second substrat de verre. Un film réfléchissant est également formé sur le second substrat de verre sur la surface en regard de la surface du film réfléchissant du premier substrat de verre. Une couche de réaction, qui est produite par l'étanchéité, est présente à la jonction entre le premier substrat de verre et la couche de verre d'étanchéité, et à la jonction entre le second substrat de verre et la couche de verre d'étanchéité.
PCT/JP2011/078489 2010-12-09 2011-12-08 Miroir réfléchissant et son procédé de fabrication WO2012077771A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010274997A JP2014038118A (ja) 2010-12-09 2010-12-09 反射鏡およびその製造方法
JP2010-274997 2010-12-09

Publications (1)

Publication Number Publication Date
WO2012077771A1 true WO2012077771A1 (fr) 2012-06-14

Family

ID=46207253

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/078489 WO2012077771A1 (fr) 2010-12-09 2011-12-08 Miroir réfléchissant et son procédé de fabrication

Country Status (3)

Country Link
JP (1) JP2014038118A (fr)
TW (1) TW201237470A (fr)
WO (1) WO2012077771A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014134114A1 (fr) * 2013-02-28 2014-09-04 Corning Incorporated Appareil à miroir de verre et procédé de fabrication d'appareil à miroir de verre
EP3179176A1 (fr) * 2015-12-07 2017-06-14 Ricardo Lozano Peña Face solaire de type sandwich thermiquement équilibrée

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678325A (zh) * 2019-01-23 2019-04-26 兰州交通大学 二次反射镜成型装置及利用其制备二次反射镜的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5860702A (ja) * 1981-10-07 1983-04-11 Nippon Sheet Glass Co Ltd 反射鏡及びその製造方法
JPS63161908A (ja) * 1986-12-26 1988-07-05 市光工業株式会社 曲面鏡の製造方法
JP2010055058A (ja) * 2008-07-28 2010-03-11 Nippon Electric Glass Co Ltd 広帯域反射鏡

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5860702A (ja) * 1981-10-07 1983-04-11 Nippon Sheet Glass Co Ltd 反射鏡及びその製造方法
JPS63161908A (ja) * 1986-12-26 1988-07-05 市光工業株式会社 曲面鏡の製造方法
JP2010055058A (ja) * 2008-07-28 2010-03-11 Nippon Electric Glass Co Ltd 広帯域反射鏡

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014134114A1 (fr) * 2013-02-28 2014-09-04 Corning Incorporated Appareil à miroir de verre et procédé de fabrication d'appareil à miroir de verre
CN105392749A (zh) * 2013-02-28 2016-03-09 康宁股份有限公司 玻璃镜子设备和制造玻璃镜子设备的方法
JP2016518298A (ja) * 2013-02-28 2016-06-23 コーニング インコーポレイテッド ガラスミラー装置及びガラスミラー装置を作製する方法
JP2019194148A (ja) * 2013-02-28 2019-11-07 コーニング インコーポレイテッド ガラスミラー装置及びガラスミラー装置を作製する方法
US10551590B2 (en) 2013-02-28 2020-02-04 Corning Incorporated Glass mirror apparatus and methods of manufacturing a glass mirror apparatus
EP3179176A1 (fr) * 2015-12-07 2017-06-14 Ricardo Lozano Peña Face solaire de type sandwich thermiquement équilibrée
WO2017097709A1 (fr) 2015-12-07 2017-06-15 Ricardo Lozano Peña Facette d'héliostat de type en sandwich thermiquement équilibrée
CN108369034A (zh) * 2015-12-07 2018-08-03 理查德·洛萨诺·佩纳 热平衡夹层型定日镜刻面
EP3179176B1 (fr) 2015-12-07 2019-03-13 Ricardo Lozano Peña Face solaire de type sandwich thermiquement équilibrée

Also Published As

Publication number Publication date
JP2014038118A (ja) 2014-02-27
TW201237470A (en) 2012-09-16

Similar Documents

Publication Publication Date Title
TWI497466B (zh) Electronic device and manufacturing method thereof
WO2012117978A1 (fr) Élément étanche à l'air et son procédé de production
WO2013008724A1 (fr) Double vitrage et son procédé de fabrication
JP5418594B2 (ja) 封着材料層付きガラス部材とそれを用いた電子デバイスおよびその製造方法
JP5716743B2 (ja) 封着材料ペーストとそれを用いた電子デバイスの製造方法
JP2013239609A (ja) 気密部材とその製造方法
WO2012043787A1 (fr) Boîtier d'élément électrique
JP4821033B2 (ja) 集光型太陽光発電ユニットおよびその柱状光学ガラス部材
JP5494831B2 (ja) 封着材料層付きガラス部材とそれを用いた電子デバイス及びその製造方法
KR20110098894A (ko) 봉착 유리, 봉착 재료층 부착 유리 부재, 및 전자 디바이스와 그 제조 방법
JPWO2011158873A1 (ja) 電子デバイス
JP2011126722A (ja) レーザ封着用封着材料、封着材料層付きガラス部材、およびそれを用いた太陽電池とその製造方法
WO2012090695A1 (fr) Dispositif électronique et procédé de fabrication de celui-ci
JP2012014971A (ja) 電子デバイス及びその製造方法
WO2012077771A1 (fr) Miroir réfléchissant et son procédé de fabrication
WO2010137667A1 (fr) Élément de verre avec une couche de matériau d'étanchéité attachée à celui-ci, dispositif électronique obtenu à l'aide de celui-ci et son procédé de fabrication
TW202145615A (zh) 密封封裝及有機電激發光元件
WO2012128227A1 (fr) Miroir réfléchissant
TW201222847A (en) Electronic device and method of manufacturing thereof
JP2013227181A (ja) 封着構造体およびその製造方法
JP2013216502A (ja) 接合層付きガラス部材
JP2014005177A (ja) 気密部材とその製造方法
JP2014221695A (ja) 封着パッケージ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11846176

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11846176

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP