WO2012128227A1 - Miroir réfléchissant - Google Patents

Miroir réfléchissant Download PDF

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Publication number
WO2012128227A1
WO2012128227A1 PCT/JP2012/056926 JP2012056926W WO2012128227A1 WO 2012128227 A1 WO2012128227 A1 WO 2012128227A1 JP 2012056926 W JP2012056926 W JP 2012056926W WO 2012128227 A1 WO2012128227 A1 WO 2012128227A1
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WIPO (PCT)
Prior art keywords
glass
glass substrate
sealing
layer
reflecting mirror
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PCT/JP2012/056926
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English (en)
Japanese (ja)
Inventor
暢子 満居
壮平 川浪
山田　和夫
諭司 竹田
恭行 亀山
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旭硝子株式会社
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Publication of WO2012128227A1 publication Critical patent/WO2012128227A1/fr

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    • 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

Definitions

  • the present invention relates to a reflecting mirror.
  • a solar thermal power generation system that condenses sunlight, generates high-temperature and high-pressure steam by the thermal energy, and drives a turbine using the steam has been studied.
  • a solar heat collector a solar light collecting system, and the like, a reflecting mirror is generally used to increase the light collecting efficiency of sunlight.
  • the reflecting mirror is manufactured by coating a metal thin film such as aluminum or silver as a reflective film on a transparent substrate such as a glass substrate.
  • Mirrors coated with a metal thin film on a transparent substrate have a problem that the metal thin film on the surface is likely to deteriorate due to moisture, oxygen, etc. in the environmental atmosphere.
  • a reflecting mirror in which a protective film made of an acrylic resin, an epoxy resin or the like is formed on the metal thin film is known.
  • a protective film made of resin has insufficient water resistance, it is difficult to prevent deterioration of the metal thin film over a long period of time when installed outdoors.
  • Patent Document 1 describes a reflecting mirror coated with an elastic sealant made of silicone sealant or the like along the entire periphery of a laminated glass mirror.
  • Patent Document 2 a silver mirror film, a metal protective film made of copper or the like and a backing coating film are sequentially laminated on a glass substrate, and a coating made of an acrylic silicone resin is formed on the edge of these laminated films. A mirror is described.
  • water barrier properties such as silicone sealants and acrylic silicone resins are not perfect, and it is difficult to maintain water resistance over a long period of time.
  • the metal protective film is very thin, cracks are likely to occur gradually due to thermal expansion or the like, and there is a problem that reliability is poor.
  • palladium is activated by an activation treatment with a solution containing a palladium compound on the glass substrate in order to suppress deterioration or peeling of the silver film due to intrusion of moisture.
  • (Pd) is deposited as a base of a silver film, thereby improving the adhesion between the glass substrate and the silver film.
  • palladium as a base layer is very expensive, it causes an increase in the manufacturing cost of the reflecting mirror.
  • the reflectance of the silver film itself is lowered, which is a factor that degrades the performance of the reflecting mirror.
  • An object of the present invention is to provide a reflecting mirror that is excellent in water resistance and that can reduce the manufacturing cost while improving the reflectance.
  • the reflecting mirror of the present invention includes a first glass substrate having a first surface, a reflective film formed on the first surface of the first glass substrate, and a second facing the first surface.
  • the first glass substrate and the second glass so as to hermetically seal the second glass substrate having a surface with a predetermined gap from the first glass substrate and the reflective film.
  • a sealing glass layer formed in a peripheral portion of the substrate and between the first glass substrate and the second glass substrate; and on the first surface of the first glass substrate.
  • the Pd concentration is 0.15 atomic% or less (atomic % percent) or less.
  • the sealing glass layer having excellent water resistance is hermetically sealed between the first glass substrate and the second glass substrate, deterioration of the reflecting film due to moisture and the like over a long period of time. Can be suppressed. Therefore, even when the Pd concentration as the base of the reflective film is reduced, the reflective film can be prevented from being deteriorated or peeled off. ADVANTAGE OF THE INVENTION According to this invention, the reflective mirror which can maintain the outstanding reflectance over a long period of time can be provided at low cost.
  • FIG. 1 is a cross-sectional view showing the configuration of the reflecting mirror according to the first embodiment
  • FIG. 2 is a cross-sectional view showing the configuration of the reflecting mirror according to the second embodiment.
  • the reflecting mirror 1 shown in these drawings includes a first glass substrate 2 having a first surface 2a and a second glass substrate 3 having a second surface 3a.
  • the first glass substrate 2 and the second glass substrate 3 are laminated and arranged with a predetermined gap so that the first surface 2a and the second surface 3a face each other.
  • the reflecting mirror 1 has a reflecting film 4 formed on the surface 2 a of the first glass substrate 2.
  • the reflective film 4 is made of a metal such as silver, a silver alloy (Ag—Pt alloy, Ag—Pd alloy, etc.), aluminum or the like.
  • a metal reflective film (metal reflective film) 4 can be formed by various thin film forming methods such as vapor deposition, sputtering, CVD, ion plating, ion beam irradiation, and spray coating.
  • the reflective film 4 may be formed not only on the surface 2 a of the first glass substrate 2 but also on the surface 3 a of the second glass substrate 3.
  • the reflecting mirror 1 according to the second embodiment includes a first reflecting film 4A formed on the surface 2a of the first glass substrate 2 and a second reflecting film formed on the surface 3a of the second glass substrate 3. 4B.
  • both surfaces of the first glass substrate 2 and the second glass substrate 3 can be used as reflection surfaces.
  • the reflecting mirror 1 is inverted and the second glass substrate 3 is used as the reflecting surface. By doing so, it is possible to further extend the life of the reflecting mirror 1.
  • the sealing glass layer 5 is formed so as to hermetically seal the reflective film 4 including 4A and 4B. That is, the reflecting mirror 4 is positioned in an airtight space 6 of a glass package constituted by the first glass substrate 2, the second glass substrate 3, and the sealing glass layer 5.
  • the sealing glass layer 5 contains a low melting point glass as an essential component, and may contain an inorganic filler such as a thermal expansion adjusting material or an electromagnetic wave absorbing material as an optional component as will be described in detail later.
  • the sealing glass layer 5 is made of a melt-solidified material of a sealing glass material including a low melting point glass as an essential component and an inorganic filler as an optional component.
  • the sealing glass layer 5 is substantially composed only of an inorganic material, the sealing glass layer 5 is superior in airtightness compared to a sealing material made of a conventional organic material, and has long intrusion of moisture or the like that causes deterioration of the reflective film 4. Can be prevented over time. This means that the sealing glass layer 5 can suppress deterioration and peeling of the reflective film 4. Therefore, unlike the prior art, the first glass substrate 2 and the second glass of the reflective film 4 are not deposited on the reflective film 4 without depositing palladium (Pd) as the base of the reflective film 4 in order to improve the durability of the reflective film 4. It becomes possible to maintain the adhesion to the substrate 3 over a long period of time.
  • the amount can be made extremely small. That is, it is sufficient to deposit palladium in an amount that can form the reflective film 4 without unevenness without considering improvement in the adhesion of the reflective film 4 and the like.
  • the palladium (Pd) concentration on the surface 2a of the first glass substrate 2 which is the formation surface of the reflecting film 4 (or 4A) and also reflected on the second glass substrate 3 are reflected.
  • the palladium (Pd) concentration on the surface 3a of the second glass substrate 2 is set to 0.15 atomic% or less.
  • the palladium (Pd) concentration of 0.15 atomic% or less includes the case where the palladium (Pd) concentration is 0.00 atomic%.
  • the manufacturing cost of the reflective film 1 can be reduced by setting the Pd concentration of the glass substrate 2 or the surface 2a of the glass substrates 2 and 3 or the Pd concentration of the surfaces 2a and 3a to 0.15 atomic% or less. Furthermore, it is possible to suppress a decrease in the reflectance of the reflective film 4 due to palladium. Therefore, it is possible to provide a reflecting mirror 1 that can maintain an excellent reflectance over a long period of time, and to reduce the manufacturing cost of such a reflecting mirror 1.
  • the Pd concentration on the surface of the glass substrate described above is a value obtained as follows. That is, the Pd concentration on the surface of the glass substrate is measured by depth direction analysis from the surface using X-ray photoelectron spectroscopy (XPS) combined with sputter etching using an Ar ion beam. More specifically, a depth direction analysis of elements of Pd, Ag, Sn, Si, Na, and O is performed, and a concentration graph in the depth direction as shown in FIG. 3 is created. Next, as shown in an enlarged view in FIG. 4, the concentration at the point where the XPS peak intensity of Pd3d is maximum (point A in FIG. 4) is defined as the Pd concentration (number of atoms%).
  • XPS X-ray photoelectron spectroscopy
  • each element is measured within the following energy range.
  • Pd3d is 330 to 348 eV
  • Ag3d is 364 to 380 eV
  • Sn3d5 / 2 is 480 to 500 eV
  • Si2p is 95 to 110 eV
  • Na1s is 1066 to 1082 eV
  • O1s is 525 to 540 eV.
  • the quantification was performed by ULVAC-PHI PHI MultiPak Data Analysis Software TM Ver. This was performed using 8.2 (trade name). For quantification, a spectrum obtained by subtracting the background using the Shirley method and repeating 5-point Savitzky-Golay smoothing three times was used.
  • the sputter etching time by the Ar ion beam corresponds to the depth from the surface, that is, the film thickness.
  • the conversion from the sputter etching time to the film thickness was obtained from a calibration curve prepared using a standard sample having a known film thickness and the same composition. That is, it calculated as 0.5 nm / min in terms of SiO 2 .
  • the XPS spectrometer used was model 5500 manufactured by Phi, and X-ray AlK ⁇ rays monochromatized with a monochromator were used as the X-ray source. Further, the detection angle of X-ray photoelectrons was 45 °, and measurement was performed by irradiating an electron shower to correct charging.
  • the measurement conditions were a path energy of 117.4 eV, a step energy of 0.5 eV, and an energy resolution of 1.70 eV with a half width of Ag3d5 / 2.
  • Ar sputtering was performed on an area of 3 ⁇ 3 mm 2 at an acceleration energy of 1 kV.
  • a protective film made of a metal film or a resin film for improving durability may not be formed on the surface of the reflective film 4. That is, the reflective film 4 is exposed in a space 6 hermetically sealed with the first glass substrate 2, the second glass substrate 3, and the sealing glass layer 5. Even if a protective film or the like is not formed on the surface of the reflective film 4, the glass package constituted by the first glass substrate 2, the second glass substrate 3, and the sealing glass layer 5 has excellent hermetic sealing properties. ing. Therefore, even when the Pd concentration is reduced as the base of the reflective film, the deterioration or peeling of the reflective film 4 can be suppressed. Furthermore, the manufacturing cost of the reflecting mirror 1 can also be reduced by omitting the formation of the protective film on the reflecting film 4.
  • a resin or the like may be filled in the hermetic space 6 formed by the glass package.
  • the exposure of the reflective film 4 to the airtight space 6 means that no other film or member exists on the reflective film 4 except for the filler.
  • the first and second glass substrates 2 and 3 are made of soda lime glass, alkali-free glass, chemically tempered glass, physically tempered glass, or the like having various known compositions.
  • Soda lime glass has a thermal expansion coefficient of about 80 to 90 ( ⁇ 10 ⁇ 7 / ° C.).
  • the alkali-free glass has a thermal expansion coefficient of about 35 to 40 ( ⁇ 10 ⁇ 7 / ° C.).
  • the soda lime glass is preferably white plate glass (high transmission glass) having high transparency.
  • the white plate glass (high transmission glass) referred to here is a glass having a visible light transmittance higher than that of ordinary soda lime glass and having a visible light transmittance of 90% or more. It is a glass having an iron content of 0.06% or less as Fe 2 O 3 .
  • Tempered glass obtained by chemically strengthening or physically strengthening soda lime glass is preferable for enhancing the strength and reliability of the reflecting mirror 1.
  • the tempered glass may be obtained by chemically strengthening or physically strengthening glass other than soda lime glass.
  • “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 3 is preferably in the range of 0.03 to 5 mm. If the thickness of the glass substrates 2 and 3 is less than 0.03 mm, the strength and reliability of the reflecting mirror 1 may be insufficient. On the other hand, when the thickness of the glass substrates 2 and 3 exceeds 5 mm, not only the reflecting mirror 1 becomes heavy, but also the reflectance may decrease due to absorption of the glass substrate itself. Considering the reflectance and weight of the reflecting mirror 1, it is desirable that the thickness of the glass substrates 2 and 3 is thin, specifically 0.03 to 2.8 mm is more preferable, and more preferably 0.03 to 1 is preferable. .1 mm. Considering the strength of the reflecting mirror 1, it is desirable that the glass substrates 2 and 3 are thicker, specifically 0.07 to 5 mm, more preferably 1.1 to 5 mm.
  • the thicknesses of the first and second glass substrates 2 and 3 are appropriately adjusted depending on the location where the reflective film 4 is formed. That is, when the reflective film 4 is formed only on the surface 2 a of the first glass substrate 2, the thickness of the first glass substrate 2 is preferably 0.03 to 0.7 mm, and the thickness of the second glass substrate 3. Is preferably 0.7 to 5 mm. Thereby, the strength can be improved while increasing the reflectance of the reflecting mirror 1. When the reflective film 4 is formed on both the surface 2a of the first glass substrate 2 and the surface 3a of the second glass substrate 3, the first and second layers are considered in consideration of the reflectance and strength of the reflecting mirror 1. The thickness of the glass substrates 2 and 3 is preferably 0.55 to 2.8 mm.
  • the shape of the glass substrates 2 and 3 is not limited to this, and may have a curved shape.
  • a reflecting mirror using a glass substrate having a curved shape is suitable for a method of collecting sunlight with a curved mirror such as a trough solar power generation.
  • a reflector using a glass substrate having a curved shape is effective in collecting sunlight.
  • the internal space (namely, airtight space) 6 of the glass package composed of the first glass substrate 2, the second glass substrate 3, and the sealing glass layer 5 may be filled with air.
  • the airtight space 6 is vacuum (for example, the pressure is preferably 100 Pa or less) or filled with an inert gas such as nitrogen gas or argon gas.
  • the airtight space 6 may be filled with resin.
  • the gap between the first glass substrate 2 and the second glass substrate 3 is used to reduce the influence of the reaction between the oxygen in the filler filled in the airtight space 6 and the reflective film 4, the thermal expansion, and the like.
  • the thickness of the reflective film 4 is narrow as long as the reflective film 4 and the arrangement thereof are not adversely affected.
  • the distance between the first glass substrate 2 and the second glass substrate 3 is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, and particularly preferably 10 ⁇ m or less. Spacers may be arranged in the airtight space 6 having such an interval (that is, thickness) in order to improve the strength.
  • the spacer is preferably a ceramic spacer such as alumina or silica having heat resistance when the entire reflecting mirror 1 is heated in a firing furnace in the sealing step.
  • a spacer made of resin or plastic may be used.
  • the reaction layer 7 with the glass layer 5 is preferably formed.
  • the reaction layer 7 is generated from the respective surface layers of the first and second glass substrates 2 and 3 toward the inside thereof in a region in contact with the sealing glass layers of the first and second glass substrates 2 and 3.
  • the reaction layer 7 has a maximum depth of 30 nm or more from the surfaces of the first and second glass substrates in the interface region in contact with the sealing glass layer 5 of the glass substrates 2 and 3. It is desirable to generate as follows.
  • the reaction layer 7 is a mixed layer of the constituent elements of the first and second glass substrates 2 and 3 and the constituent element of the sealing glass layer 5.
  • the reaction layer 7 By generating such a reaction layer 7 on the surface layers of the first and second glass substrates 2 and 3 and setting the maximum depth to 30 nm or more, the first and second glass substrates 2 and 3 and The adhesive state with the sealing glass layer 5 can be strengthened. Moreover, it can also be set as a favorable airtight structure between the glass substrates 2 and 3 sealed by the sealing glass layer 5. If the maximum depth of the reaction layer 7 is less than 30 nm, there is a possibility that the effect of increasing the adhesive strength and airtightness cannot be obtained sufficiently.
  • the maximum depth of the reaction layer 7 50 nm or more is more preferable, More preferably, it is 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 3 from the vicinity of both end portions of the sealing glass layer 5 in the cross section in the width direction. It is preferable to have. In other words, 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 3 is deeper in the vicinity of the center than the both ends of the sealing glass layer 5. . According to the reaction layer 7 having such a shape, the stress generated at the interface between the first and second glass substrates 2 and 3 and the reaction layer 7 is dispersed throughout the reaction layer 7. The adhesive strength between the glass substrates 2 and 3 and the sealing glass layer 5 can be further increased.
  • the shape of the reaction layer 7 is not limited to a shape having a substantially arc-shaped cross section as shown in FIG. 5, and 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 near the end of the sealing glass layer 5. (Ie, D1 / D2 ⁇ 1.1) is preferable (that is, a shape protruding toward the glass substrate and downward in FIG. 6).
  • 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.
  • the position of the maximum depth D1 and the distance L2 that is 1/10 of the distance L1 from the nearest end of the position to the position having the maximum depth D1. It is assumed that D1 / D2 is obtained based on the depth D2.
  • L1 indicates the length of the reaction layer 7 in the width direction, 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 first and second glass substrates 2, 3 and The adhesive strength with the sealing glass layer 5 can be further increased, and the stress dispersion effect at the interface between the first and second glass substrates 2 and 3 and the reaction layer 7 can be obtained with good reproducibility.
  • 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).
  • the cross-sectional area of the reaction layer 7 can be increased even if the width (line width) of the sealing glass layer 5 is increased, and this is also the first and second glass substrates 2 and 3 and the sealing glass layer 5. As a means for increasing the adhesive strength.
  • the generation of the reaction layer 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 3 and the sealing glass layer 5.
  • the method to show is mentioned.
  • the shape of the reaction layer 7 (depth, cross-sectional area, D1 / D2 ratio, etc.), values measured by the following method are shown.
  • the sealing glass layer 5 is removed by immersing the sample from which one glass substrate is 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 5 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 3 and the constituent element of the sealing glass layer 5, the reaction layer 7 is also removed simultaneously with the removal of the sealing glass layer 5. .
  • a glass substrate in which the formation marks of the reaction layer 7 remain as concave portions is produced.
  • a surface roughness meter By measuring the surface shape of the glass substrate having such a concave portion with a surface roughness meter, it is possible to measure and evaluate the shape of the concave portion, which is the formation trace of the reaction layer 7, that is, the shape of the reaction layer 7.
  • . 7 to 8 are diagrams showing the results of measuring the surface shape of the reaction layer 7 of the glass substrate in the reflecting mirror 1 produced in Examples 1 and 2 described later. As shown in these figures, after the reaction layer 7 is dissolved and removed from the first and second glass substrates 2 and 3, the surface shapes of the first and second glass substrates 2 and 3 are measured with a surface roughness meter. By doing so, the shape of the reaction layer 7 can be evaluated.
  • the sealing glass layer 5 is made of a molten and solidified body of a sealing glass material containing a low melting point glass which is an essential component and an inorganic filler which is an optional component.
  • the combination, blending amount, and the like of the sealing glass material are selected in consideration of the compatibility with the first and second glass substrates 2 and 3 and the respective characteristics.
  • the sealing glass material preferably contains at least a low melting glass, and its content is preferably 60 to 100% by volume.
  • the content of the inorganic filler as an optional component is preferably 0 to 40% by volume. When the content of the low-melting glass is less than 60% by volume, the fluidity of the sealing glass material at the time of sealing is lowered, and there is a possibility that good sealing cannot be performed.
  • the content of the low melting point glass is more preferably 65% by volume or more.
  • the upper limit is not particularly limited, but it is preferably 97% by volume or less, and more preferably 90% by volume or less in consideration of adjustment of the coefficient of thermal expansion with respect to the glass substrates 2 and 3.
  • the low melting point glass for example, tin-phosphate glass, bismuth glass, vanadium glass, lead glass, silica alkali borate glass and the like are used.
  • bismuth-based glass may be used in consideration of adhesion to the glass substrates 2 and 3 and reliability thereof (for example, adhesion reliability and hermetic sealing), and influence on the environment and human body. preferable.
  • the bismuth glass as the low melting point glass is 70 to 90% Bi 2 O 3 , 1 to 20% ZnO, 2 to 12% B in terms of mass percentage or mass percentage in the following oxide conversion notation. It preferably has a composition containing 2 O 3 and 10-1000 ppm of Na 2 O. Glass formed of three components of Bi 2 O 3 , ZnO, and B 2 O 3 is suitable for a low-melting glass of a sealing glass material because it has characteristics such as transparency and low glass transition point.
  • reaction layer 7 is easily generated at the bonding interface between the first and second glass substrates 2 and 3 and the sealing glass layer 5.
  • Bi 2 O 3 is a component that forms a glass network, and is preferably contained in the sealing glass in a range of 70 to 90% by mass.
  • the content of Bi 2 O 3 is less than 70% by mass, the softening temperature of the 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 low melting point glass in the range of 1 to 20% by mass. 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 that increases the range in which vitrification is possible by forming a glass skeleton, and is preferably contained in the range of 2 to 12% by mass in the low-melting glass. 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 increases the reactivity of the low-melting glass of the sealing glass material layer 8 with respect to the first and second glass substrates 2 and 3, and is contained in the low-melting glass in a mass ratio of 10 to 1000 ppm. It is preferable to make it.
  • the content of Na 2 O is less than 10 ppm, the generation efficiency of the reaction layer 7 cannot be sufficiently increased. If 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 first and second glass substrates 2 and 3 and the sealing glass layer 5.
  • Na 2 O which is particularly excellent in reactivity with the glass substrates 2 and 3 is effective, and therefore the bismuth-based glass preferably contains Na 2 O.
  • a part of 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, so the total content of any component is 10% by mass or less.
  • the lower limit of the total content of arbitrary components is not particularly limited. An effective amount of an arbitrary 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 7% by mass.
  • BaO is excellent in the contribution of stabilization, and can be contained as the fifth component in the range of 0.1 to 7% 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).
  • Examples of the inorganic filler blended as an optional component in the sealing glass material include a thermal expansion adjusting material and an electromagnetic wave absorbing material.
  • the thermal expansion adjusting material approximates the thermal expansion coefficient between the first and second glass substrates 2 and 3 and the sealing glass layer 5.
  • the thermal expansion coefficient of the low-melting glass is larger than that of the first and second glass substrates 2 and 3, so that the inorganic filler (that is, the thermal expansion coefficient is smaller than that of the first and second glass substrates 2 and 3).
  • Low expansion fillers are often used.
  • an inorganic 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 content of the inorganic filler is preferably 0 to 40% by mass.
  • the preferable lower limit of the content of the inorganic filler is 3% by volume or more, more preferably 10% by volume or more.
  • the electromagnetic wave absorbing material is a filler that enhances the electromagnetic wave absorbing ability of the sealing glass material when the sealing glass material is heated by irradiating an electromagnetic wave such as laser light or infrared light.
  • an electromagnetic wave such as laser light or infrared light.
  • the electromagnetic wave absorber at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu, or a compound such as an oxide containing the metal is used. Other pigments may be used.
  • the content of the electromagnetic wave absorbing material is preferably in the range of 0 to 40% by volume.
  • the content of the electromagnetic wave absorbing material exceeds 40% by volume, the fluidity at the time of melting of the sealing glass material is lowered, and there is a possibility that the sealing cannot be performed satisfactorily.
  • content of an electromagnetic wave absorber 25 volume% or less is more preferable, More preferably, it is 20 volume% or less.
  • the reflecting mirror 1 of this embodiment is manufactured as follows, for example. First, the manufacturing process of the reflecting mirror 1 using a baking furnace will be described with reference to FIG. First, as illustrated in FIG. 9A, the reflective film 4 is formed on the surface 2 a of the first glass substrate 2.
  • the reflective film 4 may be formed in a desired shape excluding the region where the sealing glass layer 5 is formed, or after being formed on the entire surface 2a, the region where the sealing glass layer 5 is formed is trimmed. And it is good also as a desired shape.
  • a sealing glass material layer 8 is formed in the outer peripheral region (sealing region) of the surface 3 a of the second glass substrate 3.
  • the sealing glass material layer 8 is prepared by mixing a low melting glass, which is an essential component of the sealing glass material, and an inorganic filler, which is an optional component, with a vehicle to prepare a sealing glass material paste. It forms by apply
  • 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, An organic resin such as an acrylic resin obtained by polymerizing at least one acrylic monomer such as 2-hydroxyethyl acrylate is used.
  • terpineol, butyl carbitol acetate, ethyl carbitol acetate or the like is used in the case of a cellulose resin, and methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate or the like is used in the case of an acrylic resin.
  • the viscosity of the sealing glass material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 3, and can be adjusted by the ratio of the resin and the solvent, the ratio of the sealing glass material and the vehicle.
  • the resin is a component that disappears upon firing.
  • You may add a well-known additive with a glass paste like an antifoamer and a dispersing agent to sealing glass material paste. 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.
  • the sealing glass material paste is applied to the outer peripheral region of the second glass substrate 3 over the entire circumference and dried to form a coating film of the sealing glass material paste.
  • the sealing glass material paste is applied to the outer peripheral region by applying a printing method such as screen printing or gravure printing, or is applied along the outer peripheral region using a dispenser or the like.
  • the width of the coating film is preferably 0.5 to 20 mm in order to maintain the strength.
  • the thickness of the coating film is set according to the thickness of the hermetic space between the first glass substrate 2 and the second glass substrate 3, taking into account the shrinkage of the film in the subsequent drying process or pre-baking process. It is preferable to set. For example, the thickness of the coating film is set so that the thickness of the sealing glass layer after sealing is 1 to 50 ⁇ m.
  • the coating film of the sealing glass material paste is preferably dried at a temperature of 60 to 150 ° C. for 30 seconds to 10 minutes, for example, to remove the solvent in the coating film. Subsequently, after heating to a temperature lower by 30 ° C. or lower than the glass transition point of the low-melting glass in a firing furnace to remove the binder component and the like in the coating film, the temperature is higher than the softening point of the low-melting glass (for example, By heating the sealing glass material to the second glass substrate 3 to form a frame-shaped sealing glass material layer 8 on the outer peripheral region of the second glass substrate 3. Form.
  • the glass transition point is defined by the temperature of the first inflection point of differential thermal analysis (DTA), and the glass softening point is defined by the temperature of the fourth inflection point of differential thermal analysis (DTA).
  • the first glass substrate 2 and the second glass substrate 3 are opposed to the surface 2 a having the reflective film 4 and the surface 3 a having the sealing glass material layer 8.
  • the atmosphere during firing is preferably a vacuum or an inert gas atmosphere such as nitrogen gas or argon gas in order to suppress the deterioration of the reflective film 4.
  • the state in the space 6 hermetically sealed with the first glass substrate 2, the second glass substrate 3, and the sealing glass layer 5 is determined according to the atmosphere during firing. Moreover, when installing a spacer in the airtight space 6, when laminating
  • reaction layer 7 is formed at the interface between the first and second glass substrates 2 and 3 and the sealing glass layer 5.
  • the formation state of the reaction layer 7 depends on the composition of the low melting point glass in the sealing glass material layer 8, the firing temperature, the adhesion between the sealing glass material layer 8 and the first glass substrate 2, and the like.
  • the higher the firing temperature the easier the formation of the reaction layer 7 proceeds.
  • Adhesion can be improved by applying a load with a heat-resistant clip or weight.
  • the reflective film 4 is formed on the surface 2 a of the first glass substrate 2.
  • the formation process of the reflective film 4 is the same as the manufacturing process using a baking furnace.
  • the sealing glass material layer 8 is formed in the outer peripheral region (sealing region) of the surface 3 a of the second glass substrate 3.
  • the forming process of the sealing glass material layer 8 is performed in the same manner as the manufacturing process using the firing furnace except that the sealing glass material includes an electromagnetic wave absorbing material.
  • the sealing glass material layer 8 is irradiated with an electromagnetic wave 9 such as a laser beam or an infrared ray through the second glass substrate 3 (or the first glass substrate 2).
  • an electromagnetic wave 9 such as a laser beam or an infrared ray through the second glass substrate 3 (or the first glass substrate 2).
  • the laser beam is irradiated while scanning along the sealing glass material layer 8.
  • the laser light is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used.
  • the electromagnetic wave 9 When infrared rays are used as the electromagnetic wave 9, for example, a portion other than a portion where the sealing glass material layer 8 is formed is masked with an infrared reflecting film such as Ag, and the sealing glass material layer 8 can be selectively irradiated with infrared rays. preferable.
  • an infrared reflecting film such as Ag
  • the sealing glass material layer 8 When a laser beam is used as the electromagnetic wave 9, the sealing glass material layer 8 is melted in order from the portion irradiated with the laser beam scanned along it, and is rapidly cooled and solidified upon completion of the laser beam irradiation. It adheres to the substrate 2. Then, by irradiating the entire circumference of the sealing glass material layer 8 with laser light, as shown in FIG. 10 (e), the entire circumference is provided between the first glass substrate 2 and the second glass substrate 3. A sealing glass layer 5 that is sealed over is formed.
  • the sealing glass material layer 8 is melted based on infrared irradiation, and is rapidly cooled and solidified and fixed to the first glass substrate 2 upon completion of infrared irradiation. As shown in FIG. 10 (e), a sealing glass layer 5 that seals between the first glass substrate 2 and the second glass substrate 3 over the entire circumference is formed.
  • the heating temperature of the sealing glass material layer 8 by the electromagnetic wave 9 such as laser light or infrared is set to be equal to or higher than the softening point of the low melting point glass.
  • the heating temperature is preferably (T + 200 ° C.) or more and (T + 800 ° C.) or less with respect to the softening point T (° C.) of the low-melting glass.
  • the heat of the sealing glass material layer 8 is dissipated to the outside through the glass substrates 2 and 3.
  • the transmission efficiency is low.
  • the reaction between the glass substrates 2 and 3 and the low-melting glass tends to proceed in the vicinity of the center of the sealing glass material layer 9 where heat does not easily escape. Therefore, when local heating by laser light or infrared rays is applied, the reaction layer 7 having a shape as shown in FIGS. 5 and 6 is easily generated.
  • laser light is used as the electromagnetic wave 9, it is preferable to use laser light having a protruding intensity distribution, and the reaction layer 7 is also likely to have a concave shape.
  • the atmosphere at the time of irradiation with the electromagnetic wave 9 is preferably a vacuum or an inert gas atmosphere such as nitrogen gas or argon gas in order to suppress deterioration of the reflective film 4.
  • a vacuum or an inert gas atmosphere such as nitrogen gas or argon gas
  • the active gas is filled.
  • the resin is filled in the space 6, the second glass substrate 3 and the first glass substrate 2 coated with the resin are laminated inside the sealing glass material layer 8, and the electromagnetic wave 9 is irradiated in this state. do it.
  • a spacer is arrange
  • Example 1 As a low melting point glass, the composition of Bi 2 O 3 83.2%, B 2 O 3 5.6%, ZnO 10.7%, Al 2 O 3 0.5% in the mass percentage of the following oxide conversion notation A bismuth glass frit (softening point: 410 ° C.) having an average particle size (D 50 ) of 100 ppm Na 2 O in mass parts per million and an inorganic filler (low expansion) As a filler, cordierite powder having an average particle size (D 50 ) of 4.3 ⁇ m was prepared.
  • Particle size distribution was measured using a particle size analyzer (Nikkiso Co., Ltd., Microtrac HRA) using a laser diffraction / scattering method.
  • the measurement conditions were as follows: measurement mode: HRA-FRA mode, Particle Transparency: yes, Special Particles: no, Particle Refractive index: 1.75, Fluid Refractive index: 1.33.
  • a sealing glass material was prepared by mixing 67.5% by volume of the above-described bismuth glass frit and 32.5% by volume of cordierite powder. 17% by mass of a vehicle prepared by dissolving 83% by mass of this sealing glass material and 5% by mass of ethyl cellulose as a resin binder component in 95% by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate And a sealing material paste was prepared.
  • a second glass substrate (size: 100 mm ⁇ 100 mm ⁇ 2.8 mm) made of soda lime glass is prepared, and a sealing glass material paste is applied to the entire circumference of the outer peripheral region of the glass substrate by a screen printing method. After obtaining the coating film, it was dried at 120 ° C. for 10 minutes to form a sealing glass material layer.
  • the printing pattern of the sealing glass material paste was a frame pattern having a line width of 0.5 mm, the size of the area of the glass substrate inside the coating film was 70 mm ⁇ 70 mm, and the curvature radius R of the corner portion was 2 mm.
  • the coating film is heated under conditions of 300 ° C. ⁇ 30 minutes to remove the resin binder component, and then fired under conditions of 480 ° C. ⁇ 10 minutes to form a sealing glass material layer having a thickness of 15 ⁇ m. did.
  • a silver thin film was formed as a reflective film on the surface of the first glass substrate (substrate made of soda lime glass having the same composition and shape as the second glass substrate) by spray coating.
  • the peripheral edge of the silver thin film is arranged such that the peripheral edge thereof is disposed inside the sealing glass material layer formed on the second glass substrate (that is, it does not overlap the sealing glass material layer).
  • the part was trimmed using a 30% aqueous nitric acid solution.
  • palladium was not deposited on the surface of the first glass substrate by an activation treatment using a solution containing a palladium compound as a catalyst for forming a silver thin film. Therefore, when the Pd concentration on the surface of the first glass substrate was measured according to the method described above, it was confirmed that it was below the detection limit (0.10 atomic%).
  • the above-mentioned second glass substrate having the sealing glass material layer and the first glass substrate having a silver thin film are laminated so that the sealing glass material layer and the silver thin film face each other, and the The two glass substrates and the first glass substrate were sandwiched, and the two glass substrates were put into close contact with each other and placed in a firing furnace. And the 1st glass substrate and the 2nd glass substrate were sealed by baking on 480 degreeC * 10 minute conditions in nitrogen gas atmosphere, and the sealing glass layer was obtained. The characteristics of the reflecting mirror thus obtained were evaluated.
  • Example 2 It has a composition of Bi 2 O 3 83.2%, B 2 O 3 5.6%, ZnO 10.7%, Al 2 O 3 0.5% by mass percentage in the following oxide conversion notation, and further mass Bismuth glass frit (softening point: 410 ° C.) containing 150 ppm Na 2 O in parts per million and having an average particle size (D 50 ) of 1.0 ⁇ m, and an average particle as an inorganic filler (low expansion filler)
  • a sealing glass material was prepared by mixing 66.8% by volume of the bismuth-based glass frit described above, 32.2% by volume of cordierite powder, and 1.0% by volume of the electromagnetic wave absorber. 17% by mass of a vehicle prepared by dissolving 83% by mass of this sealing glass material and 5% by mass of ethyl cellulose as a resin binder component in 95% by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate And a sealing material paste was prepared.
  • a second glass substrate (size: 100 mm ⁇ 100 mm ⁇ 2.8 mm) made of soda lime glass is prepared, and a sealing glass material paste is applied to the entire circumference of the outer peripheral region of the glass substrate by a screen printing method. After obtaining the coating film, it was dried at 120 ° C. for 10 minutes to form a sealing glass material layer.
  • the printing pattern of the sealing glass material paste was a frame-like pattern with a line width of 0.5 mm, the size of the region of the glass substrate inside the coating film was 70 mm ⁇ 70 mm, and the curvature radius R of the corner portion was 2 mm.
  • the coating film is heated under conditions of 300 ° C. ⁇ 30 minutes to remove the resin binder component, and then fired under conditions of 480 ° C. ⁇ 10 minutes to form a sealing glass material layer having a thickness of 15 ⁇ m. did.
  • a silver thin film was formed as a reflective film on the surface of the first glass substrate (substrate made of soda lime glass having the same composition and shape as the second glass substrate) by spray coating.
  • the peripheral edge of the silver thin film is arranged such that the peripheral edge thereof is disposed inside the sealing glass material layer formed on the second glass substrate (that is, it does not overlap the sealing glass material layer).
  • the part was trimmed using a 30% aqueous nitric acid solution.
  • a small amount of palladium was deposited on the surface of the first glass substrate by an activation treatment using a solution containing a palladium compound as a catalyst for forming a silver thin film. Therefore, when the Pd concentration on the surface of the first glass substrate was measured according to the method described above, it was confirmed to be 0.13 atomic%.
  • the second glass substrate having the above-described sealing glass material layer and the first glass substrate having a silver thin film were laminated so that the sealing glass material layer and the silver thin film faced each other.
  • a laser beam having a wavelength of 808 nm, an output of 70 W, and a spot diameter of 3.0 mm is applied to the sealing glass material layer through the second glass substrate in a state where a pressure of 0.25 MPa is applied from the second glass substrate.
  • semiconductor laser is irradiated at a scanning speed of 4 mm / sec to melt and rapidly cool and solidify the sealing glass material layer, thereby sealing the first glass substrate and the second glass substrate, and sealing glass layer Got.
  • the heating temperature (measured with a radiation thermometer) of the sealing glass material layer when irradiated with laser light was 620 ° C. The characteristics of the reflecting mirror thus obtained were evaluated.
  • a silver thin film was formed as a reflective film on the surface of a glass substrate (dimensions: 100 mm ⁇ 100 mm ⁇ 4 mm) made of soda lime glass by a spray coating method. Subsequently, a copper thin film was spray-coated on the silver thin film with a thickness of about 0.03 ⁇ m, and an epoxy resin protective film was further coated with a thickness of 45 ⁇ m to produce a reflecting mirror.
  • palladium was deposited on the surface of the glass substrate as a catalyst by an activation treatment using a solution containing a palladium compound. Therefore, when the Pd concentration on the surface of the glass substrate was measured according to the method described above, it was 0.20 atomic%.
  • the resin protective film cannot suppress deterioration of the silver thin film.
  • a silver thin film was formed as a reflective film on the surface of a glass substrate (dimensions: 100 mm ⁇ 100 mm ⁇ 4 mm) made of soda lime glass by a spray coating method. Conditions of 120 ° C. ⁇ 40 minutes by sandwiching a polyvinyl butyral film having a thickness of 0.38 mm between a glass substrate on which a silver thin film is formed and a glass substrate made of soda lime glass (dimensions: 100 mm ⁇ 100 mm ⁇ 2.8 mm) By heating with, a reflecting mirror in the form of a laminated glass was produced.
  • 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 glass substrate surface is excellent in water resistance without being subjected to palladium metal treatment, and deterioration of the reflective film due to moisture or the like can be suppressed over a long period of time, and the reflectance is reduced. Can be obtained at low cost.
  • a reflector is useful as a reflector used in a solar heat collector, a solar light collecting system, or the like.

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  • Physics & Mathematics (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)

Abstract

La présente invention se rapporte à un miroir réfléchissant qui présente une excellente résistance à l'eau et qui permet une meilleure réflectivité et une réduction des coûts de production. Un miroir réfléchissant (1) comprend les éléments suivants : un premier substrat de verre (2) qui présente une première surface (2a), un film réfléchissant (4) formé sur la première surface (2a) du premier substrat de verre (2) ; un second substrat de verre (3) qui présente une seconde surface (3a) opposée à la première surface (2a) et disposée avec un espace prédéterminé situé entre le second substrat de verre (3) et le premier substrat de verre (2) ; et une couche de verre d'étanchéité (5) formée entre le premier substrat de verre (2) et le second substrat de verre (3) de sorte à sceller le film réfléchissant (4) de manière étanche à l'air. La concentration en palladium (Pd) sur la première surface (2a) du premier substrat de verre (2) est établie à une valeur égale ou inférieure à 0,15 % atomique.
PCT/JP2012/056926 2011-03-23 2012-03-16 Miroir réfléchissant WO2012128227A1 (fr)

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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

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KR102185382B1 (ko) * 2018-11-28 2020-12-02 선다코리아주식회사 태양열 집광기용 반사판

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JPS5860702A (ja) * 1981-10-07 1983-04-11 Nippon Sheet Glass Co Ltd 反射鏡及びその製造方法
JPS6136703A (ja) * 1984-07-20 1986-02-21 アメリカ合衆国 金属被覆鏡およびその製造方法
JPS61266334A (ja) * 1984-07-31 1986-11-26 アメリカ合衆国 ガラス基材表面に銀を密着させる方法およびこの方法による銀被覆鏡の製造方法
JPH06186407A (ja) * 1992-12-22 1994-07-08 Matsushita Electric Works Ltd 反射体
JP2002129259A (ja) * 2000-10-31 2002-05-09 Furuya Kinzoku:Kk 高耐熱性反射膜、これを用いた積層体、液晶表示素子用反射板及び建材ガラス
JP2006106720A (ja) * 2004-09-09 2006-04-20 Hitachi Metals Ltd 反射膜
JP2006219607A (ja) * 2005-02-10 2006-08-24 Central Glass Co Ltd 水性の鏡用縁塗り液およびそれを用いた鏡

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JPS5860702A (ja) * 1981-10-07 1983-04-11 Nippon Sheet Glass Co Ltd 反射鏡及びその製造方法
JPS6136703A (ja) * 1984-07-20 1986-02-21 アメリカ合衆国 金属被覆鏡およびその製造方法
JPS61266334A (ja) * 1984-07-31 1986-11-26 アメリカ合衆国 ガラス基材表面に銀を密着させる方法およびこの方法による銀被覆鏡の製造方法
JPH06186407A (ja) * 1992-12-22 1994-07-08 Matsushita Electric Works Ltd 反射体
JP2002129259A (ja) * 2000-10-31 2002-05-09 Furuya Kinzoku:Kk 高耐熱性反射膜、これを用いた積層体、液晶表示素子用反射板及び建材ガラス
JP2006106720A (ja) * 2004-09-09 2006-04-20 Hitachi Metals Ltd 反射膜
JP2006219607A (ja) * 2005-02-10 2006-08-24 Central Glass Co Ltd 水性の鏡用縁塗り液およびそれを用いた鏡

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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

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