TW201237470A - Reflective mirror and manufacturing method therefor - Google Patents

Abstract

Provided is a reflective mirror which has excellent water resistance. The reflective mirror comprises a first glass substrate that has a reflective film, a second glass substrate that is disposed facing the reflective film-side of the first glass substrate, and sealing glass layers for sealing the first glass substrate and the second glass substrate. A reflective film is also formed on the side of the second glass substrate facing the reflective film surface of the first glass substrate. Reaction layers that result from the sealing are formed at the interface between the first glass substrate and the sealing glass layer and at the interface between the second glass substrate and the sealing glass layer.

Description

201237470 VI. Description of the invention: [Ming Huji·=^ 々 々 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅 泅mirror.

C ^Cj. 'J Background of the Invention In recent years, the focus has been on the use of concentrating solar energy to obtain the heat and system, and the development of solar collectors and solar concentrating systems has progressed, for example, A solar thermal power generation system such as a solar thermal power generation system that collects solar energy and generates high-temperature and high-pressure steam by its heat is used. Generally, a mirror is produced by coating a metal film such as aluminum go silver on a transparent substrate such as glass. However, the mirror coated with such a metal film has a problem that the metal film on the surface is deteriorated by moisture or oxygen in the ambient gas. At present, a mirror for applying a protective film made of an acrylic resin or an epoxy resin to a metal thin film coating is mainly used. However, the resin has poor water resistance, so that it is difficult to prevent deterioration of the metal thin film for a long period of time. Patent Document 1 proposes a mirror which is coated with an elastic dot agent composed of a stone sealant along the entire circumference of the laminated glass mirror. However, even if it is a sealant, the water barrier property is not complete enough and the water resistance is poor. 201237470 In Patent Document 2, there is proposed a mirror which protects the entire surface with an inorganic film. However, since the inorganic protective film is very thin, cracks occur slowly due to thermal expansion or the like, and reliability is lacking. CITATION LIST Patent Literature Patent Literature 1: JP-A-58-060702 (Patent Document 2) Japanese Patent Application Laid-Open No. Hei No. Hei. A mirror is provided which is particularly resistant to water. Means for Solving the Problem A mirror of the present invention is configured by a first glass substrate having a reflective film and a second glass substrate disposed opposite to a reflective film side of the first glass substrate. And sealing the glass layer by sealing the first glass substrate and the second glass substrate at a peripheral portion thereof. Further, a reflective film may be formed on a surface of the second glass substrate opposite to the surface of the reflective film of the first glass substrate. Further, 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, a reaction layer formed by sealing is formed, that is, by the glass substrate and the sealing The reaction layer formed by the reaction between the low-melting glass of the glass material layer in the sealing treatment is preferably one. The method for manufacturing a mirror of the present invention comprises the steps of: preparing a first glass substrate having a reflective film; forming a layer of glass material for sealing

S 4 201237470 步骤 a step of arranging the reflective film surface on the surface of the second glass substrate and a surface of the second glass substrate on which the sealing glass material layer is formed, and forming a stacked substrate; and The sealing glass substrate is heated and melted by a sealing layer to seal the first glass substrate and the second glass substrate to form a sealing glass layer. Further, the heating and melting of the glass material layer for sealing is preferably carried out by partial heating by irradiation with electromagnetic waves or by integral heating of the stacked substrates in a firing furnace. Advantageous Effects of Invention According to the present invention, the peripheral portions of the first and second barrier substrates are sealed by sealing the glass layer over the entire circumference, so that moisture or the like can be prevented from entering the inside of the mirror. Therefore, deterioration of the characteristics of the reflective film can be prevented and the reflection characteristics can be maintained for a long period of time. In particular, if the sealing glass material layer is heated and melted by electromagnetic waves and sealed as a sealing glass layer, local heating can be performed, so that deterioration of characteristics of the reflecting film due to heat during sealing can be prevented. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a mirror of the present invention. Fig. 2 is a cross-sectional view showing another embodiment of the mirror of the present invention. Fig. 3 is a cross-sectional view showing another embodiment of the mirror of the present invention. Fig. 4 is a partial cross-sectional view showing the shape of the reaction layer enlarged. Fig. 5 is a cross-sectional view schematically showing the width direction of a reaction layer formed on a glass substrate. 201237470. Fig. 6 is a view showing the measurement results of the reaction layer traces of the mirrors produced in Example 1. Fig. 7 is a view showing the results of measurement of the reaction layer traces of the mirrors produced in Example 2. Fig. 8 is a view showing the results of measurement of the reaction layer traces of the mirrors produced in Example 3. C. The cold type j is used to implement the invention. The following is a description of the form for carrying out the invention with reference to the drawings. Fig. 1 to Fig. 3 are plan views showing a schematic structure of a mirror of the present invention. First, in the mirror 1 shown in Fig. 1, the first glass substrate 2 having the reflection film 5 and the second glass substrate 4' disposed to face the reflection film 5 side are sealed by the glass layer 3 The periphery of the first glass substrate 2 and the second glass substrate 4 is sealed over the entire circumference. Further, a reaction layer 7 is formed on 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, and the reaction layer 7 is sealed by the glass substrate and It is produced by the reaction at the time of sealing treatment of the low-melting-point glass of the glass material layer for sealing. For example, the first and second glass substrates 2, 4 are made of an alkali-free glass or soda lime glass having various known compositions. The alkali-free glass has a coefficient of thermal expansion of about 35 to 40 (x10 −7 / ° C ). Soda-lime glass has a thermal expansion coefficient of about 80 to 90 (χ10·7/°〇. From the viewpoint of obtaining high reflectivity, sodium glass is preferably white glass with high transparency (high penetration glass). The whiteboard glass (high-penetration glass) indicates that the visible light transmittance is higher than that of 201237470, and the glass having the visible light transmittance is the same as the ordinary nano-glass with an iron content of less than 0.06%. In addition, from the viewpoint of strength, the glass of the nano is made of tempered glass. The strengthening method may optionally be chemical strengthening or air cooling strengthening. Also, it may be chemically strengthened glass other than soda lime glass. The symbol "~" in the numerical range is used as the lower limit and the upper limit, unless otherwise specified. Hereinafter, in the present specification, "~" is defined by the same definition. The thickness of the first and second glass substrates 2, 4 is preferably 〇.03~5mm. If the reflectance is taken into consideration, the thickness of the first and second glass substrates 2, 4 is preferably thinner, 0_03 ~2.8mm is better, more reasonable It is 0 03] lmm. If the quality of the structure is taken into consideration, the thickness of the first and second glass substrates 2, 4 is preferably as thin as 0.03 to 2.8 mm, more preferably on lmm. The thickness of the first and second glass substrates 2, 4 is preferably from 0.7 mm to 5 mm, more preferably from 1. imm to 5 mm. For example, in the case of using only the first glass substrate 2 In the case where the mirror 1 of the reflective film 5 is used only as the reflecting surface on the side of the first glass substrate 2, the thickness of the first glass substrate 2 is 〇3 to 0.7 nm, and the thickness of the second glass substrate 4 is used. It is preferably 0.7 to 5 mm. The reflective film 5 can be made of inscription, silver, and silver alloy (silver-nuclear alloy or silver alloy). The formation of the reflective film 5 can be formed by a steaming method, a sputtering method, a CVD method, or the like. According to the invention, the reflective film is sealed by the first and second glass substrates and the sealing glass layer. It is also possible to reduce the formation of acrylic resin or epoxy on the reflective film 5 formed by the various methods of 201237470 described above. The sealing glass layer 3 is obtained by melting and curing a low-melting glass containing an essential component as a required component, and a sealing glass material containing a ceramic filler or an electromagnetic wave absorbing material as an optional component. The main purpose is to adjust the difference between the thermal expansion coefficient of the low-melting glass and the glass substrate, and the main purpose of containing the electromagnetic wave absorbing material is to enhance the electromagnetic wave absorption of the sealing glass material and improve the heating efficiency. Thus, all of the inorganic materials are used. By performing sealing, it is possible to obtain higher airtightness than conventionally, and to prevent intrusion of moisture or the like which is a cause of deterioration of the reflective film 5, and to obtain a mirror 1 having good environmental resistance. Combination and blending amount of the sealing glass material The heating method for forming the sealing glass layer 3, the compatibility with the first and second glass substrates 2, 4, or various characteristics are selected. The heating method includes heating the entire mirror i using a firing furnace or using laser light which is one of electromagnetic waves, and heating only the sealed portion of the mirror 1. The sealing glass material is preferably composed of 60 to 1% by volume of the low-melting glass, 0 to 40% by volume of the ceramic filler, and 电磁4% by volume of the electromagnetic wave absorbing material. The sealing glass material may contain at least a low-melting glass, and the content of the ceramic filler and the electromagnetic wave absorbing material may be zero. As the low-melting point glass, for example, a low-melting glass such as tin-phosphate glass, a neon glass, an hunger glass, a ship glass, or an alkali glass of bismuth borate can be used. Among these, 'when considering the sealing properties (ie, adhesion) of the glass substrates 2, 4 or their reliability (for example, reliability or airtightness), and the influence on the environment or the human body, etc., A sealing glass composed of lanthanum glass should be used. 201237470 When the low-focus glass is less than 60% by volume, the fluidity of the sealed glass material is reduced when sealing, and there is no good sealing. The ratio of the low-refining glass in the sealing glass material is desirably 6% by volume or more, more preferably 65 Å or more. In consideration of the adjustment of the thermal expansion with the glass substrate, the upper limit is 97% by volume or less, preferably 9% by volume or less. The ceramic filler is preferably selected from at least one selected from the group consisting of cerium oxide, aluminum oxide, zirconium oxide, lithium H, cordierite, a phosphoric acid-based compound, saponin, and sulphate glass. The yttrium phosphate compound is, for example, (ZrO)2P2〇7. NaZr2(P〇4)3, KZr2(P〇4)3^Ca〇 5Zr2(P〇4)3^

NbZKPOA, Zr2(w〇3)(p〇4)2, and these composite compounds. The lower limit of the ceramic filler is preferably 3% by volume or more, more preferably 1% by volume or more. On the other hand, when it exceeds 40% by volume, the fluidity of the sealing glass material at the time of sealing may be lowered to make it difficult to seal well. Ideally below 4 vol% is more preferably at 35 vol. /〇The following. The electromagnetic wave absorbing material may be at least one selected from the group consisting of at least a metal selected from the group consisting of Fe, Cr, Mn, c〇, Ni, and Cu, or a compound containing an oxide of the above metal. Further, it may be an electromagnetic wave absorbing material other than these. The ideal lower limit of the electromagnetic wave absorbing material is in the phlegm volume. /. More preferably, it is 1% by volume or more. On the other hand, when it exceeds 4 vol%, the fluidity of the sealing glass material at the time of sealing may be lowered to prevent a good seal. It is preferably 25% by volume or less, more preferably 2% by volume or less. When the specific low-melting glass is suitable for bismuth-based glass, it is suitable to use Bi2〇3, 1~20% ZnO, 2~12% b 〇 and 10~100 ppm Na20 in a mass ratio of 70~90%. composition. Since the glass formed of the components of Bi2〇3, Zn〇, and b 〇 201237470 has transparency and low glass transition point, it is suitable for sealing glass materials. However, in the low-melting glass of the above three components, it is difficult to form a sufficient reaction layer 7 between the glass substrates 2, 4 and the sealing glass layer 3. Therefore, it should contain a trace amount of Na20. In order to form the reaction layer 7 at the interface between the glass substrate 2, 4 and the sealing glass layer 3, the low-melting glass contains an element which is easily diffused into the glass substrate - specifically, a light metal of a price of 1 is effective. . In particular, the presence of Nae in the lanthanide glass has a considerable effect. By using the four-component system, the bismuth-based glass formed of the three components of the above Bi2〇3, ZnO, and B203 contains an appropriate amount of Na20-low-melting glass, which can be easily applied to the glass substrates 2, 4 and The reaction layer 7 is formed by the subsequent interface of the glass layer 3. In the above-mentioned bismuth-based glass powder formed of the four components, Bi203 is formed into a component of a glass network structure, and it is preferable to contain the sealing glass in a range of 70 to 90% by mass. When the content of Bi203 is less than 70% by mass, the softening temperature of the low-melting glass becomes high. When the content of Bi203 exceeds 90% by mass, it is difficult to vitrify, and it is difficult to manufacture glass, and the coefficient of thermal expansion tends to be too high. When the sealing temperature or the like is considered, the content of Bi203 is preferably in the range of 78 to 87% by mass.

The ZnO-based component which lowers the coefficient of thermal expansion or the softening temperature is preferably contained in the sealing glass in a range of from 1 to 20% by mass. Once the content of ZnO is less than 1% by mass, it will be difficult to vitrify. Once the content of ZnO exceeds 20 mass. /〇, there is a decrease in the stability of the low-melting point glass, and it is prone to devitrification and the glass cannot be obtained. When the stability of the glass production or the like is considered, the content of ZnO is preferably in the range of 7 to 12% by mass. 10 201237470 b2o3 is a component that forms a glass skeleton and expands the vitrification range. It is preferable to have a range of 2 to 12% by mass in the low-focus glass. Once the content of b2〇3 is less than 2% by mass, it will be difficult to vitrify. When the content of B2〇3 exceeds 12% by mass, the softening point becomes high. When the stability of the glass, the sealing temperature, and the like are considered, it is preferable to set the content of B2〇3 in the range of 5 to 10% by mass.

The Na2 lanthanide-based component which improves the reactivity with respect to the low-melting-point glass of the glass material layer for sealing of the glass substrates 2 and 4 is preferably contained in the low-point glass in a range of 10 to 1000 ppm by mass ratio. Once the content of Na20 is less than 1 Oppm', the production efficiency of the reaction layer 7 cannot be sufficiently improved. On the other hand, once the content of NazO exceeds i〇〇〇ppm, the stability of the glass is impaired and devitrification is liable to occur. Considering the effect of improving the adhesion strength of the glass substrates 2, 4 and the sealing glass layer 3, the influence on the wiring, and the stability of the glass, the content of NaA is set to be i质量~ in mass ratio. The range of i〇〇〇ppm2 is preferred. Like the above Na2, Li2 or K20 is also a component which acts to form the reaction layer 7 at the interface between the glass substrate 2, 4 and the sealing glass layer 3. However, in the above-mentioned metal oxides, Na2〇 having excellent reactivity with the glass substrates 2 and 3 is most effective. Therefore, the lanthanum glass used as the low-melting glass preferably contains Na2〇. And a part of 'Na2〇' may also be selected from at least one of the groups consisting of Li20 or K20. In consideration of the formability of the reaction layer 7 in the subsequent interface, the substitution amount of Na20 of LhO or 〇 is preferably 50% by mass or less based on the amount of Na20. The bismuth-based glass formed of the above four components has a low glass transition point and is suitable for sealing materials. A1203, Ce02, SiO 2 and 11 201237470 may also contain optional components.

Ag20, W03, Mo03, Nb203, Ta2〇5, Ga203, Sb203, Cs20, CaO, SrO, BaO, P205, or SnOx (x is 1 or 2). However, if the content of the optional component is too large, the glass is unstable and devitrified, and the glass transition point or the softening point is increased. Therefore, the total content of the optional components is preferably 10% by mass or less. The lower limit of the total content of the optional components is not particularly limited. An effective amount of any component can be blended in the lanthanide glass depending on the purpose of the addition. Among the above-mentioned optional components, Al2〇3, Si〇2, CaO, SrO, and BaO are components which contribute to the stabilization of the glass, and the content thereof is preferably in the range of 〇5 to 5% by mass. Cs2〇 has an effect of lowering the softening temperature of the glass, and Ce〇2 has an effect of stabilizing the fluidity of the glass. As a component for adjusting the viscosity or thermal expansion coefficient of the glass, etc., it may contain Ag2〇, w〇3, Mo03,

Nb203, Ta205, Ga203, Sb203, P2〇5, SnOx, and the like. The content of each of the components may be appropriately set within a range of not more than 1% by mass based on the total content of the optional components. The reaction layer 7 is a mixed layer of constituent elements of the first and second glass substrates 2, 4 and constituent elements of the sealing glass layer 3. By forming such a reaction layer 7 on the surface layers of the glass substrates 2, 4 and setting the maximum depth to 3 Å or more, the glass substrates 2, 4 and the sealing glass layer 3 can be firmly bonded. Further, the space 6 between the glass substrates 2 and 4 sealed by the sealing glass layer 3 can be made into a good airtight structure. Once the maximum depth of the reaction layer 7 is less than 3 〇 nm, it is difficult to sufficiently obtain an effect of improving the adhesion strength or as a hermetic structure. The maximum depth of the reaction layer 7 is preferably 3 Å or more, more preferably 15 Å or more. The upper limit of the maximum depth of the reaction layer 7 is not particularly limited to 3 〇〇〇 nm or less. 12 201237470 is preferable, preferably 200 Å or less, and more preferably 5 Å or less. Further, the reaction layer 7 preferably has a shape in which the vicinity of both end portions of the sealing glass layer 3 is protruded toward the inside of the j-th and second glass substrates 2, 4 in the vicinity of the center portion in the cross section in the width direction thereof. Convex shape. In other words, the reaction layer 7 preferably has a deeper concave shape toward the both end portions of the depth-sealing glass layer 3 inside the first and second glass substrates 2, 4 than in the vicinity of the center portion. According to the reaction layer 7, the stress generated at the interface between the first and second glass substrates 2, 4 and the reaction layer 7 can be dispersed to the entire reaction layer 7, and the first and second glass substrates 2, 4 can be further improved. The strength of the bond with the sealing glass layer 3. If the depth of the reaction layer is the same, residual stress is concentrated on the side or the bottom surface of the reaction layer. The shape of the reaction layer 7 is not limited to a shape having a substantially circular arc shape as shown in Fig. 4, and may be a shape in which a plurality of protruding portions are present. As a specific shape of the above-mentioned reaction layer 7, as shown in Fig. 5, the depth D1 of the reaction layer 7 is 1.1 times or more with respect to the depth D2 near the end of the sealing glass layer 3 (i.e., D1/D221. 1) The protrusion is suitable. Here, the depth D2 in the vicinity of the end portion of the reaction layer 7 is set such that the distance from the end portion of the reaction layer 7 to the position of the maximum depth D1 is L1, and the depth D2 indicates the distance from the end portion to the distance L1. /1〇 The distance from the position of L2 (L2=l/l〇xLl). In addition, when there are a large number of protruding portions (for example, two), D1/D2 is calculated based on the maximum depth D1 and the depth D2 of the distance L2 which is 1/10 of the distance L1, and the distance L1 is self-protruding. The nearest end of the partial position is at the position of the maximum depth D1. The above L1 indicates the length direction of the reaction layer 7, that is, the length in the A direction in Fig. 4. And when the value of D1/D2 exceeds 500, it will be the same as the depth of the reaction layer. It is easy to cause the stress set 13 201237470. Therefore, the value of D1/D2 is below 500, which is better than β according to the maximum depth D1. The reaction layer 7 having a depth D2 ratio (D1/D2) near the end of the layer 3 of 1.1 or more can further improve the adhesion strength between the first and second glass substrates 2, 4 and the sealing glass layer 3, It is also possible to reproduce the dispersion effect of the stress in the interface between the first and third glass substrates 2, 4 and the reaction layer 7 by the I1. Namely, the amount of formation of the reaction layer 7 can be increased by setting the ratio of wm/D2 to 丨丨 or more, and the shape of the reaction layer 7 can be set to protrude into the glass substrates 2 and 4. Therefore, the effect of improving the adhesion strength of the first and second glass substrates 2, 4 and the sealing glass layer 3 and the dispersion of the stress in the interface between the first and second glass substrates 2, 4 and the reaction layer 7 can be further improved. effect. The ratio of D1/D2 is preferably 2.0 or more. Further, the amount of formation of the reaction layer 7 is preferably 50 μm or more in the cross-sectional area in the width direction. By setting the cross-sectional area of the reaction layer 7 to 5 〇m 2 or more, the glass substrates 2, 4 and the sealing layer 8 can be firmly adhered. The cross section of the reaction layer 7 is preferably 10 10 μm or more. The cross-sectional area of the reaction layer 7 can be increased, for example, by the shape of the reaction layer 7 (e.g., deepening depth, etc.). The cross-sectional area of the reaction layer 7 can also be increased by widening the width (line width) of the sealing glass layer 3, which can also be mentioned as improving the first and second glass substrates 2, 4 and the sealing glass layer 3. The mechanism of the strength. The formation of the reaction layer 7 can be confirmed by the composition analysis of the FE-EPMA line on the near side of the interface between the first and second glass substrates 2, 4 and the sealing glass layer 3, and the practical method is as shown below. Here, the value of the shape (depth, sectional area, and D1/D2 ratio, etc.) of the reaction layer 7 was measured by the method shown below.

S 14 201237470 First, a part of the sealed mirror 丨 is cut as a sample in an easy-to-grind manner. One of the glass substrates was ground and removed from the sample. On the other hand, when the strength of the sealing glass layer 3 is low and peeled off in the sealing glass layer 3, the polishing step of the glass substrate can be omitted. Then, the sample from which one of the glass substrates has been removed is immersed in the etching liquid, and the sealing glass layer 3 is removed. The residual liquid is an acid solution which does not dissolve the glass of the glass substrate but dissolves the constituent elements of the sealing glass layer. For example, when a linden glass is used as the low-melting glass in the sealing glass layer, for example, a 30% aqueous solution of nitric acid is used. Since the reaction layer 7 is a mixed layer of the constituent elements of the first and second glass substrates 2, 4 and the constituent elements of the sealing glass layer, the reaction layer 7 is also removed while the sealing glass layer 3 is removed. The glass substrate in which the formation of the reaction layer 7 was left in the concave portion was produced in the above manner. The surface shape of the glass substrate having the concave portion was measured by surface roughness, and the shape of the reaction layer 7 which is the shape of the concave portion, i.e., the shape of the reaction layer 7, was measured and evaluated. Fig. 6 is a view showing the results of measuring the surface shape of the reaction layer 7 of the glass substrate in the mirror 1 produced in the first embodiment to be described later. As shown in the figure, after the reaction layer 7 is dissolved and removed from the first and second glass substrates 2, 4, the surface shape of the first and second glass substrates 2, 4 is measured by surface roughness, and the reaction layer 7 can be evaluated. The shape. In order to form the reaction layer 7 having a deep depth, only one portion of the reflective film 5 or the reflective film 5 in which the sealing region of the sealing glass layer is formed may be trimmed, and then the sealing glass material layer and the first glass may be directly used. The substrate 2 is closely attached to perform a sealing process. In the case of the dressing method, the following two methods are included, that is, after the reflective film 5 is formed, the sealing region is immersed in the acid solution such as the acid solution; or the method of spraying; or, in the formation Before the reflection film 5, a method of masking the reflection region of the sealing region with a tape or the like to form a reflection film and forming a region of the modified reflection film is formed. The gas environment in the space 6 sealed by the first glass substrate 2, the second glass substrate 4, and the sealing glass layer 3 may be an air environment, but considering the reaction of oxygen in the air with the reflective film 5, it is preferable to The gas atmosphere is set to a vacuum or an inert gas such as nitrogen or argon. Further, in consideration of the strength, it is also preferable to fill the space 6 with a resin or to place a separator. Moreover, since the distance between the first glass substrate 2 and the second glass substrate 4 (that is, the thickness of the space 6) reduces the influence of the oxygen or the like of the filler of the space 6 on the reaction film 5 or thermal expansion, etc., Short distance is appropriate. The distance between the first glass substrate 2 and the second glass substrate 4 is preferably 500 μm or less, more preferably ΙΟΟμηη or less, more preferably ΙΟμηι or less. Next, a method of manufacturing the mirror 1 using a firing furnace will be described. The manufacturing method of the mirror 1 basically has the steps of: preparing a first glass substrate having a reflective film; and forming a sealing glass material layer on the second glass substrate (hereinafter referred to as a sealing glass material) a step of forming a layer; a step of disposing a reflective film surface of the first glass substrate and a surface of the second glass substrate on which the sealing glass material layer is formed as a stacked substrate (hereinafter referred to as a first a step of stacking the second glass substrate; and heating and melting the sealing glass material layer of the stacked substrate to seal the first glass substrate and the second glass substrate to form a sealing glass layer (hereinafter referred to as It is a sealing step of the first and second glass substrates). The step of preparing the first glass substrate having the reflective film and the step of forming the sealing glass 16 201237470 material layer on the second glass substrate may be in this order, or may be reversed or simultaneously. For example, when the sealing glass material layer is formed on the second glass substrate, the sealing glass paste can be produced in advance by the following method. [Production of Glass Paste for Sealing] The glass paste for sealing can be prepared by mixing the constituent components of the glass material for sealing and the carrier. The carrier is one in which the resin of the binder component is dissolved in a solvent. As the resin for the carrier, for example, a cellulose resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, phenyl sulfonyl cellulose, propyl cellulose or nitrocellulose can be used. And adding an acrylic monomer such as methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate or 2-hydroxyethyl acrylate. An organic resin such as an acrylic resin obtained by polymerization. In the case of a solvent, a solvent such as rosin alcohol, butyl carbitol acetate, or ethyl carbitol acetate can be used in the case of a cellulose resin; in the case of an acrylic resin, a methyl group can be used. Solvents such as ethyl ketone, rosin alcohol, butyl carbitol acetate, and ethyl carbitol acetate. The viscosity of the glass paste for sealing may be a viscosity corresponding to the device applied to the glass substrate 4, and may be a ratio of a resin (adhesive component) to a solvent or a component of a glass material for sealing or a carrier. The ratio is adjusted. For sealing, a glass paste such as an antifoaming agent or a dispersing agent may be added to the glass paste, and a known additive may be added. These additives are also components that will disappear during normal firing. The preparation of the sealing material paste can be applied to a rotary mixer equipped with a stirring blade or a known method using a rolling mill and a ball mill. 17 201237470 [Formation of a glass material layer for sealing] A sealing glass frit may be applied to a sealing region on the periphery of the second glass substrate 4 by screen printing or a dispenser. In order to maintain the strength of the mirror, the width of the coating film is preferably 0.5 mm to 20 mm. Further, the thickness of the coating film should be adjusted in accordance with the thickness of the sealing glass layer 3 after sealing (e.g., ΙΟμηι to 2000μηι), in consideration of shrinkage in the next step such as drying and preliminary baking. The second glass substrate 4 to which the glass paste for sealing has been applied is placed in a dryer at 60 to 150 ° C for 30 seconds to 1 minute, and dried to disperse the organic solvent component. Next, the resin binder component is scattered in a firing furnace at a temperature lower than the glass transition point of the sealing glass material by 30 C, and then the temperature of the sealing glass material is prepared (ie, the sealing glass material is sealed). After the glass is softened, the temperature is 10 to 100 ° C. After the firing, the sealing glass material is fired on the second glass substrate 4 to form a sealing glass material layer. Hereinafter, a glass paste for sealing is applied to a glass substrate, and the applied paste layer is dried, prepared for firing, or prepared by further firing, which is also referred to as a sealing glass material layer. The glass material layer for sealing is a layer obtained by drying a paste layer which has been applied to a glass substrate, and is prepared to be fired, or a layer which is further fired, in the case of obtaining a sealing glass layer, which is used in combination with a sealing glass layer. The sealing glass layer is formed by laminating the first and second glass substrates with a sealing glass material layer formed over the peripheral portion of one or both of the glass substrates, and sealing the glass material layer It is formed by heating and melting to form a peripheral portion of the first and second glass substrates. In this specification, the glass transition point is the i-th of differential thermal analysis (DTA).

S 18 201237470 is defined by the temperature of the inflection point, and the glass softening point is defined by the temperature of the fourth inflection point of the differential thermal analysis (DTA). [Step of laminating and sealing the first and second glass substrates] The second glass substrate 4 having the glass material layer for sealing, and the glass material layer for sealing are located inside and the reflection film 5 is located inside, and The first glass substrate 2 having the reflective film 5 is disposed to face each other and stacked, and the laminated substrate is subjected to heat-melting treatment in a firing furnace to form a sealed glass layer which has been fired. By this heat-melting treatment, the constituent components of the low-melting glass in the sealing glass material layer are passed through the reflective film 5, and the reaction layer 7 is formed on the first glass substrate 2. When the partition member is placed in the space 6 in consideration of the strength of the mirror 1, the partition member may be placed at the time of stacking to have a heat-resistant granular shape. The ceramic separator such as alumina or yttrium oxide is should. In order to prevent the deterioration of the reflective film 5, the gas atmosphere of the firing furnace is preferably an inert environment such as nitrogen or argon or a vacuum state. At the time of the firing, the composition of the low-melting glass of the glass material layer for sealing is passed through the reflective film 5, and the reaction layer 7 is formed on the first glass substrate 2, whereby a strong adhesion can be obtained. When the reaction layer 7 is too thin, the adhesion force is weakened and it is easy to peel off in a heat cycle test or a peeling test, and it is difficult to form the mirror 1 having a long life. The ease of formation of the reaction layer 7 depends on the composition of the low-melting glass in the sealing glass material layer, the firing temperature, and the adhesion between the sealing glass material layer and the reflective film 5 on the first glass substrate. In order to form the reaction layer 7 into a deeper layer, the composition of the low-melting glass in the sealing glass material layer is suitable for the use of the lanthanide, lead, and bismuth borate bases, from the environmental surface and the water resistance 19 201237470 level It seems that the bismuth glass is preferred. The higher the firing temperature, the easier the progress of the reaction layer 7. If the deformation of the glass substrate is taken into consideration, it is preferably below the transfer point of the glass substrate. The adhesion between the sealing glass material layer and the reflective film on the first glass substrate can be performed by sandwiching the first and second glass substrates with a heat-resistant clip when the first and second glass substrates are stacked Or, by means of a weight or the like, the load is increased by adding a load to the first and second glass substrates which have been stacked in the firing. The mirror 1 of Fig. 1 is produced in accordance with the above steps. Next, the mirroring step using electromagnetic waves such as lasers will be exemplified by the mirror 1 of Fig. 1. The manufacturing method of the mirror 1 also has the following steps: the step of preparing a first glass substrate having a reflective film; and the step of forming a sealing glass material layer on the second glass substrate (hereinafter referred to as a seal) a step of forming a glass 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 as a stacked substrate (hereinafter referred to as a step of stacking the first and second glass substrates); and heating and melting the sealing glass material layer of the stacked substrate to seal the first glass substrate and the second glass substrate to form a sealing glass layer Step (hereinafter referred to as a sealing step of the first and second glass substrates). The above steps of preparing the first glass substrate having the reflective film and the step of forming the sealing glass material layer on the second glass substrate may be in this order, or may be reversed or simultaneously. When the sealing glass material layer is formed on the second glass substrate, the sealing glass paste can be produced in the following manner by the following method. [Production of glass paste for sealing]

S 20 201237470 The method for producing a glass paste for sealing is the same as the method for producing the mirror 1 using a firing furnace except that the electromagnetic wave absorbing material is included. [Formation of Sealing Glass Material Layer] First, a sealing glass paste is applied to a sealing portion of a peripheral portion around the periphery of the second glass substrate 4 by screen printing or a dispenser. In order to maintain the strength, the width of the coating film is preferably from 55 mm to 20 mm. Further, the thickness of the coating film should be adjusted in consideration of the shrinkage in the next step such as drying and preliminary baking, in view of the thickness of the sealing glass layer 3 after the target sealing. The second glass substrate 4 to which the glass paste for sealing has been applied is dried at 60 to 15 Torr (for 30 seconds to 1 minute, and the organic solvent component is scattered, and then the furnace is sealed in a baking furnace) The glass transition point of the glass material is lowered by 3 〇 to 50. (The temperature of the resin adhesive component is scattered, and the temperature of the sealing glass is prepared by firing (more specifically, the sealing glass material) The glass softening point is still 10 to 50 C. After the firing, the glass material for sealing is fired on the second glass substrate 4 to form a sealing glass material layer. It can also be performed by electromagnetic waves such as laser. a step of scattering the resin binder component and a step of burning the sealing glass material to the second glass substrate 4. By local heating of electromagnetic waves such as lasers, the sealing region is not heated, so When the two glass substrates 4 have the reflection film 5, the sealing glass material can be burned to the second glass substrate 4 without deteriorating the reflection film 5 other than the sealing region. [The first and second glass substrates are phased. Stacking and sealing steps] The second glass substrate 4 having the sealing glass material layer and the first glass substrate 2 having the reflective film 5 are disposed to face each other so that the sealing glass material layer is located inside and the reflective film 5 is located inside the 21 201237470. By stacking the stacked substrates, the sealing glass material layer is formed by irradiating electromagnetic waves such as laser light from the side of the second glass substrate 4 of the stacked substrate to form a fired sealing glass layer. By this heat-melting treatment, the constituent components of the low-melting glass in the sealing glass material layer can pass through the reflective film 5, and the reaction layer 7 can be formed on the first glass substrate 2. The sealing glass material layer is used for Laser and other electromagnetic waves are locally heated. Therefore, the temperature of the glass substrate is not heated higher than the sealing glass material layer. That is, the sealing glass material layer can be heated higher than the temperature at which the entire firing furnace is heated. By heating at a relatively high temperature, the reaction layer 7 can be formed into a deeper layer. Further, when a laser is used as the electromagnetic wave, the center of the laser beam is the strongest and the outer side is toward the outer side. In a weaker manner, the layer of the sealing glass material to be irradiated is given a temperature distribution, whereby the shape of the reaction layer 7 is formed into a shape convex downward toward the first glass substrate 2 in FIG. 4, and the stress can be alleviated. Further, since the glass material layer for sealing is locally heated by electromagnetic waves such as lasers, it is difficult to heat the outside of the sealing region, and therefore, deterioration due to heat of the reflecting film 5 does not occur. Obtaining a mirror with two reflectances 1 ° The space 6 between the first glass substrate 2 and the second glass substrate 4 may be filled with air 'but if the reaction between the oxygen in the air and the reflective film is taken into consideration, it is filled with nitrogen. Or an inert gas such as argon or a vacuum is preferred.

S 22 201237470 Sealing of electromagnetic waves such as lasers in an inert gas or in a vacuum. Further, in consideration of the strength of the mirror, the space 6 may be filled with a resin or a separator as described above may be placed. The separator may be a heat-resistant granular oxide or a ceramic oxide separator such as a oxidized stone, but since it is a partial heat sealing, the separator may be a resin or plastic having no heat resistance. In order to make the film thickness of the sealing glass layer 3 after sealing, the granular separator may be placed in the sealing material. In order to further increase the strength of the mirror 1 and fill the space 6 between the first glass substrate 2 and the second glass substrate 4 with a resin, a sealing glass material may be formed in the second glass substrate 4 before being stacked. The resin is applied to the inner side of the layer region, and the second glass substrate 4 and the first glass substrate having the reflective film 5 are applied so that the sealing glass material layer and the reflective film 5 are on the space 6 side. 2 stacked and sealed with a laser. Examples of the resin include epoxy resin, acrylic acid resin, polyester resin, urethane resin, melamine resin, phenol resin, polyester, polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyoxyethylene. , ABS resin, and fluororesin. The mirror 1 of Fig. 1 is produced by the above steps. The mirror 1 preferably has a reflection film 5 on the second glass substrate 4 as shown in Fig. 2, that is, a reflection film may be formed on the surface of the space between the first and second glass substrates. When both the first and second glass substrates are formed with a reflective film, when the first glass substrate 2 is used as a reflecting surface, the mirror is damaged when the outer surface is damaged and the reflectance is lowered by diffusion or absorption. The crucible is reversed and the second glass substrate 4 side is used as a reflecting surface. By this operation, the life as the mirror 1 can be further extended. 23 201237470 For example, when the mirror 1 having the reflective film 5 is used for both the first glass substrate 2 and the second glass substrate 4, and both sides of the first glass substrate 2 and the second glass substrate 4 are used as the reflecting surface Considering the balance between the intensity and the reflectance of the mirror 1, the thickness of the first glass substrate 2 and the second glass substrate 4 is preferably 0-55 to 2.8 mm. Further, as for the shape of the mirror 1, a curved glass substrate can be used as the curved structure as in Fig. 3. Further, it can correspond to a slot type solar thermal power generation device or the like that requires a curved mirror. EXAMPLES Next, specific examples of the invention and evaluation results thereof will be explained. However, the following description is not intended to limit the invention, and may be modified in accordance with the scope of the invention. (Example 1) The low-melting-point glass was prepared in the following oxide ratio: 83 2 mass%, 2〇3, 5.6% by mass of B2〇3, 10.7 mass% 2ZnO, and 0.5 mass% of barium 2〇3 And the composition of Na02 of l〇〇ppm, and the average particle diameter (d50) is 铋.Ομιη of the bismuth-based glass powder (softening point: 410. 〇; and the cordierite powder is prepared for the ceramic filler. The average grain of the cordierite powder) The diameter (D5G) was 2.0 μm. The particle size distribution was measured using a particle size analyzer (manufactured by Seiko Co., Ltd., Microtrac HRA) using a laser diffraction scattering method. The measurement conditions were: measurement mode, HRA-FRA mode, and particle transparency. Particie Transparency: Yes, Spherical Particles: Not (no), Particle Refractive Index: 1.75, and Fluid Refractive Index: 1·33. s 24 201237470 The 75% by weight of the above-mentioned silk-based glass powder is mixed with the cordierite powder (4%) as a sealing glass material, and then the glass material for garnishing is mixed with 8 % by mass of the glass material and 20% by mass of the carrier to prepare a sealing glass. Paste. The carrier will be used as a binder. The ethyl cellulose (2.5% by mass) was dissolved in a solvent (97.5% by mass) composed of rosin alcohol. Next, a second glass substrate 4 composed of soda lime glass (size: 100 mm x 100 mm x 1.1 mm) was prepared. And applying the glass paste for sealing to the sealing area of the peripheral part of the periphery of the four sides of the glass substrate by screen printing, and drying by 120 degreeC*10 minutes. The printing pattern of a coating layer is a line. A pattern of 1.0 mm in width is applied, and the area of the glass substrate on the inner side of the coating layer (the area where the coating layer is not formed) has a size of 8 mm×mm〇mm, and the radius of curvature R of the corner portion is 2 mm. Next, The coating layer was heated under conditions of 3 ° C C 3 min, and the resin binder component was scattered. Then, the coating layer was fired at 480 ° C for 10 minutes to form a seal having a film thickness of 15 μm. Next, a silver thin film is formed on the first glass substrate 2 (a substrate composed of soda lime glass having the same shape and the same shape as the second glass substrate 4) as a reflective film 5 by a spray coating method. The glass material layer for sealing and the reflective film 5 become internal In a side manner, the second glass substrate 4 having the sealing glass material layer and the first glass substrate 2 having the silver film as the reflective film 5 are laminated, and the first glass substrate 2 and the second glass are sandwiched by the heat resistant clip. After the glass substrate 4 is in close contact with the two glass plates, it is placed in a firing furnace and then fired in a nitrogen atmosphere at 480 ° C for 10 minutes to seal the first glass substrate 2 and the second glass substrate 4 . And made 25 201237470 sealing glass layer 3. After the method was manufactured by the above method, the sealed mirror was evaluated for the characteristics described later. After confirming the state of the sealing glass layer 3 and the glass substrates 2 and 4 of the mirror 制作 which was produced by the microscope, it was found that the sealing region was It does not look like the reflective film 5 but the color of the sealing glass layer 3 can be seen, and the low-melting glass component in the sealing glass layer 3 has a solid reaction with the first glass substrate 2 through the silver film. In the case of a defect or a crack, etc., it was confirmed that a sufficient adhesion was obtained. The mirror was prepared and subjected to a high-temperature and high-humidity test (temperature: 6 Torr, and relative humidity: 90°/.) for 1000 hours to confirm the change in reflectance. Further, after the reaction layer 7 was measured by the above-described surface roughness meter, it was confirmed that a reaction layer having a convex shape was formed under about 5 Å to 60 nm as shown in Fig. 6. 2) The low-melting glass is prepared in the following oxide conversion: 83.2 mass. / 〇 Β 203 203, 5.6 mass% of b2 〇 3, 1 〇 7 mass% of Zn 〇, 〇 5 mass 罝 0 / 〇 〇 ζ〇 3, and the composition of i5〇ppn^Na〇2, and A bismuth-based glass powder having a mean particle diameter of Ι.Ομιη (softening point: 41 〇 °c); and a cordierite powder and an electromagnetic wave absorbing material having a composition of Fe2〇3_Cu〇_Mn〇_ΑΙΑ are prepared for the ceramic filler. The average particle size (〇5〇) of the bluestone powder is 2 〇|jm. Further, the average particle diameter (D5G) of the electric absorbing wave absorbing material is 〇.9|im. The above lanthanide glass powder is 72.7 vol%, and the sapite is used. 22.0% by volume of the powder and 5.3 vol% of the electromagnetic wave absorbing material (the total content of the cordierite powder and the electromagnetic wave absorbing material is 27.3% by volume) are mixed as the sealing glass material, and then the glass material for the sealing of the 2012 20123770 is 80% by mass. 20% by mass of the agent was mixed to prepare a glass paste for sealing. The carrier was prepared by dissolving ethyl cellulose (2.5% by mass) as a binder component in a solvent composed of rosin alcohol (97.5% by mass). Next, 'prepare the first glass substrate 4 (size: 90 mm x 90 mm x 0.7 mm) composed of the glass without inspection, and apply the glass paste for sealing to the four sides of the glass substrate by screen printing. After the sealing area of the peripheral portion, it is dried at 120 ° C for 10 minutes. The printing pattern of the coating layer is a 枋-shaped pattern having a line width of 0.75 mm, the area of the glass substrate inside the coating layer (the area where the coating layer is not formed) is 80 mm×80 mm, and the radius of curvature R of the corner portion is 2 mm. Next, the coating layer was heated at 300 ° C for 30 minutes to scatter the resin binder component, and then the coating layer was fired at 480 ° C for 10 minutes to form a film thickness of 7 ( a glass material layer for sealing of jm. - Next, an aluminum thin film is formed on the first glass substrate 2 by vapor deposition (a substrate composed of the same shape and alkali-free glass as the second glass substrate 4) ) as the reflective film 5. The second glass substrate 4 having the sealing glass material layer and the first glass substrate 2 having the aluminum film as the reflection film 5 are laminated so that the sealing glass material layer and the reflection film 5 are inside. In a state where a pressure of 0.1 MPa is applied from the second glass substrate 4, the sealing glass material layer is irradiated with a wavelength of 940 nm through the second glass substrate 4 at a scanning speed of 1 〇mm/s. Laser light (semiconductor laser) having a diameter of 1.6 mm and a spot diameter of 1.6 mm is melted by sealing the glass material layer for sealing, and then the first glass substrate 2 and the second glass substrate 4 are sealed by quenching and curing to obtain a seal. Glass layer 3. Ray 27 201237470 The processing temperature (measured by a radiation thermometer) at the time of irradiation is 72 (rc. After manufacturing by the above method, the sealed mirror 1 is subjected to characteristic evaluation described later. The mirror 1 produced by the microscope is confirmed by a microscope. The state of the sealing glass layer 3 and the glass substrates 2, 4 is found to be: the sealing area does not look like the reflecting film $, but the black color of the sealing glass layer 3 can be seen, and the low melting glass component in the sealing glass layer is sealed. The through-aluminum film was surely reacted with the first glass substrate 2. Further, no defects such as defects or cracks were observed, and it was confirmed that sufficient adhesion was obtained. The produced mirror 1 was put into a high-temperature and high-humidity test (temperature 60 ° C and a relative humidity of 90%) for 1000 hours to confirm the change in the reflectance, but there was almost no change. When the reaction layer 7 was measured using the surface roughness meter described above, it was confirmed that it was about 1 如 as shown in Fig. 7. A reaction layer 7 having a convex shape is formed under the 〇~i5 〇 nm. (Example 3) The low-melting glass is prepared in an amount of 8: 3.2% by mass of Bi203 and 5.6 % by mass of B2〇3 in terms of the following oxides. 1〇.7 mass% ZnO, 0.5% by mass of Al2〇3, and 150ppm of Na02, and an average particle (Ρ5〇) 1. 〇μπι of bismuth-based glass powder (softening point: 41 (rc); and prepared for the ceramic filler talite A powder and an electromagnetic wave absorbing material having a composition of Fe203-CuO-MnO-Al2〇3. The average particle diameter (D5G) of the cordierite powder is 4.3 μm, and the average particle diameter (D5G) of the electromagnetic wave absorbing material is 1.2 μm. The bismuth-based glass powder was 66.8 vol%, the cordierite powder was 32.2 vol%, and the electromagnetic wave absorbing material was 1.0 volume. (The total content of the cordierite powder and the electromagnetic wave absorbing material 28 201237470 was 33.2 vol%) was mixed as a sealing glass material. The glass paste for sealing is prepared by mixing 80% by mass of the sealing glass material with 2% by mass of the carrier. The carrier dissolves ethyl cellulose (25% by mass) as a binder component. A solvent (97.5 mass% / 〇) composed of 2,2,4-tridecyl-1,3 pentanediol monoisobutyrate. Next, a second glass substrate composed of soda lime glass is prepared. 4 (size: 100mmxl00mmx0.7mm), and the sealing glass paste is applied by screen printing to After sealing the peripheral portion of the periphery of the four sides of the glass substrate 4, it was dried at 120 ° C for 10 minutes. The printed pattern of the coating layer was a 枋 pattern of a line width of 1.0 mm, and was coated. The area of the glass substrate on the inner side of the layer (the area where the coating layer is not formed) has a size of 8 mm × 8 mm, and the radius of curvature R of the corner portion is 2 mm. Next, under the condition of 300 〇 C x 30 minutes The coating layer is heated to cause the resin binder component to scatter. Then, the coating layer was fired at 480 ° C for 10 minutes to form a sealing glass material layer having a film thickness and an outer claw. Next, a silver thin film is formed as a reflective film 5 by a spray coating method on the first glass substrate 2 (a glass substrate composed of a glass of the same shape and the same shape as the second glass substrate 4). Covering the area outside the sealing area of the first glass substrate 2 with the film for masking, and immersing the sealing area of the first glass substrate 2 in a 30% aqueous solution of wall acid for 30 seconds to 1 minute to 'make the silver on the sealing area The film is peeled off and trimmed. After rinsing the aqueous solution of nitric acid with distilled water, the water was scattered by an air knife, and then the film was removed and placed 6 inches. (: drying in a desiccator for 1 minute. The second glass substrate 4 having the sealing glass material layer of the 201237470 layer is provided in a manner that the sealing glass material layer and the reflective film 5 are inside. The silver thin film was used as the first glass substrate 2 of the reflective film 5. Further, in a state where a pressure of 0.25 MPa was applied from the second glass substrate 4, the second glass substrate 4 was placed at a scanning speed of 2 mm/s. The glass material layer is irradiated with a laser light having a wavelength of 808 nm, an output of 70 W, and a spot diameter of 〇11^1 (semiconductor laser) to melt the sealing glass material layer, and then the first glass substrate 2 is cured by quenching. Sealed with the second glass substrate 4 to obtain the sealing glass layer 3. The processing temperature (measured by a radiation thermometer) at the time of laser irradiation is 620 ° C. After the above method is manufactured, the sealed mirror 1 is supplied. When the characteristics of the sealing glass layer 3 and the glass substrate 2 of the mirror 1 produced were confirmed by a microscope, no defects such as defects or cracks were observed, and it was confirmed that sufficient defects were obtained. Then. The mirror produced was put into a warm and humid test (temperature 6 ° ° C and relative humidity 90%) for 240 hours to confirm the change of reflectance, but almost no change. In addition, the same mirror was put into more severe conditions. The high-temperature and high-humidity test (temperature: 85 ° C and relative humidity: 85%) was observed for 2000 hours to confirm the change in the reflectance, and there was almost no change. When the reaction layer 7 was measured using the surface roughness meter described above, it was confirmed that In the eighth embodiment, a convex reaction layer 形成 is formed under about 70 to 150 nm. In the above embodiment, laser light is used as a heating source, but electromagnetic waves such as infrared rays may be used in addition to the above (Comparative Example 1).

S 30 201237470 A silver thin film was formed as a reflective film by a spray coating method on a glass substrate (size: 100 mm x 100 mm x 4 mm) composed of soda lime glass. Next, a copper film of about 〇·〇3 μπι was sprayed on the silver film, and then an epoxy resin protective film 45 μηι was applied to prepare a mirror. When the produced mirror was subjected to a high-temperature and high-humidity test (temperature: 60 ° C and relative humidity: 90%) for 240 hours to confirm the change in reflectance, a reflectance of about 10 to 15% was confirmed in the wavelength band of 350 nm to 1000 nm. reduce. (Comparative Example 2) A silver film was formed into a film on a glass substrate (size: 100 mm x 100 mm x 4 mm) composed of soda lime glass by a spray method as a reflection film. A glass substrate having the silver film formed thereon and a glass substrate (size: 100 mm x 100 mm x 4 mm) composed of soda lime glass were used to sandwich a polyethylene terephthalate film having a thickness of 0.38 mm at 120 ° C for 40 minutes. The lower mirror is heated to form a mirror in the form of a laminated glass. When the mirror produced was subjected to a high-temperature and high-humidity test (temperature of 60 ° C and relative humidity of 90%) for 240 hours to confirm the change in reflectance, a reflectance of about 10 to 20% was confirmed in the wavelength band of 350 nm to 100 nm. reduce. In the present specification, although the configuration of the mirror of the present invention is described using the expressions of the first glass substrate and the second glass substrate, in the above description, the first glass substrate may be replaced with the second glass substrate, and The second glass substrate can also be replaced with a first glass substrate, which is the same in the present invention. INDUSTRIAL APPLICABILITY 31 201237470 According to the mirror of the present invention, since the first and second glass substrates are sealed by the sealing glass layer over the entire periphery thereof, it is possible to prevent intrusion of moisture or the like to form a reflective film. The internal space of the mirror prevents deterioration of the characteristics of the reflective film, and provides a mirror that can maintain the reflection characteristics for a long period of time. Further, according to the method of sealing the sealing glass material layer by using electromagnetic waves as a sealing glass layer, local heating can be performed, so that deterioration of characteristics of the reflecting film due to heat during sealing can be prevented. In particular, the mirror of the present invention has long-term durability and is useful as a solar concentrating system requiring no deterioration in characteristics and a mirror for a solar thermal power generation system. The entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. JP-A No. No.------- I: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an embodiment of a mirror of the present invention. Fig. 2 is a cross-sectional view showing another embodiment of the mirror of the present invention. Fig. 3 is a cross-sectional view showing another embodiment of the mirror of the present invention. Fig. 4 is a partial cross-sectional view showing the shape of the reaction layer in an enlarged manner. Fig. 5 is a cross-sectional view schematically showing the width direction of a reaction layer formed on a glass substrate. Fig. 6 is a view showing the results of measurement of the reaction layer trace of the mirror produced in Example 1. Figure 7 is a view showing the reaction layer trace of the mirror produced in Example 2.

S 32 201237470 Diagram of the results of the determination. Fig. 8 is a view showing the results of measurement of the reaction layer traces of the mirrors produced in Example 3. [Description of main component symbols] 1...Mirror A...width direction 2···first glass substrate D1···maximum depth of reaction layer 3...sealing glass layer D2···depth near the end of reaction layer 4· ·Second glass substrate L1...the length of the reaction layer in the width direction 5·"reflection film L2...from the end of the reaction layer to the L1 of 6...space 7...the distance of the reaction layer 1/10 33

Claims (1)

201237470 VII. Patent application scope: 1. A type of mirror, which is characterized in that: a first glass substrate having a reflective film; and a second glass substrate, which is opposite to the reflective film side of the first glass plate The glass layer is sealed, and the first glass substrate and the second glass substrate are sealed at the peripheral portion thereof. 2. The mirror of claim i, wherein the second glass substrate has a reflective film on a surface opposite to a surface of the first glass substrate on which the reflective film is formed. 3. The mirror of the invention of claim 1, wherein the interface between the first broken wall substrate and the sealing glass layer and the interface between the second glass substrate and the sealing glass layer are formed by sealing The resulting reaction layer. 4. The mirror of any one of the scopes of the third to third aspect of the invention, wherein at least a portion of the first glass substrate and/or the reflective film on the first glass substrate in which the sealing glass layer is formed is Finished. 5. The mirror of claim 3, wherein the reaction layer is formed on the first glass substrate by penetrating the reflective film formed on the first glass substrate. 6. The mirror according to claim 3, wherein the reaction layer is formed on the first glass substrate and the second glass substrate through a reflective film formed on the first glass substrate and the second glass substrate. 7. The mirror of any one of claims 3, 5 or 6, wherein the maximum depth of the reaction layer is above 3 〇 nm. The mirror according to any one of claims 1 to 7, wherein a space between the first glass substrate and the second glass substrate is less than 500 μm. 9. The mirror of any one of claims 1 to 8, wherein the first glass substrate and the second glass substrate are in a flat or curved shape. 10. The mirror of any one of clauses 1 to 9, wherein the first glass substrate and the second glass substrate have a thickness of 0.03 to 4 mm. The mirror according to any one of claims 1 to 10, wherein the first glass substrate and the second glass substrate are each of an alkali-free glass, a sodium bismuth glass, or a chemically strengthened glass, respectively. . 12. The mirror according to any one of claims 1 to 11, wherein the sealing glass layer contains a low melting point glass as an essential component, and at least one selected from the group consisting of a ceramic filler and an electromagnetic wave absorbing material as an optional component. One. The mirror according to any one of claims 1 to 12, wherein a space between the first glass substrate and the second glass substrate is filled with a material selected from the group consisting of air, an inert gas, and a resin. At least one of the groups, or in a vacuum state. The mirror according to any one of claims 1 to 13, which has a partition in a space between the first glass substrate and the second glass substrate. 15. A method of manufacturing a mirror, comprising the steps of: preparing a first glass substrate having a reflective film; and forming a sealing glass material layer on a peripheral portion of the second glass substrate surface; a step of disposing a reflective film surface of the first glass substrate and a surface of the second glass substrate having a shape of 35 201237470 with a sealing glass material layer to form a stacked substrate; and sealing the stacked substrate The step of forming a sealing glass layer by heating and melting the glass material layer to seal the first glass substrate and the first glass substrate '. 16. The method of producing a mirror according to claim 15, wherein the stacked substrate is placed in a firing furnace to heat and melt the sealing glass material layer. The method for producing a mirror according to the sixteenth aspect of the invention, wherein the sealing glass material layer is irradiated with electromagnetic waves toward the sealing glass material layer to perform heating and melting of the sealing glass material layer. S