WO2013008724A1 - Double glazed glass and method for producing same - Google Patents

Abstract

Provided is double glazed glass which has improved long-term reliability by reducing the stress based on the temperature difference between the inside and the outside of a room. Double glazed glass (1) comprises a first glass plate (2) and a second glass plate (3) that are arranged at a predetermined distance from each other. The space between the first glass plate (2) and the second glass plate (3) is vacuum-sealed by a sealing layer (4) which is formed of a material obtained by melting and solidifying a sealing glass material that has laser absorption ability. The first and second glass plates (2, 3) are formed of low expansion glass.

Description

Multi-layer glass and manufacturing method thereof

The present invention relates to a multilayer glass and a method for producing the same.

As a glass plate with high heat insulation performance, a double-layer glass in which a gap between two glass plates is hermetically sealed, and a double-layer glass in which a gap between two glass plates is hermetically sealed (vacuum sealed) in a vacuum state (vacuum) Also known as double-glazed glass). The vacuum-sealed multi-layer glass has a structure in which, for example, two glass plates are arranged opposite to each other, and a space between these two glass plates is sealed with a low-melting glass (see Patent Documents 1 and 2). In Patent Document 1, two glass plates laminated through a low melting point glass are heated using a firing furnace to melt the low melting point glass, and then cooled to room temperature to solidify the low melting point glass. It describes that a sealing layer (seal part) is formed.

In Patent Document 2, after laminating two glass plates through a low-melting glass layer, the low-melting glass layer is locally heated and melted by irradiating laser light along the low-melting glass layer. The formation of a sealing layer is described. In Patent Document 3, after the low melting point glass layer is irradiated with laser light in an air atmosphere to form a sealing layer, it is evacuated through a through hole provided in one glass plate. The internal space between the two glass plates is in a vacuum state. The through hole is sealed after the internal space is evacuated.

The sealing process using local heating by laser light has advantages such as less energy consumption and reduced manufacturing steps and costs compared to heating by a firing furnace, but the low melting point glass is locally and rapidly applied. Since this is a process of heating and quenching, there is a problem that residual stress is likely to occur at or near the bonding interface between the sealing layer made of a melt-solidified layer of low-melting glass and the glass plate. When the double-glazed glass is applied to a window glass of a building such as a house or a building, an indoor and outdoor temperature difference is added to the double-glazed glass. At this time, if residual stress occurs in the sealing layer or in the vicinity thereof, the adhesive interface between the glass plate and the sealing layer or the sealing layer may be caused by a temperature difference between the inside or outside of the room or warpage of the multilayer glass based on the difference. Cracks and cracks are likely to occur.

Japanese Unexamined Patent Publication No. 2004-182567 International Publication No. 99/059931 Japanese Unexamined Patent Publication No. 2001-316137

As mentioned above, when local heating by laser light is applied to the sealing of multi-layer glass, residual stress is likely to occur due to the rapid heating / cooling process, thereby maintaining the reliability of the multi-layer glass over a long period of time. There is a problem that it is difficult to do. In other words, in addition to the residual stress generated in the sealing layer and its vicinity during laser sealing, the multilayer glass is subject to stress over time due to expansion and contraction of the members constituting the multilayer glass based on the temperature difference between the inside and outside the room. Therefore, cracks and cracks are likely to occur at the adhesive interface between the glass plate and the sealing layer and the sealing layer. In order to suppress such cracks and cracks, it is required to reduce the stress based on the temperature difference between the inside and outside of the room and improve the long-term reliability of the multilayer glass.

An object of the present invention is to provide a double-glazed glass and a method for producing the same capable of improving long-term reliability by reducing stress based on a temperature difference between indoors and outdoors.

The present inventors have found that “stress based on a temperature difference between the inside and outside of the room” is related to the amount of warpage of the double-glazed glass after sealing, and have completed the present invention.

The multilayer glass according to an aspect of the present invention has a first surface including a first sealing region, a first glass plate made of low expansion glass, and a first glass plate corresponding to the first sealing region. A second surface having two sealing regions, and disposed on the first glass plate with a predetermined gap so that the second surface faces the first surface; The first sealing region and the second glass plate are vacuum-sealed so that a gap between the second glass plate made of low expansion glass and the first glass plate and the second glass plate is vacuum-sealed. And a sealing layer made of a material obtained by melting and solidifying a sealing glass material having a laser absorption ability, which is formed between the sealing region and the sealing region.

The multilayer glass according to another aspect of the present invention has a first surface including a first sealing region, and corresponds to the first glass plate made of low expansion glass and the first sealing region. A second surface having a second sealing region that is disposed on the first glass plate with a predetermined gap so that the second surface faces the first surface. In addition, the first sealing region and the first glass plate are vacuum-sealed so that the second glass plate made of low expansion glass and the gap between the first glass plate and the second glass plate are vacuum-sealed. And a sealing layer formed between two sealing regions, and the thickness of the first glass plate disposed on the high temperature side is T1, and the second glass plate is disposed on the low temperature side. When the thickness of the second glass plate is T2, the thickness T2 of the second glass plate satisfies the condition of T2 <T1.

The method for producing a multilayer glass according to an aspect of the present invention includes a step of preparing a first glass plate having a first surface including a first sealing region and made of low expansion glass; A second sealing region comprising a second sealing region corresponding to the sealing region, and a sealing material layer formed on the second sealing region and made of a material obtained by baking a sealing glass material having laser absorption ability. A second glass plate made of low-expansion glass, and the first surface and the second surface facing each other while the first material and the second surface are opposed to each other. The step of laminating the glass plate and the second glass plate, and irradiating the sealing material layer with laser light through the first or second glass plate in a vacuum atmosphere, The gap between the first glass plate and the second glass plate is vacuum sealed by melting and solidifying. It is characterized by comprising a step of forming a sealing layer.

The method for producing a multilayer glass according to another aspect of the present invention includes a step of preparing a first glass plate having a first surface including a first sealing region and made of low expansion glass, A second sealing region corresponding to one sealing region, a first sealing material layer formed on the second sealing region and made of a sealing resin material, and the second sealing region. A second surface comprising a second sealing material layer formed of a material obtained by baking a sealing glass material having a laser absorption ability, which is formed on the inner peripheral side from the first sealing material layer above; A step of preparing a second glass plate made of low expansion glass, and the first surface and the second surface are opposed to each other while the first and second sealing material layers are interposed therebetween. A step of laminating the glass plate and the second glass plate, and curing the first sealing material layer in a vacuum atmosphere, A step of forming a first sealing layer for vacuum-sealing a gap between the first glass plate and the second glass plate; and a laser beam through the first or second glass plate in an air atmosphere. And irradiating the second sealing material layer to melt and solidify the second sealing material layer to form a second sealing layer.

In the double-glazed glass of the present invention, low-expansion glass is applied to the first and second glass plates, and therefore stress based on the temperature difference between the inside and outside of the double-glazed glass, such as the temperature difference between the inside and outside, can be reduced. . Therefore, a multilayer glass excellent in long-term reliability can be provided.

It is sectional drawing which shows the structure of the multilayer glass by the 1st Embodiment of this invention. It is sectional drawing which shows the manufacturing process of the multilayer glass by the 1st Embodiment of this invention. It is a top view which shows the 1st glass plate used by the manufacturing process of the multilayer glass shown in FIG. FIG. 4 is a cross-sectional view taken along line AA in FIG. 3. It is a top view which shows the 2nd glass plate used at the manufacturing process of the multilayer glass shown in FIG. FIG. 6 is a cross-sectional view taken along line AA in FIG. 5. It is sectional drawing which shows the structure of the multilayer glass by the 2nd Embodiment of this invention. It is sectional drawing which shows the manufacturing process of the multilayer glass by the 2nd Embodiment of this invention.

Hereinafter, modes for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing the structure of a multilayer glass according to the first embodiment. FIG. 2 is a cross-sectional view showing a process for producing a multilayer glass according to the first embodiment. FIG. 3 to FIG. 6 are diagrams showing the configuration of the first and second glass plates used in the manufacturing process of the multilayer glass.

The multilayer glass 1 shown in these drawings includes a first glass plate 2 having a first surface 2a and a second glass plate 3 having a second surface 3a. The first glass plate 2 and the second glass plate 3 are laminated with a predetermined gap so that the first surface 2a and the second surface 3a face each other. The gap between the first glass plate 2 and the second glass plate 3 is hermetically sealed (vacuum) in a vacuum state by the sealing layer 4 provided in the outer peripheral region (sealing region) of the glass plates 2 and 3. Sealed). That is, the internal space 5 of the multilayer glass 1 is maintained in a predetermined vacuum state.

The sealing layer 4 is made of a material obtained by melting and solidifying a sealing glass material. It is preferable that the glass material for sealing has a laser absorption ability so that it may mention later. The sealing layer 4 may be a material layer formed by locally irradiating a laser beam to a layer obtained by baking such a sealing glass material having laser absorption ability, and melting and solidifying the sealing glass material. preferable. In the gap between the first glass plate 2 and the second glass plate 3, a plurality of spacers 6 are arranged for maintaining a desired gap. The spacer 6 is fixed to the surface 2a of the first glass plate 2, for example. A low emissivity film 7 is formed on the surface 3 a of the second glass plate 3.

The configuration of the multilayer glass 1 of the first embodiment will be described in detail below. As shown in FIGS. 3 and 4, a first sealing region 8 is provided in the outer peripheral region of the surface 2 a of the first glass plate 2. As shown in FIGS. 5 and 6, a second sealing region 9 corresponding to the first sealing region 8 is provided in the outer peripheral region of the surface 3 a of the second glass plate 3. The first and second sealing regions 8 and 9 are regions for forming the sealing layer 4 (that is, the region for forming the sealing material layer for the first sealing region 8). The sealing layer 4 is a melt in which the sealing material layer 10 formed in the sealing region 8 of the first glass plate 2 is melted with a laser beam and fixed to the sealing region 9 of the second glass plate 3. It consists of a solidified layer.

That is, as shown in FIGS. 3 and 4, a frame-shaped sealing material layer 10 is formed in the sealing region 8 of the first glass plate 2 used for producing the multilayer glass 1. The sealing material layer 10 formed in the sealing region 8 of the first glass plate 2 is melted and fixed to the sealing region 9 of the second glass plate 3 by the heat of the laser beam, so that the first A sealing layer 4 for vacuum-sealing the gap between the glass plate 2 and the second glass plate 3 (that is, the interval between the internal spaces 5) is formed. The sealing material layer 10 is made of a material layer formed by baking a sealing glass material.
In addition, in FIG. 1, although the 1st glass plate is demonstrated to the lower side and the 2nd glass plate is demonstrated about the multilayer glass, the upper and lower sides of the multilayer glass of FIG. This is the same even if the first glass plate is used as the glass plate and the second glass plate is used as the lower glass plate. The same applies to the multilayer glass of FIG.

The glass material for sealing contains a sealing glass (glass frit) made of a low melting point glass as an essential component, and an inorganic filler such as a laser absorber or a low expansion filler as an optional component. The glass material for sealing may contain other additives other than these as required. Other additives include inorganic fillers other than laser absorbers and low expansion fillers. However, other additives shall exclude components that disappear during firing.

The combination and blending amount of the glass materials for sealing are selected in consideration of compatibility with the glass plates 2 and 3. The content of the sealing glass in the sealing glass material is preferably 50 to 100% by volume. The content of the inorganic filler as an optional component is preferably 0 to 50% by volume. When the content of the sealing glass is less than 50% by volume, the fluidity of the glass material for sealing at the time of sealing is lowered, and there is a possibility that it cannot be satisfactorily sealed. As for content of sealing glass, 60 volume% or more is more preferable. The upper limit is not particularly limited, but is preferably 97% by volume or less, and more preferably 90% by volume or less in consideration of the adjustment of the thermal expansion coefficient with respect to the glass plates 2 and 3.

Unless otherwise specified, “to” indicating the numerical range described above is used to mean that the numerical values described before and after it are used as a lower limit value and an upper limit value, and hereinafter “to” Used with meaning.

As the sealing glass, for example, low-melting glass such as bismuth glass, tin-phosphate glass, vanadium glass, lead glass, and silica borate alkali glass is used. Among these, considering the sealing property (adhesiveness) to the glass plates 2 and 3, its reliability (adhesion reliability and hermetic sealing property), and the influence on the environment and human body, etc., from bismuth-based glass A sealing glass is preferred.

The bismuth glass as the sealing glass is a composition containing 70 to 90% Bi ₂ O ₃ , 1 to 20% ZnO, and 2 to 12% B ₂ O ₃ in terms of the following oxide-based mass ratio ( Basically, the total amount is preferably 100%). Since the glass formed of the three components Bi ₂ O ₃ , ZnO, and B ₂ O ₃ has properties such as transparency and low glass transition point, it serves as a main component (essential component) of the glass material for sealing. Suitable for sealing glass.

In the bismuth-based glass formed of the three components described above, 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. When the content of Bi ₂ O ₃ is less than 70% by mass, the softening temperature of the sealing glass is increased. When 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. Considering the sealing temperature and the like, the Bi ₂ O ₃ content is more preferably in the range of 78 to 87% by mass.

ZnO is a component that lowers the thermal expansion coefficient and softening temperature, and is preferably contained in the range of 1 to 20% by mass in the sealing glass. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. If the content of ZnO exceeds 20% by mass, stability during molding of the sealed glass is lowered, devitrification is likely to occur, and glass may not be obtained. Considering the stability of glass production, the ZnO content is more preferably in the range of 7 to 12% by mass.

B ₂ O ₃ is a component that increases the range in which vitrification is possible by forming a glass skeleton, and is preferably contained in the sealing glass in the range of 2 to 12% by mass. If the content of B ₂ O ₃ is less than 2% by mass, vitrification becomes difficult. The content of B ₂ O ₃ is higher softening point exceeds 12 mass%. In consideration of the stability of the glass and the sealing temperature, the content of B ₂ O ₃ is more preferably in the range of 5 to 10% by mass.

The bismuth-based glass formed by the three components described above has a low glass transition point and is suitable for sealing glass, but Al ₂ O ₃ , CeO ₂ , SiO ₂ , Ag ₂ O, WO ₃ , MoO ₃ , Nb ₂ O ₃ , Ta ₂ O ₅ , Ga ₂ O ₃ , Sb ₂ O ₃ , Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, CaO, SrO, BaO, P ₂ O ₅ , SnO _x ( x may be 1 or 2). However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, or the glass transition point and softening point may increase, so the total content of any component is 10% by mass or less. Is preferred. The lower limit of the total content of arbitrary components is not particularly limited, and an effective amount of optional components can be blended based on the content of addition.

Among the above-mentioned optional components, Al ₂ O ₃ , SiO ₂ , CaO, SrO, BaO and the like are components that contribute to glass stabilization, and the content is preferably in the range of 0 to 7% by mass. Among them, Al ₂ O ₃ and BaO are excellent, and can be contained as the fourth component in the range of 0.1 to 7% by mass. Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O and the like have an effect of lowering the softening temperature of the glass, and CeO ₂ has an effect of stabilizing the fluidity of the glass. 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, etc. 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.

Of the inorganic fillers blended in the glass material for sealing as an optional component, the low expansion filler approximates the thermal expansion coefficient between the glass plates 2 and 3 and the sealing layer 4. Generally, since the thermal expansion coefficient of the sealing glass is larger than that of the glass plates 2 and 3, a low expansion filler is used to adjust the thermal expansion coefficient. The low expansion filler is selected from the group consisting of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compounds, tin oxide compounds, and quartz solid solutions. It is preferable to use at least one selected from the above. Examples of the zirconium phosphate-based compound include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , and NbZr (PO ₄ ). ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , and composite compounds thereof.

The content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing layer 4 which is a melt-solidified layer of the sealing glass material approaches the thermal expansion coefficient of the glass plates 2 and 3. The low expansion filler is preferably contained in the range of 0 to 50% by volume with respect to the sealing glass material, although it depends on the thermal expansion coefficient of the sealing glass and the glass plates 2 and 3. When content of a low expansion filler exceeds 50 volume%, there exists a possibility that the fluidity | liquidity of the glass material for sealing may fall, and adhesive strength may fall. The lower limit of the content of the low expansion filler is not particularly limited, and is appropriately set according to the thermal expansion coefficients of the sealing glass and the glass plates 2 and 3. The preferable lower limit of the content of the low expansion filler is 3% by volume or more, more preferably 10% by volume or more.

The laser absorbing material is a filler that enhances the ability of the sealing glass material to absorb laser light when the sealing glass material is heated by irradiating the laser beam. In addition, when the sealing glass itself has a laser absorption ability, it is not necessary to add a laser absorber. As the laser absorber, at least one metal (including an alloy) selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu, or an oxide containing at least one metal of the metal, Ni At least one compound such as —Mn—Fe—Co—O, Co—Cr—Fe—O, and Cu—Cr—Mn—O is used. The laser absorbing material may be a pigment other than these. The content of the laser absorber in the sealing glass material is preferably in the range of 0.1 to 40% by volume. When the content of the laser absorber exceeds 40% by volume, the fluidity at the time of melting of the glass material for sealing is lowered, and there is a possibility that the sealing cannot be performed satisfactorily. As for content of a laser absorber, 25 volume% or less is more preferable, More preferably, it is 20 volume% or less.

In the multilayer glass 1 according to the first embodiment, the first and second glass plates 2 and 3 are made of low expansion glass. The low expansion glass constituting the first and second glass plates 2 and 3 has a thermal expansion coefficient of 55 × 10 ⁻⁷ / ° C. or less (thermal expansion coefficient in a temperature range of 0 to 300 ° C., and so on). Is preferred. Examples of such low expansion glass include one selected from the group consisting of borosilicate glass, aluminoborosilicate glass, alkali-free aluminoborosilicate glass, alkali-free aluminosilicate glass, quartz glass, and crystallized glass. . The 1st glass plate 2 and the 2nd glass plate 3 consist of the same kind or different kind of low expansion glass.

By constructing the first and second glass plates 2 and 3 with low expansion glass, a multilayer such as a temperature difference between the interior and the exterior when the multilayer glass 1 is applied to a window glass of a building such as a house or a building. The stress generated based on the temperature difference between the inside and outside of the glass 1 can be reduced. The first glass plate 2 is disposed on the high temperature side (for example, the indoor side in a cold region and the outdoor side in a warm region where the temperature rises in summer), and the second glass plate 3 is disposed on the low temperature side (for example, a cold region). When the glass is placed on the outdoor side in the room or on the indoor side in a warm area where the temperature rises in summer), the double-glazed glass 1 is based on the temperature difference between the inside and outside (temperature difference between the inside and outside), etc. A difference arises in the expansion amount of the plate 2 and the second glass plate 3. For this reason, although the curvature which the 2nd glass plate 3 becomes concave shape arises in the multilayer glass 1, the 1st and 2nd glass plates 2 and 3 are comprised by low expansion glass. The amount of warpage of the multi-layer glass 1, and further the warpage and stress due to repetition thereof can be reduced.

Therefore, according to the multilayer glass 1 having the first and second glass plates 2 and 3 made of low expansion glass, the adhesion between the glass plates 2 and 3 and the sealing layer 4 due to repeated warping and stress described above. Generation | occurrence | production of a crack, a crack, etc. of an interface and the sealing layer 4 can be suppressed over a long period of time. That is, it becomes possible to provide the multilayer glass 1 having excellent long-term reliability. Moreover, the temperature difference which the multilayer glass 1 can accept | permit can be expanded by reducing the stress which generate | occur | produces based on the temperature difference inside and outside the multilayer glass 1, the curvature of the multilayer glass 1, etc. When the double-glazed glass 1 is used in an environment where the temperature difference between the outside and the inside is large, for example, when the double-glazed glass 1 is installed in a cold district, the allowable range for the temperature difference between the inside and outside of the double-glazed glass 1 is Can be spread. Specifically, the long-term reliability of the multi-layer glass 1 can be maintained even when the multi-layer glass 1 is installed in an environment where the temperature difference between the room and outside is, for example, 50 ° C. or more.

The first and second glass plates 2 and 3 have a coefficient of thermal expansion of 55 × 10 ⁻⁷ / ° C. or less in order to reduce stress due to the above-described temperature difference between the inside and outside of the room and the warp of the multilayer glass 1. It is preferable to comprise with the low expansion glass which has. By applying the low expansion glass having such a thermal expansion coefficient, it is possible to reduce stress based on the temperature difference between inside and outside of the multilayer glass 1 and warpage with good reproducibility. However, if the thermal expansion coefficient of the glass plates 2 and 3 becomes too small, the difference in thermal expansion from the glass material for sealing increases, and conversely, the stress generated in the vicinity of the sealing layer 4 may increase. Therefore, although depending on the thermal expansion coefficient of the sealing glass, the thermal expansion coefficients of the glass plates 2 and 3 are preferably 20 × 10 ⁻⁷ / ° C. or more. In addition, when the plate | board thickness of the 1st and 2nd glass plates 2 and 3 is adjusted so that it may mention later, it is not this limitation.

The thicknesses of the first and second glass plates 2 and 3 are preferably in the range of 0.5 mm to 6 mm, respectively. If the thickness of the glass plates 2 and 3 is less than 0.5 mm, the strength and reliability of the multilayer glass 1 may be insufficient. On the other hand, when the thickness of the glass plates 2 and 3 exceeds 6 mm, not only the multi-layer glass 1 becomes heavy, but also warpage and stress based on the temperature difference between the inside and outside may increase. Considering the weight and reliability of the multilayer glass 1, the thickness of the glass plates 2 and 3 is more preferably 1 mm to 5 mm, still more preferably 2 mm to 5 mm.

Further, when the first glass plate 2 is arranged on the high temperature side and the second glass plate 3 is arranged on the low temperature side, the thickness T2 of the second glass plate 3 is the thickness T1 of the first glass plate 2. Thinner (T2 <T1) is preferred. Specifically, when the thickness T1 of the first glass plate 1 is in the range of 2 mm to 5 mm, the thickness T2 of the second glass plate 3 is different from the thickness T1 of the first glass plate 2 (T1 -T2) is preferably 1 mm to 4 mm. By using the second glass plate 3 that satisfies such a plate thickness difference, the stress based on the temperature difference between the inside and outside of the multi-layer glass 1, warpage, or the like can be further reduced.

That is, by setting the difference (T1−T2) between the thickness T1 of the first glass plate 2 and the thickness T2 of the second glass plate 3 to 1 mm or more, tensile stress is generated by being disposed on the low temperature side. Since the glass thickness of the second glass plate 3 is relatively thinner than the first glass plate 2 facing, the tensile stress is released by deformation. For this reason, the stress based on the temperature difference between inside and outside of the multilayer glass 1 and warpage is further reduced. Therefore, the long-term reliability of the multilayer glass 1 can be further improved. The difference (T1−T2) between the thickness T1 of the first glass plate 2 and the thickness T2 of the second glass plate 3 is more preferably 2 mm or more. However, if the difference in thickness between the first glass plate 2 and the second glass plate 3 becomes too large, the second glass plate 3 becomes thin and causes a problem in strength. The thickness difference (T1−T2) between the two glass plates 3 is preferably 4 mm or less. In addition, when it shows with the plate | board thickness ratio (T2 / T1) of the 1st glass plate 2 and the 2nd glass plate 3, 0.2 or more and 0.8 or less are preferable.

Further, when the difference in thickness (T1-T2) between the first glass plate 2 and the second glass plate 3 as described above is satisfied, the stress and deformation are reduced as the glass having a smaller thermal expansion coefficient is used. Since it becomes possible to suppress further, low expansion glass having a smaller thermal expansion coefficient can be applied to the glass plates 2 and 3. Accordingly, it is possible to further reduce the stress based on the temperature difference between the inside and outside of the multilayer glass 1 and the warp. However, from the viewpoint of a practical thermal expansion coefficient of the low expansion glass, the thermal expansion coefficient of the glass plates 2 and 3 is preferably 20 × 10 ⁻⁷ / ° C. or more.

The pressure of the internal space 5 of the multilayer glass 1, that is, the internal space 5 formed in the gap between the first glass plate 2 and the second glass plate 3 is appropriately determined according to the characteristics required for the multilayer glass 1. Although set, it is preferable that the vacuum state of 1.0 Pa or less is maintained. Thereby, the favorable heat insulation characteristic by the multilayer glass 1 can be obtained. The pressure in the internal space 5 is more preferably 0.1 Pa or less. According to the double-glazed glass 1 according to the first embodiment, the inner space 5 in a higher vacuum state can be obtained as is apparent from the manufacturing process described later. That is, it becomes possible to provide the double-glazed glass 1 having excellent heat insulating properties.

In the internal space 5 of the multilayer glass 1, the spacer 6 described above is preferably disposed, although it depends on the size of the multilayer glass 1 and the like. Thereby, the shape of the internal space 5 which is in a vacuum state such as 1.0 Pa or less can be stably maintained. The spacer 6 is formed of, for example, a glass column, a resin column, or the like having a columnar shape, a prismatic shape, a ball shape, or the like. As will be described later, the spacer 6 is preferably formed of a glass column in consideration of the firing conditions at the time of forming the sealing material layer 10. The spacer 6 made of a glass column can be formed, for example, by applying and baking glass frit paste. For example, as shown in FIG. 3, the spacers 6 are preferably provided so as to be scattered in a predetermined pattern in the internal space 5 of the multilayer glass 1. The number and arrangement interval of the spacers 6 are appropriately set depending on the size of the multilayer glass 1, the pressure in the internal space 5, and the like.

Here, when the first glass plate 2 is arranged on the high temperature side and the second glass plate 3 is arranged on the low temperature side, the spacer 6 is not fixed to the surface 3a of the second glass plate 3, It is preferable that the first glass plate 2 is fixed only to the surface 2a. Thus, by fixing the spacer 6 only to the surface 2 a of the first glass plate 2, it is possible to further reduce the stress based on the temperature difference between inside and outside of the multilayer glass 1, warpage, and the like. That is, tensile stress is generated in the second glass plate 3 arranged on the low temperature side, but it can be freely deformed by not being fixed to the spacer 6. The stress based on it can be made still smaller. Therefore, the long-term reliability of the multilayer glass 1 can be further improved.
In addition, about the positional relationship of arrangement | positioning in the multilayer glass of a 1st glass plate and a 2nd glass plate, when it is not necessary to consider having arrange | positioned a 1st glass plate on the high temperature side by use environment. The relation between the thicknesses of the first glass plate and the second glass plate is not limited to the above. Similarly, the glass plate surface on which the spacer 6 is formed is not limited to the above relationship.

The gap between the first glass plate 2 and the second glass plate 3 (that is, the gap of the internal space 5) takes into consideration the thermal conductivity of the multi-layer glass 1, the formability of the sealing layer 4, and the like. It is preferably 30 μm or less, and more preferably 15 μm or less. That is, by narrowing the gap between the first glass plate 2 and the second glass plate 3, the sealing material layer 10 can be easily melted uniformly with the laser beam. Accordingly, it becomes possible to improve the formability of the sealing layer 4, the adhesiveness with the glass plates 2 and 3, and the reliability thereof. Further, the lower limit of the gap between the first glass plate 2 and the second glass plate 3 is not particularly limited, but is preferably 5 μm or more from the viewpoint of ensuring the heat insulating property of the multilayer glass.

Furthermore, in order to improve the heat insulation properties of the multilayer glass 1, it is preferable to form the low emissivity film 7 on the surface 3a of the second glass plate 3 disposed on the low temperature side, for example. Various known materials can be used for the low emissivity film (Low-E film) 7. For example, the Low-E film is formed by laminating a dielectric layer and a metal layer on a base material (for example, a glass plate). (For example, see Japanese Patent Application Laid-Open No. 2000-229378 and Japanese Patent Publication No. 08-032436). For example, “base material / dielectric layer / metal layer / dielectric layer”, “base material / dielectric layer / dielectric layer / metal layer / dielectric layer”, “base material / dielectric layer / metal layer / dielectric” Body layer / metal layer / dielectric layer ”,“ substrate / dielectric layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ substrate / dielectric layer / metal layer / dielectric ” Body layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ substrate / dielectric layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ” Or the like. The dielectric layer present between the base material and the metal layer closest to the base material may be one layer or two or more layers. Similarly, the dielectric layer on the metal layer may be one layer or two or more layers. Here, as the dielectric layer, a metal oxide layer is generally used, and tin oxide, zinc oxide, titanium oxide and the like are typical. Typical examples of the metal layer are gold and silver. Here, when the metal layer is silver, it may be 100% silver, or may be added with 3 atomic% or less of palladium. The low emissivity film 7 is preferably formed inside the sealing region 9 so as not to impair the formability of the sealing layer 4.
When the low emissivity film is formed on the second glass plate, the gap between the first glass plate 2 and the second glass plate 3 is the same as the surface of the low emissivity film and the first glass plate. The distance from the glass plate surface.
In the above example, an example in which a low emissivity film is formed on the surface of the second glass plate (the surface on the gap side of the multilayer glass) is shown, but depending on the specification mode of the multilayer glass, the first A low emissivity film may be formed on the surface of the glass plate (the surface on the gap side of the multi-layer glass), or on both surfaces of the surface on the gap side of the multi-layer glass of the first and second glass plates May be.
In addition, regarding the positional relationship of the arrangement of the first glass plate and the second glass plate in the multilayer glass, depending on the use environment, it is not necessary to consider that the second glass plate is arranged on the low temperature side. The above-described low emissivity film may be formed on either the first glass plate or the second glass plate, or may be formed on both in some cases.

The multi-layer glass 1 of the first embodiment is produced, for example, as follows. First, as shown in FIG. 2A, the sealing material layer 10 is formed in the sealing region of the surface 2 a of the first glass plate 2. The sealing material layer 10 is made of a sealing glass material paste prepared by mixing a sealing glass, which is an essential component of a sealing glass material, and an inorganic filler, which is an optional component, with a vehicle. After being applied to the surface 2a of the film, it is formed by drying and baking. When the spacer 6 is formed using sealing glass, a spacer glass paste prepared by mixing sealing glass with a vehicle is applied to the surface 2a of the first glass plate 2 with a predetermined coating pattern. After that, the spacer 6 is formed by drying and baking.

The vehicle is obtained by dissolving a resin as a binder component in a solvent. Examples of resins for vehicles include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, and nitrocellulose; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, An organic resin such as an acrylic resin obtained by polymerizing at least one acrylic monomer such as 2-hydroxyethyl acrylate is used. As the solvent, terpineol, butyl carbitol acetate, ethyl carbitol acetate or the like is used in the case of a cellulose resin, and methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate or the like is used in the case of an acrylic resin.

The viscosity of the glass material paste for sealing and the glass paste for spacers may be adjusted to the viscosity corresponding to the device applied to the first glass plate 2, the ratio of the resin and solvent, the ratio of the glass material for sealing and the vehicle, It can be adjusted according to the type of sealing glass and the type of vehicle. The resin is a component that disappears upon firing. You may add a well-known additive with a glass paste like a defoamer and a dispersing agent to the glass material paste for sealing, or the glass paste for spacers. These additives are also components that usually disappear during firing. A known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of each paste.

As shown to Fig.2 (a), the glass material paste for sealing is apply | coated to the sealing area | region (periphery area | region) of the 1st glass plate 2, this is dried, and the coating film of the glass material paste for sealing is formed. . The glass material paste for sealing is applied by applying a printing method such as screen printing or gravure printing, or is applied using a dispenser or the like. The width of the coating film is preferably 0.5 mm to 20 mm in order to maintain strength. The thickness of the coating film is set according to the distance between the first glass plate 2 and the second glass plate 3 and can be set in consideration of the shrinkage of the film in the subsequent drying process or pre-baking process. preferable. Similarly, a coating film of the glass paste for spacers is formed on the surface 2 a of the first glass plate 2.

The coating film of the glass material paste for sealing and the glass paste for spacers is preferably dried at a temperature of 60 to 150 ° C. for 30 seconds to 10 minutes, for example, to remove the solvent in the coating film. Subsequently, after heating to a temperature 30 ° C. or more lower than the glass transition point of the sealing glass in a baking furnace to remove the binder component and the like in the coating film, the temperature above the softening point of the sealing glass (for example, the temperature of the softening point). The glass material for sealing and the glass frit for spacers are baked on the first glass plate 2 by heating to a surface 2a of the first glass plate 2 to a frame-like sealing material layer. 10 and spacer 6 are formed. The formation process of the sealing material layer 10 and the spacer 6 may be performed simultaneously or separately. In this specification, 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).

Next, as shown in FIG. 2B, a low emissivity film 7 is formed on the surface 3a of the second glass plate 3 as necessary. The low emissivity film 7 may be formed in a desired shape excluding the region where the sealing layer 4 is formed, or a low emissivity film is formed on the entire surface 3a of the second glass plate 3 in advance. Thereafter, a region where the sealing layer 4 is formed may be trimmed to have a desired shape.

Next, as shown in FIG. 2 (c), the first glass plate 2 and the second glass plate 3 are placed in the vacuum chamber 11, and the inside of the vacuum chamber 11 is exhausted to a desired vacuum state. The first glass plate 2 and the second glass plate 3 are laminated so that the first surface 2a having the sealing material layer 10 and the spacer 6 and the surface 3a having the low emissivity film 7 face each other. . Then, in the vacuum chamber 11 in a predetermined vacuum state, the sealing material layer 10 is irradiated with the laser beam 12 through the second glass plate 3 (or the first glass plate 2). The laser beam 12 is irradiated while scanning along the sealing material layer 10. The laser light is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used.

The sealing material layer 10 is melted in order from the portion irradiated with the laser beam 12 scanned along the sealing material layer 10, and is rapidly solidified at the end of the irradiation of the laser beam 12 to be fixed to the second glass plate 3. Then, by irradiating the entire circumference of the sealing material layer 10 with the laser beam 12, the space between the first glass plate 2 and the second glass plate 3 is hermetically sealed as shown in FIG. The sealing layer 4 is formed. Since the laser beam 12 is irradiated in the vacuum chamber 11 in a desired vacuum state, the gap between the first glass plate 2 and the second glass plate 3 is kept in the vacuum state in the vacuum chamber 11. Hermetic sealing is performed in a state where the pressure is maintained (for example, 1 Pa or less).

That is, the multi-layer glass 1 having the internal space 5 maintained in a desired vacuum state can be obtained. Since the sealing layer 4 made of a material obtained by melting and solidifying the sealing material layer 10 with the laser beam 12 is excellent in airtightness, the internal space 5 having a vacuum state corresponding to the vacuum pressure of the vacuum chamber 11 can be obtained with good reproducibility. The internal space 5 having such a vacuum state can be maintained for a long period of time. The internal space 5 of the multilayer glass 1 according to the first embodiment can be in a vacuum state such as 1.0 Pa or less, and further 0.1 Pa or less. Furthermore, since the laser beam 12 is irradiated in the vacuum chamber 11, there is no need for a through hole or the like for evacuating the internal space later. Since the through-hole and the suction part attached to the through-hole cause a reduction in the strength of the double-glazed glass, the reliability of the double-glazed glass 1 can be improved.

The heating temperature of the sealing material layer 10 by the laser beam 12 is set to be equal to or higher than the softening point of the sealing glass. When the local heating by the laser beam 12 is applied, the temperature of the glass plates 2 and 3 is lower than the temperature of the sealing material layer 10, so that the heating temperature of the sealing material layer 10 can be set higher than the manufacturing process using the firing furnace. . The heating temperature is preferably (T + 200 ° C.) or more and (T + 800 ° C.) or less, for example, with respect to the softening point temperature T (° C.) of the sealing glass. Here, since the glass plates 2 and 3 are made of low-expansion glass, the difference in thermal expansion from the sealing glass tends to increase. In contrast, low expansion glass such as borosilicate glass, alumino borosilicate glass, quartz glass, and crystallized glass has a smaller distortion than soda lime glass. The formability of the sealing layer 4 can be improved by increasing the uniform meltability of the glass. It is also effective to reduce the thickness of the sealing material layer 10.

Next, the multilayer glass according to the second embodiment will be described with reference to FIG. 7 and FIG. FIG. 7 is a cross-sectional view showing the structure of the multilayer glass according to the second embodiment. FIG. 8 is a cross-sectional view showing a process for producing a multilayer glass according to the second embodiment. The double-layer glass 21 shown in these drawings is similar to the first sealing layer (sealing resin layer) 22 made of a material obtained by solidifying the sealing resin material and the sealing layer 4 in the first embodiment. And a second sealing layer (sealing glass layer) 23 made of a material obtained by melting and solidifying a sealing glass material. The first sealing layer (sealing resin layer) 22 is provided on the outer peripheral side of the second sealing layer (sealing glass layer) 23. Other configurations are the same as those in the first embodiment.

The multi-layer glass 21 of the second embodiment is produced as follows, for example. First, as shown to Fig.8 (a), in the sealing area | region of the surface 2a of the 1st glass plate 2, the 1st sealing material layer which consists of the sealing resin material for formation of the sealing resin layer 22 ( A sealing resin material layer) 24 and a second sealing material layer (sealing glass material layer) 25 made of a sealing glass material for forming the sealing glass layer 23 are formed. The 2nd sealing material layer 25 is formed in the sealing area | region of the 1st glass plate 2 similarly to the sealing material layer 10 of 1st Embodiment. In addition, the spacer 6 is formed in the same manner as in the first embodiment simultaneously with the formation of the second sealing material layer 25 or separately from the formation of the second sealing material layer 25.

The first sealing material layer 24 is applied by applying a resin composition paste containing an ultraviolet curable resin such as an acrylate resin or an epoxy resin by applying a printing method such as screen printing or gravure printing, or a dispenser. Etc. are applied and formed. The resin composition paste is applied to the outer peripheral side of the second sealing material layer 25 and subjected to ultraviolet treatment as necessary. For example, when an ultraviolet curable resin composition is used as the material for forming the first sealing material layer 24, an ultraviolet treatment or the like may be performed before the sealing treatment to make it semi-cured. Thus, while forming the 1st sealing material layer 24 which consists of resin materials for sealing on the outer peripheral side of the sealing area | region of the 1st glass plate 2, it is 2nd which consists of glass material for sealing on the inner peripheral side. The sealing material layer 25 is formed.

As in the first embodiment, a low emissivity film 7 is formed on the surface 3a of the second glass plate 3 as necessary (FIG. 8B). The low emissivity film 7 may be formed in a desired region excluding the region where the sealing layer 4 of the second glass plate 3 is formed, or may be formed on the entire surface of the second glass plate 3 in advance. An emissivity film may be formed, and a region where the sealing layer 4 is formed may be trimmed to form a low emissivity film 7 having a desired shape. Next, as shown in FIG. 8C, the first glass plate 2 and the second glass plate 3 are disposed in the vacuum chamber 11, and the inside of the vacuum chamber 11 is evacuated to a desired vacuum state. The first glass plate 2 and the second glass plate 3 are laminated so that the first surface 2a having the sealing material layers 24 and 25 and the spacer 6 and the surface 3a having the low emissivity film 7 face each other. To do. Then, in the vacuum chamber 11 in a predetermined vacuum state, the first sealing material layer 24 is cured by ultraviolet treatment to form the first sealing layer 22.

Next, as shown in FIG. 8 (d), the laminate of the first glass plate 2 and the second glass plate 3 on which the first sealing layer (sealing resin layer) 22 is formed is placed in an air atmosphere. Immediately after the exposure, the second sealing material layer (sealing glass material layer) 25 is irradiated with the laser beam 12 through the second glass plate 3 (or the first glass plate 2). The laser beam 12 is irradiated in the same manner as in the first embodiment except that the laser beam 12 is irradiated in an air atmosphere. The laser beam 12 is irradiated over the entire circumference of the second sealing material layer 25 to hermetically seal between the first glass plate 2 and the second glass plate 3 as shown in FIG. 2 sealing layers (sealing glass layers) 23 are formed.

In the second embodiment, since the first sealing layer 22 is formed in the vacuum chamber 11 in a desired vacuum state, the inside of the first sealing layer 22 is the vacuum in the vacuum chamber 11. The pressure is maintained according to the state. Therefore, even if the laser beam 12 is irradiated to the second sealing material layer 25 disposed inside the first sealing layer 22 in the air atmosphere, the inner side of the second sealing layer 23 is not affected. The space, that is, the internal space 5 of the multilayer glass 21 can be maintained in a desired vacuum state (for example, 10 Pa or less). And since the 2nd sealing layer 23 is excellent in airtightness, the internal space 5 which has a desired vacuum state can be obtained with sufficient reproducibility, and also the internal space 5 which has such a vacuum state is maintained over a long period of time. it can.

Next, specific examples of the present invention and evaluation results thereof will be described. In addition, the following description does not limit this invention, The modification | change in the form along the meaning of this invention is possible.

Example 1
It has a composition of Bi ₂ O ₃ 83.2%, B ₂ O ₃ 5.6%, ZnO 10.7%, Al ₂ O ₃ 0.5% in terms of mass ratio in terms of oxide, and further 150 ppm in mass ratio by weight of Na ₂ O, an average particle diameter _{(D 50)} 1.0μm bismuth-based glass (softening point: 410 ° C.) and an average particle diameter _{(D 50)} is cordierite of 4.3μm as a low expansion Hama material A powder and a laser absorber having a composition of Fe ₂ O ₃ —CuO—MnO—Al ₂ O ₃ and an average particle diameter (D ₅₀ ) of 1.2 μm were prepared.

Particle size distribution was measured using a particle size analyzer (Nikkiso Co., Ltd., Microtrac HRA) using a laser diffraction / scattering method. The measurement conditions were as follows: measurement mode: HRA-FRA mode, Particle Transparency: yes, Special Particles: no, Particle Refractive index: 1.75, Fluid Refractive index: 1.33.

A glass material for sealing and a glass material for spacer were prepared by mixing 66.8% by volume of the bismuth-based glass, 32.2% by volume of cordierite powder, and 1.0% by volume of the laser absorber. 83% by mass of this glass material was mixed with 17% by mass of a vehicle prepared by dissolving 5% by mass of ethyl cellulose as a resin binder component in 95% by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. Thus, a glass paste for sealing and spacers was prepared.

Next, a first glass plate (dimensions: 370 mm × 370 mm × 3 mm) made of borosilicate glass having a thermal expansion coefficient (0 to 300 ° C.) of 32.5 × 10 ⁻⁷ / ° C. is prepared. The spacer glass paste was applied to the inner region of the sealing region with a desired printing pattern by a screen printing method to form a spacer coating layer, and then dried under conditions of 120 ° C. × 10 minutes. The printing pattern of the spacers was arranged such that dots having a diameter of 0.25 mm were arranged in a range of 340 mm × 340 mm at intervals of 20 mm according to the spacer arrangement pattern. Subsequently, this coating film is heated under conditions of 300 ° C. × 30 minutes to remove the resin binder component, and then baked under conditions of 480 ° C. × 10 minutes in an air atmosphere, whereby a spacer having a height of 12 μm. Formed.

Next, as shown in FIG. 3, after applying the sealing glass paste to the sealing region of the first glass plate in a frame shape with a dispenser to form a sealing material layer, the condition is 120 ° C. × 10 minutes. And dried. This print pattern was a frame-like pattern of 340 mm × 340 mm with a line width of 0.5 mm. Subsequently, the coating film is heated at 300 ° C. for 30 minutes to remove the resin binder component, and then fired in an air atmosphere at 480 ° C. for 10 minutes to seal the film thickness to 15 μm. A material layer (sealing glass material layer) was formed.

Next, “ZnO / Ag / ZnO / Ag / ZnO as a low emissivity film is formed on the surface of the second glass plate (a plate made of borosilicate glass having the same composition, shape, and dimensions as the first glass plate). Was formed by sputtering. The film formation by the sputtering method was performed by masking so that the film did not adhere to the sealing region. The masking tape was peeled off after film formation. Moreover, only the sealing area | region was wash | cleaned with the organic solvent so that the adhesive of a masking tape might not remain in a sealing area | region.

The above-described first glass plate having the sealing material layer and the spacer, and the second glass plate having the low emissivity film, the first surface 2a having the sealing material layer and the spacer, and the low emissivity. After disposing in the vacuum chamber so as to face the surface 3a having the film, the inside of the vacuum chamber was evacuated. After the pressure in the vacuum chamber reached 0.1 Pa, the first glass plate and the second glass plate were laminated. Then, the sealing material layer is irradiated with a laser beam (CW semiconductor laser) having a wavelength of 808 nm and an output of 16 W through the second glass plate at a scanning speed of 4 mm / second to melt and rapidly solidify the sealing material layer. A sealing layer for vacuum-sealing the gap between the first glass plate and the second glass plate was formed. The characteristics of the multilayer glass thus obtained were evaluated as follows.

When the state of the sealing layer of the obtained multilayer glass was observed, adhesion failure such as unbonded portions and cracks was not observed, and it was confirmed that sufficient adhesion was obtained. A temperature difference of −20 ° C. on the low temperature side and + 30 ° C. on the high temperature side was given to the inside and outside of the laminated glass after sealing, and the amount of warpage at a point 50 cm from the center of the laminated glass was measured. Moreover, 100 double-glazed glass was produced and the incidence rate of the crack by laser sealing was measured. These measurement results are shown together in Table 1.

(Examples 2 to 6)
A multilayer glass was produced in the same manner as in Example 1 except that glass plates having a thermal expansion coefficient and a thickness as shown in Table 1 were used as the first and second glass plates. The characteristics and the like of these multilayer glasses were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.

(Comparative Example 1)
Except for using glass plates (dimensions: 370 mm × 370 mm × 3 mm) made of soda lime glass having a thermal expansion coefficient (0 to 300 ° C.) of 85 × 10 ⁻⁷ / ° C. as the first and second glass plates. A multilayer glass was produced in the same manner as in Example 1. The characteristics and the like of this multilayer glass were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.

(Reference Example 1)
A multilayer glass was produced in the same manner as in Example 1 except that the distance (that is, the gap) between the first glass plate and the second glass plate was 200 μm. The characteristics and the like of this multilayer glass were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.

(Comparative Example 2)
A multilayer glass was produced in the same manner as in Comparative Example 1 except that the distance between the first glass plate and the second glass plate was 200 μm. The characteristics and the like of this multilayer glass were measured in the same manner as in Example 1. The measurement results are also shown in Table 1.

In Table 1, the expression “low temperature side / vacuum layer / high temperature side” means “low temperature side (second glass plate) / vacuum layer / high temperature side (first glass plate)”. In Table 1, “the distance between the glass plates” means “the gap between the first glass plate and the second glass plate”.
As is clear from Table 1, it can be seen that the multilayer glass of Examples 1 to 6 has less warpage of the glass plate when used as the multilayer glass compared to Comparative Example 1.

(Example 7)
A first glass plate (dimensions: 370 mm × 370 mm × 3 mm) made of borosilicate glass having a thermal expansion coefficient (0 to 300 ° C.) of 32.5 × 10 ⁻⁷ / ° C. is prepared. In the same manner as in Example 1, a spacer and a second sealing material layer made of a sealing glass material were formed. Then, the 1st sealing material layer which consists of a resin material for sealing was formed by apply | coating the resin paste of a urethane acrylate composition with a dispenser on the outer side of the 1st sealing material layer.

Next, the above-described first glass plate and a second glass plate having a low emissivity film formed in the same manner as in Example 1 (borosilicate glass having the same composition, shape, and dimensions as the first glass plate) After the glass plate is disposed in the vacuum chamber so that the first surface 2a having the sealing material layer, the spacer, and the sealing resin material, and the surface 3a having the low emissivity film are opposed to each other. The inside of the vacuum chamber was evacuated. After the pressure in the vacuum chamber reached 0.1 Pa, the first glass plate and the second glass plate were laminated. And the 1st sealing layer (sealing resin layer) was formed by performing an ultraviolet curing process in a vacuum chamber.

Subsequently, the laminated body on which the first sealing layer is formed is exposed to the atmosphere, and in this state, a laser beam (CW semiconductor laser having a wavelength of 808 nm and an output of 18 W is applied to the second sealing material layer through the second glass plate. ) At a scanning speed of 4 mm / second, and the second sealing material layer is melted and rapidly cooled and solidified to vacuum seal the gap between the first glass plate and the second glass plate. A sealing layer (sealing glass layer) was formed. The characteristics of the multilayer glass thus obtained were evaluated in the same manner as in Example 1. As a result, the amount of warpage of the glass plate when it was made into a multilayer glass was not deteriorated.

In the above embodiment, the spacer is formed with the glass material paste, but a spherical spacer such as silica particles may be used. More specifically, silica particles having a particle diameter of about 10 μm that are widely used for liquid crystal displays can be used.

According to the present invention, since the low expansion glass is applied to the first and second glass plates, it is possible to reduce stress based on the temperature difference between the inside and outside of the multilayer glass, such as the temperature difference between the inside and outside, and therefore It is possible to provide a multilayer glass having excellent long-term reliability.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2011-152320 filed on July 8, 2011 are incorporated herein as the disclosure of the present invention. .

DESCRIPTION OF SYMBOLS 1,21 ... Multi-layer glass, 2 ... 1st glass plate, 3 ... 2nd glass plate, 4 ... Sealing layer, 5 ... Internal space (vacuum airtight space), 6 ... Spacer, 7 ... Low emissivity film | membrane , 8 ... 1st sealing area | region, 9 ... 2nd sealing area | region, 10 ... Sealing material layer, 11 ... Vacuum chamber, 12 ... Laser beam, 22 ... 1st sealing layer (sealing resin layer) , 23 ... second sealing layer (sealing glass layer), 24 ... first sealing material layer (sealing resin material layer), 25 ... second sealing material layer (sealing glass material layer).

Claims (20)

1. A first glass plate having a first surface with a first sealing region and made of low expansion glass;
   The first glass plate has a second surface having a second sealing region corresponding to the first sealing region, and the second surface is opposed to the first surface. A second glass plate made of low expansion glass, disposed with a predetermined gap between
   Laser absorption is formed between the first sealing region and the second sealing region so as to vacuum-seal the gap between the first glass plate and the second glass plate. And a sealing layer made of a material obtained by melting and solidifying a sealing glass material having a function.
2. The multilayer glass according to claim 1, wherein the low expansion glass has a thermal expansion coefficient of 55 × 10 ⁻⁷ / ° C. or less.
3. The first and second glass plates may be the same or different selected from the group consisting of borosilicate glass, aluminoborosilicate glass, alkali-free aluminoborosilicate glass, alkali-free aluminosilicate glass, quartz glass, and crystallized glass. The multilayer glass according to claim 1 or 2, wherein the glass is made of glass.
4. The multi-layer glass according to any one of claims 1 to 3, wherein a gap between the first glass plate and the second glass plate is 30 µm or less.
5. 5. The multi-layer glass according to claim 1, wherein a plurality of spacers are arranged in a gap between the first glass plate and the second glass plate.
6. When the plate thickness of the first glass plate arranged on the high temperature side is T1, and the plate thickness of the second glass plate arranged on the low temperature side is T2, the plate thickness T2 of the second glass plate is The multilayer glass according to any one of claims 1 to 5, wherein a condition of T2 <T1 is satisfied.
7. The thickness T1 of the first glass plate is in the range of 2 mm to 5 mm, and the difference (T1−T2) between the thickness T1 of the first glass plate and the thickness T2 of the second glass plate is The multi-layer glass according to claim 6, wherein the thickness is 1 mm to 4 mm.
8. A plurality of spacers are disposed in a gap between the first glass plate and the second glass plate, and the spacers are fixed only to the first surface of the first glass plate. The multilayer glass according to claim 6 or 7, wherein
9. The sealing glass material is made of a bismuth-based glass containing 70 to 90% Bi ₂ O ₃ , 1 to 20% ZnO, and 2 to 12% B ₂ O ₃ in a mass ratio in terms of the following oxides. 0.1 to 40% by volume of the laser absorbing material and 0 to 50% by volume of the low expansion filler are contained in a total amount of the laser absorbing material and the low expansion filler. The multilayer glass according to any one of claims 1 to 8, which is contained in a range of -50% by volume.
10. The multi-layer glass according to any one of claims 1 to 9, wherein the first and second glass plates do not have a through hole for vacuuming.
11. The multi-layer according to any one of claims 1 to 10, wherein a gap between the first glass plate and the second glass plate is maintained in a vacuum state of 1.0 Pa or less. Glass.
12. The low emissivity film | membrane is provided in at least any one of the 1st surface of the said 1st glass plate, and the 2nd surface of the said 2nd glass plate of Claim 1 thru | or 11 characterized by the above-mentioned. The multilayer glass of any one of Claims.
13. A sealing resin layer made of a material obtained by further curing a sealing resin material is provided on the outer peripheral side of the sealing layer made of a material obtained by melting and solidifying the sealing glass material. Item 13. The multilayer glass according to any one of Items 1 to 12.
14. A first glass plate having a first surface with a first sealing region and made of low expansion glass;
    The first glass plate has a second surface having a second sealing region corresponding to the first sealing region, and the second surface is opposed to the first surface. A second glass plate made of low expansion glass, disposed with a predetermined gap between
    Sealing formed between the first sealing region and the second sealing region so as to vacuum seal a gap between the first glass plate and the second glass plate. Comprising a layer,
    When the plate thickness of the first glass plate arranged on the high temperature side is T1, and the plate thickness of the second glass plate arranged on the low temperature side is T2, the plate thickness T2 of the second glass plate is A multilayer glass characterized by satisfying a condition of T2 <T1.
15. The thickness T1 of the first glass plate is in the range of 2 mm to 5 mm, and the difference (T1−T2) between the thickness T1 of the first glass plate and the thickness T2 of the second glass plate is The multilayer glass according to claim 14, wherein the thickness is 1 mm to 4 mm.
16. Providing a first glass plate having a first surface with a first sealing region and made of low expansion glass; and
    A second sealing region corresponding to the first sealing region; and a sealing material layer formed on the second sealing region and made of a material obtained by baking a sealing glass material having a laser absorption capability; Preparing a second glass plate made of low expansion glass having a second surface comprising:
    Laminating the first glass plate and the second glass plate via the sealing material layer while facing the first surface and the second surface;
    The sealing material layer is irradiated with laser light through the first or second glass plate in a vacuum atmosphere, and the sealing material layer is melted and solidified so that the first glass plate and the second glass are used. And a step of forming a sealing layer for vacuum-sealing a gap between the plate and the plate.
17. Providing a first glass plate having a first surface with a first sealing region and made of low expansion glass; and
    A second sealing region corresponding to the first sealing region; a first sealing material layer formed on the second sealing region and made of a sealing resin material; and the second sealing. A second sealing material layer formed on the inner peripheral side of the first sealing material layer on the stop region and having a second sealing material layer made of a fired sealing glass material having a laser absorption capability. And preparing a second glass plate made of low expansion glass;
    Laminating the first glass plate and the second glass plate through the first and second sealing material layers while facing the first surface and the second surface; ,
    Curing the first sealing material layer in a vacuum atmosphere and forming a first sealing layer for vacuum-sealing a gap between the first glass plate and the second glass plate;
    A second sealing layer is formed by irradiating the second sealing material layer with laser light through the first or second glass plate in an air atmosphere to melt and solidify the second sealing material layer. And a step of forming a glass.
18. The method for producing a multilayer glass according to claim 16 or 17, wherein a gap between the first glass plate and the second glass plate is maintained in a vacuum state of 1.0 Pa or less.
19. The method for producing a multi-layer glass according to any one of claims 16 to 18, wherein the low expansion glass has a thermal expansion coefficient of 55 x 10 ^-7 / ° C or less.
20. When the plate thickness of the first glass plate arranged on the high temperature side is T1, and the plate thickness of the second glass plate arranged on the low temperature side is T2, the plate thickness T2 of the second glass plate is The method for producing a double-glazed glass according to any one of claims 16 to 19, wherein a condition of T2 <T1 is satisfied.

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