JP2013216502A - Glass member with bonding layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-layered glass which enables to enhance long-term reliability by reducing stress due to the difference between indoor and outdoor temperatures, or the like.SOLUTION: A multi-layered glass 1 includes a first glass plate 2 and a second glass plate 3 arranged at a predetermined interval. The space between the first glass plate 2 and the second glass plate 3 is vacuum-sealed with a bonding layer 14 comprising a material formed by melting and solidifying a bonding glass material having laser absorbing ability. First and second glass plates 11, 12 are made of low expansion glass.

Description

  The present invention relates to a glass member with a bonding layer in which a pair of glass plates are bonded by a bonding glass material.

  As a method of joining a pair of glass plates in a multi-layer glass or the like, a pair of glass plates are laminated via a joining glass material, and the joining glass material is melted in a firing furnace, and then cooled to room temperature. A method of solidifying and bonding a pair of glass plates with a bonding layer made of a bonding glass material is known (for example, see Patent Document 1). Moreover, after laminating a pair of glass plates via the bonding glass material, the laser beam is irradiated along the bonding glass material to locally heat and melt the bonding glass material, so that the pair of glass plates There is known a method of bonding a film with a bonding layer made of a bonding glass material (for example, see Patent Document 2).

  However, the conventional joining method basically joins only the vicinity of the outer peripheral portion of a pair of glass plates with a joining layer, and the center portion of the pair of glass plates is not joined. When only the vicinity of the outer peripheral portion is bonded by the bonding layer, the pair of glass plates are bonded in a bent state, for example, in a deformed state in which the central portion of the other glass plate approaches one glass plate, and is bonded to the bonding layer. The applied stress is large, and damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral part.

  In addition, when only the vicinity of the outer peripheral portion is joined by a joining layer, when applied to a window glass of a building such as a house or a building, a pair of glass plates may be deformed so as to swell with each other under a strong wind. Since a large stress is applied to the peripheral portion, damage such as cracks and cracks is likely to occur, and damage such as cracks and cracks is likely to occur in the glass plate itself.

  In addition, a spacer is disposed between a pair of glass plates, for example, in order to maintain the gap between them, but it is basically bonded only to one glass plate, and its bonding area is not necessarily large. Therefore, it is not possible to suppress the deformation such that the pair of glass plates as described above swell each other. In addition, since the constituent material of the spacer is usually different from the constituent material of the bonding layer, steps such as manufacturing and arranging the spacer are necessary, and the productivity is not necessarily excellent.

  In addition, from the viewpoint of reducing the weight of a multi-layer glass or the like, a reduction in the thickness of the glass plate constituting the glass is being studied. However, the reduced thickness of the glass plate is easily deformed, and particularly in a strong wind as described above. The glass plates are easily deformed so as to swell with each other, and damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral portion, and damage such as cracks and cracks are likely to occur in the glass plate itself.

  Furthermore, the bonding by laser light is less energy consumption than the bonding by the firing furnace, so that the manufacturing cost can be reduced and the number of manufacturing steps can be reduced. However, the bonding glass material is locally heated and rapidly cooled. For this reason, residual stress is likely to occur in the bonding layer and its peripheral part. For those having such residual stress, damage such as cracks or cracks is likely to occur particularly in the bonding layer and its peripheral part.

  The problem when only the vicinity of the outer peripheral portion is bonded by the bonding layer is not necessarily limited to the double-glazed glass, but is used outdoors, for example, a solar cell having a structure in which a solar cell element is sealed between a pair of glass plates The same phenomenon occurs in a reflector having a structure in which a reflective film is sealed between a pair of glass plates used in a solar thermal power generation system. In addition, although not as much as these, the same problem also occurs in electronic devices mainly used indoors, such as a flat panel display device.

JP 2004-182567 A International Publication No. 99/059931

  A method of bonding a pair of glass plates with a bonding glass material is known. Basically, only the vicinity of the outer peripheral portion of a pair of glass plates is bonded by a bonding layer, and stress applied to the bonding layer is increased. It is large, and damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral part. In addition, it is known that a spacer is disposed between a pair of glass plates. Basically, the spacer is bonded only to one glass plate, and the bonding area is not necessarily large. Since deformations such that the plates swell with each other cannot be suppressed, and steps such as manufacture and arrangement of spacers are required, productivity is not necessarily excellent.

  The present invention was made to solve the above problems, and can suppress damage such as cracks and cracks in the bonding layer and its peripheral part, and can also suppress damage such as cracks and cracks in the glass plate itself, It aims at provision of the glass member with a joining layer which is excellent in productivity.

  The glass member with a bonding layer of the present invention has a pair of glass plates arranged to face each other with a gap therebetween, and a bonding layer that is arranged between the pair of glass plates and bonds the pair of glass plates. . The bonding layer is made of a material obtained by melting and solidifying a bonding glass material. Moreover, this joining layer is comprised from a linear part, and is in the range of 0.005-0.02 in the ratio of the area on this opposing surface with respect to the area of one opposing surface of a pair of glass plate. It is provided as follows.

  In the glass member with a bonding layer of the present invention, the bonding layer is formed of a linear portion, and is provided in a wider area as compared with the case where the bonding layer is provided only in the vicinity of the outer peripheral portion. Accordingly, the stress applied to the bonding layer can be reduced, and damage such as cracks and cracks in the bonding layer and its peripheral portion can be suppressed. Further, deformation of the glass plate can be suppressed, and damage such as cracks and cracks in the glass plate can be suppressed. Furthermore, since the bonding layer is composed of linear portions, it can be manufactured only by bonding with laser light, for example, and the productivity is excellent.

It is a top view which shows an example of the glass member with a joining layer of 1st Embodiment. The AA sectional view taken on the line of the glass member with a joining layer shown in FIG. The top view which shows the modification of the glass member with a joining layer of 1st Embodiment. The top view which shows the other modification of the glass member with a joining layer of 1st Embodiment. The top view which shows the further another modification of the glass member with a joining layer of 1st Embodiment. It is a top view which shows an example of the glass member with a joining layer of 2nd Embodiment. Sectional view on the AA line of the glass member with a joining layer shown in FIG. Explanatory drawing explaining an example of the manufacturing process of the glass member with a joining layer. The figure which shows the planar shape of the joining layer in the glass member with a joining layer of Example 1. FIG. The figure which shows the planar shape of the joining layer in the glass member with a joining layer of the comparative example 1. FIG.

Hereinafter, embodiment of the glass member with a joining layer is described.
The glass member with a bonding layer includes a pair of glass plates disposed to face each other with a gap therebetween, and a bonding layer that is disposed between the pair of glass plates and bonds the pair of glass plates. The bonding layer is made of a material obtained by melting and solidifying a bonding glass material. The bonding layer is composed of linear portions, and the ratio of the area on the facing surface to the area of one facing surface of the pair of glass plates (the bonding layer on one facing surface of the pair of glass plates) The area of the one opposing surface of the pair of glass plates) is within a range of 0.005 to 0.02.

  Note that the bonding layer needs to be composed of a linear portion, but the overall shape composed of such a linear portion does not have to be linear. It may have a straight part or the like, or may have a plurality of mutually independent frame-like parts. Each linear portion has a length of at least 1.5 mm. That is, the area of the bonding layer for calculating the ratio includes only the area of the linear portion that is longer than the length. Here, the length of each linear portion includes a curved portion other than the straight portion and the entire continuous portion. The length of each linear portion is preferably 50 mm or more, and more preferably 100 mm or more from the viewpoint of bonding strength and the like.

  When only the vicinity of the outer peripheral portion of the pair of glass plates is bonded by the bonding layer, the stress applied to the bonding layer is large, and damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral portion. In addition, the pair of glass plates are easily deformed so as to swell with each other. In this case as well, damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral portion. Damage is likely to occur.

  In particular, as the glass plate becomes larger, the stress applied to the bonding layer increases, and damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral part. Moreover, it becomes easy to deform | transform as a glass plate becomes thin, and damages, such as a crack and a crack, are easy to generate | occur | produce in glass plate itself. Furthermore, in the case of bonding with a laser beam, since rapid heating and quenching locally, residual stress is likely to occur in the bonding layer and its peripheral part, and damage such as cracks and cracks occur in the bonding layer and its peripheral part. Cheap.

  In the glass member with a bonding layer of the embodiment, the bonding layer is composed of linear portions as described above, and the area ratio on the facing surface is 0 with respect to the area of one facing surface of the pair of glass plates. A bonding layer is provided so as to be in the range of 0.005 to 0.02. By forming the bonding layer from linear portions, that is, by making each portion linear, not only a pair of glass plates can be bonded satisfactorily, but also the whole can be bonded by laser light, and productivity can be improved.

  And, by providing the bonding layer at a predetermined ratio, it is possible to bond in a wider area compared to the case where only the vicinity of the outer peripheral part is bonded, and the stress applied to the bonding layer is reduced, and cracks in the bonding layer and its peripheral part are obtained. Damage such as cracks and cracks can be suppressed. Further, deformation of the glass plate can be suppressed, and damage such as cracks and cracks in the glass plate can be suppressed. In particular, the glass plate is easily deformed when it is large or thin, and damage such as cracks and cracks is likely to occur. In such a case, damage such as cracks and cracks can be effectively suppressed.

  When the ratio is less than 0.005, there is no great difference in the bonding area compared to the case where the bonding layer is provided only in the vicinity of the outer peripheral portion, the crack is broken in the bonding layer and its peripheral portion, and the glass plate is cracked. There is a possibility that damage such as cracks and cracks cannot be suppressed. On the other hand, if the ratio is 0.02, it is sufficient to suppress damage, and if it exceeds this, productivity may be reduced in the case of bonding by laser light or the like. In addition, the appearance is different between the portion where the bonding layer is provided and the portion where the bonding layer is not provided, and when the ratio is exceeded, the portion where the bonding layer is provided is conspicuous, so the overall appearance of the glass member with the bonding layer is good There is a risk that it will disappear.

  Here, the area of one opposing surface of a pair of glass plates means the area of the opposing surface of one glass plate, including the area where the bonding layer is provided, It corresponds to the area in plan view. The area of the bonding layer is the area on the facing surface of the one glass plate described above. For example, when the bonding layer is provided in a frame shape, the area of the portion where the bonding layer is actually provided. Yes, it does not include a portion within the frame and not provided with a bonding layer. The ratio is preferably in the range of 0.007 to 0.02, more preferably in the range of 0.01 to 0.02, from the viewpoint of suppressing damage to the bonding layer and its peripheral portion and the pair of glass plates. preferable.

  The width of the linear portion constituting the bonding layer is preferably in the range of 0.5 to 1.5 mm. By setting the width of the linear portion to 0.5 mm or more, the bonding strength can be sufficient. On the other hand, by setting the width of the linear portion to 1.5 mm or less, it is possible to efficiently join in the case of joining with a laser beam or the like, and the appearance of the glass member with the joining layer as a whole can be improved. The width of the linear portion is more preferably within the range of 0.5 to 1.0 mm. In addition, although it is preferable that all the parts are in the said range, the width | variety of a linear part does not necessarily need to be the same in all the parts, and may differ for every part.

  In particular, the bonding layer is provided in the vicinity of the outer peripheral portion which is a range from the outer peripheral portion to the 20 mm of the pair of glass plates, and is provided in the central portion region which is an inner region of the peripheral portion vicinity region. Is preferred. The joining layer provided in the outer peripheral portion vicinity region may be either continuous or discontinuous, but in the case of discontinuity, the total length is 70% or more of the length of one circumference in the circumferential direction. The length is preferably 80% or more, more preferably 90% or more. In addition, the bonding layer provided in the central region is a ratio of the area on the opposing surface to the area of the one opposing surface of the pair of glass plates (the central region on the one opposing surface of the pair of glass plates). The area of the bonding layer / the area of one opposing surface of the pair of glass plates) is preferably provided in a range of 0.002 to 0.008.

Although a pair of glass plate changes also with uses of the glass member with a joining layer, the magnitude | size of 400 cm < ² > or more is preferable at an area, respectively. In the case of such a size, since the stress applied to the bonding layer increases, damage such as cracks and cracks is likely to occur in the bonding layer and its peripheral part, and the glass plate is cracked and cracked due to deformation of the glass plate. Therefore, the effect of providing the joining layer so as to have a predetermined area ratio is great. Each area of the glass plate pair is more preferably 1600 cm ² or more, 10000 cm ² or more is more preferable. Usually, the area of each of the pair of glass plates is 160000 cm ² or less.

  Moreover, it is preferable that at least one thickness of a pair of glass plates is 2.0 mm or less. In the case of such a thickness, the deformation of the glass plate is likely to cause damage such as cracks and cracks, and the effect of providing the bonding layer so as to have a predetermined area ratio while forming the bonding layer from a linear portion is great. . As for a pair of glass plate, the other glass plate may be thin compared with one glass plate, for example. In this case, the thickness of the thicker glass plate is preferably 0.5 to 4.0 mm, more preferably 0.5 to 2.0 mm, and the thinner glass plate is thicker than the thicker glass plate. In the thin range, it is preferably 0.1 to 2.0 mm, more preferably 0.5 to 2.0 mm.

  Although the space | interval of a pair of glass plate can be suitably selected according to the use of the glass member with a joining layer, 30 micrometers or less are preferable and 15 micrometers or less are more preferable. By narrowing the distance between the pair of glass plates, the bonding layer can be uniformly melted by bonding with a laser beam and can be bonded well.

  The bonding layer is usually provided so as to form at least one frame-shaped sealing region (sealing region) between a pair of glass plates. In this case, the pressure in the sealing region may be a vacuum or about atmospheric pressure. When the pressure in the sealing region is set to about atmospheric pressure, a pair of glass plates are easily deformed so as to swell together when used under a strong wind outdoors, etc. The effect of providing the layer in a wide area as well as constituting the layer from the linear part is great.

The pair of glass plates is composed of soda lime glass, alkali-free glass, chemically tempered glass, physical tempered glass, and the like having various known compositions. Soda lime glass has a thermal expansion coefficient of about 80 to 90 (× 10 ⁻⁷ / ° C.). The alkali-free glass has a coefficient of thermal expansion of about 35 to 40 (× 10 ⁻⁷ / ° C.). From the viewpoint of obtaining a high reflectance, the soda lime glass is preferably white plate glass (high transmission glass) having high transparency. Here, the so-called white glass (high transmittance glass) is a glass having a visible light transmittance higher than that of ordinary soda lime glass and 90% or more, such as iron content compared to ordinary soda lime glass. Is a glass containing 0.06% or less as Fe ₂ O ₃ . From the viewpoint of strength, the soda lime glass is desirably tempered glass. The strengthening method may be either chemical strengthening or air cooling strengthening. Further, chemically strengthened glass other than soda lime glass may be used.

The pair of glass plates may be made of low expansion glass. The low expansion glass has a thermal expansion coefficient of 55 (× 10 ⁻⁷ / ° C.) or less, for example. 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. .

  Based on the difference in temperature between the inside and outside of the glass member with the bonding layer, such as the temperature difference between the inside and outside, when the glass member with the bonding layer is applied to the window glass of a building such as a house or a building by configuring with low expansion glass. The generated stress can be reduced. In other words, the glass member with a bonding layer may be warped due to a temperature difference between the inside and outside, but by constituting a pair of glass plates with low expansion glass, the amount of warpage, and further the stress due to warpage and repetition thereof. Can be reduced.

However, if the thermal expansion coefficient of the pair of glass plates becomes too small, the difference in thermal expansion from the bonding glass material increases, and conversely, the stress generated near the bonding layer may increase. For this reason, although depending on the thermal expansion coefficient of the glass material for bonding, the thermal expansion coefficient of the pair of glass plates is preferably 20 (× 10 ⁻⁷ / ° C.) or more.

  The bonding glass material includes a fixed glass (glass frit) made of a low-melting glass, and includes an inorganic filler such as a laser absorber or a low expansion filler as an optional component. The glass material for joining contains other additives other than these as needed. Other additives include inorganic fillers other than laser absorbers and low expansion fillers. However, other additives exclude components that disappear during firing.

  The combination and blending amount of the glass materials for bonding are selected in consideration of the compatibility with the glass plate. The content of the fixing glass in the bonding glass material is preferably 50 to 100% by volume. The content of the inorganic filler, which is an optional component, is preferably 0 to 50% by volume. If the content of the fixed glass is less than 50% by volume, the fluidity of the bonding glass material at the time of sealing is lowered, and there is a possibility that it cannot be satisfactorily sealed. The content of the fixed glass is more preferably 60% by volume or more. 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 adjustment of the thermal expansion coefficient with respect to the glass plate.

  As the fixing glass (low-melting glass), for example, low-melting glass such as bismuth glass, tin-phosphate glass, vanadium glass, lead glass, and silica borate alkali glass is used. Of these, fixed glass made of bismuth-based glass is preferable in consideration of bondability to the glass plate and its reliability (bonding reliability and hermetic sealing property), influence on the environment and human body, and the like.

The bismuth-based glass as the fixed glass has 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 mass ratio in terms of oxide (basic The total amount is preferably 100%). The glass formed of the three components of Bi ₂ O ₃ , ZnO, and B ₂ O ₃ has characteristics such as transparency and low glass transition point. Therefore, as a main component (essential component) of the bonding glass material Suitable for low melting 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 fixed 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 fixed glass increases. 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 the softening temperature, and is preferably contained in the range of 1 to 20% by mass in the fixed glass. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. If the content of ZnO exceeds 20% by mass, the stability during molding of fixed glass is lowered, devitrification is likely to occur, and glass may not be obtained. Considering the stability of glass production and the like, 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 fixed 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%. Considering the stability of the glass, the sealing temperature, etc., the content of B ₂ O ₃ is more preferably in the range of 5 to 10% by mass.

The bismuth-based glass formed by the three components described above has a low glass transition point and is suitable for fixed 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 an optional component such as 1 or 2. However, if the content of the optional component is too large, the glass becomes unstable and devitrification may occur, or the glass transition point and the softening point may increase. Therefore, the total content of the optional 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, etc. have the effect of lowering the softening temperature of the glass, and CeO ₂ has the effect of stabilizing the fluidity of the glass. Ag ₂ O, WO ₃ , MoO ₃ , Nb ₂ O ₃ , Ta ₂ O ₅ , Ga ₂ O ₃ , Sb ₂ O ₃ , P ₂ O ₅ , SnO _{x and the} like adjust the viscosity and thermal expansion coefficient of the glass. It can be contained as a component. The content of each of these components can be appropriately set within a range where the total content of arbitrary components does not exceed 10% by mass.

Of the inorganic fillers blended as optional components in the bonding glass material, the low expansion filler approximates the thermal expansion coefficient between the glass plate and the bonding layer. Generally, since the thermal expansion coefficient of fixed glass is larger than that of a glass plate, a low expansion filler is used to adjust the thermal expansion coefficient. The low expansion filler is at least one selected from silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate compound, tin oxide compound, and quartz solid solution. It is preferable to use seeds. As the zirconium phosphate-based compound, (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , 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 bonding layer, which is a melt-solidified layer of the bonding glass material, approaches the thermal expansion coefficient of the glass plate. The low expansion filler is preferably contained in the range of 0 to 50% by volume with respect to the bonding glass material, although it depends on the thermal expansion coefficient of the fixed glass or glass plate. When the content of the low expansion filler exceeds 50% by volume, the fluidity of the bonding glass material is lowered and the bonding strength may be lowered. The lower limit value of the content of the low expansion filler is not particularly limited, and is appropriately set according to the thermal expansion coefficient of the fixed glass or the glass plate. 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 bonding glass material to absorb laser light when the bonding glass material is heated by irradiation with laser light. In addition, when the fixed glass itself has a laser absorption ability, it is not necessary to add a laser absorber. As the laser absorber, at least one metal selected from Fe, Cr, Mn, Co, Ni, and Cu, or a compound (pigment) such as an oxide containing the metal is used. The laser absorbing material may be a pigment other than these. The laser absorber content in the bonding glass material is preferably in the range of 0.1 to 40% by volume. When the content of the laser absorbing material exceeds 40% by volume, the fluidity at the time of melting the bonding glass material 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.

  Hereinafter, specific embodiments of the glass member with a bonding layer, particularly specific embodiments of the bonding layer will be described.

  In the glass member with a bonding layer of the first embodiment, the first bonding layer is provided so that the planar shape is a frame shape, particularly in the vicinity of the outer peripheral portion of the pair of glass members, and the inner side of the first bonding layer. A second bonding layer is provided in the region. Note that each of the first bonding layer and the second bonding layer includes a linear portion.

  1 and 2 are a plan view and a cross-sectional view illustrating an example of a glass member with a bonding layer according to the first embodiment. This glass member 10 with a joining layer is used as, for example, a multilayer glass for building materials. In the glass member 10 with a bonding layer, a pair of glass plates 11 and 12 are disposed to face each other with a predetermined interval. One glass plate 12 is provided with a low emissivity film 13 on the opposite surface, for example. Further, a bonding layer 14 is provided between the glass plates 11 and 12, and the glass plates 11 and 12 are bonded and fixed by the bonding layer 14. In FIG. 1, only the bonding layer 14 that can be seen through the glass plate 12 is shown, and the illustration of the low emissivity film 13 is omitted.

  The bonding layer 14 is composed of a linear portion, and is provided so as to be within a range of 0.005 to 0.02 in terms of the area ratio with respect to the area of one facing surface of the pair of glass plates 11 and 12. It is done. Moreover, the width w of the linear part which comprises the joining layer 14 shall be in the range of 0.5-1.5 mm, for example.

  The bonding layer 14 of the first embodiment has a first bonding layer 141 whose planar shape is a frame shape in the vicinity of the outer peripheral portions of the glass plates 11 and 12. For example, the first bonding layer 141 bonds the glass plates 11 and 12 and forms a sealing region between the glass plates 11 and 12. The first bonding layer 141 is provided so that, for example, a part or all of the outer periphery thereof is within a range of 20 mm from the outer periphery of the glass plates 11 and 12.

  In addition, the bonding layer 14 of the first embodiment includes the second bonding layer 142 in the inner region of the first bonding layer 141. The second bonding layer 142 functions, for example, as a spacer that keeps the distance between the glass plates 11 and 12, and suppresses deformation of the glass plates 11 and 12 so that they swell with each other. Thereby, the stress applied to the first bonding layer 141 is reduced to suppress damage to the first bonding layer 141 and its peripheral portion, and the deformation of the glass plates 11 and 12 is suppressed to suppress the deformation of the glass plates 11 and 12. Reduce damage.

  For example, when the planar shape of the second bonding layer 142 is substantially linear and the planar shape of the first bonding layer 141 is a square shape, the second bonding layer 142 is substantially parallel to a pair of sides of the rectangular shape. It is provided at a substantially central portion of the pair of sides. Both end portions of the second bonding layer 142 are provided so as to be connected to the first bonding layer 141, for example. By providing such a second bonding layer 142 in addition to the first bonding layer 141, the area ratio of the bonding layer 14 can be within the range of 0.005 to 0.02 described above. Here, “substantially” refers to a state that looks like that when observed with the naked eye or a state close to such a concept (the same applies to the following description).

  According to the glass member 10 with the bonding layer, the glass plates 11 and 12 are not only bonded by the first bonding layer 141 in the vicinity of the outer peripheral portion, but also the inner region is bonded by the second bonding layer 142. Therefore, compared with the case where the first bonding layer 141 is provided only in the vicinity of the outer peripheral portion, damage to the first bonding layer 141, the vicinity thereof, and the glass plates 11 and 12 can be suppressed.

  As the low emissivity film 13, a Low-E film in which a dielectric layer and a metal layer are stacked can be used. As the low emissivity film 13, for example, in order from the glass plate 12 side, “dielectric layer / metal layer / dielectric layer”, “dielectric layer / dielectric layer / metal layer / dielectric layer”, “ Dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ dielectric layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ dielectric layer / metal layer ” / Dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ”,“ dielectric layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer / metal layer / dielectric layer ” The structure which provided etc. is mentioned. The dielectric layer existing between the metal layer closest to the glass plate 12 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 palladium added with 3 atomic percent or less (atomic percent) or less. Note that the low emissivity film 13 is preferably formed excluding a portion where the bonding layer 14 is actually formed so as not to impair the formability of the bonding layer 14.

  FIG. 3 is a plan view showing a modified example of the glass member 10 with the bonding layer of the first embodiment, and particularly a plan view showing a modified example of the second bonding layer 142. In FIG. 3, only the bonding layer 14 that can be seen through the glass plate 12 is shown, and the illustration of the low emissivity film 13 is omitted.

  The glass member 10 with a bonding layer is similar to the glass member 10 with a bonding layer shown in FIGS. 1 and 2 in the configuration of the glass plates 11 and 12 and the first bonding layer 141, but both ends of the second bonding layer 142. The difference is that the portion is not connected to the first bonding layer 141 and is disposed close to the first bonding layer 141. As described above, the second bonding layer 142 is not necessarily connected to the first bonding layer 141. When the second bonding layer 142 is connected to the first bonding layer 141, stress may concentrate on the connection portion. By providing the first bonding layer 141 so that the second bonding layer 142 is not connected to the first bonding layer 141, damage to the connection portion can be effectively suppressed. From the viewpoint of suppressing damage to the connection portion, the distance d between the end of the second bonding layer 142 and the first bonding layer 141 on the extension line is preferably 5 mm or more, and more preferably 10 mm or more.

  However, if the distance d is excessively large, the second bonding layer 142 is relatively shortened, and the bonding area is reduced as a whole, so that damage to the bonded portion and its vicinity or the glass plates 11 and 12 is effectively prevented. Can not be suppressed. For this reason, although the space | interval d changes also with the magnitude | sizes of the glass plates 11 and 12, 300 mm or less is preferable and 100 mm or less is more preferable.

  FIG. 4 is a plan view illustrating another modification of the glass member 10 with the bonding layer of the first embodiment, and in particular, a plan view illustrating another modification of the second bonding layer 142. In FIG. 4, only the bonding layer 14 that can be seen through the glass plate 12 is shown, and the illustration of the low emissivity film 13 is omitted.

  In this glass member 10 with a bonding layer, the glass plates 11 and 12 and the first bonding layer 141 have the same configuration as the glass member 10 with a bonding layer shown in FIGS. The difference is that the shape is substantially cross-shaped. The second bonding layer 142 is not necessarily limited to a single straight line, and may have a substantially cross shape in which the two straight lines are substantially orthogonal. By making the planar shape substantially cross-shaped, the inner region of the first bonding layer 141 can be divided into a more uniform size, and damage to the first bonding layer 141 and its vicinity or the glass plates 11 and 12 is effective. Can be suppressed.

  For example, when the planar shape of the first bonding layer 141 is a quadrangle, the two straight lines constituting the second bonding layer 142 are arranged so that each of the two straight lines is substantially parallel to a pair of sides of the quadrangular shape. It is provided at a substantially central portion of the pair of sides. Also, one straight line, for example, the vertical line in FIG. 4 is provided so as to be continuous, and the other straight line, for example, the horizontal line in FIG. 4, is provided so as not to be connected to the one straight line. preferable. Even in the case where two straight lines serving as the second bonding layer 142 intersect, stress may be concentrated if the intersecting portions are connected. For this reason, it is assumed that one is continuous and the other is divided so as not to be connected thereto, so that damage at the intersection can be effectively suppressed.

  FIG. 5 is a plan view showing still another modified example of the glass member 10 with the bonding layer of the first embodiment, and particularly a plan view showing still another modified example of the second bonding layer 142. In FIG. 5, only the bonding layer 14 that can be seen through the glass plate 12 is illustrated, and the low emissivity film 13 is not illustrated.

  In this glass member 10 with a bonding layer, the glass plates 11 and 12 and the first bonding layer 141 have the same configuration as the glass member 10 with a bonding layer shown in FIGS. The difference is that the shape is substantially a lattice. For example, the second bonding layer 142 may have a substantially lattice shape in plan view. By setting it as a substantially lattice shape, the inner region of the first bonding layer 141 can be finely divided, and damage to the bonded portion, its vicinity, or the glass plates 11 and 12 can be effectively suppressed. Note that the second bonding layer 142 includes a linear portion in one direction, for example, a vertical linear portion in FIG. 5 and a linear portion in the other direction, for example, a horizontal linear portion in FIG. May be continuous so that they are connected at the intersection, or one may be discontinuous so that they are not connected at the intersection, although not shown.

  As described above, the glass member 10 with the bonding layer according to the first embodiment has been described. However, the second bonding layer 142 does not necessarily have a continuous linear shape, and has a discontinuous linear shape such as a dotted line shape. May be. In this case, the length of the individual linear portions constituting the dotted line is preferably 1.5 mm or more, more preferably 50 mm or more, further preferably 100 mm or more, and the length of the blank portion between the individual linear portions is 300 mm or less, more preferably 100 mm or less, and even more preferably 50 mm or less.

The second bonding layer 142 is preferably provided so that the areas of the divided regions in the inner region of the first bonding layer 141 substantially divided by the second bonding layer 142 are equal. Moreover, it is preferable that each divided region is provided so that the area thereof is within a range of 100 to 1600 cm ² . For example, as shown in FIG. 5, when the inner region of the first bonding layer 141 is divided into m × n divided regions by the second bonding layer 142, the area s (m, It is preferable to provide the second bonding layer 142 so that n) is in the range of 100 to 1600 cm ² . Specifically, it is preferable to adjust the number, the arrangement, and the like of the straight portions that constitute the second bonding layer 142. By doing in this way, damage can be suppressed more effectively.

Note that the area of the divided region does not include the area of the first bonding layer 141 or the second bonding layer 142 itself. For example, as shown in FIG. 4, when the second bonding layer 142 is not connected to the first bonding layer 141, or when the second bonding layer 142 is not connected, the second bonding layer It is preferable to provide the second bonding layer 142 so that a region divided when 142 is extended is regarded as the divided region, and the area of each divided region is in the range of 100 to 1600 cm ² .

Next, the glass member 10 with a bonding layer according to the second embodiment will be described.
In the glass member 10 with the bonding layer of the second embodiment, in particular, the bonding layer 14 is composed of a plurality of frame-shaped portions whose planar shape is a frame shape, and the plurality of frame-shaped portions are not in contact with each other. It is provided. Also about the glass member 10 with a joining layer of 2nd Embodiment, the joining layer 14 (frame-shaped part) is comprised from a linear part, and is with respect to the area of one opposing surface of a pair of glass plates 11 and 12. The area ratio is within the range of 0.005 to 0.02. Moreover, the width w of the linear part which comprises the joining layer 14 (frame-shaped part) shall be in the range of 0.5-1.5 mm, for example.

  6 and 7 are a plan view and a cross-sectional view illustrating an example of the glass member 10 with a bonding layer according to the second embodiment. Also about the glass member 10 with a joining layer of 2nd Embodiment, a pair of glass plates 11 and 12 are provided facing predetermined intervals. One glass plate 12 is provided with, for example, a low emissivity film 13 on the opposite surface. A bonding layer 14 is provided between the glass plates 11 and 12, and the glass plates 11 and 12 are bonded and fixed by the bonding layer 14.

  The bonding layer 14 of the glass member 10 with the bonding layer is composed of a pair of frame-like portions 143 provided symmetrically with respect to the substantially central portion of the glass plates 11 and 12 in the planar direction. Also by configuring the bonding layer 14 from such a frame-shaped portion 143, the ratio of the area of the bonding layer 14 can be within the range of 0.005 to 0.02.

  Each frame-like portion 143 joins the glass plates 11 and 12 and forms a sealing region between the glass plates 11 and 12. In addition, each frame-like portion 143, particularly a portion located at a substantially central portion in the plane direction of the glass plates 11, 12 functions as a spacer for maintaining a space between the glass plates 11, 12, and the glass plates 11, 12. Are prevented from deforming so that they swell with each other.

  When a pair of frame-like portions 143 are provided symmetrically with respect to the substantially central portion of the glass plates 11 and 12 in the planar direction, the individual frame-like portions 143 are arranged at the substantially central portions of the glass plates 11 and 12 in the planar direction. The three sides excluding the positioned portion are preferably provided such that the outer peripheral portion thereof is within a range of 20 mm from the outer peripheral portions of the glass plates 11 and 12. Moreover, it is preferable that one side located in the substantially center part of the planar direction of the glass plates 11 and 12 provides the outer peripheral part in the range of 20 mm from the center part of the planar direction of the glass plates 11 and 12. FIG.

  The number of frame-like portions 14 constituting the bonding layer 14 is not necessarily limited to two as shown in FIG. 2, and may be three or more, and is not particularly limited as long as it is plural. Usually, the number of the frame-like portions 14 is preferably 100 or less, and more preferably 20 or less, from the viewpoint of productivity, appearance, and the like. Further, the arrangement of the frame-like portions 14 constituting the bonding layer 14 is not necessarily limited to the left-right symmetrical one as shown in FIG.

  Further, the individual frame portions 14 do not necessarily have a continuous line shape, and can be formed into a discontinuous line shape such as a dotted line shape as necessary. In this case, the length of the individual linear portions constituting the dotted line is preferably 1.5 mm or more, more preferably 50 mm or more, further preferably 100 mm or more, and the length of the blank portion between the individual linear portions is 300 mm or less, more preferably 100 mm or less, and even more preferably 50 mm or less.

From the viewpoint of effectively suppressing damage to the frame-shaped portion 14 and the vicinity thereof and the glass plates 11, 12, the individual frame-shaped portion 14 is the area of the inner region of each frame-shaped portion 14, that is, the frame-shaped portion 14 itself. It is preferable to provide such that the area excluding is in the range of 100 to 1600 cm ² . From the same viewpoint, the area of the inner region surrounded by the individual frame-like parts 14 as a whole is 0. 0 as a ratio of the area to the area of one of the opposing surfaces of the glass plates 11 and 12. It is preferable to provide it within the range of 01 to 0.095. That is, when the frame-like portion 14 is provided, the size of each frame-like portion 14 is set to a certain size such that the size of each frame-like portion 14 is not excessively small or large, and this is one of the opposing surfaces of the glass plates 11 and 12. It is preferable to set the ratio to a certain level so as not to be excessively small or large with respect to the area.

  As described above, the glass member 10 with the bonding layer has been described by taking the multi-layer glass suitable for the window glass of a building such as a house or a building as an example. However, the glass member 10 with the bonding layer is not necessarily limited to this. Instead, it may be one used outdoors, for example, a thin film silicon solar cell, a compound semiconductor solar cell, a solar cell such as a dye-sensitized solar cell, a reflector used in a solar thermal power generation system, or the like. Moreover, as the glass member 10 with a bonding layer, it may be used mainly indoors, such as an organic EL display (Organic Electro-Luminescence Display: OELD), a field emission display (Feed Emission Display: FED), a plasma display. It may be an electronic device such as a panel (PDP), a flat panel display (FPD) such as a liquid crystal display (LCD), or an illumination device (OEL illumination or the like) using a light emitting element such as an OEL element.

  As a solar cell, although not shown, a thin-film silicon solar cell element, a compound semiconductor solar cell element, a dye-sensitized solar cell element, etc. are sealed instead of the low emissivity film 13 of the glass member 10 with a bonding layer described above. The thing which was done is mentioned. The structure of the solar cell element is not particularly limited, and has various known structures.

  As a reflecting mirror used in the solar thermal power generation system, although not shown, a reflecting film is sealed instead of the low emissivity film 13 of the glass member 10 with the bonding layer described above. The reflective film is formed in a desired shape excluding a portion where the bonding layer 14 is formed, and is made of a metal such as silver, a silver alloy (Ag—Pt alloy, Ag—Pd alloy, etc.), aluminum, or the like. Such a reflective film made of metal can be formed by various thin film forming methods such as vapor deposition, sputtering, CVD, ion plating, ion beam irradiation, and spray coating.

  As an electronic device, although not shown, instead of the low emissivity film 13 of the glass member 10 with the bonding layer described above, an electronic device that constitutes the electronic device is sealed. Examples of the electronic element include a plasma light emitting element for PDP, a liquid crystal display element for LCD, and a light emitting element such as an OEL element for OELD and OEL illumination. The structures of the display element and the light emitting element are not particularly limited, and have various known structures.

Next, the manufacturing method of the glass member 10 with a joining layer is demonstrated,
Below, the glass member 10 with a joining layer shown by FIG. 1, 2 is mentioned as an example, and is demonstrated.

  For example, as shown in FIG. 8A, a low emissivity film 13 is formed on the opposing surface of one glass plate 12. The low emissivity film 13 may be formed in a desired shape in advance so as to exclude a region where the bonding layer 14 is formed. Alternatively, the low emissivity film 13 is formed on the entire opposite surface of the glass plate 12 and then the bonding layer 14 is formed. The region to be formed may be trimmed to have a desired shape.

  Separately, as shown in FIG. 8B, a bonding material layer 14a to be the bonding layer 14 is formed on the opposing surface of the glass plate 11 by, for example, laser light irradiation. The bonding material layer 14a includes, for example, a first bonding material layer 141a that becomes the first bonding layer 141 when irradiated with laser light, and a second bonding material layer 142a that becomes the second bonding layer 142 when irradiated with laser light. Are formed into a predetermined shape.

  The bonding material layer 14a, that is, the first bonding material layer 141a and the second bonding material layer 142a are formed by mixing a bonding glass material containing a fixed glass (low melting glass) and an inorganic filler as an optional component with a vehicle. Then, a bonding glass material paste is prepared, applied, and then dried and fired.

  The vehicle is obtained by dissolving a resin as a binder component in a solvent. Examples of the resin for the vehicle include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, An organic resin such as an acrylic resin obtained by polymerizing one or more acrylic monomers 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 bonding glass material paste may be adjusted to the viscosity corresponding to the coating apparatus, and can be adjusted by the ratio of the resin and the solvent and the ratio of the bonding glass material and the vehicle. The resin is a component that disappears upon firing. You may add a well-known additive with a glass paste like a defoamer and a dispersing agent to the glass material paste for joining. 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.

  A glass material paste for bonding is applied to the opposing surface of the glass plate 11 and dried to form a coating film of the glass material paste for bonding. The bonding glass material paste 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 to 2 mm in order to maintain strength. The thickness of the coating film is set according to the distance between the glass plates 11 and 12 in the glass member 10 with the bonding layer, and is preferably set in consideration of the shrinkage of the film in the subsequent drying process or the preliminary baking process. For example, 10-100 micrometers is preferable.

  The coating film of the glass material paste for bonding is dried at a temperature of 60 to 150 ° C. for 30 seconds to 10 minutes, for example, and the solvent in the coating film is removed. Subsequently, after heating to a temperature 30 ° C. or lower than the glass transition point of the fixed glass in a baking furnace to remove the binder component in the coating film, the temperature is higher than the softening point of the fixed glass (for example, 10 to 100 from the softening point). The glass material for bonding is baked onto the glass plate 11. Thus, the bonding material layer 14a, that is, the first bonding material layer 141a and the second bonding material layer 142a are formed on the opposing surface of the glass plate 11. The steps of forming the first bonding material layer 141a and the second bonding material layer 142a 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. 8C, the opposing surface of the glass plate 11 provided with the bonding material layer 14a and the opposing surface of the glass plate 12 provided with the low emissivity film 13 are opposed to each other. Then, the glass plate 11 and the glass plate 12 are laminated. Then, for example, the bonding material layer 14 a is irradiated with the laser beam 16 through the glass plate 12. The laser beam 16 is irradiated while scanning along the bonding material layer 14a. Although it does not specifically limit as the laser beam 16, The laser beam from a semiconductor laser, a carbon dioxide laser, an excimer laser, a YAG laser, a HeNe laser etc. is used. When the inner region of the first bonding layer 141 is in a vacuum state, for example, a laminated body of the glass plate 11 and the glass plate 12 is disposed in the vacuum chamber 11, and the inside of the vacuum chamber 11 is set to a desired vacuum state. After evacuating to the end, the laser beam 16 is irradiated in the vacuum chamber 11 in a predetermined vacuum state.

  The bonding material layer 14 a is melted in order from the portion irradiated with the laser beam 16, and is rapidly cooled and solidified and fixed to the glass plate 12 when the irradiation of the laser beam 16 is completed. Then, by irradiating the entire bonding material layer 14a, that is, the entire first bonding material layer 141a and the second bonding layer 142a, with the laser beam 16, as shown in FIG. Is obtained by bonding the bonding layer 14, that is, the first bonding layer 141 and the second bonding layer 142.

  The heating temperature of the bonding material layer 14a by the laser light 16 is set to be equal to or higher than the softening point of the fixed glass (low melting point glass). When local heating by the laser beam 16 is applied, the temperature of the glass plates 11 and 12 is lower than the temperature of the bonding material layer 14a. Therefore, the heating temperature of the bonding material layer 14a can be set higher than the manufacturing process using the firing furnace. it can. For example, the heating temperature is preferably (T + 200 ° C.) or more and (T + 800 ° C.) or less with respect to the softening point T (° C.) of the fixed glass.

  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
Bismuth-based glass (softening point: 410 ° C.) having a composition of Bi ₂ O ₃ 83%, B ₂ O ₃ 5%, ZnO 11%, Al ₂ O ₃ 1% by mass ratio, average particle diameter as a low expansion filler Cordierite powder having a (D ₅₀ ) of 4.3 μm and a specific surface area of 1.6 m ² / g, Fe ₂ O ₃ 16.0% by mass ratio, MnO 43.0%, CuO 27.3%, Al ₂ O ₃ A laser absorber (electromagnetic wave absorber) having a composition of 8.5% and SiO ₂ 5.2%, an average particle diameter (D ₅₀ ) of 1.2 μm and a specific surface area of 6.1 m ² / g is prepared. did.

  The particle size distribution of the cordierite powder was measured using a particle size analyzer (manufactured by Nikkiso Co., Ltd., Microtrac HRA). The measurement conditions were measurement mode: HRA-FRA mode, Particle Transparency: yes, Specialty Particles: no, Particle Refractive index: 1.75, Fluid Refractive index: 1.33. The measurement was performed after a slurry in which the powder was dispersed in water was dispersed with ultrasonic waves.

  The particle size distribution of the laser absorber was measured using a particle size analyzer (manufactured by Nikkiso Co., Ltd., Microtrac HRA). The measurement conditions were measurement mode: HRA-FRA mode, Particle Transparency: yes, Specialty Particles: no, Particle Refractive index: 1.81, and Fluid Refractive index: 1.33. The measurement was performed after a slurry in which the powder was dispersed in water was dispersed with ultrasonic waves.

The specific surface areas of the cordierite powder and the laser absorber were measured using a BET specific surface area measuring device (Macsorb HM model-1201, manufactured by Mountec Co., Ltd.). Measurement conditions are: adsorbate: nitrogen, carrier gas: helium, measurement method: flow method (BET 1-point system), degassing temperature: 200 ° C., degassing time: 20 minutes, degassing pressure: N ₂ gas flow / atmospheric pressure The sample mass was 1 g.

Bismuth glass 85.2% by mass, cordierite powder 13.9% by mass and laser absorber 0.9% by mass were mixed to form a glass material for bonding (thermal expansion coefficient (50 to 350 ° C.): 66 × 10 ^{− 7} / ° C.). 85% by mass of the glass material for bonding was mixed with 15% by mass of a vehicle prepared by dissolving 5% by mass of ethyl cellulose as a binder component in 95% by mass of ethylene glycol mono-2-ethylhexyl ether. Next, the glass material paste for joining was prepared by passing the mixture through a three-roll mill seven times and sufficiently dispersing the cordierite powder and the laser absorber in the paste.

Next, a glass plate made of soda lime glass (Asahi Glass Co., Ltd., AS (thermal expansion coefficient: 85 × 10 ⁻⁷ / ° C.), dimension: 370 × 470 × 1.8 mmt) is prepared, The sealing material paste was applied to the sealing area by dispensing.

The dispensing pattern finally obtained a bonding layer 14 as shown in FIG. That is, the bonding layer 14 having the frame-shaped first bonding layer 141 and the substantially cross-shaped second bonding layer 142 provided in the inner region is obtained. The first bonding layer 141 has an inner portion with a size of 350 mm × 450 mm and a corner radius of curvature R of 2 mm. The widths of the linear portions of the first bonding layer 141 and the second bonding layer 142 are both 0.5 mm. In this case, since the area of the facing surface of the glass plate is 173900 mm ² and the area of the bonding layer 14 is 1107 mm ² , the ratio of the area of the bonding layer 14 to the area of the facing surface of the glass plate is 0.0063 [− It becomes.

  Thereafter, the coating layer of the glass material paste for bonding is dried at 120 ° C. for 10 minutes, and then fired at 480 ° C. for 10 minutes to obtain a bonding material having a film thickness of 15 μm and a line width of 0.5 mm. A layer was formed.

Next, a glass plate on which the bonding material layer was formed and a glass plate having the same composition and the same shape as this glass plate, but different in thickness only from 1.1 mm were laminated. Next, a laser beam (semiconductor laser) having a wavelength of 808 nm, a spot diameter of 2.2 mm, and an output of 24.0 W (output density: 6.34 W / mm ² ) is passed through the glass plate on which the bonding material layer has been formed. ) Was irradiated at a scanning speed of 4 mm / sec to melt and rapidly solidify the bonding material layer, thereby sealing the pair of glass plates described above to produce a glass member with a bonding layer. The intensity distribution of the laser beam was not shaped uniformly, and a laser beam having a protruding intensity distribution was used. As the spot diameter at this time, the radius of the contour line at which the laser intensity becomes 1 / e ² was used.

  When the heating temperature of the bonding material layer when the laser beam was irradiated was measured with a radiation thermometer, the temperature of the bonding material layer was 630 ° C. Since the softening point of the bismuth glass described above is 410 ° C., the heating temperature of the bonding material layer corresponds to (softening point + 220 ° C.). When the state of the glass plate and the bonding layer was observed after laser bonding, no cracks or cracks were observed, and it was confirmed that the pair of glass plates were well sealed.

(Comparative Example 1)
A glass member with a bonding layer was produced in the same manner as in Example 1 except that the bonding layer 21 as shown in FIG. 10 was finally obtained. In addition, this glass member with a bonding layer has the same configuration as the glass member with a bonding layer of Example 1 except that it does not have the substantially cross-shaped second bonding layer. In this case, since the area of the opposing surface of the glass plate (one) is 173900 mm ² and the area of the bonding layer is 797 mm ² , the ratio of the area of the bonding layer to the area of the opposing surface of the glass plate is 0.0046 [ −].

  Next, the amount of deflection of the glass member with the bonding layer sealed by laser was determined. That is, using a fiber-type ultraviolet-visible spectroscope (manufactured by Ocean Optics, USB4000), the corner portion of the bonding layer (first bonding layer in Example 1) (the frame-shaped bonding layer shown in FIGS. 9 and 10). ), And the interference peak wavelength in the wavelength region 700 nm to 900 nm of a pair of glass plates 30 mm to the right and 30 mm to the bottom from the above corner, and the following relational expression: From D, the distance between the pair of glass plates was calculated, and the difference between the two was taken as the amount of deflection. Further, since the stress value in the bonding layer is proportional to the amount of bending according to the stress-strain relational expression, the stress value of the bonding layer was obtained based on the amount of bending. The results are shown in Table 1. The stress value is a relative value with respect to Example 1.

m × λm = 2 × n × D
(M + 1) × λm + 1 = 2 × n × D

m: integer λm: mth order peak wavelength n: refractive index (= 1)
D: Distance between glass plates

  As is clear from Table 1, according to the glass member with a bonding layer of Example 1 in which the ratio of the area of the bonding layer was 0.005 or more, Comparative Example 1 in which the ratio of the area of the bonding layer was less than 0.005 It can be seen that the stress can be greatly reduced as compared with the glass member with a bonding layer.

  Moreover, according to the glass member with a joining layer of Example 1, in addition to the frame-shaped first joining layer, a pair of glass plates is provided in the central portion of the inner region thereof. Therefore, it is possible to suppress deformation such that the pair of glass plates swell with each other, and it is possible to suppress damage such as cracks and cracks in the glass plates. Furthermore, according to the glass member with the bonding layer of Example 1, the entire bonding layer, that is, the frame-shaped first bonding layer and the substantially cruciform second bonding layer provided in the central portion of the inner region are laser Can be joined by light and has excellent productivity.

  DESCRIPTION OF SYMBOLS 10 ... Glass member with a joining layer, 11, 12 ... Glass plate, 13 ... Low emissivity film | membrane, 14 ... Joining layer, 14a ... Joining material layer, 141 ... 1st joining layer, 141a ... 1st joining material layer, 142: second bonding layer, 142a: second bonding material layer, 143: frame-shaped portion

Claims (17)

A pair of glass plates arranged to face each other with a gap therebetween, and a bonding layer made of a material obtained by melting and solidifying a bonding glass material, and arranged between the pair of glass plates to bond the pair of glass plates A glass member with a bonding layer having
The bonding layer is composed of a linear portion and is in the range of 0.005 to 0.02 in terms of the ratio of the area on the facing surface to the area of one facing surface of the pair of glass plates. A glass member with a bonding layer, which is provided as described above.   The said glass material for joining is a glass member with a joining layer of Claim 1 which has laser absorptivity.   The glass member with a bonding layer according to claim 1 or 2, wherein a width of the linear portion is in a range of 0.5 to 1.5 mm.   The bonding layer includes a first bonding layer having a frame shape in a planar shape provided in the vicinity of the outer peripheral portion of the pair of glass plates, and a second bonding layer provided in an inner region of the first bonding layer. The glass member with a joining layer of any one of Claims 1 thru | or 3 which has these.   The glass member with a bonding layer according to claim 4, wherein the second bonding layer has a substantially linear planar shape.   The planar shape of the first bonding layer is a quadrangular shape, and the second bonding layer is provided along substantially the center of a pair of sides of the rectangular shape of the first bonding layer. Glass member with bonding layer.   The pair of end portions of the second bonding layer is a glass member with a bonding layer according to claim 5 or 6 connected to the first bonding layer.   7. The glass member with a bonding layer according to claim 5, wherein the pair of end portions of the second bonding layer is disposed in the vicinity of the first bonding layer without being connected to the first bonding layer. .   The glass member with a bonding layer according to claim 4, wherein the second bonding layer has a substantially cross-shaped planar shape.   The glass member with a bonding layer according to claim 4, wherein the second bonding layer has a substantially lattice shape in plan view. The planar shape of the second bonding layer is adjusted so that the area of each divided region in which the inner region of the first bonding layer is divided by the second bonding layer is in the range of 100 to 1600 cm ^2. The glass member with a bonding layer according to any one of claims 4 to 10.   4. The bonding layer according to claim 1, wherein the bonding layer includes a plurality of frame-shaped portions whose planar shape is a frame shape, and the plurality of frame-shaped portions are provided so as not to contact each other. Glass member. 13. The glass member with a bonding layer according to claim 12, wherein the plurality of frame-shaped portions are provided so that an area of each inner region is in a range of 100 to 1600 cm ² . The glass member with a bonding layer according to claim 1, wherein the pair of glass plates has a size of 400 cm ² or more in area.   The glass member with a bonding layer according to claim 1, wherein the pair of glass plates has a thickness of at least one glass plate of 2 mm or less.   The glass member with a bonding layer according to any one of claims 1 to 15, wherein the glass member with a bonding layer is a multilayer glass for building materials.   The said glass member with a joining layer is a solar cell, The glass member with a joining layer of any one of Claims 1 thru | or 15.

Images