JP2008201662A - Method for manufacturing evacuated double glazing unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a double glazing unit having a vacuum layer and excellent in heat insulating property. <P>SOLUTION: The method for manufacturing the double glazing unit includes (1) a step of arranging low melting point glass bulk along the peripheral end part of a glass plate and providing evacuation opening parts communicating with the inside and the outside of a region surrounded by the glass bulk and, at the same time, arranging spacers in the region surrounded by the glass bulk, (2) a step of forming a laminate by laminating a glass plate on the glass plate where the glass bulk and the spacers are arranged and (3) a step of reducing the pressure of the laminate in a reduced-pressure chamber and, at the same time, heating the laminate to close the evacuation opening parts by molten glass bulk and to seal and fix the peripheral end part of the laminate in such a state that the inside of the laminate is evacuated through the evacuation opening parts. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing exhaust multilayer glass in which peripheral edges of glass plates separated by a vacuum layer are sealed with a sealing glass bulk, and a plurality of spacers are arranged in the vacuum layer.

  As one of the multi-layer glass, a multi-layer glass formed by sealing the peripheral edge of the glass layer with a plurality of spacers disposed in the vacuum layer while maintaining a vacuum layer (reduced pressure layer) between the glass plates. (Hereinafter referred to as “exhaust multilayer glass”) is known. In this exhaust multilayer glass, since the glass plates are separated by a vacuum layer, a normal multilayer obtained by enclosing dry air or inert gas in the hermetic layer of two glass plates sealed at the periphery. Compared to glass, it has a feature that high heat insulation performance can be obtained even if the thickness of the vacuum layer is about 1 mm, for example.

  In such an exhaust multi-layer glass, the peripheral edge is conventionally sealed with resin or frit glass. However, when sealed with resin, it is difficult to maintain airtightness for a long time. A method of wearing is proposed. For example, according to the method described in Patent Document 1, a plurality of support columns (spacers) are arranged between two glass plates constituting the exhaust multi-layer glass, and the peripheral ends of these glass plates are connected for bonding in this state. It is manufactured through a process of sealing with glass and a process of exhausting the airtight layer of the two glass plates whose peripheral edges are sealed.

That is, when this manufacturing method is described in more detail according to Patent Document 1, the exhaust multilayer glass is manufactured by the following steps (a) to (e).
(A) The process of arrange | positioning a some support | pillar between two glass plates, and hold | maintaining it with a predetermined space | interval (b) The process of arrange | positioning bonding glass (liquid slurry) in the peripheral edge part of the hold | maintained glass plate. c) A step of heating the glass plate to dissolve the bonding glass and sealing the peripheral edges of the two glass plates with the bonding glass. (d) One side of one glass plate of the sealed glass plate. (E) A step of exhausting the airtight layer of the two glass plates by pumping them through the exhaust tube.
JP-T 9-500430

  However, the method for producing an exhaust multilayer glass described in Patent Document 1 has the following problems.

  That is, since the bonding glass (frit glass) is disposed as a slurry, when the frit glass melts, the gas at the powder interface expands to generate bubbles, and the bubbles are joined together to form a sealing portion. There is a possibility that a hole penetrating the hermetic layer and the outside may be generated, and the performance as the exhaust multilayer glass may not be obtained.

  Also, after sealing the peripheral edges of the two glass plates, the airtight layer formed between the glass plates is evacuated, and the sealing of the peripheral edges and the exhaust of the airtight layer are performed in completely independent two-stage processes. For this reason, the manufacturing apparatus becomes complicated and the working time becomes longer, resulting in an increase in cost. In particular, since exhaust pipes must be individually provided by post-processing for exhaust of the hermetic layer (see FIG. 4b of Patent Document 1), not only high technology is required for mounting the exhaust tubes, but also labor is required for mounting. Take it.

  Even if the exhaust tube is provided as close as possible to the end of the glass plate so that the exhaust part is not noticeable, the exhaust part remains on the glass surface of the exhaust double-glazed glass, thereby deteriorating the appearance of the product.

  The object of the present invention is to seal the peripheral edge of the glass plate in a decompression chamber, so that a vacuum layer can be formed simultaneously with the sealing of the peripheral edge without providing an exhaust tube and exhausting the airtight layer. , A method for producing exhaust double-glazed glass that can efficiently and inexpensively produce exhaust double-glazed glass with excellent appearance and quality, and excellent airtightness and strength of the sealing part, and excellent appearance in which the exhaust part does not remain in the product The object is to provide exhaust multilayer glass.

In order to achieve the above object, according to the present invention, a peripheral edge of a glass plate separated by a vacuum layer is sealed by a sealing glass bulk, and a plurality of spacers are arranged in the vacuum layer. A method for producing layer glass, comprising:
(1) A sealing glass bulk having a low melting point is arranged along the peripheral edge of one glass plate, and an exhaust opening that communicates the inside and outside of the region surrounded by the sealing glass bulk is provided and sealed. Placing the spacer in a region surrounded by glass bulk;
(2) forming a laminate by stacking another glass plate on the glass plate on which the sealing glass bulk and the spacer are disposed;
(3) Putting the laminated body into a decompression chamber, depressurizing and heating the decompression chamber, and in the state where the inside of the laminated body is exhausted through the exhaust opening, the exhaust opening is melted with a molten sealing glass bulk. And sealing the peripheral edge of the laminate, and a method for producing exhaust double-glazed glass (hereinafter referred to as the production method of the present invention).

  In the manufacturing method of the present invention, it is preferable that a plurality of the exhaust openings are provided along the peripheral edge of the laminate. Moreover, it is preferable that the height of the glass bulk for sealing is larger than the height of a spacer.

  In the production method of the present invention, in the step (3), it is preferable that the laminate is pressed from above and / or below when the peripheral edge of the laminate is sealed with a sealing glass bulk.

  Moreover, the manufacturing method of this invention can improve heat insulation by forming a laminated body further on the laminated body obtained at the said (2) process, and making it a laminated body of a multilayered structure.

In the production method of the present invention, the average thermal expansion coefficient of the sealing glass bulk at 50 ° C. to 300 ° C. is preferably 70 × 10 ⁻⁷ / ° C. to 100 × 10 ⁻⁷ / ° C., and its glass transition temperature. Is preferably 500 ° C. or lower.

In the production method of the present invention, the sealing glass bulk is preferably formed of glass having the following composition in terms of mol%.
P ₂ O _5: 20~45%
SnO: 20-40%
ZnO: 25-50%
B ₂ O ₃ : 0 to 10%
CaO: 0 to 15%
Al ₂ O ₃ : 0 to 6%
In ₂ O ₃ : 0 to 6%
La ₂ O ₃ : 0 to 6%
_{Al 2 O 3 + In 2 O} 3 + La 2 O 3: 0~10%
In the production method of the present invention, it is preferable that the sealing glass bulk is made of glass with (crystallization temperature-glass transition temperature) ≧ 185 ° C.
The present invention also provides an exhaust multilayer glass manufactured by the manufacturing method of the present invention.

  According to the present invention, the peripheral edge of the laminated body formed by separating the glass plates constituting the exhaust multilayer glass with the spacer is sealed with the sealing glass bulk in the decompression chamber, thereby sealing the peripheral edge. A vacuum layer can be formed simultaneously with the deposition to obtain an exhaust multilayer glass. This eliminates the need for providing an exhaust tube and exhausting the hermetic layer as in the prior art, thus simplifying the manufacturing process and manufacturing the exhaust multilayer glass efficiently and at low cost.

  Moreover, since the generation of bubbles during sealing is prevented by sealing the peripheral edge of the glass plate constituting the exhaust double-glazed glass with a sealing glass bulk, the exhaust composite is excellent in hermeticity and strength of the sealed part. A layer glass can be obtained. In addition, since the exhaust part does not remain in the product, the appearance of the exhaust multilayer glass is excellent.

  In addition, the present invention can improve the workability at the time of sealing by suppressing crystallization of the glass bulk for sealing at the time of sealing, and obtain an exhaust multilayer glass having a high adhesive strength at the sealing part. it can.

  The present invention relates to an exhaust double-glazed glass (hereinafter sometimes referred to as double-glazed glass) formed by sealing a peripheral edge of a glass plate arranged with a plurality of spacers arranged in a vacuum layer. This exhaust double-glazed glass is provided with the vacuum layer between the glass plates, so it has excellent heat insulation and sound insulation performance, and can be widely used as heat insulation glass or sound insulation glass in the construction field, industrial field, etc. .

In the present invention, an ordinary architectural glass sheet can be generally used as the glass sheet constituting the exhaust multilayer glass. This architectural plate glass includes, for example, a glass plate that has been surface-treated with a heat ray reflective coating. A typical exhaust multilayer glass is manufactured by combining two rectangular glass plates, but the shape is not limited thereto. Moreover, the thickness of the two glass plates to be combined may be different. The composition of the glass plate is preferably soda lime glass, and the average coefficient of thermal expansion at 50 ° C. to 300 ° C. is preferably 70 × 10 ⁻⁷ / ° C. to 100 × 10 ⁻⁷ / ° C. (general soda The average coefficient of thermal expansion of lime glass at 50 ° C. to 300 ° C. is 85 × 10 ⁻⁷ / ° C. to 90 × 10 ⁻⁷ / ° C.).

  In the present invention, a sealing glass bulk (hereinafter referred to as a glass bulk) is used for sealing the peripheral edge of the glass plate. Here, the glass bulk means a molded body made of a glass material previously formed in a predetermined shape, and the sealing step in the present invention is completed like a glass material such as powder, liquid, or paste. It does not include indeterminate shapes whose shape is not fixed. Since this glass bulk is used as solder glass for sealing the peripheral edge of the glass plate, a low melting point glass having a softening point temperature (also referred to as a softening point) of about 580 ° C. or lower, preferably about 440 ° C. or lower is preferable. Can be used. The low melting point glass bulk in the present invention refers to a glass bulk formed of such a low melting point glass having a softening point temperature of about 580 ° C. or less. Generally, since the softening point temperature of glass correlates with the glass transition temperature, it is specified by the glass transition temperature for convenience in the present invention.

  In the present invention, the glass transition temperature of the glass bulk is preferably 500 ° C. or lower. When the glass transition temperature is higher than 500 ° C., the peripheral edge of the multilayer glass must be sealed at a high temperature, which is not preferable because the heating energy at the time of sealing increases. The glass transition temperature varies depending on the composition of the glass bulk, and the sealing temperature can be lowered as the glass bulk has a lower glass transition temperature. Therefore, in order to seal at a low temperature, it is preferable to select a sealing temperature as low as possible by using a glass bulk having a low glass transition temperature.

The glass bulk preferably has an average coefficient of thermal expansion at 50 ° C. to 300 ° C. of 70 × 10 ⁻⁷ / ° C. to 100 × 10 ⁻⁷ / ° C., and 75 × 10 ⁻⁷ / ° C. to 95 × 10 more preferably from ^-7 / ° C., further preferably at ^{80 × 10 -7 / ℃ ~90 ×} 10 -7 / ℃. In the manufacturing process of the exhaust multilayer glass, the glass plate is heated to the glass transition temperature or higher of the glass bulk. In addition, as exhaust multi-layer glass as a product is used under various temperature conditions, if the difference in thermal expansion coefficient between the glass bulk and the glass plate is large, the glass plate and the sealing part will heat up when subjected to a large temperature change. There is a risk of damage due to stress. If the thermal expansion coefficient of the glass bulk is in the above range, the difference from the thermal expansion coefficient of the glass plate can be within an allowable range, and thus such breakage can be prevented.

As the glass bulk of the present invention, a glass having the following composition range in terms of mol% can be preferably used. Since the glass has a transition temperature of about 300 ° C. to 420 ° C., the sealing temperature can be lowered (about 400 ° C. to 520 ° C.). Moreover, since the average thermal expansion coefficient in 50 to 300 degreeC is 70 * 10 < ^-7 > / degreeC-100 * 10 < ^-7 > / degreeC, matching with the thermal expansion coefficient of a glass plate is also obtained. The glass transition temperature of this glass is more preferably 400 ° C. or less, further preferably 380 ° C. or less, and most preferably 360 ° C. or less.

P ₂ O _5: 20~45%
SnO: 20-40%
ZnO: 25-50%
B ₂ O ₃ : 0 to 10%
CaO: 0 to 15%
Al ₂ O ₃ : 0 to 6%
In ₂ O ₃ : 0 to 6%
La ₂ O ₃ : 0 to 6%
_{Al 2 O 3 + In 2 O} 3 + La 2 O 3: 0~10%

Hereinafter, each component will be described.
P ₂ O ₅ is a network-forming oxide, and is an effective component for stabilizing the glass. If the content is less than 20 mol%, vitrification may be difficult. On the other hand, when it exceeds 45 mol%, the water resistance of the sealing portion may be lowered. The preferable content of P ₂ O ₅ is 27 to 35 mol%, and in order to improve the water resistance, it is preferably 32 mol% or less.

  SnO has an effect of increasing fluidity, and if the content is less than 20 mol%, the softening point becomes too high and the fluidity deteriorates, so that the strength and hermeticity of the sealing portion may be lowered. If the content exceeds 40 mol%, vitrification becomes difficult. Preferably it is 25-35 mol%.

  ZnO has the effect of improving water resistance and lowering the thermal expansion coefficient. If the content is less than 25 mol%, the thermal expansion coefficient becomes too large, and the consistency with the thermal expansion coefficient of the glass plate cannot be obtained. May occur. If the content exceeds 50 mol%, devitrification tends to precipitate, and the softening point becomes too high. Preferably, it is 30-40 mol%.

B ₂ O ₃ is effective in stabilizing the glass and suppressing crystallization during sealing. If the content exceeds 10 mol%, the softening point may be too high. The preferred content is 5 mol% or less.

  CaO acts as an active ingredient that improves water resistance, lowers the thermal expansion coefficient, and suppresses crystallization during sealing. If it exceeds 15 mol%, the softening point may be too high. The preferred content is 10 mol% or less, more preferably 5 mol% or less.

Al ₂ O ₃ may be included to improve water resistance and stabilize the glass. If it exceeds 6 mol%, the softening point may be too high. The preferred content is 3 mol% or less.

In ₂ O ₃ may be included to improve water resistance and stabilize the glass. If it exceeds 6 mol%, the softening point may be too high. The preferred content is 3 mol% or less.

La ₂ O ₃ may be included to improve water resistance and stabilize the glass. If it exceeds 6 mol%, the softening point may be too high. The preferred content is 3 mol% or less.

Al ₂ O ₃ + In ₂ O ₃ + La ₂ O ₃ may be contained up to 10 mol% in total. If it exceeds 10 mol%, the softening point may be too high. Preferable content is 7 mol% or less in total.

In the glass, in order to suppress crystallization of the glass bulk at the time of sealing, it is preferable to contain a certain amount of B ₂ O ₃ and CaO, and the content is 0.5 as (B ₂ O ₃ + CaO). -6 mol% is preferable and 1-4 mol% is more preferable. When the glass bulk melted at the time of sealing the glass plate is crystallized, the adhesion to the glass plate is deteriorated, and when the degree of crystallization is large, the desired adhesive strength may not be obtained. The reason why the adhesive strength is reduced by crystallization is that the thermal expansion coefficient of the glass bulk is matched with the thermal expansion coefficient of the glass plate in the state of the glass that is not crystallized, so that the glass bulk crystallizes during sealing. This is because the thermal expansion coefficient increases and does not match the thermal expansion coefficient of the glass plate, and the adhesive strength at the bonding surface between the glass bulk and the glass plate decreases. Further, the fact that the crystallization of the glass bulk does not contribute to the formation of the adhesive layer at the interface with the glass plate also causes a decrease in the adhesive strength.

  Therefore, in the case of glass bulk that may be crystallized at the time of sealing, it is necessary to set the sealing conditions so that crystallization can be avoided, so that the workability is generally deteriorated and it is difficult to adapt to mass production. On the other hand, in the case of a glass that does not easily cause crystallization, the degree of freedom of sealing conditions increases, so that the work becomes easier and is suitable for mass production. In addition, when the glass for glass bulk is easily devitrified, crystals are generated in the glass bulk manufacturing process, which is not suitable for mass production of the glass bulk. Therefore, in the present invention, it is preferable that the glass for glass bulk is not crystallized both during the production of the glass bulk and during the sealing of the multilayer glass.

The glass bulk of the present invention is not limited to the above glass. For example, as other glass bulk, Bi-based glass having the following composition range in terms of mol% can be exemplified.
Bi ₂ O ₃ : 20 to 60%
Other oxides (Al ₂ O ₃ , SiO ₂ , Ga ₂ O ₃ , B ₂ O ₃ , La ₂ O ₃ , Yb ₂ O ₃ , CeO _2, etc.): 40 to 80%

  In addition, the glass for glass bulk of the present invention preferably has (crystallization temperature−glass transition temperature) ≧ 185 ° C. in order to suppress or prevent crystallization in the sealing process of the multilayer glass. In other words, glass for glass bulk has a crystallization temperature higher than the glass transition temperature by 185 ° C. or more, which is effective for increasing the degree of freedom of sealing conditions and suppressing or preventing crystallization under normal sealing conditions. Become. In glass for glass bulk having a (crystallization temperature-glass transition temperature) lower than 185 ° C., crystallization may occur during sealing. It is more preferable that (crystallization temperature−glass transition temperature) ≧ 190 ° C., and (crystallization temperature−glass transition temperature) ≧ 200 ° C. is still more preferable. Here, the crystallization temperature is a crystallization peak temperature obtained by differential thermal analysis (DTA). When no crystallization peak is observed, the crystallization temperature is ∞. Below, crystallization of the glass for glass bulk at the time of sealing is demonstrated.

  FIG. 10 is a schematic diagram of differential thermal analysis (DTA) of the glass bulk of the present invention. In FIG. 10, the horizontal axis represents temperature, the vertical axis represents heat generation-endotherm, Tg represents glass transition temperature, Tx represents crystallization start temperature, and Tc represents crystallization temperature. In the figure, a is a crystallization region that may cause crystallization. Further, this differential thermal analysis shows that the glass transition is an endothermic reaction and the glass crystallization is an exothermic reaction, and the peak of the exothermic-endothermic amount in the crystallization region a is the crystallization temperature Tc. In the present invention, Tg, Tx, and Tc are all temperatures (° C.) specific to the composition of glass for glass bulk, and can be determined as inflection points of the DTA curve from differential thermal analysis (DTA) of the glass.

  In sealing of multi-layer glass by glass bulk, if sealing temperature <Tx, the glass does not crystallize at the time of sealing, but if Tx ≦ sealing temperature <(Tc-30), it crystallizes depending on conditions. In some cases, it is necessary to control the heat treatment time. When (Tc-30) ≦ sealing temperature <(Tc + 40), most of the glass crystallizes during sealing. Therefore, it is preferable to determine the sealing temperature based on the above crystal condition so that crystallization can be avoided in the sealing of the multilayer glass with the glass bulk. The actual sealing temperature is adjusted depending on whether or not the pressure is applied at the time of sealing, or the magnitude of the applied pressure when the pressure is applied, but is preferably Tg + 155 ° C. ± 10 ° C.

  In the present invention, it is preferable that the moisture content of the glass bulk is small. The present inventor has determined that the moisture in the glass bulk is a cause of bubbles by analyzing the foam component generated in the sealing portion of the multilayer glass by the glass bulk, and based on this, the water content of the glass bulk is determined. When the rate was lowered, it was found that bubbles generated in the sealing glass were reduced or prevented. As a result, when the moisture content of the glass bulk for sealing is reduced, the generation of bubbles can be suppressed regardless of the glass composition.

In the present invention, as a method for reducing the moisture content of the glass bulk, a method of using a powder raw material such as high purity zinc phosphate / calcium / aluminum powder instead of a regular phosphoric acid raw material (liquid) as a glass bulk raw material, or a method of bubbling upon dissolution of the glass bulk material, for example, N ₂ gas is preferable. The former method that uses powder raw materials prevents moisture from entering the glass bulk by using raw materials that do not substantially contain moisture, and the latter bubbling method is a process that dissolves residual water contained in the raw materials. This is a method of removing by the bubbling effect. All of the glass bulks obtained by these methods have a low water content and can reduce or prevent foaming during sealing. Each of the above methods can be sufficiently effective even when used alone, but a greater effect can be obtained when used in combination.

  The present invention is characterized in that the peripheral edge of the multilayer glass is sealed with a glass bulk. Pre-formed glass bulk in a predetermined shape makes it easy to place the glass plate with an exhaust opening, which will be described later, at the peripheral edge of the glass plate, and prevents the generation of bubbles when sealing the double-glazed glass. It is also effective. In particular, for the prevention of foam generation during sealing, it is possible to remove bubbles and moisture during the production of glass bulk. Does not occur. For example, if frit glass is supplied in a paste form (slurry form) as in the prior art, bubbles are likely to be generated when the frit glass is melted.

  In the present invention, the glass bulk preferably has a circular, elliptical, rectangular or polygonal cross section, and its shape is block, ribbon or fiber. It should be noted that the corners of the rectangular cross section may be chamfered to form a substantially rectangular shape. In this case, strictly speaking, the cross sectional shape is a polygon. The block-shaped glass bulk is formed in advance to a predetermined length, and the cross section thereof may be any of a circle, an ellipse, a rectangle, and the like. Ribbon-like and fiber-like glass bulks are formed in long string-like and linear shapes and can be used by cutting them. Ribbon-like ones preferably have a rectangular or nearly rectangular cross section, and are fiber-like Preferably, the cross-section is circular or close to circular.

  In addition, the height (thickness) of these glass bulks may be set to be slightly higher than the spacers disposed in the vacuum layer of the multilayer glass when the glass bulk is disposed at the peripheral edge of the glass plate. preferable. The reason is that when a glass bulk higher than the spacer is placed between the glass plates and the glass bulk is heated and melted, it is pressurized and deformed by the weight of the upper glass plate and the pressing force applied as necessary. This is because the distance between the peripheral edges of the multilayer glass can be made substantially the same as the height of the spacer. And since the glass bulk fuse | melted by this flow deformation is extended along a glass plate surface, adhesiveness with a glass plate can be improved and the opening part for exhaust can be obstruct | occluded. Thereby, the favorable sealing part which has a high air density and intensity | strength is obtained. The extent to which the height of the glass bulk is set with respect to the spacer may be appropriately determined in consideration of the glass composition and shape of the glass bulk, the manner of arrangement, and the like.

  In this invention, when arrange | positioning the said glass bulk along the peripheral edge part of a glass plate, the opening part for exhaust_gas | exhaustion is provided in this glass bulk along the peripheral edge part of a glass plate. Next, the exhaust opening will be specifically described with reference to the drawings. For convenience of explanation, the glass plates constituting the exhaust multilayer glass are a lower glass plate and an upper glass plate.

  FIG. 1 shows a lower glass plate 1 in which a block-shaped glass bulk 2 is arranged at a peripheral end, (A) is a plan view, and (B) is a front view. In FIG. 1, reference numeral 4 denotes a spacer disposed in an inner region 6 surrounded by the glass bulk 2, which will be described later. As shown in FIG. 1, the glass bulk 2 disposed on the lower glass plate 1 is provided with an exhaust opening 3 along the peripheral edge of the lower glass plate 1. In this example, a plurality of exhaust openings 3 are provided on each side of the lower glass plate 1 by opening a predetermined gap between the block-shaped glass bulks 2. Then, an upper glass 5 is placed on the lower glass plate 1 on which the glass bulk 2 and the spacer 4 are arranged, more precisely on the glass bulk 2 and the spacer 4 to form a laminate.

FIG. 2 is a front view of the laminate. As shown in FIG. 2, an exhaust opening 3 is provided in the glass bulk 2 disposed at the peripheral edge of the laminate. The exhaust opening 3 is an opening that communicates the region 6 formed inside the laminated body to the outside, that is, communicates the inside and outside of the region 6. In the present invention, the air inside the laminated body (region 6) is discharged to the outside through the exhaust opening 3 in the decompression chamber, and the region 6 is exhausted to 1 Pa or less (about 10 ⁻² Torr or less), for example. Then, the exhaust opening 3 is closed by the molten glass bulk 2, and at the same time, the peripheral edge of the laminate is sealed. Thus, the laminated body is sealed at the peripheral end in a state where the inside is sufficiently exhausted through the exhaust opening 3, and the exhausted interior becomes a vacuum layer to form an exhaust multilayer glass.

  In the present invention, the number of exhaust openings 3 and the manner of installation can be changed as appropriate. For example, FIG. 3 is an example in which one exhaust opening 3 is provided along the peripheral edge of the lower glass plate 1 on which the glass bulk 2 is disposed. In the case where one or a plurality of exhaust openings are provided in the glass bulk disposed at the peripheral edge of the laminated body, the installation position is not limited as long as it is a peripheral edge of the laminated body. It is preferable to disperse as uniformly as possible at the peripheral edge of the laminate.

  Further, as illustrated in FIGS. 1 and 3, the exhaust opening 3 is installed so that the opening direction is perpendicular to each side of the lower glass plate 1, and each side of the lower glass plate 1. You may install so that a predetermined angle may be made with respect to.

  In addition, the exhaust opening 3 is normally provided as a notch between adjacent glass bulks 2 as illustrated in FIGS. 1 and 3, but the manner and method of installation can be changed. For example, FIG. 4 does not provide the exhaust opening 3 as a notch in the glass bulk 2, but when the glass bulk 2 is disposed at the peripheral edge of the lower glass plate 1, the glass bulk is disposed on each adjacent side. As shown in FIG. 4, two end portions are overlapped at the corners of the lower glass plate 1 and arranged in a grid pattern, and the upper glass plate is placed thereon to form a laminated body. An exhaust opening is obtained at the peripheral end.

  FIG. 5 is a side view of the laminate. A gap 7 is formed between the glass bulk 2 arranged as shown in FIG. 5 and the lower glass plate 1 and the upper glass plate 5. That is, since the thickness (height) of the glass bulk 2 is twice the thickness of the side due to the overlap of the glass bulk 2 at the corner of the laminate, the thickness of the glass bulk 2 is on the side of the laminate. A gap corresponding to is formed. The gap 7 is this gap. When this laminated body is put in a decompression chamber and depressurized, the inside of the laminated body (region 6) is exhausted with the gap portion 7 serving as the exhaust opening 3. When the laminate is heated in the decompression chamber in a state where the inside of the laminate is sufficiently evacuated, the glass bulk 2 is melted and the thickness of the glass bulk 2 at the corner is pressed and reduced. The glass bulk seals with the upper and lower glass plates, and the gap 7 disappears and is closed. Thereby, the peripheral edge part of a laminated body is airtightly sealed with a glass bulk, and exhaust multilayer glass is obtained.

  In the present invention, the size of the exhaust opening is not limited, but it is necessary to set the exhaust opening to a size that can be reliably closed by the molten glass bulk. If the exhaust opening is too large, it may not be able to be completely blocked by the molten glass bulk. In particular, when the exhaust opening 3 is provided as a notch in the glass bulk 2 as shown in FIGS. 1 and 3, if the notch is widened to form a large exhaust opening 3, the notch is completely removed. It becomes difficult to block. On the other hand, if the exhaust opening 3 is too small, the exhaust time becomes longer and the productivity is lowered. The width of the glass bulk notch can be about 1 to 3 mm.

  Next, the spacer 4 (see FIG. 1) will be described. Since the exhaust multilayer glass has a vacuum layer, the glass plate receives a large pressure from both sides due to the atmospheric pressure. This is a characteristic of exhaust double-glazed glass having a vacuum layer.If the glass plate constituting the exhaust double-glazed glass is not supported from the inside in the vacuum layer, the tensile stress exceeding the allowable value is applied to the glass plate at atmospheric pressure. Cause damage. The spacer 4 supports the glass plate that receives the atmospheric pressure in this way in the exhaust multilayer glass so that it can withstand the pressure, and separates the glass plates so that the vacuum layer of the exhaust multilayer glass has a desired thickness. A plurality of means are arranged in the vacuum layer.

  In the present invention, the spacer only needs to have an appropriate compressive strength that can withstand a large pressure given by atmospheric pressure, and a material having a compressive strength of about 500 MPa or more is preferable. Furthermore, since the entire laminate may be heated to 500 ° C. or higher in the process of producing the exhaust double-glazed glass, it must have heat resistance that does not cause a problem even at such a high temperature.

  In the present invention, the material of the spacer, the arrangement method, and the like can be the same as those of the support described in Patent Document 1. For example, examples of the material for the spacer include tungsten, molybdenum, nickel, titanium, high-strength alloy steel, stainless steel, high-strength alumina, zirconia, and ceramics containing many of these materials.

  In the present invention, columnar spacers formed from these materials can be preferably used. However, the shape of the spacer is not limited to this, and may be, for example, spherical or hemispherical. When the spacers are arranged at predetermined intervals in the vacuum layer of the exhaust multilayer glass, tensile stress is generated on the surface of the glass plate where the spacers are installed. Therefore, when the spacer is disposed in the vacuum layer of the exhaust double-glazed glass, the shape and arrangement method are selected so that the tensile stress does not exceed the breaking strength of the glass plate. Specifically, the arrangement interval of the spacers and the diameter (average diameter) are selected so that the tensile stress is a predetermined value or less. In general, the tensile stress is increased as the arrangement interval increases and the spacer diameter decreases. On the other hand, the smaller the arrangement interval and the larger the spacer diameter, the larger the contact area between the spacer and the glass plate and the greater the heat conduction through the spacer, so that the heat insulation performance of the exhaust multilayer glass decreases. Therefore, it is preferable to appropriately select the spacer arrangement interval and the spacer diameter in consideration of such heat conduction. The height of the spacer is the same as the thickness of the vacuum layer of the exhaust multilayer glass, and is typically about 0.1 to 1 mm.

Next, the manufacturing method of the exhaust multilayer glass of this invention is demonstrated.
As shown in FIG. 6, the exhaust multilayer glass of the present invention comprises (A) a step of placing a glass bulk, (B) a step of placing a spacer, (C) a step of forming a laminate, and (D) a laminate. It is manufactured through a step of exhausting, and a step (E) of sealing the peripheral edge of the laminate. Each of these steps is performed in approximately this order in the preferred embodiment of the present invention. However, the glass bulk and the spacer may be arranged after the spacer is arranged.

  The present invention is characterized in that the peripheral edge of the laminate is sealed in a state where the laminate is evacuated. That is, an exhaust opening is provided in a glass bulk disposed at the peripheral edge of the laminate, and the laminate is evacuated (depressurized) through the exhaust opening by placing the laminate in a decompression chamber and reducing the pressure. Further, the laminated body is heated in the decompression chamber to melt the glass bulk, and the exhaust opening is closed with the melted glass bulk in a state where the inside of the laminated body is evacuated to seal the peripheral edge of the laminated body. . This is clearly different from the conventional method in which the method for producing an exhaust multilayer glass according to the present invention produces exhaust multilayer glass by exhausting the inside of the sealed laminate after sealing the peripheral edge of the laminate. It is a different point.

Hereinafter, a preferred embodiment of the present invention will be described for each step with reference to FIG.
(A) Step of placing glass bulk Prepare upper and lower glass plates constituting the exhaust multilayer glass, and first place the glass bulk 2 along the peripheral edge of the lower glass plate 1 as shown in FIG. To do. The glass bulk 2 is a block shape having a rectangular cross section, for example, which is pre-formed from a low melting point glass and having a height larger than the height of the spacer. The glass bulk 2 is arranged at a position slightly inward from the end of the lower glass plate 1 along the peripheral end of the lower glass plate 1 with an interval of, for example, about 1 to 3 mm between adjacent glass bulks 2. Then, an exhaust opening 3 is formed between the glass bulk 2 and the glass bulk 2 arranged. In this case, the glass bulk 2 can be disposed simply by being placed at the peripheral edge of the lower glass plate 1. In addition, the glass bulk is mixed with raw material reagents of each component, put in a crucible (made of quartz glass in the case of phosphate glass / platinum in the case of bismuth glass), and put the whole crucible in an electric furnace at 1000 to 1500 ° C. After being charged and made into a homogeneous melt (dissolution process), the melt is poured into a carbon mold, the bulk body is molded (molding process), solidification of the bulk body is confirmed, and immediately after that the glass transition temperature +30 It is obtained by putting a bulk body in an electric furnace at 0 ° C. and holding it for several hours and then cooling it at 1 to 2 ° C./min (slow cooling process). Moreover, in order to prevent generation | occurrence | production of the bubble at the time of the seal | sticker in the (E) process mentioned later, it is preferable to remove a bubble and a water | moisture content at the time of manufacture of a glass bulk.
(B) Step of Disposing Spacer Spacer 4 is disposed in region 6 surrounded by glass bulk 2 of lower glass plate 1 as shown in FIG. As the spacer 4, a columnar body having a height corresponding to the thickness of the vacuum layer of the exhaust multilayer glass is used. In addition, the distance between the glass plates is considered to be the tensile stress generated on the surface of the glass plate where the spacers are placed when the exhaust double-layer glass is subjected to atmospheric pressure or external force, while taking into account heat conduction that is a cause of deterioration in heat insulation performance. Is selected to be below a predetermined value.
(C) Step of Forming Laminate Next, the upper glass plate 5 is placed on the lower glass plate 1 on which the glass bulk 2 and the spacers 4 are arranged, and the laminate shown in FIG. 7C is formed. In this laminated body, the glass bulk 2 is disposed at the peripheral end portion, and the spacer is disposed in the interior (region 6) surrounded by the glass bulk 2. A plurality of exhaust openings 3 are formed along the peripheral edge of the laminated body in the glass bulk 2 disposed at the peripheral edge of the laminated body. These exhaust openings 3 communicate with the outside.

In addition, when the glass bulk 2 and the spacer 4 are arranged in the same manner on the laminate, and another glass plate is placed thereon, a single laminate is used to form a laminate having a two-layer structure. If this is repeated, a desired number of multilayer structures can be obtained. By sealing the peripheral edge of the multilayer structure, it is possible to manufacture an exhaust multilayer glass having a vacuum layer and high heat insulation performance. The exhaust multilayer glass of the present invention also includes such a multilayer multilayer glass.
(D) Step of exhausting the laminated body The laminated body is put in a decompression chamber, the decompression chamber is decompressed, and the interior of the laminate is exhausted. That is, the decompression chamber is decompressed in a state where the laminated body is put, the air in the laminated body is sucked out through the exhaust opening 3 and exhausted, and finally the inside of the laminated body is evacuated by the exhaust multi-layer glass. The pressure is reduced to, for example, 1 Pa or less (about 10 ⁻² Torr or less) necessary for the layer, more preferably 0.1 Pa or less (about 10 ⁻³ Torr or less).
(E) The process of sealing the peripheral edge part of a laminated body In this process, in the state where the inside of the laminated body was exhausted to the predetermined pressure reduction degree in the decompression chamber, the peripheral edge part of the laminated body was melted by glass bulk. It is the process of sealing. When the laminate is heated in the decompression chamber, the entire laminate is heated, so that the glass bulk disposed at the peripheral edge of the laminate is also heated. FIG. 8 shows an example of the heating temperature transition of the glass bulk in this sealing step. The vertical axis in FIG. 8 is the heating temperature of this glass bulk, and Tg is the glass transition temperature of the glass bulk.

As shown in FIG. 8, the vacuum chamber can be heated by either vacuum (decompression) or atmospheric pressure until the glass bulk reaches the glass transition temperature. However, when heating to the glass transition temperature or higher, it is necessary to carry out by a vacuum process (reduced pressure state) in order to keep the inside of the laminate at a certain pressure or lower. This is because when the glass bulk is melted at a sealing temperature equal to or higher than the glass transition temperature, if the inside of the laminate is not sufficiently exhausted, the glass bulk in which the exhaust openings are melted in an insufficiently exhausted state. This is because it is blocked. Therefore, when the glass bulk is heated to the glass transition temperature, the inside of the laminate is decompressed to, for example, 1 Pa or less (about 10 ⁻² Torr or less).

  When the laminate is heated in the vacuum chamber to a sealing temperature equal to or higher than the glass transition temperature of the glass bulk for a certain period of time, the glass bulk placed at the peripheral edge of the laminate is melted and the molten glass bulk is pressed against the upper glass plate. The same height as the spacer. The glass bulk melted during this time flows in the peripheral direction of the laminate in the glass surface direction, closes the exhaust opening and seals the peripheral end of the laminate in an exhausted state. The sealed laminated body is taken out from the decompression chamber as exhaust multilayer glass after the sealing portion is cooled and solidified.

  In addition, if the laminate at the time of sealing in which the glass bulk is heated to the glass transition temperature or more is positively pressed from above and / or below as necessary, the sealing height (thickness) by the molten glass bulk The uniformity is improved, and a good sealing portion can be formed.

  FIG. 7D is an exhaust multilayer glass produced by the above method. A vacuum layer 8 is formed inside the exhaust multi-layer glass, and a spacer 4 is disposed in the vacuum layer 8. Since a large pressure is applied to the exhaust multilayer glass from the outside due to atmospheric pressure, the lower glass plate 1 and the upper glass plate 5 are firmly clamped and fixed from both sides of the spacer 4 arranged in the vacuum layer. The spacer 4 may be bonded and fixed to either the lower glass plate 1 or the upper glass plate 5.

Hereinafter, the present invention will be described in more detail by way of examples.
(Example 1)
Two glass plates having a thickness of 3 mm and the same size (300 mm × 300 mm) (Float plate glass “AS” manufactured by Asahi Glass Co., Ltd.) are prepared, and the glass bulk 1 shown below is arranged at the peripheral edge of the one glass plate. . At that time, two gaps of about 1 mm are provided on each side of the glass plate between adjacent glass bulks in order to form an exhaust opening.
<Glass bulk 1>
Glass composition: P ₂ O ₅ 30 mol%, SnO 30 mol%, ZnO 40 mol%
-Cross section: rectangular (height: about 0.5 mm, width: about 5 mm)
・ Shape: Block shape (Length: about 100mm)
Glass transition temperature: 345 ° C
Average coefficient of thermal expansion (50 ° C. to 300 ° C.): 90 × 10 ⁻⁷ / ° C.
Furthermore, 169 columnar spacers (diameter: 0.5 mm, height: about 0.2 mm) made of stainless steel (SUS304) were arranged at equal intervals in a region surrounded by the glass bulk 1 arranged on the glass plate. Thereafter, another glass plate is placed on the glass plate to form a laminate.

The laminated body is put into a decompression chamber, and heating is started with a hot plate from both the upper and lower sides of the laminated body simultaneously with decompression, and the glass bulk 1 is heated to the glass transition temperature (345 ° C.) by exhausting the inside of the laminated body. Until then, the decompression chamber is decompressed to about 10 ⁻³ Pa, and this decompressed state is maintained. After maintaining the heating temperature at 450 to 500 ° C. for about 15 minutes in this reduced pressure state, pressing at about 0.2 MPa, stopping the heating and gradually cooling the reduced pressure chamber to cool and solidify the sealing portion of the laminate. Then, it is taken out from the decompression chamber, and the sealing part of the taken-out laminated body is observed and evaluated.

  As a result, the peripheral edge of the laminate is sealed by sealing all the exhaust openings of the glass bulk 1, and there is no foaming that impairs hermeticity in the sealed part. Exhaust multilayer glass with excellent strength and excellent appearance that does not leave exhaust parts in the product can be manufactured. In addition, since the peripheral edge of the glass plate is sealed in the decompression chamber, a vacuum layer can be formed simultaneously with the sealing of the peripheral edge without providing an exhaust tube and exhausting the airtight layer. Excellent exhaust multilayer glass can be manufactured efficiently and at low cost.

(Example 2)
Prepare two glass plates (float plate glass “AS” manufactured by Asahi Glass Co., Ltd.) of the same size (50 mm × 50 mm) with a thickness of 0.7 mm, and a glass bulk 2 shown below at the peripheral edge of the one glass plate. Nine were arranged along one side of the glass plate.
<Glass bulk 2>
Glass _Composition: Bi ₂ O 3 42.6 _mol%, Al ₂ O 3 3.6 _mol%, SiO 2 34.2 _{mol%, Ga} 2 O 3 17.8 _mol%, La ₂ O 3 1.4 mole %, CeO ₂ 0.2 mol%
・ Cross section: Circular (diameter 0.1mm)
・ Shape: Fiber (length: about 50mm)
Glass transition temperature: 497 ° C
Average coefficient of thermal expansion (50 ° C. to 300 ° C.): 85 × 10 ⁻⁷ / ° C.
A laminated body was formed by stacking another glass plate on the glass plate on which the glass bulk 2 was placed, and a zirconia weight weighing 405 g was placed thereon. This was put in a vacuum furnace, depressurized to 0.5 kPa, and then heat-treated according to the heating temperature transition shown in FIG. By this treatment, the fiber-shaped glass bulk 2 was melted and flattened, and the two glass plates were firmly bonded to each other by the melted glass bulk 2. It was also confirmed that there was no foaming from the glass bulk 2. Therefore, the glass bulk 2 can be suitably used for sealing the peripheral edge of the exhaust multilayer glass.

(Example 3)
Block-shaped glass bulk (height: about 0.5 mm, width: about 5 mm, length: about 100 mm) having the glass composition (mol%) and physical properties (Tg, Tx, Tc) in Table 1 Two were prepared. Then, two glass plates (Float plate glass “AS” manufactured by Asahi Glass Co., Ltd.) having a thickness of 3 mm and the same size (200 mm × 200 mm) are prepared for each glass bulk, and on the vicinity of the left and right ends of one glass plate. The glass bulks were respectively disposed, and another glass plate was placed thereon to form the laminates of Examples 1 to 17. Each of the laminates was put in a heating furnace and heated to maintain the sealing temperature shown in Table 1 for about 15 minutes, and the glass plate was bonded with the molten glass bulk.

  The crystallization state of the bonded portion of each bonded glass plate was visually observed. The results are shown in Table 1. In Table 1, ○ indicates that no crystallization was observed, Δ indicates that some crystallization was observed, and × indicates that crystallization was observed almost entirely.

  As shown in Table 1, in Example 5, Example 7, Example 8, Example 11, Example 12, Example 13, Example 15, Example 16, and Example 17 in which Tc−Tg ≧ 185 ° C., the crystallization state is ○ or Δ. It can be seen that bonding can be performed without causing excessive crystallization. However, in all cases where Tc−Tg <185 ° C., crystallization was observed almost entirely, and good adhesion was not obtained.

Example 4
The following experiment was conducted on the foamability of a glass bulk having the glass composition of Example 13 of Example 3.
In Table 2, the glass bulk of Example 18 is the case where the countermeasure against foaming is not implemented, and Examples 19 to 21 are the cases where the countermeasure against foaming is implemented. That is, Example 18 is a case where an orthophosphoric acid raw material (liquid) is used as a raw material composition of P ₂ O ₅ and a glass bulk is prepared by melting the prepared glass raw material at about 1100 ° C. without N ₂ bubbling. 19 is a case where a glass bulk was prepared by performing N ₂ bubbling when the same glass raw material as in Example 18 was melted at about 1100 ° C. Moreover, Example 20 and Example 21 use zinc phosphate / calcium / aluminum high-purity powder as a raw material composition, and when dissolved at about 1100 ° C., Example 20 has no N ₂ bubbling and Example 21 has N ₂ bubbling. This is a case where a glass bulk is produced. The glass bulks were all (height: about 0.5 mm, width: about 5 mm, length: about 100 mm).

  Furthermore, the state of foaming was investigated by video-shooting the state when each glass bulk of Examples 18 to 21 was heated to the sealing temperature (500 ° C.) in a vacuum furnace (about 1 kPa). The results are shown in Table 2. In Table 2, A: no foaming, B: some foaming, and C: many foaming are shown.

As shown in Table 2, the foaming status of the glass bulks of Examples 19 to 21 in which countermeasures against foaming were implemented is less than that of Example 18 in which countermeasures against foaming were not implemented. In particular, in Examples 19 and 21 in which N ₂ bulling was performed, foaming did not occur, and it was found that the decrease in the moisture content of the glass bulk due to N ₂ bulling was excellent as a foaming suppression effect.

  The present invention relates to the manufacture of exhaust multi-layer glass in which peripheral edges of glass plates spaced via a vacuum layer are sealed by a sealing glass bulk, and a plurality of spacers are arranged in the vacuum layer. Is preferred.

1A and 1B are explanatory views showing an example of a glass plate in which a block-like glass bulk is arranged at the peripheral end of the present invention, where FIG. 1A is a plan view and FIG. 1B is a front view. FIG. 2 is a side view of a laminate obtained by placing another glass plate on the glass plate of FIG. FIG. 3 is a plan view showing another example of a glass plate on which a glass bulk is arranged. FIG. 4 is a plan view showing another example of a glass plate on which a glass bulk is arranged. FIG. 5 is a side view of a laminate obtained by placing another glass plate on the glass plate of FIG. FIG. 6 is a process diagram of a preferred method for producing an exhaust multilayer glass of the present invention. FIG. 7 is an explanatory view of a preferable manufacturing process of the exhaust multilayer glass of the present invention. FIG. 8 is a graph showing an example of temperature transition in the sealing step of the present invention. FIG. 9 is a graph showing changes in temperature in the sealing step of the reference example. FIG. 10 is a schematic diagram of differential thermal analysis (DTA) of the glass bulk of the present invention.

Explanation of symbols

1: Lower glass plate 2: Glass bulk 3: Exhaust opening 4: Spacer 5: Upper glass plate 6: Area 7: Cavity 8: Vacuum layer

Claims (10)

A peripheral glass glass plate separated by a vacuum layer is sealed by a sealing glass bulk, and a method for producing a double-glazed glass in which a plurality of spacers are arranged in the vacuum layer,
(1) A sealing glass bulk having a low melting point is arranged along the peripheral edge of one glass plate, and an exhaust opening that communicates the inside and outside of the region surrounded by the sealing glass bulk is provided and sealed. Placing the spacer in a region surrounded by glass bulk;
(2) forming a laminate by stacking another glass plate on the glass plate on which the sealing glass bulk and the spacer are disposed;
(3) Putting the laminated body into a decompression chamber, depressurizing and heating the decompression chamber, and in the state where the inside of the laminated body is exhausted through the exhaust opening, the exhaust opening is melted with a molten sealing glass bulk. Sealing the peripheral edge of the laminate,
A method for producing an exhaust double-glazed glass, comprising:   The method for producing an exhaust multilayer glass according to claim 1, wherein a plurality of the exhaust openings are provided along the peripheral edge of the laminate.   The method for producing an exhaust multilayer glass according to claim 1 or 2, wherein a height of the sealing glass bulk is larger than a height of the spacer.   The exhaust multilayer according to any one of claims 1 to 3, wherein, in the step (3), the laminate is pressed from above and / or below when the peripheral edge of the laminate is sealed with a sealing glass bulk. Glass manufacturing method.   The method for producing an exhaust multilayer glass according to any one of claims 1 to 4, wherein a laminate is further formed on the laminate obtained in the step (2) to obtain a laminate having a multilayer structure. 6. The exhaust multilayer glass according to claim 1, wherein the sealing glass bulk has an average coefficient of thermal expansion at 50 ° C. to 300 ° C. of 70 × 10 ⁻⁷ / ° C. to 100 × 10 ⁻⁷ / ° C. 6. Production method.   The method for producing an exhaust multilayer glass according to any one of claims 1 to 6, wherein the sealing glass bulk has a glass transition temperature of 500 ° C or lower. The method for producing an exhaust multilayer glass according to any one of claims 1 to 7, wherein the sealing glass bulk is formed from a glass having the following composition in terms of mol%.
P ₂ O _5: 20~45%
SnO: 20-40%
ZnO: 25-50%
B ₂ O ₃ : 0 to 10%
CaO: 0 to 15%
Al ₂ O ₃ : 0 to 6%
In ₂ O ₃ : 0 to 6%
La ₂ O ₃ : 0 to 6%
_{Al 2 O 3 + In 2 O} 3 + La 2 O 3: 0~10%   The method for producing an exhaust multilayer glass according to claim 8, wherein the sealing glass bulk is made of glass of (crystallization temperature−glass transition temperature) ≧ 185 ° C.   An exhaust multilayer glass produced by the method for producing an exhaust multilayer glass according to claim 1.

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