JP2016040212A - Method for producing vacuum double layer glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method suitable for vacuum double layer glass having a metal-frit composite encapsulating member.SOLUTION: The method for producing vacuum double layer glass comprises: (A) a step of composing a laminate comprising first and second glass substrates laminated so as to form a gap between them and a seal member arranged so as to encircle the gap, where the seal member comprises a frame-like metal member and first and second glass solidified layers which soften at a temperature of about 400°C or more; and (B) a step of vacuum treating the gap of the laminate. The step (B) comprises heat treating the laminate under conditions that, when the treating temperature and a holding time are denoted by T(K) and t (hour) respectively, satisfy a formula: T≤620×t(1), where 0.1(hour)<t<100(hour).SELECTED DRAWING: Figure 10

Description

  The present invention relates to a method for producing a vacuum multilayer glass.

  A vacuum double-layer glass constructed by laminating a pair of glass substrates through a gap and holding the gap at a low pressure or in a vacuum state has an excellent heat insulating effect. For example, buildings such as buildings and houses Widely used for window glass applications.

  In the vacuum double-glazed glass, the sealing performance of the sealing member installed around the gap in order to keep the gap in a vacuum state greatly affects the heat insulation of the entire vacuum double-glazed glass. This is because, when the sealing performance of the sealing member is inferior, components such as air and / or water vapor easily enter the gap through the sealing member, thereby reducing the degree of vacuum in the gap. . For this reason, the examination of the sealing member excellent in the sealing performance is advanced.

  Recently, a seal member composed of a metal member and a non-metal member has been developed. For example, Patent Document 1 discloses a seal member configured by arranging vitrified layers on the upper and lower surfaces of a frame-shaped metal member. Moreover, it is disclosed that the configuration of such a seal member can mitigate the influence of the difference in thermal expansion between the two glass substrates due to the deformation function of the metal member.

International Publication No. 2014/061639

  As described above, in recent years, as a sealing member for vacuum double-glazed glass, a sealing member composed of a metal member and a glass solidified layer (hereinafter, such a sealing member is referred to as a “metal / frit composite sealing member”). ) Has been proposed.

  However, such a metal / frit composite sealing member is a technology belonging to a relatively new field, and therefore, a manufacturing technique is sufficient for a vacuum double-layer glass having a metal / frit composite sealing member. It is difficult to say that it has been established. In particular, since the metal / frit composite sealing member has a completely different structure from the conventional seal member, the vacuum having the conventional seal member is produced in the manufacture of the vacuum double-glazed glass having the metal / frit composite seal member. There is a possibility that the manufacturing technology for double-glazed glass cannot be applied as it is.

  The present invention has been made in view of such a background, and an object of the present invention is to provide a manufacturing method suitable for a vacuum double-glazed glass having a metal / frit composite sealing member.

In the present invention, the first and second glass substrate is a method for producing a vacuum double-layer glass laminated through a gap,
(A) A step of configuring a laminated body having first and second glass substrates laminated so that a gap is formed between them, and a sealing member arranged so as to surround the gap. ,
The sealing member includes a frame-shaped metal member and first and second vitrified layers, and the first and second vitrified layers are softened at a temperature of about 400 ° C. or higher; and ,
(B) a step of decompressing the gap portion of the laminate;
Have
In the step (B), when the processing temperature is T (K) and the holding time is t (hour),

T ≦ 620 × t− ^0.015 (1) (where 0.1 (hour) <t <100 (hour))

The manufacturing method of the vacuum double layer glass characterized by satisfy | filling satisfy | fills is provided.

  The present invention can provide a production method suitable for a vacuum double-glazed glass having a metal / frit composite sealing member.

It is sectional drawing which showed typically the example of 1 structure of the vacuum multilayer glass which has a metal / frit composite sealing member. It is the figure which showed roughly an example of the manufacture flow of the vacuum double layer glass by one Embodiment of this invention. The first glass substrate (a) in which the first glass solidified layer is arranged on the first surface and the second glass substrate (b) in which the second glass solidified layer is arranged on the third surface are schematically shown. FIG. It is the figure which showed roughly an example of the temperature-time curve of the assembly (and laminated body) used in the case of "single implementation system". It is the figure which showed schematically an example of the temperature-time curve of the assembly (and laminated body) used in the case of "continuous implementation system". It is the figure which showed roughly an example of the structure of another vacuum double glazing (2nd vacuum double glazing) which has a metal / frit composite sealing member. It is the figure which showed roughly an example of the structure of another vacuum double glazing (3rd vacuum double glazing) which has a metal / frit composite sealing member. It is the figure which showed schematically an example of the structure of another vacuum double glazing (4th vacuum double glazing) which has a metal / frit composite sealing member. It is sectional drawing which showed schematically the structure of the conjugate | zygote manufactured in the Example of this invention. It is the figure which plotted the soundness evaluation result obtained in the test piece which concerns on each example on the graph represented by holding time t (horizontal axis) of simulated heat processing, and heat processing temperature T (vertical axis) of simulated heat processing. .

  Embodiments of the present invention will be described below with reference to the drawings.

(Vacuum double-layer glass with metal / frit composite sealing member)
In order to better understand the characteristics of the present invention, first, the structure of a vacuum double-glazed glass having a metal / frit composite sealing member will be briefly described with reference to FIG.

  FIG. 1 schematically shows a cross section of a vacuum double-glazed glass 100 having a metal / frit composite sealing member.

  As shown in FIG. 1, the vacuum double-glazed glass 100 includes a first glass substrate 110, a second glass substrate 120, a gap 130 formed between the two glass substrates 110, 120, and the gap And a seal member 150 that holds the portion 130 in a sealed state.

  The first glass substrate 110 has a first surface 112 and a second surface 114. In the vacuum multi-layer glass 100, the first glass substrate 110 is disposed so that the second surface 114 side is the outside. Similarly, the second glass substrate 120 has a third surface 122 and a fourth surface 124. In the vacuum double-glazed glass 100, the second glass substrate 120 is disposed such that the fourth surface 124 side is the outside. Accordingly, the gap 130 is formed between the first surface 112 of the first glass substrate 110 and the third surface 122 of the second glass substrate 120.

  In the normal case, the gap 130 is maintained in a vacuum state. Here, the degree of vacuum of the gap 130 is not particularly limited, and may be any pressure lower than atmospheric pressure. In general, the pressure in the gap 130 is about 0.2 Pa to 0.001 Pa.

  Note that the gap 130 may be filled with an inert gas such as argon at a pressure lower than atmospheric pressure. That is, in the present application, the “vacuum multilayer glass” is not limited to the one in which the pressure in the gap is in a vacuum state, and the term “vacuum multilayer glass” means that the pressure in the gap is less than atmospheric pressure. It shall mean all double-glazed glass.

  If necessary, the vacuum multilayer glass 100 may include one or more spacers 190 in the gap 130. The spacer 190 has a role of holding the gap 130 in a desired shape. However, when the gap 130 can be maintained in a desired shape without the spacer 190, for example, when the degree of vacuum of the gap 130 is low, or when an inert gas or the like is applied to the gap 130 at a certain pressure. In the case of filling, the spacer 190 may be omitted.

  The seal member 150 is a member for holding the gap 130 in a sealed state, and the seal member 150 is configured over the entire periphery of the gap 130.

  Here, the seal member 150 is a metal / frit composite sealing member, that is, has a first vitrified layer 160, a metal member 155, and a second vitrified layer 165.

  In the example shown in FIG. 1, the first vitrified layer 160 is installed in a “frame shape” around the first glass substrate 110 on the first surface 112 side of the first glass substrate 110. Yes. Similarly, the second glass solidified layer 165 is provided in a “frame shape” over the periphery of the second glass substrate 120 on the third surface 122 side of the second glass substrate 120.

  Here, in the present application, the term “frame shape” means a general term for a shape constituted by a “frame” having an outer outline and an inner outline, with the inside of a flat plate shape removed in plan view. However, the outer contour and / or inner contour of the “frame-shaped” member is not necessarily limited to a substantially rectangular parallelepiped shape such as a forehead, and may be, for example, a substantially trapezoidal shape, a substantially circular shape, or a substantially elliptical shape. . Further, the outer and inner contours of the “frame-shaped” member do not necessarily have similar shapes, and may be completely different, for example.

  Further, the metal member 155 has a first surface 170 and a second surface 172, and has a “frame shape” shape. The first surface 170 of the metal member 155 is partially bonded to the first vitrified layer 160, and the second surface 172 of the metal member 155 is partially bonded to the second vitrified layer 165. Has been.

  Here, when the vacuum double-glazed glass 100 is viewed from above (thickness direction: Z direction in FIG. 3), the first vitrified layer 160 does not overlap with the second vitrified layer 165. Placed in. For example, in the example of FIG. 3, the first vitrified layer 160 is disposed inside the second vitrified layer 165.

  In the vacuum double-glazed glass 100 having such a “metal / frit composite sealing member” 150, even when a temperature difference occurs between the first glass substrate 110 and the second glass substrate 120, the metal member 155. Because of the deformation function in the direction parallel to the third surface 122 of the second glass substrate 120 (or the first surface 112 of the first glass substrate 110) (the X direction in FIG. 3), both glass substrates 110, The influence of the difference in thermal expansion between 120 can be mitigated.

  Therefore, in the vacuum multilayer glass 100, generation | occurrence | production of a distortion, a deformation | transformation, etc. can be suppressed significantly.

(Problems of vacuum double glazing with metal / frit composite sealing member)
By the way, the vacuum double-glazed glass having such a “metal / frit composite sealing member” is a technique which has recently begun to attract attention, and therefore, a vacuum having a metal / frit composite sealing member. For double-glazed glass, it is difficult to say that manufacturing technology is well established.

  In fact, according to the inventors of the present invention, a general “reduced pressure” used in the manufacture of a vacuum double-glazed glass having a conventional sealing member is used for a vacuum double-glazed glass having a metal / frit composite sealing member. When the “treatment” is applied as it is, it has been found that a defect (peeling phenomenon between members) occurs in the metal / frit composite sealing member.

  Here, when manufacturing the vacuum double-glazed glass, it is necessary to seal the gap between the first glass substrate and the second glass substrate in a reduced pressure and vacuum state. The “decompression treatment” of the vacuum double-glazed glass means that the gap portion is vacuum-sucked at a high temperature through a through opening provided in the first or second glass substrate in the final stage of manufacturing the vacuum double-glazed glass. Then, the process which seals a through-opening is said.

  The problem with the metal / frit composite sealing member described above is that a general “decompression treatment” condition applied in the production of a conventional vacuum double-layer glass is a vacuum multi-layer having a metal / frit composite sealing member. It is thought that it occurred because it was not appropriate as a “depressurization treatment” for glass.

  The inventors of the present application have conducted extensive research and development in order to optimize the manufacturing conditions of the vacuum double-glazed glass having the metal / frit composite sealing member after finding such a problem. As a result, the inventors have found that the above-described problems that may occur in the metal / frit composite sealing member can be suppressed by performing the decompression process under predetermined conditions, and the present invention has been achieved.

That is, in the present invention, the first and second glass substrates are a method for producing a vacuum double-layer glass in which the gaps are stacked,
(A) A step of configuring a laminated body having first and second glass substrates laminated so that a gap is formed between them, and a sealing member arranged so as to surround the gap. ,
The sealing member includes a frame-shaped metal member and first and second vitrified layers, and the first and second vitrified layers are softened at a temperature of about 400 ° C. or higher; and ,
(B) a step of decompressing the gap portion of the laminate;
Have
In the step (B), when the temperature of the laminate is T (K) and the holding time is t (hour),

T ≦ 620 × t ^−0.015 (1) Formula (where 0.1 hour <t <100 hour)

There is provided a method for producing a vacuum double-glazed glass, characterized by comprising a step performed under conditions that satisfy

  As will be described in detail later, when the first and second vitrified layers included in the metal / frit composite sealing member have a property of softening at a temperature of about 400 ° C. or higher, the expression (1) is satisfied. By carrying out the decompression treatment of the vacuum double-glazed glass under the conditions, the defects of the metal / frit composite sealing member can be significantly suppressed.

(Method for producing vacuum double-glazed glass according to one embodiment of the present invention)
Next, with reference to drawings, the manufacturing method of the vacuum double layer glass by one Embodiment of this invention is demonstrated.

  In FIG. 2, the flowchart of an example of the manufacturing method of the multilayer glass by one Embodiment of this invention is shown.

As shown in FIG. 2, a method for manufacturing a vacuum double-glazed glass according to an embodiment of the present invention (hereinafter simply referred to as “first manufacturing method”)
Forming a first glass solidified layer in a frame shape on the first surface of the first glass substrate, and forming a second glass solidified layer in a frame shape on the third surface of the second glass substrate; (Step S110),
Preparing a frame-shaped metal member having a first surface and a second surface (step S120);
Laminating the first glass substrate, the metal member, and the second glass substrate in this order to form an assembly,
The first glass substrate is disposed such that the first vitrified layer is in contact with the first surface of the metal member;
The second glass substrate is disposed such that the second vitrified layer is in contact with the second surface of the metal member (step S130);
A step of firing the assembly, wherein a sealing member is formed, and a laminated body in which the first glass substrate and the second glass substrate are combined is formed by the sealing member ( Step S140),
The step of subjecting the gap between the first glass substrate and the second glass substrate of the laminated body to a reduced pressure treatment, wherein the reduced pressure treatment sets the temperature of the laminated body to T (K) and the holding time to t (Hour)

T ≦ 620 × t ^−0.015 (1) Formula (where 0.1 hour <t <100 hour)

A step (step S150) performed under the conditions satisfying
Have

  Hereinafter, each step will be described in detail. In the following description, for the sake of clarity, the reference numerals shown in FIG.

(Step S110)
First, the first and second glass substrates 110 and 120 are prepared.

  The first glass substrate 110 has first and second surfaces 112 and 114. The second glass substrate 120 has third and fourth surfaces 122 and 124.

  The glass composition of the first and second glass substrates 110 and 120 is not particularly limited. The glass of the glass substrates 110 and 120 may be, for example, soda lime glass or non-alkali glass. The compositions of the first glass substrate 110 and the second glass substrate 120 may be the same or different.

  Next, a first glass solidified layer 160 is formed in a frame shape on the first surface 112 of the first glass substrate 110, and a second frame shape is formed on the third surface 122 of the second glass substrate 120. The vitrified layer 165 is formed.

  The first and second glass solidified layers 160 and 165 are formed by baking a paste containing glass frit. The vitrified layers 160 and 165 include a glass component, but may further include ceramic particles.

The composition of the glass component contained in the vitrified layers 160 and 165 is not particularly limited as long as the softening point of the vitrified layer is about 400 ° C. or higher. The glass component contained in the vitrified layers 160 and 165 may be, for example, ZnO—Bi ₂ O ₃ —B ₂ O ₃ based glass.

Table 1 shows an example of the composition of ZnO—Bi ₂ O ₃ —B ₂ O ₃ -based glass that can be used for the glass components contained in the vitrified layers 160 and 165.

以下、第１のガラス基板１１０の第１の表面１１２の周囲に、第１のガラス固化層１６０を形成する一例について説明する。

Hereinafter, an example in which the first glass solidified layer 160 is formed around the first surface 112 of the first glass substrate 110 will be described.

  When the first glass solidified layer 160 is formed around the first surface 112 of the first glass substrate 110, first, a paste for the first glass solidified layer 160 is prepared. Usually, the paste includes glass frit, ceramic particles, a polymer, an organic binder, and the like. However, the ceramic particles may be omitted. The glass frit eventually becomes a glass component constituting the first vitrified layer 160.

  The prepared paste is applied around the first surface 112 of the first glass substrate 110.

  Next, the first glass substrate 110 containing the paste is dried. The conditions for the drying treatment are not particularly limited as long as the organic binder in the paste is removed. The drying process may be performed, for example, by holding the first glass substrate 110 at a temperature of 100 ° C. to 200 ° C. for about 30 minutes to 1 hour.

  Next, in order to pre-fire the paste, the first glass substrate 110 is heat-treated at a high temperature. The heat treatment conditions are not particularly limited as long as the organic substances contained in the paste are removed. The heat treatment may be performed, for example, by holding the first glass substrate 110 in a temperature range of 300 ° C. to 470 ° C. for about 30 minutes to 1 hour. Thereby, the paste is baked and the first vitrified layer 160 is formed. In addition, this temporary baking process can also be skipped.

  Similarly, a second glass solidified layer 165 is formed around the third surface 122 of the second glass substrate 120.

  In FIG. 3, the first glass substrate 110 (FIG. 3A) in which the first glass solidified layer 160 is disposed on the first surface 112, and the second glass solidified layer 165 on the third surface 122. The 2nd glass substrate 120 (FIG.3 (b)) by which is arrange | positioned is shown typically.

  Here, the second glass solidified layer 165 does not overlap with the formation position of the first glass solidified layer 160 when the two glass substrates 110 and 120 are laminated to each other and viewed from the lamination direction. It is arranged at such a position.

(Step S120)
Next, a frame-shaped metal member 155 having first and second surfaces 170 and 172 is prepared.

  The metal member 155 may be made of any metal. The metal member 155 may be selected from, for example, aluminum and aluminum alloy, copper and copper alloy, titanium and titanium alloy, and stainless steel.

  The metal member 155 is, for example, a foil or a plate, and when the gap is under atmospheric pressure, the thickness is in the range of 5 μm to 500 μm, and the gap is filled with an inert gas at a certain pressure. If it is, it may have a thickness in the range of 5 μm to 1500 μm.

  In addition, the shape of the metal member 155 in the preparation stage is not particularly limited as long as the final provided shape is a frame shape. Therefore, for example, the frame-shaped metal member 155 may be configured by joining a plurality of elongated plate-shaped members. Alternatively, the frame-shaped metal member 155 may be provided as an integrated product (seamless member) by cutting the plate-shaped member into a frame shape or punching the plate-shaped member into a frame shape.

  The metal member 155 may be formed with a convex portion along the longitudinal direction of the frame of the metal member in a region in contact with the glass frit, or may include a concave or convex island portion on the surface. Irregularities of a dimensional island pattern may be formed.

(Step S130)
Next, the first and second glass substrates 110 and 120 and the frame-shaped metal member 155 are combined to form an assembly.

  At this time, the metal member 155 has a part of the first surface 170 in contact with the first vitrified layer 160 and a part of the second surface 172 in contact with the second vitrified layer 165. Thus, the first and second glass substrates 110 and 120 are laminated.

  At this time, one or more spacers 190 may be disposed between the first glass substrate 110 and the second glass substrate 120 as necessary.

  Moreover, you may apply a pressing force to the assembly from the 1st glass substrate 110 and / or the 2nd glass substrate 120 side as needed.

(Step S140)
Next, the assembly is fired.

  The firing temperature and firing time of the assembly also vary depending on the softening point of the vitrified layers 160 and 165 and the like. The firing temperature of the assembly may be, for example, in the range of 470 ° C. to 530 ° C., and the firing time of the assembly may be in the range of, for example, 5 seconds to 180 minutes.

  For example, the assembly is baked by holding the assembly in a chamber maintained at 470 ° C. to 530 ° C. for about 5 seconds to 180 minutes, preferably about 15 seconds to 30 minutes (for example, 20 minutes), You may implement by taking out more and cooling to room temperature.

  In addition, you may implement baking by heating the 1st and 2nd glass solidification layers 160 and 165 locally instead of heating the whole assembly.

  The baking treatment can be performed in an air atmosphere, but can also be performed in a gas atmosphere such as nitrogen or a reduced-pressure atmosphere of atmospheric pressure or lower.

The firing process of the assembly, while adding the pressure of 25kg ^{/ m 2} ~1000kg ^/ m 2 to the assembly, may be implemented. Alternatively, the firing process of the assembly may be performed in a state where the first glass substrate 110 and the second glass substrate 120 are sandwiched between clamping means or the like.

  By heating the assembly, the first and second vitrified layers 160 and 165 are softened. Thereby, the first surface 170 of the metal member 155 is bonded to the first vitrified layer 160, and the second surface 172 of the metal member 155 is bonded to the second vitrified layer 165. Therefore, after the assembly is fired, a gap 130 surrounded by the seal member 150 is formed between the first and second glass substrates 110 and 120.

(Step S150)
In the laminated body configured in step S140 described above, the gap 130 between the first glass substrate 110 and the second glass substrate 120 is not maintained in a reduced pressure state.

  Therefore, next, a decompression process is performed. By performing this decompression process, a decompression space is formed in the gap 130, and the vacuum double-glazed glass 100 can be manufactured.

  The decompression process is usually performed using a through opening provided in advance in the first or second glass substrate 110 or 120. That is, by using the through-opening, the gas in the gap 130 is sucked to reduce the pressure in the gap 130, and then the through-opening is sealed to form a reduced pressure space in the gap 130. it can. For example, a rotary pump or a turbo molecular pump is used to connect to a through opening through piping such as a flexible pipe, and after the pressure of the gap 130 is reduced to 1.33 Pa or less through the through opening, the through opening is sealed. be able to.

  Usually, the reduced pressure treatment is performed in a state where the laminate is heated. This is because moisture and / or organic components contained in the laminate can be more effectively removed when the reduced pressure treatment is performed in a heated state. Not only can a higher vacuum be obtained in a certain period of time, but also the moisture and / or organic components contained in the laminate will be reduced, and the reduced pressure state of the gap can be maintained for a long time. The improvement of the life of the layer glass can be expected.

Here, in the first manufacturing method, when the processing temperature is T (K) and the holding time is t (hour)

T ≦ 620 × t ^−0.015 (1) Formula

Implemented under conditions that satisfy Here, the holding time t is 0.1 (hour) <t <100 (hour).

  In particular, the processing temperature T is preferably in the range of 473 (K) ≦ T ≦ 653 (K).

  As described above, in the manufacturing process of the vacuum double-glazed glass including the metal / frit composite sealing member, a defect (such as a peeling phenomenon between the members) may occur in the seal member after the pressure reduction treatment of the laminated body.

  However, when the pressure-reducing treatment of the laminated body is performed under the above conditions, the gap portion 130 can be appropriately reduced in pressure without adversely affecting the seal member 150.

  Note that the decompression process may be performed in a state where the stacked body is disposed in a vacuum chamber.

  The processes of firing the assembly (step S140) to depressurizing the laminate (step S150) may be performed “single” or “continuously”. Hereinafter, each implementation method is demonstrated with reference to FIG. 4 and FIG.

(Single implementation method)
FIG. 4 schematically shows an example of a temperature-time curve of an assembly (and a laminate) used in the “single implementation method”.

  As shown in FIG. 4, in this method, two heat treatments (first heat treatment I and second heat treatment II) are performed separately. That is, first, the first heat treatment I is performed for firing the assembly (step S140). Thereafter, the assembly is sufficiently cooled to form a laminate. Next, the second heat treatment II is performed for the decompression process (step S150) of the stacked body.

Treatment temperatures _{T 1} in the first heat treatment I, for example, in the range of 470 ° C. to 530 ° C.. The holding time _{t 1} in the first heat treatment I, for example, in the range of 5 seconds to 180 minutes. On the other hand, the processing temperature T ₂ and the holding time t ₂ in the second heat treatment II are performed under the conditions satisfying the above-described expression (1). However, as described above, 0.1 (hour) <t ₂ <100 (hour).

(Continuous implementation method)
Next, FIG. 5 schematically shows an example of a temperature-time curve of the assembly (and the laminated body) used in the “continuous execution method”.

As shown in FIG. 5, in this method, two heat treatments (first heat treatment I and second heat treatment II) are performed “continuously”. That is, in this system, after the assembly is fired (step S140) in the first heat treatment I, before the assembly (laminate) is cooled to room temperature (that is, the temperature T of the laminate). = At T ₂ ), the second heat treatment II is performed, and the stack is decompressed.

  Such a “continuous execution method” can significantly reduce the heat treatment period and cost compared to the “single execution method”. Therefore, in the “continuous execution method”, the manufacturing cost and the manufacturing period of the vacuum double-glazed glass can be shortened.

  The vacuum multilayer glass 100 is manufactured by the above process.

  In such a first manufacturing method, the vacuum multilayer glass 100 can be manufactured without causing problems such as peeling to the seal member 150.

(About another configuration of vacuum double-glazed glass)
In the above, the manufacturing method by one Embodiment of this invention was demonstrated taking the vacuum double-glazed glass 100 which has the sealing member 150 as shown in FIG. 1 as an example.

  However, the application example of the manufacturing method of the vacuum double-glazed glass according to the present invention is not limited to the vacuum double-glazed glass having such a configuration. That is, the method for producing a vacuum double-glazed glass according to the present invention can be similarly applied to any vacuum double-glazed glass having a metal / frit composite sealing member.

  Accordingly, with reference to FIGS. 6 to 8, another configuration example of the vacuum double-glazed glass having a metal / frit composite sealing member to which the vacuum double-glazed glass manufacturing method according to the present invention can be applied will be described below. .

  FIG. 6 schematically shows an example of the configuration of another vacuum double glazing (second vacuum double glazing) having a metal / frit composite sealing member.

  As shown in FIG. 6, the second vacuum multilayer glass 300 basically has the same configuration as the vacuum multilayer glass 100 shown in FIG. Therefore, in FIG. 6, the same reference numerals as those in FIG. 1 plus 200 are used for the same members as in FIG. However, the second vacuum multilayer glass 300 shown in FIG. 6 is different from the vacuum multilayer glass 100 shown in FIG. 1 in the structure of the sealing member.

  That is, the second vacuum double-glazed glass 300 has a gap 330 formed between the first and second glass substrates 310 and 320 and a seal member 350 disposed over the entire periphery of the gap 330. The cross section of the seal member 350 is substantially “Z”. More specifically, the seal member 350 joins the metal member 355 to the second surface 314 of the first glass substrate 310 via the first glass solidified layer 360 and the second glass solidified layer 365. It is comprised by joining to the 3rd surface 322 of the 2nd glass substrate 320 via.

  In the second vacuum multi-layer glass 300, the region in contact with the first vitrified layer 360 of the metal member 355 and the region in contact with the second bonding layer 365 are both of the metal member 355. Note that it is on the first surface 370 side.

  Next, FIG. 7 schematically shows an example of the configuration of still another vacuum double-glazed glass (third vacuum double-glazed glass) having a metal / frit composite sealing member.

  As shown in FIG. 7, the third vacuum multilayer glass 400 basically has the same configuration as the vacuum multilayer glass 100 shown in FIG. Therefore, in FIG. 7, the same reference numerals as those in FIG. 1 plus 300 are used for the same members as in FIG. However, the third vacuum multilayer glass 400 shown in FIG. 7 is different from the vacuum multilayer glass 100 shown in FIG. 1 in the structure of the sealing member.

  That is, the third vacuum multilayer glass 400 covers the gap 430 formed between the first and second glass substrates 410 and 420 and the end portions of the first and second glass substrates 410 and 420. And a seal member 450 arranged in this manner. The seal member 450 has a substantially “bracket” shape in cross section.

  More specifically, the seal member 450 joins the metal member 455 to the second surface 414 of the first glass substrate 410 via the first glass solidified layer 460 and the second glass solidified layer 465. It is comprised by joining to the 4th surface 424 of the 2nd glass substrate 420 via.

  In the third vacuum double-glazed glass 400, the metal member 455 has a region in contact with the first glass solidified layer 460 and a region in contact with the second glass solidified layer 465, both of which are metal members 455. Note that it is on the first surface 470 side.

  FIG. 8 schematically shows an example of the configuration of still another vacuum double-glazed glass (fourth vacuum double-glazed glass) having a metal / frit composite sealing member.

  As shown in FIG. 8, the fourth vacuum multilayer glass 500 basically has the same configuration as the vacuum multilayer glass 100 shown in FIG. Therefore, in FIG. 8, the same reference numerals as those in FIG. 1 plus 400 are used for the same members as in FIG. However, the fourth vacuum glass 500 shown in FIG. 8 is different from the vacuum glass 100 shown in FIG. 1 in the structure of the sealing member.

  That is, the third vacuum double-glazed glass 500 is disposed on the gap portion 530 formed between the first and second glass substrates 510 and 520 and the end face side of the first and second glass substrates 510 and 520. And a sealed member 550. The seal member 550 has a substantially “I” cross section.

  More specifically, the seal member 550 joins the metal member 555 to the end surface 516 of the first glass substrate 510 through the first glass solidified layer 560 and also through the second glass solidified layer 565. It is configured by bonding to the end surface 526 of the second glass substrate 520.

  In the fourth vacuum double-glazed glass 500, the region in contact with the first glass solidified layer 560 of the metal member 555 and the region in contact with the second glass solidified layer 565 are both metal members 555. Note that it is on the first surface 570 side.

  Also in the vacuum double-glazed glass 300, 400, 500 having the configuration shown in FIGS. 6 to 8, in the manufacturing process, the deaeration process is performed under the conditions satisfying the above-described formula (1), thereby providing a seal. Those skilled in the art will readily understand that defects that may occur in the members 350, 450, and 550 can be significantly suppressed.

  Next, examples of the present invention will be described.

(Example 1)
A sample simulating a part of the vacuum double-glazed metal / frit composite sealing member was manufactured by the following method.

  First, a glass solidified layer was formed on the first surface of the glass substrate.

  As the glass substrate, soda lime glass having dimensions of 600 mm in length, 150 mm in width, and 6 mm in thickness was used.

  The vitrified layer was formed by applying a paste prepared by mixing glass frit, ceramic powder, polymer, and organic binder to a glass substrate, drying the paste, and heating the paste. The heating conditions were implemented in the following two stages. That is, after holding the glass substrate at 350 ° C. for 30 minutes in the atmosphere (first stage heat treatment), by holding the glass substrate at 410 ° C. for 10 minutes in the atmosphere (second stage heat treatment), Carried out.

  The glass frit having the composition shown in Table 1 was used. Further, the vitrified layer was formed in an I shape (about 2 mm in width) in the vicinity of the end face of one long side of the glass substrate along the end face. The softening point of the vitrified layer is about 400 ° C.

  Next, an aluminum sheet (1N30) having a length of 600 mm, a width of 150 mm, and a thickness of 80 μm was prepared, and this was placed on the first surface of the glass substrate so as to overlap the glass substrate.

An aluminum sheet having a two-dimensional island pattern on the surface was used. The islands are irregularly arranged, and each island has a convex shape. The maximum length L _max of the islands is 1800 μm, the minimum pitch of the islands is 400 μm, the maximum pitch is 3600 μm, and the average pitch Was used, and the unevenness difference H was about 102 μm in any island part.

  Next, this assembly was baked at 490 ° C. for 30 minutes in an air atmosphere to produce a joined body.

  FIG. 9 schematically shows the structure of the obtained joined body.

  As illustrated in FIG. 9, the bonded body 600 includes a glass solidified layer 660 disposed along the long side in the vicinity of one end surface 616 of the first surface 612 of the glass substrate 610. The bonded body 600 includes an aluminum sheet 655 disposed on the first surface 612 side of the glass substrate 610, and the glass substrate 610 and the aluminum sheet 655 are bonded to each other by the glass solidified layer 660.

  Next, the obtained bonded body 600 was cut at intervals of 50 mm in a direction perpendicular to the long side, and a plurality of strip-shaped samples having a length of 150 mm and a width of about 50 mm were manufactured.

  Next, the sample thus manufactured was heat-treated in the atmosphere. The heat treatment temperature of the sample was 360 ° C. (633 K), and the holding time was 0.17 hours. This heat treatment is performed to simulate the “decompression treatment” in the actual manufacturing process of the vacuum double-glazed glass, and this heat treatment is hereinafter referred to as “simulated heat treatment”.

  Thereafter, the obtained heat-treated sample was cut so as to have a width of 10 mm (the length remains 150 mm) to produce a test piece according to Example 1. At least 10 test pieces according to Example 1 were produced.

  For comparison, a sample that has not been subjected to simulated heat treatment (a strip-shaped sample having a length of 150 mm × a width of about 50 mm) is also cut to have a width of 10 mm (the length remains 150 mm), An unsimulated heat treatment test piece was prepared.

(Examples 2 to 17)
Test pieces according to Examples 2 to 17 were manufactured in the same manner as the test piece according to Example 1 described above. However, in Examples 2 to 17, different conditions from those in Example 1 were adopted as conditions (simulation heat treatment temperature and holding time) for the simulated heat treatment of the strip-shaped sample.

  Thereby, the test pieces according to Examples 2 to 17 were obtained.

  Table 2 below collectively shows the conditions of the simulated heat treatment employed in the test pieces according to Examples 1 to 17.

（健全性評価試験）
次に、前述の方法で製造した例１〜例１７に係る試験片の健全性を評価した。

(Soundness evaluation test)
Next, the soundness of the test pieces according to Examples 1 to 17 manufactured by the method described above was evaluated.

  The peel test method was used for evaluation of soundness. The peel test method was performed by a method based on JIS Z237.

  More specifically, the test piece according to each example is arranged substantially horizontally and fixed on the jig for tensile test movable in the substantially horizontal direction so that the aluminum sheet is on the upper side.

  In this state, the aluminum sheet of the test piece is pulled up at a speed of 1 mm / min in the vertical direction (substantially vertical direction) at room temperature. The tensile load generated at this time was measured, and the maximum load when the aluminum sheet peeled from the vitrified layer was measured. The test piece according to each example was measured 10 times, and the average value of the obtained maximum loads was defined as the peel strength of the test piece according to the example.

  In addition, the same measurement was implemented using the non-simulation heat processing test piece. As a result, the peel strength of the unsimulated heat treatment test piece was 14.4N.

(Judgment)
From the obtained peel test result, the soundness of the test piece according to each example was determined.

  At the time of determination, the case where the obtained peel strength is equal to or greater than 80% of the peel strength (14.4N) of the unsimulated heat treatment test piece was evaluated as good (good soundness). Moreover, it was set as x (unhealthy) when the obtained peeling strength fell more than 20% rather than the peeling strength (14.4N) of an unsimulated heat processing test piece.

  Table 2 described above collectively shows the determination results obtained in the test pieces according to the respective examples.

  From these results, it was found that in the test pieces according to Examples 1 to 10, the peel strength did not change much before and after the simulated heat treatment, that is, the peel strength was not significantly lowered by the simulated heat treatment. On the other hand, in the test pieces according to Examples 11 to 17, it was found that the peel strength was significantly reduced by performing the simulated heat treatment.

  This means that in the manufacturing process of vacuum double-glazed glass having a metal / frit composite sealing member, there is an appropriate condition for the decompression process, and the decompression process is performed under conditions other than such an appropriate condition. This suggests that the metal / frit composite sealing member may be defective (decrease in bonding force between members).

  In FIG. 10, the result of the soundness evaluation test obtained in the test piece which concerns on each example is shown collectively. In FIG. 10, the horizontal axis represents the simulated heat treatment holding time t (hour), and the vertical axis represents the simulated heat treatment temperature T (K).

  In FIG. 10, the conditions of the simulated heat treatment of the test piece according to each example are plotted. In particular, as a result of soundness evaluation, the test pieces according to Examples 1 to 10 in which ○ determination was obtained are plotted by ○ marks, and Examples 11 to 17 in which × determination was obtained as a result of soundness evaluation. The test piece according to is plotted with Δ marks.

  As shown in FIG. 10, it can be seen that the temperature and holding time of the simulated heat treatment increase, and the soundness evaluation result tends to be “x” determination, that is, the peel strength of the test piece tends to decrease.

In addition, FIG. 10 shows a straight line L1 indicating the boundary between “◯” and “x” of the determination result in the soundness evaluation test. The straight line L1 has a simulated heat treatment temperature T (K) and a holding time t (hour).

T = 620 × t− ^0.015 (2) Formula

It is represented by

  Therefore, it can be said that when the simulated heat treatment is performed under the conditions included on the straight line L1 or in the region below the straight line L1, a decrease in peel strength between the aluminum sheet and the vitrified layer can be significantly suppressed.

  This is because, under the assumption that the manufacturing process of the vacuum double-glazed glass having the metal / frit composite sealing member is included, the vacuum double-glazed glass is used under the condition that it is included in the region above or below the straight line L1. It means that the malfunction of a metal / frit composite sealing member can be significantly suppressed by carrying out the decompression process. That is, a vacuum double-glazed glass having a “sound” metal / frit composite sealing member is provided by performing a vacuum treatment of the vacuum double-glazed glass under the conditions satisfying the above-mentioned formula (1). Can be said to be possible.

  INDUSTRIAL APPLICABILITY The present invention can be used for vacuum double glazing and the like used for building window glass and the like.

DESCRIPTION OF SYMBOLS 100 Vacuum multilayer glass 110 1st glass substrate 112 1st surface 114 2nd surface 120 2nd glass substrate 122 3rd surface 124 4th surface 130 Gap part 150 Sealing member 160 1st glass solidification layer 165 Second glass solidified layer 155 Metal member 170 First surface of metal member 172 Second surface of metal member 190 Spacer 300 Second vacuum multilayer glass 310 First glass substrate 314 Second surface 320 Second Glass substrate 322 third surface 330 gap portion 350 seal member 355 metal member 360 first glass solidified layer 365 second glass solidified layer 370 first surface of metal member 400 third vacuum multilayer glass 410 first Glass substrate 414 second surface 420 second glass substrate 424 fourth surface 430 gap 450 Metal member 455 Metal member 460 First glass solidified layer 465 Second glass solidified layer 470 First surface of metal member 500 Fourth vacuum multi-layer glass 510 First glass substrate 516, 526 End surface 520 Second Glass substrate 530 Gap 550 Seal member 555 Metal member 560 First glass solidified layer 565 Second glass solidified layer 570 First surface 600 of metal member 600 Bonded body 610 Glass substrate 612 First surface 616 End surface 655 Aluminum sheet 660 Vitrified layer

Claims (8)

(A) laminating so that a gap is formed between the first and second glass substrates;
A step of forming a laminated body by disposing a frame-shaped metal member and a sealing member having first and second vitrified layers softened at a temperature of about 400 ° C. or more so as to surround the gap (B )When,
A step (C) of depressurizing the gap of the laminate under the following conditions;
A method for producing a vacuum double-glazed glass, comprising:
(Condition for decompression treatment) When the treatment temperature is T (K) and the holding time is t (hour),

T ≦ 620 × t− ^0.015 (1) (where 0.1 (hour) <t <100 (hour)) In the step (B), when forming the seal member,
The manufacturing method according to claim 1, further comprising: heating the first and second vitrified layers to a temperature in the range of 470 ° C. to 530 ° C. The step (B)
(A) The first glass solidified layer is formed in a frame shape on the first surface of the first glass substrate, and the second glass plate is formed on the third surface of the second glass substrate. Forming a vitrified layer; and
(B) preparing the frame-shaped metal member having a first surface and a second surface;
(C) The first glass substrate, the metal member, and the second glass substrate are laminated in this order, and the first glass substrate has the first glass solidified layer on the first surface of the metal member. Placed in contact with
The second glass substrate is disposed such that the second vitrified layer is in contact with the second surface of the metal member to form an assembly; and
The manufacturing method of Claim 1 or 2 which has these.   The manufacturing method according to claim 3, wherein when the assembly is viewed from the stacking direction, the second vitrified layer is disposed so as to be displaced from the first vitrified layer.   The manufacturing method according to claim 1, wherein the metal member is made of aluminum or an aluminum alloy.   The manufacturing method according to claim 1, wherein the first and / or second vitrified layer is made of glass containing bismuth. The step (C)
The manufacturing method according to claim 1, further comprising: sucking the gap using a through opening provided in the first or second glass substrate.   The manufacturing method according to claim 7, wherein the step (C) is performed in a vacuum chamber.

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