JPH05124839A - Heat insulating glass which can be thermally worked - Google Patents

Abstract

PURPOSE:To easily obtain the subject glass by forming and laminating metallic or nitride thin films having a thermal ray reflective function on the surface of a transparent glass base plate in such a manner that these films are sandwiched by nitride thin films of Si, Al, etc. CONSTITUTION:The heat insulating glass which can be thermally worked is produced by forming and laminating at least one layer of the metallic or nitride thin films consisting of Ti, Ta, Cr, Zr, Ni or the alloys thereof and having 3 to 100nm film thickness on the surface of the transparent glass base plate in such a manner that these films are sandwiched by the nitride thin films consisting of the Si, Al, or alloys thereof and having 5 to 30nm film thickness to form the multilayered films. A transparent dielectric thin film having 10 to 150nm film thickness is preferably formed and laminated as the substrate material of the multilayered films or/and the outermost side surface layer which is the coating layer of the multilayered films. The resulted heat insulating glass does not generate a change in the transmittance of visible light, transmittance of sunshine, color tones, durability, etc., even if the glass is subjected to thermal hardening and bending in the air.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a heat ray reflecting ability to effectively shield solar radiant energy, and in particular, when film formation is followed by quenching treatment and / or heat bending forming treatment, heat insulation thereof is performed. The present invention provides a thermally processable heat-insulating glass which can substantially maintain optical properties such as performance, color tone and transparency and is useful for construction or automobiles.

[0002]

2. Description of the Related Art In recent years, bent glass and tempered glass of various shapes and sizes having heat insulating properties in window glass for buildings and vehicles have excellent design and safety, and have a better society. It is rapidly increasing due to the ability to obtain the environment and the more effective cooling, etc., and better habitability. For example, corners and doors are being used more frequently. There is.

On the other hand, as the heat insulating glass, a metal film of SUS (stainless steel), Cr, Ti or the like and a nitride film due to their color tone and thermal characteristics are mass-produced and cost-effective. Films have been put to practical use in combination with a transparent interference film by the sputtering method.When using these films for bent glass and tempered glass, these heat ray reflection functional films are sputtered on glass that has been bent or tempered in advance. Although it was obtained by forming a film in, the bending glass or tempered glass is prepared in advance,
Since the film is formed afterwards, there is a large loss of quality, such as process loss in terms of manufacturing schedules, difficulty in workability during film formation, and film defects such as uneven film thickness. Therefore, there is a need for a manufacturing method and product that can be stocked with flat insulating glass with a film as a normal product in advance and, if necessary, can be cut into a predetermined shape and then subjected to thermal strengthening or heat bending. It is rare.

However, in the conventional film forming structure, the film reacts with, for example, oxygen in the atmosphere during the thermal strengthening process or the heat bending process to oxidize, so that the film becomes an oxide and the permeability increases, and Due to the change in the optical characteristics of the, the color tone changes and the heat insulating property is greatly reduced, and there is a stable and reliable and high quality, for example, visible light transmittance before and after the treatment or processing. It was difficult to achieve a change of 10% or less.

On the other hand, for example, a heat-reflecting film made of a noble metal is a heat-resistant metal A in order to prevent oxidation during heat treatment.
Although a method of sandwiching with 1, 1, Ni, NiCr or the like to form a barrier layer, or a method of thickly sandwiching Zn, Ti or the like so as not to reach the heat ray reflective film even if oxidation occurs, these methods have been tried. Since the purpose of the barrier layer is to protect the heat ray reflective film by oxidizing the metal film, it is unavoidable that the visible light transmittance is increased by 5 to 10% or more and the color tone is changed. Therefore, for example, it is difficult for the products before and after thermal processing after film formation to be used on the same wall surface of the building at the same time, with sufficient resolution or discomfort in color tone, so that the products can be used with peace of mind without concern. It is in.

For example, Japanese Patent Laid-Open No. 63-265844 discloses a method for producing a bent heat ray reflective glass in which an absorption film containing a metal nitride film is formed on the surface of a glass substrate and then bent in a non-oxidizing atmosphere. That the non-oxidizing atmosphere is an atmosphere consisting of one or more selected from the group consisting of N ₂ , Ar and H ₂ , and the metal nitride is chromium nitride, titanium nitride or titanium aluminum nitride. It is disclosed that the absorbing film is composed of a metal nitride film and a metal oxide film, titanium oxide or tin oxide formed on the metal nitride film.

Further, for example, in Japanese Patent Laid-Open No. 63-265846, a chromium nitride film is formed on the surface of a glass substrate, and at least one selected from the group consisting of aluminum, aluminum oxide, aluminum nitride and aluminum oxynitride. A bent heat ray reflective glass obtained by bending a heat ray reflective glass on which one kind of coating is formed, and a method for producing the same are disclosed.

Further, for example, in Japanese Patent Application Laid-Open No. 1-206035, a base material having visible light transparency, a heat ray reflective layer made of a noble metal formed on the base material, and formed on the heat ray reflective layer. And a heat ray reflector having visible light transmittance, which comprises a metal mainly composed of aluminum or a coating layer composed of a nitride or oxynitride of a metal mainly composed of aluminum and silicon, and the base material and the heat rays. A transparent dielectric layer made of a metal oxide, a nitride or an oxynitride may be formed between the reflective layer and the reflective layer, and a transparent dielectric layer made of a metal oxide is formed on the coating layer. What has been done is disclosed.

[0009]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in the manufacturing method disclosed in Japanese Patent Laid-Open No. 63-265844, at least in the bending apparatus, in order to achieve a non-oxidizing atmosphere, a vacuum exhaust apparatus is used. In addition, an inert gas supply device etc. are required, resulting in an extremely expensive bending apparatus and method, the bending heat ray reflection glass also becomes expensive, and it becomes largely permeable in the heating bending forming process in air. It is apt to cause a change in color tone and a decrease in heat insulating property.

Further, for example, in Japanese Patent Laid-Open No. 63-265846 and its manufacturing method, even if a metal film such as an aluminum film is coated as a protective film, it is nitrided when heat-treated in the air, for example. Oxidation of the chromium film is unavoidable, the visible light transmittance or the visible light reflectance is largely changed, and a feeling of color discomfort with that without heat treatment is unavoidable, and it cannot be used in the same place.

Further, for example, in the heat ray reflective plate having visible light transparency disclosed in Japanese Patent Laid-Open No. 1-206035, the sputtering atmosphere can be an oxygen-free or trace-amount inert gas or nitrogen gas atmosphere, Although it is not necessary to form a metal layer for preventing deterioration and deterioration of the heat ray reflective layer made of a noble metal, it may be said that the constituent thin film described in the publication may be subjected to thermal processing after film formation. However, it is difficult to say that silver can be sufficiently protected and prevented from being oxidized, and that visible light transmittance, color tone or heat insulation performance, durability, chemical resistance, etc. can be sufficiently satisfied and can remain unchanged. ..

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has SUS, Ti, Ta, Cr, Zr, Ni or alloys thereof having a heat ray reflecting function. Skillfully combining at least one layer of a metal or nitride thin film made of, a nitride thin film of Si, Al or an alloy thereof having a barrier function, and a transparent dielectric thin film, for example, as substantially five layers. By coating and laminating a multilayer film, a multilayer film that does not depend on the amount of oxygen in the processing furnace even in thermal processing and has heat resistance, chemical resistance, durability, wear resistance, etc. The glass plate with a multilayer film can be stably and efficiently formed on a large-area glass plate for a long time, and the obtained glass plate with a multilayer film can be subjected to a quenching treatment such as a thermal strengthening treatment or a treatment under various conditions as well as in the air. Together to bending processing can be freely appropriately, and the change in visible light transmittance and heat insulating performance is within always about 10% before and after the treatment process, 5
%, It can be achieved satisfactorily, and changes in color tone can also be significantly reduced in a stable and reliable manner, and changes in its optical properties, durability, and wear resistance are insignificant, and high. It is intended to provide a thermally processable insulating glass having high workability, high efficiency and high quality.

That is, according to the present invention, SUS, Ti, Ta, C having a film thickness of 3 to 100 nm is formed on the surface of a transparent glass substrate.
A metal or nitride thin film of at least one layer made of r, Zr, Ni or an alloy thereof, and having a film thickness of 5 to 30 nm.
2. A thermally processable insulating glass comprising at least a multi-layered film in which a film is laminated so as to be sandwiched by a nitride thin film of Si, Al or an alloy thereof.

In the heat-processable heat-insulating glass, a film thickness of 10 to 10 is provided as a base material of the multilayer film and / or an outermost surface layer which is a coating layer of the multilayer film.
The above-mentioned thermally processable heat-insulating glass comprising a multilayer film formed by laminating a transparent dielectric thin film of 150 nm. . And the transparent dielectric thin film is made of Ti, Sn, T
The above-mentioned thermally processable heat-insulating glass comprising an oxide thin film or an oxynitride thin film of a, Cr, Zr, or Si.

Further, the above-mentioned heat-insulating glass which can be thermally processed is characterized in that the heat-insulating glass is formed by laminating and forming the above-mentioned multilayer film, followed by quenching and / or thermal bending. Furthermore, after the quenching process and / or the heat bending process, the visible light transmittance of the heat insulating glass changes within 10% before and after the thermal process. It provides each possible insulating glass.

Here, as described above, the film thickness is 5 to 30.
The reason for using the nitride thin film of Si, Al or its alloy of 5 nm is that the thin film is almost transparent in the visible region.
If the thickness is at least nm, the above SUS,
It serves as a barrier layer for protecting at least one metal or nitride thin film made of Ti, Ta, Cr, Zr, Ni or an alloy thereof, and nitride of Si, Al or an alloy thereof by oxygen. Even if the thin films are oxidized, they are still nearly transparent with only a slight decrease in refractive index. Therefore, such a change in the refractive index does not significantly affect the optical interference, and as a result, an extremely small change can be obtained. When it exceeds 30 nm, the sputtering rate of the nitride thin film of Si, Al or its alloy is relatively low, and when it is too thick, the economical efficiency is deteriorated, and the effect as a barrier is not improved so much, and the maximum thickness is 30 nm.
There is enough.

The nitride thin film of Si, Al or its alloy is sandwiched between SUS, Ti, Ta, Cr and Z due to the movement of oxygen during the heat treatment.
The purpose of this is to prevent oxidation of at least one metal or nitride thin film made of r, Ni or an alloy thereof by sandwiching, and in particular, the nitride thin film of Si, Al or an alloy thereof must be Ar + N ₂ It is necessary to sputter in atmospheric gas. Further, these barrier-like thin films are not sufficient in terms of moisture resistance and chemical resistance, especially when used as a single plate, and an overcoat layer, for example, a transparent dielectric layer, of about 10 nm is formed thereon. It is necessary to do the above. Further, unless sandwiched, the above-mentioned SUS, Ti, and T during heat treatment are processed by moisture or oxygen from the interface or outer surface of the glass substrate.
Since at least one metal or nitride thin film made of a, Cr, Zr, Ni or an alloy thereof is altered,
It is difficult to obtain a material having a small change in optical characteristics such as visible light transmittance, and the necessary SUS, Ti, Ta, Cr, Z
It is necessary to sandwich at least one layer of metal or nitride thin film made of r, Ni or an alloy thereof.

Further, the SU having a thickness of 3 to 100 nm is used.
The reason why at least one layer of metal or nitride thin film made of S, Ti, Ta, Cr, Zr, Ni or an alloy thereof is used is that it is relatively stable and has a heat ray reflecting function. If it is less than 3 nm, the visible light transmittance becomes too high and the heat insulating property is low, and if it exceeds 100 nm, the transparency deteriorates and it becomes difficult to obtain the original function of the window glass such as daylight. There is also a relationship with the transmittance and the visible light reflectance, and it is set to 3 to 100 nm. The film thickness is preferably about 5 to 80 nm.

Further, the reason why the transparent dielectric thin film having a film thickness of 10 to 150 nm is used is as follows.
It is not sufficient in terms of moisture resistance and chemical resistance, and when a film-formed glass substrate after film formation is stored, for example, in a harsh storage environment, deterioration occurs due to alteration of each thin film. This is because there is a possibility that it may be difficult to prevent, and a film thickness of 10 nm or more is necessary, and if it exceeds 150 nm, it cannot be said to be economically sufficient. Further, the control of the color tone due to the interference is also performed at about 15 to 100 nm, so that the preferable film thickness range is from this range.

Furthermore, after the above-mentioned multi-layered film is laminated and formed, when it is subjected to quenching treatment and / or heat bending forming, the treatment or / and processing is carried out particularly in a temperature range of 550 to 680 ° C. Yes, within this temperature range, SUS, Ti, Ta,
At least one layer of a metal or nitride thin film made of Cr, Zr, Ni or an alloy thereof is a nitride thin film of Si, Al or an alloy thereof, and a transparent dielectric thin film is used for preventing oxidation, durability or chemical resistance. This is because it can sufficiently exhibit its function as a protective film. The preferred temperature range is 580-6
It is 50 ° C.

Furthermore, it is the high temperature thermal treatment that the change in visible light transmittance of the heat insulating glass before and after the treatment and / or bending is within 10%. The change in color tone and heat insulating property after treatment is sufficiently small, and it is comparable to the heat-insulating glass before heat treatment.For example, the high temperature heat treated glass and the heat treated glass do not interfere with the same building surface. This is because it can be used without being used. A more preferable change in visible light transmittance is within about 5%.

Further, the transparent glass substrate may be a so-called inorganic transparent plate glass or a colored glass, and is not particularly limited in its kind, color tone, shape, etc., and further as a bent plate glass. Needless to say, it can be used as various tempered glass, strengthened glass, flat plate or single plate, and can also be used as multi-layer glass or laminated glass.

[0023]

As described above, the heat-processable heat insulating glass of the present invention has a relatively stable SUS, Ti, Ta, Cr, Zr, Ni or a combination thereof having a heat ray reflecting function on a transparent glass substrate. At least one layer of metal or nitride thin film made of an alloy is laminated at least so as to be sandwiched between nitride thin films of Si, Al or its alloy having a barrier function, and is further appropriately used as a base material and / or an outermost surface layer. , Skillfully combining a transparent dielectric thin film having durability, chemical resistance and abrasion resistance, for example, a multilayer film consisting of substantially 5 layers is efficiently laminated on the surface of the glass substrate both on the device and in manufacturing. By forming a film, oxidation of the thin film having the heat ray reflecting function is likely to occur even during thermal processing at a relatively high temperature. The protective thin film and these barrier thin films complement each other, exhibiting particularly excellent antioxidant properties, chemical resistance, abrasion resistance, durability and heat resistance, etc. During cutting, quenching, and / or heating and bending, or even after that, there is no risk of occurrence of defects, breakage, or destruction. In addition, mass production is of course possible as well as a small number of types. It is excellent in productivity, and can be used in high-temperature heat treatment in air, for example, and in terms of durability, as well as optical characteristics such as transparency, heat insulation and color tone after that. The change is remarkably small, and it can be said that it is not an exaggeration to say that it is unchanged, and even when it is installed in a building, the above-mentioned thermal Etc. can be freely and appropriately selected employed interchangeably without and limitation of insulating glass which is not subjected to those subjected to engineering process, it is to provide a useful thermal processable insulating glass.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.

Example 1 A float glass plate (FL6) having a size of 300 mm × 300 mm and a thickness of 6 mm was sequentially washed with a neutral detergent, water rinse, alcohol and dried, and then set in a vacuum chamber of a DC magnetron sputtering apparatus. Sn, Si ₃ N
_4. Set so as to be able to reciprocate upwards facing the Cr target, and then, inside the chamber with a vacuum pump, approximately 5 × 10 ⁻⁶ T
After degassing up to orr, Ar gas and oxygen gas were introduced into the vacuum chamber to maintain the degree of vacuum at about 2 × 10 ⁻³ Torr, and a power of about 0.5 kw was applied to the Sn target. In the DC reactive sputtering with the mixed gas,
200mm speed above the Sn target
By transporting the glass plate at / min, about 2
A 0 nm SnOx thin film was formed as the first layer. After the film formation was completed, the application to the Sn target was stopped.

Then, the inside of the chamber is vacuum-pumped to about 5 × 1.
After degassing to 0 ^-6 Torr, a mixed gas of Ar and nitrogen was introduced into the vacuum chamber to adjust the degree of vacuum to about 3 × 10 ^-3 Torr.
Held in, the Si ₃ N ₄ by applying a power of about 1.0kw targeting, through the RF reactive sputtering by the mixed gas, the Si ₃ N ₄ the glass plate at the target upward at a speed of about 100 mm / min Was carried to form a SiNx thin film of about 10 nm as a second layer. After the film formation was completed, the application to the Si ₃ N ₄ target was stopped.

Then, after degassing the inside of the chamber to about 5 × 10 ^-6 Torr with a vacuum pump, A is placed in the vacuum chamber.
r gas was introduced, the degree of vacuum was maintained at about 3 × 10 ⁻³ Torr, and about 0.5 kw of electric power was applied to the Cr target, and the DC sputtering by the gas was performed at a speed of about about above the Cr target. By transporting the glass plate at 1000 mm / min, Cr of about 5 nm can be obtained.
A thin film was formed as the third layer. After the film formation is completed, the Cr
The application to the target was stopped.

Then, successively, similarly as in the case of the second layer, a SiNx thin film having a film thickness of about 10 nm is formed as a fourth layer, and further in the same manner as the case of the first layer, and the transport speed is the same. By setting only about 400 mm / min, a SnOx thin film with a film thickness of about 10 nm is used as the fifth layer.
A film was formed as shown in to obtain a heat-processable heat-insulating glass.

The optical characteristics of the obtained five-layer laminated film were measured by a Hitachi Model 340 self-recording spectrophotometer, and then inserted into a heating furnace, heated from room temperature to about 600 ° C. in about 1 hour, and then about 60 ° C.
It was held at 0 ° C. for about 10 minutes and was subjected to a bending process, and then naturally cooled. The optical properties after the heat bending process were measured in the same manner as above.

As shown in Table 1, the optical properties of the obtained bent insulating glass before and after the heating and bending process are, for example, a change in visible light transmittance of 2.3% and a change in solar radiation transmittance of 0.7%. The color tone was the same, and there was no significant change, which was extremely excellent.

Examples 2 to 4 Each thin film having a predetermined film thickness shown in Table 1 was formed under the same conditions and operations as in Example 1 to form a multilayer laminated film having the film structure shown in Table 1 on a glass substrate. .. Then, as in Example 1, changes in optical properties before and after the heat bending were measured.

As shown in Table 1, the bending insulating glass thus obtained had little change in optical characteristics as in Example 1, for example, visible light transmittance change of 2.2 to 1.6%, and solar radiation transmission. The change in the ratio was 0.7 to 0.1% and the respective color tones were unchanged, and the changes in various characteristics were remarkably small, and the color tone and the like did not feel uncomfortable.

Example 5 Each thin film having a predetermined film thickness shown in Table 1 was formed under the same conditions and operations as in Example 1, and as shown in Table 1, the first layer was made of a nitride or the like. The multilayer laminated film having the changed film structure was formed on the glass substrate. Then, as in Example 1, changes in optical properties before and after the heat bending were measured.

As shown in Table 1, the obtained bent insulating glass showed little change in optical characteristics as in Example 1. For example, change in visible light transmittance was 3.1%, and change in solar radiation transmittance was 3.1%. 1%, each color tone is unchanged, and the changes in various characteristics are somewhat numerically large, but it is significantly smaller than in the past and no discomfort is seen in the color tone.

Comparative Examples 1 to 3 As shown in Table 1, using a metal thin film which is not a noble metal, a transparent dielectric thin film or a nitride is used to form three layers under the same conditions and operations as those of the examples. A comparison before and after the heat bending process is performed, but the change in the visible light transmittance is 3 before and after the process due to the action estimated to be due to the oxidation reaction or the like.
5.2 to 19.3%, change in solar radiation transmittance is 33.7 to 1
7.8%, the change in color tone is large and the transparency is deteriorated and the heat insulating property is deteriorated. It is also difficult to simultaneously use those having a large optical discomfort before and after the construction, and the like. It is not an exaggeration to say that it is not possible to simultaneously adopt the one that is thermally processed and the one that is not thermally processed, which is clearly inferior to the thermally processable insulating glass of the present invention.

[0036]

[Table 1]

[0037]

As described above, the present invention has SUS, Ti, Ta, Cr, Zr, N having a heat ray reflecting function.
At least one layer of a metal or nitride thin film made of i or an alloy thereof is sandwiched between nitride thin films of Si, Al or an alloy thereof, and is skillfully combined with a transparent dielectric thin film to form, for example, substantially five layers. By forming a multilayer film on the surface of a glass substrate efficiently in terms of both device and manufacturing, it is possible to perform thermal quenching processing and heat bending processing in air after the film formation. Also, the visible light transmittance, solar radiation transmittance, color tone, and other optical characteristics before and after the change can be significantly reduced, and the transparency and color tone can be reduced. It has no discomfort and retains heat insulation performance, and can be thermally processed if necessary,
The present invention provides a thermally processable insulating glass that is useful for construction, automobiles, etc. and that can be commercialized at a relatively low cost without waste.

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Claims (5)

[Claims] 1. A transparent glass substrate having a film thickness of 3 to 1 on the surface thereof.
A metal or nitride thin film of at least one layer made of 00 nm SUS, Ti, Ta, Cr, Zr, Ni or an alloy thereof is sandwiched between nitride thin films of Si, Al or an alloy thereof having a thickness of 5 to 30 nm. A heat-processable insulating glass comprising at least a multilayer film formed by stacking such coatings. 2. In the heat-processable heat-insulating glass, a film thickness of 10 to 150 is used as a base material of the multilayer film and / or an outermost surface layer which is a coating layer of the multilayer film.
The thermally processable insulating glass according to claim 1, which is composed of a multilayer film formed by laminating a transparent dielectric thin film of nm. 3. The transparent dielectric thin film comprises Ti, Sn, T
The thermally processable insulating glass according to claim 2, which is made of an oxide thin film or an oxynitride thin film of a, Cr, Zr, or Si. 4. The thermally processable glass according to claim 1, wherein the heat insulating glass is formed by performing a quenching process and / or a thermal bending process after stacking the multilayer films. Insulated glass. 5. The change in visible light transmittance of the insulating glass before and after the thermal processing after the quenching treatment and / or the heat bending forming process is within 10%. Thermally processable insulating glass as described.