JPH064498B2 - Insulated glass plate and its colored glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is intended to improve the heating and cooling effect and to have a relatively low visible light transmittance of, for example, about 50% or less, Moreover, it relates to a single-plate heat insulating glass plate having excellent chemical resistance and abrasion resistance and its colored glass, and is particularly useful as a veneer heat-reflecting glass for buildings or its colored glass formed by laminating a sputtered film. Of course, it is also particularly useful as a heat insulating glass for vehicles, especially when it is viewed from the glass side or the heat insulating glass of the veneer for vehicles with a relatively low visible light transmittance such as sunroof, side or window glass for doors. The present invention provides a single-plate heat-insulating glass plate and a single-plate heat-insulating color glass plate that are useful as a single-plate heat-insulating colored glass for vehicles exhibiting a color tone.

[Prior Art] In recent years, for example, in high-rise buildings, high-performance heat-insulating glass having a high proportion of reflection on the outer surface has been increasingly adopted due to the harmony with the surrounding environment of the building. Method, spatter method, etc., but the sputter method is being adopted as a manufacturing method that can freely adjust the reflection color tone and is suitable for the production of a wide variety of products, and its application is being broadly expanded not only to construction but also to vehicles. In addition, it has been proposed that even if it is used as a single plate, it has weather resistance and durability.Among them, a SUS / TiN film or the like is formed on a transparent substrate as a building insulating glass formed by the sputtering method. It is known to obtain silver-based or gold-based products by forming them. For example, Japanese Patent Laid-Open No. 63-242948 describes a heat-reflecting glass, which is formed by laminating a metal film, a nitride film, and an oxide film on a glass substrate surface in this order from the substrate side. A heat ray reflective glass having a light reflectance of 20% or less is disclosed, and as a metal film, Cr, Ti, Zr,
Hf, Ta, Si and their alloys, and those selected from stainless steel, nitrides such as Ti, Zr, Ta, Cr, Hf nitrides and their composite nitrides, and oxides. The material is selected from oxides of Ti, Cr, Zr, Si, Al, Hf, Ta, Nb and composite oxides thereof, and specifically, glass substrate / chromium film / titanium nitride film / Titanium oxide film or glass substrate / stainless steel film /
The structure of the titanium nitride film / titanium oxide film and the like is described, and the one that is considered to have a silver color is disclosed. Further, JP-A-64-14130 describes a heat ray reflective glass, and a nitride layer (for example, TiN film) and an oxide layer (for example, TiO 2) are sequentially formed on a glass substrate from the substrate side.
₂ , SnO ₂ etc.), metal layer (eg SUS, Ti, Cr etc.), oxide layer (eg TiO ₂ , SnO ₂ ) or sequentially from the substrate side eg TiO ₂ layer, TiN layer, TiO ₂ layer, SUS layer , The TiO ₂ layer is laminated on the glass substrate, the reflection color on the glass substrate is gold, and the reflection color on the film formation surface side is neutral, and the reflectance is 20%.
The following is disclosed. Further, Japanese Patent Application No. 1-53567, which has already filed by the present applicant, describes a heat-reflecting glass plate, such as G / SUSNx / TiN or TiNx.
Oy / TiO ₂ multi-layer film, or even TiO ₂ film surface with Al
We have proposed a structure in which SiNxOy is laminated and has various silver color tones that can be used even with a single plate.
Furthermore, JP-A-63-247352 describes a transparent coating by reactive sputtering, which is a coated article having a structure including a substrate, a coating film on the substrate, and a protective film on the coating. , The target whose protective film is an alloy containing aluminum and silicon is 10% in reactive gas, especially O ₂ % in N ₂ + O ₂ gas.
It is described that it is a film containing an amorphous layer of a reaction product formed by sputtering in about 30%,
Specifically, a protective film of Al.SiRx (however, R; for example, 0.30 ₂ + 0.7N ₂ etc. reactive gas) is disclosed.

[Problems to be Solved by the Invention] In the conventional one described above, for example, in Japanese Patent Application Laid-Open No. 63-242948, the visible light reflectance when viewed from the glass side is likely to be large and the film as a whole is It is hard to say that it is sufficiently durable in terms of adhesion, abrasion resistance, chemical resistance, etc., and further improvement is desired as a heat insulating window glass for veneer for construction, especially, for example, heat insulating window for automobiles. It is hard to say that it can be sufficiently adopted for doors or side windows used as a single plate among glass, and the one described in JP-A-64-14130 uses a SUS film as one of the multilayer films. However, it is hard to say that it has a gold color tone when viewed from the glass surface, and in particular, it is difficult to say that the change in haze value and chemical resistance are sufficiently satisfactory, and it is described in Japanese Patent Application No. 1-53567. The ones listed are more excellent in wear resistance, corrosion resistance and weather resistance than those described in both of the above-mentioned publications, and can be said to be sufficiently useful as a heat ray reflective glass for construction veneer. However, it is hard to say that the heat ray-reflecting glass for a vehicle veneer is still sufficiently satisfactory in long-term durability or in harsh environments or conditions, and further it is disclosed in JP-A-63-247352. The above-mentioned ones have improved wear resistance and chemical resistance as the outermost surface film on the surface, but it cannot be said that the laminated films as a whole have sufficiently excellent weather resistance. It is a thing.

In any case, the veneer insulating glass and the colored glass thereof are sufficiently excellent in heat insulating performance, abrasion resistance, chemical resistance, weather resistance, etc., and have sufficient desired long-term durability. It was hard to say that.

[Means for Solving the Problems] The present invention has been made in view of the above-mentioned drawbacks of the related art, and a specific thin film having a specific thickness is provided on the glass surface side and the outermost surface side, and at least SUS film or SUSNx (usually 0 <x ≦ 1) film and TiNx (0 <x ≦ 1) film, and
By combining and stacking TiOx (0 <x ≦ 2) films as appropriate, wear resistance superior to conventional ones,
A single insulating glass plate that has chemical resistance and weather resistance and can be satisfactorily adopted as a single-plate vehicle window glass that is effective for air conditioning and heating, and that can present a silver color tone on the glass surface and its A colored glass is provided.

That is, according to the present invention, one surface of the transparent glass substrate has a thickness of 100 as the first layer and the fifth layer from the glass surface.
~ 1000Å SiOx (1 <x ≤ 2) or Al-SiOx (2 <x
≤7 / 2) film, SUS or SUSNx (0 <x ≤ 1) film with a film thickness of 50 to 100Å as the second layer, and film thickness of 200 to 40 as the third layer
0 Å TiNx (0 <x ≤ 1) film, 0 <thickness ≤ 2 as the fourth layer
A single heat insulating glass plate, which is obtained by laminating and coating each sputtered film of TiOx (0 <x ≦ 2) film of 00Å. Also, on one surface of the transparent glass substrate, SiOx (1 <x ≦ 2) or Al having a film thickness of 100 to 300Å as the first layer from the glass surface.
・ SiOx (2 <x ≦ 7/2) film, the thickness of the second layer is 50-100
Å SUS or SUSNx (0 <x ≤ 1) film, the third layer has a film thickness of 200 to 400 Å TiNx (0 <x ≤ 1) film, and the fourth layer has 0 <film thickness ≤ 200 Å TiOx (0 <X ≦ 2) film, fifth
SiOx (1 <x ≤ 2) with a thickness of 300-500Å as a layer or
A single-plate heat-insulating glass plate characterized by a laminated coating of sputtered Al / SiOx (2 <x ≦ 7/2) films and a reflection color tone seen from the glass surface side being silver. . Furthermore, on one surface of the transparent glass substrate, SiOx (1 <x ≦ 2) or Al.SiOx having a film thickness of 100 to 300Å as the first layer from the glass surface.
(2 <x ≤ 7/2) film, SU with a thickness of 50-100 Å as the second layer
S or SUSNx (0 <x ≤ 1) film, the thickness of the third layer is
200-400Å TiNx (0 <x ≤ 1) film, the fourth layer is 300-500 Å SiOx (1 <x ≤ 2) or Al-SiOx (2
<X ≦ 7/2) A single heat-insulating colored glass plate, which is formed by laminating and coating each sputtered film of a film and has a reflection color tone of silver color when viewed from the glass surface side. Furthermore, in the above-mentioned single plate heat insulating glass plate and single plate heat insulating color glass plate, in a Taber test using a wear wheel by CS-10F,
The amount of change in the haze value after 1000 rotations is within 5% of that before the test, and the above-mentioned single-plate heat-insulating glass plate and single-plate heat-insulating colored glass plate are provided, respectively.

Here, as described above, the first layer and the fifth layer are arranged from the glass surface.
SiOx (1 <x ≤ 100-1000 Å each as a layer
2) or Al.SiOx (2 <x ≦ 7/2) film is used because it is transparent in order to relieve the stress generated between the transparent substrate and the third layer film and enhance the adhesion of the film. SiOx which is a part of the composition component of the substrate (hereinafter, the range of x of the SiOx is 1 <x ≦ 2)
Or Al.SiOx (hereinafter, the range of x of the Al.SiOx is 2 <x ≦
7/2) In order to improve wear resistance and chemical durability especially as the 5th layer, which is the outermost surface layer, and exerts adverse effects such as stress development on the adhesion of each of the lower layers. That is, since the above-mentioned SiOx or Al.SiOx film is used in order to sufficiently improve various durability as a whole laminated film, it is possible to achieve the above-mentioned effects in a stable and reliable manner, and considering the productivity. It is necessary to have a film thickness of 100 to 1000Å, and a preferable film thickness for the fifth layer is about 200 to 800Å, and more preferable is
250 to 700Å. Furthermore, as an interference layer with a low refractive index, it contributes to the color tone though it causes interference with the thin film of the constituent layers, and it is seen from the glass surface side by matching with each of the above-mentioned SUS, TiNx, and TiOx layers that are the structure of the intermediate layer. The reflected color tone is a neutral color that does not change much before the sputtered film is formed, that is, a so-called silver color tone, which is weather resistant and durable with almost no change in the optical characteristics of the conventional components. Since it is possible to improve only the performance, it is most effective that the thickness of the SiOx or Al.SiOx layer is 100 to 300Å as the first layer and 300 to 500Å as the fifth layer. is there. Next, as the second layer, SUS or SUSNx (0 <x ≤ 1) with a film thickness of 50 to 100 Å
The reason why the film is used is that not only the adhesion but also the chemical resistance is excellent among the metal films, and in particular, the ratio of SUSNx (N ₂ : Ar, which is a nitride of SUS, of 1: 1 to 1: 0). By sputtering in an atmosphere of, x is usually 0 <x
≦ 1, and the range of x of the nitride will be referred to below.)
This tendency is stronger in the case of the film, especially the acid resistance is improved, and the strength of the film itself is improved, and the reflection color tone shows a silver color system when viewed from the glass surface side. Is necessary for the third layer to have a film thickness of 200 to 400
Å TiNx (hereinafter, the range of x of TiNx is 0 <x ≦ 1) film, and the fourth layer is 0 <thickness ≦ 200Å TiOx (hereinafter, the range of x of TiOx is 0 <x ≦ 2) film or Since the fourth layer film is appropriately laminated and coated, the layers work together to assist in adjusting adhesion, film strength, weather resistance, and as an interference film in color tone and visible light transmittance. In particular, the third and fourth layers can have variations in color tone as viewed from the film surface side.

Regarding the film thickness of these intermediate layers, the second layer of SUS or SUSNx film has a thickness of 50 to 100Å and the third layer of TiNx film has a thickness of 200 to 400.
Å, the 4th layer TiOx film is combined with 0 <thickness ≤ 200Å and laminated and coated to provide better wear resistance, chemical resistance, weather resistance and other strength of the entire film, as well as the desired silver color. It is necessary and most preferable in order to obtain a system color tone with high productivity. Even when the TiOx film of the fourth layer was not provided, each of the above strengths was superior to the conventional one.

It goes without saying that any transparent or colored inorganic or organic glass substrate can be used as the transparent glass substrate. It goes without saying that the above-mentioned single-plate heat insulating glass plate and its colored glass cannot be used by being adopted as, for example, double glazing or laminated glass.

[Operation] As described above, the single insulating glass plate and the colored glass thereof of the present invention are provided with a specific thin film having a specific film thickness on the glass surface side and the outermost surface side, and at least SUS or SUS.
The Nx film, TiNx film, and TiOx film are combined and laminated as appropriate, so that the visible light transmittance is relatively low, for example, around 50% or less, and the amount of change in haze due to the Taber test as abrasion resistance. Can be reduced to 5% or less, and the adhesion between the films of each layer can be enhanced. Corrosion by acids or alkalis is improved to improve chemical resistance. It is excellent in weather resistance, such as eliminating the need to attach a sheet to prevent deterioration and scratches, and also improves productivity and workability, which can be sufficiently adopted as a single plate. In addition, it provides a moderate interference effect, has a heat insulating function, and can develop a silver color tone when viewed from the glass side, providing high safety and comfort. Become shall, in the architectural window glass, of course, sunroof also as a window glass for a vehicle,
It is possible to provide a single-plate heat insulating glass plate and its colored glass that can be sufficiently used even in a side or door glass, especially in a part that is operated up and down.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the embodiment.

Example 1 Transparent glass substrate (FL6) having a size of 600 × 600 mm ² and a thickness of 6 mm
Is washed with a neutral detergent, rinsed with water, isopropyl alcohol, dried, and then set so that it can reciprocate upwards facing the targets of SiO ₂ , SUS, and Ti set in the vacuum chamber of the magnetron reactive sputtering device. Then, the inside of the tank is about 5 × 10 ⁻⁶ To with a vacuum pump (not shown).
After deaeration to rr, the same amount of Ar and O ₂ gas was introduced into the vacuum chamber to maintain the vacuum degree at about 2 × 10 ^-3 Torr, and RF power of about 2.5 KW was applied to the SiO ₂ target. And O ₂ gas (however, Ar and O
The flow rate ratio of the _two gases may be in the range of 1: 0 to 0: 1. During the RF magnetron sputtering by the method (1), the SiOx thin film having a thickness of about 300Å was formed by transporting the plate glass above the SiO ₂ target at a speed of about 50 mm / min. After the formation of the SiOx film is completed, the application to the SiO ₂ target is stopped.

Next, while leaving the above glass substrate in the vacuum chamber,
Approximately 1.0 KW was applied to the SUS target, and the glass substrate was conveyed above the SUS target at about 500 mm / min during DC magnetron sputtering with Ar gas to form a SUS film with a thickness of about 50Å. After the formation of the SUS film is completed, the application to the SUS target is stopped.

Next, with the above-mentioned glass substrate being placed in the vacuum chamber, about 2.0 KW was applied to the Ti target, and D was generated by N ₂ gas.
A TiNx film having a thickness of about 200Å was formed by transporting the glass substrate above the Ti target at about 225 mm / min during C magnetron reactive sputtering. After the formation of the TiNx film is completed, the application to the Ti target is stopped.

Then, in the same manner as described above, the glass substrate was transported at about 50 mm / min to form a SiOx film of about 300 Å.

Regarding the single-plate heat insulating glass plate having the obtained four-layer film,
Visible light transmittance (380 ~ 780 nm), visible light reflectance (380 ~ 780 nm)
nm) and solar radiation transmittance (340 to 1800 nm) are 340
Type self-recording spectrophotometer (Hitachi) and JISZ8722, JISR31
The optical characteristics of each of them were determined by 06. Regarding the haze (cloudiness) value in the Taber test, a 10 cm square test piece with the film surface facing up was set in a Taber tester (MODEL 503, manufactured by TYBER), and a wear ring with a load of 500 g was applied to the film surface. (CS-10F) is designed to hit at two places. After rotating 1000 times, measure with a haze meter (NDH-20D, manufactured by Nippon Denshoku Industries Co., Ltd.) and compare it with the measured value before the test. The amount of change, that is, the difference (ΔH) is a numerical value expressed by the haze value rate.

Next, regarding the acid resistance test of chemical resistance, test pieces (10 cm × 10 cm) of about 4 in 0.15N HC1 solution at a temperature of about 60 ° C.
After immersing for 8 hours, it was judged by observing the deterioration state of the film by measuring the visible light transmittance and the reflectance (film surface).
After dipping a test piece of the same size in 15N NaOH solution for about 48 hours, the same measurement as above was performed, and it was judged by observing the deterioration state of the film. The change in transmittance and reflectance was 3% or less, and the change in appearance was scarcely observed. The mark X indicates that the same change was 5% or more, and the change in appearance was conspicuous. The same change is 3 to 5%, which is an intermediate change in appearance. In addition, 1 standard HCl, which is a JIS for construction,
The test was also carried out under the condition that there was no change in immersion in 1N NaOH solution at room temperature for 6 hours.

The above-mentioned respective measured values are as shown in Table 1 and have optical characteristics such as excellent heat insulation and excellent habitability, sufficient abrasion resistance and corrosion resistance, and improved weather resistance. As a result, it became useful as a single insulating glass plate, the desired product was obtained, and the color tone seen from the glass surface was silver. In addition, the JIS for construction
Of course, it passed the test according to the plan.

Example 2 The same method as in Example 1 was performed, and only a partial film thickness was changed as shown in Table 1 to obtain a 4-layer film, which was measured by the measurement method shown in Example 1 and the like, and the same evaluation means was used. The results are shown in Table 1.

The same thing as in Example 1 was obtained.

Example 3 The same method as in Example 1 was performed, except that only the second layer was made of SUS.
Change from film to SUSNx film, that is, using SUS target,
Vacuum degree about 2.5 × 10 ^-3 Torr, in N ₂ gas, applied power about 2.5KW,
A SUSNx film with a thickness of about 100Å was formed under the condition of a transparent glass substrate transfer speed of about 600 mm / min.

The obtained single-plate heat-insulated colored glass plate was measured by the measuring method shown in Example 1 and the like, and the same evaluation means was used. The results are shown in Table 1 and similar to the above-mentioned Examples. The color tone was almost the same. The use of the SUSNx film as the second layer was superior to the same film using the SUS film and the film thickness configuration thereof.

Example 4 The same method, measurement, and evaluation means as in Example 1 were used, and only the fourth layer was changed from a SiOx film to an Al.SiOx film, that is, Al.Si.
Using an alloy (Al: Si = 1: 1) target, the degree of vacuum is approximately 2.
Approx. 300 Å depending on the conditions of 5 × 10 ^-3 Torr, O ₂ gas, applied power of about 2.5 KW, and transfer speed of transparent glass substrate of about 20 mm / min.
A thick Al.SiOx film was formed.

The obtained single-plate heat-insulating colored glass plate was the same as that of each of the above-mentioned Examples, and the color tone was almost the same.

Example 5 The same method, measurement, and evaluation means as in Example 1 were used, and a TiOx film was formed and inserted on the upper surface of the third layer to form a 5-layer film. That is, a Ti target was used, the degree of vacuum, the gas and the applied power were the same as in Example 4, and the transfer speed of the transparent glass substrate was about 5 mm / min.
A film was formed.

The single-plate heat-insulating colored glass plate obtained was the same as that in each of the above-mentioned Examples, and the color tone thereof was almost the same.

Examples 6 to 10 The same procedure as in each of the above Examples was carried out, and as shown in Table 1, 5
Each film thickness of the layer-stacked multilayer film was obtained, measured by the measuring method shown in Example 1, and the like, and the same evaluation means was used. The results are shown in Table 1.

The single-plate heat-insulating colored glass plate obtained was the same as that in each of the above-mentioned Examples, and the color tone thereof was almost the same.

Comparative Examples 1 to 5 The same method as in each of the above Examples was performed to obtain a laminated multilayer film of 2 to 4 layers and each film thickness thereof as shown in Table 1, and the measurement was performed by the measurement method and the like shown in Example 1. The same evaluation means was used, and the results are shown in Table 1.

The obtained heat-insulated colored glass is inferior in wear resistance, chemical resistance, etc. to the heat-insulated colored glass plate of the single plate of each example, and it is difficult to use it as a heat-insulated colored glass for vehicles. However, it is difficult to say that it has excellent characteristics even for construction, and it is difficult to adopt it.

[Advantages of the Invention] As described above, according to the present invention, a transparent glass substrate is provided with a specific thin film having a specific thickness on the upper surface and outermost surface of the glass by a sputtering method, and at least a SUS or SUSNx film and a TiNx film are provided. In addition, by combining and coating each TiOx film appropriately, it has a relatively low visible light transmittance, has heat insulation performance, excellent abrasion resistance, corrosion resistance and weather resistance, Seen in a silver color tone, it can be used not only for multiple layers or laminated glass but also for vehicular use as a vehicle, and can effectively provide a useful and effective single-insulated glass plate and its colored glass. Is.

Claims (4)

[Claims] 1. A transparent glass substrate having a surface having a thickness of 100 to 1000Å as a first layer and a fifth layer, respectively, from the glass surface.
SiOx (1 <x ≤ 2) or Al-SiOx (2 <x ≤ 7/2)
Membrane, as the second layer, SUS or SUSNx with a film thickness of 50-100Å
(0 <x ≦ 1) film, Ti having a film thickness of 200 to 400Å as the third layer
Thermal insulation of a single plate, which is formed by laminating each sputtered film of Nx (0 <x ≦ 1) film and TiOx (0 <x ≦ 2) film with 0 <thickness ≦ 200Å as the fourth layer. Glass plate. 2. An SiOx (1 <x ≦ 2) or Al.SiOx (2 <x ≦ 7/2) film having a film thickness of 100 to 300Å as a first layer on one surface of a transparent glass substrate, The thickness of the second layer is 5
SUS or SUSNx (0 <x ≤ 1) film of 0 to 100 Å, TiNx (0 <x ≤ 1) film of 200 to 400 Å as the third layer, 4th
TiOx (0 <x ≦ 2) where 0 <thickness ≦ 200Å as a layer
SiOx (1 <x ≤ 300-500 Å as the 5th layer
2) or Al.SiOx (2 <x≤7 / 2) sputtered films are laminated and coated, and the reflection color tone when viewed from the glass surface side is silver. Insulated color glass plate of veneer. 3. An SiOx (1 <x ≦ 2) or Al.SiOx (2 <x ≦ 7/2) film having a film thickness of 100 to 300Å as a first layer on one surface of a transparent glass substrate, The thickness of the second layer is 5
SUS or SUSNx (0 <x ≤ 1) film of 0 to 100 Å, TiNx (0 <x ≤ 1) film of 200 to 400 Å as the third layer, 4th
SiOx (1 <x ≤ 2) with a thickness of 300-500Å as a layer or
A single-plate heat-insulating glass plate characterized by a laminated coating of sputtered Al / SiOx (2 <x ≦ 7/2) films and a reflection color tone seen from the glass surface side being silver. . 4. In the Taber test using a wear wheel of CS-10F, the change amount of the haze value after 1000 rotations before the test was conducted on the above-mentioned single plate heat insulating glass plate and single plate heat insulating colored glass plate. It is within 5% compared to the above. The single-plate heat-insulating glass plate and the single-plate heat-insulating colored glass plate according to claim 1 and claims 2 and 3.