JPH0664940A - Electric ray-transmitting and heat ray-shielding glass - Google Patents

Abstract

PURPOSE:To improve the durability of the subject glass by coating a glass substrate with a laminated layer of an Sn oxide film or Sn oxynitride film having a specific thickness, a Cr oxynitride film having a prescribed surface resistivity and an Sn oxide film or Sn oxynitride film. CONSTITUTION:A glass substrate is placed in a vacuum chamber and Sn and Cr targets are placed opposite to the glass substrate. O2 gas or a mixture of N2 and O2 gas is introduced into the vacuum chamber and the Sn target is sputtered to form an Sn oxide (SnOx) thin film or an Sn oxynitride (SnOxNy) thin film having a film thickness of 20-100nm on the substrate as the 1st layer. A fresh N2/O2 mixed gas is introduced into the chamber and the Cr target is sputtered to form a Cr oxynitride (CrNxOy) thin film as the 2nd layer having a film thickness of 1-50nm and a surface resistivity of >=1KOMEGA/square. The chamber is further charged with O2 or a mixture of N2 and O2 gas and the Sn target is sputtered to deposit an SnOx thin film or an SnOxNy thin film having a film thickness of 10-70nm as the 3rd layer. The objective electric ray-transmitting and heat ray-shielding glass produced by this process has a visible light transmittance of >=40% and a visible light reflectance from the glass surface of <=30% and exhibits golden reflection color.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shielding glass with a film for shielding solar radiation energy, which is mainly used for a window glass of a building or the like, and can improve the heating and cooling effect, and has a relatively high visibility. It has a light transmittance, and its radio wave transmission is similar to that of a normal or unprocessed float plate glass, which can reduce radio wave interference such as a ghost phenomenon in a TV image in a house around a building. The present invention relates to a radio wave transmission type heat ray shielding glass which has a light gold color tone from the glass surface side and a neutral color tone from the film surface side, and is particularly useful as a window glass for high-rise buildings.

[0002]

2. Description of the Related Art In recent years, when receiving TV radio waves, ghost damage due to building reflection has become a problem, and it is becoming practical to install a ferrite radio wave absorber on a concrete wall of a building, etc., while saving energy and improving cooling and heating efficiency. Therefore, for example, even in window glasses of high-rise buildings, metal, coating with a film of a metal oxide, or those having a function such as heat insulating performance by sticking a film having such a film are increasing, When a film that has a higher reflectance for radio waves than glass is coated or a film is attached, the reflectance becomes a very high value, for example, and as a heat ray reflective glass that exhibits a gold color tone, radio wave interference is inevitable. There was a face.

Further, in recent years, environmental problems have been highlighted, and there is a demand for environmentally friendly products. The conventional heat-ray reflective glass has a relatively low transmittance in order to emphasize heat insulation performance. For example, in JP-A-60-36355, the visible light transmittance is 5 to 40%, which makes it difficult to see through the room. It is hard to say that it is excellent. Furthermore, the conventional heat-reflecting glass has a relatively high reflectance from the glass surface side, which may cause light pollution to the surrounding living environment.

Further, the conventional heat ray reflecting glass is
From the evening to the night, the light of the indoor light is reflected by the heat ray reflective film, and the film surface on the indoor side is reflected like a glaring mirror, which is a big problem in terms of comfort.

For example, Japanese Patent Application Laid-Open No. 63-190742 describes a method for producing a heat ray reflective glass. In order to obtain a gold color tone of reflection color from a glass substrate, a TiO ₂ layer which is a _first layer. Film thickness of 8.5-12.5nm, the second layer of TiNx
It is disclosed that the film thickness of the (x> 1) layer is 72 to 81 nm, and the film thickness of the TiO ₂ layer as the third layer is 5 to 16 nm.

Further, for example, Japanese Patent Application Laid-Open No. 1-208344 describes a transparent plate having a reflection color of gold. For example, a film thickness of 36 to 47 nm is formed on one surface of a transparent plate such as a glass plate.
A high-refractive-index metal oxide dielectric film on titanium nitride film, especially with a refractive index of 1.9-2.6, especially TiO ₂ , Sn
There is disclosed a transparent plate to which O ₂ , ZnO and the like are attached and whose reflected light from the other surface of the transparent plate is gold.

Further, for example, the above-mentioned JP-A-60-36355 describes a method for producing a plate having a transmittance of 5 to 40% in the visible light spectrum band and a reflectivity for heat rays, and the first layer Forming a metal oxide film with a thickness of 20 to 280 nm as a second layer on the metal oxide film with a thickness of 10 to 40 nm
Of the above-mentioned chromium nitride film, and further, an oxide thin film is sequentially formed as a third layer if necessary.

Therefore, a proposal has been made as a heat ray reflective glass exhibiting a gold color tone with reduced radio interference. That is, for example, Japanese Patent Application Laid-Open No. 3-252332 has filed a heat ray reflection glass having a low radio wave reflection, and the first layer and the third layer are formed on one surface of a transparent glass substrate. As the second layer, and as the second layer, a metal thin film or a metal nitride thin film having a surface resistivity of 200 Ω / n or more as a second layer, and the reflection color viewed from the opposite side of the coating surface is blue or Those that are gold colored are disclosed.

Further, for example, as a heat ray reflective glass exhibiting a gold color tone with reduced radio interference, Japanese Patent Application No. 4-36667 already filed by the present applicant describes a heat ray shielding glass having a low radio wave reflection characteristic. The first layer, which is a nitride thin film of Cr having a film thickness of 1 to 25 nm, is formed on one surface of the transparent glass substrate, and Ta or TiSi having a film thickness of 30 to 75 nm is formed on the first layer. Alternatively, at least one kind of Zr nitride thin film is selected and coated as the second layer, and the surface resistivity of the heat ray shielding film is 10 kΩ / mouth or more, and the reflection tone from the glass surface side is It is disclosed that the color tone is gold.

[0010]

[Problems to be Solved by the Invention] As described above, for example, JP-A-63-190742 and JP-A-1-208344.
In the publication, etc., in order to obtain a gold color, the thickness of the TiN layer thin film is relatively large, resulting in a low resistance film, and when it is installed as a window glass of a high-rise building, it becomes a radio wave reflector. There may be a case where a ghost phenomenon occurs in a TV image seen in a general home located between a high-rise building and a broadcasting station. Further, for example, in Japanese Unexamined Patent Publication No. 3-252332, a metal thin film or a metal nitride thin film of about 5 to 13 nm is sandwiched by an oxide thin film and the like, which is a radio wave low reflection glass, but has a surface. Although it has a relatively low resistivity and its radio wave low reflection performance is equal to or lower than that of reinforced concrete, a material having further excellent radio wave low reflection performance in recent years is desired.

Further, for a highly conductive film such as a metal, the thicker the film in order to improve the heat insulating property, the lower the resistance becomes, and the low radio wave reflection performance is impaired. Even if the thickness is made thin, it is difficult to obtain a large surface resistivity, and similarly, it is difficult to obtain the above-mentioned performance.

Further, for example, in JP-A-60-36355, the transmittance is 5 to 40% in the visible light spectrum band,
Since the transmittance is relatively low, it is difficult to say that the transparency is necessarily excellent in consideration of the habitability in the room, and the surface resistivity of the laminated coating is relatively low and the radio wave transmission characteristics are not sufficient. Further, for example, in Japanese Patent Application No. 4-36667, the heat ray reflective glass with low radio wave reflection has a relatively high reflectance even though the opposite color tone from the glass surface side is a gold color tone, and the film surface Since the reflectance from the side is relatively high, it was not always sufficient from the viewpoint of preventing light pollution or the habitability of the room from evening to night. Especially when it is adopted for heat ray shielding glass which has a reflection color tone on the glass side of gold and can be used as a single plate, especially for high-rise buildings, it cannot be said to be sufficiently useful depending on the location. It was something I couldn't help but know.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a Sn oxide thin film or an oxynitride thin film having a specific thickness is formed on one surface of a glass substrate. It is coated as one layer, then a specified nitrogen oxide thin film of Cr having a surface resistivity of, for example, at least 1 kΩ / port or more is coated as a second layer, and a Sn oxide thin film of a specific thickness or oxygen is further coated thereon. By coating a nitride thin film as the third layer, it is possible to develop a light gold color tone that is reflected from the glass surface side, making it excellent in design and comparing the visible light reflectance from the glass surface side. Since it is relatively low, the influence of light pollution on the surrounding environment such as buildings is reduced, the color tone reflected from the film surface side is a neutral color tone, the visible light reflectance from the film surface side is also low, and it is transmitted. High rate of over 40% By squeezing it, the habitability in the room can be greatly improved, and the radio wave reflectance is about 3% in the TV radio wave band, especially around the frequency of 150MHz.
Provided is a heat ray-shielding glass which can be made as low as the following, and which is sufficiently excellent in abrasion resistance and durability while maintaining heat insulation performance, and which has radio wave transmission characteristics that can be sufficiently used in a single plate. Is.

That is, according to the present invention, one surface of a transparent glass substrate is coated with a Sn oxide thin film or an oxynitride thin film having a film thickness of 20 to 100 nm as a first layer, and In addition, the film thickness is 1 to 50 nm and the surface resistivity is 1 kΩ /
After coating a nitrogen oxide thin film of Cr having a thickness not less than that of the second layer as a second layer, an oxide thin film of Sn or oxynitride having a film thickness of 10 to 70 nm is laminated as a third layer on the second layer. A radio wave transmission type heat ray shielding glass characterized by being coated.

Further, the above-mentioned radio wave transmission type heat ray shielding glass, wherein the surface resistance of the heat ray shielding performance film coated with the laminate is 1 kΩ / mouth or more. Further, in the radio wave transmission type heat ray shielding glass, the reflection color tone from the glass surface side of the glass is a light gold color tone, and the visible light reflectance from the glass surface side is 30% or less. The radio wave transmission type heat ray shielding glass described above.

Furthermore, in the radio wave transmission type heat ray shielding glass, the reflection color tone from the film surface side of the glass is a neutral color tone, and the visible light reflectance from the film surface side is 30% or less. The radio wave transmission type heat ray shielding glass as described above.

Furthermore, the above-mentioned radio wave transmission type heat ray shielding glass is provided, in which the visible light transmittance of the glass is 40% or more.

Here, the Sn oxide thin film or the nitrogen oxide thin film having a film thickness of 20 to 100 nm as the first layer is a film excellent in durability or mass productivity and has a light gold color. This is because it is possible to develop, and when the film thickness is less than 20 nm, it is not possible to develop a light gold color, and when the film thickness exceeds 100 nm, the glass surface side reflection color tone has various color tones. Although it is possible to express, the visible light reflectance on the glass surface side becomes high, and the reflection color tone on the film surface side of the laminated coating becomes glaring golden color, which is not preferable from the viewpoint of indoor habitability,
Moreover, it is not preferable from the viewpoint of productivity. The film thickness is preferably about 30 to 70 nm.

A second layer having a thickness of 1 to 50 nm and a surface resistivity of 1 kΩ / port or more is formed on the first layer.
We decided to coat the nitrogen oxide thin film of Cr because the nitrogen oxide thin film of Cr has a higher visible light transmittance than the nitride thin film of Cr and achieves 40% or more of the visible light transmittance. This is because it is a film that is capable of producing a gold-based color tone in which the color tone reflected from the glass surface side is light, and that it has excellent durability, and that it has stable radio wave transmission characteristics. Yes, especially the TV band, especially the frequency 150MHz
This is because the heat ray shielding film can reduce the radio wave reflectance in the vicinity to 3% or less, which is comparable to that of ordinary float glass. If the film thickness is less than 1 nm, the thin film becomes an island structure and becomes uneven, and it is difficult to form a continuous film.
When it exceeds, the visible light transmittance becomes small and it becomes difficult to achieve 40% or more. The film thickness is preferably about 10 to 30 nm.

Further, a film thickness of 10 to 70 is formed on the second layer.
The Sn oxide thin film or the oxynitride thin film of Sn having a thickness of 3 nm is coated as the third layer, because the thin film of the first layer and the second layer is skillfully combined to reflect from the glass surface side by the optical interference effect. This is because the color tone is easy to develop a light gold color, and it is to further strongly improve the durability of the laminated coating film.When the film thickness is less than 10 nm, the light gold color cannot be expressed, and the film When the thickness exceeds 70 nm, the reflectance on the film surface side becomes high and the color tone becomes glaring and strong golden color. Therefore, in order to make the reflection color tone on the film surface side neutral, the film thickness of the third layer Is better to be thin. The film thickness is preferably about 15 to 40 nm.

Above all, the heat-shielding film having the above-mentioned laminated coating has a surface resistivity of 1 kΩ / mouth or more, and a reflection color tone from the glass surface side of the glass exhibits a light gold color tone, and from the glass surface side. The visible light reflectance of the above is 30% or less in order to have sufficient radio wave transmission performance and to prevent the radio wave interference such as a ghost phenomenon in TV images from occurring more reliably. This is because, by exhibiting a light gold color tone reflected from the surface side, a building or the like has an excellent design and becomes environmentally friendly without causing light pollution to the surrounding environment.

Further, the reflection color tone from the film surface side of the glass exhibits a neutral color tone, the visible light reflectance from the film surface side is 30% or less, and the visible light transmittance of the glass is
The reason why the ratio is 40% or more is that the habitability inside the room is particularly comfortable from the evening to the night, and that the outside view seen from the daytime indoor side has a proper see-through property without any discomfort. This is because it is environmentally friendly to people in the room.

Next, as the glass substrate, an organic material as well as an organic material may be used as long as it is a transparent glass, and a colorless or colored glass or the like can be used as long as it is easy to obtain a gold color tone having a light reflection tone when viewed from the glass surface side. It is more preferable. It goes without saying that it can be used not only as a single plate, but also as various kinds of plate glass products such as multi-layer glass, laminated glass, and tempered glass.

It goes without saying that, for example, window glass for automobiles, especially radio waves in the satellite broadcasting band can be transmitted.
It is also possible to receive satellite broadcasts indoors. Therefore, it is also useful as a heat ray shielding glass for a roof of an automobile.

[0025]

As described above, in the radio wave transmission type heat ray shielding glass of the present invention, one surface of the glass substrate is coated with the Sn oxide thin film or the oxynitride thin film of the specific thickness as the first layer, A specified layer of Nitrogen Oxide thin film of Cr having a specific film thickness and a surface resistivity of at least 1 kΩ / port is coated as a second layer on the first layer, and Sn of a specific film thickness is further formed thereon.
By coating and laminating the oxide thin film or the oxynitride thin film of No. 3 as the third layer, the reflection color tone from the glass surface side exhibits a light gold color tone, which is excellent in designability and also from the glass surface side. The visible light reflectance is relatively low,
The influence of light pollution on the surrounding environment such as a building is reduced, and the habitability and landscape of the outside of the building are remarkably excellent, and moreover, the color tone reflected from the film surface side can be a neutral color tone. In addition, the visible light reflectance from the film surface side is low, and the visible light transmittance is increased to 40% or more, so that the habitability in the room can be significantly improved, and the radio wave reflectance can be further improved by the TV. It can be lowered to about 3% or less in the radio frequency band, especially around 150MHz, which is as low as that of ordinary float glass, and the radio wave transmission performance is remarkably excellent. As a result, the effect of cooling and heating is enhanced, the wear resistance and corrosion resistance of the entire laminated multilayer film are good, and the durability is sufficiently excellent.
(EN) Provided is a heat ray-shielding glass that can be sufficiently used as a single plate, has appropriate transparency, is comfortable to the environment and is environmentally friendly, and has useful radio wave transmission characteristics.

[0026]

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 Clear glass having a size of about 600 mm x 600 mm and a thickness of about 6 mm
(FL12) can be sequentially washed with a neutral detergent, water rinse, isopropyl alcohol, dried, and then reciprocated upwards facing the Sn and Cr targets set in the vacuum chamber of the DC magnetron sputtering device. And then the inside of the chamber was degassed by a vacuum pump to about 5 × 10 ⁻⁶ Torr or less, and then the gas flow ratio of O ₂ and N _{2 in} the vacuum chamber was N ₂ / O ₂ + N ₂ = 0.
05 mixed gas of O ₂ and N ₂ (however, gas flow rate ratio N ₂ / O ₂ +
The value of N ₂ may be in the range of 0.01 to 0.50, and Ar gas may be introduced in order to increase the film formation rate if necessary, and the amount of Ar gas with respect to the total gas at this time is common sense. Range of 50% or less)
Hold at 2x10 ^-3 Torr and add about 0.4kw to the Sn target.
Power is applied, and the plate glass is transported at a speed of about 65 mm / min above the Sn target by DC magnetron reactive sputtering with the mixed gas to form a SnOxNy thin film having a thickness of about 55 nm as a first layer. A film was formed. After the film formation is completed, the application to the Sn target is stopped.

Next, with the plate glass being placed in the vacuum chamber, the inside of the vacuum chamber was degassed by a vacuum pump to about 5 × 10 ⁻⁶ Torr or less, and then N ₂ and O ₂ gas was introduced into the vacuum chamber. Flow ratio is O ₂ / N ₂
+ O ₂ = 0.01 mixed gas of N ₂ and O ₂ (however, gas flow ratio
The value of O ₂ / N ₂ + O ₂ should be in the range of 0.003 to 0.05, and if necessary, the surface resistivity of the CrNxOy film should be 1 even when the film thickness is 50 nm.
Ar gas may be introduced in order to increase the film-forming rate if kΩ / hole or more) and the degree of vacuum is maintained at about 2 × 10 ⁻³ Torr, and the Cr target has about 1.2 kw. Apply power,
By DC magnetron reactive sputtering with the mixed gas, the speed was about 219 mm / mi above the Cr target.
The CrNxOy thin film having a thickness of about 18 nm is secondly deposited on the SnOxNy thin film surface of the flat glass by transporting the flat glass at n 2.
Laminated films were formed as layers. After the film formation is completed, the application to the Cr target is stopped.Next, while the plate glass is placed in the vacuum chamber, the vacuum chamber is operated with a vacuum pump.
After degassing to less than 5x10 ^-6 Torr, put O ₂ and N ₂ in the vacuum chamber.
Mixed gas of O ₂ and N ₂ having a gas flow rate ratio of N ₂ / O ₂ + N ₂ = 0.05 (however, the value of the gas flow rate ratio N ₂ / O ₂ + N ₂ may be in the range of 0.01 to 0.50, If necessary, Ar gas may be introduced to increase the film formation rate. At this time, the amount of Ar gas with respect to the total gas is 50% or less in vol% in a common sense range.) And maintain the vacuum at about 2x10 ^-3 Torr.
By applying a power of about 0.4 kw to the Sn target and carrying the plate glass at a speed of about 83 mm / min above the Sn target by DC magnetron reactive sputtering with the mixed gas, A SnOxNy thin film having a thickness of about 43 nm was laminated and formed as a third layer on the surface of the CrNxOy thin film. After the film formation is completed, the application to the Sn target is stopped. That is, as shown in Table 1.

Regarding the radio wave transmission type heat ray shielding glass having the obtained three-layer film, visible light transmittance (380 nm to 780 nm), visible light reflectance (380 nm to 780 nm) and solar radiation transmittance (340 nm to 18 nm).
For (00 nm), the optical characteristics of each were measured using a 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JISZ8722 and JISR3106. Further, regarding the amount of change in the haze value (ΔH%) by the taper test, about 10 cm square with the film surface facing up on a taper tester (MODEL 503, manufactured by TABER). Set a test piece and wear a ring (C
S-10F) is designed to hit in two places, 300
After rotating, the haze meter (made by Nippon Denshoku Industries, NDH-
20D), and compared with the measured value before the test and expressed as the amount of change (ΔH%), the smaller the value, the better the abrasion resistance.

Next, the acid resistance test of the chemical resistance was judged by observing the deterioration state of the film after immersing the test piece in a 1N HCl solution at room temperature for about 6 hours.
Regarding the alkali resistance test, after immersing the test piece in 1N NaOH solution at room temperature for about 6 hours, check the deterioration state of the film and see
It was judged according to SR3221. In each case, the ○ marks show almost no deterioration, and the X marks clearly show the deterioration.

Further, regarding the surface resistivity, the one having a resistance of 10 ⁵ Ω / port or less is measured by a four-point probe resistance measuring device RT-8 (manufactured by NASON), and the one having a resistivity of 10 ⁵ Ω / port to 10 ⁵ MΩ / port is Mitsubishi. It is measured by a surface high resistance meter (HIRESTA HT-210) made by Yuka.

Further, the radio wave reflectance was obtained by measuring it by the large waveguide method. As is clear from Table 2, it has almost the same heat insulation performance as conventional heat-shielding glass, has excellent habitability, wear resistance, corrosion resistance, weather resistance, durability, and is sufficiently transparent to radio waves. Therefore, it becomes useful as a window glass for high-rise buildings, etc. as a radio wave transmission type heat ray shielding glass, and in particular, the reflection color tone from the glass surface side is a pale gold color tone, and the visible light reflectance from the glass surface Is as low as about 20.7%, and the reflection color tone of the film surface is neutral, and its visible light reflectance is about 21.4%.
As low as%, I got what I was aiming for. For example, the solar reflectance is about 15.9% on the glass side and about 2% on the film side.
It was 1.6%.

Examples 2 to 5 In the same manner as in Example 1, the transport speed and the like shown in Example 1 and the following were adjusted to obtain a desired film thickness, and Table 1
The three-layer film shown in and the respective film thicknesses thereof were obtained, and the film constitution was performed by the same evaluation means by the measuring method shown in Example 1 and the like, and the results are shown in Table 2.

The radio wave transmission type heat ray-shielding glass having the obtained three-layer film has a gold color tone in which the reflection color tone from the glass surface side is pale and has the same excellent radio wave transmission performance and optical characteristics as in Example 1. Each physical property is shown. For example, the solar reflectance in Example 2 is about 14.3 on the glass surface side.
% And about 23.0% on the film surface side.

Regarding the thin film forming conditions, for SnOx thin films, a Sn target was used in a DC magnetron reaction sputtering apparatus, and the same degree of vacuum and a mixed gas of O ₂ and Ar (however,
The flow rate ratio should be such that the value of Ar / O ₂ + Ar is in the range of 0 to 0.5), and when the applied power is about 0.4 kw, for example, a SnOx thin film with a thickness of about 60 nm was obtained at a plate glass transporting sud of about 55 mm / min. . Further, especially for only the CrNxOy thin film shown in Example 5, a Cr target was used in the same apparatus and the same vacuum degree and N ₂
O ₂ gas flow ratio O ₂ / N ₂ + O ₂ = 0.03 mixed gas of N ₂ and O ₂ (however, the value of gas flow ratio O ₂ / N ₂ + O ₂ should be in the range of 0.003 to 0.05) Also, if necessary, Ar gas may be introduced to increase the film formation rate if the surface resistivity of the CrNxOy film is 1 kΩ / port or more even at a film thickness of 50 nm).
At 2.3kw, for example, plate glass transport speed of about 56mm /
A CrNxOy thin film with a thickness of about 50 nm was obtained at min.

Comparative Example 1 The glass treated in the same manner as in Example 1 was used, and SUS was used in the same apparatus.
Set two targets and move the inside of the vacuum chamber to about 5 x 10 ^-6 torr
After degassing to the following, O ₂ gas was introduced into the vacuum chamber, the degree of vacuum was maintained at about 2 × 10 ⁻³ torr, power of about 1.5 kw was applied to the SUS target, and the plate glass conveyance speed was about 150 m.
A SUSOx thin film having a thickness of about 20 nm was formed as a first layer at m / min. Next, using the other SUS target, an Ar gas pressure of about 2 × 10 ^-3 torr and an applied power of about 1.0 kw was used to obtain a SUS thin film having a film thickness of about 5 nm at a plate glass transport speed of about 600 mm / min. Further, as in the case of the first layer, a SUSOx thin film having a film thickness of about 30 nm at a plate glass conveying speed of about 100 mm 3 / min was used as a third layer, and a film was laminated as shown in Table 1.

With respect to the film structure, the same measurement method and the same evaluation means as in Example 1 were used, and the results are shown in Table 2. For example, the surface resistivity is lower than that in Examples and 1 kΩ.
/ Port or less, the radio wave transmission performance is equal to or less than that of reinforced concrete, and it is hard to say that it is sufficient for desired characteristics.

Comparative Examples 2 to 5 For the CrOx thin film and the TiNx thin film, the CrNx thin film, the TaNx thin film, and the ZrNx thin film, the plate glass conveyance speed shown below was applied to the desired film thickness in the same manner as in the above Examples and Comparative Example 1. Was adjusted to obtain the 1 to 3 layer film and each film thickness thereof shown in Table 1.

For the CrOx thin film, the same apparatus, the same degree of vacuum, the O ₂ gas, and the applied power of about 2.2 kw, for example, a plate glass transfer speed of about 240 mm / min and a film thickness of about 20 nm were used.
A CrOx thin film was obtained. For the TiNx thin film,
Using a target and the same vacuum degree, N ₂ gas (However, Ar gas may be introduced in some cases, in which case the flow ratio of Ar and N ₂ gas Ar / N ₂ + Ar is in the range of 0-0.5. If the applied power is about 1.5 kw, a TiNx thin film having a film thickness of about 80 nm was obtained at a plate glass transport speed of about 38 mm / min, for example.

Furthermore, for the CrNx thin film, a Cr target was used in the same apparatus, the same vacuum degree, N ₂ gas, and applied power of about
At 1.2kw, for example, plate glass transport speed of about 437mm
A CrNx thin film having a film thickness of about 10 nm was obtained at the same time / min. Furthermore, for TaNx thin film, Ta target was used in the same equipment, the same vacuum degree,
A TaNx thin film having a film thickness of about 40 nm was obtained at a plate glass conveying speed of about 37 mm / min with the above N ₂ gas and an applied power of about 1.7 kw. Furthermore, for the ZrNx thin film, a Zr target was used in the same apparatus, the same vacuum degree, the N ₂ gas, and an applied power of about 1.5 k
At w, for example, plate glass transport speed of about 25 mm / min
A ZrNx thin film with a thickness of about 60 nm was obtained.

By such a method, a laminated film of 1 to 3 layers as shown in Table 1 was obtained, and the film constitution was performed by the same measuring method and the same evaluation means as in Example 1, and the results are shown in the table. 2 respectively.

In Comparative Examples 2 and 3, the conventional heat ray-shielding glass has a surface resistivity lower than that of each Example, for example, a surface resistivity of about 280 Ω / hole or less, and a radio wave reflection. The ratio is about 9% or more, which is lower than the radio wave reflectance of reinforced concrete in a building, and is likely to cause radio wave interference around the building.

Further, Comparative Examples 4 and 5 are radio wave transmission type which does not cause radio interference in the vicinity of the building and are heat ray shielding glass having a glass surface side reflection color tone of gold, but the visible light thereof is The transmittance is comparatively low, and the visible light reflectance of the glass and film surfaces is 44% or more, which is a very high value, and it is hard to say that it is friendly to the living environment inside and outside the building.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

As described above, according to the radio wave transmission type heat ray shielding glass of the present invention, one surface of the glass substrate is coated with the Sn oxide thin film or the oxynitride thin film having a specific thickness as the first layer. Then, on the first layer, a specified nitrogen oxide thin film of Cr having a specific film thickness and a surface resistivity of at least 1 kΩ / port or more is coated as a second layer, and further a specific film thickness of A heat-insulating glass is obtained by laminating a Sn oxide thin film or an oxynitride thin film as a third layer,
It has excellent wear resistance, corrosion resistance and durability, good radio wave transmission, low radio wave reflectance similar to that of ordinary float glass, and does not cause radio interference to the surroundings of high-rise buildings. It has a light gold color tone and has a good design, and the visible light reflectance from the glass surface side is relatively low, and the effect of light pollution on the surrounding environment such as buildings is reduced, and It has excellent habitability and scenery, and has excellent habitability even indoors. It can be effectively used as a useful radio wave transmission type heat ray shielding glass that can be used as laminated glass or double glazing as well as single glass. It is provided.

Claims (5)

[Claims] 1. A transparent glass substrate, one surface of which is coated with a Sn oxide thin film or an oxynitride thin film having a thickness of 20 to 100 nm as a first layer, and the film is formed on the first layer. 1-50 thickness
After coating a nitrogen oxide thin film of Cr having a thickness of 1 nm and a surface resistivity of 1 kΩ / n or more as a second layer, an oxide thin film of Sn having a thickness of 10 to 70 nm is formed on the second layer, or A radio wave transmission type heat ray shielding glass comprising an oxygen oxynitride thin film as a third layer. 2. The radio wave transmission type heat-shielding glass according to claim 1, wherein the heat-shielding film laminated and coated has a surface resistivity of 1 kΩ / port or more. 3. In the radio wave transmission type heat ray shielding glass, the reflection color tone from the glass surface side of the glass is a light gold color tone and the visible light reflectance from the glass surface side is 30.
% Or less, the radio wave transmission type heat ray shielding glass according to claim 1 or 2. 4. In the radio wave transmission type heat ray shielding glass, the reflection color tone from the film surface side of the glass is a neutral color tone, and the visible light reflectance from the film surface side is 30% or less. The radio wave transmission type heat ray shielding glass according to claim 1, which is characterized in that. 5. The radio wave transmission type heat ray shielding glass according to claim 1, wherein the visible light transmittance of the radio wave transmission type heat ray shielding glass is 40% or more.