JPH05238778A - Heat ray shielding glass having radio wave low-reflection characteristic - Google Patents

Abstract

PURPOSE:To obtain the above heat ray shielding glass which allows the efficient transmission of radio waves to the same extent as glass and has heat insulating performance by successively forming two layers of nitride thin films having specific compsns. and film thicknesses on one surface of a transparent glass substrate. CONSTITUTION:The first layer consisting of the nitride thin film of Cr having 1 to 25nm film thickness is formed on one surface of the transparent glass substrate. At least one kind of the nitride thin films of Ta or TiSi or Zr having 30 to 75nm film thickness are then selected and are formed as the second layer on the first layer, by which the heat ray shielding glass having the radio wave low-reflection characteristic is produced. Further, an oxide thin film of Ta or TiSi or Cr having 5 to 30nm film thickness is formed as a third layer on the second layer, by which the durability, etc., are additionally improved. The generation of radio interferences, such as ghosts of television images, is obviated even around multistoried buildings if the resulted heat ray shielding glass is used for the multistoried buildings.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray-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 low visibility. It has a light transmittance, and its radio wave transmission is similar to that of ordinary or unprocessed float plate glass, and it can reduce radio wave interference such as ghost phenomenon in TV images in houses around buildings, and more particularly, The present invention relates to a heat ray shielding glass which has a gold-based color tone reflected from the glass surface side, and particularly has low radio wave reflection characteristics useful as a window glass for high-rise buildings.

[0002]

2. Description of the Related Art In recent years, when receiving television radio waves, ghost interference 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 or the like. Due to improvements, for example, even in windowpanes of high-rise buildings, the number of those that are provided with functions such as coating with a film of metal or metal oxide, or affixing a film having such a film, such as heat insulation performance, is increasing. , If you coat a film that has a higher reflectance to radio waves than glass or attach a film, the reflectance will be a considerably high value, especially as a heat ray reflection glass with a gold color tone, radio wave interference is inevitable. There was a face.

For example, Japanese Patent Application Laid-Open No. 63-190742 describes a method for producing heat ray reflective glass. In order to obtain a gold color tone of reflection from a glass substrate, a TiO ₂ layer which is the first layer is used. Film thickness of 8.5-12.5nm, the second layer of TiN
The thickness of the layer is 72 to 81 nm, and the thickness of the TiO ₂ layer which is the third layer is 5 to 5 nm.
It is disclosed that the thickness is 16 nm, and, for example, JP-A-1-208344 describes a transparent plate having a gold reflection color, and one surface of the transparent plate such as a glass plate is
For example the film thickness is high refractive index metal oxide dielectric film on the titanium nitride film of about 36～47Nm, in particular a refractive index of 1.9 to 2.6, and in particular attaching TiO _2, SnO _2, ZnO and the like, and It is known that a transparent plate in which light reflected from the other surface of the transparent plate is gold is disclosed.

Therefore, a proposal has been made as a heat ray reflective glass exhibiting a gold-based color tone with reduced radio interference. That is, for example, in Japanese Patent Laid-Open No. 3-252332 filed by the present applicant, a colored dielectric thin film is laminated as a first layer and a third layer on one surface of a transparent glass substrate,
The second layer is made by laminating a metal thin film or a metal nitride thin film having a surface resistance of 200 Ω / mouth or more, and the reflection color tone seen from the opposite side of the coating is blue or gold. Glass and the like are disclosed.

[0005]

[Problems to be Solved by the Invention] As described above, for example, JP-A-63-190742 and JP-A-1-208344.
In the gazette, etc., the TiN layer thin film is relatively thick in order to obtain a gold color, resulting in a low-resistance film and a radio wave reflector when applied as a window glass of a high-rise building. This causes the ghost phenomenon in TV images seen in ordinary homes between high-rise buildings and broadcasting stations. Further, for example, in Japanese Unexamined Patent Publication No. 3-252332, an ultra thin film of about 5 to 13 nm of a metal thin film or a metal nitride thin film is sandwiched by oxide thin films and the like, which is a radio wave low reflection glass, but has a surface. Although it has relatively low resistance 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 being demanded.

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 it is thin, it does not become a large surface resistance, similarly there is a problem that the above-mentioned performance is difficult to obtain sufficiently, especially the reflection color tone on the glass surface side is gold color and heat ray shielding glass that can be used in a single plate, especially It must be said that it is not yet useful as a high-rise building.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a gold-based color tone with a specified nitride having a specific film thickness and a surface resistance of at least 10 MΩ / port or more. In the membrane that can be expressed,
By using a laminated film structure in which Cr nitride having a specific film thickness is used as an undercoat, the visible light transmittance and the like are in a specific range, for example,
It is possible to adjust arbitrarily at 10 to 50%, and by skillfully combining those films, the reflectance of the film surface is lowered and the color tone of the film surface is made neutral,
The color tone of the glass surface is gold, and the radio wave reflectance can be lowered to about 3% or less in the TV radio wave band, especially around the frequency of 150MHz, which is as low as that of float glass. Wear resistance, durability, especially overcoating with a specific oxide to further improve stubbornly, and make it possible to delicately control the color tone, low radio wave reflection characteristics that can be fully used with a single plate The present invention provides a heat ray shielding glass having the same.

That is, according to the present invention, a 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 a transparent glass substrate, and a film thickness of 30 is formed on the first layer. ~ 75nm Ta or
A heat ray shielding glass having a low radio wave reflection characteristic, characterized in that at least one nitride thin film of TiSi or Zr is selected and coated as a second layer. As a third layer on the second layer, Ti or TiSi having a film thickness of 5 to 30 nm or
A heat ray shielding glass having the above-mentioned low radio wave reflection characteristics, characterized by being coated with a Cr oxide thin film. And in the heat ray shielding glass having the low radio wave reflection property, the sheet resistance value of the coated heat ray shielding performance film is 10 kΩ / mouth or more, and the reflection color tone from the glass surface side of the glass exhibits a gold-based color tone. The present invention provides the heat ray shielding glass having the above-described characteristic of low radio wave reflection.

Here, the reason why the Cr nitride thin film having a thickness of 1 to 25 nm is used as the first layer is that the visible light transmittance is, for example,
This is because it is possible to adjust it arbitrarily within the range of 10 to 50%, and considering the indoor habitability within the range of the film thickness that does not cause radio interference, the reflectance of the film surface is reduced and the film This is for making the color tone of the surface neutral, and preferably the film thickness is about 1 to 20 nm.

A film thickness of 30 to 75 nm is formed on the first layer.
At least one Ta or TiSi or Zr nitride thin film
The surface electric resistance is 10 because the second layer is coated by selecting more than one kind.
This is because the film has a resistance of MΩ / mouth or more and is excellent in durability so that the reflection color tone from the glass surface can express a gold-type color tone, and the thickness is preferably about 40 to 65 nm.

Furthermore, by skillfully combining the first layer and the second layer appropriately, the reflectance of the film surface can be lowered, the color tone of the film surface can be made to be a neutral tone, and low radio wave reflection is achieved. The radio wave reflectance in the TV radio wave band, especially around the frequency of 150 MHz can be lowered to 3% or less, which is comparable to that of ordinary float glass, while maintaining the heat insulation function, enhancing the adhesion of the film and abrasion resistance, It has excellent durability and chemical resistance, and can be sufficiently used as a single plate.

Above all, by overcoating a thin oxide film of Ti or TiSi or Cr having a film thickness of 5 to 30 nm as the third layer on the second layer, the durability is further improved. In addition, the color tone reflected from the glass surface can be delicately controlled, and is preferably about 10 to 25 nm. Also,
The sheet resistance value of the coated heat ray shielding film is 10 kΩ /
The color tone above the mouth and the color tone reflected from the glass surface side of the glass is a gold-type color tone because it has sufficient radio wave low reflection performance and more reliable radio wave interference such as ghost phenomenon in TV images. The reason is that the building and the like are excellent in design and eco-friendly because the reflection color tone from the glass surface side exhibits a gold-based color tone.

Next, as the glass substrate, it is sufficient if it is an inorganic material as well as an organic material as long as it is a transparent glass, and it is more preferable if it is colorless or colored and the reflection color tone seen from the glass surface side easily obtains a gold color tone. Is.
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.

[0014]

As described above, the heat ray shielding glass of the present invention having a low radio wave reflection characteristic has the nitride thin film of Cr having a specific film thickness as the first layer, and Ta or TiSi or Zr having a specific film thickness thereon.
Since the nitride thin film of (1) was laminated as the second layer and the first layer and the second layer were skillfully combined, the surface resistance value was as high as 10 kΩ / mouth or more, and the visible light transmittance was 10% to Fifty
It can be controlled arbitrarily within the range of about%,
Moreover, the reflection from the film surface is low and the reflection color tone can be made neutral, and the reflection color tone from the glass surface side in particular exhibits a gold-based color tone, which enhances the adhesion of each thin film and the entire laminated multilayer film. It has improved abrasion resistance and corrosion resistance, has excellent durability, and can be sufficiently adopted as a single plate, and because it has extremely low radio wave reflection performance in the TV band and is similar to ordinary float glass. Even when used in high-rise buildings, it is possible to reduce radio interference such as the ghost phenomenon in TV images that has been conventionally exhibited in the surrounding area, and also to provide heat ray reflection with a moderate interference effect and heat insulation function. It is possible to enhance the effect of air conditioning and heating, and to suppress the see-through property to make it richer in color tone. The present invention provides a heat ray-shielding glass having useful radio wave low reflection characteristics, which can further improve the above.

[0015]

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 (Fl having a size of 600 mm x 600 mm and a thickness of 6 mm)
After cleaning 6) with a neutral detergent, water rinse, isopropyl alcohol, and drying, set it so that it can reciprocate upwards facing the targets of Cr and Ta set in the vacuum chamber of the DC magnetron sputtering device. Next, after degassing the inside of the tank with a vacuum pump to about 5 × 10 ⁻⁶ Torr or less, N ₂ gas (however, the flow rate ratio of Ar and N ₂ is 1:
It may be in the range of 1 to 0: 1. ) Is introduced and the degree of vacuum is maintained at about 2 × 10 ^-3 Torr, and the Cr target is about 1.
A CrN _x thin film with a thickness of about 10 nm was used as the first layer by transporting the plate glass at a speed of about 437 mm / min above the Cr target in a DC magnetron reactive sputtering with N ₂ gas by applying a power of 2 kw. A film was formed. After the film formation is completed, the application to the Cr target is stopped.

Next, with the plate glass in the vacuum chamber, a power of about 1.7 kw was applied to the Ta target, and N ₂ gas (however, the flow ratio of Ar and N ₂ was 1: 1 to 0: 1). In the DC magnetron reactive sputtering by the above-mentioned Ta target at a speed of about 37 mm /
By transporting at a min, a TaN _X thin film having a thickness of about 40 nm was formed as a second layer on the CrN _x film forming surface of the plate glass. After the film formation is completed, the application to the Ta target is stopped.

With respect to the heat ray shielding glass having a low radio wave reflection characteristic having the obtained two-layer film, the visible light transmittance (380 to
780 nm), visible light reflectance (380 to 780 nm) and solar radiation transmittance (340 to 1800 nm) were determined by using a 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JISZ8722 and JISR3106. Regarding the amount of change in the haze value (△ H%) due to the Taber test, set a 10 cm square test piece with the film surface up on a Taber tester (MODEL 503, manufactured by TYBER) Load 500g
A worn wear wheel (CS-10F) is designed to hit at two points. After rotating 300 times, measure it with a haze meter (NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd.), and measure before the test. It is a numerical value expressed by the amount of change (ΔH%) in comparison with the value.

Next, regarding the acid resistance test of the chemical resistance, it 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 JISR
Judgment was made according to 3221. In each case, ○ indicates almost no deterioration, and × indicates deterioration is clearly noticeable.

Further, regarding the surface resistance, those having a resistance of 10 ⁵ Ω / port or less are measured by a four-point probe resistance measuring device RT-8 (manufactured by NAPSON), and those having a resistance of 10 ⁵ Ω / port to 10 ⁵ MΩ / port are manufactured by Mitsubishi Oil. It was measured with a chemical surface high resistance meter (HIRESTA HT-210).

Further, the radio wave reflectance was obtained by measuring it by the large waveguide method. As is clear from Table 1, it has almost the same heat insulation performance as conventional heat-reflecting glass, has excellent habitability, wear resistance, corrosion resistance, weather resistance, durability, and is sufficiently transparent to radio waves. As a result, it has become a useful heat-shielding glass having a low radio wave reflection property for window glass of high-rise buildings and the like, and in particular, the desired reflection color tone from the glass surface side has been obtained in a gold color tone.

Examples 2 to 16 By the same method as in Example 1, the two-layer film or the three-layer film shown in Table 1 and the respective film thicknesses thereof were obtained, and the measurement method and the like shown in Example 1 in the film structure were obtained. By the same evaluation means, and the results are shown in Table 1.

The heat ray-shielding glass having a low radio wave reflection characteristic having the obtained two- or three-layered film showed excellent physical properties such as desired optical characteristics as in Example 1. For the CrO _x thin film, use a Cr target in a DC magnetron reaction sputtering device, and at the same vacuum level, the O ₂ gas, and an applied power of 2.2 kw, for example, a plate glass transport speed of about 480 mm / min and a film thickness of about 10 nm of the CrO _x thin film. Got For a TiSi _x N _y thin film, a TiSi target was used in the same equipment, and a TiSi _x N _y thin film with a film thickness of about 50 nm was obtained at the same vacuum degree, N ₂ gas, and applied power of 1.4 kw, for example, at a plate glass transport speed of about 48 mm / min. Obtained. For ZrN _X thin film, a Zr target was used in a DC magnetron reaction sputtering apparatus, the same vacuum degree, the N ₂ gas, and an applied power of 1.5 kw, for example, a plate glass transfer speed of about 25
A ZrN _X thin film with a thickness of about 60 nm was obtained at mm / min.

For a TiO _x thin film, a Ti target was used in the same apparatus, the same vacuum degree, O ₂ gas, and applied power of about 1.9 kw.
In, for example, a TiO _x thin film having a film thickness of 20 nm was obtained at a plate glass conveying speed of about 56 mm / min. For the TiSi _x O _y thin film, a TiSi target was used in the same equipment, and a TiSi _x O _y thin film of about 20 nm was formed at the same vacuum degree, O ₂ gas, and applied power of 1.8 kw, for example, at a plate glass conveying speed of about 68 mm / min. Obtained.

[0025]

[Table 1]

Comparative Examples 1 to 5 Glass treated in the same manner as in Example 1 was used, and SUS was used in the same apparatus.
Set two targets and set 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 SUSO _X thin film having a thickness of about 20 nm was formed as the first layer at m 2 / min. Then, using the other SUS target, an Ar gas pressure of about 2 × 10 ^-3 Torr and an applied power of about 1.0 kw were used to obtain a SUS thin film having a film thickness of about 5 nm at a plate glass conveying speed of about 600 mm / min. Further, in the same manner as the first layer, a SUSO _X thin film having a film thickness of about 30 nm was formed and laminated as a third layer at a plate glass conveying speed of about 100 mm / min.

The CrO _X thin film and the TiO _X thin film were obtained by adjusting the plate glass conveying speed to a desired film thickness in the same manner as in the above-mentioned embodiment. As for the TiN _X thin film, a Ti target was used in the same device, and at the same vacuum degree, N ₂ gas, and applied power of about 1.5 kw, for example, a TiN _X thin film with a film thickness of about 40 nm was obtained at a plate glass transport speed of about 75 mm / min. ..

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

Compared to the respective examples, in these conventional heat ray-reflecting glasses, for example, the surface resistance value is low, 320 Ω / port or less, and the radio wave reflectance is 9% or more. It is worse than the radio wave reflectivity of reinforced concrete, and is likely to cause radio interference in the vicinity of buildings.

[0030]

[Table 2]

[0031]

As described above, according to the present invention, a thin film having a high surface electric resistance, which is a Cr nitride thin film having a specific film thickness and another nitride film having a specific film thickness, is uniquely formed by the sputtering method. It is a heat-insulating glass with excellent abrasion resistance, corrosion resistance, and durability, good radio wave transmission, low radio wave reflectance similar to ordinary float glass, and high layer due to the fact that it is a heat-insulating glass by combining it appropriately and properly to form a laminated film. Without causing radio interference to the surroundings of the building, good habitability that the reflection color tone from the glass surface side exhibits a gold-based color tone, and can be used as laminated glass or double glazing as well as single glass, The present invention efficiently provides a heat ray-shielding glass having useful low radio wave reflection characteristics.

Claims (3)

[Claims] 1. A first layer, which is a nitride thin film of Cr having a film thickness of 1 to 25 nm, on one surface of a transparent glass substrate, and a Ta film having a film thickness of 30 to 75 nm on the first layer. Alternatively, a heat ray-shielding glass having a low radio wave reflection characteristic, characterized in that at least one nitride thin film of TiSi or Zr is selected and coated as a second layer. 2. The radio wave low reflection characteristic according to claim 1, wherein a Ti or TiSi or Cr oxide thin film having a thickness of 5 to 30 nm is coated as a third layer on the second layer. A heat ray shielding glass having. 3. The heat ray shielding glass having a low radio wave reflection characteristic, wherein the coated heat ray shielding performance film has a sheet resistance value of 10 kΩ / mouth or more, and the reflection tone from the glass surface side of the glass is a gold-based tone. The heat ray-shielding glass having low radio wave reflection characteristics according to claim 1 or 2, characterized in that: