JPH0912339A - Heat wave-shielding glass which transmits radio wave - Google Patents

Abstract

PURPOSE: To obtain such a glass that has light-shielding property which is useful for protection of privacy, that has excellent wear resistance, corrosion resistance and durability, transmits radio waves comparable to normal float glass, has shielding property against heat wave which improves the effect of cooling and heating a room without giving a hot feeling to a user, and can be used as a single plate for windows of a car. CONSTITUTION: Layers are formed on a transparent glass substrate in such a manner that, from the glass surface, SUS or a Cr nitrogen oxide thin film having a film thickness between >=15 nm and <=55nm is formed as the first film and a Ta or Ti oxide thin film having a film thickness between >=4nm and <=12nm is formed as the second layer. The SUS or Cr nitrogen oxide thin film consists of SUSNxOy or CrNxOy, wherein (x) and (y) are determined by sputtering a SUS or Cr target in a vacuum chamber containing a mixture gas of N2 and O2 by the ratio of 98:2 to 93:7. The obtd. heat wave-shielding glass transmits radio waves and has the transmittance for visible rays between >=25% and <=50 % and >=10MΩ/sq. surface resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a heat-shielding glass with a coating for vehicles and the like, and in particular, it can prevent the feeling of heat and heat, block ultraviolet rays, and improve the heating and cooling effect, and it is relatively low. It has a light-shielding property with visible light transmittance and has privacy protection performance.
It is possible to reduce reception obstacles such as FM radio broadcasts, or to reduce radio disturbances such as ghost phenomenon.
It is a glass that requires radio wave transmission performance equivalent to that of glass, especially a radio wave transmission type heat ray shielding glass that can be used as a single plate glass.

In particular, window materials for automobiles, such as front and rear window shade bands, or rear and side window privacy glass,
Further, the present invention relates to a radio wave transmission type heat ray shielding glass useful for a glass including a glass antenna (antenna conductor), such as a light shielding glass for a sunroof.

[0003]

2. Description of the Related Art In recent years, a heat ray shielding glass has been adopted for a vehicle for the purpose of shielding solar radiation energy flowing into the vehicle through the glass for the vehicle, and increasing the temperature inside the vehicle and reducing the cooling load. Recently, particularly in the glass for vehicles, in addition to high heat ray shielding performance, it has also been required to have a light shielding property with a relatively low visible light transmittance, a privacy protection property, and various radio wave transmitting properties. Is coming.

Further, the conventional heat ray absorbing glass can appropriately select the transmittance of visible light and the like and can increase the radio wave transmittance. The on-line heat ray reflective glass has high heat ray shielding properties and radio wave transmittance, but cannot be patterned for high mount lamps.

Regarding the heat ray shielding glass for the vehicle, for example, Japanese Patent Laid-Open No. 1-145351 discloses an infrared ray shielding glass, and a transparent dielectric film and a nitride film are sequentially arranged on a glass substrate from the substrate side. And an infrared shielding glass formed by forming at least a three-layer structure film of a transparent dielectric film, it is disclosed that at least the transparent dielectric film is made of tantalum oxide, and the nitride film is titanium nitride, zirconium nitride, hafnium nitride, It is disclosed that it is made of at least one of tantalum nitride and chromium nitride.

On the other hand, regarding a vehicle glass having a radio wave transmission property and a heat ray shielding property, for example, Japanese Patent Application Laid-Open No. 2-177601 describes a vehicle window glass having a radio wave transmission performance. And the antenna conductor are provided, and the film having the surface resistivity of the heat ray reflective film of less than 20 kΩ / port cannot exhibit the original glass antenna performance, and the heat ray reflective film contacts the antenna conductor. It is disclosed that the surface resistivity of the heat ray reflective film is preferably 500 KΩ / port or more, and more preferably 1 MΩ / port or more when in a state.

Regarding the glass for vehicles which has radio wave transmission properties and heat ray shielding properties and also has light shielding properties, for example, Japanese Patent Application Laid-Open No. 5-170485 describes a heat ray shielding film and a window glass for automobiles. , Visible light transmittance of 35% or less, 20K
A heat ray shielding film having a sheet resistance value of Ω / mouth or more. The heat ray shielding film is one of nitride, boride, oxynitride and oxide.
A film made of seeds or a film containing NbOx (1.1 ≤ x ≤ 1.8) as a main component. A window glass for an automobile, which has the above-mentioned film and an antenna conductor, and the heat ray shielding film is not in contact with the antenna conductor and has a sheet resistance value of 20 KΩ / mouth or more. Further, such a heat ray shielding film is in contact with an antenna conductor, and an automobile window glass having a sheet resistance value of 500 KΩ / mouth or more is disclosed.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in Japanese Patent Laid-Open No. 1-145351, the film thickness of nitride such as titanium nitride is usually 5 in order to obtain the heat ray shielding performance. ~ 60 nm, and the thickness of the tantalum oxide film is relatively thick, preferably 40 to 90 nm, more preferably 55 to 75 nm.
As a result, it cannot be said that the radio wave transmission is necessarily excellent, and the reception performance of the glass antenna for automobiles such as televisions, radios, and mobile phones is reduced, and the relatively low visible light transmission rate. There is a problem that it is difficult to obtain the desired properties as a window material for automobiles, which has a sufficiently well-balanced low visible light reflectance, film color tone, stimulus purity, heat ray shielding performance and radio wave transmission performance.

On the other hand, for example, in the one disclosed in Japanese Patent Laid-Open No. 2-177601, if the heat ray reflective film is in contact with the antenna conductor, the heat ray reflective film has a surface resistivity of 500 KΩ / port or more, for example, 1 to With 8 MΩ / mouth or so, the receiving performance of the antenna is met, but a slight decrease in performance is unavoidable. For example, an infinite surface resistivity, that is, an insulating film can be formed, and the receiving performance of the antenna is sufficient. However, various performances such as insufficient optical characteristics and uneven film thickness are not satisfied, and privacy protection performance is not obtained, and it has excellent radio wave transmission performance and is well balanced. It is difficult to say that it is a desired window material for automobiles, which has optical characteristics and various performances and is sufficiently satisfactory.

Further, for example, in the one disclosed in Japanese Patent Application Laid-Open No. 5-170485, if the heat ray shielding film is in contact with the antenna conductor, the surface resistivity of the heat ray shielding film is 500 KΩ / port or more, and further, for example, 1 MΩ. / For those with a mouth or more, although the reception performance of the antenna is met for some time, a slight deterioration in performance is unavoidable, especially the whip antenna (pol antenna)
It is difficult to receive the AM radio wave band without any obstacles without using the glass antenna, and even if the antenna reception performance is sufficient even if an infinite surface resistivity, that is, an insulating film can be formed, various optical characteristics Does not satisfy various performances such as inadequate and uneven film thickness, and it has excellent radio wave transmission performance and privacy protection performance with well-balanced various optical characteristics and various performances. It is hard to say that it is a desired window material for automobiles.

Further, in the conventional method, for example, the glass body color or hot spray is used, so that although the characteristics such as the privacy protection performance can be obtained, the post-processing is difficult. In recent years, heat ray-shielding glass has become useful as a window glass for vehicles to improve indoor comfort. Recently, in addition to this characteristic, there is a tendency for various radio waves to be received by a back window print antenna (glass antenna). Yes, especially AM radio waves that were previously received by whip antennas are now being received by glass antennas.

For this reason, it is necessary to have a surface resistance value of 10 MΩ / port or more, which is higher than the conventional one, for radio wave transmission. In addition, from the viewpoint of comfort, the visible light transmittance is 25% in order to secure the privacy inside the vehicle. Low as low as ~ 50% and reflectance of 15
% Or more has been desired. Further, in order to secure the safety to the rear of the vehicle, it has become common to mount a high mount stop lamp on the back window, and in order to prevent a decrease in light intensity in this part, only the high mount stop lamp area is covered with a film. It has become necessary to have patterning that doesn't have to be attached.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and a specified glass oxide of SUS or Cr and Ta or Ti are formed on a transparent glass substrate.
The oxide of the, by sputtering method, patterning by masking the portion where film formation is not necessary, and forming a laminated film by combining and forming a nitrogen oxide film with a trace amount of O ₂ control in a specific film thickness, Visible light transmittance 25 to 50%
By setting the surface resistance value to 10 KΩ / mouth or more, the light-shielding property can be expressed, privacy can be secured and reflectance of 15% or more can be secured, excellent heat-ray shielding properties and well-balanced characteristics are exhibited. , It is possible to obtain a radio wave transmission type heat ray shielding glass having better radio wave transmission characteristics, and it can be sufficiently used for various automobile window materials including those with a single plate and a glass antenna. It is intended to provide a most suitable and useful radio wave transmission type heat ray shielding glass.

That is, according to the present invention, a transparent glass substrate surface has a film thickness of 55 nm or less and 15 nm or less as a first layer from the glass surface side.
The SUS or Cr nitrogen oxide thin film and the Ta or Ti oxide thin film having a thickness of 4 nm or more and 12 nm or less are laminated and formed as a second layer. The x and y values are selected and determined by applying sputtering to a SUS or Cr target in a vacuum system device in an atmosphere gas in which the ratio of N ₂ gas to O ₂ gas is 98: 2 or 93: 7. Made of SUSNxOy or CrNxOy and has a visible light transmittance of
25% or more and 50% or less and a surface resistance value of 10 MΩ / mouth or more, a radio wave transmission type heat ray shielding glass.

Further, the above-mentioned radio wave transmission type heat ray shielding glass, wherein the surface resistance of the two-layer laminated film is a high resistance value of 15 MΩ / port or more and 10 GΩ / port or less. Further, the radio wave transmission type heat ray shielding glass is characterized in that the radio wave transmission type heat ray shielding glass is a single plate.

Further, each of the above-mentioned radio wave transmission type heat ray shielding glasses is characterized in that the radio wave transmission type heat ray shielding glass comprises at least an antenna conductor and a laminated film formed of the two layers. As described above, as described above, a nitrogen oxide thin film of SUS or Cr having a film thickness of 55 nm or less and 15 nm or more as the first layer from the glass surface side, and Ta or Ti having a film thickness of 4 nm or more and 12 nm or less as the second layer.
The reason why the oxide thin films are laminated is that, first, for SUS or Cr nitrogen oxide thin films with a thickness of 55 nm or less and 15 nm or more, the specific resistance is high and therefore relatively high radio wave permeability is obtained. Of course, it also has heat ray shielding performance, and the radio wave transmission performance of the laminated film formation is almost SUS.
Alternatively, although it is determined by the nitrogen oxide thin film of Cr and it is necessary to balance the heat ray shielding performance of the laminated film formation, other optical characteristics such as privacy protection performance are also substantially determined. For example, if the film thickness is less than 15 nm, it becomes difficult to reduce the visible light transmittance to 50% or less, and if the film thickness exceeds 55 nm, it becomes difficult to increase the visible light transmittance to 25% or more.
Visible light transmittance can be ensured to be 25% or more and 50% or less, and the surface resistance value is higher than 10 MΩ / mouth, for example 15 MΩ / mouth or more, to improve radio wave transmission performance, 20 nm is preferable.
It is about 50 nm or less.

Moreover, the nitrogen oxide thin film of SUS or Cr is used as a SUS or Cr target in a vacuum system apparatus in an atmosphere gas in which the ratio of N ₂ gas to O ₂ gas is 98: 2 to 93: 7. It is SUSNxOy or CrNxOy that is formed by selecting and determining the values of x and y by applying and sputtering.
The surface resistance value (sheet resistance value MΩ) of the laminated film formation is determined not only by the film thickness but also by the x and y values by controlling the atmosphere gas in reactive sputtering.
/ Mouth), because it has a delicate influence on its optical properties and physical and chemical performance.
When the value as the ratio of N ₂ gas and O ₂ gas (the value of O ₂ gas) is less than 2, the surface resistance value decreases to 10 M due to the shift to the conductive direction.
It becomes less than Ω / port and the radio wave transmission performance decreases, and it may be difficult to clear the visible light transmittance value of 25% or more even if considering the balance with the film thickness. Yes, and for example with respect to the value of x
When the value as the ratio of N ₂ gas and O ₂ gas (value of O ₂ gas) exceeds 7, it shifts to the insulating direction and the surface resistance value increases to increase the radio wave permeability. However, the values of visible light transmittance and solar radiation transmittance are large, and it is difficult to clear the visible light transmittance of 50% or less. Considering the balance with the film thickness, it is clear that the heat ray blocking performance is excellent. However, it can be difficult in some cases.

Next, the oxide thin film of Ta or Ti having a film thickness of 4 nm or more and 12 nm or less as the second layer has a high surface resistance value and can be said to be an insulating film, and is the first layer.
Adhesion to nitrogen oxide thin film of SUS or Cr is good, and there is almost no effect on visible light transmittance, visible light reflectance, stimulation purity, etc., as well as chemical resistance, abrasion resistance, scratch resistance and weather resistance. It is excellent in durability such as properties.

The thickness of 12 nm or less and 4 nm or more is because if it exceeds 12 nm, it is not necessary because of the interaction with the glass and the nitrogen oxide thin film of SUS or Cr, and it is not economical. This is because the durability such as the chemical resistance, abrasion resistance, scratch resistance and weather resistance described above becomes insufficient. It is preferably 10 nm or less and 5 nm or more.

As for the wear resistance, the TaOx film is better than the TiOx film, and the SUSNxOy film is better than the CrNxOy film.
The structure of G (glass substrate) / SUSNxOy film / TaOx film is the best.

Further, the radio wave transmission type heat ray-shielding glass having the above-mentioned constitution can be used as a single plate, not only as a laminated glass particularly as a window material for automobiles but also as a single plate for a rear glass, a side glass or a sunroof glass. It can be used.

Further, when used under various conditions or environments, the surface of the outermost surface layer, which is the second layer, correspondingly corresponds to this, for example, a silicon oxide-based protective film made of silazane or the like. It goes without saying that a hard coat may be applied with the above materials, or a functional film having a reflection reducing function may be further coated.

In addition, the surface resistance value of the two-layer laminated film formation is
The high resistance value of 10 MΩ / mouth or more is 10 M
If the surface resistance value is less than Ω / port, it cannot be kept within the variation difference within 1 dB (as an absolute value) with sufficient stability and reliability compared with the radio wave transmission of the glass plate before coating the laminated film. To be more stable and stable within a fluctuation range of less than 1 dB, for example, within a fluctuation range of 0.8 dB, it is preferable to have at least 15 MΩ / port and to further satisfy radio wave transmission performance, optical characteristics, and physical / chemical characteristics. The surface resistance of the laminated film is in the range of 20 M Ω / port or more and 10 G Ω / port or less, and more preferable surface resistance value is 22 M Ω / port or more.
It is in the range of 10 GΩ / port or less.

Further, the radio wave transmission type heat ray shielding glass is a transparent glass substrate having a visible light transmittance of about 80%.
Degree, visible light reflectance about 7%, solar radiation transmittance about 62%
If you use a green toned glass substrate (for example, about 3.5 mm thickness) that has a degree of stimulation purity of about 2 to 3%, is kind to people and the environment, does not glare at night or in the rain, and can also give ultraviolet absorption performance, The laminated film having substantially the same radio wave transmission performance as that of the substrate (the difference is less than 1 dB, for example, 0.8 to 0 dB compared to the radio wave transmittance of only the colored glass substrate before coating the laminated film). In particular, it is possible to improve radio wave transmission performance and heat ray shielding performance by skillfully entwining with each other in terms of optical characteristics so as to bring about a synergistic effect. It will be the most suitable window glass.

Further, in the radio wave transmission type heat ray shielding glass, a transparent glass substrate has, for example, a visible light transmittance of about
About 79%, visible light reflectance about 7%, solar radiation transmittance about
A bronze-type toned glass substrate (for example, about 3.5 mm thick) that is 72% or so and has an excitation purity of 2 to 3% and is equivalent to or slightly inferior to a green-type toned glass substrate that is kind to people and the environment and does not glare in the night or rain. By using it, almost the same radio wave transmission performance as the substrate (less than 1 dB compared to the radio wave transmission of only the colored glass substrate before coating the laminated film, for example, 0.8
~ 0 dB) and by making it possible to create a synergistic effect by skillfully entwining with the above-mentioned laminated film with respect to optical characteristics, unlike the conventional case of simply using a radio wave transmission type heat ray shielding glass, Not only is the heat-shielding performance improved, but it is also suitable as an outstanding window glass for automobiles, which has a remarkably excellent optical function.

Further, the radio wave transmission type heat ray shielding glass is a window glass provided with an antenna conductor and a laminated film formed of at least the two layers, for example, an automobile window glass,
Particularly, it is useful as a rear glass and a rear quarter glass (side glass). Specifically, as a cross-sectional structure, for example, an antenna conductor is provided between the glass substrate and the laminated film, and the laminated film is formed on a plane. Based on coating on the entire surface of the glass substrate, for example, coating on the peripheral portion of the glass substrate in a certain width from the peripheral edge except the entire peripheral portion or a portion slightly larger than the feeding point portion, or the feeding The molding can be performed in the same manner as the point portion, and the molding can be performed by excluding a portion where the molding (frame body) is integrally molded or retrofitted, and further, by excluding all or a part of the antenna conductor portion. Needless to say, the configuration can be variously configured.

Furthermore, by setting the surface resistance value of the coated film having a heat ray shielding property to a high value as described above, reception failure in broadcasting of AM radio waves, FM radio waves or the like or a ghost in TV images This is because it is possible to more surely prevent the occurrence of radio interference such as a phenomenon, and to obtain a glass having sufficient radio wave transmission performance, which is environmentally friendly. Further, for example, even when the coated film having the high-resistance heat ray shielding performance is directly laminated on the glass antenna element, it can be said that there is no influence on the deterioration of the radio wave reception performance at all.

Further, as described above, the glass substrate is an inorganic transparent colorless or colored glass manufactured by the so-called float method, preferably green glass or bronze glass, and further gray glass, for example. It can also be used for blue glass. In addition to being able to be used as a single plate, it can be used as a double-layer glass or laminated glass (this radio wave transmission type heat ray shielding glass includes a combination of clear and colored glass substrates as well as clear ones), glass with a shade band, bilayer. Needless to say, it can be used as various kinds of sheet glass products such as glass, tempered glass, etc., and further, flat or bent sheets. The thickness is preferably, for example, about 1.5 mm or more and about 4.5 mm or less, more preferably about 2.0 mm or more and about 4.0 m or more.
Colorless or colored glass of about m or less.

[0029]

As described above, the radio wave transmission type heat ray-shielding glass of the present invention is SU represented by SUSNxOy or CrNxOy whose x and y values are uniquely controlled on a transparent glass substrate.
A nitrogen oxide thin film of S or Cr and an oxide thin film of Ta or Ti represented by TaOx or TiOx covering the thin film are formed in at least two layers each with a specific film thickness, and have a visible light transmittance of 25 % Or more and 50% or less, and surface resistance value is 10 MΩ /
By having the thickness above the mouth, the first layer of the at least two-layer laminated film has a very high surface resistance value and the value can be controlled, and the target optical characteristics of the glass substrate can be controlled. SUSNxOy or CrNx that is easy to control so as to skillfully match and balance the optical characteristics
Oy is arranged to give sufficient radio wave transmission characteristics to the laminated film. In addition, TaOx film or Ti, which has chemical resistance, weather resistance, wear resistance, durability, and insulating properties even for a single plate
By arranging the Ox film on the outermost surface layer, it is possible to obtain a film having high wear resistance and high durability. Even with a single plate, the radio wave transmission, high wear resistance, It has a function of maintaining a high durability and making the visible light transmittance, the visible light reflectance, the solar radiation transmittance, and the stimulation purity of reflection well balanced in a remarkable manner.

In particular, when the visible light transmittance is 25% or more and 50% or less, it can be cleared as a light-shielding functional film, and further, the solar radiation transmittance can be improved and the optical characteristics such as the visible light reflectance can be appropriately balanced. With excellent heat-shielding performance that protects the interior privacy of the vehicle, dirt, such as fingerprints, is not easily attached, and the feeling of heat and heat is mitigated, the effect of heating and cooling is improved, and comfort is improved, as well as AM band, FM band, The low reflection of radio waves in the TV band is remarkably excellent and the radio wave transmission performance is the same as that of normal float glass, so the reception performance of the glass antenna for TVs, radios, mobile phones, etc. for vehicles is deteriorated. It is possible to reduce the radio wave interference such as ghost phenomenon, to demonstrate the original glass antenna performance, and to secure a comfortable environment inside and outside the vehicle, especially with the glass antenna. Hindrance Receiving can, and is intended to provide an excellent radio wave transmission of solar control glass available in veneer to accommodate high mount stop lamp or the like.

[0031]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 A bronze color tone glass substrate (NFL3.5) having a size of about 300 mm × 300 mm and a thickness of about 3.5 mm was sequentially washed with a neutral detergent, water rinse, isopropyl alcohol, and dried, and then a DC magnetron spatula was used. It is set in the vacuum tank of the ring device.
The Cr targets are set so as to face each other so as to be able to reciprocate upward, and then the inside of the chamber is degassed to 5 × 10 ^-6 Torr or less by a vacuum pump, and then N ₂ gas and O ₂ gas are mixed in the vacuum chamber. A gas (however, the flow rate ratio of N ₂ gas and O ₂ gas is 95: 5) is introduced to maintain the degree of vacuum at 5 × 10 ⁻³ Torr, and about 1.0 kW of electric power is applied to the Cr target to mix the mixture. A CrNxOy thin film having a thickness of about 45 nm was formed as a first layer on a glass substrate at a speed of about 200 mm / min above a Cr target in a DC magnetron reaction sputtering by gas. After the film formation is completed, the application to the Cr target is stopped.

Next, the Ti targets set in the vacuum tank of the above-mentioned apparatus are set so as to be able to reciprocate upwards facing each other, and then the inside of the tank is set to 5 × 10 ⁻⁶ by a vacuum pump.
After degassing to less than Torr, O ₂ gas was introduced into the vacuum chamber to maintain the vacuum at 5 × 10 ⁻³ Torr, and about 2.0 kW of electric power was applied to the Ti target to generate O ₂ gas. By transporting the glass substrate at a speed of about 300 mm / min above the Ti target in the DC magnetron reaction spatula, the first layer of about 5 mm was formed on the glass substrate.
A TiOx (x is about 1.5 to 2) thin film having a thickness of nm was formed. After the film formation is completed, the application to the Ti target is stopped.

The radio wave transmission type heat ray shielding glass of two layers of the obtained single plate is as shown in Table 1. The radio wave transmission type heat ray shielding glass was evaluated by the following measurements. (Measurement and evaluation methods) Optical properties: For the visible light transmittance (380 nm to 780 nm), visible light reflectance (380 nm to 780 nm), solar transmittance (340 nm to 1800 nm), etc., use the 340 type recording spectrophotometer (Hitachi, Ltd.) Optical properties were determined by JISZ8722 and JISR3106.

Mechanical properties: (Traverse test) (Abrasion resistance) Broad cloth # 40, load 100 g / cm ² , stroke: 100 mm, change amount of haze (fog condition) value after 5,000 times (H) %).

* In each case, the ΔH% was 4% or less, which was regarded as acceptable. Chemical characteristics: (Acid resistance) (Chemical resistance) After immersing the test piece in 0.1N H ₂ SO ₄ solution at room temperature for about 24 hours, the appearance is visually judged.

(Alkali resistance) After the test piece was immersed in a 0.1N NaOH solution at room temperature for about 24 hours, the appearance was visually judged.

* In both cases, the appearance was visually inspected and no change was observed, and the result was regarded as acceptable. Displayed with OK mark. Electrical characteristics: Measured by Mitsubishi Yuka's surface high resistance meter (HIRESTA HT-210).

(Surface resistance value) (M Ω / mouth). Radio wave transparency: In the AM band (about 520 to 1630 kHz range) of radio waves, (gain difference) (gain difference) the gain of a glass substrate without a coating and the gain of the radio wave transmission type heat ray shielding glass of the present invention are measured, Absolute value of the difference (△ dB).

Cold-heat test Normal temperature → approx. 80 ° C. (4 hours) → normal temperature (0.5 hours) → −30 ° C. (1.5 hours) → normal temperature (0.5 hours) After 10 cycles, the appearance is visually judged. * Appearance was visually observed and no change was seen as passing.

Displayed with OK mark. Note that the film thickness of each thin film was obtained by forming a non-coated portion at the time of coating each thin film, measuring the step difference with a surface roughness meter (DEKTAK II A, manufactured by SLOAN), and then supplementarily.

As a result, as shown in Table 1, the excellent light-shielding property can protect the privacy of the interior of the vehicle, the optical properties such as the excellent heat-ray shielding property, the sufficiently high surface resistivity, and the sufficiently stable acid resistance. Heat resistance, cold and heat resistance, and excellent wear resistance, it is possible to obtain the desired radio wave transmission type heat ray shielding glass that shows a good balance of physical properties, and has excellent habitability and is suitable for drivers, passengers and the environment. It could be used well for automobile window glass that can receive various radio waves including AM band comfortably while maintaining gentleness and safety, especially for automobile window glass equipped with an antenna conductor.

Alkali resistance, weather resistance (eg, about 1000 hours using a Sunshine weather meter: no abnormality in appearance), humidity resistance (eg, about 30 ° C., about 95% RH for about 15 days:
When there were no abnormalities in appearance) and other various characteristics were evaluated, all passed.

Example 2 A green color tone glass substrate (MFL3.5) having the same size and thickness as in Example 1 was sequentially washed in the same manner as in Example 1, dried and then DC magnetron sputtering. The SUS target set in the vacuum tank of the equipment is set so as to be able to reciprocate upwards facing each other, and then the inside of the tank is degassed by a vacuum pump to 5x10 ^-6 Torr or less, and then the vacuum tank A mixed gas of N ₂ gas and O ₂ gas (however, the flow rate ratio of N ₂ gas and O ₂ gas is 95: 5) was introduced to maintain the degree of vacuum at 5 × 10 ⁻³ Torr, and the above SUS target was used. Approximately 1.0 kW of electric power was applied, and SUS was put into the DC magnetron reaction spatter by the mixed gas.
A 45 nm thick SUSNxOy thin film was formed as a first layer on the glass substrate above the target at a speed of about 200 mm / min. After the film formation is completed, the application to the SUS target is stopped.

Next, the Ta targets set in the vacuum chamber of the above-mentioned apparatus are set so as to face each other so as to be able to reciprocate upward, and then the inside of the chamber is set to 5 × 10 ^-6 by a vacuum pump.
After degassing to less than Torr, O ₂ gas was introduced into the vacuum chamber to maintain the vacuum degree at 5 × 10 ⁻³ Torr, and power of about 2.0 kW was applied to the Ta target to generate O ₂ gas. By transporting the glass substrate in the DC magnetron reaction spatula above the Ta target at a speed of approximately 500 mm / min, approximately 5% of the first layer is formed on the glass substrate.
A TaOx (x is about 4/2 to 5/2) thin film having a thickness of nm was formed. After the film formation is completed, the application to the Ta target is stopped.

As described above, the film thicknesses shown in Table 1 were obtained in the same manner as in Example 1 above, and the film structure was evaluated by the same evaluation means as in Example 1 by the measuring method and the like. . Table 1 shows the results.

In the AM band (in the range of about 520 to 1630 kHz), the absolute value (Δ) of the difference between the surface resistance value (M Ω / mouth) and the gain of the radio wave transmission type heat-shield glass of the present embodiment. It has been found that the relationship with (dB) is as shown in FIG.

It can be confirmed that this relationship can be sufficiently applied to the radio wave transmission type heat ray shielding glass of the present invention. For example, the absolute value (ΔdB) of the gain difference is set to 1 dB or less in order to obtain sufficient radio wave transmission. , A surface resistance value of about 10 MΩ / mouth or more is good, and if it is about 0.8 to 0.6 dB or less, it is a surface resistance value of about 16 to 20 MΩ / mouth or more, for example, about 0.5 to 0.3 dB or less. Then, it was found that the surface resistance value of about 30-40 MΩ / mouth or more is good.

The radio wave transmission type heat ray-shielding glass of each of the obtained Examples was expected to show excellent physical properties such as excellent optical characteristics in a well-balanced manner as in Example 1. Examples 3 to 7 The film thicknesses shown in Table 1 were obtained in the same manner as in Example 1 or 2 above, and the film constitution was measured by the same evaluation means as the measuring method shown in Example 1. Table 1 shows the results.
Shown in

The radio wave transmission type heat ray-shielding glass of each of the obtained Examples was expected to show excellent physical properties in a well-balanced manner as in Example 1. In particular, Examples 3, 4, 5 and 7 exhibited remarkably excellent radio wave transmission performance.

Comparative Example 1 CrNxOy as shown in Table 1 was treated in the same manner as in Example 1.
A glass coated with only a thin film was obtained. The same measurement method and evaluation as in Example 1 were performed. Table 1 shows the results.

The glass coated with only the obtained CrNxOy thin film has a sufficiently high surface resistance value of 20 MΩ / mouth and good radio wave transmission, but has sufficient abrasion resistance as can be seen from the traverse test. However, it is hard to say that it is sufficient for use as a single plate as a window glass for automobiles, and it was not the intended radio wave transmission type heat ray shielding glass.

Comparative Example 2 The respective film thicknesses shown in Table 1 were obtained in the same manner as in the above-mentioned Example 2, and the film structure was measured by the same evaluation means as the measuring method shown in Example 1. Table 1 shows the results.

The obtained glass of the comparative example is particularly 3 MΩ.
The radio wave transmission performance becomes inadequate at about /
Similarly, it was not the intended radio wave transmission type heat ray shielding glass.

Comparative Example 3 The film thicknesses shown in Table 1 were obtained in the same manner as in Example 1 above, and the film structure was measured by the same evaluation means as in Example 1. Table 1 shows the results.

The obtained glass of the comparative example did not reach a visible light transmittance of 25 to 50% at all, had a low light-shielding property, and it was difficult to secure the privacy protection performance, and the solar radiation transmittance was 6%.
It was not relatively low at 8.2%, and it was hard to say that the heat ray blocking property was sufficiently excellent, so it was not the intended radio wave transmission type heat ray shielding glass.

[0057]

[Table 1]

[0058]

As described above, according to the present invention, at least a nitrogen oxide thin film of SUS or Cr having a high surface resistance value of a specific thickness is coated with a Ta or Ti oxide thin film by a sputtering method. A heat ray shielding glass coated in two layers, with excellent wear resistance, corrosion resistance, and durability, as well as excellent optical characteristics in a well-balanced manner, and with low radio wave reflectance, similar to ordinary float glass with good radio wave transmission. However, without exhibiting radio interference, the gain of the antenna conductor arranged in the heat-shielding glass shows the same level as that of the float glass, and the laminated glass or the double-layer glass can be used as a single glass, as a matter of course. Not to mention window glass for construction,
In particular, the present invention efficiently provides a radio wave transmission type heat ray shielding glass useful as a window glass for automobiles.

[Brief description of the drawings]

FIG. 1 shows the relationship between the surface resistance value (MΩ / mouth) of the radio wave transmission type heat ray shielding glass of Example 2 and the gain difference (ΔdB) between the colored glass substrate having no coating and the radio wave transmission type heat ray shielding glass. It is an explanatory view shown.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication C23C 14/08 C23C 14/08 N (72) Inventor Takao Tomioka 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass In the laboratory

Claims (4)

[Claims] 1. A SUS or Cr film having a thickness of 55 nm or less and 15 nm or more as a first layer on the transparent glass substrate surface from the glass surface side.
Nitrogen oxide thin film and a second layer of Ta or Ti oxide thin film having a thickness of 4 nm or more and 12 nm or less, and the nitrogen oxide thin film of SUS or Cr is N ₂ gas and O _{2. With} SUSNxOy or CrNxOy, the values of x and y are selected and determined by applying and sputtering to a SUS or Cr target in a vacuum system device in an atmosphere gas in which the ratio of the _two gases is 98: 2 or 93: 7. The radio wave transmission type heat ray shielding glass having a visible light transmittance of 25% or more and 50% or less and a surface resistance value of 10 MΩ / mouth or more. 2. The surface resistance of the two-layer laminated film formation is 1
The radio wave transmission type heat ray shielding glass according to claim 1, which has a high resistance value of 5 MΩ / mouth or more and 10 GΩ / mouth or less. 3. The radio wave transmission type heat ray shielding glass according to claim 1, wherein the radio wave transmission type heat ray shielding glass is a single plate. 4. The radio wave transmission type heat ray shielding glass according to claim 1, wherein the radio wave transmission type heat ray shielding glass comprises at least an antenna conductor and a laminated film formed of the two layers.