JPH1045434A - Radio wave transmission type insulating glass for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject glass excellent in moisture resistance, wear resistance, corrosion resistance and durability transmission of radio waves comparable to an ordinary float glass, and heat rays interruption, and capable of improving a cooling.heating effect without a thermally heated feeling and capable of being used as a window profile for an automobile in a single plate. SOLUTION: In a radio wave transmission type insulating glass for the automobile, an aluminum-silicon oxide thin film having a film thickness of >=1nm to <=10nm as the first layer from a glass surface side, a tungsten-silicon oxide thin film having the film thickness of >=5nm to <=50nm as the second layer and the aluminum-silicon oxide thin film having the film thickness of >=10nm to <=100nm as the third layer are laminated on a surface of a transparent glass substrate by sputtering by energizing an aluminum-silicon target or a tungsten- silicon target in a vacuum device containing an atmosphere gas having a ratio of a gaseous argon to a gaseous oxygen to within a range of (95%:5%) to (70%:30%). The glass is high in resistance and has surface resistant value of >=60MΩ/square to <=10GΩ/square.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to be used as a heat insulating glass having a coating for a vehicle or the like.
It has a relatively high transmittance of visible light, and in particular, by using green glass, it can block ultraviolet rays and improve the habitability, and also reduce the reception obstacle in broadcasting of AM radio waves, FM radio waves, etc. The object of the present invention is to provide a glass which can reduce radio interference such as a strike phenomenon and requires a radio wave transmission performance equivalent to that of ordinary float glass, and particularly a radio wave transmission type heat insulating glass for automobiles which can be used as a single glass.

[0002] Particularly, the present invention relates to a radio wave transmission type heat insulating glass for automobiles, which is useful as a window material for automobiles, for example, a glass having a glass antenna (antenna conductor), such as a front window, a rear window, a side window, or 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. In recent years, in particular, in the glass for vehicles, in addition to high heat ray shielding performance, transparency of various radio waves with relatively high visible light transmittance has been required.

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.

[0005] As the heat ray shielding glass for a vehicle, for example, Japanese Patent Application Laid-Open No. 1-145351 describes an infrared ray shielding glass, and a transparent dielectric film and a nitride film are sequentially formed on a glass substrate from the substrate side. In an infrared shielding glass formed by forming at least three layers of transparent dielectric films, it is disclosed that at least the transparent dielectric film is made of tantalum oxide, and the nitride film is made of titanium nitride, zirconium nitride, hafnium nitride, It is disclosed that it is composed of at least one of tantalum nitride and chromium nitride.

On the other hand, as for glass for vehicles having radio wave transmission performance and heat ray shielding performance, for example, Japanese Patent Application Laid-Open No. 2-177601 discloses a vehicle window glass having radio wave transmission performance. When the heat ray reflective film has a surface resistivity of less than 20 kΩ / port, the original glass antenna performance cannot be exhibited, and the heat ray reflective film is in contact with the antenna conductor. It is disclosed that when in a state, the surface resistivity of the heat ray reflective film is preferably 500 KΩ / port or more, and more preferably 1 MΩ / port or more.

For example, Japanese Patent Application Laid-Open No. 8-12378, which has already been proposed by the present applicant, describes a heat-shielding glass and a method for manufacturing the same. A first layer is placed on a transparent glass substrate from the substrate side. A first dielectric film is provided, a tungsten oxide film is provided as a second layer on the first layer, and a second dielectric film is provided as a third layer on the second layer. .

For example, as the second layer, II of the periodic table
Providing a composite tungsten oxide film containing at least one metal element selected from the group consisting of Group Ia, Group IVa, Group Vb, Group VIb and Group VIIb;
And at least one oxide selected from the group consisting of silicon, titanium, aluminum, tin, zirconium, tantalum, chromium, stainless steel, nichrome and niobium as the first and second dielectric films, or a composite oxide thereof Was used.

Furthermore, for example, a visible light transmittance of about 70% or more provides sufficient visibility with sufficient visible light transmittance, and a solar light transmittance of about 60% or less provides sufficient heat for sunlight. And the sheet resistance of the membrane is 500KΩ / port ~ 200M
Useful for construction or automobile windows, such as being in the range of Ω / mouth and allowing mobile phones to be used without any problems, and having good radio and FM radio wave reception and sufficient radio wave transparency. It has been disclosed that it will be a glass.

[0010] For example, Japanese Patent Application Laid-Open No. Hei 8-59298, which has already been proposed by the present applicant, describes a heat insulating film.
Tungsten and IV of the periodic table on a transparent glass substrate
A heat insulating film formed by forming a composite oxide film made of at least one element selected from the group consisting of group a, group IIIa, group VIIb, group VIb and group Vb has been disclosed.

Furthermore, for example, Japanese Patent Application Laid-Open No. 8-59300, which has already been proposed by the present applicant, describes a heat insulating film, and it includes a transparent glass substrate / a composite tungsten oxide film / a transparent dielectric film / a composite oxide film. A heat blocking glass which is a tungsten film and has a refractive index of a transparent dielectric film lower than that of a composite tungsten oxide film has been disclosed.

[0012]

As described above, for example, those described in Japanese Patent Application Laid-Open No. 1-145351 are disclosed in Japanese Patent Application Laid-Open No. 1-145351. It is 60 nm, and the thickness of the tantalum oxide is preferably 40 to 90 nm, which is relatively thick, more preferably 55 to 75 nm.As a result, it is difficult to say that the radio wave transmission performance is always excellent. Reception performance of glass antennas for radio and mobile phones will be reduced, and high visible light transmittance and low visible light reflectance, film color tone, stimulus purity, heat ray shielding performance and radio wave transmission performance will be well balanced. There is a problem that it is difficult to obtain the desired characteristics as a window material for an automobile.

On the other hand, for example, in Japanese Patent Application Laid-Open No. 2-177601, if the heat ray reflective film is in contact with the antenna conductor, the surface resistivity of the heat ray reflective film is not less than 500 KΩ / port, for example, 1 to 1. With about 8 MΩ / port, the receiving performance of the antenna is satisfactorily satisfied, 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. As a matter of fact, various optical characteristics are not satisfied, such as insufficient optical characteristics and unevenness in film thickness, so that it has a sufficiently excellent radio wave transmission performance and has various optical characteristics and various performances in a well-balanced manner. However, it is hard to say that the desired automotive window material is sufficiently satisfactory.

As described above, for example, Japanese Patent Application Laid-Open No. 8-12378, which has already been filed by the present applicant, discloses that a visible light transmittance of about 70% or more is sufficient. It has good visibility, and the solar transmittance is about 60% or less. It blocks the heat rays of sunlight effectively enough, and the sheet resistance value of the film is
In the range of 500KΩ / mouth to 200MΩ / mouth, the mobile phone can be used without any trouble, and the radio can receive FM and AM radio waves well and has sufficient radio wave transparency.
Among the useful and useful architectural or automotive glazings, it has been desired to withstand even more severe conditions and / or long term periods.

Further, in recent years, a heat ray shielding glass has become useful as a window glass for vehicles in order to improve the livability in a room. In recent years, in addition to this characteristic, a printed antenna (glass antenna) having a back window for transmitting various radio waves. In particular, AM radio waves which have been received by a conventional whip antenna have come to be received by a glass antenna. In particular, mobile phones, car navigation systems and the like have become remarkably popular.

For this reason, radio wave transmission requires a surface resistance value higher than that of the prior art, for example, about 60 MΩ / mouth or more, and a relatively high visible light transmittance from the viewpoint of safety and habitability. What has a heat-shielding property is desired.

[0017]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made by forming a specified aluminum silicon oxide thin film and a tungsten silicon oxide thin film on a transparent glass substrate. Moisture resistance is improved by using a sputtering method to combine the layers with a specific film thickness to achieve a relatively high visible light transmittance and heat ray blocking property and a surface resistance value of 60 MΩ / port or more. It is more durable than it does, enhances visibility, is excellent in heat ray shielding,
In addition, it exhibits its characteristics in a well-balanced manner, and can provide a radio wave transmission type insulating glass with even better radio wave transmission characteristics, and can be used for various automotive window materials, including those with a single plate and a glass antenna. An object of the present invention is to provide a useful automotive radio wave transmission glass which can be used sufficiently and can be adapted to recent needs such as maintaining its excellent performance even under severer conditions and environments.

That is, according to the present invention, the thickness of the first layer is 1 nm or more and 10 nm
The following aluminum silicon oxide thin film, a tungsten silicon oxide thin film having a thickness of 5 nm or more and 50 nm or less as a second layer,
An aluminum silicon oxide thin film having a thickness of 10 nm or more and 100 nm or less as a third layer, in a vacuum system in an atmosphere gas in which the ratio of Ar gas and O ₂ gas is 95%: 5% or 70%: 30%. A radio wave transmission type heat insulating glass for automobiles, characterized in that it is applied to an aluminum silicon target or a tungsten silicon target and sputtered to form a multilayer film, and has a high surface resistance of 60 MΩ / port to 10 GΩ / port.

In addition, the above-mentioned radio wave transmission type heat insulating glass for automobiles, wherein the reflection color of the three-layered laminated film has a neutral color tone. Further, the radio wave transmission type heat insulating glass for an automobile described above is a single plate.

Further, the present invention provides the above-mentioned radio wave transmission type heat insulating glass for automobiles, characterized in that the radio wave transmission type heat insulating glass for automobiles comprises at least an antenna conductor and a laminated film composed of the three layers.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, an aluminum silicon oxide thin film having a thickness of 1 nm or more and 10 nm or less as a first layer from a glass surface side, and a film thickness of 5 nm or more and 50 nm or less as a second layer.
The following tungsten silicon oxide thin film, the third layer is an aluminum silicon oxide thin film having a thickness of 10 nm or more and 100 nm or less, and the ratio of Ar gas and O ₂ gas is 95%: 5% or 70%:
The reason why the film is formed by applying a film to an aluminum silicon target or a tungsten silicon target in a vacuum system in an atmosphere gas in a range of 30% and by sputtering to form a multilayer film is as follows. Regarding the tungsten silicon oxide thin film, the tungsten silicon oxide thin film has a high specific resistance and therefore has a relatively high radio wave permeability and, of course, has excellent heat insulating performance, but it is said that the tungsten silicon oxide thin film has a somewhat excellent moisture resistance. However, the tungsten silicon oxide thin film is used as a second layer to protect it by undercoating and overcoating, thereby improving moisture resistance.

When the thickness of the tungsten silicon oxide thin film is less than 5 nm and thin, the heat insulation performance is poor,
If the thickness is more than 50 nm, the visible light transmittance is reduced and the visible light reflectance is increased.
It was as follows.

Next, as the undercoat, an aluminum silicon oxide thin film having a thickness of 1 nm or more and 10 nm or less is formed as a first layer from the glass surface side, and a third layer is formed as the overcoat.
Regarding the selection of the aluminum silicon oxide thin film having a film thickness of 10 nm or more and 100 nm or less for the layer, the tungsten silicon oxide thin film as the second layer is protected with good adhesion,
It can be used well for various automotive window materials, has better durability such as improved moisture resistance, enhances visibility, has excellent heat ray blocking properties, and exhibits its properties in a well-balanced manner, and further excellent radio wave transmission properties This is because it is most suitable to be more adaptable to recent needs such as maintaining its excellent performance even under more severe conditions and environments.

Further, as the undercoat, the thickness of the aluminum silicon oxide thin film is set to 1 nm or more and 10 nm or less,
If the thickness is less than 1 nm, the uniformity of the film is not sufficient, and the adhesion to the glass substrate becomes uneven, and the film does not become a sufficient protective film for the tungsten silicon oxide thin film. The film thickness is 1 nm or more and 10 nm because it is not effective in terms of productivity
It was as follows.

The aluminum oxide thin film having a thickness of 10 nm or more and 100 nm or less as the overcoat means that if the thickness is less than 10 nm and the film thickness is small, the moisture resistance can be satisfied. If the thickness is more than 100 nm, the effect as a protective film is so small as to increase the film thickness, which is not effective in terms of productivity, and the visible light transmittance tends to decrease and the visible light reflectivity tends to increase. Because it becomes.

Further, the aluminum silicon oxide thin film and the tungsten silicon oxide thin film are placed in a vacuum system in an atmosphere gas in which the ratio of Ar gas to O ₂ gas is 95%: 5% or 70%: 30%. Is applied to an aluminum silicon target or a tungsten silicon target to perform sputtering when the ratio of O ₂ gas is less than 5% in the ratio of Ar gas to O ₂ gas when forming an aluminum silicon oxide thin film. If it exceeds 30%, the film-forming rate becomes low, and the productivity is reduced. In addition, when forming a tungsten silicon oxide thin film, the ratio of Ar gas to O ₂ gas
If the proportion of the O ₂ gas is less than 5%, the conductivity will be high, so that no radio wave transmission will be exhibited, and if it exceeds 30%, no excellent heat insulating performance will be exhibited.

Further, by increasing the ratio of the Ar gas in the mixed gas when forming the aluminum silicon oxide thin film and the tungsten silicon oxide thin film, the film formation rate is increased and the productivity is improved. In addition, the thickness of the overcoat can be increased, and the moisture resistance can be further improved.

Furthermore, by making the ratios of the Ar gas and the O ₂ gas in the mixed gas the same when forming the aluminum silicon oxide thin film and the tungsten silicon oxide thin film, the time required for switching the gases is reduced. It can be shortened and the productivity can be improved.

Further, the surface resistance of the three-layer film formation is
The high resistance value of 60MΩ / port or more and 10GΩ / port or less is considered that the surface resistance value of less than 60MΩ / port is sufficient compared to the radio wave transmission of the glass plate before coating the multilayer film. It cannot stably and reliably fall within a fluctuation difference of, for example, 1 dB (as an absolute value).
In order to keep the fluctuation difference within dB, for example, within the fluctuation difference of 0.8 dB or more, 65MΩ / port or more, and furthermore, the surface resistance of the laminated film that sufficiently satisfies the radio wave transmission performance, the optical characteristics, and the physical and chemical characteristics. The value is 70MΩ / 1GΩ or more.
/ Port or less, more preferably about 75 MΩ / port or more and 1 GΩ / port or less.

Further, the radio wave transmitting type heat ray shielding glass having the above-mentioned configuration can be used as a single plate, and in particular, as a single plate for a rear glass, a side glass, a sun roof glass, etc., as well as a laminated glass together with a window material for automobiles. It can be used.

Further, the radio wave transmission type heat insulating glass for automobiles has a transparent glass substrate having a visible light transmittance of about 80, for example.
%, Visible light reflectivity about 7%, solar transmittance about 58%
%, The stimulus purity is about 2 to 3%, it is friendly to people and the environment, does not glare at night or in rainy weather, and can also impart ultraviolet absorption performance.
If the thickness is used, the difference is less than 1 dB, for example, 0.8 to 0 dB compared to the radio wave transmission performance of only the colored glass substrate before coating the laminated film.
The above-mentioned layered film having the above-mentioned structure is skillfully entangled with each other particularly on the optical characteristics so as to bring about a synergistic effect. It is an excellent material with excellent optical function, especially suitable as an automotive window glass.

Further, in the above-mentioned radio wave transmission type heat insulating glass for automobiles, the transparent glass substrate may have a visible light transmittance of about 79%, a visible light reflectance of about 7%, and a solar transmittance of about 72%. Use a bronze color tone glass substrate (e.g., about 3.5 mm thick) that is equivalent to or slightly inferior to a green color tone glass substrate that is gentle to people and the environment and does not glare at night or in rainy weather, with a stimulus purity of about 2 to 3%. The radio wave transmission performance substantially equal to that of 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, 0.1%).
8 to 0 dB), and by specially entanglement with each other on the optical characteristics to bring about a synergistic effect, the radio wave transmission performance is different from the conventional radio wave transmission type heat ray shielding glass. In addition to enhancing the heat ray shielding performance, it is excellent as an excellent window glass especially for automobiles having a remarkably excellent optical function.

Further, the radio wave transmission type heat insulating glass for a vehicle is a window glass including an antenna conductor and a laminated film formed of at least the three layers, for example, a window glass for a vehicle, particularly a rear glass, a rear quarter (side) glass. Specifically, as a configuration on a cross section, for example, an antenna conductor is provided between the glass substrate and the laminated film, and on a plane, the laminated film is coated on the entire surface of the glass substrate. Basically, for example, in a black frame around the periphery of the glass substrate, coating is performed except for a portion around the entire periphery or a portion slightly larger than the feeding point portion with a certain width from the peripheral edge, or a molding (frame) like the feeding point portion. Body) except for a part to be integrally molded or added later, and further to cover all or a part of the antenna conductor part. Are those, the arrangement is of course that various configurations could make freely.

Further, by increasing the surface resistance value of the film having the heat insulation performance as described above, it is possible to prevent reception failure in broadcasting of AM radio waves, FM radio waves, etc., or ghost phenomenon in TV images. This is because it is possible to more reliably prevent the occurrence of radio wave disturbances such as those described above, and to obtain glass having sufficient radio wave transmission performance, thereby making it 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.

As described above, the glass substrate is an inorganic transparent colorless or colored glass manufactured by a so-called float method, preferably, for example, a green glass or a bronze glass, and further, for example, a gray glass or a glass. It can be used for blue glass and the like. 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.

As described above, the radio wave transmission type heat insulating glass for automobiles of the present invention is coated on a transparent glass substrate so as to wrap a SiWOx thin film having a specifically controlled x value with an AlSiOx thin film having a specifically controlled x value. By laminating and forming at least three layers with a specific thickness, and having a surface resistance value of 60 MΩ / port or more and 10 GΩ / port or less, of the at least three layers of the laminated film, An AlSiOx thin film that has a very high surface resistance value and heat insulation properties as two layers, and that can control the values, and that can easily be controlled so that the target optical properties are skillfully matched to the optical properties of the glass substrate and balanced. In addition, a sufficient radio wave transmission characteristic is given to the laminated film. In addition, even if it is a single plate, a film with high abrasion resistance and high durability can be obtained by arranging an AlSiOx thin film with chemical resistance, weather resistance, abrasion resistance and durability and insulating properties on the outermost layer. It is a three-layer structure that retains radio wave transmission, high abrasion resistance, and high durability even in a single plate, and has a visible light transmittance, a visible light reflectance, a solar transmittance, and a stimulating purity of reflection. And the effect of making the balance remarkable.

In particular, the visible light transmittance can be cleared to 70% or more, the reflection color of the laminated film is of a neutral type, the solar transmittance is improved, and the optical characteristics such as the visible light reflectance are appropriately balanced. In particular, by adopting a green glass substrate, it can also shield ultraviolet rays, alleviate the feeling of heat and heat, enhance the effect of cooling and heating, improve the livability, and
Band, FM band, TV band, etc.
It is possible to reduce the radio interference such as the ghost phenomenon without deteriorating the reception performance of the glass antenna for the TV, radio, mobile phone, etc. for vehicles, and to exhibit the original glass antenna performance, An object of the present invention is to provide an excellent radio wave insulating glass for automobiles that can ensure a comfortable environment inside and outside, can receive AM charged waves with a glass antenna without any trouble, and can be used as a single plate.

[0038]

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 green color tone glass substrate (MFL3.5) having a size of about 300 mm.times.300 mm and a thickness of about 3.5 mm was sequentially washed with a neutral detergent, water rinse, and isopropyl alcohol, dried, and then dried with a DC magnetron. Set in the vacuum chamber of the sputtering device
The target of AlSi was set so as to be able to reciprocate upwards facing each other, and then the inside of the tank was evacuated to 5 × 10 ⁻⁶ Torr or less by a vacuum pump, and then a mixed gas of Ar gas and O ₂ gas was introduced into the vacuum tank. (However, the flow rate of O ₂ gas in the mixed gas is 18%)
The vacuum was maintained at 5 × 10 ⁻³ Torr, and about 1.0 kW of electric power was applied to the AlSi target. The DC magnetron reaction sputter by the mixed gas was flown at a speed of about 1161 mm above the AlSi target. An AlSiOx thin film having a thickness of about 5 nm was formed as a first layer on a glass substrate at a rate of / min. After the film formation is completed, the application to the AlSi target is stopped.

Next, the target of SiW set in the vacuum chamber of the above-mentioned apparatus is set so as to be able to reciprocate upward and oppose each other, and then the inside of the chamber is vacuum-pumped by 5 × 10 5.
After degassing to ^-6 Torr or less, Ar gas and O ₂
Gas mixture gas (However, the flow rate of O ₂ gas in the mixture gas is 18
%) And maintain the vacuum at 5 × 10 ^-3 Torr,
An electric power of about 0.5 kW is applied to the SiW target, and a DC magnetron reaction sputter by the mixed gas flows at a speed of about 615 mm / above the SiW target.
By transporting the glass substrate with a thickness of about 25 nm, a SiWO layer having a thickness of about 25 nm is formed as a second layer on the first layer of AlSiOx thin film.
x (x is about 1.5 to 2) thin film was formed. After the film formation is completed, the application to the SiW target is stopped.

Next, similarly to the film of the first layer, the target of AlSi set in the vacuum tank of the above-described apparatus is set so as to be able to reciprocate upward and oppose each other. After degassing to 5 × 10 ⁻⁶ Torr or less with a vacuum pump, a mixed gas of Ar gas and O ₂ gas (however,
The flow rate of O ₂ gas in the mixed gas is 18%), the degree of vacuum is maintained at 5 × 10 ⁻³ Torr, and about 1.0 kW of electric power is applied to the AlSi target. By transporting the glass substrate through the reaction sputter at a speed of about 194 mm / min above the AlSi target, an AlSiOx (x is about 30 nm thick as a third layer on the second SiWOx thin film. (Approximately 1.5 to 2). After the film formation is completed, the application to the AlSi target is stopped.

The obtained three-layer single-panel radio wave transmission type insulating glass for automobiles had the film configuration shown in Table 1. The radio wave transmitting type thermal insulation glass for automobiles 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.

* The results are shown in Tables 1 and 2. The light source was an A light source with a transmittance and a D ₆₅ light source with a reflectivity.

Mechanical properties: (Taber test) (Abrasion resistance) Abrasion wheel (CS-10F), change in haze (fogging degree) value after 1000 rotations with a load of 500 g (ΔH%) .

(Traverse test) The amount of change in haze (fogging degree) value after broadband cloth # 40, load 100 g / cm ² , stroke: 100 mm, 5000 times (ΔH%).

* If ΔH% is 4% or less in each case, it can be used as a single plate, and is regarded as acceptable. Chemical properties: (Acid resistance) (Chemical resistance) After immersing the test piece in a 3% H ₂ SO ₄ solution at room temperature for about 4 hours, the appearance was visually judged.

(Alkali Resistance) After immersing the test piece in a 3% NaOH solution at room temperature for about 4 hours, the appearance was visually judged.

* In either case, the external appearance was visually observed and no change was found, or those within the allowable range were accepted. Electrical characteristics: Surface resistance value (point-to-point) (MΩ / port) was measured with a Mitsubishi Yuka surface high resistance meter (HIRESTA HT-210).

* If the surface resistance value was about 60 MΩ / port or more (preferably about 60 MΩ / port or more and 10 GΩ / port or less), the radio wave transmittance was judged to be acceptable. That is, for example, in the AM band (about 520 to 1630 kHz) of the radio wave, the gain of the glass substrate without a coating and the gain of the radio wave transmission type heat insulating glass for an automobile of the present invention are measured, and the absolute value of the difference is obtained. The dB is about 1 or less, indicating that sufficient radio wave transmission performance is obtained.

Moisture resistance: After standing in an environment of about 50 ° C. and a relative humidity of about 95% RH for about 2 weeks, the external appearance was visually judged. * The appearance was visually observed, and no change was observed or within the acceptable range. The mark was marked with 、.

Further, those that were outside the acceptable range but were barely marginal were marked with a 、, and those that showed a change in the entire surface and were completely outside the acceptable range were marked with a cross.

For the thickness of each thin film, an uncoated portion was formed at the time of coating for each thin film, and the level difference was measured with a surface roughness meter (manufactured by SLOAN, DEKTAK IIA). I asked.

As a result, a part of the results is shown in Tables 1 and 2. The visible light transmittance is 71.2%, and the excellent transparency makes it possible to secure safety inside and outside the vehicle, for example, and the solar transmittance is 51.4%.
%, With excellent heat shielding properties, visible light reflectance of 11.4% on the film surface side and its stimulus purity of 11.1% on the glass surface side.
10.2% and its stimulus purity is 12.3%. For example, it is an optical characteristic aiming to exhibit a neutral color tone when the stimulus purity is about 13% or less, and the surface resistance value is as high as 83 MΩ / mouth. It had radio wave transmission and also had a moisture resistance of ◎, indicating sufficient durability.

Further, no change was observed in the chemical property test, and sufficiently stable chemical resistance was exhibited. In both the Taber test and the Traverse test, ΔH was 4% or less, indicating excellent wear resistance. Was something.

Therefore, it is possible to obtain a desired radio wave transmission type heat insulating glass for an automobile, which exhibits various physical properties in a well-balanced manner.
Automobile window glass that has excellent visibility and comfort, and is safe for drivers, passengers, and the environment, and can receive various radio waves including the AM band comfortably, especially with the antenna conductor. It could be used sufficiently for automotive window glass.

In addition, when the weather resistance (eg, about 1000 hours with a sunshine weather meter: no abnormalities in appearance) and other various properties were evaluated, all were aimed at and passed.

Example 2 A green color tone glass substrate (MFL3.5) having the same size and thickness as in Example 1 was sequentially washed, dried and used.

In the same manner as in Example 1, the first
An AlSiOx thin film having a thickness of about 5 nm is formed as a layer, and then a SiWO film having a thickness of about 25 nm is formed as a second layer on the first AlSiOx thin film.
x (x is about 1.5 to 2) thin film, and then a third layer is formed on the second SiWOx thin film as a third layer by changing the thickness to about 50 nm thick AlSiOx (x is about 1.5 to 2). A thin film was formed.

As described above, the film configurations and the respective film thicknesses shown in Table 1 were obtained in the same manner as in the first embodiment, and were evaluated by the same evaluation means according to the measuring method shown in the first embodiment. Was.
Some of the results are shown in Tables 1 and 2.

The obtained radio wave transmission type heat insulating glass for automobiles has a visible light transmittance of 71.8%, a solar light transmittance of 52.0%, a visible light reflectance of 11.0% on the film surface side and an excitation purity of 6.0%.
10.6% on the glass side and its stimulating purity is 7.5%,
Excellent optical characteristics such as neutral color tone, surface resistance value of 99 MΩ / port, moisture resistance of 印, sufficiently stable chemical resistance, excellent abrasion resistance, etc. It was the intended radio wave transmission type heat insulating glass for automobiles that exhibited excellent physical properties in a well-balanced manner.

Example 3 In the same manner as in Example 1 or 2, only the thickness of the third layer was changed to about 100 nm, and the film configurations and thicknesses shown in Table 1 were obtained.

The film structure and each film thickness were evaluated by the same evaluation means according to the measuring method shown in Example 1.
Some of the results are shown in Tables 1 and 2. The obtained radio wave transmission type heat insulating glass for automobiles of this example has a surface resistance value of 13
5 MΩ / mouth, which was the expected value, showing excellent physical properties such as optical properties in a well-balanced manner as in Example 1.

Example 4 The film configuration and the respective film thicknesses shown in Table 1 were obtained by merely changing the glass substrate in Example 1 to a bronze color tone system.

The film structure and each film thickness were evaluated by the same evaluation means according to the measuring method shown in Example 1.
Some of the results are shown in Tables 1 and 2. The obtained radio wave transmission type heat insulating glass for an automobile of the example has a solar radiation transmittance of 6%.
The surface resistance is 135MΩ although the shielding performance is slightly reduced to 4.6%
, And all were intended to show well-balanced properties such as excellent optical properties as in Example 1.

Example 5 In the same manner as in Example 1, only the thickness of the third layer was changed to about 20 nm, and the film configurations and thicknesses shown in Table 1 were obtained.

The film structure and each film thickness were evaluated by the same evaluation means according to the measuring method shown in Example 1.
Some of the results are shown in Tables 1 and 2. Each of the obtained radio wave transmission type heat insulating glasses for automobiles of the present example was the expected one that exhibited well-balanced properties such as excellent optical properties as in Example 1.

[0067] processed in the same manner as in Comparative Example 1 Example 1, as shown in Table 1, in the second layer in Example 1, O ₂ in the atmosphere at the time of film formation
Only the film thickness was changed to about 20 nm while the gas amount was 4%, and the film configurations and the respective film thicknesses shown in Table 1 were obtained.

The film structure and each film thickness were evaluated by the same evaluation means according to the measuring method shown in Example 1.
Some of the results are shown in Tables 1 and 2. The obtained glass with a film of the comparative example has a solar radiation transmittance of 45.4% and a heat ray shielding property and has a moisture resistance of ◎, but has a visible light transmittance of 6
The visibility is relatively poor at 4.9%, and the visible light reflectance is 1
5.8% and its stimulation purity is 12.9%, 13.7% on the glass side
And the stimulus purity is 16.5%, for example, the stimulus purity is 13
% Or more, it is difficult to say that it has a neutral color tone, and its surface resistance is as low as 2 MΩ / mouth, which is not sufficient for radio wave transmission. It was not a transmission type insulating glass.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

As described above, the present invention relates to a radio wave transmission type heat insulating glass for automobiles, which is formed by sputtering and has at least three layers having a specific film configuration and a specific film thickness. It has excellent abrasion resistance, corrosion resistance and durability, and has well-balanced optical characteristics. No, the gain of the antenna conductor disposed on the heat insulating glass is comparable to that of float glass,
An object of the present invention is to efficiently provide a radio wave transmission type heat-insulating glass for an automobile useful as a window glass for an architectural use, in particular, a window glass for an automobile, which can be used as a single-pane glass as well as a laminated glass or a double-glazed glass.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C23C 14/08 C23C 14/08 N (72) Inventor Tadashi Shibata Nissan 2, Takaracho, Kanagawa-ku, Yokohama-shi, Kanagawa Inside Nissan Motor Co., Ltd. (72) Inventor Riichi Nishiide 2 Takaracho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture

Claims (4)

[Claims] 1. An aluminum silicon oxide thin film having a thickness of 1 nm or more and 10 nm or less as a first layer and a tungsten silicon oxide film having a thickness of 5 nm or more and 50 nm or less as a first layer on a transparent glass substrate surface from the glass surface side. Film thickness as thin film, third layer
An aluminum silicon oxide thin film of 10 nm or more and 100 nm or less is
A laminated film is formed by applying a sputtering to an aluminum silicon target or a tungsten silicon target in a vacuum system in an atmosphere gas having a gas to O ₂ gas ratio of 95%: 5% or 70%: 30%, Surface resistance value is 60M
A radio wave insulating glass for automobiles having a high resistance of Ω / port or more and 10 GΩ / port or less. 2. The reflected color of the three-layer film formation is a new color.
2. The radio wave transmission type heat insulating glass for an automobile according to claim 1, wherein the glass has a neutral color tone. 3. The radio wave transmission type heat insulating glass for an automobile,
3. The radio wave transmission type heat insulating glass for an automobile according to claim 1, which is a single plate. 4. The radio wave transmission type heat insulating glass for an automobile,
4. The radio wave transmission type heat insulating glass for an automobile according to claim 1, comprising at least an antenna conductor and a laminated film formed of the three layers.