JPH07237936A - Ultraviolet and heat-ray shielding glass for automobile - Google Patents

Abstract

PURPOSE:To obtain a UV and heat-ray shielding glass capable of shielding IR heat rays and UV rays at the same time with a simple laminated film constitution and useful for automotive glass having good antenna function. CONSTITUTION:This UV and heat-ray shielding glass for automobile is produced by laminating a transparent glass substrate 1 with an antenna conductor 4 and a multilayered film consisting of a heat-ray shielding film 3 composed mainly of a composite nitrogen oxide containing at least one kind of group IVb element and at least one kind of group Vb, group IIIa and group IVa elements of the Periodic Table and a UV shielding film 2 composed mainly of an oxide containing either one of Zn, Ce or Cd or a double oxide of the elements.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass having a function of blocking ultraviolet rays and heat rays and an antenna function, which is suitable as a window glass for automobiles, and has a high visible light transmittance and a good ability to block ultraviolet rays and heat rays. It is preferably used as a window glass for automobiles having various antenna functions.

[0002]

2. Description of the Related Art Conventionally, from the viewpoint of energy saving, a specific portion of sunlight radiated into a vehicle compartment is cut off through a window glass to reduce a temperature rise in the vehicle compartment and a load on a cooling device. Therefore, a window glass having a high heat ray shielding property is required.

As a method of blocking heat rays, there is known a method of blocking heat rays by forming a transparent conductive film typified by an ITO film or a ZnO film added with aluminum on a transparent substrate, which is so-called Dol-Demira. Has been. This type of glass blocks heat rays, but the blocking wavelength is 1.5 μm
As above, the heat ray blocking performance is not so good. It is also known that various metal films are laminated to combine a dollar-demirer effect with an optical interference effect to reflect or transmit light of a specific wavelength. As a heat ray reflective film in this method, for example, a structure in which Ag is sandwiched between transparent dielectric films in JP-B-47-6315 is disclosed in JP-A-63-20633.
Japanese Patent No. 3 discloses a structure in which a nitride is sandwiched between transparent dielectrics.

On the other hand, with respect to ultraviolet rays, it is said that when the ultraviolet rays are absorbed by the human body, sunburn occurs, and melanin pigments are deposited to form spots and freckles, which causes skin aging. In addition, it is said that the interior materials inside the vehicle are faded and deteriorated by the irradiation of ultraviolet rays. From this point of view, a glass having a high ultraviolet blocking performance is also required for automobiles.

Recently, in automobiles, radio waves such as AM and FM waves, TV waves such as VHF and UHF, car phones,
An antenna for GPS is provided to know information such as a traveling position by using an artificial satellite. Conventionally, whip antennas and pillar antennas have been widely used as these antennas, but glass antennas with an antenna conductor formed on the window glass have come to be used due to reduction of air resistance during traveling and demands for appearance. It was This antenna is mainly obtained by forming a conductive metal wire or metal film on glass in a predetermined pattern.

When the above-mentioned conductive film is formed as the infrared / heat-shielding glass, as described in JP-A-3-122032, when a conductive film is formed on the antenna wire, a current flows between the antenna wires. Since it flows, the performance of the glass antenna deteriorates, and inconvenience such as tuning becomes impossible, and there is a problem in that these radio waves cannot be normally transmitted and received by the glass antenna.
Further, the conventional infrared shielding glass with a glass antenna has a problem that it cannot block ultraviolet rays unless a laminated glass is used.

Further, as described in JP-A-5-170485, although the antenna performance and the visible light transmittance are sufficient, it is difficult to say that the solar radiation transmittance is always a low value. There is a problem that it does not block UV rays and there is no description suggesting this. Furthermore, JP-A-5
As described in JP-A-170489, although the antenna performance and the solar radiation transmittance are sufficient, the visible light transmittance is as low as about 35% or less, which makes it difficult to use as a window glass for automobiles, and blocks ultraviolet rays. However, there is a problem in that it cannot block ultraviolet rays. JP-A-5-1704
Even if the inventions described in Japanese Patent Application Laid-Open No. 89 and Japanese Patent Application Laid-Open No. 5-170485 are simply combined with an ultraviolet blocking film, they do not necessarily have the same configuration or operational effect as the invention of the present application. Things are hard to become.

Therefore, the main object of the present invention is to solve the above problem, that is, a functional film having a heat ray-shielding property is formed by the above technique.
The g film has a surface resistivity of several Ω to several tens of Ω / mouth, and the plasma frequency of Ag is in the ultraviolet region.
Since it reflects electromagnetic waves with a higher frequency than this, it has a high radio wave shielding property. Since the radio waves received by the glass antenna are electromagnetic waves, when the above-mentioned metal-based film or metal nitride-based heat ray reflective film is formed on the glass antenna, the radio waves to be received by the glass antenna are blocked by the conductive film. Therefore, in order to solve the problem that the gain of the antenna at the time of reception is lowered and a sufficient antenna function cannot be obtained, ultraviolet rays and infrared rays are blocked, and various radio waves can be satisfactorily transmitted and received by the glass antenna. , It is to provide a window glass for a vehicle that can be used as a single plate.

A further specific object of the present invention is to block ultraviolet rays and infrared rays for automobiles having a glass antenna having an ultraviolet ray blocking function capable of efficiently blocking heat rays and ultraviolet rays simultaneously with a simple layer structure and a good radio wave transmitting / receiving performance. To provide glass.

[0010]

The present invention has been made in view of the above problems and objects, and the present invention provides a transparent glass substrate on which at least one group IVb of the periodic table and V are added.
A heat ray-shielding film having a composite nitrogen oxide containing at least one of b group, IIIa group, and IVa group as a main component and prepared by a sputtering method, and an oxide containing any one of Zn, Ce, and Cd, or a composite oxide of these. An ultraviolet heat ray-shielding glass for an automobile, comprising: a multi-layered film including an ultraviolet ray blocking film containing a substance as a main component; and an antenna conductor.

Furthermore, IV of the periodic table is attached to a transparent glass substrate.
at least one of Ti, Hf, and Zr, which is a group b, and V,
A heat ray-shielding film having a composite nitrogen oxide containing at least one of Nb, B, Al, C, and Si as a main component and prepared by a sputtering method, and an oxide containing any one of Zn, Ce, and Cd, or a composite oxide of these. An ultraviolet heat ray-shielding glass for an automobile, which is provided with a multi-layered film including an ultraviolet ray shielding film containing a substance as a main component and an antenna conductor, wherein the antenna conductor enables reception of radio waves. UV heat ray blocking glass for automobiles.

[0012] In addition, Ti and B on the transparent glass substrate,
A heat ray-shielding film which is a composite nitrogen oxide containing at least one of C, Al and Si and which is produced by a sputtering method;
An ultraviolet heat ray-shielding glass for automobiles, comprising a multilayer film comprising an ultraviolet ray blocking film, which is a complex oxide obtained by doping Cr into the oxide of Zn or Zn oxide, and an antenna conductor. The above-mentioned UV heat ray shielding glass for automobiles, which is capable of receiving.

Furthermore, the surface resistivity of the multilayer film is 10 k.
The present invention relates to the above-mentioned UV heat ray-shielding glass for automobiles, which has a resistance of Ω / mouth or more and 100 MΩ / mouth or less.

FIG. 1 shows the construction of an ultraviolet / infrared ray shielding glass for automobiles according to the present invention. In FIG. 1, (1) shows various glass plates such as soda lime glass and aluminosilicate glass, or polymethylmethacrylate. -To (PMM
A) shows a transparent glass substrate selected from transparent resin substrates such as polycarbonate (PC). Bronze,
It goes without saying that colored glass such as gray, blue or green, and even translucent glass can be used depending on the case. (2) shows an ultraviolet blocking film containing an oxide containing any one of Zn, Ce, and Cd or a composite oxide thereof as a main component. (3) is at least one member of group IVb of the periodic table and at least one member of group Vb, group IIIa, or group IVa.
1 shows a heat ray-shielding film produced by a sputtering method containing a composite nitrogen oxide containing a seed as a main component.

Here, the ultraviolet ray blocking film of the above (2) can be arbitrarily selected from the above oxide film or its composite oxide film, but in particular, zinc oxide, zinc oxide and cerium oxide, cadmium oxide, silicon oxide and the like are used. And a composite oxide film obtained by adding titanium oxide to cerium oxide are preferable. Further, a complex oxide film in which iron, chromium, silicon, and titanium are added to zinc oxide in an amount of 1 to 10 atom% is also preferable. The reason for this is that these films have excellent ultraviolet blocking performance and transparency in the visible light region, and the film thickness is 100 nm or more and 1000 nm or less, preferably 150 nm.
m or more and 900 nm or less, more preferably 200 nm or more and 800 nm or less, and this film thickness is necessary for enhancing the ultraviolet shielding performance, and as a characteristic thereof, the transmittance at a wavelength of 370 nm or less is 15% or less, preferably 13% or less, The film thickness is more preferably 10% or less. The reason why the ultraviolet ray transmittance is preferably small is that it is more effective in preventing sunburn, fading, deterioration and the like on an object or a human body. For example, if it is 10% or less, a markedly excellent thing is sufficient. A product that can be used with satisfaction.

To this end, a ZnO film produced by a sputtering method or a sol-gel method having a high UV blocking performance, or a composite oxide film in which ZnO is doped with Cr in order to enhance the durability of the ZnO film is transparent. Is also preferable.

Further, as the heat ray blocking film of the above (3), at least one kind of IVb group and Vb group, I of the periodic table is used.
A thin film prepared by a sputtering method containing a composite nitrogen oxide containing at least one of Group IIa and Group IVa as a main component can be arbitrarily selected, but is Ti which is Group IVb of the periodic table.
At least one of Hf and Zr and V, Nb, B, Al,
It is desirable to select from a thin film whose main component is a composite nitrogen oxide containing at least one of C and Si. Ti, H
Nitride of f and Zr is a heat ray blocking film having high heat insulation property, but its surface resistivity is low, and the film thickness is very thin to meet the surface resistivity of 10 kΩ / port or more required in the present invention. Since the film becomes island-shaped, the performance as a heat ray blocking film cannot be sufficiently exhibited. Therefore, Ti, which has high heat insulation,
Vf, Nb, B, Al, which have relatively low conductivity to Hf and Zr,
By using an alloy-type nitrogen oxide film containing at least one of C and Si, a heat insulating film having a high surface resistivity can be obtained, which can be 10 kΩ / mouth or more necessary for the present invention. Is.

Of these, it is preferable to use Ti as the main component, which has high productivity and excellent heat insulating properties. By adding a trace amount of oxygen to this, the surface resistivity can be increased while maintaining relatively high heat insulating properties. B, C, Al, Si that can be changed
It is most preferable to use an alloy-type nitrogen oxide film to which one of the above is added to achieve the intended purpose, and the surface resistivity required for the present invention is 1 at 10 kΩ / port or more.
Achievable with less than 00 MΩ / port, 10 kΩ
If it is less than / mouth, the heat ray blocking performance is high, but the antenna performance deteriorates and radio waves cannot be received sufficiently through the glass antenna. If it exceeds 100 MΩ / mouth, there is no problem with the radio wave receiving performance, but the heat ray blocking performance drops significantly. This is because it will be done.

(4) shows an antenna conductor, which is made of a linear or film-like material.

Further, the thickness of the heat ray blocking film is 2 nm or more because it is a film thickness that does not form an island shape, and is 100 nm or less from the economical point of view. Stable and reliable in the above two points and in the whole film structure. In order to obtain the performance, preferably 5 nm or more and 80 nm or less, more preferably 10 nm
It is above 60 nm. This heat ray blocking film is a composite metal nitrogen oxide film, and is mainly formed on the composite metal target by reactive sputtering of nitrogen gas and oxygen gas.
The O / N ratio at this time is preferably 0.01 to 0.2. The reason for this is that the oxygen ratio is less than 0.01, for example 0.
The reason is that the purpose cannot be achieved due to conductivity,
This is because if the ratio exceeds 0.2, the ratio of oxygen is too high, and the heat insulating property is greatly deteriorated so that the desired heat ray-shielding film cannot be obtained. For this reason, the O / N ratio is sufficiently stable and is preferably 0.01 to 0.1 in order to ensure reliable operation and commercialization.
5, more preferably 0.01 to 0.1, and the O / N ratio can be adjusted according to the required surface resistivity and visible light transmittance. That is, if the ultraviolet ray / heat ray blocking film and the glass antenna conductor are provided in contact with each other, 100 k
If it is not more than Ω / mouth, the reception performance of the glass antenna will deteriorate, and if it is not in contact with it, the antenna performance will deteriorate if it is less than 10 kΩ / mouth.
The heat ray-shielding film that achieves the object of the present invention can be expressed by adjusting Therefore, when considering the contact, 1
It is preferable to set it to 00 kΩ / mouth or more.

Further, as the above-mentioned antenna conductor, a printed antenna formed by baking a conductive paste such as silver paste on the surface of a glass plate is generally used. After baking the conductive paste, plating treatment may be further performed with nickel or chromium. Further, as the antenna wire, a wire antenna formed by wiring a conductive metal thin wire such as a copper wire or a film antenna formed with a transparent conductive film is selected according to desired requirements and antenna characteristics. It is possible to use the one formed in.

Further, these ultraviolet ray and heat ray blocking films are formed by a vacuum film forming method such as a sputtering method, a vapor deposition method, an ion plating method, a chemical vapor phase method (CVD method) or a wet film forming method such as a sol-gel method. it can. Among these, the sputtering method and the sol-gel method are excellent in terms of large area and productivity.

Furthermore, the ultraviolet ray, the heat ray blocking film, and the antenna wire may be formed on the same surface of the glass or on the opposite surface. Further, either the ultraviolet ray shielding film or the heat ray shielding film may be an upper layer or the lower layer, and the ultraviolet ray shielding film and the heat ray shielding film may be laminated in two or more layers to form a multi-layered film. Film may be formed.

Further, the order of laminating the antenna wire or film, the ultraviolet ray blocking film, and the heat ray blocking film is not limited, and it goes without saying that a multi-layer laminated glass having two or more layers may be used, and silicon oxide may be provided between these films. It goes without saying that other films such as the above may be formed.

Further, according to the present invention, ultraviolet rays and heat rays can be efficiently blocked, and sufficient antenna reception performance can be obtained. Furthermore, although the ultraviolet heat ray-shielding glass for automobiles of the present invention can be used as a single plate, laminated glass,
It goes without saying that it can be used in double glazing. Further, it is not limited to automobiles, and of course, it can be used as window glass for construction, window glass for various vehicles such as ships, and the like.

The visible light transmittance of the UV heat ray-shielding glass for automobiles is preferably about 60% or more for a rear window or a side window, and about 65% for a sash that places importance on perspective manufacturing. It is above, and about 70% is preferable in the front window.

[0027]

As described above, according to the present invention, a transparent glass substrate is provided with at least one group IVb and Vb III of the periodic table.
A heat ray-shielding film mainly composed of a composite nitrogen oxide containing at least one of Group a and Group IVa and an oxide containing any one of Zn, Ce, and Cd, or a composite oxide of these. Ultraviolet heat ray shielding glass for automobiles, which comprises an ultraviolet ray shielding film as a component and an antenna conductor, and further has a surface resistivity of 10 kΩ / mouth or more and 100 MΩ / mouth or less With the heat-shielding glass, a useful window glass for automobiles that has a simple structure and at the same time enables a glass antenna with a UV-ray blocking function that has the ability to block both heat rays and ultraviolet rays simultaneously and sufficiently and good radio wave reception performance is obtained. To be

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

Example 1 A transparent glass substrate was washed with water and then a silver paste containing glass frit was used.
The strike was printed on a predetermined glass antenna pattern by screen printing. This substrate was baked in an atmosphere of about 620 ° C. for about 2 minutes to form a glass antenna on the surface of the substrate. The glass substrate with the antenna was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried with nitrogen. This substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. Z used as an ultraviolet blocking film in the vacuum chamber
Zn target for nO film and T used as heat ray blocking film
Ti-Si alloy target for i-SiNO film (T
i: Si = 8: 2) was installed. First, a mixed gas of argon and oxygen was adjusted to Ar: O ₂ = 1: 1 as a sputter gas, and the exhaust speed and the gas flow rate were adjusted so that the pressure in the vacuum chamber was 2 × 10 ⁻³ Torr, and then the sputter power was adjusted to about 1. Approximately 150n of ZnO film of ultraviolet blocking film was formed by reactive sputtering of 1kW.
m was formed into a film. After film formation, discharge and gas introduction were stopped and 5 ×
It was evacuated to 10 ^-6 Torr. Next, a mixed gas of nitrogen and oxygen was adjusted to N ₂ : O ₂ = 90: 10 as a sputter gas, the exhaust rate and the gas flow rate were adjusted so that the pressure in the empty tank was 2 × 10 ⁻³ Torr, and then the sputter was performed. Approximately 25n of Ti / SiNO film, which is a heat ray blocking film, is formed by reactive sputtering with power of approximately 1kW
m layers were formed.

The optical characteristics of the ultraviolet heat ray-shielding glass formed as described above have a visible light transmittance of about 71%, which is sufficient visibility required for a window glass for automobiles, and have a solar radiation transmittance of about 60%. The heat rays of light were sufficiently blocked. Further, the ultraviolet ray blocking performance was about 8% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. Further, when this glass was used as a rear window of an automobile, the surface resistivity was about 100 kΩ / mouth and FM radio waves could be sufficiently received.

The visible light transmittance (380 nm
~ 780nm), solar radiation transmittance (340nm ~ 1800n
Regarding m), the respective optical characteristics were determined by a 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JISZ8722 and JISR3106. For the surface resistivity, see Mitsubishi Yuka's surface high resistance meter (HIRESTA HT
-210) and Mitsubishi Yuka's surface low resistance meter (LORE
STA IP-MCP-T250). Furthermore, in the present invention as well as in each of the following Examples and the like, the values are values measured and obtained in the same manner by applying the respective measuring instruments and the JIS.

Example 2 A transparent glass substrate was washed with water and then a silver paste containing glass frit was used.
The strike was printed on a predetermined glass antenna pattern by screen printing. This substrate was baked in an atmosphere of about 620 ° C. for about 2 minutes to form a glass antenna on the surface of the substrate. This substrate glass with an antenna was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried with a nitrogen blower. This substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. Z used as an ultraviolet blocking film in the vacuum chamber
Zn target for nO film and T used as heat ray blocking film
Ti-Si alloy target for i-SiNO film (T
i: Si = 8: 2) was installed. First, a mixed gas of argon and oxygen was adjusted to Ar: O ₂ = 1: 1 as a sputter gas, and the exhaust speed and the gas flow rate were adjusted so that the pressure in the vacuum chamber was 2 × 10 ⁻³ Torr, and then the sputter power was adjusted to about 1. Approximately 350n of ZnO film as an ultraviolet blocking film was formed by reactive sputtering of 1kW.
m was formed into a film. After film formation, discharge and gas introduction were stopped and 5 ×
It was evacuated to 10 ^-6 Torr. Next, a mixed gas of nitrogen and oxygen was adjusted to N ₂ : O ₂ = 80: 20 as a sputter gas, the exhaust rate and the gas flow rate were adjusted so that the pressure in the empty tank was 2 × 10 ⁻³ Torr, and then the sputter was performed. Approximately 35n of Ti / SiNO film as a heat ray blocking film is formed by reactive sputtering with power of about 1kW.
m layers were formed.

The optical characteristics of the ultraviolet heat ray-shielding glass thus formed have a visible light transmittance of about 71%, which is sufficient visibility required for automobile window glass, and a solar radiation transmittance of about 63%. The heat rays of light were sufficiently blocked. Further, the ultraviolet ray blocking performance was about 4% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. Further, when this glass was used as a rear window of an automobile, the surface resistivity was about 50 MΩ / mouth, FM radio waves could be remarkably received, and excellent performance was exhibited.

Example 3 A transparent glass substrate was washed with water and then a silver paste containing glass frit was used.
The strike was printed on a predetermined glass antenna pattern by screen printing. This substrate is about 2 at about 620 ℃
Minute baking was performed to form a glass antenna on the surface of the substrate. This substrate glass with an antenna was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried with a nitrogen blower. This substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. Cr used as an ultraviolet blocking film in the vacuum chamber
A ZnO.Cr alloy target for the doped ZnO film and a Ti / Al alloy target (Ti: Al = 9: 1) for the Ti.AlNO film used as a heat ray blocking film were set. First, argon gas was introduced as a sputtering gas into the vacuum chamber, the exhaust speed and the gas flow rate were adjusted so that the pressure was 3 × 10 ⁻³ Torr, and the sputtering power C was about 1 kW.
An r-doped ZnO film was formed to a thickness of about 200 nm. After the film formation, the discharge and the gas introduction were stopped, and the gas was evacuated to 5 × 10 ⁻⁶ Torr. Next, a mixed gas of nitrogen and oxygen was adjusted to N ₂ : O ₂ = 90: 10 as a sputtering gas, and the pressure in the vacuum chamber was adjusted to 2
After adjusting the exhaust rate and the gas flow rate so as to be × 10 ^-3 Torr, a Ti / AlNO film as a heat ray blocking film having a thickness of about 30 nm was formed by reactive sputtering with a sputtering power of about 1 kW.

The optical characteristics of the ultraviolet heat ray-shielding glass thus formed are as follows: visible light transmittance of about 70%, sufficient visibility required for automobile window glass, and solar transmittance of about 59%. The heat rays of light were sufficiently blocked. Further, the ultraviolet ray blocking performance was about 7% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. Furthermore, when this glass was used as a rear window of an automobile, the surface resistivity was about 5
It was 00KΩ / mouth and was able to receive FM radio waves sufficiently excellently.

Example 4 A transparent glass substrate was washed with water and then a silver paste containing glass frit was used.
The strike was printed on a predetermined glass antenna pattern by screen printing. This substrate is about 2 at about 620 ℃
Minute baking was performed to form a glass antenna on the surface of the substrate. This substrate glass with an antenna was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried with a nitrogen blower. This substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. Cr used as an ultraviolet blocking film in the vacuum chamber
A ZnO / Cr alloy target for the doped ZnO film and a Ti / B alloy target (Ti: B = 9: 1) for the Ti / BNO film used as a heat ray blocking film were set. First, argon gas was introduced as a sputtering gas into the vacuum chamber, the exhaust speed and the gas flow rate were adjusted so that the pressure was 3 × 10 ⁻³ Torr, and then the sputtering of the ultraviolet blocking film was performed with the sputtering power of about 1 kW.
A ZnO film having a thickness of about 300 nm was formed. After the film formation, the discharge and the gas introduction were stopped, and the gas was evacuated to 5 × 10 ⁻⁶ Torr.
Next, as a sputtering gas, a mixed gas of nitrogen and oxygen was added with N ₂ :
The pressure inside the vacuum chamber was adjusted to 2 × 10 ^-3 by adjusting O ₂ = 95: 5.
After adjusting the exhaust speed and gas flow rate to Torr, Ti of the heat ray blocking film is formed by reactive sputtering with a sputtering power of about 1 kW.
-A BNO film having a thickness of about 20 nm was laminated.

The optical characteristics of the ultraviolet heat ray-shielding glass thus formed have a visible light transmittance of about 70% and sufficient visibility required for automobile window glass, and have a solar radiation transmittance of about 59% for the sun. The heat rays of light were sufficiently blocked. Further, the ultraviolet ray blocking performance was about 7% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. Further, when this glass was used as a rear window of an automobile, the surface resistivity was about 50 KΩ / mouth, and FM radio waves could be sufficiently received.

Example 5 After washing a transparent glass substrate with water, a ZnO film as an ultraviolet blocking film was formed by the sol-gel method by the following method. Zinc 2-ethylhexanoate (18%) 100 g, dehydrated castor oil fatty acid (lino-acid content 86%) 80 g, TS as a leveling agent
5 g of F400 (manufactured by Toshiba Silicon Co., Ltd.) and 320 g of mixed xylene as a diluting solvent were mixed with stirring to obtain a coating liquid for ZnO film. A substrate with one side masked is dipped in this coating solution and pulled up at a speed of about 20 cm / min.
An O coating film was obtained. This coating film was dried and hardened in a far infrared furnace at about 150 ° C. for about 15 minutes and further baked at about 500 ° C. for about 15 minutes in an electric furnace to obtain a ZnO film of about 750 nm. A silver paste containing glass frit was printed on a predetermined glass antenna pattern by screen printing. This substrate was baked in an atmosphere of about 620 ° C. for about 2 minutes to form a glass antenna. This substrate glass with an antenna was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried with a nitrogen blower. Transfer this substrate into the sputtering system and
It was evacuated to 10 ^-6 Torr. An alloy target of Ti and B (Ti: B = 9: 1) for a Ti / BNO film used as a heat ray blocking film was installed in the vacuum chamber. As a sputter gas, a mixed gas of nitrogen and oxygen was adjusted to N ₂ : O ₂ = 95: 5, the exhaust speed and the gas flow rate were adjusted so that the pressure in the vacuum chamber was 2 × 10 ⁻³ Torr, and the sputter power was adjusted to about Approximately 25 Ti / BNO films, which are heat ray blocking films, are formed by reactive sputtering of 1 kW.
nm film formation was performed.

Thus, the optical characteristics of the UV heat ray-shielding glass formed by reversing the order of the antenna printed surface and the UV-shielding film in comparison with the above-mentioned embodiment are as follows.
At 0%, it had sufficient visibility required for automobile window glass, and at a solar radiation transmittance of about 58%, it sufficiently shielded the heat rays of sunlight. Further, the ultraviolet ray blocking performance was about 5% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. Further, when this glass was used as a rear window of an automobile, the surface resistivity was about 20 KΩ / mouth, and FM radio waves could be sufficiently received.

[0040]Example 6 A ZnO film of about 550 nm was obtained in the same manner as in Example 5.
Add a silver paste with glass frit to it
Printing was performed on a predetermined glass antenna pattern.
This substrate was baked in an atmosphere of about 620 ° C. for about 2 minutes to obtain a glass substrate.
Formed the antenna. This substrate glass with an antenna
After degreasing and cleaning with propyl alcohol and rinsing with pure water, nitrogen
Blow dried. Transport this substrate into the sputter device,
5 x 10 ^-6Exhausted to Torr. Shields heat rays in the vacuum chamber
Target of Ti and C for Ti / CNO film used as breaking film
Set (Ti: C = 95: 5). Sputter gas
A mixed gas of nitrogen and oxygen as N₂: O₂= 85: 15
Adjust the pressure in the vacuum chamber to 2 x 10^-3Become Torr
After adjusting the exhaust speed and gas flow rate, the sputtering power is about 1k
Approximately the Ti / CNO film of the heat ray blocking film is reduced by reactive sputtering of W
A 25 nm laminated film was formed.

The optical characteristics of the ultraviolet heat ray-shielding glass thus formed have a visible light transmittance of about 72%, which is sufficient visibility required for automobile window glass, and a solar transmittance of about 62%. The heat rays of light were sufficiently blocked. Further, the ultraviolet ray blocking performance was about 10% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. Further, when this glass was used as a rear window of an automobile, the surface resistivity was about 30 MΩ / mouth, and FM radio waves could be remarkably received.

Comparative Example 1 In the same manner as in Example 1, a silver paste containing glass frit was printed on a predetermined glass antenna pattern by screen printing. A ZnO film as an ultraviolet blocking film was formed on this substrate to a thickness of about 150 nm. After the film formation, the discharge and the gas introduction were stopped, and the gas was evacuated to 5 × 10 ⁻⁶ Torr. Next, using a Ti target, nitrogen gas N ₂ = 1 as a sputtering gas.
After adjusting the exhaust rate and gas flow rate so that the pressure in the empty tank is 2 × 10 ⁻³ Torr, the sputtering power is about 1
Approximately 10 times the TiN film as a heat ray blocking film by reactive sputtering of kW
nm film formation was performed.

The optical characteristics of the ultraviolet heat ray-shielding glass thus formed are visible light transmittance of about 71% and sufficient visibility required for automobile window glass, and solar transmittance of about 58%. The heat rays of light were sufficiently blocked. Further, the ultraviolet ray blocking performance was about 7% at a wavelength of 370 nm, which was sufficient to block harmful ultraviolet rays. However, when this glass was further used as a rear window of an automobile, the surface resistivity was about 1 kΩ / mouth, and it could not be said that FM radio waves could be received. Therefore, it cannot be said to be the desired UV heat ray blocking glass for automobiles.

Comparative Example 2 A ZnO film of about 550 nm was obtained in the same manner as in Example 5.
A silver paste containing glass frit was printed on a predetermined glass antenna pattern by screen printing.
This substrate was baked in an atmosphere of about 620 ° C. for about 2 minutes to form a glass antenna. The substrate is transferred into the sputtering apparatus, and Ti / AlNO used as the heat ray blocking film in the vacuum chamber.
Alloy target of Ti and Al for film (Ti: Al = 9:
1) was installed and exhausted to 5 × 10 ⁻⁶ Torr. Next, as a sputtering gas, a mixed gas of nitrogen and oxygen is N ₂ : O ₂
= 70: 30, the pressure in the vacuum chamber is 2 × 10 ^-3 T
After adjusting the exhaust speed and gas flow rate to be orr, Ti.
An AlNO film was laminated to a thickness of about 50 nm.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of visible light transmittance of about 78% and sufficient visibility required for automobile window glass, but it has a solar radiation transmittance of about 75%. It does not block the heat rays of sunlight, and also has a UV blocking performance of approximately 12% at a wavelength of 370 nm.
And it does not completely block harmful ultraviolet rays. However, when this glass was used as a rear window of an automobile, the surface resistivity was about 10 ¹² Ω / mouth or more, and FM radio waves could be sufficiently received. Therefore, it cannot be said that the desired UV heat ray-shielding glass for automobiles has been reached at all.

[0046]

[Table 1]

[0047]

As described above, according to the present invention, the periodic table
A heat ray-shielding film containing Zn, Ce, which is prepared by a sputtering method containing as a main component a composite nitrogen oxide containing at least one of group IVb and at least one of group Vb, group IIIa, and group IVa.
By skillfully combining an oxide containing any of Cd or an ultraviolet blocking film containing these composite oxides as a main component, the surface resistivity is 10 kΩ / mouth or more and 100 MΩ / mouth or less, and various kinds of glass antenna conductors can be used. It is possible to provide a UV heat ray-shielding glass for automobiles having sufficient UV ray shielding performance and heat ray shielding performance without deteriorating the radio wave reception performance with a simple configuration.

[Brief description of drawings]

FIG. 1 is a partially enlarged explanatory view showing a multilayer film structure and an antenna conductor relating to an ultraviolet heat ray shielding glass for an automobile of the present invention.

[Explanation of symbols]

 (1) Transparent glass substrate (2) UV blocking film (3) Heat ray blocking film (4) Antenna conductor

Front page continuation (72) Inventor Shibata No. 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Riichi Nishide No. 2 Takara-cho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd.

Claims (4)

[Claims] 1. A transparent glass substrate is produced by a sputtering method containing as a main component a composite nitrogen oxide containing at least one group IVb and at least one group Vb, IIIa or IVa of the periodic table. And a multi-layered film comprising an ultraviolet ray blocking film containing an oxide containing any one of Zn, Ce and Cd or a composite oxide of these as a main component, and an antenna conductor. UV heat ray blocking glass for automobiles. 2. On a transparent glass substrate, at least one of Ti, Hf, and Zr, which is group IVb of the periodic table, and V, Nb,
A heat ray-shielding film having a composite nitrogen oxide containing at least one of B, Al, C, and Si as a main component and prepared by a sputtering method, and an oxide containing any one of Zn, Ce, and Cd, or a composite oxide thereof. An ultraviolet heat ray-shielding glass for an automobile, which is provided with a multilayer film composed of an ultraviolet ray shielding film as a main component and an antenna conductor, wherein the antenna conductor can receive radio waves. UV heat ray blocking glass for automobiles. 3. Ti, B, C and A on a transparent glass substrate
1. A heat-ray shielding film which is a composite nitrogen oxide containing at least one of Si and 1, which is produced by a sputtering method, and an ultraviolet shielding film which is an oxide of Zn or a composite oxide of Zn oxide doped with Cr. An ultraviolet heat ray-shielding glass for automobiles provided with a multilayer film and an antenna conductor, wherein the antenna conductor allows reception of radio waves. 4. The ultraviolet heat ray shielding glass for automobiles according to claim 1, wherein the surface resistivity of the multilayer film is 10 kΩ / port or more and 100 MΩ / port or less.