JPH07138048A - Ultraviolet light heat screening glass - Google Patents

Abstract

PURPOSE:To improve performances for simultaneously screening heat rays, infrared rays and ultraviolet rays by a simple layer constitution by laminating a first transparent dielectric material film to a transparent substrate and laminating a dielectric material layer having a different refractive index to the first transparent dielectric material film. CONSTITUTION:A substrate 1 comprising any of various glass plates or a transparent resin substrate is successively provided with a first transparent dielectric material film 2 which is selected from oxides consisting essentially of Zn, Ce or Cd, having ultraviolet light screening performances and compound oxides prepared by mixing these oxides with 1-10 atomic % of a metal element or metal nitride and has 50-1,200nm film thickness and >=1.55 refractive index, with a second transparent dielectric film 3 selected from an oxide of (A) silicon, titanium, etc., having 10-300nm film thickness and >=1.55 refractive index, prepared by mixing an oxide, with a third transparent dielectric material film 4 selected from the component A, having 10-300nm film thickness and <=1.65 refractive index and with a forth transparent dielectric material film 5 selected from the component A, having 10-300nm film thickness and <=1.65 refractive index by a vacuum film-forming method such as sputtering method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass which shields ultraviolet rays and heat rays and is suitable as a window glass for automobiles, and has a visible light transmittance of 50% or more, more preferably 7%.
It is suitable for use in 0% or more of the area, has a deterioration of interior materials due to ultraviolet rays, has a heat ray shielding performance that flows into the vehicle interior, and is suitably used as a window glass that can enhance comfort. . The present invention is most preferably used for automobiles, but is not limited to this, and can be used as various windows and interior materials. Furthermore, it can be applied to single-plate glass, laminated glass, and double-glazing.

[0002]

2. Description of the Related Art Conventionally, from the viewpoint of energy saving, a specific wavelength portion of sunlight radiated into a vehicle compartment through a window glass is cut off 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 for blocking heat rays and infrared rays, a transparent conductive film typified by a mixed film of indium oxide and tin oxide (ITO film) or a film obtained by adding aluminum to zinc oxide, which is called a drude mirror, is used. A method of forming a film to block heat rays and infrared rays is known. This type of glass certainly blocks infrared rays, but the blocking wavelength is 1.5 μm.
As above, the heat ray and infrared ray shielding performance is not so good.
It is also known that various metal films and dielectric films are laminated to reflect or transmit light of a specific wavelength by utilizing an optical interference effect. As a heat ray reflective glass utilizing the optical interference effect, there is a glass disclosed in Japanese Patent Publication No. Sho 47-6315, in which a silver film is sandwiched between transparent dielectric films. There is also a heat ray reflective glass disclosed in JP-A-63-206333 in which a nitride is sandwiched between transparent dielectric films.

Since these glasses have only the purpose of reflecting heat rays, they do not have the UV blocking property described later. As an optical filter that transmits or reflects only a specific wavelength, a method is known in which a high-refractive index layer and a low-refractive index layer are alternately laminated in multiple layers with a specific thickness, and is mainly formed of titanium oxide and silicon oxide. However, in this case, the purpose is to filter a specific wavelength, and it is not always possible to obtain the shielding performance that is the object of the present invention, and it is necessary to make a very large number of layers.

As another method, there is known a method of absorbing a heat ray by mixing a specific metal element or the like into a glass plate. In this type of glass, the heat ray blocking property is obtained by adding a specific metal element to the glass, but increasing the addition amount weakens the mechanical strength of the glass plate itself, and in order to obtain a good heat ray blocking property. Since the metal elements used are limited, there is a problem in terms of hue.

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 or melanin pigments are deposited to form spots or 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, there is also a demand for glass having an ultraviolet shielding property.

As a method for simultaneously blocking heat rays, infrared rays and ultraviolet rays to meet the above needs, there is known a method in which a heat ray, an infrared ray shielding layer and an ultraviolet ray shielding layer are separately formed in layers on a glass surface. , JP-A-61-132
No. 902 discloses an ultraviolet / infrared shielding glass in which a zinc oxide film having an ultraviolet absorbing ability is formed, and zinc oxide contains 0.4 to 10 atomic% of aluminum to impart heat ray and infrared ray shielding properties. .

However, the conventional ultraviolet / infrared ray shielding glass has a problem that the ultraviolet ray / infrared ray shielding performance is not always sufficient. Therefore, an object of the present invention is to provide an ultraviolet heat ray shielding glass having a simple layered structure and having an improved ability to simultaneously shield heat rays, infrared rays and ultraviolet rays.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is an ultraviolet and heat ray blocking glass suitable as a window glass for automobiles and constructions.
On a transparent substrate, as the first layer from the substrate side, an oxide having an ultraviolet ray-shielding property containing zinc, cerium, or cadmium as a main component, or a composite oxide thereof, or a trace amount of a metal element in these oxides or 50 to 1 of the first transparent dielectric film made of a composite oxide to which a metal nitride is added
200 nm is provided, and a dielectric layer having a lower refractive index than the first layer is further laminated thereon as a second n-layer (n = 1, 2, 3 ...) In a thickness of 10-300 nm, and a second n-layer is further formed thereon. A dielectric layer having a higher refractive index than the second n + 1th layer (n =
1, 2, 3 ...) and 10 to 300 nm of the laminated layers are related to the ultraviolet heat ray-shielding glass.

FIG. 1 shows the constitution of the glass for blocking ultraviolet rays and heat rays according to the present invention. In the figure, (1) shows various glass plates such as soda lime glass and aluminosilicate glass.
Alternatively, a transparent substrate selected from transparent resin substrates such as polymethylmethacrylate (PMMA) and polycarbonate (PC), and (2) an oxide mainly containing zinc, cerium, or cadmium and having an ultraviolet blocking property. Alternatively, a first transparent dielectric film selected from these complex oxides or complex oxides obtained by adding a trace amount of a metal element or metal nitride to these oxides, (3) is silicon, titanium, aluminum, tin, A second transparent dielectric film having a low refractive index selected from oxides of zirconium, tantalum, chromium, stainless steel, nichrome, or their composite oxides or nitrogen oxides, (4) is silicon, titanium,
Aluminum, tin, zirconium, tantalum, chromium,
A third transparent dielectric film having a high refractive index selected from the oxides of stainless steel and nichrome, or their composite oxides or nitrogen oxides, (5) is silicon, titanium, aluminum, tin, zirconium, tantalum, 4 shows a fourth transparent dielectric film having a low refractive index selected from oxides of chromium, stainless steel, nichrome, or their composite oxides or nitrogen oxides.

The first dielectric film can be arbitrarily selected from the above-mentioned dielectrics. Particularly, zinc oxide and a dielectric film in which iron, chromium, silicon, and titanium are added to zinc oxide at 1 to 10 atomic%, zinc oxide. And a composite dielectric film made of a transparent dielectric material such as cerium oxide, cadmium oxide, and silicon oxide, and a composite dielectric film obtained by adding titanium oxide to cerium oxide. 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 at least 50 nm or more, more preferably 100 to 12 nm.
By setting the thickness to 00 nm, good ultraviolet blocking performance can be obtained. Further, the refractive index of the first transparent dielectric film is preferably a high refractive index, and preferably has a refractive index of at least 1.55 or more. More preferably 1.55 to 2.5
Is the value of.

The low refractive index film formed as the second layer on the first transparent dielectric layer can be arbitrarily selected from the above-mentioned transparent dielectric films, but the refractive index thereof is the first dielectric film. It is a dielectric film having a refractive index lower than that of, and more preferably 1.55 or less.

The high refractive index film formed as the third layer on the second transparent dielectric film is arbitrarily selected from the above transparent dielectric films, and the refractive index thereof is the second dielectric film. It is a dielectric film having a refractive index higher than that of the film, and more preferably 1.65 or more.

The low-refractive index film formed as the fourth layer on the third high-refractive index film can be arbitrarily selected from the above-mentioned transparent dielectric films, but its refractive index is the third dielectric film. The refractive index of the dielectric film is lower than that of the above-mentioned, and more preferably 1.65 or less, and may be the same as or different from the low-refractive-index film formed as the second layer.

Further, a high refractive index film can be formed as a fifth layer thereover. This film may be the same as or different from the high refractive index film formed as the third layer. As for the film thickness of each layer, the first layer has a thickness of 50 nm or more, more preferably 10 nm or more, in order to exhibit the ultraviolet shielding performance.
It is 0 nm or more and 1200 nm or less. The second n-th layer and the second n + 1-th layer (n = 1, 2, ...)
It is 300 nm. This is because if the thickness is smaller than that, sufficient infrared ray blocking performance cannot be obtained due to the light interference effect, and if it is thicker than this, the interference effect is obtained but the time required for film formation becomes long, which is preferable. I can't say. Further, the higher the number of layers, the higher the performance can be obtained, but since the film formation becomes complicated, the number of layers is preferably 7 or less, more preferably 5 or less.

In the ultraviolet heat ray-shielding glass of the present invention,
The function of shielding heat rays is exhibited by the optical interference effect of the first layer and at least two or more low refractive index films and high refractive index films formed thereon. Here, the first layer functions as a high-refractive index film for exhibiting an optical interference effect, as well as a function as an ultraviolet shielding film. Therefore, the refractive index is preferably at least 1.55 or more. If the refractive index is lower than that, the difference in refractive index from the low refractive index film laminated on top is small and the optical interference effect is small, resulting in poor heat ray and infrared ray shielding power. The refractive index of the low refractive index film formed thereon is lower than that of the first layer, and is preferably 1.55 or less. When the refractive index is higher than that, the difference in refractive index from the high refractive index film is small, the optical interference effect is small, and the heat ray and infrared ray shielding power is poor.

The high refractive index film of the third layer or more preferably has a refractive index of 1.65 or more, and the low refractive index film preferably has a refractive index of 1.65 or less. The greater the difference between the refractive index of the high refractive index film and the refractive index of the low refractive index film, the greater the heat ray and infrared ray shielding effect. By shielding the ultraviolet ray by the first ultraviolet ray shielding layer and using this layer as the high refractive index layer, by alternately forming at least two or more layers of the low refractive index film and the high refractive index film thereon, It has not been known so far to efficiently shield both heat rays and infrared rays,
The combination of these makes it possible to efficiently use ultraviolet rays and heat rays,
The ability to block infrared radiation is surprising.

According to the present invention, since ultraviolet rays and heat rays can be efficiently shielded and visible light can be sufficiently transmitted, sufficient transparency can be exhibited, and an ultraviolet heat ray shielding glass for automobiles and constructions can be provided. . Further, the ultraviolet heat ray-shielding glass of the present invention is made by laminating multiple layers of dielectrics, and its surface resistance is at least 10 kΩ / □ or more, and in most cases it is 1 MΩ / □, which allows sufficient transmission of external radio waves. In addition, even if a glass antenna is formed on this film, the antenna reception performance is not impaired. Further, the ultraviolet heat ray-shielding glass of the present invention can be used as a single plate, but it goes without saying that it can be used as a laminated glass or a double-glazing.

These films can also be formed by a vacuum film forming method such as a sputtering method, a vapor deposition method, an ion plating method, a chemical vapor deposition method (CVD method) or a wet film forming method such as a sol-gel method. Among them, the sputtering method and the sol-gel method are excellent in terms of increasing the area and productivity.

[0020]

According to the present invention, a first transparent dielectric film having a high refractive index and having a UV-shielding property is provided as a first layer on the transparent substrate from the side of the substrate, and a transparent dielectric layer having a low refractive index is provided thereon. Is formed as a second n layer, and a transparent dielectric layer having a refractive index higher than that of the second n layer is formed as a second n + 1 layer, so that ultraviolet rays, heat rays, and infrared rays are efficiently shielded by the ultraviolet heat ray shielding glass. In addition, a useful window glass for automobiles and buildings having a good visible light transmittance and a sufficient radio wave transmission performance can be obtained.

[0021]

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

Example 1 A transparent glass substrate was degreased and washed with isopropyl alcohol, rinsed with pure water, and then blown dry with nitrogen. This transparent glass substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. In the vacuum chamber, a zinc target for the zinc oxide film used as the first transparent dielectric film, a silicon oxide target for silicon oxide used as the second and fourth transparent dielectric films, and a transparent dielectric film of the third layer. A titanium target for the titanium oxide film used as was installed.

First, a mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 1: 1 as a sputtering gas, and the gas pressure in the vacuum chamber was 5 ×.
Adjust the pumping speed and gas flow rate so that it becomes 10 ^-3 Torr,
Sputtering power of about 300 W, the first in reactive sputtering
Zinc oxide film as the transparent dielectric film of the layer is about 150 nm thick
A film was formed. The refractive index of this film was about 2.0.

Next, a mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 1: 1 as a sputtering gas, and the gas pressure in the vacuum chamber was 4 ×.
Adjust the pumping speed and gas flow rate so that it becomes 10 ^-3 Torr,
Sputtering power is about 500W and the second is reactive sputtering.
A silicon oxide film having a thickness of about 170 nm was formed as a transparent dielectric film having a low refractive index of the layer. The refractive index of this film was about 1.46.

Next, a mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 1: 1 as a sputtering gas, and the gas pressure in the vacuum chamber was 5 ×.
Adjust the pumping speed and gas flow rate so that it becomes 10 ^-3 Torr,
Sputtering power is about 400W, and it is the third by reactive sputtering.
A titanium oxide film having a thickness of about 90 nm was formed as a transparent dielectric film having a high refractive index of the layer. The refractive index of this film is about 2.3.
Met.

Next, a silicon oxide film as a transparent dielectric film having a low refractive index of the fourth layer is formed in a thickness of about 20 nm in the same manner as above.
A film was formed. The refractive index of this film was about 1.46. The UV heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of about 71% and sufficient visibility required for an automobile window glass, and a solar radiation transmittance of 60%.
The heat rays of sunlight are sufficiently cut off in a certain degree. Further, the ultraviolet ray blocking performance was 8% or less in terms of transmittance at a wavelength of 380 nm, which was sufficient to block harmful ultraviolet rays.

Example 2 Under the same film material and film forming conditions as in Example 1, the thickness of the first zinc oxide film was set to about 300 nm, and the transparent dielectric film having the second and fourth low refractive indexes was formed. The thickness of the silicon oxide film is about 100
nm, and the thickness of the titanium oxide film of the transparent dielectric film having the third high refractive index was set to about 50 nm.

The optical characteristics of this structure are such that the visible light transmittance is about 71%, which is sufficient visibility required for automobile window glass, and the solar radiation transmittance is about 58%, so that the heat rays of sunlight can be sufficiently absorbed. It is shut off. Further, the ultraviolet ray blocking performance was 5% or less in terms of transmittance at a wavelength of 380 nm, which was sufficient to block harmful ultraviolet rays.

Example 3 A film material different from those in Examples 1 and 2 will be described. The transparent glass substrate was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried with nitrogen blow. This transparent glass substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. In the vacuum chamber, a chromium-doped zinc oxide target for the chromium-doped zinc oxide film used as the transparent dielectric film of the first layer, and an oxide for silicon oxide used as the low-refractive-index transparent dielectric films of the second and fourth layers. Silicon target,
A titanium oxide target for the titanium oxide film used as the high refractive index transparent dielectric film of the third layer was set.

First, argon gas was used as a sputtering gas, the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr, and the sputtering power was about 400 W.
A chromium-doped zinc oxide film having a thickness of about 150 nm was formed as a transparent dielectric film of the first layer. The refractive index of this film was 1.9. Next, argon gas was used as a sputtering gas, the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr, and the sputtering power was about 500 W, and the low refractive index transparent dielectric material of the second layer was used. About 160 silicon oxide film
nm film was formed. The refractive index of this film was 1.47. Next, an argon mixed gas was used as a sputtering gas, the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr, and the sputtering power was about 500. With W, a titanium oxide film having a thickness of about 100 nm was formed as a high refractive index film of the third layer. The refractive index of this film was about 2.3.

Next, as the fourth layer, silicon oxide was deposited to a thickness of about 60 nm by the same method as the second layer. The refractive index of this film was about 1.47. The optical characteristics of this structure are such that the visible light transmittance is about 70% and sufficient visibility is required as a window glass for automobiles, and the solar radiation transmittance is about 55% to sufficiently block the heat rays of sunlight. There is. Further, the ultraviolet ray blocking performance was 4% or less at a transmittance of a wavelength of 380 nm, and the harmful ultraviolet rays were sufficiently blocked.

Example 4 Since zirconium oxide was used instead of titanium oxide as the high refractive index transparent dielectric film of the third layer in Example 3, a zirconium oxide target was placed instead of the titanium oxide target and zirconium oxide was used as the third layer. (Thickness: about 100 nm, refractive index: about 2.1)

The optical characteristics of this structure are such that the visible light transmittance is about 70%, which is sufficient visibility required for a window glass for automobiles, and the solar radiation transmittance is about 54%, so that the heat rays of sunlight can be sufficiently absorbed. It is shut off. Further, the ultraviolet ray blocking performance was 4% or less at a transmittance of a wavelength of 380 nm, and the harmful ultraviolet rays were sufficiently blocked.

Example 5 An example in which the first and second transparent dielectric films are formed by the sol-gel method will be described. A zinc oxide film was formed as the first transparent dielectric film by the sol-gel method as follows. Two
-Zinc ethylhexanoate (18%) 100 g, dehydrated castor oil fatty acid (linoleic acid content 86%) 80 g, TSF400 (manufactured by Toshiba Silicone Co., Ltd.) as a leveling agent
5 g and 320 g of mixed xylene as a dilute solution were stirred and mixed to obtain a coating liquid for zinc oxide film. A transparent glass substrate having one surface masked was dipped in this coating solution and pulled up at a speed of about 20 cm / min to obtain a coating film on one surface. This coating film is about 1
Drying and curing in a far-infrared furnace at 50 ° C for about 15 minutes, and baking in an electric furnace at about 500 ° C for about 15 minutes to obtain a film thickness of about 750n.
m transparent zinc oxide film was formed. The refractive index of this film was about 1.8.

Next, a silicon oxide film was formed by the sol-gel method as follows. Methyltrimethoxysilane 400g
And tetramethoxysilane (150 g) are mixed and added to n-butanol (1600 g) and mixed. Further, 84 g of a 5% acetic acid aqueous solution was removed, stirred for about 3 hours, and allowed to stand at room temperature for about 1 day to obtain a coating solution for silicon oxide. The transparent glass substrate having the zinc oxide film formed thereon was dipped in this coating solution and pulled up at a speed of about 20 cm / min to obtain a coating film on one surface. This coating film is dried at about 120 ° C. for about 15 minutes, baked at about 500 ° C. for about 30 minutes in an electric furnace, and then about 65
It was baked in an electric furnace at 0 ° C. for about 2 minutes. A mixed film of zinc oxide and silicon oxide having a film thickness of about 700 nm and a refractive index of about 1.55 is formed as a first transparent dielectric film, and a second film is formed on the mixed film.
A silicon oxide film having a thickness of about 50 nm was formed as the transparent dielectric film. The refractive index of this film was about 1.46.

As described above, a titanium oxide film as a third high-refractive-index transparent dielectric film of about 60 nm is formed on the transparent glass substrate on which the mixed film of the zinc oxide film and the silicon oxide film and the silicon oxide film are formed by the sol-gel method. (Refractive index; about 2.
3) A silicon oxide film was formed as a low refractive index transparent dielectric film of four layers by a sputtering method with a thickness of about 50 nm (refractive index: about 1.46). The sputtering film formation conditions were the same as in Example 1.

The optical characteristics of this structure are such that the visible light transmittance is about 70%, which is sufficient visibility required for a window glass for automobiles, and the solar radiation transmittance is about 58%, so that the heat rays of sunlight can be sufficiently absorbed. It is shut off. Further, the ultraviolet ray blocking performance was 7% or less at a transmittance of a wavelength of 380 nm, which was sufficient to block harmful ultraviolet rays.

Example 6 This is another example in which the first and second transparent dielectric films were formed by the sol-gel method as in Example 5.

A zinc oxide film and a silicon oxide film were formed as the first and second transparent dielectric films by the same method as in Example 5, but the film thicknesses were about 650 nm and about 150 n, respectively.
It was produced in the same manner as in the example except that m was used.

As described above, the zinc oxide film is formed by the sol-gel method,
About 6 parts of zirconium oxide film was used as the third layer of high-refractive-index transparent dielectric film on the transparent glass substrate on which the silicon oxide film was formed.
A silicon oxide film having a thickness of 0 nm (refractive index: about 2.0) and a low refractive index transparent dielectric film of the fourth layer was formed by a sputtering method with a thickness of about 40 nm (refractive index: about 1.4). The sputtering film formation conditions were the same as those in Examples 1 and 4.

The optical characteristics of this structure are such that the visible light transmittance is about 70%, which is sufficient visibility required for a window glass for automobiles, and the solar radiation transmittance is about 59%, which is sufficient for heat rays of sunlight. It is shut off. Further, the ultraviolet ray blocking performance was 7% or less at a transmittance of a wavelength of 380 nm, which was sufficient to block harmful ultraviolet rays.

Example 7 This is an example of forming the first transparent dielectric film by using another sol-gel. In Example 5, except that the first layer was a film obtained by adding titanium oxide to cerium oxide by the following method,
Same as Example 5.

Cerium chloride 2.8 g was added to ethanol 35c.
It was added to c and dissolved. To this solution was added 0.17 g of titanium tetraisopropoxide, 0.9 g of silicon tetraethoxide, 5.0 g of 2- (2-methoxyethoxy) ethanol, and the mixture was stirred at 80 ° C. for 1 minute,
Heated. After cooling to room temperature, 0.35 ml of water and 61
0.1 ml of% nitric acid was stirred and heated at 80 ° C. for about 1 hour. The pH at this time was about 2. This solution was cooled to room temperature and then applied on soda lime glass by a spinner. The spinner coating conditions were about 1000 rpm and about 30 seconds. The coated sample was dried in the air, placed in an electric furnace, and baked at about 500 ° C. for about 10 minutes. The obtained thin film sample had a film thickness of about 400 nm and a refractive index of about 1.9.

The optical characteristics of this structure are such that the visible light transmittance is about 73%, which is sufficient visibility required for a window glass for automobiles, and the solar radiation transmittance is about 56%, and the heat rays of sunlight are sufficiently absorbed. It is shut off. Further, the ultraviolet ray blocking performance was 3% or less at a transmittance of a wavelength of 380 nm, which was sufficient to block harmful ultraviolet rays.

Comparative Example 1 In the structure in which the thickness of the zinc oxide film of the first dielectric film is set to about 30 nm by the material and the manufacturing method of Example 1, the transmittance at a wavelength of 380 nm is 30% or more and harmful ultraviolet rays are emitted. It was not possible to block it sufficiently.

Comparative Example 2 With the material and manufacturing method of Example 1 and the thickness of the zinc oxide film of the first dielectric film is set to about 2000 nm, the wavelength is 380 nm.
The transmittance was 5% or less and it was possible to sufficiently block harmful ultraviolet rays, but since zinc oxide was formed thickly,
A strong interference color was generated in the visible light region, which was not preferable as a window.

Comparative Example 3 With the material and the manufacturing method of Example 3, the visible light transmittance was 65 when the amount of chromium added to the first dielectric film was increased to 15 atom%.
%, And it was not possible to obtain sufficient visibility.

Comparative Example 4 With the material and the manufacturing method of Example 3, the amount of chromium added to the first dielectric film was reduced to 0.3 atom%, the optical characteristics were that the visible light transmittance was about 71%. It has sufficient visibility required as a window glass for automobiles, and has a solar radiation transmittance of about 60% and sufficiently blocks the heat rays of sunlight. Further, the ultraviolet ray blocking performance was 8% or less at a transmittance of a wavelength of 380 nm, which was sufficient to block harmful ultraviolet rays, but the effect of adding chromium in Example 3 was not recognized.

[0049]

According to the present invention, a first high-refractive index transparent dielectric film having a UV-shielding property is provided as a first layer on the transparent substrate from the substrate side in a thickness of 50 to 1200 nm, and the first transparent dielectric film is formed on the first transparent dielectric film. A transparent dielectric layer having a refractive index lower than that of the first layer as the second n layer 1
A transparent dielectric layer having a thickness of 0 to 300 nm and having a higher refractive index than the second n-th layer is used as the second n + 1th layer, and is 10 to 30.
By forming 0 nm, ultraviolet rays, heat rays, and infrared rays are efficiently shielded, and further, it has a good visible light transmittance and has sufficient radio wave transmission performance. It is possible to provide a window glass that shields heat rays.

[Brief description of drawings]

FIG. 1 shows an example of a film structure relating to an ultraviolet heat ray-shielding glass of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Shibata 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Riichi Nishide 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. Within

Claims (3)

[Claims] 1. An oxide, a composite oxide thereof, or an oxide thereof having an ultraviolet ray-shielding property containing zinc, cerium, or cadmium as a main component as a first layer on a transparent substrate from the substrate side. A first transparent dielectric film made of a composite oxide to which a trace amount of a metal element or a metal nitride is added is provided in a thickness of 50 to 1200 nm, and a dielectric layer having a refractive index lower than that of the first layer is formed on the second n layer. (N = 1,
2, 3 ...), and a dielectric layer having a higher refractive index than the second n-layer is further laminated thereon.
10 to 300 as n + 1 layers (n = 1, 2, 3 ...)
nm heat-shielding glass characterized by being laminated in a thickness of 1 nm. 2. The second n layer and the second n + 1 layer are oxides of silicon, titanium, aluminum, tin, zirconium, tantalum, chromium, stainless steel, nichrome, or a complex oxide or nitrogen oxide thereof. The ultraviolet heat ray-shielding glass according to item 1, which is characterized in that 3. The metal or metal nitride added to the ultraviolet shielding film of the first layer is iron, chromium, silicon, or titanium, and the addition amount is 1 to 10 atomic%. The ultraviolet heat ray-shielding glass according to item 1.