JPH0859301A - Ultraviolet heat shielding glass - Google Patents

Abstract

(57) [Summary] [Object] To provide an ultraviolet heat ray-shielding glass that can be suitably used in a site where high visible light transmittance and good ultraviolet ray heat-shielding performance are required. [Structure] On a transparent glass substrate, as a first layer from the side of the substrate, an oxide having an ultraviolet-blocking property containing at least one selected from the group consisting of zinc, cerium, titanium and cadmium, and a composite oxide of these. A first transparent dielectric film containing a compound or a complex oxide obtained by adding a trace amount of a metal element to these oxides, and providing a second transparent dielectric film as a second layer on the first layer, On the second layer, as a third layer, a group IIIa, a group IVa, a group Vb, and a group VIb of the periodic table.
At least one selected from the group consisting of Group VIIb and Group VIIb
An ultraviolet heat ray-shielding glass, comprising a composite tungsten oxide film containing one kind of metal element, and a third transparent dielectric film as a fourth layer provided on the third layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet heat ray-shielding glass suitable as a window glass for automobiles and constructions, and is particularly suitable for use in a part where a high visible light transmittance and a good ultraviolet heat ray-shielding performance are required. It relates to an ultraviolet heat ray-shielding glass capable of

[0002]

2. Description of the Related Art Conventionally, from the viewpoint of energy saving, a specific wavelength portion of sunlight radiated to the interior of an automobile or a building through a window glass is cut off to reduce the temperature rise in the interior. At the same time, in order to reduce the load on the cooling equipment, a window glass having a high heat ray-shielding property is required.

As a method of blocking heat rays, a transparent conductive film typified by a mixed film of indium oxide and tin oxide (ITO film) or a zinc oxide film added with aluminum is formed on a transparent substrate called a so-called drude mirror. A method of forming a film to block heat rays is known. This type of glass blocks heat rays, but has a wavelength of 1.5 μm or more, which is not very good.

Further, it is known that various metal films are laminated to combine a drude mirror effect with an optical interference effect to reflect or transmit light of a specific wavelength. As this heat ray reflective film, for example, a structure in which a silver film is sandwiched between transparent dielectric films is proposed (Japanese Patent Publication No. 47-6315), and a structure in which a nitride film is sandwiched between transparent dielectric films is proposed. (JP-A-63
-206333 publication).

However, since the heat ray-shielding glass described in the above publication is intended only for heat ray-reflecting property, it does not have the ultraviolet ray-shielding performance described later. Further, 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, and are mainly formed of titanium oxide and silicon oxide. However, in this case, the purpose is a filter of a specific wavelength, and the cut-off performance intended by the present invention is not always obtained, and an extremely large number of layers are required.

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. This type of glass can be obtained by adding a specific metal element to the glass to obtain heat-ray shielding properties.However, increasing the addition amount weakens the mechanical strength of the glass plate itself, and is used to obtain good heat-ray shielding properties. There is a problem in terms of hue because the metal elements to be used are limited.

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. Further, it is said that the interior materials inside the vehicle are faded and deteriorated by the irradiation of ultraviolet rays. From such a point of view, a glass having an ultraviolet blocking performance is required.

As a method for simultaneously blocking ultraviolet rays and heat rays in response to the above needs, there is known a method in which a heat ray blocking layer and an ultraviolet ray blocking layer are separately formed in layers on the glass surface. JP-A-61-132902 discloses an ultraviolet heat ray-shielding glass in which a zinc oxide film having an ultraviolet absorbing ability is formed, and zinc oxide contains aluminum in an amount of 0.4 to 10 atomic% to impart heat ray shielding performance. It is disclosed.

[0009]

However, although the heat ray blocking function described in the above publication is formed by the above technique, it has a drawback that it cannot yet exhibit satisfactory performance. Further, for example, when a silver film is used, the silver film has a sheet resistance value of about several Ω-10 Ω / □, and has a high radio wave blocking property. When such a conductive film is used as a heat-shielding glass, it also blocks radio waves, and places where it is necessary to transmit radio waves, such as mobile phones, radios, etc. in the interior of automobiles, radios, buildings where TVs are installed, etc. It has a drawback that it cannot be used by televisions and the like.

When used as architectural glass, it is said that the window glass affects the surrounding radio wave intensity in high-rise buildings and the like. Further, the conventional UV heat ray blocking glass has a drawback that the UV and heat ray blocking 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 ultraviolet rays and heat rays.

[0011]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
Zinc as the first layer from the substrate side on the transparent glass substrate,
Containing an oxide having an ultraviolet ray blocking performance, which contains at least one selected from the group consisting of cerium, titanium and cadmium, a composite oxide of these, or a composite oxide obtained by adding a trace amount of a metal element to these oxides. A first transparent dielectric film, a second transparent dielectric film is provided as a second layer on the first layer, and a third layer is a third layer on the second layer. , Vb, VIb and VI
Providing a composite tungsten oxide film containing at least one metal element selected from the group consisting of Group Ib,
This has been achieved by an ultraviolet heat ray-shielding glass characterized in that a third transparent dielectric film is provided as a fourth layer on the layer.

The present invention will be described in more detail below. FIG.
Shows the constitution of the heat ray shielding glass of the present invention. In FIG. 1, reference numeral 1 denotes a transparent glass substrate. This transparent glass substrate includes various glass plates such as soda lime glass and aluminosilicate glass, colored glass plates such as gray, blue, bronze and green, and transparent resins such as polymethylmethacrylate (PMMA) and polycarbonate (PC). It can be appropriately selected from the substrates.

In FIG. 1, reference numeral 2 denotes an oxide, which is provided as a first layer on the transparent glass substrate 1 and has an ultraviolet ray-shielding property containing zinc, cerium, titanium or cadmium as a main component, and a composite thereof. 1 shows a first transparent dielectric film containing an oxide or a composite oxide obtained by adding a trace amount of a metal element to these oxides.

Reference numeral 3 denotes a second transparent dielectric film provided as a second layer on the first transparent dielectric film 2. Reference numeral 4 indicates a group IIIa, IVa, Vb, VIb and VII of the periodic table provided as a third layer on the second transparent dielectric film 3.
2 shows a composite tungsten oxide film containing at least one metal element selected from the group consisting of group b. Reference numeral 5 denotes a third transparent dielectric film provided on the composite tungsten oxide film 4 as a fourth layer.

The first transparent dielectric film 2 can be arbitrarily selected from the above-mentioned dielectrics, but in particular, it is a composite dielectric composed of a transparent dielectric such as zinc oxide, zinc oxide and cerium oxide, cadmium oxide, or silicon oxide. A body film and a composite dielectric film composed of titanium oxide and cerium oxide are preferable. This is because these films have excellent ultraviolet blocking performance and transparency in the visible light region.

Iron, chromium, and silicon are preferably used as the trace metal, and the addition amount thereof is in the range of 1 to 10 atomic%. If the amount added exceeds this range, the ultraviolet blocking performance will not be improved. Particularly preferred is zinc oxide to which at least one kind of iron, chromium, and silicon is added in the range of 1 to 10 atomic%. This is because these films have excellent ultraviolet blocking performance and transparency in the visible light region.

The refractive index of the first transparent dielectric film 2 is preferably at least 1.5 or more, and particularly preferably in the range of 1.5 to 2.5. When the refractive index is less than 1.5, the ultraviolet ray blocking performance is poor, and conversely, when it exceeds 2.5, the color reflected from the glass side is strong.

The second transparent dielectric film 3 may be any of those described above, but especially oxides of silicon, titanium, aluminum, tin, zirconium, tantalum, chromium, stainless steel and nichrome, and the like. The complex oxide or nitride oxide of is used. The refractive index of this transparent dielectric film is preferably equal to or lower than the refractive index of the first transparent dielectric film, and particularly preferably in the range of 1.4 to 2.5. If it exceeds this range, a sufficient optical interference effect cannot be obtained.

The film formed as the third layer 4 on the second transparent dielectric layer is a group IIIa, IVa or Vb of the periodic table.
It is a composite tungsten oxide film containing at least one metal element selected from the group consisting of Group VI, Group VIb and Group VIIb. In the present invention, the function of blocking heat rays has the function of the composite tungsten oxide film used as the third layer, the first transparent dielectric film 2, the second transparent dielectric film 3, the composite tungsten oxide film 4, and the third transparent dielectric film 3. This is due to optical interference caused by the laminated structure of the transparent dielectric film 5.

In general, tungsten has a hexavalent valence in the most oxidized state in the tungsten oxide film. In this state, the tungsten oxide film is transparent and has no ability to block heat rays. The presence of pentavalent tungsten, which is slightly reduced from the most oxidized state, has a high ability to block heat rays and causes absorption especially in the near infrared region. Tungsten oxide with this absorption has an oxygen / tungsten ratio in the range of 2.50 to 2.98. If the ratio is outside this range, heat ray absorption cannot be expected.

It is generally known that tungsten oxide has insufficient durability, although it depends on the manufacturing method. Furthermore, the conductivity is in the range of several KΩ / □ to several tens of KΩ / □ depending on the film thickness, and is not a sufficiently high resistance value in consideration of the above-mentioned problem of radio wave transparency.

According to the present invention, a group IIIa, a group IVa, a group Vb, a group VIb and a group VI of the periodic table are provided on a glass substrate.
A composite tungsten oxide film containing at least one metal element selected from the group consisting of Group Ib is used. This composite oxide film essentially has strong light absorption in the infrared region of tungsten oxide.

IIIa group, IVa group, Vb of the periodic table
At least one metal element selected from the group consisting of Group VI, Group VIb, and Group VIIb coexists with tungsten oxide as a stable oxide in the composite tungsten oxide film. By adding these elements to tungsten oxide, the durability of the film can be further improved, and the resistance value of the film can be increased to several hundreds KΩ / □ to several hundreds MΩ / □.

The composite tungsten oxide film of the present invention is a group IIIa, a group IVa, a group Vb, a group VIb and a group V of the periodic table.
It is obtained by incorporating at least one selected from the group consisting of Group IIb into the tungsten film. IIIa
Preferably, Al is used as the group, Si is used as the IVa group, V is used as the Vb group, Nb is Cr as the VIb group, and Mn is used as the VIIb group. By using these elements, better heat ray shielding performance and durability can be obtained, and the resistance of the composite tungsten oxide film can be increased.

The refractive index of the composite tungsten oxide film is preferably higher than that of the first and second transparent dielectric films, and is preferably in the range of 2.2 to 2.8. If the refractive index of the composite tungsten oxide film is lower than 2.2, sufficient optical interference with other films cannot be obtained, and conversely, if it is higher than 2.8, the reflected color is strong and it is not practical.

The third transparent dielectric film 5 can be appropriately selected from arbitrary ones, but in particular, oxides of silicon, titanium, aluminum, tin, zirconium, tantalum, chromium, stainless steel and nichrome, and composite oxides thereof. It is preferable to use an oxide or a nitride oxide. The refractive index of the third transparent dielectric film 5 is preferably lower than that of the composite tungsten oxide film 4, and particularly preferably in the range of 1.4 to 2.5. The third transparent dielectric film 5 may be the same as or different from the second transparent dielectric film 3, and the film thickness and the refractive index thereof may be the same or different.

These ultraviolet heat ray blocking films are formed by the sputtering method,
Vapor deposition method, ion plating method, chemical vapor deposition method (CVD
Method) and a wet film forming method such as a sol-gel method. In addition, these methods can be combined to form an arbitrary layer.

Of these, the sputtering method and the sol-gel method are preferably used from the viewpoints of increasing the area and productivity.
For example, the composite tungsten oxide film 3 can be formed by the following sputtering method. Tungsten as a sputtering target and IIIa group, IVa group, and Vb of the periodic table
Using an alloy target containing a predetermined concentration of at least one element selected from the group consisting of Group VI, Group VIb and Group VIIb, argon (Ar) and oxygen (O ₂ ) adjusted to have a predetermined gas ratio as a sputtering gas. It is possible to form a composite oxide film on a glass substrate by a so-called reactive sputtering method using the mixed gas of (1).

Further, for example, the zinc oxide film for blocking the ultraviolet rays of the first transparent dielectric film 2 can be formed by the following sol-gel method. Prepare a coating liquid containing zinc metal soap,
A transparent glass substrate having one surface masked is dipped in this coating solution and pulled up at a constant speed to obtain a coating film on one surface. A transparent zinc oxide film can be formed by firing this coating film in an electric furnace.

As for the film thickness of each layer, the first transparent dielectric film 2 of the first layer has a thickness of 50 nm in order to exhibit ultraviolet blocking performance.
As described above, particularly in the range of 100 to 9,000 nm, good ultraviolet blocking performance can be obtained. The thickness of the second transparent dielectric film 3 of the second layer may be such that the optical interference effect appears, but it is particularly preferably in the range of 2 to 300 nm. When the thickness of the second transparent dielectric film 3 is less than 2 nm, the second transparent dielectric film 3 has an island shape, and when it exceeds 300 nm, the economy is poor.
In addition to both of these, in order to obtain stable and reliable performance in the entire film constitution, it is preferably in the range of 5 to 200 nm.

The thickness of the third layer composite tungsten oxide film 4 may be a thickness capable of exhibiting a heat ray blocking function, but is particularly preferably in the range of 2 to 300 nm. If the thickness of the composite tungsten oxide film 4 is less than 2 nm, it becomes island-shaped, and conversely, if it exceeds 300 nm, the economy is poor. In addition to both of these, in order to obtain stable and reliable performance in the entire film constitution, it is preferably in the range of 5 to 200 nm.

The thickness of the third transparent dielectric film 5 of the fourth layer may be any thickness as long as an optical interference effect is exhibited and a protective function is exhibited, but it is particularly preferably in the range of 2 to 300 nm. preferable. If the thickness of the third transparent dielectric film 5 is less than 2 nm, it becomes island-shaped, and conversely, if it exceeds 300 nm, the economy is poor. In addition to both of these, in order to obtain safe and reliable performance in the whole film constitution, it is preferably in the range of 5 to 200 nm.

According to the present invention, ultraviolet rays and heat rays can be efficiently shielded and visible rays can be sufficiently transmitted, so that sufficient transparency can be exhibited, and ultraviolet rays for automobiles and constructions can be expressed. A heat ray shielding glass can be provided. Further, the ultraviolet heat ray-shielding glass of the present invention is formed 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. be able to. Further, although the ultraviolet heat ray-shielding glass of the present invention can be used as a single plate, it may be used as a laminated glass or a double glazing.

[0034]

According to the present invention, an oxide having an ultraviolet ray-shielding property, which is composed of at least one selected from the group consisting of zinc, cerium, titanium and cadmium as a first layer on the transparent glass substrate from the substrate side, A first transparent dielectric film containing these complex oxides or a complex oxide obtained by adding a trace amount of a metal element to these oxides is provided, and a second transparent dielectric layer is formed as a second layer on the first layer. A film is provided, and a group IIIa, IVa, Vb of the periodic table is provided as a third layer on the second layer.
A composite tungsten oxide film containing at least one metal element selected from the group consisting of Group VI, Group VIb, and Group VIIb, and providing a third transparent dielectric film as a fourth layer on the third layer. To provide a window glass for an automobile or a building, which efficiently shields ultraviolet rays and heat rays, has a good visible light transmittance, and has sufficient radio wave transmission performance, by using the ultraviolet heat ray-shielding glass characterized in that You can

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A transparent glass substrate was degreased and washed with isopropyl alcohol, rinsed with pure water, and then dried by nitrogen blowing. This transparent glass substrate was transferred into the sputtering device and transferred to 5 × 10 ^-6
Exhausted to Torr. In the vacuum chamber, a zinc target for a zinc oxide film used as the ultraviolet blocking film 2 and a transparent dielectric film 3
And 5, a silicon oxide target for silicon oxide used as Nos. 5 and 5, and an alloy target of silicon and tungsten (Si: W = 0.1: 1 atomic ratio) for the tungsten oxide film containing silicon used as the heat ray blocking film 4.

First, a mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 1: 1 as a sputtering gas, and the exhaust speed and the gas pressure in the vacuum chamber were adjusted to 3 × 10 ^-3 Torr. Adjusting the gas flow rate, sputtering power 300W
Then, a zinc oxide film having a thickness of 150 nm was formed as the ultraviolet blocking film 2 by reactive sputtering. The refractive index of this film was 2.0.

Next, a mixed gas of argon and oxygen was adjusted to Ar: O ₂ = 1: 1 as a sputtering gas, and the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 4 × 10 ^-3 Torr. Of the silicon oxide film as the transparent dielectric film 3 by reactive sputtering with the sputtering power of 500 W.
The film was formed to 0 nm. The refractive index of this film was 1.46.

Further, a mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 30: 4 as a sputtering gas, and the exhaust rate and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr. The composite tungsten oxide film 4 containing silicon was adjusted to 90 nm by reactive sputtering with the sputtering power adjusted to 500 W. The O / W ratio at this time is 2.
96, and the membrane resistance was 50 MΩ / □. Next, a silicon oxide film is formed as the transparent dielectric film 5 as described above.
The film was formed to 0 nm. The refractive index of this film was 1.46.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of visible light transmittance of 74% and sufficient visibility required for automobile window glass, and solar radiation transmittance of 58%. I was blocking the heat rays of sunlight.
Further, the ultraviolet ray transmittance was 20%, which was sufficient to block harmful ultraviolet rays.

When this glass was used as a window glass for buildings, a mobile phone could be used without any trouble, and a radio could receive FM and AM radio waves satisfactorily. In addition, even if it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM can be used for radio.
And AM radio waves could be received well.

Example 2 Under the same film material and film forming conditions as in Example 1, the thickness of the zinc oxide film 2 was set to 300 nm, the thickness of the silicon oxide film of the transparent dielectric films 3 and 5 was set to 100 nm, and complex oxidation was performed. The film thickness of the tungsten film 4 was set to 50 nm.

The UV heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of 72% and sufficient visibility required for a window glass for automobiles, and a solar radiation of 56% for sunlight. Had sufficiently cut off the heat rays. Also,
The ultraviolet ray transmittance was 15%, which was sufficient to block harmful ultraviolet rays.

When this glass was used as a window glass for a building, a mobile phone could be used without any trouble and a radio could receive FM and AM radio waves satisfactorily. Furthermore, even if it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM is used for radio.
And AM radio waves could be received well.

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 by nitrogen blowing.
Transfer this transparent glass substrate into the sputtering equipment and
Evacuated to 0 ^-3 Torr. In the vacuum chamber, a chromium-doped zinc oxide target for the chromium-doped zinc oxide film used as the ultraviolet blocking film 2, aluminum for the aluminum oxide film used as the second transparent dielectric film 3 and the third transparent dielectric film 5. A target, an alloy target of aluminum and tungsten for an aluminum-containing tungsten oxide film used as the composite tungsten oxide film 4 (A
(l: W = 0.1: 1 atomic ratio).

First, argon gas was used as the sputtering gas, the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 2 × 10 ⁻³ Torr, and the sputtering power was 400 W.
Then, a chromium-doped zinc oxide film is used as the ultraviolet blocking film 2.
The film was formed to 50 nm. The refractive index of this film was 1.8.

Next, a mixed gas of argon and oxygen was adjusted to Ar: O ₂ = 30: 5 as a sputtering gas, and the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr. The aluminum oxide film is adjusted to 20 n with the sputtering power of 400 W as the second transparent dielectric film 3.
m was formed into a film. The refractive index of this film was 1.6.

Next, a mixed gas of argon and oxygen was adjusted to Ar: O ₂ = 30: 4 as a sputtering gas, and the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr. Was adjusted, and an aluminum-containing tungsten oxide film having a thickness of 80 nm was formed as the composite tungsten oxide film 4 by reactive sputtering with a sputtering power of 500 W.
At this time, the O / W ratio was 2.98 and the membrane resistance was 150.
It was MΩ / □. The refractive index was 2.4. Further, the second transparent dielectric film 3 is used as the third transparent dielectric film 5.
An aluminum oxide film was formed to a thickness of 10 nm in the same manner as in.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of 74% and sufficient visibility required for automobile window glass, and a solar radiation transmittance of 57%. I was blocking the heat rays of sunlight.
Further, the ultraviolet ray transmittance was 17%, which was sufficient to block harmful ultraviolet rays.

When this glass was used as a window glass for buildings, a mobile phone could be used without any trouble, and a radio could receive FM and AM radio waves satisfactorily. In addition, even if it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM can be used for radio.
And AM radio waves could be received well.

Example 4 As the second transparent dielectric film 3, a tin oxide film having a thickness of 15 nm was used instead of the silicon oxide film, and as the composite tungsten oxide film 4, a tungsten oxide film containing manganese was used instead of the silicon-containing tungsten oxide film. An ultraviolet heat ray-shielding glass was formed in the same manner as in Example 1 except that 50 nm was used. At this time, a tin oxide target was used instead of the silicon oxide target, and an alloy target of manganese and tungsten (Mn: W ratio was 0.1: 1) was used instead of the alloy target of silicon and tungsten. The manganese-containing tungsten oxide film had an O / W of 2.72, a refractive index of 2.5, and a film resistance of 60 MΩ / □. The refractive index of the tin oxide film was 1.9.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of 72% and sufficient visibility required for an automobile window glass, and a solar radiation transmittance of 54%. The heat rays of sunlight were sufficiently blocked.
Further, the ultraviolet ray transmittance was 20%, which was sufficient to block harmful ultraviolet rays. Furthermore, when this glass was used as a window glass for buildings, a mobile phone could be used without any trouble, and FM and AM radio waves could be satisfactorily received by a radio. Further, even when used as a window glass for an automobile, the mobile phone can be used without any trouble, and the radio can receive FM and AM radio waves satisfactorily.

Example 5 An example in which the first transparent dielectric film 2 and the composite tungsten oxide film 3 are formed by the sol-gel method will be described. First
A zinc oxide film was formed as the transparent dielectric film 2 by the sol-gel method as follows. Zinc 2-ethylhexanoate (18
%) 100 g, dehydrated castor oil fatty acid (linoleic acid content 86%) 80 g, TSF400 (product number of Toshiba Silicone Co., Ltd.) 5 g as a leveling agent, and mixed xylene 320 g as a diluting solvent with stirring, and coating for zinc oxide film A liquid was obtained.

A transparent glass substrate having one surface masked was dipped in this coating solution and pulled up at a speed of 20 cm / min to obtain a coating film on one surface. This coating film was dried and cured in a far infrared furnace at 150 ° C. for 15 minutes, and then baked in an electric furnace at 500 ° C. for 15 minutes to form a transparent zinc oxide film having a thickness of 750 nm. The refractive index of this film was 1.8.

Next, a silicon oxide film was formed as the composite tungsten oxide film 3 by the sol-gel method as follows.
400 g of methyltrimethoxysilane and 150 g of tetramethoxysilane were mixed and added to 1600 g of n-butanol and mixed. Furthermore, 284 g of a 5% acetic acid aqueous solution was added dropwise, and the mixture was stirred for about 3 hours and left at room temperature for 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 20 cm / min to obtain a coating film on one surface. Apply this coating film at 120 ℃ for 15
After drying for 1 minute and baking at 500 ° C. for 30 minutes in an electric furnace, baking was further performed at 650 ° C. for 2 minutes in an electric furnace to form a silicon oxide film of 50 nm on the transparent zinc oxide film. The refractive index of this film was 1.46.

In this way, the zinc oxide film by the sol-gel method,
The transparent glass substrate on which the silicon oxide film was formed was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. In the vacuum chamber, a silicon-tungsten alloy target (Si: W =) for the tungsten oxide film containing silicon used as the heat ray blocking film of the composite tungsten oxide film 4 is provided.
(0.1: 1 atomic ratio), and a silicon oxide target for silicon oxide used as the third transparent dielectric film 5 was set.

Silicon-containing oxidation on the transparent glass substrate
A tungsten film was formed by the reactive sputtering method.
A mixed gas of argon and oxygen is used as a sputtering gas.
r: O ₂= 30: 4, the gas pressure in the vacuum chamber is 5 ×
10^-3Adjusting the exhaust speed and gas flow rate to Torr
And sputter power of 500 W, silicon-containing tan oxide
A Gusten film was formed to a thickness of 80 nm. The O / W ratio of this film is
It was 2.98 and the membrane resistance was 60 MΩ / □. Well
The refractive index of the film was 2.3.

Then, silicon oxide was deposited as the third transparent dielectric film 5 by the reactive sputtering method as follows. A mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 30: 5 as a sputter gas, and the exhaust speed and the gas flow rate were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr. A silicon oxide film having a thickness of 50 nm was formed as the third transparent dielectric film 5 with a sputtering power of 400 W. The refractive index of this film was 1.46.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of 70% and sufficient visibility required for an automobile window glass, and a solar radiation transmittance of 52%. The heat rays of sunlight were sufficiently blocked.
Further, the ultraviolet ray transmittance was 20%, which was sufficient to block harmful ultraviolet rays.

When this glass was used as a window glass for buildings, a mobile phone could be used without any trouble, and a radio could receive FM and AM radio waves satisfactorily. In addition, even if it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM can be used for radio.
And AM radio waves could be received well.

Example 6 Another example in which the first transparent dielectric 2 and the second transparent dielectric 3 are formed by the sol-gel method in the same manner as in Example 5 will be described. A zinc oxide film and a silicon oxide film were formed as the first transparent dielectric film 2 and the second transparent dielectric film 3 by exactly the same method as in Example 5, but the film thicknesses were 650 each.
The ultraviolet heat ray-shielding glass was formed in exactly the same manner as in Example 5 except that the thickness was set to 150 nm and 150 nm.

The transparent glass substrate on which the zinc oxide film and the silicon oxide film were thus formed by the sol-gel method was conveyed into the sputtering apparatus and evacuated to 5 × 10 ^-6 Torr. In the vacuum chamber, a niobium-tungsten alloy target for a tungsten oxide film containing niobium used as a heat ray blocking film of the composite tungsten oxide film 4 (Nb: W = 0.
(1: 1 atomic ratio), and a titanium target for titanium oxide used as the third transparent dielectric film 5 was set.

A niobium-containing tungsten oxide film was formed on the transparent glass substrate by the reactive sputtering method. Ar mixed gas of argon and oxygen is used as a sputtering gas:
The gas pressure in the vacuum chamber was adjusted to 5 × 10 by adjusting O ₂ = 30: 4.
-Adjust the exhaust speed and gas flow rate to become ^-3 Torr,
A niobium-containing tungsten oxide film was formed to 90 nm with a sputtering power of 400 W.

At this time, the O / W ratio was 2.6 and the film resistance was 170 MΩ / □. The refractive index was 2.4. Then, titanium oxide was deposited as the third transparent dielectric film 5 by the reactive sputtering method as follows.
A mixed gas of argon and oxygen is used as a sputtering gas.
Adjusting r: O ₂ = 1: 1, adjusting the exhaust speed and gas flow rate so that the gas pressure in the vacuum chamber is 5 × 10 ⁻³ Torr, and using sputter power 400 W, the third transparent A titanium oxide film having a thickness of 10 nm was formed as the dielectric film 5.
The refractive index of this film was 2.2.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of 75% and sufficient visibility required for automobile window glass, and a solar radiation transmittance of 54%. I was blocking the heat rays of sunlight.
Further, the ultraviolet ray transmittance was 25%, which was sufficient to block harmful ultraviolet rays.

When this glass was used as a window glass for buildings, a mobile phone could be used without any trouble, and a radio could receive FM and AM radio waves satisfactorily. In addition, even if it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM can be used for radio.
And AM radio waves could be received well.

Example 7 An example of forming the first transparent dielectric film 2 by another sol-gel method will be described. An ultraviolet heat ray-shielding glass was formed in exactly the same manner as in Example 5 except that the first transparent dielectric film 2 was a TiO ₂ + CeO film formed by the following method.

Cerium chloride 2.8 g was added to ethanol 35c.
It was added to c and dissolved. 1.7 g of titanium tetraisopropoxide was added to this solution, 0.9 g of silicon tetraethoxide was added, 5.0 g of 2- (2-methoxyethoxy) ethanol was further added, and the mixture was stirred at 80 ° C. for 1 hour. , Heated.

After cooling to room temperature, 0.35 ml of water and 0.1 ml of 61% nitric acid were added, and the mixture was heated at 80 ° C. for 1 hour with stirring. The pH at this time was 2. This solution was cooled to room temperature and then applied on soda lime glass by a spinner. Spinner coating condition is 1000 rpm
It was 30 seconds. After drying the coated sample in the atmosphere,
It was put in an electric furnace and fired at 500 ° C. for 10 minutes. The obtained thin film sample had a film thickness of 400 nm and a refractive index of 1.9.
Met.

The ultraviolet heat ray-shielding glass thus formed has an optical characteristic of a visible light transmittance of 72% and sufficient visibility required for an automobile window glass, and a solar radiation transmittance of 53%. I was blocking the heat rays of sunlight.
Further, the ultraviolet ray transmittance was 20%, which was sufficient to block harmful ultraviolet rays.

When this glass was used as a window glass for buildings, a mobile phone could be used without any trouble, and a radio could receive FM and AM radio waves satisfactorily. In addition, even if it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM can be used for radio.
And AM radio waves could be received well.

[0073]

According to the ultraviolet heat ray-shielding glass of the present invention, at least one selected from the group consisting of zinc, cerium, titanium and cadmium is contained as a first layer from the substrate side on a transparent glass substrate. First, containing an oxide having an ultraviolet blocking ability, a composite oxide of these oxides, or a composite oxide obtained by adding a trace amount of a metal element to these oxides.
A transparent dielectric film, a second transparent dielectric film is provided as a second layer on the first layer, and a third layer is provided as a third layer on the second layer in the IIIa group, the IVa group, and the Vb group of the periodic table. , A composite tungsten oxide film containing at least one metal element selected from the group consisting of VIb group and VIIb group, and a third transparent dielectric film as a fourth layer on the third layer. With the ultraviolet heat ray-shielding glass characterized by the above, it is possible to obtain a window glass for automobiles and buildings that efficiently shields ultraviolet rays and heat rays, has a good visible light transmittance, and has sufficient radio wave transmission performance.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a film structure of a heat ray-shielding glass of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent glass substrate 2 1st transparent dielectric film 3 2nd transparent dielectric film 4 Composite tungsten oxide film 5 3rd transparent dielectric film

Claims (2)

[Claims] 1. A transparent glass substrate having a first side from the substrate side.
As a layer, an oxide having an ultraviolet ray-shielding property containing at least one selected from the group consisting of zinc, cerium, titanium and cadmium, a composite oxide of these, or a composite of these oxides to which a trace amount of a metal element is added. A first transparent dielectric film containing an oxide is provided, and a second transparent dielectric film is formed on the first layer.
A second transparent dielectric film is provided as a layer, and a third transparent dielectric film is provided on the second layer.
As a layer, IIIa group, IVa group, Vb group, V of the periodic table
A composite tungsten oxide film containing at least one metal element selected from the group consisting of Ib group and VIIb group is provided, and a third transparent dielectric film is provided as a fourth layer on the third layer. A glass that blocks UV heat rays. 2. The second transparent dielectric film of the second layer and the third transparent dielectric film of the fourth layer are selected from the group consisting of silicon, titanium, aluminum, tin, zirconium, tantalum, chromium, stainless steel and nichrome. The ultraviolet heat ray-shielding glass according to claim 1, which is at least one selected oxide, a composite oxide or a nitrided oxide thereof.