JPH0859300A - Heat blocking glass - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a heat ray-shielding glass that can be suitably used in a site where high visible light transmittance and good heat ray-shielding performance are required. [Structure] On a transparent glass substrate, as a first layer at least from the substrate side, IIIa group, IVa group, Vb of the periodic table
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of Group VI, Group VIb and Group VIIb, and providing a transparent dielectric film as a second layer on the first layer; III of the periodic table as the third layer on the layer
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of a-group, IVa-group, Vb-group, VIb-group and VIIb-group is provided, and the transparent dielectric of the second layer has a refractive index of A heat ray-shielding glass having a refractive index lower than that of the composite tungsten oxide films of the first layer and the third layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray-shielding glass suitable as a window glass, and more particularly to a heat ray-shielding glass which can be suitably used in a site where high visible light transmittance and good heat ray-shielding performance are required. .

[0002]

2. Description of the Related Art Conventionally, from the viewpoint of energy saving, a specific wavelength portion of sunlight radiated into a passenger compartment through a window glass is blocked to reduce a temperature rise in the passenger compartment and to cool the vehicle. In order to reduce the load on the equipment as well, 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).

[0005]

However, the heat ray blocking film described in the above publication has a drawback that it cannot yet exhibit satisfactory performance. Further, for example, when a silver film is used, the sheet resistance value of the silver film is several Ω-10 Ω /
It has a value of about □ 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 radio field intensity in the surroundings such as in high-rise buildings. Furthermore, when the above-mentioned conductive film is used as the heat insulating film, when a conductive film is formed on the antenna wire as disclosed in Japanese Patent Laid-Open No. 3-122032, a current flows between the antenna wires and the antenna performance deteriorates. There was a drawback to do. Also, depending on the conductivity of the heat insulating film, if the conductivity is good, the problem of radio wave transmission will occur in addition to the problem that the antenna performance is deteriorated.

As described above, a heat insulating film such as a drew demirror type or a silver film is not preferable. Therefore, an object of the present invention is to provide a heat ray-shielding glass that can shield heat rays with a simple layered structure and can transmit radio waves without problems.

[0008]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
On a transparent glass substrate, as a first layer at least from the substrate side, IIIa group, IVa group, Vb group, VIb of the periodic table
At least one selected from the group consisting of Group VIIb and Group VIIb
Providing a composite tungsten oxide film containing seed metal ions, and providing a transparent dielectric film as a second layer on the first layer,
A group IIIa, IV of the periodic table as a third layer on the second layer
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of a-group, Vb-group, VIb-group and VIIb-group is provided, and the transparent dielectric film of the second layer has a refractive index of the first group. This is achieved by a heat ray-shielding glass having a refractive index lower than that of the composite tungsten oxide films of the first layer and the third 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 is various glass such as soda lime glass and aluminosilicate glass, colored glass plate such as gray, blue, bronze and green, and transparent resin substrate such as polymethylmethacrylate (PMMA) and polycarbonate (PC). Although various glass plates and colored plates can be preferably used, glass having a green color can be preferably used.

The color of glass having a green color can be defined by a chromaticity diagram of Yxy display. Y is 1.00
It is preferable that the range is 1.40, x is 0.24 to 0.32, and y is 0.30 to 0.41. The green glass in this range has a high visible light transmittance and an absorption in the near-infrared region, so that the heat insulating effect is remarkably improved by the combined use with the above-mentioned heat ray blocking film. Further, glass having a greenish tint contains iron ions, and exhibits excellent heat insulating performance due to a synergistic effect with the tungsten oxide heat insulating film of the present invention.

In FIG. 1, 2 is a group IIIa of the periodic table provided on the transparent glass substrate 1 as a first layer,
It is a composite tungsten oxide film containing at least one metal ion selected from the group consisting of IVa group, Vb group, VIb group and VIIb group.

Reference numeral 3 is a transparent dielectric film provided as a second layer on the composite tungsten oxide film 2. The transparent dielectric film 3 is a transparent dielectric film having a refractive index lower than that of the composite tungsten oxide films 2 and 4, and may be appropriately selected from silicon, aluminum, tin oxide films, or composite oxide films thereof. it can.

Reference numeral 4 denotes a group IIIa, IVa, Vb of the periodic table provided on the transparent dielectric film 3 as a third layer,
It is a composite tungsten oxide film containing at least one metal ion selected from the group consisting of VIb group and VIIb group. The material of the film 4 may be the same as or different from the composite tungsten oxide film 2. Further, the refractive index and the film thickness of the film 4 may be the same as or different from those of the film 2.

In the present invention, the function of blocking heat rays is mainly the IIIa group, the IVa group, the Vb group and the VI group of the periodic table.
Composite tungsten oxide film containing at least one metal ion selected from the group consisting of Group b and Group VIIb 2
And 4, due to optical interference caused by the laminated structure of the transparent dielectric film 3.

Generally, 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. In the presence of pentavalent tungsten which is slightly reduced from the most oxidized state, the ability to block heat rays is high and absorption occurs particularly 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, infrared absorption cannot be expected.

It is generally known that tungsten oxide has insufficient durability, although it depends on the manufacturing method. Further, 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 film in view of the above-mentioned problems of the antenna and 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 ion 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 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, and improves the poor durability of tungsten oxide alone. , A function of increasing the resistance of the tungsten oxide film to several hundreds KΩ / □ to several hundreds MΩ / □.

In consideration of the ease of producing an alloy target for a composite oxide, IIIa is Al, IVa is Si, Vb is V or Nb, VIb is Cr, and VIIb is Cr. Mn is preferably used.

These heat ray blocking films can be appropriately selected and used from known film forming methods, for example, sputtering method, vapor deposition method, ion plating method, chemical vapor deposition method (C
The film can be preferably formed by a vacuum film forming method such as a VD method) or a wet film forming method such as a sol-gel method, but it is particularly preferable to form the film by a sputtering method from the viewpoint of increasing the area and productivity.

The composite oxide can be formed by, for example, the following sputtering method. As a sputtering target, tungsten and IIIa group, IVa group, Vb group of the periodic table,
An alloy target containing at least one element selected from the group consisting of VIb group and VIIb group at a predetermined concentration is used, and argon (Ar) and oxygen (O ₂ ) are adjusted as a sputtering gas at a predetermined gas ratio. A mixed oxide film can be formed on a glass substrate by a so-called reactive sputtering method using a mixed gas.

This composite tungsten oxide film is formed on glass, a low refractive index film is formed thereon, and a composite tungsten oxide film is further formed thereon, and the low refractive index film is sandwiched between the composite tungsten oxide films. With this structure, the optical interference effect appears, the transmittance in the visible region increases, the reflection in the infrared region increases, and heat rays can be absorbed and reflected at the same time. With such a structure, the heat ray blocking effect is further enhanced, and the present invention is achieved.

The film thickness of each layer is not limited as long as at least the composite tungsten oxide films 2 and 4 can exhibit a heat ray blocking function, but it is particularly preferably in the range of 2 to 300 nm. When the film thickness of the composite tungsten oxide films 2 and 4 is less than 2 nm, the film does not have an island shape,
On the contrary, 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 structure, the range of 5 to 200 nm is preferable.

The transparent dielectric film 3 is not particularly limited as long as it has a thickness capable of exhibiting an optical interference effect with the composite tungsten oxide films (2) and (4), but is particularly 2 to 200 nm.
It is preferably in the range of. When the film thickness of the transparent dielectric film 3 is less than 2 nm, the film does not have an island shape, and on the contrary, 200
If it exceeds nm, the economy is poor. In addition to both of these, the range of 5 to 100 nm is preferable in order to obtain safe and reliable performance in the entire film structure.

In the present invention, an arbitrary metal oxide film, nitride film or nitrogen oxide film can be further formed on these films as a protective film against the problem of oxidation and scratch of the tungsten oxide film. . Further, in order to improve the adhesion to the substrate under these films, an arbitrary metal oxide film layer, a zinc oxide film having an ultraviolet blocking function, or the like can be formed.

According to the heat ray-shielding glass of the present invention, heat rays can be efficiently shielded with a simple structure and sufficient radio wave transmission can be obtained. Further, although the heat ray-shielding glass of the present invention can be used as a single plate, it goes without saying that it can be used as a laminated glass or a multi-layer glass.

[0027]

The present invention provides a transparent glass substrate, at least from the substrate side, as a first layer of the periodic table of groups IIIa and IVa.
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of Group Vb, Group VIb and Group VIIb is provided, and a transparent dielectric film is provided 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, a group VIb and a group VII of the periodic table.
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of group b is provided, and the transparent dielectric material of the second layer has a refractive index of the first layer and the third layer.
The heat ray-shielding glass, which is characterized by having a refractive index lower than that of the composite tungsten oxide film of the layer, effectively shields heat rays with a simple layered structure, and a window glass having good radio wave transparency is obtained.

[0028]

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 purely, 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 silicon-tungsten alloy target (Si: W = 0.1: 1 atomic ratio) for the tungsten oxide film containing silicon used as a heat ray blocking film for the composite tungsten oxide films 2 and 4, and a low refractive index A silicon target for silicon oxide used as the transparent dielectric film 3 having a high index was set.

First, a mixed gas of argon and oxygen was adjusted as Ar: O ₂ = 30: 4 as a sputter gas, and the exhaust speed and gas were adjusted so that the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr. Adjusting the flow rate, sputtering power 500W
Then, a tungsten oxide film 2 containing silicon was formed to a thickness of 40 nm by reactive sputtering. Next, as a sputtering gas, a mixed gas of argon and oxygen is Ar: O ₂ = 1:
Adjust so that the gas pressure in the vacuum chamber is 5 × 1.
Adjust the pumping speed and gas flow rate so that it becomes 0 ^-3 Torr,
A silicon oxide film having a thickness of 10 nm was formed as the transparent dielectric film 3 by reactive sputtering with a sputtering power of 300 W.
Further, as the composite tungsten oxide film 4, a tungsten oxide film containing silicon was formed to a thickness of 40 nm like the composite tungsten oxide film 2. The silicon oxide film had a refractive index of 1.48, and the silicon-containing tungsten oxide film had a refractive index of 2.3.

The optical characteristics of the heat ray-shielding glass thus formed are: visible light transmittance 83%, sufficient visible light transmittance and visibility, and solar radiation transmittance 58%, sufficient heat ray of sunlight. Was shut off. 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 of an automobile, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily.

Example 2 Under the same film material and film forming conditions as in Example 1, Y = 1.27, x = 0.856, y = 0.3 instead of the transparent glass substrate.
A green glass having a value of 176 was used, the thicknesses of the tungsten oxide films 2 and 4 containing silicon were set to 25 and 35 nm, and the thickness of the silicon oxide film was set to 20 nm as the transparent dielectric film 3. A heat ray-shielding glass was deposited in the same manner as in Example 1.

The optical characteristics of this constitution are 77% of visible light transmittance and sufficient visible light transmittance and visibility required for a window glass, and 45% of solar radiation transmittance sufficiently block heat rays of sunlight. Was. Further, when this glass was used as a window glass for buildings, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily. Further, even when it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and the radio can receive FM and AM radio waves satisfactorily.

Example 3 A film material different from those in Examples 1 and 2 will be described. The green glass substrate used in Example 2 was degreased and washed with isopropyl alcohol, purely rinsed, and then dried by nitrogen blowing. This transparent glass substrate was conveyed into the sputtering apparatus and exhausted to 5 × 10 ⁻⁶ Torr. An aluminum / tungsten alloy target (Al: W = 0.1: 1 atomic ratio) for the aluminum-containing tungsten oxide film used as the composite tungsten oxide films 2 and 4 and aluminum oxide used as the transparent dielectric 3 in the vacuum chamber. An aluminum target for the membrane was installed.

First, 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 pressure in the vacuum chamber were adjusted to 5 × 10 ⁻³ Torr. Adjusting the gas flow rate, sputtering power 500W
Then, an aluminum-containing tungsten oxide film having a thickness of 30 nm was formed by reactive sputtering. Next, argon gas was used as a sputtering gas and the gas pressure in the vacuum chamber was 5 × 10 ⁻³ Torr.
The exhaust speed and the gas flow rate were adjusted so that the sputtering power was 400 W, and an aluminum oxide film was formed as the transparent dielectric film 3 to a thickness of 15 nm. Further, as the composite tungsten oxide film 4, an aluminum-containing tungsten oxide film having a thickness of 30 nm was formed in the same manner as the composite tungsten oxide film 2. The aluminum-containing tungsten oxide film thus obtained had a refractive index of 2.4, and the aluminum oxide film had a refractive index of 1.6.

The optical characteristics of this structure are a visible light transmittance of 73%, sufficient visible light transmittance and visibility required for a window glass, and a solar radiation transmittance of 42% to sufficiently block the heat rays of sunlight. Was. Further, when this glass was used as a window glass for buildings, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily. Further, even when it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and the radio can receive FM and AM radio waves satisfactorily.

Example 4 As the composite tungsten oxide films 2 and 4 in Example 3, instead of the alloy target of aluminum and tungsten, an alloy target of chromium and tungsten (Cr: W) was used.
= 0.1: 1), a tungsten oxide film containing chromium was formed to a thickness of 20 and 30 nm, respectively, and an aluminum oxide film as the transparent dielectric film 3 was formed to a thickness of 7 nm. A heat ray shielding glass was formed in exactly the same manner. The refractive index of the chromium-containing tungsten oxide film was 2.4.

The optical characteristics of this constitution are a visible light transmittance of 78%, sufficient visible light transmittance and visibility required for a window glass, and a solar radiation transmittance of 49% to sufficiently block the heat rays of sunlight. Was. 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 A tin oxide film having a thickness of 15 nm is used instead of the silicon oxide film as the transparent dielectric film 3 in Example 1, and manganese is contained instead of the silicon-containing tungsten oxide film as the composite tungsten oxide films 2 and 4. A heat ray-shielding glass was formed in exactly the same manner as in Example 1 except that the tungsten oxide film having a thickness of 35 nm was used. The manganese-tungsten alloy target used at this time had a Mn: W ratio of 0.1: 1. The refractive index of the manganese-containing tungsten oxide film is 2.
5, and the tin oxide film had a refractive index of 1.9.

The optical characteristics of this constitution are 79% of visible light transmittance and sufficient visible light transmittance and visibility required for window glass, and 59% of solar radiation transmittance to sufficiently block heat rays of sunlight. Was. Further, when this glass was used as a window glass for buildings, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily. Further, even when it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM and AM radio waves can be satisfactorily received by the radio.

Example 6 Instead of the transparent glass substrate in Example 5, Y = 1.3
Using green glass having values of 0, x = 0.30, y = 0.38, tungsten oxide films containing vanadium were used instead of the tungsten oxide films containing manganese as the composite tungsten oxide films 2 and 4, respectively. 60
Example 5 except that aluminum oxide having a thickness of 40 nm and aluminum oxide having a thickness of 40 nm instead of silicon oxide as the transparent dielectric film 3 is used.
A heat ray-shielding glass was formed into a film in exactly the same manner as. The V: W of the vanadium-tungsten alloy target used at this time was 0.4: 1. The vanadium-containing tungsten oxide film had a refractive index of 2.8 and the aluminum oxide had a refractive index of 1.6.

The optical characteristics of this constitution are a visible light transmittance of 70%, sufficient visible light transmittance and visibility required for a window glass, and a solar radiation transmittance of 44% to sufficiently block the heat rays of sunlight. Was. Further, when this glass was used as a window glass for buildings, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily. Further, even when it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM and AM radio waves can be satisfactorily received by the radio.

Example 7 Instead of the transparent glass substrate in Example 5, Y = 1.3
Using green glass having values of 0, x = 0.30, y = 0.38, a tungsten oxide film containing niobium was used instead of the tungsten oxide film containing manganese as the composite tungsten oxide films 2 and 4, respectively. 30 nm
A heat ray-shielding glass was formed in exactly the same manner as in Example 5, except that aluminum oxide was used as the transparent dielectric film 3 in place of silicon oxide to have a thickness of 15 nm. The Nb: W of the alloy target of niobium and tungsten used at this time was 0.1: 1. The niobium-containing tungsten oxide film had a refractive index of 2.4, and the aluminum oxide had a refractive index of 1.6.

The optical characteristics of this structure are as follows: visible light transmittance of 74%, sufficient visible light transmittance and visibility required for a window glass, and solar radiation transmittance of 45% to sufficiently block heat rays of sunlight. Was. Further, when this glass was used as a window glass for buildings, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily. Further, even when it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM and AM radio waves can be satisfactorily received by the radio.

Example 8 A tungsten oxide film containing niobium having a thickness of 40 nm was used instead of the tungsten oxide film containing manganese as the composite tungsten oxide film 4 in Example 5.
A heat ray-shielding glass was formed in the same manner as in Example 5.
The Nb: W of the alloy target of niobium and tungsten used at this time was 0.1: 1. The refractive index of the niobium-containing tungsten oxide film was 2.4.

The optical characteristics of this constitution are a visible light transmittance of 76%, sufficient visible light transmittance and visibility required for a window glass, and a solar radiation transmittance of 47% to sufficiently block the heat rays of sunlight. Was. Further, when this glass was used as a window glass for buildings, the mobile phone could be used without any trouble, and the radio could receive FM and AM radio waves satisfactorily. Further, even when it is used as a window glass for automobiles, the mobile phone can be used without any trouble, and FM and AM radio waves can be satisfactorily received by the radio.

[0047]

According to the heat-shielding glass of the present invention, at least the first layer from the substrate side is composed of IIIa group, IVa group, Vb group, VIb group and VIb group of the periodic table on the transparent glass substrate. A composite tungsten oxide film containing at least one metal ion selected from the group is provided, and a transparent dielectric film is provided as a second layer on the first layer.
As a third layer on the layer, IIIa group, IVa group of the periodic table,
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of Vb group, VIb group and VIIb group is provided, and the transparent dielectric film of the second layer has a refractive index of the first layer and The heat ray-shielding glass characterized by having a refractive index lower than that of the composite tungsten oxide film of the third layer effectively shields heat rays with a simple layered structure, and a window glass having good radio wave transparency can be obtained.

[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]

 1 Transparent Glass Substrate 2 First Composite Tungsten Oxide Film 3 Transparent Dielectric Film 4 Second Composite Tungsten Oxide Film

Claims (4)

[Claims] 1. A group IIIa, IVa group of the periodic table as a first layer at least from the substrate side on a transparent glass substrate,
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of Vb group, VIb group and VIIb group is provided, and a transparent dielectric film is provided as a second layer on the first layer. I of the periodic table as the third layer on the second layer
A composite tungsten oxide film containing at least one metal ion selected from the group consisting of Group IIa, Group IVa, Group Vb, Group VIb and Group VIIb is provided, and
A heat ray-shielding glass, wherein the transparent dielectric film of the layer has a refractive index lower than that of the composite tungsten oxide film of the first layer and the third layer. 2. The composite tungsten oxide films of the first layer and the third layer have the same composition and have a refractive index of 1.9 to.
The heat ray-shielding glass according to claim 1, which is in a range of 2.8. 3. The composite tungsten oxide films of the first layer and the third layer have different compositions and have a refractive index of 1.9 to.
The heat ray-shielding glass according to claim 1, which is in a range of 2.8. 4. The transparent dielectric film of the second layer is an oxide film of silicon, aluminum and tin or a composite oxide film thereof, and its refractive index is in the range of 1.4 to 1.9. The heat ray-shielding glass according to claim 1, wherein: