JPH08295540A - Glass for cutting off heat ray - Google Patents

Abstract

PURPOSE: To produce a heat ray cut-off glass high in transparency and radio wave transmissivity by providing a transparent protective film of a metal and/or a nitride on one surface of a WSiO film of the heat ray cut-off glass composed mainly of the WSiO film. CONSTITUTION: The tungsten-silicon multiple oxide film and an oxide dielectric film are successively formed on the surface of glass and the transparent protective film composed of the metal and/or the nitride is provided on one surface of the WSiO film. The transparent protective film is formed for improving the durability of the WSiO film and is composed of the metal and/or the nitride of Ti, Zr, Al, Si. A particularly preferable example is ZrSi2 Nx (X=2-4) or the like. The film is formed by a sputtering method using a target obtained by pressing and sintering a film forming element mixture or by a well-known method such as vacuum deposition method. The film thickness of the WSiO film is preferably 100-1300Å. As the dielectric film, the oxide film of Zn, Sn, Al or the like is preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass which blocks heat rays, and more particularly to a glass which is useful as a window glass for vehicles, a glass for building materials and the like and has an excellent heat ray blocking property and radio wave transmission property.

[0002]

2. Description of the Related Art Conventionally, in an automobile window glass or the like, a heat ray reflective film is formed on the surface of the window glass in order to prevent heat from entering and accumulating in the room due to direct sunlight or the like. These conventional heat ray reflective films are titanium nitride, silver,
A relatively highly conductive substance such as aluminum is formed on the glass surface by vapor deposition or sputtering.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the above-mentioned conventional heat ray reflector glass, the heat ray reflection film has high conductivity, has a high electromagnetic wave shielding property due to its nature, and does not allow radio waves to pass therethrough. There is a problem that communication devices such as mobile phones do not function sufficiently. Also,
When the film made of titanium nitride, silver, aluminum or the like has a certain thickness, it has a high reflectance for visible light and a low visible light transmittance, and cannot be used as a window glass for vehicles. Further, if the film is thin enough to have sufficient transparency, there is a problem that sufficient heat ray reflection performance cannot be obtained.

Further, a composite oxide of a mixture of tungsten and silicon is formed into a film which is radio wave permeable and has an excellent heat ray shielding property, and which is sufficiently transparent and permeable to visible light. be able to. In order to use this film in various environments, it is necessary to provide a protective film effective for imparting sufficient environment resistance to heat, ultraviolet rays and the like. Therefore, an object of the present invention is to provide a glass which has excellent heat ray shielding properties and radio wave transparency and which shields heat rays and is useful as a window glass for vehicles and a glass for building materials.

[0005]

The above object can be achieved by the present invention described below. That is, according to the present invention, a tungsten silicon composite oxide film and an oxide dielectric film are sequentially formed on at least one surface of a glass substrate, and at least one surface of the tungsten silicon composite oxide film, A glass for shielding heat rays, which is characterized in that a transparent protective film made of metal and / or nitride is provided.

[0006]

Function: Tungsten-silicon composite oxide film (hereinafter WSiO)
(A film) as a heat ray-shielding film that blocks heat rays. By providing a transparent protective film on at least one surface of the WSiO film, it has excellent heat ray-shielding properties and radio wave transmission properties, and is used for vehicle window glass and building material glass. It is possible to provide a highly durable glass that shields heat rays.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The glass for blocking heat rays of the present invention has at least one layer of a WSiO film 2 and the WSiO film 2 on at least one surface of a plate glass 1 (1 ′) as a substrate, as shown in a schematic cross section in FIG. The transparent protective film 3 is provided on at least one surface of the film 2. The example shown in FIG. 1a is an example in which the present invention is applied to a laminated glass. In this example, a WSiO film 2, a transparent protective film 3 and a dielectric film are provided between an outer plate glass 1 ′ which is a substrate and an inner plate glass 1. 4 and an intermediate film 5 made of polyvinyl butyral resin or the like are laminated in the order shown. Figure 1b
In the example shown in FIG. 1C, the transparent protective films 3 are formed on both sides of the WSiO film 2. In the example shown in FIG. 1C, the transparent protective film 3 is further provided between the dielectric film 4 and the intermediate film 5 in the example shown in FIG. 1B. This is an example in which the film 3 is formed.

The above example is an example in which the present invention is applied to laminated glass, but the present invention is not limited to laminated glass,
It goes without saying that the present invention can also be applied to other glass substrates such as single glass and double glazing. The glass substrate used in the present invention may be ordinary glass, tempered glass plate, partially tempered glass plate, etc., and may be colored to such an extent that transparency is not impaired. These glass substrates are not limited to flat plates, and may have curved surfaces processed into various shapes and curvatures, and the shape is not particularly limited, but particularly the front, rear, side, and roof of various vehicles. It is useful for window glass and the like. The thickness of these glass substrates is not particularly limited, but is usually about 1.5 to
A thickness of about 5 mm is common.

The WSiO film used in the present invention is
Tungsten (W) and silicon (Si) are, for example, W1
A known method such as a method of sputtering a target obtained by mixing Si at a ratio of about 3 to 20 atoms per 100 atoms and pressure sintering in an oxygen atmosphere, a vacuum vapor deposition method, a sol-gel method, a flexo printing method, a spray method and the like. It can be formed by depositing and forming a film on the surface of a glass substrate.
The preferred composition of the WSiO film thus formed is
It is a composite oxide containing 5 to 15 atomic% of Si with respect to W. In addition, as the thickness of the WSiO film formed, if the thickness is too thin, desired performance cannot be obtained, and if it is too thick, the transparency of the glass decreases, so a preferable thickness is about 100 to 1
It is 300Å.

In the present invention, as the transparent protective film for improving the durability of the WSiO film, a metal of group IVa element, a group Va element, a group IIIb element and a group IVb element, or a nitride or complex nitride of these metals is used. Is preferably used,
Preferred specific metals include, for example, at least one metal selected from the group consisting of titanium, zirconium, aluminum, and silicon and / or a nitride of the metal. More specifically, as particularly preferable _{examples, ZrSI 2 N x (X =} 2~4), Ti x Si y N z (T
i: Si = 90: 10 to 33:67 atomic ratio), TiN
_x (X = 0.5 to 1.3), SiN _x (X = 0.5 to 1.
3), AlN _x (X = 0.5 to 1.0), Ti, Ti / T
iN _x (X = 0.5 to 1.3) (two layers), ZrSi ₂ / Zr
_{Si 2 N x (X = 2~4} ) (2 layers), and the like.

These transparent protective layers can be formed by, for example, a method of sputtering a target obtained by mixing a film-forming element or two or more kinds of elements in a desired ratio and sintering the mixture under pressure in an inert atmosphere or a nitrogen atmosphere, or vacuum deposition. By a known method such as a method, by depositing and forming an elemental film and / or a nitride film on at least one surface of the WSiO film in the case of FIG. 1a and a desired surface in the other example. Can be formed. The thickness of the transparent protective film thus formed is, for example, about 10 in the example shown in FIG.
It is 200Å, and in the example shown in FIG.
100 Å, and in the example shown in FIG.
It is preferably 150Å, and the total thickness of the entire transparent protective film is preferably about 10 to 200Å. If these transparent protective films are too thin, the desired performance cannot be obtained, and if they are too thick, the transparency of the glass decreases, which is not preferable.

In the present invention, a dielectric film is formed on the side of the WSiO film opposite to the glass substrate. As the dielectric film, for example, Zn, Sn, Al, Si, Ti, Zr, T
Oxides and complex oxides of elements such as a, Nb, and Bi are preferable, and are formed by a known film forming technique such as a sputtering method like the WSiO film. The dielectric film is shown in FIG.
In each of the examples shown in c, the dielectric film is formed at a position in contact with the intermediate film, but the dielectric film is not limited to the illustrated position.
Further, the dielectric film may be further formed between the glass substrate and the WSiO film. These dielectric films are formed for the purpose of reducing the visible light blocking rate or adjusting the reflection color tone, and the thickness of the dielectric film formed is about 900 to 1700Å in total for the WSiO layer and the dielectric layer. is there.

The intermediate resin film used when the glass for blocking heat rays in the present invention is a laminated glass means, when the laminated glass is used, the two sheet glasses disposed on both sides of the laminated glass are solidified. Along with bonding, even when the laminated glass is broken, it has a function of preventing glass fragments from scattering and a penetration resistance, and generally has improved physical properties such as adhesion, light resistance, and heat resistance. Butyral resin sheet is preferably used. The thickness of these intermediate resin films is not particularly limited, but is generally about 0.2 to 0.9 mm.

The method for producing the laminated glass may be a known method, for example, two sheet glasses having a predetermined shape are bent as required, and after washing and drying, one of the sheet glasses has the WSiO film and the transparent layer as described above. A protective layer and a dielectric film are formed. On the other hand, the intermediate resin film is also washed and dried and then cut into a predetermined shape. A desired laminated glass is manufactured by laminating the above two sheets of glass so as to sandwich a resin sheet, and performing steps such as pre-adhesion, autoclave treatment, washing and drying.

[0015]

EXAMPLES Next, the present invention will be described with reference to Comparative Examples and Examples.
Will be specifically described. Comparative Example 1 Green glass (10
cm × 10 cm × 2 mm thickness) and Si in W
Adds 4.8 atom% and is inactive at temperatures around 1,500 ° C
Using a target that has been pressure-sintered in a gas atmosphere,
Pressure during sputtering on the above substrate by the flow sputtering method.
1.0 mTorr, Ar: O₂ = Mixed at a ratio of 30:16
W with a film thickness of 500Å in a combined gas atmosphere ₉₅Si_FiveO_x(X
A transparent WSiO film consisting of
Using a Zn metal target continuously without opening,
Pressure at putter = 4.0 mTorr, Ar: O₂= 2
Film thickness 700Å in gas atmosphere mixed with 0:40 ratio
ZnO transparent dielectric film of was formed. In addition, during film formation
No heating was done.

[0016] The glass coated with the above-mentioned
A polyvinyl butyral sheet (thickness: 0.76 mm) was laminated with a green glass sheet having a thickness of 0.7 mm, pre-pressed, and then heat-pressed by an autoclave to obtain a laminated glass. The film resistance of the WSiO film was 10 MΩ / □ or more. The visible light transmittance of this laminated glass with a film was 72%, and the solar light transmittance was 47%. On the other hand, the visible light transmittance of ordinary glass having no film formed in the same manner as above except that the WSiO film and the ZnO film were not provided was 79%, and the solar light transmittance was 54%.

A heat resistance test was conducted on the laminated glass with a film, and when it was allowed to stand in a constant temperature bath at 110 ° C. for 24 hours, the slightly absorbed coloring due to the WSiO film disappeared, and it was almost completely colorless and transparent. Also, the heat ray blocking performance was almost lost. After that, it was left for 30 days for observation, but no change was observed while it remained transparent. FIG. 2 shows changes with time in coloring of the laminated glass with a film.
ΔT in FIG. 2 is the change rate of the visible light transmittance before and after the start of the test. Next, the influence of ultraviolet rays was examined on the laminated glass with a film. The above glass with film is JIS-R
In accordance with 3212, when a carbon arc lamp was used to irradiate ultraviolet rays from the opposite surface of the intermediate film for 100 hours,
The slightly absorbed color density of the film is increased and the visible light transmittance is 7
It had dropped to 0.2%. After 300 hours, the coloring density by the WSiO film was further increased and the visible light transmittance was 68%. After that, the evaluation was continued for 1000 hours, but the darkening by WSiO proceeded.
Finally, the visible light transmittance dropped to 67%. These changes with time are shown in FIG.

Example 1 As shown in FIG. 1c, between the WSiO film and the green glass (outer plate glass), between the WSiO film and the ZnO film and Z
A laminated glass was produced in the same manner as in Comparative Example 1 except that a transparent protective film was formed between the nO film and the polyvinyl butyral film. For each of the three layers of transparent protective films, Zr and Si were mixed at a ratio of Zr: Si = 1: 2, and
Using a target pressure-sintered in an inert gas atmosphere at a temperature of around 0 ° C., the pressure during sputtering = 3.0 mTorr
A ZrSi ₂ N _x film (X = about 4) having a film thickness of 50Å was formed by sputtering in a gas atmosphere mixed with r and Ar: N ₂ = 20: 20. The film resistance of the WSiO film was 10 MΩ / □ or more. This film-coated laminated glass has a visible light transmittance of 72% and a solar light transmittance of 47%.
%Met.

A heat resistance test was conducted on the laminated glass with a film, and when it was left in a constant temperature bath at 110 ° C. for 24 hours, the slight absorption color development by the WSiO film was hardly changed, and the heat ray blocking performance was also almost changed. I didn't. After that, the sample was left for 30 days for observation, but no change in slightly absorbed color was observed. FIG. 2 shows changes with time in coloring of the laminated glass with a film. Next, with respect to the laminated glass with a film, the effect of ultraviolet rays was examined in the same manner as in Comparative Example 1. As a result, visible light transmittance and sunlight transmittance were hardly changed even after 30 days and 1000 hours. The absolute value of the change was within 0.5%.
The results of these tests are shown in FIG.

Example 2 As shown in FIG. 1a, a ZrSi ₂ N _x film having a film thickness of 50 Å was provided as a transparent protective film between the WSiO film and the dielectric film by sputtering as in Example 1. A laminated glass was produced in the same manner as in Comparative Example 1 except for the above. The above WS
The film resistance of the iO film was 10 MΩ / □ or more. The visible light transmittance of this laminated glass with a film was 72%, and the solar light transmittance was 47%. When a heat resistance test and an ultraviolet resistance test were conducted on the above laminated glass with a film, there was almost no change in the optical characteristics of the glass as in Example 1, and the absolute value of the change was within 1%. The results of the heat resistance test and the ultraviolet light resistance test are shown in FIG.

Example 3 A laminated glass was produced in the same manner as in Example 2 except that a titanium metal film having a film thickness of 25 Å was formed by DC sputtering instead of the ZrSi ₂ N _x film in Example 2. The visible light transmittance of this laminated glass with a film is 70%,
The solar ray transmittance was 45%. When the heat resistance test and the ultraviolet light resistance test were performed on the above 25Å titanium film-coated laminated glass in the same manner as in Example 1, the absolute values of changes in the visible light transmittance and the sunlight transmittance were within 1%. The results of the above heat resistance test are shown in FIG.

[0022]

As described above, according to the present invention, WS
In a glass for blocking heat rays using an io film as a heat ray blocking film, by providing a transparent protective film on at least one surface of the WSiO film, it has excellent heat ray blocking properties and radio wave transmission properties, and is used as a window glass for vehicles or a glass for building materials. It is possible to provide a useful highly durable glass that blocks heat rays.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a cross section of glass for blocking heat rays according to the present invention.

FIG. 2 is a diagram showing the results of comparative examples and examples.

[Explanation of symbols]

 1: Inner plate glass 1 ': Outer plate glass 2: WSiO film 3: Transparent protective film 4: Dielectric film 5: Intermediate film

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

Claims (4)

[Claims] 1. A glass substrate is provided with a tungsten silicon composite oxide film and an oxide dielectric film formed on at least one surface of the glass substrate, and a metal film is formed on at least one surface of the tungsten silicon composite oxide film. A glass for blocking heat rays, which is characterized in that a transparent protective film made of and / or nitride is provided. 2. The transparent protective film is made of at least one metal selected from the group consisting of titanium, zirconium, aluminum, and silicon, and / or a nitride of the metal. A glass that blocks the heat rays of. 3. A laminated glass in which two glass substrates are laminated via an intermediate resin film, and a tungsten silicon composite oxide film and an oxide dielectric film are provided between at least one of the glass substrates and the intermediate resin film. Is sequentially formed from the glass substrate side, and a transparent protective film made of a metal and / or a nitride is provided on at least one surface of the tungsten silicon composite oxide film. 4. The transparent protective film comprises at least one metal selected from the group consisting of titanium, zirconium, aluminum and silicon, and / or a nitride of the metal. Laminated glass.