JPH0952738A - Heat ray interrupting glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a heat ray interrupting property and the resistance to a radio wave transmissibility by laminating an outer ply glass, an intermediate resin film, a coating film containing a composite oxide layer of tungsten and silicon and an inner ply glass. SOLUTION: Two sheets of plate glasses 1 and 2 each having 1.5-5mm thickness and a prescribed shape are washed and dried after bending at need. The oxide layer 4 of the tungsten and the silicon containing 5-15atom% siliconbased on atomic amt. of tungsten and having 100-1,300Å thickness, a dielectric film 5 and a transparent protective layer 6 having 10-200Å thickness are formed on a surface of the plate glass 2. Then, the glass plate 2 and the glass plate 1 are laminated by interposing an intermediate resin film 3 having 0.2-0.9mm thickness.

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, and more particularly, it relates to a laminated glass excellent in heat ray-shielding property and radio wave transmission which is useful for, for example, window glass for vehicles and glass for building materials.

[0002]

2. Description of the Related Art Conventionally, in a window glass for an automobile 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. In these conventional heat ray reflective films, a relatively highly conductive substance such as titanium nitride, silver or aluminum is formed on the glass surface by vapor deposition or sputtering.

[0003]

In the above conventional heat ray reflective glass, the heat ray reflective film has a high conductivity, has a high electromagnetic wave shielding property due to its nature, and does not allow radio waves to pass therethrough. Therefore, the indoor antenna, the glass printed antenna, the portable telephone, etc. There is a problem that communication devices such as telephones do not function sufficiently. Also, the above-mentioned film made of titanium nitride, silver, aluminum, etc., becomes more reflective to visible light and has a lower visible light transmittance when it has a certain thickness, 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 forms a film which is radio wave permeable and has an excellent heat ray shielding property, and which is sufficiently transparent and transparent 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 laminated glass which is excellent in heat ray shielding property and radio wave transmission property and is also excellent in durability, which is useful as a window glass for vehicles or a glass for building materials.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention provides a laminated glass in which an outer glass sheet, an intermediate resin film and an inner glass sheet are sequentially laminated, and includes at least one tungsten silicon composite oxide film layer between the intermediate resin film and the inner glass sheet. It is a heat ray-shielding glass characterized by being provided with a coating.

According to the present invention, by providing a film including a tungsten silicon composite oxide film (hereinafter referred to as WSiO film) layer for blocking heat rays, between the intermediate resin film of laminated glass and the inner plate glass, heat ray blocking is performed. It is possible to provide a highly durable laminated glass which has excellent properties and radio wave transparency and is useful as a window glass for vehicles and a glass for building materials. It is preferable to use an ultraviolet blocking film as the intermediate resin film.

[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 heat ray-shielding glass of the present invention is obtained by sequentially laminating an outer glass sheet 1, an intermediate resin film 3 and an inner glass sheet 2, and the intermediate resin film 3 and the inner glass sheet 2 are laminated.
The basic configuration is that a coating film including at least one WSiO film layer is provided between and. FIG. 1a is a cross-sectional view of a conventional laminated glass, and the cross-sectional view shown in FIG. 1b is a view for explaining one embodiment of the heat ray-shielding glass of the present invention. The intermediate resin film 3 and the WSiO film 4 are described above. An example is shown in which the oxide dielectric film 5 is further formed between and. FIG. 1c is a diagram showing a comparative example of the example of FIG. 1b.

The cross-sectional view shown in FIG. 1d is a view for explaining another embodiment of the heat ray-shielding glass of the present invention.
An example in which a transparent protective film 6 made of a metal and / or a nitride and a dielectric film 5 are formed on both surfaces of the SiO film 4 is shown. FIG. 1e is a diagram illustrating a comparative example of the example of FIG. 1d. The sectional view shown in FIG. 1f is a view for explaining still another embodiment of the heat ray-shielding glass of the present invention, in which the antenna wire 7 is provided between the outer glass sheet 1 and the intermediate resin film 3, and the inner glass sheet is further provided. 2 shows an example in which the WSiO film 4 and the dielectric film 5 are formed between the two. In the present invention, the WSiO film 4 may be provided in direct contact with the intermediate resin film 3 as shown in FIG. 1f, but as shown in FIGS. 1b and d, the intermediate resin film 3 may be provided.
It is preferable to interpose the various films described above between them and the WSiO film 4 so that they do not come into direct contact with each other.

The plate glass used in the present invention is
It may be ordinary glass, tempered plate glass, partially tempered plate glass, or the like, and may be colored to such an extent that transparency is not impaired. These glass substrates are not limited to flat plates, but may be 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, etc. Further, the thickness of these glass substrates is not particularly limited, but is generally about 1.5 to 5 mm.

Further, the intermediate resin film used in the present invention means, in the case of laminated glass, two sheet glasses disposed on both surfaces thereof are firmly adhered to each other, and also when the laminated glass is broken. The resin film has a function of preventing glass fragments from scattering and a penetration resistance, and is usually a resin film having improved physical properties such as adhesiveness, weather resistance and heat resistance. In particular, a film that does not substantially transmit ultraviolet rays is preferable, and a polyvinyl butyral resin sheet having a property of blocking ultraviolet rays having a wavelength of less than 370 nm is particularly preferably used.

In order to further improve the ultraviolet blocking property of these intermediate resin films, the resin film may contain an organic or inorganic ultraviolet absorber, such as fine particle titanium oxide, to the extent that its transparency is not impaired. preferable. The thickness of these intermediate resin films is not particularly limited, but is usually about 0.
Generally, the thickness is about 2 to 0.9 mm.

The WSiO film used in the present invention is
Tungsten (W) and silicon (Si) are, for example, W1
By a known method such as a method of sputtering a target obtained by mixing Si in an amount of about 3 to 20 atoms per 00 atom and pressurizing and sintering in an oxygen atmosphere, a vacuum 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 a complex oxide containing 5 to 15 atomic% of Si with respect to W. If the thickness of the WSiO film to be formed 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, a transparent protective film which further improves the durability of the WSiO film can be formed.
Examples of the transparent protective film include IVa group elements, Va group elements, III
Metals of Group b elements and Group IVb elements, or nitrides or composite nitrides of these metals are preferably used, and specific preferred metals include, for example, at least one selected from the group consisting of titanium, zirconium, aluminum, and silicon. Mention may be made of one metal and / or a nitride of said metal. More _{specifically, ZrSi 2 N x (X =} 2~4), Ti x Si
_{yN z} (Ti: Si = 90: 10 to 33:67 atomic ratio),
TiN _x (X = 0.5 to 1.3), SiN _x (X = 0.5)
~ 1.3), AlN _x (X = 0.5 to 1.0), Ti,
Ti / TiN _x (X = 0.5 to 1.3) (two layers), Zr
_{Si 2 / ZrSi 2 N x (} X = 2~4) (2 layers), and the like.

These transparent protective layers are formed, for example, by a method of sputtering a target obtained by mixing film-forming elements or two or more kinds of elements at a desired ratio and pressurizing and sintering in an inert atmosphere or a nitrogen atmosphere, and vacuum deposition. W by a known method such as a method
It is formed on at least one surface of the SiO film. The thickness of the transparent protective film thus formed is, for example,
In the example shown in FIG. 1d, it is preferably about 10 to 200Å, and when it is formed in multiple layers, one layer is about 5 to 100Å, 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 may be formed between the WSiO film and the glass substrate in order to adjust the color tone or reflectance of the laminated glass. Examples of the dielectric film include Zn, Sn, Al, Si, Ti,
Examples thereof include oxides and complex oxides of elements such as Zr, Ta, Nb and Bi, and oxides of Zn, Ti or Sn are particularly preferable from the viewpoint of productivity. However, on the other hand, when the above-mentioned preferred oxides are used, the UV deterioration of the WSiO layer is accelerated. Therefore, Zn, Ti or Sn
The effect of the present invention is remarkable when the oxide of 1 is used adjacent to the WSiO layer. The above-mentioned dielectric film is
Like the iO film, it is formed by a known film forming technique such as a sputtering method. The formation of the dielectric film is shown in FIGS.
The position shown in f is not limited. 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 WSi.
A total of about 900 to 1,700Å of the O layer and the dielectric layer is preferable.

The method for producing the heat-shielding glass of the present invention itself may be a known method. For example, two glass sheets having a predetermined shape may be bent as required, and after washing and drying, one of the glass sheets may have the above-mentioned surface. A WSiO film, a transparent protective layer, a dielectric film and the like are formed. Replace the above two sheets of glass with W
A desired laminated glass is manufactured by the steps of pre-adhesion, autoclave treatment, washing / drying, etc., with the SiO 2 film being the inner plate glass side, and the resin sheets being stuck together.

[0017]

EXAMPLES Next, the present invention will be described more specifically with reference to conventional examples, examples and comparative examples. Conventional Example In the method described in Example 1 below, the WSiO film and Z
An ordinary laminated glass without a film (see FIG. 1a) produced in the same manner as in Example 1 except that the nO film was not provided had a visible light transmittance of 79% and a solar light transmittance of 54%. Example 1 A well-cleaned green heat ray absorbing glass (10 cm x 10 cm x 2 mm thick) was used as an inner plate glass as a glass substrate. As a target, a target was used in which 4.8 atomic% of Si was added to W and pressure-sintered at a temperature of around 1,500 ° C. in an inert gas atmosphere. Using this target, a sputtering pressure of 1.0 mTorr and Ar: O ₂ = 30: 1 was applied to the substrate by DC sputtering.
W ₉₅ with a film thickness of 500Å in a mixed gas atmosphere of 6
A transparent WSiO film made of Si ₅ O _x (X is not measured) was formed. Then, using a Zn metal target continuously without opening to the atmosphere, the pressure during sputtering = 4.0 mTorr, A
A ZnO transparent dielectric film having a film thickness of 700 Å was formed in a gas atmosphere mixed with a ratio of r: O ₂ = 20: 40. The substrate was not heated during the film formation.

A polyvinyl butyral sheet (0.76 mm) having an ultraviolet ray blocking property is formed between the inner glass sheet having the above-mentioned coating formed thereon and another 2 mm green glass sheet which is the outer glass sheet.
(Thickness), laminated, pre-compressed, and then heat-pressed by an autoclave to obtain the heat ray-shielding glass of the present invention (see FIG. 1b). The film resistance of the WSiO film is 10
It was MΩ / □ or more. The visible light transmittance of this heat-shielding glass with a film was 72%, and the solar light transmittance was 47.
%Met.

Comparative Example 1 Instead of the inner glass sheet in Example 1, W was used as the outer glass sheet.
A laminated glass of Comparative Example 1 was produced in the same manner as in Example 1 except that the SiO film and the ZnO film were formed (see FIG. 1c). The film resistance of the WSiO film, the visible light transmittance and the solar light transmittance of the laminated glass with a film were the same as in Example 1.

Evaluation Example 1 The influence of ultraviolet rays was examined on the laminated glass of Comparative Example 1 above. When the carbon arc lamp ultraviolet ray was irradiated for 100 hours from the outer glass side of the laminated glass with a film in accordance with JIS-R3212, in the case of the laminated glass of Comparative Example 1, the slightly absorbed coloring density by the WSiO film became high and the visible light The transmittance had dropped to 70.2%.
After 300 hours, the coloring density of the WSiO film was further increased and the visible light transmittance was 68%. After that, the evaluation was continued for 1,000 hours.
The darkening by iO progressed, and the visible light transmittance finally decreased to 67%. These changes with time are shown in FIG.

When the heat ray-shielding glass of Example 1 was similarly irradiated with ultraviolet rays from the outer glass side in the same manner as above, the visible light ray transmittance and the sunlight ray transmittance were obtained even after 30 days and 1,000 hours had elapsed. Showed almost no change, and the absolute value of the change was within 1%. The results of these tests are shown in FIG.

Example 2 In the same manner as in Example 1, a ZnO dielectric film was first formed on a green glass having a thickness of 2 mm, which was 450 Å, as an inner plate glass. Next, a WSiO film was continuously formed to a thickness of 500 Å.
A 50 Å ZrSi ₂ N _x transparent protective film was continuously formed thereon. The substrate was not heated during the film formation.

An inner glass sheet having the above-mentioned coating formed thereon and another 2 mm green glass sheet, which is an outer glass sheet, are laminated by sandwiching a polyvinyl butyral sheet (thickness: 0.76 mm), pre-pressed, and then heated by an autoclave. It was pressed under pressure to obtain the heat ray-shielding glass of the present invention (see FIG. 1d). The film resistance of the WSiO film was 10 MΩ / □ or more. The visible light transmittance of this film-coated heat ray-shielding glass was 72%, and the sunlight transmittance was 46%.

Comparative Example 2 In the same manner as in Example 1, a ZnO dielectric film was first formed on a green glass having a thickness of 2 mm having a thickness of 450 Å as an outer glass. Next, a WSiO film was continuously formed to a thickness of 500 Å.
A 50 Å ZrSi ₂ N _x transparent protective film was continuously formed thereon. The substrate was not heated during the film formation.

An outer glass sheet having the above coating formed thereon and another 2 mm green glass sheet, which is an inner glass sheet, are laminated by sandwiching a polyvinyl butyral sheet (thickness: 0.76 mm), pre-pressed, and then heated by an autoclave. It was pressure-bonded to obtain a laminated glass (see FIG. 1e). The above W
The film resistance of the SiO 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 46%.

Example 3 In the same manner as in Example 1, first, a ZnO dielectric film of 700 Å was formed on a green glass having a thickness of 2 mm as an inner plate glass. Next, a WSiO film was continuously formed to a thickness of 500 Å.
The substrate was not heated during the film formation. Another 2 mm that is the inner plate glass on which the above coating is formed and the outer plate glass
Was laminated with a polyvinyl butyral sheet (0.76 mm thick) sandwiched therebetween, pre-pressed, and then heat-pressed by an autoclave to obtain a heat ray-shielding glass of the present invention. At this time, a thin conductive wire (antenna) was provided between the outer plate glass and the intermediate resin film to provide a so-called enclosed glass antenna (see FIG. 1f). When the above-mentioned heat-shielding glass with an enclosed antenna was attached to an actual vehicle, the appearance was good, the sun's sunshine was well prevented, and the function of the enclosed antenna was not impaired at all.

Evaluation Example 2 With respect to the laminated glass of Example 2 and Comparative Example 2 described above, the influence of ultraviolet rays was examined in the same manner as in Evaluation Example 1. From the outer glass side of the above laminated glass with a film, JIS-R3212
When a carbon arc lamp ultraviolet ray was irradiated for 100 hours in accordance with the above, discoloration was not observed in the heat ray-shielding glass of Example 2 as in Example 1, but Comparative Example 2
As for Comparative Laminated Glass, as in Comparative Example 1, WSiO
The slightly absorbed color density of the film was increased, and the visible light transmittance finally fell below 70%.

The configurations and performances of the above-mentioned examples and comparative examples are summarized below.

[0029]

As described above, according to the present invention, a resin film which is substantially impermeable to ultraviolet rays is used as an intermediate resin film for laminated glass, and heat rays are blocked between the resin film and the inner plate glass. By providing the coating having the WSiO film layer, it is possible to provide a highly durable laminated glass which is excellent in heat ray shielding properties and radio wave transmission properties and is useful as a window glass for vehicles or a glass for building materials.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a cross section of a laminated glass of a conventional example, the present invention and a comparative example.

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

[Explanation of symbols]

 1: outer plate glass 2: inner plate glass 3: intermediate resin film 4: WSiO film 5: dielectric film 6: transparent protective film 7: antenna

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

Claims (5)

[Claims] 1. A laminated glass in which an outer glass sheet, an intermediate resin film and an inner glass sheet are sequentially laminated, and at least one tungsten silicon composite oxide film layer is included between the intermediate resin film and the inner glass sheet. A heat ray-shielding glass having a coating film. 2. The heat ray blocking glass according to claim 1, wherein the intermediate resin film is an ultraviolet blocking intermediate resin film. 3. The heat ray-shielding glass according to claim 1, wherein the intermediate resin film is a polyvinyl butyral resin film. 4. The structure of the coating film including the tungsten silicon composite oxide film layer is a structure of tungsten silicon composite oxide film / dielectric film or tungsten silicon composite oxide film / dielectric film / protective layer. Item 1. The heat ray-shielding glass according to Item 1. 5. The heat ray-shielding glass according to claim 4, wherein the dielectric material used for the film containing the tungsten-silicon composite oxide film layer is an oxide of Zn, Ti or Sn.