JPH02157141A - Heat ray shielding glass showing reflected gold color - Google Patents

Abstract

PURPOSE:To obtain heat shielding glass which is excellent in weather resistance and wear resistance and shows reflected gold color by successively coating a TiO2 layer having specified thickness and an SiC layer or a layer contg. SiC as a main component having specified thickness on the surface of transparent glass. CONSTITUTION:A first layer consisting of TiO2 having 10 - 30nm film thickness is formed on the surface of a transparent glass base body. Then a second layer is formed on the first layer which has composition shown in SiCxOy (0.85 <=x <= 1.1, 0 <= y <= 0.25) and 35 - 70nm, preferably 40 - 55nm, film thickness and consists of SiC or contains SiC as a main component. The first layer can be formed by utilizing Ti as a target and sputtering Ti in the evacuated gaseous oxygen atmosphere. Further the second layer can be formed by utilizing SiC as the target and sputtering SiC in the evacuated gaseous Ar atmosphere. Thereby the heat ray shielding glass is obtained which is excellent in durability and can be utilized as a single plate and is capable of thermal bending or strengthening work and shows reflected uniform gold color.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat ray shielding glass with a coating used mainly for window glass of buildings, which shields solar radiant energy. This is heat ray shielding glass with a golden color.

[Prior Art] Conventionally, heat ray shielding glasses having a golden reflective color include those in which a silicon carbide film of about 80 nm is coated on a glass substrate, as disclosed in Japanese Patent Publication No. 47-14820;
As disclosed in Japanese Unexamined Patent Publication No. 60-187671, it is known that a glass substrate is coated with a titanium oxide film, a titanium nitride film, and a titanium oxide film in this order. Further, according to JP-A No. 61-151045, a glass substrate is coated with a film made of oxidized stainless steel, an iron film, and a film made of oxidized stainless steel in this order, and is a heat ray shielding glass that has a golden color when viewed from the glass side. It is said that

[Problems to be Solved by the Present Invention] However, the conventional heat ray shielding glass described above has a so-called gold tone in which the color reflected from the glass surface side is close to the color of a gold film deposited in a vacuum. Moreover, it has the disadvantage that it does not have the durability of a coating that allows it to be used as a single panel for architectural window glass. In other words, the above-mentioned silicon carbide film coated on a glass substrate or titanium nitride film has the ability to be used as a veneer, but the developed color tone is always perceived as golden. I can't say it's that close to the color of gold.

On the other hand, the above-mentioned iron film sandwiched between metal oxide films,
The coating is not durable enough for use on veneers. The heat ray shielding glass according to the present invention solves the problems mentioned above, that is, the reflection color from the glass surface is golden,
Another object of the present invention is to provide a heat ray shielding glass that can be used as a single sheet as a window glass for architecture.

[Means for Solving the Problems] The heat ray shielding glass according to the present invention has titanium oxide coated as a first layer on one surface of a transparent glass substrate,
As a second layer on top of the first layer, 0.85≦x≦1.
1. A film having a composition represented by silicon carbide or SiCxOy mainly composed of silicon carbide with O≦y≦0.25 is coated as the second layer. The thickness of the first layer of titanium oxide is preferably within the range of 10 to 30 nm. If the film thickness is less than 10 nm, the color reflected from the glass surface changes from gold to silvery white, while if the film thickness is 30 nm or more, it becomes brownish, which is not preferable.

Moreover, the most preferable film thickness is 15 to 25 nm, which exhibits the most beautiful golden reflective color in combination with the second layer silicon carbide film.

The main component of the second layer having a heat ray shielding function of the heat ray shielding glass of the present invention is silicon carbide, that is, X is 0.
．． If the silicon becomes smaller than 85 and the amount of silicon released in the film increases, the durability of the film will deteriorate.On the other hand, if the amount of carbon released exceeds 1 for X months, the durability of the film will deteriorate.
Preferably, silicon and carbon are within the above-mentioned range including the stoichiometric composition of silicon carbide, and most preferably, the atomic ratio of silicon to carbon is 1. Also, SiCxO
In order for the second layer film represented by the atomic ratio of y to have a sufficient heat ray shielding function, y in the chemical formula, which is related to the content of oxygen in the film, is preferably 0.25 or less. . As y becomes larger than 0.25, the film contains a large amount of SiO□ component which does not have a heat ray shielding function, which is not preferable. Most preferably, the amount of oxygen in the film is reduced to the level of impurity concentrations or is completely absent. The film thickness of the silicon carbide or the second layer mainly composed of silicon carbide is 3.
The range is preferably 5 nm to 70 nm, and most preferably 40 to 55 nm from the viewpoint of obtaining a golden color tone.

If the film thickness is less than 35 nm, the heat ray shielding performance will decrease,
If the thickness exceeds 70 nm, the reflective color tone will deviate from the golden color, so it is not preferable to exceed the above-mentioned thickness range.

The first layer of titanium oxide film and the second layer of SiCxOy (0,85≦x≦
A film having a composition (1.1.0≦y≦0.25) can be coated by physical means such as sputtering. For example, a film of titanium oxide is formed by direct current sputtering in an atmosphere of a mixed gas of argon and oxygen under reduced pressure or pure oxygen gas using titanium as a target, and a film with the composition of SiCxOy is formed using argon under reduced pressure using silicon carbide as a target. The coating can be performed by direct current sputtering in an atmosphere consisting of gas. 2nd layer SiCxO
As mentioned above, it is preferable that the amount of oxygen in the film is small, and this can be achieved by lowering the pressure in the vacuum device before coating to a predetermined pressure or less. This pressure is difficult to determine unambiguously, depending on the volume of the vacuum chamber of the sputtering equipment, the size of the glass substrate to be coated with the film, and the stoppage time of the sputtering equipment between one coating and the next coating. , usually achieved by using 1.2 x 1O-2Pa or less.

Further, the thermally bent or strengthened heat shielding glass according to the present invention has a first layer made of titanium oxide, which does not undergo thermal deterioration, and silicon carbide or silicon carbide, which has oxidation resistance. Since the second layer is a film containing as the main component, the film can be subjected to commonly used thermal bending and reinforcing processes after being coated.

[Function] The laminate consisting of the titanium oxide film coated as the first layer of the thermal VA shielding glass according to the present invention and the silicon carbide or a film mainly composed of silicon carbide coated as the second layer is light-resistant. Due to the interference effect, the reflected color of the glass surface of the transparent glass substrate becomes golden. Further, the titanium oxide film provided between the second layer of silicon carbide or a film mainly composed of silicon carbide having a heat ray shielding function and the glass substrate is a titanium oxide film provided between the silicon carbide or the film mainly composed of silicon carbide and the glass substrate. This, together with silicon carbide's inherent oxidation resistance at high temperatures, reduces the decline in the heat ray shielding function of the film during high-temperature heat treatment.

[Example] Figures 1(a) and 1(bl) show partial cross-sectional views of the heat ray shielding glass according to the present invention. 1 is a glass substrate, 2 is a titanium oxide film, and 3 is silicon carbide or silicon carbide as the main component. (b) is a film coated on a flat glass substrate;
An example of the present invention which was then subjected to bending processing is shown.

The present invention will be explained below using examples.

Figure 2 shows the sputtering equipment used to implement the present invention.
The air in the vacuum chamber 21 is exhausted by the vacuum pump 24 through the main valve 22 and the orifice valve 23 . A method was used in which a cleaned float glass 35 with a thickness of 6 fl was placed on a glass holder 34 and coated with a film while being passed in front of the target by a conveyor 33. Targets 27 and 28 set on the surfaces of cathode 25 and cathode 26 are made of titanium and silicon carbide, respectively, and the pressure inside vacuum chamber 21 is set to 6.7 x 10-'
The pressure was reduced to below Pa. From the gas supply pipe 31, the valve 32
is opened and 100cc of oxygen gas is introduced into the vacuum chamber 21.
The orifice valve 23 was adjusted to 0.27 Pa. 45 from DC power supply 29 to titanium target 27
Apply a voltage of 0V and remove the float glass 35 from one end.
Pass the iJ1 in front of the target 27 at a speed of 420 mm1n-' and transfer it to the other end and attach the float glass 3.
5 was coated with a titanium oxide film having a thickness of 20 nm, and the application of voltage and the introduction of gas were stopped. Next, the vacuum chamber 21
After reducing the internal pressure to 6.7
00cc is introduced into the vacuum chamber 21, and the orifice valve 2
3 was adjusted to 0.27 Pa. Applying a voltage of 585 V from the DC power supply 30 to the silicon carbide target 28,
The float glass 35 was moved in front of the cuget 28 from the other end to the other end at a speed of 330 im m1n-' to cover the silicon carbide film with a thickness of 50 nm. Stop applying voltage and introducing gas,
The main valve 22 was closed, the inside of the vacuum chamber 21 was brought to atmospheric pressure, and the two-layer heat ray shielding glass was taken out. The optical properties of this heat ray shielding glass were determined at 630°C and 110°C in the atmosphere, which corresponds to the heating conditions for bending and thermal strengthening.
Table 1 shows the measurements taken on the samples before and after the minute heat treatment.

In addition, in order to examine the wear resistance of these samples, we used a Taper wear tester with grinding wheel C5-10F and a load of 5.
As a result of a test at 300 rotations under the condition of 00g, the change in visible light transmittance was less than 1%, and almost no change was observed with the naked eye.

[Comparative Example Next, a conventional example using titanium nitride will be explained.

The cleaned float glass 35 with a thickness of 3 irises is placed on the glass holder 34 of the sputtering device in which the targets 27 and 28 in FIG.
3, a method was used in which the film was coated while passing through the front surface of the Couget. The pressure inside the vacuum chamber 21 is 6.7 x 1
The pressure was reduced to 0-'Pa or less.

From the gas supply pipe 31, open the valve 32 and supply nitrogen gas 50
100 cc of a mixed gas consisting of 50% argon gas was introduced into the vacuum chamber 21, and the pressure was adjusted to 0.27 Pa by adjusting the orifice valve 23. A voltage of 580 V was applied from the DC power supply 29 to the titanium target 27, and the titanium target 27 started to scatter. The float glass 35 is passed in front of the target at a speed of 760 mm m1n-' from one end and transferred to the other end, a titanium nitride film with a thickness of 30 nm is coated on the float glass 35, and a voltage is applied and Gas introduction was stopped. Next, after exhausting the pressure inside the vacuum chamber 21 to 6.7 x 10-'Pa or less, open the valve 32 from the gas supply pipe 31 to supply 100% oxygen gas.
cc was introduced into the vacuum chamber 21, and the orifice valve 23 was adjusted to 0.27 Pa. Applying a voltage of 450V from the direct type a30 to the titanium target sensor 1-28,
The float glass 35 coated with the titanium nitride film was moved in front of the target 28 in the opposite direction from the other end at a speed of 170 mm m1n-' until the film thickness was 50 nm.
m titanium oxide was coated, and voltage application and gas introduction were stopped. The main valve 22 was closed to bring the inside of the vacuum chamber 21 to atmospheric pressure, and the two-layer heat ray shielding glass was taken out. The optical properties of this heat ray shielding glass were evaluated at 63°C in the atmosphere, which corresponds to the heating conditions for bending and thermal strengthening.
Table 1 shows the measurements taken on the samples before and after heat treatment at 0°C for 110 minutes.

■ From the above, b9 of the embodiment of the heat ray shielding glass of the present invention
It can be seen that the value of is close to that of the gold vapor deposited film, and the film exhibits a more gold tone. It can also be seen that heat treatment also has the characteristic that the increase in solar transmittance is smaller.

[Effects of the Invention] Since the heat ray shielding glass of the present invention has a golden reflective color tone on the glass surface side, by applying the glass surface side to the outdoor side as a window glass of a building, it looks golden from the outside,
It can give a luxurious atmosphere to buildings. In addition, the thermally bent heat ray shielding glass of the present invention enables various designs for the exterior of buildings, and the gold-colored film is coated on a flat glass substrate before bending. Therefore, there is little unevenness in color tone. Further, according to the present invention, since the film has weather resistance and abrasion resistance, it can be used as a single sheet without requiring double glazing.

[Brief explanation of the drawing]

FIG. 1(b) is a partial cross-sectional view of the heat ray shielding glass of the present invention, and FIG. 1...Glass substrate, 2...Titanium oxide film, 3.
・Silicon carbide or a film containing silicon carbide as a main component, 21...
・Vacuum layer, 22... Main valve, 23... Orifice valve, 25.26... Cathode, 27.28.
・Target, 29.30...DC power supply, 31...
Gas supply pipe, 32... Valve, 33... Conveyor container, 34... Glass boulder, 35... Float glass. Patent applicant Nippon Sheet Glass Co., Ltd.

Claims (1)

[Claims] 1) On one surface of a transparent glass substrate, a film with a thickness of 10 to 3
A first layer of titanium oxide with a thickness of 0 nm, and a SiC layer with a thickness of 0.85≦x≦1.1 and 0≦y≦0.25 on the first layer.
Heat ray shielding glass coated with silicon carbide or a second layer mainly composed of silicon carbide having a composition represented by _xO_y and having a film thickness of 35 to 70 nm. 2) The heat ray shielding glass according to claim 1, wherein the silicon carbide or the second layer containing silicon carbide as a main component has a thickness of 40 to 55 nm. 3) Before thermal bending or strengthening is performed on one surface of the transparent glass substrate, the first layer of titanium oxide and the silicon carbide or second layer mainly composed of silicon carbide are formed. The heat ray shielding glass according to claim 1 or 2, characterized in that the heat ray shielding glass is coated with.