JP2574018B2 - Heat ray shielding glass with a reflective color of gold - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a coated heat ray shielding glass mainly used for a window glass of a building, which shields solar radiation energy, and in particular, a reflection from a glass surface side. It is a heat ray shielding glass having a golden color.

[Prior art] Conventionally, a heat ray shielding glass having a gold-based reflection color is:
As disclosed in Japanese Patent Publication No. 47-14820, a glass substrate coated with a silicon carbide film of about 80 nm,
As disclosed in US Pat. No. 1,876,71, a glass substrate is known in which a titanium oxide film, a titanium nitride film, and a titanium oxide film are coated in this order. Further Japanese Patent
According to 61-151045, a film obtained by oxidizing stainless steel, an iron film,
A film obtained by coating a glass substrate with a film obtained by oxidizing stainless steel in this order is considered to be a heat ray shielding glass which has a golden color when viewed from the glass side.

[Problems to be solved by the present invention] However, the conventional heat ray shielding glass described above is
The reflection color from the glass surface side is close to the color of the gold film deposited in vacuum, so-called gold color tone, and with the durability of the coating that can be used as a single panel as architectural window glass There is a disadvantage that there is no. That is, the above-described silicon carbide film coated on a glass substrate or a film using a titanium nitride film has the durability that can be used as a single plate, but the anti-color tone is not necessarily enough to be recognized as gold. It cannot be said that it is close to the color of gold. On the other hand, when the iron film is sandwiched between metal oxide films, the durability of the film is insufficient for use as a single plate. The heat ray shielding glass according to the present invention solves the above-mentioned problems, that is, the reflection color from the glass surface exhibits a gold color, and as a building window glass, to provide a heat ray shielding glass usable as a single plate. is there.

[Means for Solving the Problems] In a heat ray shielding glass according to the present invention, one surface of a transparent glass substrate is coated with titanium oxide as a first layer, and 0.85 is formed as a second layer on the first layer. ≦ x ≦ 1.1,
0 ≦ y ≦ 0.25 of silicon carbide or silicon carbide as a main component
A film having a composition represented by SiCxOy is coated as a second layer. The thickness of the first layer of titanium oxide is preferably in the range of 10 to 30 nm. If the film thickness is smaller than 10 nm, the reflection color from the glass surface changes from gold to silver white, while if the film thickness is 30 nm or more, it becomes undesirably brownish. Further, as the film thickness exhibiting the most beautiful gold reflected color from the combination with the second layer silicon carbide film, 15 to 25 nm is most preferable.

The second layer having a heat ray shielding function of the heat ray shielding glass of the present invention, silicon carbide or a film containing silicon carbide as a main component,
Preferably, the atomic ratio x of carbon to silicon is in the range of 0.85 ≦ x ≦ 1.1. That is, when x becomes smaller than 0.85 and the amount of silicon released in the film increases, the durability of the film deteriorates.On the other hand, when x exceeds 1.1 and the amount of carbon released increases, the durability of the film deteriorates. Silicon and carbon are preferably in the above-mentioned range including the stoichiometric composition of silicon carbide, and most preferably the atomic ratio of silicon to carbon is 1. In addition, in order for the film of the second layer represented by the atomic ratio of SiCxOy to have a sufficient heat ray shielding function, y in the above chemical formula related to the oxygen content in the film is
It is preferably 0.25 or less. As y becomes larger than 0.25, the film contains a large amount of SiO ₂ component having no heat ray shielding function, which is not preferable. Most preferably, the oxygen in the film is low or no up to the impurity concentration level. The thickness of the silicon carbide or the second layer containing silicon carbide as a main component is preferably 35 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 smaller than 35 nm, the heat ray shielding performance decreases,
If it is larger than 70 nm, it will deviate from the golden reflection color,
It is not preferable to exceed the above-mentioned thickness range.

In the heat ray shielding glass according to the present invention, the first layer of titanium oxide film and the second layer of SiCxOy (0.85 ≦ x ≦ 1.1,0 ≦
The film having the composition of y ≦ 0.25) can be coated by physical means such as a sputtering method. For example, a film of titanium oxide is formed by a direct current sputtering in an atmosphere of a mixed gas of argon and oxygen or a pure oxygen gas decompressed with titanium as a target, and the film having the composition of SiCxOy is formed of argon decompressed with silicon carbide as a target. It can be coated by DC sputtering in an atmosphere composed of gas. It is preferable that the amount of oxygen in the second-layer SiCxOy film is small as described above, and this is achieved by reducing the pressure in the vacuum apparatus before coating to a predetermined pressure or less. This pressure is difficult to determine uniquely depending on the volume in the vacuum chamber of the sputtering apparatus, the size of the glass substrate on which the film is to be coated, and the stop time of the sputtering apparatus between one coating and the next coating. Usually, it is achieved by using 1.2 × 10 ⁻² Pa or less.

Further, the thermally bent or strengthened heat ray shielding glass according to the present invention is characterized in that a film made of titanium oxide having a property of not being thermally deteriorated is used as a first layer, and silicon carbide or silicon carbide having oxidation resistance is used. Is used as the second layer, so that after the film is covered, a commonly used thermal bending process or a strengthening process can be performed.

[Operation] A laminate comprising a titanium oxide film coated as a first layer of the heat ray shielding glass according to the present invention and silicon carbide or a film containing silicon carbide as a main component, coated as a second layer, Due to the interference effect, the reflection color tone of the glass surface of the transparent glass substrate is made golden. Further, the titanium oxide film provided between the glass substrate and silicon carbide or a film containing silicon carbide as a main component and having a heat ray shielding function of the second layer may be formed of a film containing the silicon carbide or silicon carbide as a main component and a glass substrate. With the oxidation resistance at high temperatures inherent to silicon carbide, and reduces the deterioration of the coating's heat ray shielding function with respect to high-temperature heat treatment.

Example FIGS. 1 (a) and 1 (b) are partial cross-sectional views of a heat ray shielding glass according to the present invention. 1 is a glass substrate, 2 is a titanium oxide film, 3 is a film containing silicon carbide or silicon carbide as a main component, (b) is a film coated on a flat glass substrate,
An embodiment of the present invention after bending is shown.

 Hereinafter, the present invention will be described with reference to examples.

FIG. 2 shows a sputtering apparatus used in the embodiment of the present invention. Air in a vacuum chamber 21 is exhausted by a vacuum exhaust pump 24 through a main valve 22 and an orifice valve 23. A method of placing a washed float glass 35 having a thickness of 6 mm on a glass holder 34 and coating the film while passing the front surface of a target by a conveyor 33 was used. Target 2 to be set on the surface of cathode 25 and cathode 26
Vacuum tank with 7,28 as titanium and silicon carbide respectively
The pressure in 21 was reduced to 6.7 × 10 ⁻⁴ Pa or less. Gas supply pipe 3
From 1, the valve 32 was opened, 100 cc of oxygen gas was introduced into the vacuum chamber 21, and the orifice valve 23 was adjusted to 0.27 Pa. A voltage of 450 V is applied to the titanium target 27 from the DC power supply 29, and the float glass 35 is moved 420 mm from one end.
The glass was passed in front of the target 27 at a speed of n− ¹ , moved to the other end, and coated with a 20 nm-thick titanium oxide film on the float glass 35, and the application of voltage and the introduction of gas were stopped. Next, after reducing the pressure in the vacuum chamber 21 to 6.7 × 10 ⁻⁴ Pa or less, the valve 32 was opened from the gas supply pipe 31, 100 cc of argon gas was introduced into the vacuum chamber 21, and the orifice valve 23 was adjusted. It was adjusted to 0.27 Pa. A voltage of 585 V is applied from the DC power supply 30 to the silicon carbide target 28, and the float glass 35 is moved in front of the target 28 at a speed of 330 mm min ^-1 from the other end to the other end in the opposite direction, to a thickness of 50 nm. A silicon carbide film having a thickness of The application of the voltage and the introduction of the gas were stopped, the main valve 22 was closed, the inside of the vacuum chamber 21 was set to the atmospheric pressure, and the heat ray shielding glass composed of two layers was taken out. The optical properties of this heat-shielding glass are adjusted to 630 in air, which corresponds to the heating conditions for bending and thermal strengthening.
Table 1 shows the measured values of the sample before and after the heat treatment at 10 ° C. for 10 minutes.

To determine the wear resistance of these samples,
As a result of performing a test of 300 revolutions using a Taber abrasion tester under the conditions of a grindstone CS-10F and a load of 500 g, the change in visible light transmittance was 1% or less, and almost no change was observed with the naked eye.

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

A method of coating a washed float glass 35 having a thickness of 3 mm on a glass holder 34 of a sputtering apparatus using titanium as targets 27 and 28 in FIG. 2 and passing the front surface of the target by a transport conveyor 33 is described. Using. The pressure in the vacuum chamber 21 was reduced to 6.7 × 10 ⁻⁴ Pa or less. From the gas supply pipe 31, open the valve 32 and set nitrogen gas 50%
100 cc of mixed gas consisting of 50% argon gas
And orifice valve 23 was adjusted to 0.27 Pa. 580V from DC power supply 29 to titanium target 27
, And sputtering of the titanium target 27 was started. Float glass 35 from one end 760mm min
^After passing the target in front of the target at a speed of ^-1 , it was moved to the other end, a titanium nitride film having a thickness of 30 nm was coated on the float glass 35, and the application of the voltage and the introduction of the gas were stopped. Next, the pressure in the vacuum chamber 21 is evacuated to 6.7 × 10 ⁻⁴ Pa or less, and the valve 32 is opened from the gas supply pipe 31 to open the oxygen gas.
100 cc was introduced into the vacuum chamber 21 and the orifice valve 23 was adjusted to 0.27 Pa. A voltage of 450 V is applied from the DC power supply 30 to the titanium target 28, and the float glass 35 coated with the titanium nitride film is turned in the opposite direction from the other end.
The target was moved in front of the target at a speed of 170 mm min ^-1 to coat titanium oxide having a film pressure of 50 nm, and the application of the voltage and the introduction of the gas were stopped. The main valve 22 was closed to bring the inside of the vacuum chamber 21 to atmospheric pressure, and the heat ray shielding glass composed of two layers was taken out. Table 1 shows the optical characteristics of the heat ray shielding glass measured for samples before and after performing heat treatment at 630 ° C. for 10 minutes in the atmosphere, which correspond to the heating conditions of bending and thermal strengthening. .

As described above, b 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 deposited gold film and exhibits a more gold color tone. Also, it can be seen that the heat treatment also has a feature that the rise in the solar radiation transmittance is small.

[Effect of the Invention] Since the heat ray shielding glass of the present invention has a golden reflection color tone on the glass surface side, the glass surface side is applied to the outside of the building as a window glass of a building, so that it looks golden from the outside, A luxurious atmosphere can be given to the building. In addition, the heat ray shielding glass that is bent by heat of the present invention enables various designs for the appearance of a building, and
Since the coating of the gold-colored film is coated on the flat glass substrate before bending, unevenness in color tone is small. Furthermore, according to the present invention, since the film has weather resistance and wear resistance,
It can be used as a single plate without making it a double glazing.

[Brief description of the drawings]

1 (a) and 1 (b) are partial cross-sectional views of the heat ray shielding glass of the present invention, and FIG. 2 is a schematic cross-sectional view of a sputtering apparatus used for carrying out the present invention. DESCRIPTION OF SYMBOLS 1 ... Glass base, 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, 2
5,26 Cathode, 27,28 Target, 29,30 DC power supply, 31 Gas supply tube, 32 Valve, 33 Conveyor, 34 Glass holder, 35 Float Glass.

Claims (3)

(57) [Claims] 1. A film having a thickness on one surface of a transparent glass substrate.
A first layer of titanium oxide of 10 to 30 nm, and silicon carbide having a composition represented by SiCxOy of 0.85 ≦ x ≦ 1.1 and 0 ≦ y ≦ 0.25 on the first layer, the thickness of which is 35 to 70 nm; A heat ray shielding glass coated with a second layer mainly composed of silicon carbide. 2. The heat ray shielding glass according to claim 1, wherein said silicon carbide or said second layer containing silicon carbide as a main component has a thickness of 40 to 55 nm. 3. A first layer of the titanium oxide and a first layer mainly containing the silicon carbide or silicon carbide before one surface of the transparent glass substrate is subjected to thermal bending or strengthening. The heat ray shielding glass according to claim 1 or 2, wherein the glass is coated with two layers.