JPS63112441A - Transfarent heat reflecting plate - Google Patents

Abstract

PURPOSE:To obtain the titled reflecting plate having a desired reflection color and useful as a window glass for vehicle, etc., by successively applying, as necessary transparent high-refractive inner layer, a transparent metal layer and a transparent high-refractive outer layer to a transparent substrate. CONSTITUTION:A pair of magnetron cathodes 5, 6 are placed on the bottom of a vacuum tank 1 evacuated through an exhaustion port 3 and are insulated from the bottom with an insulator 4. A Ti target 13 and a Sn target 14 are individually attached to the upper face of each cathode. A transparent substrate 16 such as glass plate is held with a holder 15 placed on a reciprocative transfer belt 12 placed above the cathodes 5, 6. Ar/O2 is introduced into the tank 1 through a gas inlet 11, negative potential is imposed to the cathode 6 to start sputtering and the substrate 16 is passed above the cathode 6 by moving the belt 12 to form a transparent, highly refractive inner layer (SnO2 layer) 17 having a prescribed thickness. Ar gas is introduced through a gas inlet 10, a negative potential is imposed to the cathode 5 and a transparent metal layer 18 composed mainly of Ti and having a prescribed thickness is applied to the layer 17. Finally, a transparent, highly refractive outer layer 19 is formed on the transparent metal layer 18 by the operation similar to the first step.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention prevents solar radiant heat from penetrating indoors by using it for transparent heat ray reflecting plates, especially window glasses for buildings and window glasses for vehicles such as automobiles. Regarding transparent heat-reflecting glass that prevents heat rays.

[Conventional technology]

Conventionally, heat-reflecting glass with a gold-like reflective color has been used, which is made by adhering a transparent thin film of TiN to a glass plate.

[Problem that the invention seeks to solve]

However, since the reflected color of heat-reflecting glass with a transparent thin film of TiN changes depending on the conditions for forming the TiN film, it is necessary to continuously form a thin TiN film with the same reflected light on a large glass plate by sputtering, for example. It was difficult.

[Means for solving problems]

The present invention has been made to overcome the above-mentioned difficulties, and the present invention provides a transparent substrate and a Ti film formed on the transparent substrate.
This is a transparent heat ray reflecting plate consisting of a transparent metal layer mainly composed of a transparent metal layer and an outer transparent high refractive index layer made of a metal oxide or metal sulfide formed on the transparent metal layer.

In the present invention, an inner transparent high refractive index layer made of metal oxide or metal sulfide can be interposed between the transparent substrate and the transparent metal layer.

In the present invention, the outer transparent high refractive index layer and the inner transparent high refractive index layer usually include TiO2r Ta205 + ZrO.
Metal oxides such as 2rS nO21Z nO+ or B120, or metal sulfides such as ZnS can be used, but from the viewpoint of weather resistance and chemical resistance, TiO2+Ta2
05 or 5n02, etc., and the film thickness is usually r
onm to 1100n. These transparent high refractive index layers can be formed by vacuum evaporation, sputtering, dipping, or the like.

Further, in the present invention, the metal layer containing Tl as a main component preferably has a film thickness of 1 nm to 50 nm, and can be formed by a vacuum evaporation method, a sputtering method, a dipping method, a plating method, or the like.

[For production]

In the present invention, a metal oxide is deposited on a transparent metal mainly composed of Ti.
Alternatively, since a transparent high refractive index layer is formed on the inner surface made of metal sulfide, by changing the thickness of the high refractive index layer, it is possible to control the suppression of the blue component of the reflected light from the transparent metal layer. A bronze reflective color can be stably obtained.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a schematic diagram of a sputtering apparatus for carrying out the method of the present invention.
An exhaust port (3) with a barrier pull valve (2) is formed in a part of the fl, and is connected to a vacuum pump (not shown) through this exhaust port (3) to reduce the pressure inside the vacuum chamber (1). That's what I do. In addition, there is an electrical insulator (
41, (magnetron cathode f5 through 41) l
A pair of magnetron cathodes (5) (61 and DC power supplies (7), (7) are provided at a distance from each other).
Switch this (8).

(8). In addition, near each magnetron cathode (5), (6), there are gas supply pipes (10), (11) that penetrate the bottom of the vacuum chamber (1) and are equipped with a bar (9). is placed in front of the vacuum chamber (1), and gas is supplied into the vacuum chamber (1).

Furthermore, a reciprocating conveyor belt (12) is arranged above each cathode (5), (6) in the vacuum chamber (1).

A method of forming a heat ray reflective film using the sputtering apparatus configured as above will be described below.

Example 1 First, Ti was applied to the upper surface of the cathode (5) (1
3), attach Sn to the top surface of the cathode (6) as a target layer (14), and attach it as a holder (15).
The glass plate (16) is held on the holder (15), and this holder (15) is placed on the conveyor belt (12).

After cleaning, the barrier pull valve (2) is opened to reduce the pressure in the vacuum tank α to 10-3 Pa, and a mixed gas of argon gas and oxygen gas is supplied from the gas supply pipe (11).

The mixing ratio is 20% by volume of argon gas and 1 vol. of oxygen gas.
rO volume volume port and vacuum chamber (1) after gas introduction is 0
．． Make sure that ≠pa. Then, the switch (8) is turned on, a negative voltage of ti50V is applied to the cathode (6), sputtering is performed for 70 minutes, and then the conveyor belt (1
2), the glass plate (16) held in the holder (15) is moved over the cathode (6) at a speed of lIQ Qmm 1 minute, as shown in Fig. 2.
An inner high refractive index layer (17) having a predetermined thickness (Jjnm) is formed on the surface of the glass plate (16), specifically, a first layer made of 5n02.

Then, after turning off the switch (8) and closing the valve (9), the barrier pull valve (2) is opened again to reduce the pressure in the vacuum chamber (1) to 10-3 Pa.

After this, the pulp (9) of the gas supply pipe (10) is opened, argon gas is introduced into the vacuum chamber (1) at 11008 CC, and the barrier pull valve (2) is adjusted to bring the vacuum m (1) to o, p Pa and switch (8) on cathode (5).
) is turned on, a negative voltage of tIrov is applied to the cathode (5), and DC sputtering is performed for about 10 minutes. After this, by running the conveyor bell (12), the holder (15)
) by moving the glass plate (16) held on the cathode (5) at a speed of ≠QQmm7 minutes, the surface of the high refractive index layer (17) is coated with a predetermined thickness (2 l
1 nm), specifically a second layer made of Ti.

Thereafter, by performing DC sputtering under the same conditions as for forming the high refractive index layer (17), that is, using Sn as a target and in a mixed gas atmosphere of oxygen and argon, a metal layer is formed as shown in FIG. Thickness Jj on the surface of (Y8)
An outer high refractive index layer (19) made of 5n02 of about nm is formed as a third layer.

Example λ In Example 1, a film was made in the same manner as in Example 1, except that the substrate movement speed during film formation of the outer high refractive index layer (19) was changed to 200 h/min, so that the film thickness was 70 nm. Create transparent heat-reflecting glass.

Example 3 As in Example 1, using the sputtering apparatus shown in FIG. 1, a Ti target (13
), and also attach the glass plate (15) to the holder (15).
6) and this holder (15) with the conveyor bell) (
12) Place it on top.

After cleaning, the pressure inside the vacuum tank α) is reduced to 70-3 Pa using the barrier pull valve (2) as a gate, and a mixed gas of argon gas and oxygen gas is supplied from the gas supply pipe (10).

The mixing ratio is IO volume % for argon gas and 9% for free element gas.
0% by volume, and the vacuum chamber (1) after gas introduction is o.
, <t pa. And the switch (
8) and turn on the cathode (5)! After applying a negative voltage of 0■ and performing sputtering for 70 minutes, the transfer bell)
By running the glass plate (12), the glass plate (16) held in the holder (15) is moved over the cathode (5) at a speed of /20Tnln1 minute, as shown in Figure 2. 16) with a predetermined thickness (JOnm) on the surface.
), specifically, a first layer made of TlO2 is formed.

Then, after turning off the switch (8) and closing the valve (9), ゛ 2. Open the barrier pull valve (2) again and open the inside of the vacuum chamber (1).
Reduce the pressure to 0-3 Pa.

After that, open the valve (9) of the gas supply pipe (10), introduce 11005 CC of argon gas into the vacuum chamber (1), adjust the barrier pull valve (2), and turn the vacuum chamber (11) into the vacuum chamber (1).
Maintaining 0≠Pa, turn on the switch (8) of the cathode (5) and apply a negative voltage of 115 ov to the cathode (5).
DC shuttering is performed for about 70 minutes. After that, by running the conveyor bell (12), the glass plate (16) held in the holder (15) is moved over the cathode (5) at a speed of 1100 mtn/min, as shown in Fig. 2. A predetermined thickness (20 nm) is applied to the surface of the high refractive index layer (17).
), specifically a second layer made of Ti.

Thereafter, by performing DC sputtering under the same conditions as those used to form the high refractive index layer (Near), using Ti as a target and in an oxygen and argon mixed gas atmosphere, the noble metal layer (Near) was formed as shown in FIG. 18) is coated with an outer high refractive index layer (19) made of TiO2 with a thickness of approximately 3 onm.
) is formed as the third layer.

The example was the same as in Example 3, except that the substrate movement speed during film formation of the outer surface high refractive index #(19) was changed to 60 mm/min, and the film thickness was set to Onm. A transparent heat-reflecting glass is created by the method.

EXAMPLE In Example 3, a transparent heat-reflecting glass was prepared in exactly the same manner as in Example 3, except that the first inner high refractive index layer (17) was omitted.

The results of observing the reflected color of the transparent heat-reflecting glass obtained in each example from the glass plate side and the film side, and the wavelength s50
Table 1 shows the results of measuring the transmittance of nm light.

Table l also shows the transparent heat-reflecting glass obtained in Example 1 (solid line)
Figure 3 shows a comparison of the spectral reflectance of the glass with a heat-reflecting glass using a titanium nitride film (dashed line).

In the above examples, the coating was applied to the glass plate by sputtering, but the coating in the present invention is not limited to sputtering, and can be applied to metal oxides by vacuum evaporation or thermal decomposition. It can also be achieved by a dipping method in which the coating is coated by dipping into a solution of a metal compound that can be used as a metal compound, and then thermally decomposed to form a film.

〔Effect of the invention〕

As is clear from Table 1 and FIG. 3, the present invention changes the thickness of the 5N02 film as the outer layer of the Ti film, so that the summer radiation seen from the film surface changes from gold to a heat ray with a bronze-colored reflection color. Reflective glass can be obtained, and by selecting the thickness of the 5n02 film of the outer surface layer, a desired reflective color can be stably obtained.

[Brief explanation of the drawing]

The drawings show embodiments of the present invention, and FIG. 1 is a schematic diagram of a sputtering apparatus, FIG. 2 is an enlarged sectional view of a heat-ray reflective glass according to the present invention, and FIG. 3 is a spectral diagram of a transparent heat-ray reflective glass. It is a figure showing reflectance. In the drawings, (1) is a vacuum chamber, (5t), (6) is a magtron cathode, (10), (11) is a gas supply pipe, and (12) is a conveyor (18) is a metal layer. Figure 1 Figure 2

Claims (3)

[Claims] (1) A transparent substrate, a transparent metal layer mainly composed of Ti formed on the transparent substrate, and a transparent outer surface with a high refractive index consisting of a metal oxide or metal sulfide formed on the transparent metal layer. A transparent heat ray reflecting plate consisting of layers. (2) The transparent heat ray reflecting plate according to claim 1, wherein an inner transparent high refractive index layer made of metal oxide or metal sulfide is interposed between the transparent substrate and the transparent metal layer. (3) The transparent heat ray reflecting plate according to claim 1 or 2, wherein the transparent metal layer has a thickness of 5 nm to 50 nm.