JPH0848545A - Low reflectivity heat ray reflection glass - Google Patents

Abstract

PURPOSE:To produce the reflection glass which enables suppression of the reflectivity of visible light from the outside of the room without adversely affecting the solar radiation shielding performance and coloration in various color tones by successively laminating a transparent metal oxide film, a metallic film or metal nitride film, another transparent metal oxide film and another metal nitride film on a glass substrate in that order and specifying the visible light reflectivity and visible light transmissivity. CONSTITUTION:A transparent metal oxide film 11 as the first layer, a metallic film or metal nitride film 12 as the second layer, another transparent metal oxide film 13 as the third layer and another metal nitride film 14 as the fourth layer are successively laminated on a glass substrate 10 by the sputtering method to form the objective reflection glass. In this reflection glass, the reflectivity of visible light from the side of the glass substrate 10 is <=10% and also the visible light transmissivity is <=40%. Thus, the reflection glass which has reflectivity of light from the outside of the room equivalent to that of the conventional transparent plate glass and causes no adverse effect due to glare, etc., on the surroundings and is colored in various reflected color tones and also has <=40% visible light transmissivity can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to heat-reflecting glass for construction.

[0002]

2. Description of the Related Art In recent years, openings in buildings have tended to expand due to their design and comfort. Along with that, the amount of sunlight entering increases and the indoor cooling load increases, and the importance of the design of windows that occupy a large area in the exterior of the building increases, so heat reflection The number of cases using glass is increasing rapidly. The heat-reflecting glass used for this purpose is usually called solar control glass. Such a solar control glass has a unique aesthetic appearance due to its half mirror effect, and is widely used as a wall material for buildings.

When such heat-reflecting glass is used as a wall surface or a window of a building, its mirror effect adversely affects the surrounding environment and may be a subject of complaints from the surrounding residents. As a specific example, the reflectance in the visible light region is also increased in order to enhance the mirror effect, and as a result, the sunlight reflected on the heat ray reflective glass is dazzling and hinders the operation of the vehicle. Therefore, there is a possibility that the heat-reflecting glass cannot be used depending on the construction site of the building.

In order to solve such a problem, as a method of lowering the reflectance of the heat ray reflective glass in the visible light region, a means of reducing the thickness of the whole heat ray reflective film can be considered. However, as a result, the visible light transmittance also increases, and the solar energy transmittance also increases due to the effect, which often reduces the solar radiation shielding effect required for the solar control glass. Among the heat ray-reflecting glasses currently used, some have a visible light transmittance of about 30% and a visible light reflectance of about 10%, which is relatively low from the glass surface, but the color tone is limited. There is.

[0005]

The object of the present invention is to solve the above-mentioned drawbacks of the prior art and suppress the visible light reflectance on the outdoor side (glass substrate side) without deteriorating the solar radiation shielding performance. ,
Further, it is to provide a heat ray reflective glass capable of exhibiting various color tones in order to maintain its designability.

[0006]

The present invention has been made to solve the above-mentioned problems, and a transparent metal oxide film as a first layer and a metal film or a metal nitride as a second layer on a glass substrate. A film, a transparent metal oxide film as the third layer, and a metal nitride film as the fourth layer, which are sequentially laminated by a sputtering method, and the visible light reflectance from the glass substrate side is 10% or less, and Visible light transmittance is 40
% Or less, the low reflection heat ray reflective glass is provided.

FIG. 1 is a cross-sectional view of an essential part of a low reflection heat ray reflective glass according to the present invention, 10 is a glass substrate, 11 is a transparent metal oxide film as a first layer, 12 is a metal film as a second layer, or A metal nitride film, 13 is a metal oxide film as the third layer, and 14 is a metal nitride film as the fourth layer.

As the metal film material in the present invention, at least one selected from the group consisting of titanium, chromium, stainless steel and nichrome is used, as long as the optical characteristics in the visible region are similar to these metals. ,
Even if the metal is used, a low reflection heat ray reflection glass having a similar color tone can be obtained. However, the four kinds of metals listed here are preferable because they have a track record as heat ray reflective film materials. Further, the geometric film thickness is defined by the color tone to be expressed.

The metal nitride film in the present invention is preferably a titanium nitride film, and the titanium nitride film is formed as a sputtering gas in an atmosphere of 100% nitrogen, resulting in a stoichiometrically excessive nitrogen film. . As another method of forming a titanium nitride film by a sputtering method, a mixed gas of argon and nitrogen may be used as a sputtering gas. In this case, Ti in the titanium nitride film:
The composition ratio of N becomes close to 1: 1. Even if this titanium nitride film is used, a low reflection heat ray reflective glass can be provided depending on the color tone, but stable film quality can be obtained more easily when the film is formed in a 100% nitrogen atmosphere, and film formation is also easier. Further, the geometric film thickness is defined by the color tone to be expressed.

The visible light transmittance of the low reflection heat ray reflective glass of the present invention is mainly defined by the total film thickness of the metal nitride film and the metal film used for the second and fourth layers. Current,
Visible light transmittance of generally used heat ray reflective glass is 40% or less, and in order to obtain the same level of transmittance as those, the thickness of the second layer and the fourth layer is set to the geometrical film. It is necessary to control the thickness to 25 nm or less.

For the transparent metal oxide film in the present invention, an oxide of at least one metal selected from the group consisting of titanium, tin, zinc, zirconium and tantalum is used, but preferably an oxide of titanium or tin. Is good. The reason is that these two metal oxides have a proven track record as oxides used for single-plate heat-reflecting glass and have excellent durability. Further, the geometrical film thickness is defined by the material used and the color tone to be expressed, but if the film thickness is too thick, the production time becomes long and, as a result, the productivity also decreases.

Next, a method for obtaining low reflection heat ray reflective glass of various color tones according to the present invention will be described. In addition, the film thickness shown below means a geometric film thickness.

According to the present invention, in order to obtain a low reflection glass having a gray color tone reflected from the glass substrate side, a transparent metal oxide film having a thickness of 15 to 27 nm is formed as a first layer on the glass substrate, A titanium nitride film having a film thickness of 14 to 29 nm is formed as two layers, a transparent metal oxide film having a film thickness of 34 to 54 nm is formed as a third layer, and a titanium nitride film is formed to be 19 to 36 nm as a fourth layer. Create with the film thickness of.

As another structure, the first structure is provided on the glass substrate.
As a layer, a titanium oxide film or a tantalum oxide film having a film thickness of 31 to 47 nm, or a tin oxide film having a film thickness of 38 to 56 nm,
A zinc oxide film or a zirconium oxide film is formed, a metal film is formed as a second layer with a thickness of 4 to 14 nm, and a titanium oxide film or tantalum oxide film with a thickness of 25 to 38 nm or a film is formed as a third layer. A tin oxide film, a zinc oxide film, or a zirconium oxide film having a thickness of 33 to 49 nm is formed, and a titanium nitride film is formed as a fourth layer with a film thickness of 15 to 33 nm.

In order to obtain a low reflection glass having a blue color tone reflected from the glass substrate side according to the present invention, a titanium oxide film or a tantalum oxide film having a film thickness of 46 to 68 nm or a film thickness is formed as the first layer on the glass substrate. A tin oxide film, a zinc oxide film or a zirconium oxide film having a thickness of 63 to 85 nm, a titanium nitride film having a thickness of 13 to 26 nm as a second layer, and a film thickness of 18 to 37 nm as a third layer. A transparent metal oxide film is formed, and a titanium nitride film is formed as a fourth layer with a thickness of 15 to 34.
Created with a film thickness of nm.

As another structure, a titanium oxide film or a tantalum oxide film having a film thickness of 35 to 52 nm, or a tin oxide film, a zinc oxide film or an oxide film having a film thickness of 42 to 62 nm is formed as a first layer on a glass substrate. A zirconium film is formed, a metal film having a film thickness of 3 to 14 nm is formed as a second layer, and a third film is formed.
As a layer, a titanium oxide film or a tantalum oxide film having a film thickness of 19 to 35 nm, or a tin oxide film having a film thickness of 26 to 39 nm,
A zinc oxide film or a zirconium oxide film is formed, and a titanium nitride film is used as the fourth layer with a thickness of 18 to 33 nm or 40 to 61 nm.
Create with the film thickness of.

In order to obtain a low reflection glass having a silver bronze color tone reflected from the glass substrate side according to the present invention, a titanium oxide film or a tantalum oxide film having a thickness of 24-36 nm or a film is formed as the first layer on the glass substrate. 32 to 48n thick
m tin oxide film, zinc oxide film or zirconium oxide film, and a titanium nitride film of 8 to 14 nm or 1 as a second layer.
The film thickness is 7 to 32 nm, and the film thickness is 26 as the third layer.
-40 nm titanium oxide film or tantalum oxide film, or 5-11 nm thick tin oxide film, zinc oxide film or zirconium oxide film is prepared, and a titanium nitride film of 14-26 nm or 35-53 nm is formed as the fourth layer. Create with film thickness.

As another configuration, a titanium oxide film or a tantalum oxide film having a thickness of 26 to 40 nm is formed as a first layer on a glass substrate, and a metal film is formed as a second layer from 5 to 11 n.
The film thickness is 30 to 46 nm as the third layer.
A titanium oxide film or a tantalum oxide film is prepared, and a titanium nitride film is formed as a fourth layer with a film thickness of 15 to 27 nm.

[0019]

【Example】

[Example 1] Magnetron D. C. A metallic titanium target is set on the cathode of the sputtering apparatus. A 6 mm thick float plate glass substrate is thoroughly washed and dried by a method such as polishing, placed in a vacuum chamber, and then evacuated to 1 × 10 ⁻⁵ torr or less using a turbo pump.

Next, 300 cc / argon of argon gas was added to the vacuum system.
min, oxygen gas 60 cc / min was introduced, the pressure in the system was set to 3.0 × 10 ⁻³ torr, and in this state, a titanium target was applied with an electric power of 3.1 W / cm ² to form a titanium oxide film. A 21 nm film is formed.

Next, the gas in the vacuum system was completely replaced with 100% of nitrogen gas (introduced amount was 500 cc / min), and in this state, the titanium target was similarly applied with electric power of 3.1 W / cm ² to perform nitriding. A titanium film having a thickness of 22 nm is formed.

Next, the atmosphere in the vacuum system is returned again to 300 cc / min of argon gas and 60 cc / min of oxygen gas, and a power of 3.1 W / cm ² is applied to the titanium target to form a titanium oxide film of 42 nm. .

Finally, the gas in the vacuum system is once again set to 100% nitrogen gas (introduction amount is 500 cc / min), and power is applied to form a titanium nitride film with a thickness of 31 nm.

The visible light transmittance of the sample thus obtained was 16.4%, the reflection characteristic on the glass surface side was 7.9%, and the reflection color tone was a ^* of 1.98 and b ^*. Is -5.
In No. 17, it was a slightly bluish gray reflection color.
The solar energy transmittance was 12.0% and the shielding coefficient (SC value) was 0.47.

[Example 2] Magnetron D. C. A target of metallic titanium and metallic tin was set on the cathode of the sputtering device, and a float plate glass substrate having a thickness of 6 mm was thoroughly washed and dried by a method such as polishing, then put in a vacuum chamber, and a turbo pump was used. Evacuate to less than × 10 ^-5 torr.

Next, 100 cc / argon of argon gas was introduced into the vacuum system.
min, oxygen gas of 500 cc / min is introduced, and in this state, a tin target film having a thickness of 74 nm is formed by applying electric power of 3.1 W / cm ^{2 to} the tin target.

Next, the gas in the vacuum system was completely replaced with 100% nitrogen (introduced amount was 500 cc / min), and in this state, the titanium target was also supplied with an electric power of 3.1 W / cm ² , and titanium nitride was applied. A film of 20 nm is formed.

Next, the atmosphere in the vacuum system is returned again to 100 cc / min of argon gas and 500 cc / min of oxygen gas, and 3.1 W / cm ² of electric power is applied to the tin target to form a tin oxide film of 26 nm. .

Finally, the gas in the vacuum system is once again set to 100% nitrogen gas (introduction amount is 500 cc / min), and power is applied to the titanium target to form a titanium nitride film with a thickness of 21 nm.

The visible light transmittance of the sample thus obtained was 22.8%, the reflection characteristic on the glass surface side was 8.0%, and the reflection color tone was a ^* of -3.88, b. ^* Is −
At 9.28, it was a slightly greenish blue reflection color. The solar energy transmittance was 16.7% and the shielding coefficient (SC value) was 0.51.

[Third Embodiment] A first procedure is performed in the same manner as in the first embodiment.
The titanium oxide film is 30 nm thick as the layer, the titanium nitride film is 11 nm thick as the second layer, and the titanium oxide film is 33 n thick as the third layer.
m, a titanium nitride film having a thickness of 20 nm is formed as a fourth layer.

The visible light transmittance of the sample thus obtained was 30.4%, the reflection characteristic on the glass surface side was 6.7%, and the reflection color tone was a ^* of 2.95 and b ^*. Is 7.3
At 0, the reflection color was silver bronze. Moreover, the solar energy transmittance is 21.9%, and the shielding coefficient (SC
The value) was 0.54.

[Example 4] Magnetron D. C. A target of metallic titanium, metallic tin and stainless steel (SUS316) was set on the cathode of the sputtering device, and a float plate glass substrate with a thickness of 6 mm was thoroughly washed by a method such as polishing and dried, and then placed in a vacuum chamber, and a turbo pump was used. Evacuate below 1 × 10 ^-5 torr.

Next, 100 cc / argon of argon gas was introduced into the vacuum system.
min, oxygen gas of 500 cc / min is introduced, and in this state, an electric power of 3.1 W / cm ² is applied to the tin target to form a tin oxide inter-layer film of 47 nm.

Next, the gas in the vacuum system was completely replaced with 100% argon (introduction amount was 300 cc / min), and in this state, a power of 1.9 W / cm ² was applied to the stainless steel target to form a metallic stainless steel film. Is deposited to a thickness of 6 nm.

Next, the atmosphere in the vacuum system is returned to argon gas of 100 cc / min and oxygen gas of 500 cc / min, and a tin target film of 41 nm is formed by applying an electric power of 3.1 W / cm ² to the tin target. .

Finally, the gas in the vacuum system is 100% nitrogen gas.
(Introduction amount is 500 cc / min), and a titanium target film having a thickness of 26 nm is formed by applying electric power of 3.1 W / cm ² to the titanium target.

The visible light transmittance of the sample thus obtained was 19.9%, the reflection characteristic on the glass surface side was 8.3%, and the reflection color tone was a ^* of -0.73 and b. ^* Is −
At 2.82, the reflection color was a bluish-gray light gray color as compared with Example 1. Also, solar energy transmittance is 15.9%
The shielding coefficient (SC value) was 0.49.

Example 5 Magnetron D.M. C. Metal titanium and stainless steel (SU
The target of S316) is set. After thoroughly washing and drying a 6 mm thick float plate glass substrate by a method such as polishing, put it in a vacuum chamber and use a turbo pump to 1 ×.
Evacuate to below 10 ^-5 torr.

Next, 300 cc / argon of argon gas was introduced into the vacuum system.
min, oxygen gas 60 cc / min was introduced, the pressure in the system was set to 3.0 × 10 ⁻³ torr, and in this state, a titanium target was applied with an electric power of 3.1 W / cm ² to form a titanium oxide film. A film having a thickness of 33 nm is formed.

Next, the gas in the vacuum system was completely replaced with 100% argon (introduction amount was 300 cc / min), and in this state, a power of 1.9 W / cm ² was applied to the stainless steel target to form the metallic stainless film. Is formed to a thickness of 8 nm.

Next, the atmosphere in the vacuum system is returned to 300 cc / min of argon gas and 60 cc / min of oxygen gas, and a power of 3.1 W / cm ² is applied to the titanium target to form a titanium oxide film of 38 nm. .

Finally, the gas in the vacuum system is 100% nitrogen gas.
(Introduction amount is 500 cc / min), and electric power of 3.1 W / cm ² is applied to the titanium target to form a titanium nitride film of 21 nm.

The visible light transmittance of the sample thus obtained was 22.7%, the reflection characteristic on the glass surface side was 7.8%, and the reflection color tone was a ^* of 2.44 and b ^*. Is 8.2
In No. 2, it was a silver bronze-based reflection color similar to that in Example 3. In addition, solar energy transmittance is 16.9%
The shielding coefficient (SC value) was 0.50.

In the above five examples, the shielding coefficient (SC value) is 0.47 to 0.54, which is about the same value as a general solar control glass. Moreover, it can be confirmed that the reflectance of visible light is as low as 10% or less, which is as low as that of transparent plate glass.

[0046]

As described above, according to the present invention, the reflectance from the outside of the room is almost the same as that of ordinary transparent glass, and does not have an adverse effect due to glare in the surroundings and exhibits various reflection color tones. A heat ray reflective glass having a rate of 40% or less is obtained.

In particular, titanium oxide as a transparent metal oxide film,
In the combination using titanium nitride as the absorbing film, the titanium oxide film and the titanium nitride film can be formed separately by using different sputtering gases in the metal titanium target as seen in the examples. Therefore, the ordinary high reflection heat ray reflection glass using only titanium nitride and metal which is generally used at present and the low reflection heat ray reflection glass of the present invention can be separately produced without a job change involving opening to the atmosphere.

[Brief description of drawings]

FIG. 1 is a schematic view of a cross section of a main part of a heat ray reflective glass according to the present invention.

[Explanation of symbols]

 10: Glass substrate 11: Transparent metal oxide film 12: Metal nitride film or metal film 13: Transparent metal oxide film 14: Metal nitride film

Claims (4)

[Claims] 1. A transparent metal oxide film as a first layer, a metal film or a metal nitride film as a second layer, a transparent metal oxide film as a third layer, and a metal nitride film as a fourth layer on a glass substrate. A low reflection heat ray reflection glass characterized in that, in the heat ray reflection glass sequentially laminated by a sputtering method, the visible light reflectance from the glass substrate side is 10% or less and the visible light transmittance is 40% or less. 2. The low reflection heat ray reflective glass according to claim 1, wherein the metal nitride film is a titanium nitride film. 3. The transparent metal oxide film is an oxide film of at least one metal selected from the group consisting of titanium, tin, zinc, zirconium and tantalum. Low reflection heat ray reflective glass. 4. The low reflection heat ray reflective glass according to claim 1, wherein the metal film is at least one metal selected from the group consisting of titanium, chromium, stainless steel and nichrome.