JPH06345489A - Heat-reflective glass - Google Patents

Abstract

PURPOSE:To produce a heat-reflective glass exhibiting various vivid green colors as the exterior-side reflection color at a total film thickness of <100nm at which the color tone is easily reproducible. CONSTITUTION:The heat-reflective glass has a nitride layer 11 as the 1st layer formed on a glass substrate 10 and a metal oxide layer 12 as the second layer formed on the nitride layer. A blue-colored heat-absorbing glass is used as the glass substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray reflective glass for buildings or automobiles.

[0002]

2. Description of the Related Art In recent years, openings in buildings have tended to expand for design and comfort. Along with that, heat-reflecting glass is caused by factors such as an increase in the amount of sunlight entering and an increase in indoor cooling load, and an increase in the design importance of windows that occupy a large area in the exterior of a building. The number of cases of using is increasing rapidly. The heat-reflecting glass used for this purpose is usually called a solar control glass, and is distinguished from the heat mirror glass for reducing the heating load in cold regions.

The desirable characteristics of this solar control glass are: (1) limiting the penetration of sunlight,
(2) The reflection color of the outdoor side is rich in design. In particular, recently, the point (2) has been emphasized, and with the spread of heat ray-reflecting glass, there is an increasing tendency to demand a color tone with a high degree of design that is rich in individual expression. One of them is green.

So far, some heat ray reflective glasses exhibiting a green outdoor reflection color have been known. These can be roughly classified as follows according to their configurations. (1) Three-layer system of oxide film / nitride film / oxide film (2) Two-layer system of oxide film / nitride film or metal film (3) Utilizing reflection of green heat absorbing glass

Although (1) is the most general one (Japanese Patent Laid-Open No. 60-36355), when an attempt is made to produce vivid green as an outdoor reflection color, the oxide layer has a thickness of 200.
nm to 300 nm, which is significantly thick, resulting in poor productivity and high production cost. Further, since the color tone of reflection is sensitively affected by the thickness of the oxide layer, it is difficult to secure the color tone with good reproducibility.

Since the film thickness of (2) is smaller than that of (1), the productivity is good and the reproducibility is easily secured (Japanese Patent Laid-Open No. Hei 2-
No. 44046). However, it has a drawback that it is difficult to produce a bright green color.

(3) expresses a greenish color by observing metallic reflection of metal through the green color of the glass substrate. However, since the color tone of the glass substrate itself is used, it is possible to match the hue within the same green color. It is difficult to make different things.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a heat ray reflective glass having a bright green reflection color on the outdoor side (glass substrate side). To do.

[0009]

The present invention has been made to solve the above-mentioned problems, in which a nitride is formed as a first layer and a metal oxide is formed as a second layer on a glass substrate. The heat ray-reflecting glass is characterized in that the glass substrate is a blue heat ray-absorbing glass.

FIG. 1 is a partial sectional view of a heat ray reflecting glass according to the present invention, in which 10 is a blue heat ray absorbing glass, 11 is a nitride layer formed as a first layer, and 12 is a second layer. Shows the oxide layer.

As the nitride film in the present invention, titanium nitride or a nitride containing titanium nitride as a main component is used. However, the composition ratio of Ti: N in the titanium nitride film in this case does not necessarily have to be 1: 1 and may be stoichiometrically excessive in nitrogen or may be in a nitrogen-deficient state. Good.

The film thickness is preferably 7 nm to 30 nm. This is because if it is less than 7 nm, the reflection color tone becomes bluish, which is not preferable as a green color, while if it is higher than 30 nm, the reflection color tone becomes more yellowish, which is also not preferable as a green color.

The metal oxide in the present invention includes titanium, tin, indium, zinc, zirconium, tantalum,
And at least one oxide selected from the group of hafnium can be used.

The optical film thickness is 90 nm to 130.
nm is desirable. This is because if the thickness is less than 90 nm, the reflection color tone becomes bluish, which is not preferable as a green color, whereas if it is higher than 130 nm, the reflection color tone becomes more yellowish, which is also not preferable as a green color. Here, the optical film thickness is represented by the product of the actual film thickness and the refractive index.

The present invention is characterized in that a color variation, which is difficult to produce only with a film structure, is realized by combining it with the color of the heat ray absorbing glass as the substrate. That is, a film is laminated on a transparent substrate to make about 1
It is difficult to produce a desired green color at about 50 nm or less, but it is possible to create a yellowish to yellowish color by adjusting the structure of the film. By combining this with heat ray absorbing glass whose transmission color as the substrate is blue, it is possible to create a vivid green color by combining the color of the glass substrate with the color that can be created from the film configuration. Become.

The heat ray absorbing glass plate whose transmission color is blue is a glass plate which absorbs visible light and solar radiation heat, and for example, a blue heat ray absorbing glass plate having a main wavelength of about 450 nm to about 495 nm is mentioned. be able to. The blue heat ray absorbing glass plate is made, for example, by adding a trace amount of cobalt and, if necessary, a metal such as iron to the components of the composition of ordinary plate glass or float glass.

Further, the color produced from the structure of the film can be changed by adjusting the film thickness of each layer. As a result, a variety of green colors can be obtained as compared with the case where the green heat absorbing glass is used as the glass substrate. It is also possible to easily create variations of.

The method for producing each film in the present invention is not particularly limited, but as a physical thin film forming method,
Electron beam heating evaporation method, various ion plating method,
An arc vapor deposition method, a sputtering method or the like can be used.
In particular, the sputtering method is currently excellent as a method for forming a thin film on a large area substrate.

[0019]

【Example】

Example 1 Magnetron D. A metallic Ti target is set on the cathode of the C sputtering apparatus. After thoroughly washing and drying a 6 mm thick blue heat ray absorbing glass substrate (color code: B) by a method such as polishing, put it in a vacuum chamber and use a turbo pump to exhaust it to 1 × 10 ⁻⁵ Torr or less. To do. Next, 100% nitrogen gas was introduced into the vacuum system at 500 cc / min, the pressure in the system was set to 3.0 × 10 ⁻³ Torr, and in this state, the Ti target was supplied with an electric power of 3.1 W / cm ² . A TiN _x film is formed by applying 26 nm. Next, the gas in the vacuum system was completely replaced with 300 cc / min of argon gas and 60 cc / min of oxygen gas, and the Ti target was 3.1 W in this state.
A TiO ₂ film having a thickness of 45 nm is formed by applying an electric power of / cm ² .

The glass surface side of the sample thus obtained has a reflectance of 28.5% and a reflection color tone of a ^*.
Was -2.19 and b ^* was 2.64.

Example 2 A sample was prepared under the same conditions as in Example 1, except that a 12 mm-thick blue heat ray absorbing glass substrate was used instead of the 6 mm-thick glass substrate.

The glass surface side of the sample thus obtained has a reflectance of 21.8% and a reflection color tone of a ^*.
Was -15.31 and b ^* was 0.89.

Example 3 In the same procedure as in Example 1, a 6 mm thick blue heat ray absorbing glass substrate (color code: B) was used, and TiN _x was used as the first layer.
A sample was prepared by forming a film of 19 nm and a TiO ₂ film of 53 nm as the second layer.

The glass surface side of the sample thus obtained has a reflectance of 27.4% and a reflection color tone of a ^*.
Was 11.21 and b ^* was 6.48.

FIG. 2 is a plot of the reflection color tone on the glass surface side of the sample prepared in the example on the chromaticity diagram of the L ^* a ^* b ^* color system. The light source used was C light of 2 °.

In the figure, 13 is the result of the first embodiment, 14 is the result of the second embodiment, and 15 is the result of the third embodiment. Nos. 16 to 18 show the reflection color tone from the glass surface side of a sample in which a normal white plate is used as a glass substrate and titanium nitride and titanium oxide are laminated thereon, and are cited from JP-A-2-44046. is there.

In FIG. 2, the larger the value of a ^{* in} the negative direction, the brighter the green color becomes. However, the sample prepared in the example has a brighter green color than that formed on a white plate. It is clear from the figure that is expressed.

[0028]

As is clear from the above examples,
According to the present invention, various vivid green colors can be obtained as a reflection color on the outdoor side with a total film thickness of less than 100 nm, which makes it easy to ensure color reproducibility. Further, according to the principle of combining the color of the glass substrate itself with the color of the film constitution of the present invention, it is considered that there is a possibility that a heat ray reflective glass having a color tone which is difficult to obtain only by the film constitution alone can be easily obtained.

[Brief description of drawings]

FIG. 1 is a partial sectional view of a heat ray reflective glass according to the present invention.

FIG. 2 is a diagram showing a reflection color tone from a glass surface side of an example of the present invention and a comparative example quoted from JP-A-2-44046 on an L ^* a ^* b ^* color system chromaticity diagram.

[Explanation of symbols]

10: Blue heat absorbing glass substrate 11: Nitride film 12: Metal oxide film 13: Point showing the glass surface reflection color tone of Example 1 14: Point showing the glass surface reflection color tone of Example 2 15: Example 3 Showing the glass surface reflection color tone of Nos. 16 to 18: Point showing the glass surface reflection color tone of the sample quoted from Table 1 of JP-A-2-44046.

Claims (3)

[Claims] 1. A heat ray reflective glass comprising a glass substrate on which a first layer is formed of a nitride and a second layer on which a metal oxide is formed, wherein the glass substrate is a blue color heat ray absorbing glass. Heat ray reflection glass. 2. The nitride is titanium nitride or a nitride containing titanium nitride as a main component, and the film thickness is 7 nm.
The heat ray reflective glass according to claim 1, wherein the heat ray reflective glass has a thickness of ˜30 nm. 3. The metal oxide is at least one oxide selected from the group consisting of titanium, tin, indium, zinc, zirconium, tantalum, and hafnium, and has an optical film thickness of 90 nm to 130 nm. It exists, The heat ray reflective glass of Claim 1 or 2 characterized by the above-mentioned.