JPH05139789A - Color anisotropic glass - Google Patents

Abstract

PURPOSE:To provide a color anisotropic glass exhibiting excellent color anisotropic effect with only two layers of a mixed film of a metallic layer and tin oxide or tin oxide and tin and free from decrease in color brightness even when changing visual angle. CONSTITUTION:The glass is provided with the metallic film having 100-2000Angstrom thickness as a reflecting film of the 1st layer on the glass and the film of tin oxide or the mixed film of tin oxide and tin having 100-5000Angstrom thickness as a transparent film of the 2nd layer on the surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored anisotropic glass.

[0002]

2. Description of the Related Art Aluminum has been used as a reflective film,
Gold, silver, copper, zinc (hereinafter Al, Au, Ag, Cu, Zn
A film having a metal oxide film such as aluminum oxide, antimony oxide, titanium oxide, or zirconium oxide as a transparent film is proposed. After forming a metal film and a metal oxide film on the film,
Further, by laminating these, the uppermost layer uses a reflective film of high reflectance aluminum, silver, etc., or a heat-sensitive resin such as polyvinyl chloride, polyvinyl acetate, polyacrylic ester or a natural resin, polyvinyl ether as a base film. It is proposed that a pressure-sensitive adhesive layer formed by adhesion processing is provided (JP-A-61-16900).

In Japanese Patent Laid-Open No. 3-82881, a reflective metal film is formed on at least one side of a fiber cloth from the side of the fiber cloth.
The transparent metal compound film and the semitransparent metal film are sequentially deposited to increase the film thickness of the uppermost semitransparent metal film (200 Å or more)
There is also an example in which an interference color is expressed.

In Japanese Patent Laid-Open No. 60-23882, when a film having an interference pattern is formed by vapor-depositing a metal oxide or the like, two or more layers of film are formed by using a deposition mask, and the angle of view is changed. There has been proposed a method of imparting an iris color that does not depend on it.

Further, Japanese Patent Application Laid-Open No. 59-23882 discloses that
A titanium nitride thin film is formed on stainless steel by using sputtering, ion plating, plasma CVD or the like, and silicon nitride (hereinafter referred to as S
A bilayer film coated with i ₃ N ₄ ) has been proposed.
This also is obtained by changing the thickness of the top layer the Si ₃ N ₄ to express various colors by interference effects of light.

[0006]

Problems to be Solved by the Invention JP-A-61-1690
The method described in Japanese Patent Publication No. 0 has to have a multilayer structure in order to obtain an excellent color anisotropy effect, which causes a great problem in complexity of work and economical aspect. Further, in order to solve the work complexity or the economical problem, it is necessary to reduce the number of layers, and in this case, excellent color anisotropic effect cannot be obtained.

According to the method described in JP-A-3-82881, only a specific color is developed, or the degree of color development greatly changes depending on the viewing direction. In order to obtain the interference effect, the reflective metal film, the transparent metal compound film, and the semi-transparent metal film must have a laminated structure (three layers) and the thickness of the uppermost semi-transparent metal film must be increased. There is a great problem in terms of complexity and cost, durability, and texture.

In addition to metal oxides, for example, copper iodide, magnesium fluoride, aluminum fluoride (hereinafter CuI, M
There is also an example in which a transparent film such as gF ₂ or AlF ₃ ) is used (JP-A-60-2359). However, these treated products have poor light resistance, and the sample is discolored when left for several days, resulting in a black color. It has poor practicability due to blemishes and reduced gloss.

Conventionally, there have been glasses that have a beautiful color such as stained glass, but no example has been proposed so far in which interference colors are produced by using vacuum deposition, ion plating or sputtering and their applied techniques.

[0010]

The present inventors have completed the present invention as a result of intensive studies to improve the drawbacks of the prior art. That is, according to the first aspect of the present invention, a metal film having a film thickness of 100 to 2000Å is formed on a glass as a first layer, and a metal film having a film thickness of 100 to 50 is formed as a transparent film on a second layer.
00Å tin oxide (hereinafter referred to as SnO ₂ ) film or Sn
It is a glass having a mixed film of O ₂ and tin (hereinafter referred to as Sn).

In a second aspect of the present invention, a mixed film of Al and aluminum oxide (hereinafter referred to as Al ₂ O ₃ ) having a film thickness of 100 to 2000 Å is formed on a glass as a first layer reflective film. Layer with a thickness of 100-5000Å SnO
It is a glass having _two films or a mixed film of SnO ₂ and Sn.

The glass used in the present invention includes all known glasses such as hard glass, soft glass, transparent glass, frosted glass and quartz glass. As a pretreatment for the metal treatment, it is preferable to subject the glass surface to a physical cleaning treatment such as plasma treatment, flame treatment, ozone treatment, or chemical cleaning treatment such as hydrogen peroxide treatment or hydrofluoric acid treatment.

As the metal film used in the present invention, Au, A
Examples thereof include g, Cu, Zn, Sn and Al. Among these metals, the most preferable result is obtained by using Al which is flat and has a large reflectance in the visible region.
That is, the light reflectance at 400 to 600 nm is 30% or more, more preferably 40% or more, particularly preferably 50% or more, and the reflectance difference at the wavelength is preferably 20% or less, more preferably 10% or less. is there.

On the other hand, when Al is used for the metal film, Al ₂ O ₃ may be mixed as a constituent component of the film. By mixing Al ₂ O ₃ with Al, the reflectance of Al is reduced and a light color tone is obtained. The amount of Al ₂ O ₃ mixed in Al largely depends on the degree of vacuum in the system. That is, if the degree of vacuum in the system is low, the amount of residual oxygen is large and the generation of Al ₂ O ₃ due to the oxidation of Al is promoted. On the other hand, if the degree of vacuum in the system is high, the amount of residual oxygen is small and the amount of Al ₂ O ₃ is generated. Is suppressed.

The thickness of the metal film is usually 100 to 2000.
Å, preferably 150 to 1000Å. When the film thickness of the metal is less than 100Å, the light reflection is not sufficient and the interference effect is weakened, and the desired excellent color anisotropic glass cannot be obtained. At 2000Å or higher, saturation of the color anisotropic effect is seen and the metal coating on the glass becomes too thick,
The coating is likely to peel off and fall off, greatly affecting durability.

The transparent film used in the present invention is S
nO ₂ or a mixture of SnO ₂ and Sn (hereinafter referred to as the transparent film) is used. Surprisingly, when the transparent film is used, a very excellent color anisotropy effect is obtained, and light resistance which has been a serious problem with other conventional metal oxides such as titanium oxide, Al ₂ O _{3 and the} like. Can be improved. Further, it is possible to obtain a colored anisotropic glass in which excellent iridescent interference can be obtained by only two layers of the metal film and the transparent film, and the brightness of the color does not decrease even if the color changes depending on the viewing angle.

The weight ratio of SnO ₂ / Sn is 1/1 or more, preferably 5/1 to 3/1. When a mixed film of SnO ₂ and Sn is used, a color anisotropy effect superior to that in the case of a SnO ₂ single film is obtained. The thickness of the transparent film is usually 100 to 5
It is 000Å, preferably 200 to 2000Å. When the film thickness of the transparent film is less than 100Å, the interference effect is not good and the desired excellent colored anisotropic glass cannot be obtained. On the other hand, if the thickness of the transparent film is more than 5000Å, the color anisotropic effect is saturated and the film becomes too thick, resulting in peeling off of the film, which is not preferable in practice.

Since the hue can be changed depending on the film thickness of the transparent film, the film thickness may be selected according to the purpose. Further, if there is a film thickness change of about 50 to 1000 Å depending on the position of the glass, a wider variety of iridescent and multicolor effects are exhibited, which is preferable.

When the colored anisotropic glass obtained according to the present invention is observed from the transparent film side by a scanning electron microscope, granular particles are observed on the surface. When this is observed by X-ray microscope analysis. It was found that the granular material was an aggregate of the transparent film. The formation of this granular structure is found in almost all glasses, although the size and number of particles varies. The size of the particles having this granular structure is preferably 0.2 to 1.0 µ, and more preferably 0.3 to 0.8 µ. The number is usually 100 at most / μm ² , preferably 5 at most.
The number is 0 / μm ² .

The metal film and the transparent film can be laminated in vacuum by vacuum vapor deposition, ion plating, sputtering or their applied techniques. The composition of the interface gradually changes in atomic order. The change in composition can be analyzed by X-ray photoelectron spectroscopy, but it is roughly 30 to 7
It changes through a boundary area of about 0Å.

The colored anisotropic glass obtained by the present invention is
A metal film is formed as a reflective film of the first layer on glass, and the transparent film is obtained by vapor deposition as a transparent film of the second layer on the glass. Even when the transparent film is vapor-deposited with a metal film on the second layer, an excellent color anisotropic effect can be obtained when observed from the glass side. Moreover, by doing so, light resistance and durability are dramatically improved. Also, various glosses and patterns can be obtained by subjecting the glass surface to various processing treatments.

The above-mentioned two types of samples were prepared using transparent glass, and the color was evaluated by the naked eye and Macbeth spectrophotometer. As a result, there was almost no difference in color between the two samples, and the difference in reflectance at the maximum absorption wavelength near 500 to 600 nm was less than 10%, which was not so different.

The color anisotropic effect in the present invention means
It seems that it is basically caused by light interference phenomenon, but it is fundamentally different in size, color tone, and taste from the color phenomenon of oil film on the water and soap bubbles and the compact disc. A familiar example is that the luster of pearls is spread over a cloth. Moreover, the color tones can be made different according to the viewing direction and the wavelength of light.

[0024]

According to the method of the present invention, since the transparent film is used as the transparent film, the durability and the light resistance are excellent, and the color anisotropy effect which is excellent only by the two layers of the metal film and the transparent film and the viewing angle It is possible to obtain an excellent color anisotropic glass in which the brilliance of the color does not decrease even if it changes. At the same time, by changing the thickness of the transparent film, it is possible to arbitrarily change the underlying color and color anisotropy effect, so even if you take fashionability, economic efficiency, etc. It's so good that it doesn't happen. The colored anisotropic glass obtained by the present invention is very fashionable, and when it is used for decorative articles such as stained glass, it can be very wonderful.

[0025]

【Example】

Example 1 Using a vacuum vapor deposition apparatus, a transparent glass having a side of 10 cm was placed 15 cm below the vapor deposition source, Al was 300 Å, and then the transparent film was vapor-deposited with a thickness of 100, 300, 500, 1000 Å. The film thickness was measured by a film thickness sensor placed equidistant from the vapor deposition source and the glass. The results are shown in Table 1.

[0026]

[Table 1]

Example 2 Example 2 was repeated except that the metal film was changed to Ag or Au. The results are shown in Table 1.

Comparative Example 1 A transparent film was changed to CuI, MgF ₂ and AlF ₃ except that
The same procedure as in Example 1 was performed. The results are shown in Table 1.

The light resistance test of the color anisotropic glass was carried out by using an auto fade meter closed type (FOL-HB) using a UV long-life carbon arc, a black panel temperature of 72 to 74 ° C., a temperature of 31 ° C., and an ultraviolet irradiation of 20 hours. It was performed under the conditions of. The color evaluation was carried out by visual judgment and measurement of reflectance. As a result, no change in color of the sample was observed before and after irradiation with ultraviolet rays.

[Brief description of drawings]

FIG. 1 is a diagram showing the positions of a vapor deposition source, glass, and a film thickness sensor in a vacuum vapor deposition apparatus. The distance between the vapor deposition source and the glass and film thickness sensor is the same.

[Explanation of symbols]

 1 evaporation source 2 glass 3 film thickness sensor

Claims (2)

[Claims] 1. A film having a thickness of 1 as a first-layer reflective film on glass.
A glass having a metal film of 00 to 2000Å and a tin oxide film or a mixed film of tin oxide and tin having a film thickness of 100 to 5000Å as a transparent film of the second layer thereon. 2. A film having a thickness of 1 as a first-layer reflective film on glass.
A mixed film of aluminum and aluminum oxide having a thickness of 00 to 2000Å is used as a transparent film of a second layer on the film having a thickness of 100 to
A glass having a 5000 Å tin oxide film or a mixed film of tin oxide and tin.