JP2001322835A - Colored glass and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored glass and a method for manufacturing the glass excellent in decorating property, reflecting property against heat rays, scratching resistance and chemical resistance. SOLUTION: The colored glass consists of a glass substrate, a colored film containing Co oxide formed by sputtering on the surface of the glass substrate, and a colored ceramic film laminated on the colored film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored glass and a method for producing the same, and more particularly, to a colored ceramic film formed on a surface showing a good color development, a design property, a heat ray reflection property, and the like.
The present invention relates to a colored glass having excellent scratch resistance and chemical resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Various kinds of coatings are laminated on the surface of a window glass for a vehicle according to its use. For example, a colored ceramic film is provided as an opaque layer on the periphery of a vehicle window glass for the purpose of preventing the urethane adhesive from being deteriorated by ultraviolet rays or preventing the terminal portions of the heating wire from being seen from outside the vehicle. ing.

On the other hand, in order to reduce the cooling load, improve the design, protect the privacy of the passenger compartment, etc., the window glass for vehicles or buildings is required to reduce the amount of transmitted solar radiation energy and to provide an appropriate visible light. It is required to have a light transmittance and further to have a color tone which does not impair the vehicle design. In order to reduce the amount of transmitted solar energy, colored glass may be used, or transparent soda-lime glass or colored glass having high transmittance may be made of Co, Cr, F
Laminated glass coated with a heat ray reflective colored film made of a metal oxide such as e is used. Above all, the latter laminated glass is desirable from the viewpoint of the recyclability of the glass and the heat ray reflectivity.

When manufacturing a glass in which a colored ceramic film is laminated at a predetermined position on a heat reflective colored film, a heat reflective colored film containing a Co oxide or the like is formed on a portion where the colored ceramic film is laminated. Although it is not necessary to do so, it is difficult to prevent the heat ray reflective colored film from being laminated only in that portion in the manufacturing process. In addition, before the colored ceramic film is laminated, the step of removing the heat ray reflective colored film in that portion is a cause of an increase in cost. Therefore, a colored ceramic paste is applied on the heat ray reflective colored film. Therefore, a colored ceramic film must be formed.

[0005] Glass in which a colored ceramics film is laminated on a heat-reflective colored film containing a Co oxide or the like is conventionally known as CV.
A method in which a glass is heated by a method D, a spray method or the like to form a heat ray reflective colored film containing a Co oxide or the like, and then a colored ceramic paste is applied to a predetermined location on the colored film and fired. . However, in the laminated film manufactured by this method, the coloring of the colored ceramic film formed on the colored film containing the Co oxide or the like is poor compared with that formed directly on the glass, and the design property is significantly reduced. Was. In addition, this laminated film is inferior in abrasion resistance, and furthermore, when a conductive silver paste film is laminated on the laminated film, the strength of the conductive silver paste film is reduced, and color development is poor. There were also problems such as falling off.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a colored film, particularly a colored ceramic film formed on a colored film containing a Co oxide, which develops a good color, has good design properties, heat ray reflectivity, and scratch resistance. An object of the present invention is to provide a colored glass having excellent properties and chemical resistance and a method for producing the same.

[0007]

In the present invention, as a result of diligent studies on a colored film containing a Co oxide and a colored ceramic film laminated thereon, a colored film containing a Co oxide was formed by sputtering. It has been found that, when a colored ceramics film is formed, the colored ceramics film shows a good color development and a colored glass exhibiting excellent design properties can be obtained.

That is, the present invention provides a colored substrate having a glass substrate, a colored film containing a Co oxide formed on the surface of the glass substrate by sputtering, and a colored ceramic film laminated on the colored film. Provide glass.

After forming a laminated film in which the colored film has an oxide film (A) containing at least one selected from Fe, Cr and Ni and an oxide film (B) containing Co, it is heat-treated. It is preferable that the film is

The present invention also provides a method for producing the colored glass, wherein a colored film containing a Co oxide is formed on a surface of a glass substrate by sputtering, and then a colored ceramic paste is applied and heat-treated. A manufacturing method is provided.

[0011] The colored glass of the present invention comprises a glass substrate, a colored film containing a Co oxide on at least one surface of the glass substrate, and a colored ceramic laminated at a predetermined position on the colored film containing the Co oxide. And a membrane. The glass substrate used for the colored glass of the present invention is not particularly limited, and is appropriately selected depending on the use, function, and the like of the colored glass. For example, when the colored glass is a heat ray reflective colored glass used as a vehicle window glass, as a glass substrate, colorless and transparent soda lime glass, green, brown, glass colored tones such as gray, Zn Any glass, such as glass to which ultraviolet absorption is imparted by addition of Ag, Ce, or the like, can be used.

The colored film containing a Co oxide is made of an oxide containing Co as an essential component. In addition to Co, Fe, Cr, T
i, Ta, Nb, Mo, Mn, Si, Cu, Ba, Z
An oxide film containing n, Zr, C, or the like may be used. The coloring film containing a Co oxide may be composed of a single layer or a plurality of layers. The single-layered colored film containing Co oxide contains Co and may contain other components. The colored film including a Co oxide including a plurality of layers may be a layer including at least one layer including an oxide including Co, and the other layer may include an oxide layer including Fe, Cr, Ni, or the like, All of the plurality of layers may be an oxide layer containing Co.

As a colored film containing a Co oxide composed of a plurality of layers, an oxide film (A) containing at least one selected from Fe, Cr and Ni, and an oxide film containing Co thereon ( B) is a laminated film obtained by laminating B). The laminated film is preferable because it can be easily formed by a sputtering method. The oxide film (A) may contain other components in addition to Fe, Cr and Ni. For example, T
i, Ta, Nb, Mo, Mn, Si, Cu, Ba, Z
An oxide film containing n, Zr, C, or the like may be used. The oxide film (B) may be an oxide film containing Ti, Ta, or the like in addition to Co.

In the colored film containing a single-layer Co oxide, the Co content is preferably 50% by mass or more. When the colored glass is a heat-reflective colored glass,
The colored film containing the Co oxide preferably has a Co content of 60% by mass.

In a colored film containing a Co oxide composed of a plurality of layers, in particular, a colored film containing a Co oxide having an oxide film (A) and an oxide film (B), the oxide film (A) Are Fe 60% by mass or more and Cr 10% by mass or more with respect to all metals, respectively.
Ni is preferably 5% by mass or more. The Co content in the oxide film (B) is 60% by mass based on all metals.
It is preferable that it is above.

In the present invention, the colored film containing a Co oxide is formed by a magnetron sputtering method from the viewpoint that good coloring of a colored ceramic film laminated on the colored film containing a Co oxide is obtained. By forming a film by the magnetron sputtering method, a large-scale and in-line colored film containing a Co oxide can be formed with a uniform thickness and a uniform film composition in an industrial production process.

Co by magnetron sputtering
The formation of the colored film containing an oxide is performed by using a target whose composition is adjusted in accordance with the above components, and using discharge power, an atmosphere composition, an atmosphere gas pressure, a magnetic field strength, a plasma density on a substrate, a film formation rate, and the like. It can be selected appropriately. The colored film containing a Co oxide composed of a plurality of layers is sequentially formed in the same vacuum chamber or different vacuum chambers by using a target material selected according to each oxide film.
The film can be formed by magnetron sputtering.

The thickness of the colored film containing the Co oxide can be appropriately selected according to the optical characteristics and the like required for the colored glass. For example, when the colored glass is a heat ray reflective colored glass, the visible light transmittance is set to 20 to 40%, and the visible light reflectance of the film surface and the other surface is set to 20 to 40%, respectively.
When the thickness is set to 10 to 25%, the thickness of the oxide film is preferably set to 10 to 80 nm.

The colored film formed on the surface of the glass substrate is
Preferably, a heat treatment is applied. The heat treatment may be performed immediately after the formation of the colored film, or may be performed at the same time as the lamination of the colored ceramic film described later and the heating treatment during the bending process performed after the firing of the colored ceramic film or the lamination of the colored ceramic film. Good.

The colored ceramic film of the colored glass according to the present invention contains a crystalline glass frit (and / or an amorphous glass frit), a heat-resistant coloring pigment and a refractory filler as main components.

The crystalline glass frit used for the colored ceramic film is a PbO—SiO ₂ glass that crystallizes in a temperature range of 450 to 700 ° C.

The amorphous glass frit is added for adjusting the fluidity of the crystalline glass frit.
For example, PbO—SiO ₂ having a softening temperature of 400 to 640 ° C.
Is a glass mainly composed of

The thickness of the colored ceramic film is preferably about 15 to 20 μm.

This colored ceramic film is laminated by screen printing or the like using a colored ceramic paste containing a crystalline glass frit (and / or an amorphous glass frit), a heat-resistant colored pigment and a refractory filler.
It can be formed by firing at a predetermined location and shape on a colored film containing a Co oxide.

The preparation of the colored ceramic paste is performed by uniformly mixing a crystalline glass frit (and / or an amorphous glass frit), a heat-resistant coloring pigment and a refractory filler with an organic vehicle, and adjusting the viscosity to be suitable for coating. You can do it.

Examples of the organic vehicle include resin components such as ethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, butyl methacrylate, rosin, and rosin derivatives; A solution homogeneously dissolved in a solvent such as monobutyl ether acetate can be used.

The calcination is performed at 500 to 700 ° C., preferably 63
It can be carried out by heating at 0 to 690 ° C. in an air atmosphere for 3 to 7 minutes. The calcination can be performed simultaneously with other heat treatments as long as the heating temperature and time are almost the same. For example, when the colored glass is a heat ray reflective colored glass used as a vehicle window glass, after the color ceramic paste is screen-printed, the firing process is simultaneously performed by a bending process of forming the vehicle window glass. It can be carried out.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below more specifically based on embodiments of the present invention. (Example 1) Magnetron sputtering apparatus (HSM-5, manufactured by Shimadzu Corporation) placed in a vacuum chamber
21) At predetermined locations, 72% by mass of Co and 8% by mass of Fe
And a target made of a Co-based alloy having a composition of 20 mass% of Cr and a glass substrate (3.5 mm thick × 1 vertical)
A green colored soda lime glass plate (00 mm × 100 mm in width) was placed on a substrate holder. After the pressure in the vacuum chamber was reduced to 2 × 10 ⁻⁴ Pa using an oil diffusion pump, oxygen gas was introduced at 50 sccm to reduce the pressure to 2 × 10 ^−1.
Pa was maintained. With the glass substrate not heated, a discharge power of 0.3 kW was applied to the cathode at room temperature, a film was formed by magnetron sputtering for 145 seconds, and the thickness was 60 nm.
To form a colored film containing Co oxide. Then, a predetermined position on the color film, crystalline glass frit mainly composed of PbO-SiO _2, amorphous glass frit mainly composed of PbO-SiO _2, the heat-resistant coloring pigment and refractory filler A color ceramic paste uniformly mixed with an organic vehicle is screen-printed to a thickness of 15 μm,
A baking treatment was performed by heating at 15 ° C. for 15 minutes in an air atmosphere.

As shown in FIG. 1, the obtained laminated glass sample has a colored film 2 containing a Co oxide on the surface of a glass substrate 1 and a colored ceramic film on the colored film 2 containing the Co oxide. 3 has a laminated structure.

The one produced by the sputtering method
63% by mass of conventional Co, 26% by mass of Fe, 1% of Cr
As compared with the oxide film containing 1% by mass of the oxide film formed by the spray method, the brightness was lower, the color tone was neutral, and good color development was obtained.

(Example 2) Each of two magnetron sputtering apparatuses installed in a vacuum chamber was
SUS304 target and 99.9% pure Co
A glass substrate (thickness 3.5)
A green colored soda lime glass plate (mm × 100 mm × 100 mm) was placed on a substrate holder. next,
1.0 × 1 inside vacuum chamber by turbo molecular pump
After reducing the pressure to 0 ^-4 Pa or less, oxygen gas is supplied at 50 sccm.
The pressure was maintained at 2.6 × 10 ⁻¹ Pa by introduction. At room temperature without heating the glass substrate, a discharge power of 0.5 kW was applied to the cathode of the SUS target, a film was formed by magnetron sputtering for 30 seconds, and a 6 nm thick F was formed.
A first oxide film containing e, Cr, and Ni was formed. next,
At room temperature without heating the glass substrate, a discharge power of 0.5 kW was applied to the cathode of the Co
The second oxide film was formed over the first oxide film for 30 seconds, and a 30-nm-thick Co oxide (Co 100% by mass) was formed.

Next, a PbO-
Crystalline glass frit composed mainly of SiO ₂ , PbO
Screen printing of a 15 μm-thick colored ceramic paste obtained by uniformly mixing an amorphous glass frit containing SiO ₂ as a main component, a heat-resistant coloring pigment, and a refractory filler in an organic vehicle at a temperature of 650 ° C. for 15 minutes. A baking treatment was performed by heating in an atmosphere.

As shown in FIG. 2, the obtained laminated glass sample was made of Fe, C formed on the surface of the glass substrate 4 at a low temperature.
a first oxide film 5 containing r and Ni, and a second oxide film 6 made of Co oxide formed thereon at a low temperature;
Further, it has a structure having a colored ceramic film 7 on the second oxide film 6. Observation of the coloration state of the colored ceramic film of the laminated glass sample confirmed that the coloration state was good and a neutral color tone was obtained. Also, as a result of analyzing the composition of the second oxide film of the laminated glass sample using X-ray photoelectron spectroscopy,
The content was 74% by mass of Fe, 18% by mass of Cr, and 8% by mass of Ni.

(Evaluation of Optical Characteristics) For the laminated glass samples obtained in Examples 1 and 2, the visible light transmittance and the visible light reflectance of the film-coated surface and the other surface were measured using a C light source by a spectrometer. It measured using. As a result, Example 1
In the laminated glass sample obtained in the above, the visible light transmittance was 32.
%, The visible light reflectance of the film-coated surface was 32%, and the visible light reflectance of the other surface was 21%. In the laminated glass sample obtained in Example 2, the visible light transmittance was 31%, the visible light reflectance of the film-coated surface was 36%, and the visible light reflectance of the other surface was 2%.
1%.

[0035]

The colored glass of the present invention has a surface laminated film,
In particular, the colored ceramics film formed on the colored film containing a Co oxide develops good color, and is excellent in design, heat ray reflectivity, abrasion resistance and chemical resistance. Further, according to the method of the present invention, the colored glass can be manufactured.

[Brief description of the drawings]

FIG. 1 is a conceptual cross-sectional view of a laminated glass sample according to Example 1.

FIG. 2 is a conceptual sectional view of a laminated glass sample according to Example 2.

[Explanation of symbols]

 Reference Signs List 1 glass substrate 2 colored film containing Co oxide 3 colored ceramic film 4 glass substrate 5 first oxide film 6 second oxide film 7 colored ceramic film

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G059 AA01 AB05 AB09 AB11 AC06 AC08 AC18 CA01 CA08 CB09 EA01 EA06 EB04 GA01 GA02 GA04 GA12

Claims (4)

[Claims] 1. A colored glass comprising a glass substrate, a colored film containing a Co oxide formed on the surface of the glass substrate by sputtering, and a colored ceramics film laminated on the colored film. 2. A heat treatment after forming a laminated film in which a colored film has an oxide film (A) containing at least one selected from Fe, Cr and Ni and an oxide film (B) containing Co. The colored glass according to claim 1, which is a film formed by: 3. A method for producing a colored glass, wherein a colored film containing a Co oxide is formed on a surface of a glass substrate by sputtering, and then a colored ceramic paste is applied and heat-treated. 4. The method according to claim 1, wherein Fe, Cr and N
oxide film (A) containing at least one member selected from i
And a laminated film having a Co-containing oxide film (B), and then applying a colored ceramic paste and performing a heat treatment.