JPH0761882B2 - Tinted glass - Google Patents

Description

TECHNICAL FIELD The present invention relates to a colored glass obtained by forming a colored layer on the surface of glass having an uneven surface, and more specifically, an organic coloring agent on the uneven glass surface. The present invention relates to the provision of a colored glass having an enhanced decorative function, which is formed by forming a silicon dioxide film containing the glass.

[Conventional technology]

In order to enhance the decorative effect of glass, template glass having a pattern of unevenness on its surface has been used for a long time.
Further, roughening the surface of glass has also been widely used in order to enhance the antiglare property of glass or to suppress the transparency. For example, frosted glass in which the glass surface is rubbed with a metal brush is a typical example, and in addition to this, surface roughening by sandblasting, etching of the glass surface with a hydrofluoric acid-based solution, and the like are also available.

Such glass having an uneven surface has been widely used for various purposes such as decoration, suppression of see-through, and antiglare property.

In recent years, attempts have been actively made to color this kind of glass to improve the decorative effect and aesthetics and to realize a more comfortable living space. Two methods have been mainly attempted as a method of coloring glass having such an uneven surface. One of them is a method of changing the composition of the glass and using a colored glass. For example, C for glass raw materials
Mixing oxides of transition metals such as o, Ni, Fe and Cr, and engraving the glass colored with these transition metal ions on the glass surface with a roll having a pattern of unevenness when in a softened state during molding, a so-called Colored slabs have also been tried. However, with this method, the colors that can be developed are blue, green, yellow,
Since it is limited to cold colors such as gray and has few types of colors, and above all, it melts raw materials containing a colorant in a glass melting furnace, so it was extremely unsuitable for multi-product small-volume production colored glass. Therefore, it has been attempted to form a transparent colored layer on the glass having an uneven surface.

A typical example is a thermal decomposition method in which an organic solvent solution containing an organometallic compound and a noble metal compound is applied to flat glass as represented by a raster, and then heat treatment is performed at 450 to 550 ° C. Alternatively, apply a paste containing a noble metal compound such as Au, Ag, or Cu to flat glass, and then 500 to 600 ° C.
A method of injecting a noble metal element into the glass by an ion exchange method to cause color development was also studied. Both methods utilize the color development of the metal colloid, and the pyrolysis method produces the noble metal colloid in the metal oxide, and the ion exchange method produces the noble metal colloid in the surface layer of the glass. However, even in these methods, the color that can be developed is limited and it is a cold color system. Above all, the biggest problem with conventional coating methods such as the spray method and the dip coating method (dipping method) is that the glass surface is uneven. A uniform thick colored layer cannot be formed. That is, there was a case that the coloring unevenness was not remarkable and could not be put to practical use.

[Problems to be solved by the invention]

The inventors of the present invention have earnestly studied in view of the problem of the coloring technology of glass having irregularities on the surface, and as a result, by forming a silicon dioxide coating containing an organic coloring agent on the glass surface, the characteristics of the organic coloring agent are improved. That is, it has been found that a chemically and mechanically stable colored layer utilizing a wide variety of colors and color vividness can be obtained, and the problems of the prior art can be almost completely solved.

[Means for solving problems]

In the method of the present invention, a treatment liquid obtained by adding an organic colorant such as a dye or pigment to an aqueous solution of hydrofluoric acid containing silicon dioxide in supersaturation is brought into contact with a glass having an uneven surface It is used to form a silicon dioxide film containing an organic colorant on the. In this case, an aqueous solution of hydrosilicofluoric acid containing silicon dioxide in a supersaturated state is a solution of hydrofluoric hydrofluoric acid saturated with silicon dioxide in which boric acid, ammonia water, a metal halide, or a metal having a greater ionization tendency than hydrogen. It is obtained by adding Alternatively, it can also be obtained by adding silicon dioxide to a low temperature aqueous solution of hydrofluoric acid and then raising the temperature of the solution (temperature difference method). The organic colorant can be added directly to the treatment liquid if it is water-soluble, and even if it is insoluble in water, it is dissolved in a water-soluble organic solvent such as alcohol and then added to the treatment liquid. It can also be added. As for the method of addition, an organic colorant may be added to a silicon dioxide saturated solution of hydrofluoric acid, or may be added to a solution after the state in which silicon dioxide is contained in supersaturation. Conditionally, the concentration of hydrofluoric acid is 1.0 mol / l or more, preferably 1.5 to 3.0 mol / l. Also, the temperature of the processing liquid when contacting the glass is 15 to 60 ° C, preferably 25 to 40 ° C.
In the temperature difference method, the silicon dioxide is usually saturated at a temperature of 10 ° C or lower, and the treatment liquid and glass are brought into contact with each other at a temperature of 20 ° C or higher, preferably 40 to 60 ° C. As a method of contact, a method of immersing glass in a treatment liquid is generally used.

Examples of organic colorants include dyes and pigments. For example, Diaceritone Fast Red R [DIACELLI
TON FAST RED R] (Mitsubishi Kasei), Blue 5P R-006 [BLUE
5P R-006] (Nippon Kayaku), Rhodamine 6G [RHODAMINE
6G], Fluorescein [FLUORESCEIN], Malachite Green [MALACHITE GREEN] (Hodogaya Kagaku), Coumarin 6 [COUMARIN 6], Sulforhodamine B [SULFORHO
DAMINE B], Rhodamine 123, Rhodamine 110, Rhodamine 116, Rhodamine 19, Kayasil Yellow GG [K
AYACYL YELLOW GG] (Nippon Kayaku), Red 21P S-011
[RED 21P S-011] (Nippon Kayaku), Acridine Red [ACRDIN RED], Kayasil Rhodamine FB [KAYACYL RH]
ODAMINE FB] (Nippon Kayaku), red 3P T-016 [RED 3P
T-016] (Nippon Kayaku), Victoria Blue BH [VICT
ORIA BLUE BH] (Hodogaya Kagaku), ALIZARINE ASTOL (Tokyo Kasei), Methyl Violet Pure SP [METHYL VIOLET PURE SP] (Hodogaya Kagaku), Green 10P P-005 [GREEN 10P P-005]
(Nippon Kayaku), etc.

On the other hand, as a glass having an uneven surface, template glass
Or, a molten glass of colored low melting point glass is poured on a flat glass in a pattern and then solidified, or mechanically processed glass such as frosted glass or sandblasted glass or glass whose surface is etched with a hydrofluoric acid-based aqueous solution.・ Mostly concavo-convex glass for the purpose of suppressing see-through and anti-glare.

Next, the present invention will be described more specifically with reference to examples.
The present invention is not limited to the following examples unless it exceeds the gist.

[Example 1] 75 mm long, 25 mm wide, and 4 mm thick with the same dimensions and thickness of 1 mm as the template glass.
The mm slide glass was thoroughly washed and dried to obtain a sample base material.

Next, various laser dyes were dissolved in distilled water at room temperature to prepare a 5 wt% or saturated additive solution.

Also, silica gel saturated hydrofluoric acid aqueous solution 100c
8 ml of 0.5 mol / l boric acid solution added to c, or 100 cc of the above hydrofluoric acid solution,
What dissolved 0.4g was made into the process liquid. This processing liquid 100cc
Was placed in a beaker, 1 cc of each laser dye was added and stirred, and the mixture was set on a water bath at 35 ° C. and heated. Each of the above sample substrates was immersed in this solution for 1 hour, held for 16 hours, taken out, washed and dried.

Table 1 shows the types of added laser dyes and the experimental results. The film thickness of the silicon dioxide film was measured on a slide glass with a contact needle type film thickness measuring device.

These laser dyes are available in X-ray photoelectron spectroscopy (ESC
A), secondary ion mass spectrometry (SIMS), infrared spectroscopy (I
As a result of analysis by R), etc., it was confirmed that they were uniformly incorporated in the film. The substrate on which the silicon film was formed was immersed in a 99.5% alcohol solution for 24 hours, but no elution of the organic dye was observed.

Further, no peeling of the silicon dioxide film was observed by the tape test or the sponge wiping test.

[Example 2] 75 mm long, 25 mm wide, and 4 mm thick with the same dimensions as the template glass, but with a thickness of 1
The mm slide glass was thoroughly washed and dried to obtain a sample base material.

Next, various dyes were dissolved in distilled water at room temperature to obtain 5% by weight.
Alternatively, a saturated addition solution was prepared.

Also, silica gel saturated hydrofluoric acid aqueous solution 100c
8cc of 0.5 mol / l boric acid solution added to c, or 100cc of the above hydrofluoric acid solution, to
g Dissolved product was used as a treatment liquid. Take 100cc of this treatment liquid in a beaker, add 1cc of each dye and stir.
Set on a water bath and heated. Each of the above sample substrates was immersed in this solution for 1 hour, held for 16 hours, taken out, washed and dried.

Table 2 shows the types of added dyes and the experimental results. The thickness of the silicon dioxide film was measured on a slide glass with a contact needle type film thickness measuring device.

As a result of analysis by ESCA, SIMS, IR, etc., it was confirmed that these dyes were uniformly incorporated in the film.

Further, the substrate after the silicon dioxide film formation was immersed in a 99.5% alcohol solution for 24 hours, but no elution of the organic dye was observed. Further, no peeling of the silicon dioxide film was observed by the tape test or the sponge wiping test.

[Example 3] 75 mm long, 25 mm wide, and 4 mm thick with the same dimensions and thickness of 1 mm.
The mm slide glass was thoroughly washed and dried to obtain a sample base material.

Next, the disperse dye Diaceritone Fast Red (Mitsubishi Kasei) was dispersed in distilled water at room temperature to give a 5% by weight additive solution.

Also, silica gel saturated hydrofluoric acid aqueous solution 100c
A solution obtained by dissolving 0.4 g of metallic aluminum in c was used as a treatment liquid. Take this treatment liquid in a beaker and add 1cc of the above disperse dye.
Was added and stirred, set on a water bath at 35 ° C. and heated. One sample substrate was immersed in this solution, held for 16 hours, taken out, washed and dried.

The created silicon dioxide film shows a red color, and the film thickness of the slide glass measured with a contact needle type film thickness meter is 7300Å
Met.

As a result of analysis by ESCA, SIMS, IR, etc., it was confirmed that this disperse dye was uniformly incorporated in the film.
Furthermore, the substrate after the silicon dioxide film formation was immersed in a 99.5% alcohol solution for 24 hours, but no elution of the disperse dye was observed.

Further, no peeling of the silicon dioxide film was observed by the tape test or the sponge wiping test.

Claims (5)

[Claims] 1. A colored glass obtained by forming a silicon dioxide coating containing an organic coloring agent on the surface of glass having irregularities on the surface. 2. The colored glass according to claim 1, wherein the glass having irregularities is a template glass. 3. The colored glass according to claim 1, wherein the glass having irregularities is a glass whose surface is roughened by chemical etching or mechanical grinding. 4. The colored glass according to claim 1, wherein the organic coloring agent is a dye or a pigment. 5. A silicon dioxide coating containing an organic colorant,
Formed on the glass surface by contacting the treatment liquid consisting of an aqueous solution of hydrofluoric silicic acid in a supersaturated state of silicon dioxide with an organic colorant such as a dye / pigment with the glass with an uneven surface The colored glass according to any one of claims 1 to 4, wherein the colored glass is formed.