JP2598521B2 - Manufacturing method of colored mirror - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a colored mirror formed by forming a colored layer on the surface of a transparent substrate, and more particularly, to a method of forming a silicon dioxide film containing an organic colorant on the surface of a transparent substrate. The present invention relates to a formed mirror having excellent chemical and mechanical durability.

[Conventional technology]

For a long time, colored mirrors have been desired to enhance the decorative effect of mirrors. Recently, it has been considered to apply the present invention to a filter mirror that utilizes the effect of increasing or decreasing the reflectance in a specific wavelength region seen in the spectrum of a colored mirror.

By the way, in the case of decorative applications, as a coloring method, a method of coloring the transparent substrate itself or forming a colored layer on the transparent substrate has been adopted. Of these, the coloring of the transparent substrate itself varies depending on the type of substrate material, but basically, a method of mixing a colorant into the substrate material is used.For example, in the case of a glass substrate, an inorganic colorant is mixed into the raw material in a glass manufacturing process. For plastic substrates, a method of mixing a coloring agent such as an organic dye or an organic pigment into raw materials in a plastic manufacturing process has been adopted.

However, the method using an inorganic colorant found on a glass substrate has considered a decorative effect such that it is impossible to apply coloring to a part of the substrate in addition to a small number of colors that can be developed, lack of color saturation, and the like. There were many restrictions above. In this regard, the coloring of plastics using organic colorants is said to be satisfactory in the type and color of the color, but problems common to organic materials, such as moisture and oxygen entering the plastics, etc. However, there are difficulties such as chemical durability against UV light, physical durability against UV light, and the like, and local decoration cannot be performed.

Therefore, a method of forming a colored layer on the surface of a transparent substrate and thereafter forming a metal film has been widely used.
With this method, local coloring can be achieved. However, in this method, for example, in the case of a glass substrate, the formation of an inorganic colored layer is generally performed as seen in a tinting raster. There was a limit. For this reason, attempts have been made to form an organic coloring layer on the surface, mainly of plastic substrates, but since the organic coloring agent is present in the surface layer of the substrate, there are more problems with durability and weather resistance than the coloring of the substrate itself. Was.

On the other hand, in the case of a filter mirror, generally, a multilayer film of three or more layers is required, and it is difficult to apply the filter mirror to a large area due to the difficulty in controlling the film thickness, and there are also problems in terms of cost due to the large number of processes. .

[Problems to be solved by the invention]

In view of the problems of such a colored mirror, the present inventors have conducted intensive studies and as a result, by using a silicon dioxide film containing an organic colorant on the surface of a transparent substrate, the type and color of the color, local coloring can be reduced. It has been found that a colored mirror having high durability and high weather resistance is obtained.

[Means to solve the problem]

The present invention is realized by coating the surface of a transparent substrate with a silicon dioxide film containing an organic colorant such as an organic dye or pigment. As such a method, there is a so-called sol-gel method in which a solution obtained by adding an organic colorant to a hydrolysis solution of a metal alkoxide is brought into contact with a transparent substrate.

For example, as a literature on this manufacturing method, "J. Non
-Cryst. Solids, 74 (1985) 395 ", in which an organic fluorescent dye was introduced into a silicon dioxide thin film, but the obtained organic substance-containing thin film was porous. "Ceramics,
21, No. 2 (1986) 111 ”, organic molecules are doped into amorphous quartz by the sol-gel method, but the resulting glass structure contains residual impurities, strains, defects, etc. It has been reported.

However, in the sol-gel method, it is necessary to heat in the final step in order to fix the film to the substrate, and it is not possible to perform heat treatment at a high temperature at which organic substances are decomposed. There was a problem. Further, an organic substance which is decomposed by heating at a low temperature cannot be introduced into the film. Further, the fact that heating can be performed only at a low temperature further exacerbates the problem inherent in the sol-gel method, and impurities such as undecomposed raw materials and solvents remain in the film. Another problem is that the use of expensive metal alkoxide as a starting material increases the production cost of the membrane. In addition, dip coating or the like is used as a coating method, and this method cannot be applied to a substrate having a complicated shape.

According to the method of the present invention, a transparent substrate is brought into contact with a treatment liquid obtained by adding an organic colorant such as a dye or a pigment to an aqueous solution of hydrosilicofluoric acid containing silicon dioxide in supersaturation, whereby the surface of the substrate is organically colored. The method utilizes formation of a silicon dioxide film containing an agent. In this case, the aqueous solution of hydrosilicofluoric acid containing silicon dioxide in supersaturation is obtained by adding an aqueous solution of hydrosilicofluoric acid to a saturated solution of silicon dioxide with boric acid.
It can be obtained by adding aqueous ammonia / metal halide or a metal having a higher ionization tendency than hydrogen.
Alternatively, it can be obtained by adding silicon dioxide to a low-temperature aqueous solution of hydrosilicofluoric acid and then raising the temperature of the solution (temperature difference method). The organic colorant can be added directly to the treatment liquid as long as 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. In addition, an organic colorant may be added to a saturated solution of hydrosilicofluoric acid in silicon dioxide, or may be added to a solution after silicon dioxide is included in supersaturation. Conditionally, the concentration of hydrosilicofluoric acid is 1.0 mol / or more, preferably
1.5-3.0 mol / is used. Further, the temperature of the processing solution when contacting the transparent substrate is 15 to 60 ° C, preferably 25 to 40 ° C.
In the temperature difference method, silicon dioxide is usually saturated at a temperature of 10 ° C. or lower, and the treatment liquid is brought into contact with the transparent substrate at a temperature of 20 ° C. or higher, preferably 40 to 60 ° C. The method of contact is generally a method of immersing a transparent substrate in a processing solution.

Examples of the organic colorant include dyes and pigments. For example, Diaceriton Fast Red R [DIACELLI
TON FAST RED R] (Mitsubishi Chemical), Blue 5P R-006 [B
LUE 5P R-006] (Tokyo Kasei), Rhodamine 6G [RHODA
MINE 6G], fluorescein [FLUORESCEIN], malachite green [MALACHITE GREEN] (Hodogaya Chemical), coumarin 6 [COUMARIN 6], sulfolodamine B [SULF
O-RHODAMINE B], rhodamine 123, rhodamine 110,
Rhodamine 116, Rhodamine 19, Kayasil Yellow G
G [KAYACYL YELLOW GG] (Nippon Kayaku), Red 21P S
-011 [RED 21P S-011] (Tokyo Kasei), acridine
Red [ACRDIN RED], Carasil Rhodamine FB [KAYA
CYL RHODAMINE FB] (Nippon Kayaku), Red 3P T-01
6 [RED 3P T-016] (Tokyo Kasei), Victoria Blue BH [VICTORIA BLUE BH] (Hodogaya Chemical), Alizarin Astor [ALIZARINE ASTOL] (Tokyo Kasei), Methyl Violet Pure SP [METHYL VIOLET PURE]
SP] (Hodogaya Chemical), Green 10P P-005 [GREEN
10P P-005] (Tokyo Kasei).

On the other hand, the transparent substrate may be a transparent inorganic crystalline substrate other than glass, or an organic material such as plastic. Further, in the method of the present invention, since the silicon dioxide film is formed through the lamination process, a uniform thick layer can be obtained regardless of the surface shape of the substrate. -It may have a convex surface or a complicated surface shape. Further, a substrate made of an organic material such as a polycarbonate resin and an acrylic resin may be used. In this case, in order to form a colored layer having good adhesion, the surface of the organic transparent substrate must be formed by forming at least one selected from the group consisting of an organosilicon compound comprising a silane coupling agent, a hydrolyzate thereof, and colloidal silica. After coating with a silicon compound of some kind, it is desirable to immerse the coating in a processing solution to form a silicon dioxide film containing an organic colorant.

Further, in the method of the present invention, a colored portion and a non-colored portion are provided in a colored mirror, and these are made to look like letters, numbers, pictures, figures, patterns, and patterns, so that prior to the formation of the organic colorant-containing silicon dioxide film, After the transparent substrate surface is masked and the coating is formed in a pattern, a metal film can be formed to enhance the decorative effect.

In this case, the symbol part may be either a colored part or a non-colored part. Further, by forming an organic colorant-containing silicon dioxide film on the entire surface of the transparent substrate, masking the film in a pattern on the film, and removing the film of the non-mask portion by chemical etching or mechanical polishing means. Alternatively, a colored mirror that is locally colored can be formed.

 Hereinafter, embodiments of the present invention will be described.

Example 1 An organic dye-containing silicon dioxide film shown in Table 1 was formed on a glass surface of 1.1 mm thick × 25 mm wide × 50 mm long by an apparatus shown in FIG. 1 to obtain a colored glass. In this case, the water 2 filled in the outer tank 1 was maintained at 35 ° C. by the heater 3.

An inner tank 4 of 500 cc is provided in the outer tank, and an aqueous solution of 2.5 mol / hydrofluoric hydrofluoric acid containing silica gel in saturation is provided therein.
Treatment solution 5 containing 15 cc of a 0.5 mol / boric acid aqueous solution added to 50 cc is maintained at 34 ° C. Further, in order to add a coloring agent to the treatment liquid, the dyes shown in Table 1 were dissolved in water at room temperature to obtain a 5% by weight or saturated addition solution, and 1 cc was added per 100 cc of the hydrosilicofluoric acid aqueous solution. A coloring operation was carried out for each of the dyes shown in FIG. The coloring operation was performed by immersing the sample glass plate 6 in the treatment liquid 5 for 16 hours.

The colored layer thus obtained was analyzed by X-ray photoelectron spectroscopy (ESCA), secondary ion mass spectroscopy (SIMS), infrared spectroscopy (IR), etc. It was confirmed that it was uniformly taken in. Further, the colored glass after the formation of the silicon dioxide was immersed in a 99.5% alcohol solution for 24 hours, but no elution of the organic dye was observed.

Of the organic dye-containing silicon dioxide-coated glass thus obtained, for malachite green, an aluminum (Al) thin film was formed on one side of the glass by a vacuum evaporation method to produce a colored mirror. FIG. 2 shows the reflection spectrum of the colored mirror.

[Example 2] Thickness 1.1 mm x width 25 mm x length 50 m by the apparatus shown in Fig. 1
An organic dye-containing silicon dioxide coating as shown in Table 2 was formed on the glass surface of m to obtain a colored glass. In this case, the treating solution was saturated with an aqueous solution of hydrosilicofluoric acid at −3 ° C. for about 2 hours, and then, in the same manner as in the example shown in Table 2, per 100 cc of the aqueous solution of hydrosilicofluoric acid. Adjusted by adding 1 cc. Thereafter, the treatment liquid was transferred to the inner tank shown in FIG.
The water in the outer tank was heated so that the glass plate was immersed.

The coloring operation was performed for 16 hours, and the results shown in Table 2 were obtained. The obtained colored glass is placed in a 99.5% alcohol solution for 24 hours.
After soaking for an hour, no elution of the organic dye was observed.

Of the organic dye-containing silicon dioxide-coated glass thus obtained, an aluminum (Al) thin film was formed on one surface of Blue 5P R-006 and Diaceriton Fast Red R by a vacuum evaporation method to produce a colored mirror. FIG. 3 and FIG. 4 show reflection spectra of the colored mirror.

From these examples, it can be seen that the present invention can provide a colored mirror having good durability.

[Brief description of the drawings]

FIG. 1 shows an apparatus for producing a silicon dioxide film used in Examples. 2 to 4 show reflection spectra of the colored mirror. 1 ... outer tank, 2 ... water, 3 ... electric heater, 4 ... inner tank, 5 ... treatment liquid, 6 ... transparent substrate, 7 ... stirrer

Claims (4)

(57) [Claims] 1. A method for producing a colored mirror, comprising forming an organic colorant-containing silicon dioxide film on the surface of a transparent substrate and then forming a metal film, wherein the organic colorant-containing silicon dioxide film contains an organic colorant. A method for producing a colored mirror, characterized in that the transparent substrate is formed by immersing the transparent substrate in a treatment liquid comprising an aqueous solution of hydrosilicofluoric acid in which silicon dioxide is in a supersaturated state. 2. The method for producing a colored mirror according to claim 1, wherein the treatment liquid is obtained by adding a dye or a pigment to an aqueous solution of hydrosilicofluoric acid in which silicon dioxide is in a supersaturated state. 3. The method for manufacturing a colored mirror according to claim 1, wherein said substrate is a flat or convex or concave glass or plastic. 4. The method for producing a colored mirror according to claim 1, wherein the organic colorant-containing silicon dioxide film is formed on the substrate in a character, figure, pattern or pattern.