JPH03100184A - Colored metal body - Google Patents

Abstract

PURPOSE:To produce a metal body with a colored layer having high durability and a significant ornamental effect by coating the surface of a metal body with a coating film of an inorg. compd. and further forming a silicon dioxide coating film contg. an org. colorant. CONSTITUTION:An inorg. coating film of a metal oxide such as TiO2 or ZrO2 or an inorg. compd. contg. Si such as SiO2 or Si3N4 is formed on the surface of a metal body by a thin film forming process. The metal body is then brought into contact with a treating soln. prepd. by adding an org. colorant such as a dye or pigment to an aq. soln. of hydrosilicofluoric acid contg. supersatd. silicon dioxide to form a silicon dioxide coating film contg. the org. colorant on the inorg. coating film. A stable colored layer having a vivid color can be formed on the surface of the metal body and the color can be chosen from various colors.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a metal body subjected to a coloring treatment.
The present invention relates to a metal body having a highly durable and highly decorative colored layer formed by forming a silicon dioxide film containing an organic colorant on its surface.

[Conventional technology]

BACKGROUND OF THE INVENTION In order to enhance the decorative effect of metal bodies, it has been practiced for a long time to form a colored layer on the surface of the metal body.

For example, in the chemical coloring method represented by the black dyeing method, a metal object is immersed in an aqueous solution containing potassium sulfide, potassium persulfate, etc., and the surface is sulfurized or oxidized. This is a method that utilizes This method is
Although it can be applied to metal bodies such as copper, iron, and aluminum, it is not necessarily common, and there is a problem in that the colors that can be produced are limited to black. In contrast, an anodizing method was devised for the purpose of applying this method to metal bodies to which this chemical coloring method cannot be applied, such as stainless steel, and has come to be widely put into practical use. Anodizing aluminum is a typical example; the resulting oxide layer is porous and colorless, but it was possible to color it by contacting it with a solution containing an organic dye.

In addition, metal bodies are treated with phosphates or chromates,
Although it is possible to form a porous colored layer on the surface, the types of colors are extremely limited, and organic dyes have to be used for coloring. However, when coloring the porous layer with dye through these anodizing and chemical conversion treatments, most of the processes are opaque and the bare surface of the metal body cannot be seen, and the pores are sealed after the dye itself is adsorbed into the porous pores. In addition to requiring a sealing process and requiring a complicated process, the dye is susceptible to deterioration due to moisture that enters through the sealing wall, resulting in discoloration. Also,
There are only a limited number of metal bodies that can be treated with such pores, and it is difficult to say that this method is suitable for boat fishing.

For this reason, attempts have been made to use the dispersion plating method to co-deposit metal particles with organic and inorganic pigment particles to color the surface of the metal body, but this also results in a thick coating layer, making the surface of the metal body visible. In addition, there were practical limitations such as the acid resistance of the eutectoid metal particles.

[Problem that the invention seeks to solve]

Adding arbitrary colors to the surface of metal objects has long been a topic of great interest, but there are many problems such as the type of color, the types of metal objects to which it can be applied, and the durability of the colored layer. I couldn't get anything satisfactory.

[Means to solve problems]

The inventors of the present invention have conducted extensive research in view of the problems in the coloring technology for the surface of metal bodies. After coating the metal surface with an inorganic compound film in advance, a silicon dioxide film containing an organic colorant is coated on the inorganic compound film. By forming a chemically and mechanically stable colored layer that takes advantage of the characteristics of organic colorants, namely the rich variety of colors and the vividness of the colors, the problems of conventional technology are almost completely resolved. I discovered that.

In this case, the inorganic compound coating may be formed by chemically treating the surface of the metal body and oxidizing or sulfurizing the surface to form an oxide layer or sulfide layer, or by electrochemically forming anodization. It may be a layer. Well-known chemical conversion treatment and anodic oxidation treatment are used as means for modifying the surface of the metal body. Furthermore, instead of such a surface modification layer, a metal body having an inorganic compound coating formed on its surface may also be used. In this case, the inorganic compounds include 5iOz,
T i 02.7. r02, Fe2O3, Cr, ○8,
Al2O3, Coo, C0203, Nip, Ta2
Most inorganic compounds can be applied, such as oxides such as e, carbides such as SiC and Tic, and nitrides such as 5iaN4, TiN, and CrN, but from the decorative effect of seeing through the metal surface. Oxides with good light transmittance are desirable; on the other hand, SiO2 and Sin are preferable in terms of adhesion to the silicon dioxide film containing the organic colorant.

Inorganic compounds containing Si such as Si3N or metal silicide are preferred. Further, it goes without saying that these inorganic compounds may be used alone or in a mixture of a plurality of compounds.

Furthermore, a film in which these inorganic compounds are dispersed in an organic substance can also be used.

As a method for forming such a free compound film, most thin film forming methods such as spray method, CVD method, dipping method, vacuum evaporation method, sputtering method, ion blating method,
The Metsuki method and the like are used, and there is no need to explain them in detail. However, organic thin films using inorganic compounds as a medium,
In other words, it is desirable to use the generally known dispersion plating method for forming the composite film.

Further, the metal body does not necessarily have to be entirely made of metal, and may be an inorganic substance other than metal or an organic substance whose surface is coated with a metal film. The shape is also flat,
It does not particularly matter whether it is a curved molded body, spherical shape, fine particle shape, etc.

On the other hand, regarding the formation of a silicon dioxide film containing an organic colorant, in the method of the present invention, a treatment solution is prepared by adding an organic colorant such as a dye or a pigment to an aqueous solution of hydrosilicofluoric acid containing supersaturated silicon dioxide. This method utilizes the fact that a silicon dioxide film containing an organic colorant is formed on the surface of the metal body by bringing the metal body previously coated with an inorganic compound film into contact with the metal body. In this case, an aqueous solution of hydrosilicofluoric acid containing supersaturated silicon dioxide is prepared by adding boric acid, aqueous ammonia, a metal halide, or a metal having a greater ionization tendency than hydrogen to an aqueous solution of hydrosilicofluoric acid that is saturated with silicon dioxide. Obtained by adding. Alternatively, it can also be obtained by adding silicon dioxide to a low-temperature aqueous solution of hydrosilicofluoric acid and then increasing the temperature of the solution (temperature difference method). When adding an organic colorant, if it is water-soluble, it can be added directly to the processing solution, or even if it is insoluble in water, it can be added to the processing solution after being dissolved in a water-soluble organic solvent such as alcohol. It can also be added. Further, the organic colorant may be added to a saturated solution of silicon dioxide in hydrosilicofluoric acid, or may be added to a solution that has been made to contain silicon dioxide in a supersaturated state. In terms of conditions, the concentration of hydrosilicofluoric acid is 1.0 mol/2 or more, preferably 1.5 to 3.0 mol/J2
is used.

In addition, the temperature of the treatment liquid when contacting the inorganic compound-coated metal body is 15 to 60°C, preferably 25 to 40°C, and in the temperature difference method, silicon dioxide is usually saturated at a temperature of 10°C or less, and 20°C As mentioned above, the treatment liquid and the metal body are preferably brought into contact at a temperature of 40 to 60°C. The method of contact is - For boat fishing, a method is used in which the metal body coated with an inorganic compound is immersed in the treatment liquid.

Examples of organic colorants include dyes, pigments, etc. For example, Diaceliton Fast Red R [DIACEL
LITON FAST RED R] (Mitsubishi Chemical),
BLUE 5P R-006 [BLUE 5P R-00
6co (Nippon Kayaku), Rhodamine 6G [R) IOD
AMINE 6G, Fluorescein [FLUORE]
SCEIN, malachite green [MALACI(
ITE GREEN] (Hodogaya Chemical), Coumarin 6
[COUMARIN 6], Sulforhodamine B [5
ULFO-R [(ODAMINE B, Rhodamine
123, Rhodamine 11010-Damine 116, Rhodamine 19, Kayacyl Yellow〇G [KAYACY
L YELLOW GG] (Nippon Kayaku), Red 21
P S-011 [RED 21P S-〇11 (Nippon Kayaku), Acridine Red [ACRDIN RED
KAYACYL Rhodamine F B [KAYACYL R
HODAMINE FB] (Nippon Kayaku), Red 3P
T-018 [RED3P T-016] (Nippon Kayaku)
, Victoria Blue BH [VICTORIA BLUE
BH Co (Hodogaya Chemical), Alizarin Astol [AL
IZARINE ASTOL] (Nippon Kayaku), Methi/L
/ Violet t:' Near-8P [METHY
L VIOLETPURE SF3 (Hodogaya Chemical),
Green IOP P-005' [GREEN IO
Examples include PP-005 (Tokyo Kasei).

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

[Example 1] A sample substrate was prepared by forming 1,000 SiO2 films by a sol-gel method on a stainless steel plate measuring 75 mm long, 25 mm wide, and 1 mm thick.

Next, various laser dyes were dissolved in distilled water at room temperature to give 5% by weight or saturated additive solutions.

In addition, silica gel saturated hydrosilicofluoric acid aqueous solution 10
Add 8 cc of 0.5 mol/1 boric acid aqueous solution to 0 cc.
or the above aqueous solution of hydrosilicofluoric acid 100c
A treatment solution was prepared by dissolving 0.4 g of metallic aluminum in c. Take 100 cc of this treatment liquid in a beaker,
Add 1 cc of each laser dye and stir at 35°C.
was placed on a water bath and heated. Each of the sample substrates was immersed one by one in this solution and held for 16 hours, then
It was taken out, washed and dried.

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

These laser dyes can be used for X-ray photoelectron spectroscopy (ESC).
As a result of analysis using secondary ion mass spectrometry (SIMS), infrared spectroscopy (IR), etc., it was confirmed that the particles were uniformly incorporated into the film.

Further, the substrate after the silicon dioxide film was formed was immersed in a 99.5% alcohol solution for 24 hours, but no elution of the organic dye was observed.

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

[Example 2] 1000 AI films were formed by sputtering on a glass slide measuring 75 mm long, 25 mm wide, and 1 mm thick, and then a 5in2 film was formed on the surface by sputtering again for 300 people, and this was used as a sample base. It was used as a material.

Next, various dyes were dissolved in distilled water at room temperature, and 5% by weight
Or a saturated additive solution.

In addition, silica gel saturated hydrosilicofluoric acid aqueous solution 10
Add 8 cc of 0.5 mol/1 boric acid aqueous solution to 0 cc.
or the above aqueous solution of hydrosilicofluoric acid 100c
A treatment liquid was prepared by dissolving 0.4 g of metallic aluminum in c. 100 cc of this treatment solution was placed in a beaker, 1 cc of each dye was added and stirred, and the beaker was placed on a 35° C. water bath and heated. Each of the sample substrates was immersed one by one in this solution, held for 16 hours, and then taken out and washed and dried.

Table 2 shows the types of dyes added and the experimental results.

The thickness of the silicon dioxide film was measured using a contact needle type film thickness measuring device.

Table 2 These dyes were analyzed by ESCA, SIMS, IRl, etc., and it was confirmed that they were uniformly incorporated into the film.

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

[Example 3] A sample substrate was prepared by forming 1000 TiO□ films by a sol-gel method on a stainless steel plate measuring 75 mm long, 25 mm wide, and 1 mm thick.

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

In addition, silica gel saturated hydrosilicofluoric acid aqueous solution 10
A treatment liquid was prepared by dissolving 0.4 g of metallic aluminum in 0 cc of aluminum. This treatment solution was placed in a beaker, 1 cc of the above disperse dye was added thereto, stirred, and placed on a 35° C. water bath to warm it. One piece of the above sample base material was immersed in this solution.
After holding for 6 hours, it was taken out, washed and dried.

The produced silicon dioxide film exhibited a red color, and the film thickness measured with a contact needle type film thickness measuring device was 7,300.

As a result of analysis using ESCASSIMS, IR, etc., it was confirmed that this disperse dye was uniformly incorporated into the film. Furthermore, the substrate after silicon dioxide film formation was heated to 99.
Although it was immersed in a 5% alcohol solution for 24 hours, no elution of the disperse dye was observed.

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

Claims (6)

[Claims] (1) A metal body that has been subjected to a coloring process by forming a silicon dioxide film containing an organic colorant on the surface of a metal body coated with an inorganic compound film. (2) Claim 1, characterized in that the inorganic compound coating is an inorganic compound containing a metal oxide or Si.
A metal object that has been subjected to the coloring treatment described in . (3) A metal body subjected to a coloring treatment according to claims 1 to 2, wherein the organic colorant is a dye or a pigment. (4) The silicon dioxide film containing the organic colorant is coated with a dye in an aqueous solution of hydrosilicofluoric acid that is supersaturated with silicon dioxide.
It is characterized in that it is formed on the inorganic compound coating on the surface of the metal body by bringing a treatment liquid containing an organic coloring agent such as a pigment into contact with a metal body whose surface has been previously coated with an inorganic compound coating. A metal body subjected to a coloring treatment according to claims 1 to 3. (5) A metal body subjected to a coloring treatment according to any one of claims 1 to 4, characterized in that the metal body is made of a non-metal body whose surface is coated with a metal film. (6) A metal subjected to a coloring treatment according to claims 1 to 5, wherein the inorganic compound coating is a composite coating in which an organic substance is used as a dispersion medium and an inorganic compound is used as a medium. body.