JPS6017066A - Formation of colored hard film - Google Patents

Abstract

PURPOSE:To improve the wear and corrosion resistances of a colored film by forming a film of Ti-base nitride, Ti-base carbide or a mixture thereof on the colored film by an ion plating method. CONSTITUTION:A compound film of 0.05-1mum thickness is formed by an ion plating method on a colored film such as an electroplated colored film or a chemically plated colored film on spectacle frames, a wrist watch or the like. The compound film is made of Ti-base nitride, Ti-base carbide or a mixture thereof. The colored film is converted into a colored hard film, and the wear and corrosion resistances are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a colored hard coating, and includes a colored coating such as a coating formed by conventional electroplating or a chemically colored coating, and a coating of a compound containing titanium as a main component. The present invention relates to a method for forming a colored hard coating which can be used in combination with a colored coating having excellent wear resistance and corrosion resistance.

BACKGROUND ART Conventionally, the demand for products coated with electrically colored coatings or chemically colored coatings has been rapidly increasing because they give off an elegant and high-class image. However, each of the above-mentioned coatings has the problem of poor wear resistance, and if used as is, the range of use is limited to areas where there is no effect on wear, that is, areas where frictional contact does not occur.

Therefore, the coating of each of the above-mentioned films in places where frictional contact is frequent, such as glasses and wristwatches, is carried out by applying a further resin coating after this coating, but the fire resistance is still incomplete, especially As a luxury product, the current situation is that it can only be put into practical use.

Therefore, a method has been announced in which a colored film with excellent wear resistance is formed using a titanium compound as a product on the surface of corrugated materials by direct ion plating method, but the color is light (although it can be darkened). At present, it is far from practical use as it is proportionally more brittle (as it is).Also, a method of forming a colored film by thermal spraying has been put into practical use as a colored film with excellent wear resistance. However, the workpiece material itself must be made of a material that can withstand high temperatures, and the surface must not be polished after thermal spraying, which are very big problems that have yet to be resolved. As the demand for products with colored coatings is rapidly increasing, there has been a desire for the rapid development of a method for forming colored coatings with excellent wear resistance at low cost.

This invention was created in view of the above-mentioned points, and is intended to make it possible to easily obtain a beautiful colored coating with excellent wear resistance and corrosion resistance at a low cost.

The details of this invention will be explained below.

The inventor focused on the fact that the skin 11i, which is made mainly of titanium by the ion fist plating method, is hard and highly corrosion resistant.
~, this skin) As a result of various research and experiments based on the idea that if a colored film is formed using 1σ, a colored hard film with excellent wear resistance and corrosion resistance can be obtained. It has been found that a colored coating with excellent abrasion resistance can be obtained by combining a coating of a compound containing titanium as a main component with a colored coating such as a conventional electroplating coating or a chemical colored coating.

Furthermore, in order to reliably obtain this colored film, (after careful research and consideration), on top of a colored film layer such as a film formed by electroplating or a chemically colored film,
By forming a film with a thickness of 0.05μ to 1μ using a titanium-based compound such as nitride, carbide, or a mixture thereof using the ion grating method, it has excellent wear resistance and corrosion resistance. It is now possible to easily obtain an excellent and elegant colored film.

That is, on top of a colored film layer such as a film formed by conventional mixed air colored plating or a chemically colored film formed by chemical plating, two layers are applied by the ion-plating method.
By depositing a compound such as a titanium-based carbide, nitride, or a mixture thereof in a thickness of 0.05μ to 1μ under heating to a temperature of 000 to 500C, porous electroplating is performed. Carbides, nitrides, or mixtures thereof, mainly composed of titanium, are incorporated into the film or chemically colored film, which improves the density of the film itself, improving wear resistance.Moreover, because the film is thin, it is inexpensive. It is something that can be formed. The film thickness of the compound mainly composed of titanium is effective if it is 0.05μ or more.
If the thickness exceeds 1 μm, the color tone of the colored film layer will become the color tone of the compound containing titanium as a main component, and the color tone of the colored film layer as a base will not be utilized at all.

Furthermore, if a film is made of only a compound containing titanium as a main component, the film itself is weak and has poor wear resistance.

The base material may be any material as long as it can form a colored film layer, but preferably stainless steel, iron, copper, alloy of copper and zinc, aluminum, cadmium, zinc, tin, and silver. , nickel-chromium alloys, nickel-based alloys, etc. are even better.

Embodiment 8 of this invention will be described below.

Example 1 Stainless steel 'fi (sus304) i! as base material! !
! The watch band was washed and subjected to cathodic electrolysis for 2 minutes in a solution of 30 ml of sulfuric acid and 150 t/l of citric acid at a current density of 5 A/dmt. After activation, wash with water and apply a commercially available black chrome plating solution Chemicron OR (manufactured by Murayama Chemical) to stain flow density 30A/blood! Plating was performed for 10 minutes under the following conditions to form a colored film layer of black chrome plating with a plating thickness of 1.2 μm.

Further, an ion plating apparatus was placed on top of the above under the conditions of inflowing 300 ml/m of acetylene gas, setting the gas pressure to 5 x 10-TOrr, ionizing voltage of 40 V and current of 10 A, substrate voltage of 0.8 KV, and substrate current of 300 A. When ion plating was performed on titanium (AIH-161108B, manufactured by Shinko Seiki Co., Ltd.) for 30 minutes, a film of a compound mainly composed of titanium was formed with a film thickness of 64 μm without changing the color tone of black chromium.

Therefore, we applied a force of 10 kf using a commercially available abrasive cloth (manufactured by Silvo Shokai, Silvoi) to remove the black chrome plating as-is and the black chrome plating with a film of the titanium-based compound formed on top of the black chrome plating. When we compared the abrasion resistance by rubbing it 910 times (Y test), we found that the stainless steel base of the black chrome plating was exposed, and the stainless steel base of the one with a titanium-based compound film was formed. No abnormality was observed.

Example 2 An eyeglass frame made of nickel silver material (Cu-Zn-Ni alloy) was cleaned, and after nickel plating, black chrome plating was applied for 15 minutes under the same conditions as in Example 1. As a result, The plating thickness of the black chrome plating layer is 1.5
It was μ~1.7μ. Then, on top of this plating layer, add 250ψ-1 nitrogen gas of acetylene gas? :40rn
The ions used in Example 1 were prepared under the following conditions: 1/- inflow, gas pressure of 4XIO Torr, ionization voltage and current of 35V, 1A, substrate voltage and current of 0,1V, and 500 μm.・40% titanium by plating device d
When ion plating was performed for a minute, a film of a compound mainly composed of titanium was formed with a film thickness of 0.5 μm without changing the color tone of black chromium.

Therefore, Example 1. We conducted a wear resistance test using the same method as above, and compared those without and with ion plating, and found that the black chrome plating was worn out and the nickel plating was foggy in the case of the one without ion plating. However, no abnormalities were observed in the ion-plated products. And furthermore,
The ion-plated material was immersed in artificial sweat (corrosion resistance test) for 168 hours, but no abnormalities were observed.

Example 3゜Example 1. , and Example 2. Aeon and
Under the same conditions as plating, the stainless steel base material was directly plated, the nickel silver base material was nickel plated, then regular chrome plating was applied, and titanium was ion-plated on top of that. Example 18, Example 2.
A film of a compound containing titanium as a main component was formed with a film thickness that was almost the same as that of t't.

When the resulting film was subjected to a corrosion resistance test, no abnormalities were observed and good results were obtained. In order to create an image of a luxury product in the color tone, black was strongly applied (ion plating was performed with a large amount of acetylene gas flow, and in terms of color tone, Example 1. Although a black color similar to Example 2 was obtained, when abrasion resistance test and corrosion resistance test were conducted, Example 16 and Example 2
．． The results showed that the quality was very poor compared to the gray case described above.

Example 4゜Example 1. After applying gold-palladium alloy plating to the same core material as in Example 1. When titanium was ion plated under the same conditions as above, a film with a beautiful brown color was formed. At that time, the film thickness of the compound containing titanium as the main component was 0.4 μm. When a wear resistance test and a corrosion resistance test were conducted, very good results were obtained.

Example 5゜Example 2. After applying chemical cobalt plating to the same base material as in Example 2. When titanium was ion-plated under the same conditions as above, a film was formed that had the same color tone as chemical cobalt plating. At that time, the film thickness of the compound containing titanium as the main component was 0.5μ, and a wear resistance test and a corrosion resistance test were conducted, and it was found that it had excellent wear resistance and corrosion resistance. The results were obtained.

As explained above, the present invention provides a method for applying nitrides and carbides containing titanium as a main component, or their titanium-based nitrides and carbides, by an ion plating method on a colored film layer such as an electrically colored film or a chemically colored film. By forming compound skin 1IIIX, such as a mixture, to a film thickness of 0.05μ to 1μ, it is possible to easily create a beautiful hard film that takes advantage of the color tone of the colored film layer as the base and has excellent corrosion resistance and abrasion resistance. Moreover, it can be formed at low cost.

Patent applicant Katsuhiro Okubo 2

Claims (1)

[Claims] 1. On a colored coating layer such as a colored coating or a chemically colored coating, a compound such as a titanium-based nitride, carbide, or a mixture thereof is coated using an ion plating method. A method for forming a colored hard film, characterized in that the film is formed at a film thickness of 0.05 μm to 1 μm.