JPH0684537B2 - Gold exterior manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a gold-colored exterior having an expensive and beautiful color tone appearance such as gold color and having excellent surface hardness and corrosion resistance.

[Conventional technology]

BACKGROUND ART Conventionally, exterior parts such as eyeglass frames, watch bands, watch cases, and accessories have been required to have a good color tone, be resistant to scratches, and have good corrosion resistance.

As a processing method satisfying such a condition, for example, Japanese Patent Publication Sho 59
There is a method disclosed in the gold-colored exterior part of Japanese Patent No. 26664.

This method is a method in which a base material such as a watch band or a case made of stainless steel or the like is coated with a hard metal compound such as titanium nitride (TiN) or tantalum nitride (TaN) by an ion plating method.

[Problems to be solved by the invention]

However, in the conventional method, the amount of Au vaporized is relatively large, and it becomes difficult to collect it because it becomes a mixture with a metal compound such as TiN in the vacuum tank of the ion plating apparatus, which is problematic in terms of cost. In addition, when the surface layer is formed by the ion plating method, it is difficult to control the color tone that changes under delicate conditions, and the color tone varies widely. Further, when the Au layer as the surface layer is formed by the wet plating method, there is a problem that TiN itself is in a passive state and thus lacks in adhesion and is easily peeled off.

Therefore, the present invention solves the above-mentioned drawbacks of the related art.
It is an object of the present invention to provide a treatment method which is free from variations in color tone, is not costly, and has no problem in adhesion due to peeling of a surface layer or the like.

[Means for solving problems]

In order to solve the above problems, the present invention forms a titanium nitride, titanium carbonitride, tantalum nitride, tantalum carbide, zirconium nitride or hafnium nitride film on a metal or heat resistant substrate, and One kind of metal film selected from Ni, Cr, Cu, Pd, Co, etc. is formed, and a gold or gold alloy film is formed thereon as a surface layer by a wet plating method. Then, heat treatment was performed to cause thermal diffusion and solve problems such as adhesion.

[Action]

A metal film is formed on a titanium nitride or titanium carbonitride film, etc., and a gold or gold alloy film is formed on the film by wet plating and heat treatment is performed to diffuse the metal film and the gold or gold alloy film on the surface layer. As a result, the metal film on the titanium nitride or titanium carbonitride film is alloyed to form a gold film having very high adhesion and being difficult to peel off.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Example 1 A stainless steel watch band was used as a substrate, degreased and washed with an organic solvent, an acid and an alkali, and then set on a jig provided in an ion plating apparatus called an active reaction vapor deposition system, After evacuation to 5 × 10 ^-5 Torr, 1
Ti was evaporated by electron beam heating in a nitrogen atmosphere of × 10 ^-3 Torr, and discharge plasma was formed by the ion plating mechanism to form titanium nitride (TiN) of about 1 μm on the watch band set on the jig. It was Next, the vacuum was evacuated to 5 × 10 ⁻⁵ Torr again without breaking the vacuum with the same apparatus, and Ni was vapor-deposited with an electron beam to form a Ni film of about 0.02 μm. After that, the watch band is taken out into the atmosphere, pretreated with alkaline acid, etc., and gold alloy plating is performed to about 0.
Form 5 μm and dry. And 5 in a non-oxidizing atmosphere
When heat-treated at 00 ° C for 40 minutes, the Ni metal film thermally diffused into the gold alloy film of the surface layer and was alloyed to form a beautiful color tone with excellent corrosion resistance and adhesion.

Example 2 A stainless steel watch band was used as a base material, degreased and washed with an organic solvent, an alkali and an acid, and then set on a jig provided in an ion plating apparatus called an active reaction vapor deposition system. After evacuating to × 10 ^-5 Torr, 1 ×
Ti is evaporated by electron beam heating at 10 ^-4 Torr to form ionized Ti in a watch band, and Ti is evaporated in a nitrogen atmosphere into which a nitrogen gas is introduced to form a TiN film. Ti
And a TiN film to form about 1.0 μm. Next, the same apparatus was used to evacuate to 5 × 10 ⁻⁵ Torr again without breaking the vacuum, and Pd was evaporated by an electron beam to form a Pd film of about 0.02 μm. After that, remove the watch band into the atmosphere, degrease it with alkali, acid, etc., wash it, and apply gold alloy plating to about 1.
Form 0 μm and dry. When heat treatment was performed at 500 ° C for 1 hour in a non-oxidizing atmosphere, the Pd metal film was thermally diffused into the metal layer of the surface layer and was alloyed to have good corrosion resistance and adhesion, and was beautiful. It became a golden color.

As described above, the watch bands treated by the methods of Examples 1 and 2 showed good results in the artificial sweat intermittent test. In particular, the tape adhesion test further confirmed the good adhesion.

〔The invention's effect〕

As described above, in the treatment method according to the present invention, a titanium nitride or titanium carbonitride film is formed on a metal or heat resistant substrate by an ion plating method, and then N
A metal film of i, Pd, Co, Cu or the like is formed by an ion plating method, a sputtering method, or a vacuum evaporation method, and a gold or gold alloy film is formed as a surface layer by a wet plating method. Then, a treatment method in which the gold or gold alloy film of the surface layer and the metal film on the titanium nitride or titanium carbonitride film are thermally diffused by heat treatment.

Therefore, according to this treatment method, not only the color tone and surface hardness but also the corrosion resistance are excellent, and in particular, the surface layer having excellent adhesion can be formed.

Further, the following points can be listed as effects associated with the heat treatment.

First, if the metal film on the titanium nitride or titanium carbonitride film is made of nickel, cobalt, copper, etc., which has a relatively poor chemical resistance, the pinhole should be thinned as the surface gold is thinned. If the heat treatment is not performed, the above-mentioned layer is corroded by sweat or the like and the gold is peeled off. The heat treatment has the effect of reducing the cost by diffusing this point with gold and reducing the thickness of gold.

Also, because heat treatment is performed, a gold alloy, which is usually difficult to perform by wet plating, is formed on titanium nitride or titanium carbonitride as a metal layer that is difficult to plate as a gold alloy. It is also possible to make it as an alloy and make gold alloys of various tones.

Although the heat treatment conditions were limited in the examples, the heat treatment condition in the treatment method according to the present invention is set to a heat treatment temperature of 250 depending on the substrate.
It can be appropriately selected within the range of to 500 ° C. Similarly, the thickness of the metal film is limited to 0.02μ in the example, but this is for adjusting the color tone at the time of each alloying with gold plating, and the alloying can be performed depending on the required gold plating thickness and color tone. Easy thickness,
It is preferably 0.1 μ or less and can be appropriately selected.

Front page continuation (72) Inventor Matsuo Kishi 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Co., Ltd. (56) References Japanese Patent Publication No. 59-26664 (JP, B2) Japanese Patent Laid-Open No. 59- 53669 (JP, A) JP-A-59-53670 (JP, A)

Claims (1)

[Claims] 1. A titanium nitride, titanium carbonitride, tantalum nitride, tantalum carbide, zirconium nitride, or hafnium nitride film is formed on a metal or heat-resistant substrate, and then Ni, Cr, Cu, Pd, or Co is formed thereon. A gold-colored exterior characterized by forming a selected one kind of metal film by an ion plating method, a sputtering method or a vacuum deposition method, further forming a gold or gold alloy film by a wet plating method, and then performing heat diffusion. Manufacturing method.