JP2719560B2 - Exterior parts having a gold layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention can be used for a gold exterior article, for example, a watch side, a band or a finger ring, a necklace, eyeglasses, and other accessories.

[Prior Art] A watch, a hand thereof, or a jewelry material such as a finger ring, a necklace, eyeglasses, or the like has conventionally been made of gold or plated with gold because of its excellent color tone and corrosion resistance. .

However, since gold is an expensive metal, forming a thick coating layer having sufficient corrosion resistance and abrasion resistance puts a great economic burden.

In order to reduce this burden, various gold-colored alloys have been conventionally proposed and widely used, but they have not been satisfactory.

At this time, a base layer made of a metal nitride exhibiting a golden color, for example, titanium nitride (hereinafter referred to as TiN) is provided by a method such as ion plating or sputtering, and a finishing layer made of gold or a gold alloy is provided thereon. There has been proposed an exterior component having a gold coating layer.

However, although the color tone is monotonous because of the simple composition of TiN, if the formation conditions of the layer slightly change, the physical properties of the formed TiN layer change and it is difficult to make the quality as a product uniform. there were.

[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems of the prior art, and has an object to provide an exterior component having a coating layer having a wider color tone range than TiN and having high wear resistance. I have.

[Means for Solving the Problems] According to the structure of the present invention for solving the above problems, the molar ratio of titanium (Ti) to aluminum (Al) is 2/8 to 8
/ 2, a base layer composed of a composite nitride of titanium and aluminum in the range of 2, and an exterior component having a finishing layer made of gold or a gold alloy provided thereon, and in particular, the alloy of the finishing layer is made of nickel and palladium. And an outer package made of gold and indium.

The color tone of the base layer changes depending on the molar ratio between Ti and Al in the base layer. If the Ti content is less than 2/8 in molar ratio, the gray color tends to increase, and if it exceeds 5/5, the color tends to brown. The optimal molar ratio is 7/3, which tends to be golden. Further, when it exceeds 8/2, it takes on a green color, practicability as a gold color is lost, and the hardness is significantly reduced.

The thickness of the base layer is suitably 0.5 μm, and if it is less than 0.1 μm, color tone cannot be stabilized, and there is a problem in corrosion resistance.
If it exceeds 5.0 μm, there is a risk of generation of microcracks. A range of approximately 0.1-5.0 μm is suitable.

Although a suitable means for forming the base layer is sputtering, it can also be formed by ion plating.

This base layer is harder than the conventional TiN layer (Vickers hardness about 1000 HV) and has a Vickers hardness of about 2000
HV or more. Since the surface is slightly rougher than the surface of gold or gold alloy plating, plating gold or gold alloy on the surface of the base layer made of this Ti-Al composite nitride only strongly bonds these metal plating layers. Instead, even if the surface metal plating layer wears, the metal plated in the recesses of the base layer is protected by the hard nitride layer of the projections and does not wear away, so the color of the metal plating layer on the surface is It is not lost at all and has a long life as an exterior product.

The gold or gold alloy layer (finish layer) to be plated on the base layer will be described. First, the thickness of this plating layer is
0.1 μm is appropriate. If it is less than 0.05 μm, the color tone is unstable, and if it exceeds 1.0 μm, it is uneconomical. About 0.05-1.0
The range of μm is appropriate.

Among the components of the finishing layer, gold is a target gold base component, and its amount is suitably 90 to 99.9%.

Indium is a component that adjusts the color tone.
0.1% to 3%.

Nickel is a component that adjusts the color tone and increases the hardness, and its appropriate amount is 0.1 to 5%.

Palladium is a component that adjusts the color tone and increases hardness and corrosion resistance, and its amount is 0.1 to 5%.

In order to form the gold or gold alloy plating layer, vacuum evaporation or ordinary electrochemical plating is used.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples.

Example A stainless steel watch band was washed with an organic solvent and set in a sputtering apparatus. In this case, a Ti-Al target having a molar ratio of 7/3 was prepared on one side, and the other was Au-N
A target composed of a 23.5 kt gold alloy of i-In was prepared.

The sputtering apparatus is then evacuated to 3 × 10 ^-5 mbar, argon gas is introduced to a partial pressure of 1.7 × 10 ^-2 mbar for the purpose of etching the watch band, and a DC voltage of 1400 V is applied to the watch band. The etching was performed for about 25 hours.

After the etching is completed, exhaust is performed and nitrogen gas is supplied at 50 ml / s.
ec and argon gas were introduced into the apparatus under the condition of 180 ml / sec.

Then apply a board voltage of 157V to the wristband,
A DC voltage of 550 V is applied to the Ti-Al target to form a plasma, and a gold 7/3 molar ratio of T
An i-AlN film was formed with a thickness of 1.0 μm. Further, a substrate voltage of 95 V is applied to the wristwatch band coated with the Ti-AlN film, and a 550 V DC voltage is applied to the Au-Ni-In target to form a plasma, and the Au-Ni film is formed on the Ti-AlN film. −In
Was formed in a thickness of 0.1 μm.

The watch band thus obtained had the same international standards as conventional wet gold plating in the range of 1N14 and 2N18, and also had better appearance and quality than wet gold plating.

Although the thickness of the gold of the finishing layer is extremely thin as compared with the wet plating, the Ti-AlN color tone of the base layer is similar to that of the finishing Au-Ni-In layer, so even if the finishing layer is worn, it is almost conspicuous. And the base Ti-AlN layer is about 2 times that of a general gold TiN layer.
Because it has twice the hardness (2000 HV or more), the stainless steel substrate is not exposed.

The Ti-AlN layer is not only hard but also has excellent corrosion resistance due to its dense film properties.
In the results of the 24-hour continuous test and the artificial sweat total immersion test for 24 hours, no abnormalities such as rust and discoloration were observed at all.

In the abrasion resistance test, the test was carried out with a 500 g load cowhide, but the abrasion resistance was more than 100 times that of the conventional gold plating.

Example 2 A watch case made of brass and a nickel-white material was treated with nickel plating and Pd-Ni plating by wet plating, and then a Ti-AlN and Au-Ni-In finishing layer was formed under the same conditions as in Example 1. Do.

Brass and nickel-white materials have poor corrosion resistance as they are, and by applying nickel plating and Pd-Ni plating on the material, the corrosion resistance is greatly improved, and golden Ti-Al
By coating with N and Au-Ni-In, a color tone and appearance superior to those of conventional wet gold plating quality were obtained, and a watch case excellent in corrosion resistance and abrasion resistance was obtained.

Example 3 A stainless steel watch case was washed with an organic solvent and set in an ion plating apparatus.

The ion plating apparatus was evacuated to 5 × 10 ⁻⁵ mbar, argon gas was introduced to 2 × 10 ⁻² mbar, a DC voltage of about 800 V was applied to the set watch case, bombardment was performed, and exhaust was performed. Thereafter, nitrogen gas was introduced, and Ti and Al of the evaporation sources separately prepared under conditions of 7 × 10 ⁻⁴ mbar were evaporated by separate electron beam heating, and a 7/3 molar ratio of Ti—AlN was added to the watch case. Alloy film
It was formed with a film thickness of 1.0 μm.

Then, after evacuation to 2 × 10 ⁻⁵ mbar with the same ion plating apparatus, argon gas was introduced up to 3 × 10 ⁻³ mbar, and Au—Ni—In was evaporated by a resistance heating source to 0.1 μm.
The finish layer made of an Au-Ni-In alloy was coated with a film thickness of?

On the wristwatch side thus obtained, the same characteristics as in Example 1 were obtained.

In the embodiment, among the exterior parts for a watch, stainless steel used for a band and a case, nickel plating, and brass or nickel-plated material plated with Pd-Ni alloy are used as a material, and a base layer and a finishing layer are further formed thereon. Although the example of forming is shown, the present invention can be practiced with materials other than these materials. For example, nickel plating and nickel-plated zinc and plastic materials, or nickel plating
The present invention can also be applied to copper or a copper alloy material plated with a Pd-Ni alloy.

In addition, in the case of an eyeglass frame, the present invention can be applied to a titanium material, a Ni—Cr alloy, a nickel-plated nickel-plated nickel-white material, or the like.

[Effects of the Invention] As described above, the exterior component having the gold layer of the present invention exhibits excellent gold even when the gold or gold alloy as the finishing layer is thin, and has excellent abrasion resistance, and the base layer has a Ti layer. -Exterior with excellent corrosion resistance due to excellent coverage of AlN.

Claims (2)

(57) [Claims] (1) The molar ratio of titanium to aluminum is 2/8
And a base layer made of a composite nitride of titanium and aluminum in the range of 1 to 8/2, and a finishing layer made of gold or a gold alloy provided thereon. 2. The exterior part having a gold layer according to claim 1, wherein the gold alloy of the finishing layer is made of one of nickel and palladium and gold and indium.