JPS58144443A - Au alloy for use in formation of physical vapor deposition film - Google Patents

Abstract

PURPOSE:To obtain the gold alloy for forming a hard film excellent in scratching and wear resistance and having a golden color in a physical vapor deposition process, by alloying the specific amounts of Cu, Fe, Zr and optionally Ni and Zn to Au. CONSTITUTION:An Au alloy contg. 10-20% Cu, 1-6% Fe, 0.1-5.0% Zr, and optionally 0.5-3.0% Ni and 1-10% Zn is deposited onto the surface of a decorative part required to have a decorative color tone, e.g. a watchcase, the band of a watch, the frame of a pair of spectacles, a necklace or an earing by a physical vapor deposition process such as vacuum deposition, ion plating or magnetron spattering. As a result, the deposition film having large hardness, excellent resistance to scratches and abrasion and a beautiful golden color tone is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention uses physical vapor deposition to produce watch bands and eyeglass frames where decorative coloring is required.

An Au alloy for forming a physical vapor deposition film that can form a hard film with excellent scratch resistance and abrasion resistance and a golden yellow tone when vapor-deposited on the surface of necklaces, earrings, etc. It is.

Traditionally, decorative tones are generally required for the above products;
In particular, there is a strong demand for a golden color tone, and therefore the surfaces of these products are widely plated with Au by wet electroplating or the like.

However, in the conventional Au plating film described above,
The plating layer thickness is very thin at 2000~3000X,
In addition, since it is prone to pinholes, it is not only necessary to plate the base with N1 as a pretreatment to give it corrosion resistance, but also requires plating equipment to be large-scale due to recent pollution regulations. There are problems such as high cost, and furthermore, the above Au plating film is made of pure Au.
Because it is very soft and easily scratched, it is also easily worn out.

Therefore, from the above-mentioned viewpoint, the present inventors have developed a material that is not subject to pollution regulations, has excellent scratch resistance and abrasion resistance, and has a golden color tone with excellent corrosion resistance. As a result of research to form a film on the surface of the above product, we found that, in terms of weight, C1]: 10-20%, Fe: 1-20%.
6%, Zr: 0.1 to 5.0%, and optionally Ni: 0.5 to 30% and Zn: 1 to 10%.
%, with the balance consisting of Au and unavoidable impurities] alloy is subjected to a physical vapor deposition method such as a vacuum evaporation method, an ion blating method, and a magnetron sputtering method, particularly preferably a magnetron sputtering method. When vapor-deposited on the surface of the product, the resulting vapor-deposited film has a significantly higher hardness than an Au alloy of the same composition after melting and casting, and has a Vickers hardness of 300 kg/- or more. Excellent scratch resistance and abrasion resistance,
Furthermore, they gained knowledge and insight that it has a golden yellow color with excellent corrosion resistance.

This invention has been made based on the above knowledge, and the reason why the composition of the Au alloy for forming a physical vapor deposition film is limited to the above-mentioned standard will be explained below.

(a) Cu The Cu component improves the oxidation resistance of the deposited film, maintains the color tone to golden yellow, and further reduces the solid solubility of the alloy component in AlF, resulting in remarkable precipitation hardening with a small amount of the alloy component. However, if the content is less than 10%, the desired effect cannot be obtained, while if the content exceeds 20%, the properties of Au are The content was determined to be 0 to 20%.

(b) Fe The Fe component has the effect of precipitating finely and uniformly in the substrate to improve the hardness of the vapor-deposited film, but if its content is less than 1%, the desired high hardness cannot be achieved. On the other hand, if the content exceeds 6%, it becomes difficult to obtain the desired golden color tone, so the content was set at 1 to 6%.

(c) Zr When Zr coexists with Fe, it precipitates into the substrate together with Fe and has the effect of further improving the hardness of the deposited film, but if its content is less than 0.1%, the desired high hardness cannot be achieved. On the other hand, if the content exceeds 50%, the color tone of the film will not be golden yellow, so the content was set at 01 to 5.0%.

(alNi and Zn N1 and Zn components have a color tone of the vapor-deposited film in a state where both of these components coexist according to the Swiss watch industry standard N-[1
-2 and N -1i It has the effect of giving a golden color that corresponds to the middle of -3, but even if the content is less than 1.05% of N and less than 1% of Zn, and Ni: 3.0
% and Zn: Since it was not possible to secure the golden color according to the above specifications even if the content exceeded 10%, the contents were determined to be Ni2O, 5 to 3.0%, and Zn: 1 to 10%, respectively. .

Next, the Au alloy for forming a physical vapor deposition film of the present invention will be specifically explained using examples.

Example Au alloys 1 to 15 of the present invention and comparative Au alloys 1 to 3 having the compositions shown in Table 1 were respectively melted in an Ar atmosphere using a high frequency induction heating vacuum melting furnace, After casting, diameter: 125m, φ x thickness 5
It was processed into a disk of 1 mm in diameter, a wire rod with a diameter of 1 mm, and a bar material with a diameter of 15 mm. Next, a magnetron sputtering method, which is a physical vapor deposition method, is performed using these various Au alloy disks, wires, and rods.

50. Applying either the vacuum evaporation method or the high frequency ion blating method. ,,mX50BH
A vapor deposited film was formed on the surface of a stainless steel substrate having dimensions of x3 mm.

To form a film using the magnetron sputtering method, first, a substrate that has been ultrasonically cleaned with acetone is attached to a holder in a vacuum chamber, and the inside of the vacuum chamber is first set in a 5 x 1 space.
．． After degassing to a pressure of Otorr, Ar gas was introduced to set the pressure to 5 x 103 Torr, and at this atmospheric pressure, a 300 W 13.56 MHz high frequency was applied to the substrate to cause glow discharge and etching. A direct current voltage of 350 μm was applied to the built-in disc target to generate a magnetron glow discharge, and this was continued for 20 minutes.

In addition, film formation by vacuum evaporation can be performed using vacuum chamber internal pressure.
The test was carried out using a wire feeding method under the following conditions: X 10 torr, substrate heating temperature: 100° C., and one reaction time of 3 minutes.

Furthermore, film formation by the high frequency ion blating method is performed by melting and evaporating using a bar supply method,
In torr Ar atmosphere, frequency: 13.56MH
This was carried out by ionizing the film through high-frequency glow discharge under the conditions of z, and then depositing it on the substrate. The reaction time in this case was 5 minutes.

Next, the average layer thickness and Vickers hardness of the resulting vapor-deposited film were measured, the color tone was observed, and the component composition was quantitatively analyzed using an X-ray microanalyzer. These results are also shown in Table 1.

From the results shown in Table 1, the vapor deposited films formed using the Au alloys 1 to 5 of the present invention all have a beautiful golden color tone, and are formed under the same conditions using the magnetron spa and tuttering methods. 90 kg of pure Au vapor-deposited film
It is extremely hard, with a Vickers hardness of 300 kg/mtA or more, compared to the Vickers hardness of -300 kg/mtA. On the other hand, the alloy components Cu, Fe
Comparative Au alloy 1 having a composition in which the content of any one of , and Zr is lower than the range of the present invention.
It is clear that a vapor deposited film with high hardness cannot be formed when using No. 3 to 3.

As mentioned above, according to the Au alloy of the present invention, when it is formed into a vapor-deposited film using the physical vapor deposition method, the resulting vapor-deposited film has a beautiful golden color tone and high hardness that have an extremely high decorative value. Therefore, in practical use, industrially useful effects such as excellent scratch resistance and abrasion resistance can be obtained.

Applicant: Mitsubishi Metals Corporation Agent Tomi 1) Kazuo

Claims (2)

[Claims] (1) Cu: 10-20%, Fe: 1-6%, Z
An Au alloy for forming a physical vapor deposition film, characterized in that it contains r: 0.1 to 50%, and the remainder consists of All and unavoidable impurities (weight %). (2) Cu: 1ON20%, Fe: 1-6%,
Contains Zr: 0.1 to 50%, and further contains Ni: 0.5 to 50%.
3.0% and Zn: 1 to 10%, and the remainder is Au.
An Au alloy for forming a physical vapor deposition film, characterized in that it has a composition (the above weight %) consisting of and unavoidable impurities.