JPS61133379A - Hard and golden facing parts - Google Patents

Abstract

PURPOSE:To improve the wear resistance of an upper layer and to prevent the exposure of a film having low decorative value as an under layer by using a golden hard compound such as titanium carbonitride or tantalum nitride as the material of the under layer and forming a layer of a mixture of gold or a gold alloy with a hard metallic nitride, carbide or boride as the upper layer. CONSTITUTION:An under layer of a golden hard compound selected among titanium carbonitride, tantalum nitride, tantalum carbide, zirconium nitride and hafnium nitride is formed on each metallic or heat resistant substrate. An upper layer of a mixture of gold or a gold alloy with a white hard compound selected among the nitrides, carbides and borides of Fe, Cr, Ti, Mn, Mo, Ni, Co, Zr, etc., is then formed on the under layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hard golden exterior part having a beautiful golden color and excellent corrosion and wear resistance.

C. Prior Art] Conventionally, gold-colored exterior parts such as watches and ornaments require functional elements such as corrosion resistance as well as decorative elements, and gold plating has been used for a long time, but recently, ion blating, sputtering, etc. I'VD of b is C'ID
As a result, gold coatings made of titanium nitride, titanium carbonitride, zirconium nitride, tantalum nitride, etc. have been put into practical use. Furthermore, in some cases, a combination of these materials has been announced in which a gold film is formed on a film of titanium nitride or the like. (%Komei 59
(Publication No. 26664) [Problems to be Solved by the Invention] However, the conventional golden exterior parts had the following problems.

Gold plating has a beautiful golden color, but in order to satisfy functions such as corrosion resistance, it requires plating with a thickness of several microns or more, and as gold is a very expensive metal, it has become increasingly popular in recent years. There were limits to meeting the demand for low-cost gold-colored exterior parts. Furthermore, regarding wear resistance, since gold is used as a material, there is a drawback that it is easily worn even by means of alloy plating with other metals. In addition, in the case of gold-colored coatings such as titanium nitride and titanium carbonitride, although they have excellent functional properties such as corrosion resistance and abrasion resistance, they have lower reflectance than gold in terms of color tone, resulting in a dark color tone and decorative properties. There was a problem with that.

Furthermore, in the case of a titanium nitride coating with a swirling gold coating, there is no problem with corrosion resistance, and various decorations can be achieved by using not only gold on the surface but also a gold alloy. In terms of wear resistance, the underlying titanium nitride coating has excellent wear resistance, but the upper layer gold coating is easily abraded and thin, as described above, so the underlying layer is exposed in a short period of time and the appearance deteriorates. There was a problem of damaging the

It is an object of the present invention to solve the above-mentioned problems and provide an exterior component that has a beautiful golden color and is excellent in corrosion resistance and wear resistance.

[Means for solving problems]

In order to solve the above problems, the present invention forms a golden hard compound different from titanium nitride, titanium carbonitride, tantalum nitride, tantalum carbide, zirconium nitride, and hafnium nitride on a metal or heat-resistant substrate, and then A mixture of gold and a hard compound of nitride, carbide, or boride is formed into a beautiful golden color, resulting in a golden hard exterior part with excellent corrosion resistance and wear resistance. Preferably, the hard compounds mixed with gold as the upper layer include iron, chromium, titanium, manganese, molypide/,
It is a nitride, carbide, or boride of nickel, cobalt, zirconium, molybdenum, etc., and is a white hard compound. 1 In the golden exterior component configured as above, the golden hard coating usually has a thickness of 0.5 to 2
Formed to a total thickness of microns, this layer retains the basic corrosion and wear resistance, and the upper layer of gold and nitride, carbide or boride hard compounds form the beautiful golden color of gold. Uniform mixing of the compounds improves the decorative properties and the abrasion resistance of the hard gold-based layer.

Here, by using the above-mentioned white hard compound as the hard compound mixed with gold, this layer can be formed not in pure gold color but in a calm golden color (for example, Hamilton gold color) that is preferred in watches and ornaments. be.

〔Example〕

The present invention will be explained in detail below with reference to Examples.

Example 1 A watch case made of stainless steel was cleaned with an organic solvent, etc., placed in an ion brating device, and nitrogen gas was introduced after exhausting to lXl0-'Torr.
A golden titanium nitride film 2 was formed by ion blating using the ARI! method by evaporating titanium with NB under a pressure of XI (1-"TOfF. The probe current at this time was
It was set to A. Further, the film thickness at this time is required to be 0.5 to 2 microns from the viewpoint of ensuring corrosion resistance, and in this example, it was set to 1 micron.

Next, argon gas was introduced into gold containing 8 to 5 chromium using a resistance heating method from a separate evaporation source in the same ion blating device, and 8XIOTO? ” evaporated under pressure of ?l, RIF ion blating (output aoo
A gold-chromium alloy film of t-0.1 micron was formed by w). At this time, the thickness of the alloy coating is not limited as long as it is at least thick enough to show the color tone of the coating (usually about 0.05 microns), but from the point of view of reducing costs, thinner coatings are better. - The watch case thus formed was taken out of the ion brating device, placed in an ion electrification device, and glow discharged in a nitriding and argon atmosphere to perform nitriding treatment. When such nitriding treatment is performed, the primary crystals of chromium exist in a separated state in the gold alloy as described above, so this part hardens as a nitride, and the gold (partially gold-chromium alloy) and nitride A hard layer mixed with chromium is formed.

The golden hard exterior parts formed in this way had a subdued golden color, had excellent corrosion resistance, and exhibited unprecedented abrasion resistance.

Here, if titanium nitride is replaced with titanium carbonitride, which is formed by introducing nitrogen and acetylene gas, not only can the same effect be expected, but the color tone is closer to gold, so even if the upper layer is worn out, it will not be noticeable. It has the advantage of being hard to break.

Example 2 A wrist watch band made of stainless steel was cleaned with an organic solvent, etc., placed in an ion blating device, and after exhausting to IXII)''''rorr, nitrogen gas was introduced into the band under a pressure of blXlo-''Torr. Then evaporate titanium iKB and ARC! i-method ion brating,
A 2 micron golden titanium nitride coating was formed. The probe current at this time was 50A. Next, nitrogen gas is introduced from a separate evaporation source in the same ion blating device using a resistance heating method, and the IXI (J″″” Torf
Gold and iron were evaporated while adjusting the evaporation rate 't' under RF ion blating (output 500
W) to coat the gold with a hard coating containing 2 to 5 nitrides of iron nitride.
．． 2 microns were formed.

The golden hard exterior parts formed in this way have a subdued golden color, have excellent corrosion resistance, and have excellent wear resistance, not only the lower layer titanium nitride but also the upper layer mixed film of gold and iron nitride. It had good characteristics that made it difficult to scratch.

Further, as in Example 1, if titanium nitride is replaced by titanium carbonitride, the same effects as in Example 1 can be expected.

Example 8 After cleaning a watch case made of we-cO-based superhard material with an organic solvent, it was placed in an ion blating device and subjected to IXIU''''TO? After exhausting the gas, nitrogen gas was introduced and the zirconium i
After evaporating KB and performing ARE method ion blating to form a 0.5 micron golden zirconium nitride film, gold containing 8 to 101 t of cobalt was extracted from another evaporation source placed in the same ion blating equipment. The alloy was evaporated under a pressure of 7
) was used to form a gold-cobalt alloy film i0.1 micron.

The watch case thus formed is taken out of the ion blating device, and boron hydrogenation VlJ is introduced in an airtight atmosphere to perform boriding treatment to convert the gold-cobalt alloy coating into gold (partially cobalt alloy). The hard coating was made of a mixture of cobalt boride.

The golden hard exterior parts formed by this method have a subdued golden color and excellent corrosion resistance, as well as wear resistance due to not only the lower layer of zirconium nitride but also the upper layer of a mixed layer of gold and cobalt boride. It also had good properties of being resistant to wear.

〔Effect of the invention〕

As described above, according to the present invention, the lower layer includes titanium nitride, titanium carbonitride, tantalum rat, tantalum carbide,
Forming a golden hard compound selected from zirconium enriched and hafnium nitride provides basic corrosion resistance and wear resistance from fζ, and at the same time, the upper layer is a mixture of gold and a nitride, carbide or boride hard compound. This makes it possible to improve the abrasion resistance of the upper layer, maintain the beautiful golden color of the upper layer for a long time, and prevent exposure of the lower layer, which has a somewhat lower decorative value.

At the same time, the abrasion resistance of the upper layer is improved, making it possible to reduce the thickness of the upper layer as much as possible, reducing the amount of gold used, and reducing costs.

Furthermore, the compound mixed with gold in the upper layer is a hard compound of nitride, carbide, or boride such as iron, chromium, titanium, manganese, molybdenum, nickel, cobalt, zirconium, or molybdenum, and the white hard film has a dark gold color. This makes it possible to express the calm golden color that is preferred in exterior parts.

It should be noted that the present invention can be applied to metals used in exterior parts such as copper alloys and aluminum alloys, ceramics, and superhard materials other than those in the examples, and similar effects can be obtained.

Furthermore, the lower layer and upper layer coatings are not limited to the examples, and the same characteristics can be achieved by combining various compounds in the specification.

Furthermore, regarding the film formation method, not only ion blasting but also sputtering, PVD or CVD can be used for gold-colored hard compounds, and in the formation of mixtures of gold and quantified, carbide or boride hard compounds, pvp, cvp, etc. Introducing active gas and nitriding.
Mixing with gold while performing carbonization or boriding treatment! [The entire forming method can be appropriately selected depending on the material, such as mixed kt-forming by commonly used nitriding, carbonizing, or boriding treatment after forming the gold alloy film.

that's all

Claims (2)

[Claims] (1) A lower layer of a golden hard compound selected from titanium nitride, titanium carbonitride, tantalum nitride, tantalum carbide, zirconium nitride, and hafnium nitride on a metal or heat-resistant substrate, and an upper layer of gold or gold alloy and nitride. , a hard golden exterior part characterized in that it is formed of a mixture of carbide or boride hard compounds. (2) In the upper layer, the hard compound mixed with gold is iron,
The hard golden exterior component according to claim 1, which is a white hard compound made of nitride, carbide, or boride of chromium, titanium, manganese, molybdenum, nickel, cobalt, zirconium, molybdenum, etc. .