JPH069006Y2 - Precious metal ornaments - Google Patents

Description

[Detailed Description of the Invention] [Industrial field of application] The present invention is an accessory such as a watch, a spectacle frame, a lighter, a fountain pen, or a brooch, or a product having decorative elements (in the present invention, these are simply referred to as ornaments (Referred to) as a noble metal surface layer.

[Conventional technology]

Conventionally, ornaments such as watches, spectacle frames, lighters, fountain pens or broaches are known in which colored films such as gold, black, blue and dark black and precious metal films such as gold are formed by vacuum deposition or wet plating. (For example, JP-A-64-
36757).

The above-mentioned conventional ornaments include a gold base film made of titanium nitride, a black film made of titanium oxide, a blue film made of tungsten oxide, and a dark black made of titanium carbide by ion plating of a base metal on a decoration substrate made of metal, plastic, glass, or the like. A colored base metal layer is formed by depositing a film of various colors such as a film, and a noble metal such as gold is further deposited on the surface of the colored base metal layer by dry plating by vapor deposition or electrolytic or electroless plating wet method. Then, a noble metal layer is formed and the noble metal layer is etched along the mask pattern.

However, in the above conventional products, although the metal oxide by ion plating of the base metal, the metal carbide, the adhesion of the colored base metal layer such as the metal nitride to the decorative substrate has sufficient performance, There is a drawback that the adhesion between the colored base metal layer formed by ion plating and the precious metal layer formed by vacuum deposition or wet plating of the precious metal on the surface of the colored base metal layer is poor.

[Problems to be solved by the device]

The present inventor has made various investigations to solve the above-mentioned drawbacks of the prior art, and after forming a colored base metal layer by depositing a base metal on a decorative substrate by ion plating,
It has been found that if a noble metal layer is formed on the surface of the colored base metal layer by ion plating, the adhesion between the colored base metal layer and the noble metal layer is improved as compared with the conventional product.

However, it is still insufficient to obtain a good adhesion sufficient for practical use, and there is room for improvement.

That is, according to an experiment by the present inventor, the noble metal layer has a thickness of 0.3 μm.
It was found that the adhesion is good up to a certain thickness, but the adhesion of the noble metal layer becomes poor at a thickness of 0.3 μm or more.

If the thickness of the noble metal layer is 0.3 μm or less in order to improve the adhesion between the colored base metal layer and the noble metal layer, the wear resistance of the noble metal layer is reduced, and the strength of the noble metal layer is reduced, and the color tone of the noble metal disappears due to abrasion. It was also found that there is a problem that the decorativeness is deteriorated due to the damage.

The present invention solves the above-mentioned drawbacks of the prior art,
The present invention provides a precious metal decorative article having excellent adhesion, abrasion resistance, and corrosion resistance.

[Means for Solving the Problems]

The present invention provides (1) a decorative base material, a colored base metal layer formed by forming a base metal film on the surface of the decorative base material by ion plating, and a noble metal film by ion plating on the surface of the colored base metal layer. And a noble metal layer formed by forming the noble metal, wherein the noble metal is a noble metal containing 0.1 to 4.5% by weight of chromium.

(2) The precious metal ornament according to (1) above, wherein the precious metal layer is partially provided on the surface of the colored base metal layer.

Is the gist.

Hereinafter, the present invention will be described with reference to the drawings.

As shown in FIG. 1, a precious metal decorative article 1 of the present invention comprises a decorative base material 2, and a colored base metal layer 3 formed by forming a base metal film on the surface of the decorative base material 2 by ion plating.
It has a basic structure composed of a noble metal layer 4 formed by forming a noble metal film on the surface of the colored base metal layer 3 by ion plating, and the noble metal layer 4 contains chromium in an amount of 0.1 to 4. It is composed of a noble metal containing 5% by weight.

The decorative base material 2 is, for example, a watch, a spectacle frame, a lighter,
It is a base material for fountain pens, broaches, etc.
Materials for high-grade decorative products such as metals such as titanium, titanium alloys, stainless steel, nickel-chromium alloys, and copper alloys are used.

The colored base metal layer 3 can be formed by known ion plating of base metals.

As shown in FIG. 2, the ion plating device 5 is
In the vacuum chamber 6, a cathode electrode 7 and an evaporation source board 9 having a heating power source 8 are installed below the cathode electrode 7, and the evaporation source board 9 is connected to the cathode electrode 7 via a DC power source 10. ing. The vacuum chamber 6 has a vacuum exhaust port 11 and a reaction gas introduction port 12.

The method for forming the colored base metal layer 3 is as follows. The base metal such as titanium, titanium alloy, chromium, chromium alloy, niobium, zirconium, vanadium, or these alloys is put into the evaporation source board 9 of the ion plating device 5 as an evaporation source. ,
The decorative base material 2 is hung on the cathode electrode. Then, the evaporation source is heated to bring the inside of the vacuum chamber 6 to a predetermined degree of vacuum, and after introducing a reaction gas such as acetylene, nitrogen and oxygen, the base metal of the evaporation source board 9 is irradiated with an electron beam to ionize the base metal. The ionized base metal reacts with the reaction gas and is deposited on the decorative base material 2 in the form of a base metal carbide, nitride or oxide.
The colored base metal layer 3 is formed.

The colored base metal layer 3 can obtain various color tones by changing the types of base metal and reaction gas. For example, in the case of titanium and titanium alloys, the nitride is gold-based, and the carbide is black-based, and in the case of a mixture of nitrides, carbides and oxides, brown-based or pink-based. In the case of chromium and chromium alloys, nitrides, carbides and oxides are white to gray to black, and in the case of niobium, zirconium, vanadium and these alloys, the color tone is similar to that based on titanium and titanium alloys.

The thickness of the colored base metal layer 3 is 0.1 to 2.0 μm,
It is preferably 0.2 to 0.8 μm.

The coating of the noble metal layer 4 is formed on the surface of the colored base metal layer 3 formed as described above.

The noble metal layer 4 can be formed by ion plating using a noble metal containing 0.1 to 4.5% by weight of chromium as an evaporation source and using the same device and means as described above.
As the kind of the noble metal, those usually used for known ornaments can be used, and can be selected according to a desired color tone. For example, gold is used for gold, and palladium or platinum is used for white.

The amount of chromium added is 0.1 to 4.5% by weight,
If it is less than wt%, the effect of improving adhesion cannot be obtained.
If it exceeds 5% by weight, the appearance as a noble metal cannot be obtained. The noble metal layer 4 can be formed to have a thickness of 0.1 to 1 μm.

In the precious metal ornament 1 of the present invention, the precious metal layer 4 can be partially provided on the surface of the colored base metal layer 3.

As shown in FIG. 3 (A), after the noble metal layer 4 is entirely formed on the surface of the colored base metal layer 3 by ion plating, masking 13 is applied to a portion where the noble metal layer 4 is left,
By immersing in the noble metal stripping solution to dissolve and remove the noble metal layer in the portion where the masking 13 is not applied, the masking 13 is removed to remove the noble metal on the surface of the colored base metal layer 3 as shown in FIG. 4 (B). It is possible to obtain the precious metal ornament 1 according to the present invention in which the layer 4 is partially formed.

After forming the noble metal layer 4 by ion plating,
The method to remove the unnecessary precious metal layer by masking is
Compared to a method of masking the colored base metal layer 3 and providing a noble metal layer by ion plating, there is no risk of the masking being decomposed during ion plating or the ion mask being disturbed by the decomposed masking. After forming the layers, the noble metal layer can be continuously formed. It is also easy to remove the masking.

In the present invention, when it is desired to obtain a noble metal layer having a large thickness (for example, when the thickness exceeds 1 μm), the fourth
As shown in the figure, the noble metal plating layer 14 can be further formed on the surface of the noble metal layer 4 by a method such as wet plating.

〔Example〕

 The present invention will be described in more detail with reference to specific embodiments.

Example 1 A spectacle frame made of titanium was hung on a cathode electrode in a vacuum chamber of an ion plating apparatus, titanium was put on an evaporation source board, nitrogen and acetylene gas were introduced as reaction gases, and a vacuum degree was 10 ^-2. -10 ^-6 Torr and a deposition rate of 0.0
Ion plating was performed for 30 minutes at a rate of 1 to 0.02 μm / min to form a 0.5 μm colored base metal layer on the surface of the titanium spectacle frame. The color of this colored base metal layer was gray. Next, the reaction gas was stopped, gold containing 2% by weight of chromium was charged as a noble metal into the evaporation source board, the vacuum degree was adjusted to 10 ^-4 to 10 ^-5 Torr, and ion plating was performed for 8 minutes to obtain the surface of the colored base metal layer. Then, a noble metal layer made of gold containing 2% by weight of 0.3 μm chromium was formed. The obtained eyeglass frame had good adhesion between the colored base metal layer and the noble metal layer, and when 10 eyeglass frames were manufactured by repeating the above operation, the incidence of poor adhesion was 0%. .

Example 2 An eyeglass frame made of titanium was hung on the cathode electrode in the vacuum chamber of the ion plating apparatus, titanium was placed on the evaporation source board, and nitrogen and acetylene gas were introduced as reaction gases, and the degree of vacuum was 10 ^-2. -10 ^-6 Torr and a deposition rate of 0.0
Ion plating was performed for 30 minutes at a rate of 1 to 0.02 μm / min to form a 0.5 μm colored base metal layer on the surface of the titanium spectacle frame. The color of this colored base metal layer was gray. Then, the reaction gas was stopped, palladium containing 3% by weight of chromium was charged into the evaporation source board, and the degree of vacuum was adjusted to 1
Ion plating was performed for 8 minutes by adjusting to 0 ^-4 to 10 ^-5 Torr, and 0.3 μm of chromium was applied on the surface of the colored base metal layer to 3 μm.
A noble metal layer consisting of palladium by weight% was formed. The titanium spectacle frame on which the palladium noble metal layer is formed is taken out from the vacuum tank of the ion plating device, the bridge portion of the spectacle frame is coated with an acrylic paint for masking, and then immersed in a noble metal stripping solution to be masked. After peeling off the palladium noble metal layer in the unexposed areas, the masking material is removed, and the colored base metal layer is exposed on the rim and temple parts to become gray, and the palladium noble metal layer remains on the bridge part to become white, and then to white. A titanium eyepiece frame having an appearance color tone in combination with a gray color was obtained.
The obtained eyeglass frame had good adhesion between the colored base metal layer and the noble metal layer, and when 10 eyeglass frames were manufactured by repeating the above operation, the incidence of poor adhesion was 0%. .

Example 3 A spectacle frame made of titanium was hung on the cathode electrode in the vacuum chamber of the ion plating apparatus, titanium was charged on the evaporation source board, and nitrogen and acetylene gas were introduced as reaction gases, and the degree of vacuum was 10 ^-2. -10 ^-6 Torr and a deposition rate of 0.0
Ion plating was performed for 30 minutes at a rate of 1 to 0.02 μm / min to form a 0.5 μm colored base metal layer on the surface of the titanium spectacle frame. The color of this colored base metal layer was gray. Then, the reaction gas was stopped, gold containing 2% by weight of chromium was charged into the evaporation source board, and the degree of vacuum was ^adjusted to 10 ^-4 to 1
Adjust to 0 ^-5 Torr, perform ion plating for 8 minutes,
A noble metal layer made of gold containing 2% by weight of chromium having a thickness of 0.3 μm was formed on the surface of the colored base metal layer. The titanium spectacle frame on which the noble metal layer was formed was taken out of the vacuum tank of the ion plating apparatus, and a 20-carat gold-palladium noble metal plating layer having a thickness of 1 μm was further formed on the surface of the noble metal layer by known wet plating.

Then, the bridge portion of the spectacle frame on which the gold-palladium noble metal plating layer is formed is coated with an acrylic paint for masking, and then immersed in a gold stripping solution to apply gold-palladium alloy plating to the unmasked portion. After peeling off the layer, the masking material is removed, and the colored base metal layer is exposed on the rim and temple parts to become dark black, and the bridge part is gold-
The palladium alloy plated layer remained and became gold, and thus a titanium eyepiece frame having an appearance tone composed of a combination of gold and gray was obtained. The obtained eyeglass frame had good adhesion between the colored base metal layer and the noble metal layer, and when 10 eyeglass frames were manufactured by repeating the above operation, the incidence of poor adhesion was 0%. .

Comparative Example 1 For comparison, a titanium eyeglass frame was used in the same manner as in Example 1 except that a noble metal layer was formed using only chromium-free gold instead of the noble metal of Example 1 containing chromium. Was treated to form a noble metal layer containing only gold and not containing chromium on the surface of the colored base metal layer. The obtained eyeglass frame had poor adhesion between the colored base metal layer and the noble metal layer, and when 10 eyeglass frames were manufactured by repeating the above operation, the occurrence rate of poor adhesion was 40%.

[Effect of device]

As described above, the noble metal ornament of the present invention has a colored base metal layer formed by ion plating on which a noble metal layer formed by ion plating of a noble metal containing 0.1 to 4.5% by weight of chromium is formed. Since it was formed, the adhesion between the precious metal layer and the colored base metal layer is improved compared to the conventional precious metal decorative article in which the precious metal layer containing no chromium is formed on the surface of the colored base metal layer, and the adhesion during manufacturing is poor. There is no generation of product, and there is no fear that the noble metal layer will peel off when the product is used.

Further, since the precious metal decorative article of the present invention has good adhesion between the precious metal layer and the colored base metal layer, even if the precious metal layer is formed thick, the problem of poor adhesion does not occur. For example, the precious metal layer has a thickness of 0.3.
Even if the thickness is more than μm, good adhesion is obtained and there is no fear that the noble metal layer is peeled off. Thus, according to the present invention, the thickness of the noble metal layer can be increased, and as a result, the wear resistance of the product can be improved.

Furthermore, by partially providing the noble metal layer on the surface of the colored base metal layer, it is possible to change the color tone of the colored base metal layer and the color tone of the noble metal layer, which is rich in variety.
It has the effect of improving decorativeness.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing an example of a precious metal ornament of the present invention,
FIG. 2 is a schematic explanatory view of an ion plating device, FIGS. 3 (A) and 3 (B) are explanatory views showing a process of manufacturing a precious metal ornament in another embodiment of the present invention, and FIG. It is a longitudinal section showing another example of a precious metal ornament. 1 ... noble metal ornament, 2 ... decorative base material 3 ... colored base metal layer, 4 ... noble metal layer 5 ... ion plating device

Claims (2)

[Scope of utility model registration request] 1. A decorative base material, a colored base metal layer formed by forming a base metal film on the surface of the decorative base material by ion plating, and a precious metal film formed on the surface of the colored base metal layer by ion plating. And a precious metal layer containing the precious metal layer, wherein the precious metal layer is a precious metal containing 0.1 to 4.5% by weight of chromium. 2. The precious metal decorative article according to claim 1, wherein the precious metal layer is partially provided on the surface of the colored base metal layer.