JPH09310166A - Production of plated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesive strength of a plating layer by plating the sulfidized surface of the body to be plated with colored metal composed of a prescribed allay by vapor deposition. SOLUTION: As the body to be plated, the material in which at least the surface layer contains silver and/or copper is used as the object. In the primary stage, the surface is subjected to sulfidizing treatment. As for the treatment itself, the conventional technology may be adopted as it is. In this way, a layer of sulfide of constituting metal for the body to be plated such as silver sulfide, copper sulfide or the like with many fine pares is formed on the surface of the body to be plated. In the secondary stage, a prescribed surface region is plated with at least one or two kinds selected from gold, silver and gold-silver by vapor deposition. As for the method of the vapor deposition itself, the conventional technology may be adopted as it is. For example, with only the plate requiring the vapor deposition left, the balance is coated with metallic foil, and the vapor deposition is executed. After the completion of the vapor deposition, the metallic foil is removed, and the vapor-deposited material is cleaned in an organic solvent and is dried.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a plated body, and more particularly to a method for producing a plated body suitable for producing metal products, particularly, decorated metal crafts.

[0002]

2. Description of the Related Art In the past, for example, in the production of medals and the like, silver or copper substrates were partially plated with gold or silver. Incidentally, in the case of partial plating, it is generally troublesome to mask portions that do not require plating. Employing the vapor deposition method makes this easy, but there is a problem that the plating layer formed by the vapor deposition method has weak adhesion to the object to be plated.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a plated body with improved adhesion of a metal plating layer by a vapor deposition method.

[0004]

A method of manufacturing a plated body according to the present invention comprises a first step of subjecting a surface of a body to be plated whose at least a surface layer is formed of a material containing silver and / or copper to a sulfurating treatment; And a second step of plating at least one kind of a colored metal made of gold, silver and an alloy containing at least one kind selected from gold and silver by vapor deposition on the sulfurized surface of the object to be plated. I do.

[0005]

When at least the surface of the object to be plated whose surface layer is made of the above-mentioned specific material is subjected to a sulfurating treatment and then the above-mentioned specific metal is plated by vapor deposition, a strong, that is, hard-to-peel, plating layer with frequent adhesion is obtained. Can be formed. Therefore, according to the present invention, a plated body having excellent handling properties and long-term storage properties can be manufactured. Further, the first aspect of the present invention
In the process, by applying the sulfurizing treatment not only to the part to be subjected to the vapor deposition plating of the object to be plated, but also to the other surface part or the whole surface, as will be described later, the high-grade harmony of the background color of the non-plated part and the metal plating A plated body having a feeling can be produced by the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The object to be plated in the present invention is various articles whose at least the surface layer is made of the above-mentioned materials, for example, raw materials, intermediate products, or substantially finished products that leave only the plating step. These plated objects may be entirely formed of the above-described material, or only the surface layer thereof is formed of such a material, and the surface layer is subjected to a sulfurating treatment described later. However, the article may not be removed by peeling or dissolving. Examples of such a plated object include building materials, furniture, office supplies, industrial goods such as everyday goods, or medals,
Examples include commemorative or commemorative items such as shields and cups, ornaments, metal crafts such as swords, pots, containers, pictures, and sculptures.

In the present invention, an object to be plated whose at least a surface layer is formed of a material containing silver and / or copper is targeted. by the way,
As the content of silver or copper in the surface layer of the body to be plated is larger, a plating layer having a strong adhesive force can be formed on the surface layer by performing a later-described sulfidation treatment and subsequent vapor deposition plating. it can. For this reason, in the present invention, silver and / or copper is preferably at least 20% by weight, preferably at least 60% by weight, particularly preferably at least 90% by weight. When the surface layer of the object to be plated contains both silver and copper, the total content of both may be the above value. The surface layer in the present invention may be composed of various materials. Examples thereof include silver, a silver alloy, copper, a copper alloy, an alloy of silver and copper, an organic polymer composition containing at least one of such metals, and a ceramic containing at least one of such metals. Among these, those made of only metal such as silver, silver alloy, copper, copper alloy, or alloy of silver and copper are particularly preferable.

The above-mentioned metal forming at least the surface layer of the object to be plated will be described below. In the case of silver alone and copper alone, each may be of various purities.
As the silver alloy, those having a silver content of 20% or more can be used, preferably 60% or more, particularly 90% or more. However, there is no particular limitation on the alloying element, for example, zinc, tin, palladium, etc., and sterling silver is a preferred example of a silver alloy. As the copper alloy, those having a copper content of 20% by weight or more can be used, preferably 60% by weight or more, particularly 90% or more. However, there is no particular limitation on the alloying elements, for example, zinc, tin,
Aluminum and the like, and bronze and aluminum bronze are preferable examples of the copper alloy. The alloy of silver and copper may be an alloy having any ratio of both, and may be a silver-copper alloy containing zinc, tin, aluminum, nickel, and other alloy elements. In that case, the total content of silver and copper is 20%
Above, preferably 60% or more, especially 90% or more.

In the first step of the present invention, the surface of the object to be plated is subjected to a sulfurating treatment. The sulfurizing treatment itself has been well known in the field of plating technology, and such a conventional technology may be employed as it is in the present invention. For example, the object to be plated is usually immersed in a mixed aqueous solution of boiled potassium sulfide and sodium sulfide for 10 to 15 seconds, or this operation is repeated twice or more as necessary. The sulfidation treatment may be performed with a normally gaseous sulfide such as hydrogen sulfide. By these sulfurization treatments, a layer of a sulfide of a metal constituting the object to be plated, such as silver sulfide or copper sulfide with a large number of micropores, is formed on the surface of the object to be plated, and the surface becomes dark gray or black.

[0010] The first step is applied to at least the surface portion of the object to be deposited on which the later-described metal plating is to be performed. By applying it to the other surface portion or the entire surface, the color tone of the surface of the object to be plated is rich in taste. Can be discolored. By partially depositing the deposited metal plating on the background with the discoloration, it is possible to manufacture a high-grade plated body in which the background color and the metal plating are harmonized. This method is particularly suitable for the production of the metal crafts mentioned above.

The surface subjected to the sulfidation treatment is then buffed with an abrasive such as gold sand as necessary to remove a part of the sulfide on the surface. In the case of a silver-plated object, as the buffing proceeds, the surface shifts from dark gray to white. On the other hand, in the case of a copper-plated object, the surface approaches black to the original color of copper. Therefore, the degree of buffing can be adjusted so that the surface of the object to be plated has a desired color tone.

In the case where the surface of the object to be plated before the sulfurizing treatment is relatively smooth, as in many press-formed products, it is necessary to apply an appropriate roughening treatment to the surface prior to the sulfurizing treatment. preferable. A preferred example of the rough surface treatment is sand blowing. The purpose of this sand blowing is to moderately roughen the surface of the object to be plated. Specifically, appropriate sand is sprayed to roughen the surface to form a satin finish. As sand for sand blowing, various high-hardness particles harder than the hardness of the surface of the body to be plated, for example, ceramic sand such as quartz sand,
Steel balls, glass balls, etc. may be used. Above all, the average particle size is 10 to 200 mesh, especially 20 to 100 mesh,
Further, fine particles of about 40 to 80 mesh are preferable. By the above-mentioned sand blowing, rough unevenness is formed on the surface of the object to be plated, and a state in which a larger number of pores are formed on the surface of each unevenness by the subsequent sulfurization treatment can be observed with a microscope.

[0013] In the second step, the object to be plated is at least one selected from a colored metal selected from gold, silver and an alloy containing at least one selected from gold and silver in a desired portion of the surface subjected to the sulfurizing treatment. Alternatively, two or more types are plated. In the case of gold alone and silver alone, they may be of various purities, respectively. As the gold alloy, those having a gold content of 10% or more can be used, preferably 50% or more.
In particular, it is at least 75%. However, the alloying element is not particularly limited, and examples thereof include copper, aluminum, zinc, nickel, and palladium. Specifically, as the gold alloy, for example, 75% Au-5% Ag-2 showing pink color
0% Cu alloy, purple 78.5% Au-21.5%
Examples thereof include an Al alloy and a 75% Au-25% Cu alloy showing a red color. As the silver alloy, those having a silver content of 10% or more can be used, preferably 50% or more, particularly 75% or more.
% Or more. Specific examples of the silver alloy include, for example, a 92.5% Ag-7.5% Cu alloy having a silver color. The alloy containing gold and silver may be an alloy having an arbitrary ratio of both, and may be a gold-silver alloy containing copper, nickel, aluminum, palladium, zinc and other alloy elements. In that case, the total content of gold and silver is 1
Those having 0% or more, preferably 50% or more, particularly 75% or more are preferable.

In the present invention, in addition to using only one kind of coloring metal, two or more kinds of coloring metals having different hues and saturations may be vapor-deposited on desired or predetermined surface portions and plated in various colors. it can. Example 7 described later is an actual example thereof.

In the present invention, a conventional technique may be employed as it is for the vapor deposition method itself. The vapor deposition is generally performed according to the following procedure. After the object to be plated, which has been subjected to the sulfurizing treatment in the first step, is usually washed with an organic solvent and then dried, the remaining portion is masked except for the portion that requires vapor deposition. This masking may be performed by any method.For example, it is preferable to cover a wide portion of the remaining portion with a metal foil, and to apply an ink that can be easily removed, such as a magic pen, on the outer periphery of the portion requiring vapor deposition and the vicinity thereof. . Ink coating has the advantage that the mask can be masked accurately, even if the periphery of the deposition section is intricate. In addition, industrial high-speed and high-precision masking is also possible using computer processing technology.

The time required for vapor deposition depends on the type of vapor deposition used and the amount of power applied, but is usually about 20 seconds to 10 minutes, preferably about 1 to 2 minutes. In general, as the deposition time is increased, in other words, as the thickness of the deposited layer is increased, the color of the layer may change. For example, in the case of gold deposition, as the thickness of the deposition layer increases, it becomes more reddish. Therefore, in such a case, the color of the plating layer can be controlled by adjusting the deposition time. After the deposition, the metal foil mask is removed, the deposit is ultrasonically cleaned in an organic solvent and dried, thus obtaining a plated body. If the ink masking has been performed, it can be removed during the ultrasonic cleaning together with the gold deposited thereon.

[0017]

The present invention will be described below in more detail with reference to examples and comparative examples. Example 1 A silver medal having a thickness of 5 mm and a diameter of 70 mm, which was made of silver having a purity of 99.9% and had a pattern centered on Kinkaku-ji Temple on one side, was formed by pressing using a mold. Sand was blown for about 40 seconds using ceramic particles having an average particle size of about 80 mesh to bring the design surface into a satin state. Next, a mixed aqueous solution of potassium sulfide and sodium sulfide obtained by boiling the silver medal (water 1)
0.3 g of potassium sulfide and 0.2 g of sodium sulfide per 00 g)
For 15 seconds to obtain a dark gray silver medal. This dark gray color was made a grayish white color by buffing for 10 minutes thereafter. The buffed silver medal was subjected to ultrasonic cleaning in acetone to remove oil and the like adhering to the medal surface and dried. In order to apply gold vapor deposition only to the Kinkaku-ji temple in the design, the whole area within about 8 mm from the Kinkaku-ji temple is painted with a magic pen and masked, and then the whole area about 5 mm from the Kinkaku-ji temple is covered with aluminum foil. Complete the masking. Then, using a vapor deposition machine JEE-400 manufactured by JEOL Ltd., power of AC25V-30 was used.
A, gold was vapor-deposited on the non-masking portion under the conditions of a vapor deposition time of 100 seconds. Finally, the aluminum foil mask was removed, and the silver medal was ultrasonically cleaned in acetone to dissolve and remove the magic pen masking, thus obtaining a decorative silver medal.
The decorative silver medal obtained has a very tasty color tone, with Kinkakuji embossed against a grayish-white background, and the gold vapor-deposited film has high adhesion that passes the following peel test. Was. Peeling test: Measured in accordance with JIS H8504 "Testing method for adhesion of plating", those that did not peel were passed, and those that were peeled were rejected.

Example 2 A silver alloy medal consisting of 92.5% Ag-7.5% Cu alloy was used in place of the medal used in Example 1 consisting of pure silver having a purity of 99.9%. A gold-plated decorative medal was obtained for the Kinkaku-ji Temple in the same manner and under the same conditions as in 1. The gold plating exhibited an adhesion that passed the peel test described above.

Example 3 A pure copper having a purity of 99.9% and having a surface of 199 A.D.
A 6-year zodiac "rat" was formed by pressing a 2 mm thick, 32 mm diameter bronze medal with a pattern depicting a calendar depicting the year Sunday and holidays on the back. Sand was blown for about 40 seconds using ceramic particles having an average particle size of about 60 mesh, and both sides of the medal were in a matte state. Thereafter, a decorative bronze medal was obtained in the same manner and under the same conditions as in Example 1 except that silver was vapor-deposited only on the mouse design. The decorative bronze medal thus obtained has an extremely tasty color tone with a “rat” emerging from the silvery background of the anodized copper background, and the silver plating has an adhesive force that passes the peel test described above. Indicated.

Example 4 Instead of the bronze medal used in Example 3, 93% Cu-7 was used.
Example 3 except that a copper alloy medal made of% Zn alloy was used.
A decorative copper alloy medal was obtained in the same manner and under the same conditions.
The obtained decorative copper alloy medal had a tasteful color tone of decoration, and the plating showed an adhesive force that passed the above peel test.

Example 5 A decorative bronze medal was obtained in the same manner and under the same conditions as in Example 3 except that gold was vapor-deposited only on the mouse design instead of silver vapor deposition. The decorative bronze medal obtained in this way is a “mouse” that shines in gold against the background of an anodized copper-colored background
The gold plating exhibited an adhesive force that passed the peel test described above.

Example 6 A decorative copper alloy medal was obtained in the same manner and under the same conditions as in Example 4 except that gold was vapor-deposited only on the mouse design instead of silver vapor deposition. The thus-obtained decorative bronze medal has an extremely tasty color tone with a "mouse" that appears golden in the background of a smoky copper-colored background, and the gold plating shows an adhesive force that passes the above peeling test. It was

Example 7 A silver medal having a purity of 99.9% by weight (thickness: 5) having a design in which a profile of a woman wearing a corolla is raised on one side.
mm, 55 mm in diameter) by a press using a mold to obtain a plated object. This was subjected to sand blowing, sulfurizing treatment, buffing, ultrasonic cleaning, and drying in the same manner as in Example 1, followed by vapor deposition. However, pure gold having a purity of 99.9% by weight to give a gold color as a metal for vapor deposition and 75% Au- to give a pink color.
5% Ag-20% Cu alloy, and 78.5 to produce purple
% Au-21.5% Al alloy was used, and the corolla portion was color-coded and plated in three colors. At that time, the entire corolla was first colored purple, and then red was deposited by masking only the necessary portions, and gold was deposited by finally masking only the required portions. At the time of vapor deposition of each color, the steps of masking, vapor deposition, and ultrasonic cleaning of each necessary portion were repeated in the same manner as in Example 1. The plating thus obtained exhibited an adhesion that passed the peel test described above.

Example 8 Instead of the bronze medal used in Example 3, 23% Cu-7
A decorative copper alloy medal was obtained in the same manner and under the same conditions as in Example 3 except that a copper alloy medal made of a 7% Zn alloy was used. The decorative copper alloy medal thus obtained was satisfactory in both the taste of decoration and the adhesive force of the silver plating.

Comparative Example 1 A decorative silver medal was produced in the same manner as in Example 1 except that the sulfurating treatment was omitted. The result is that the shine of the golden Kinkaku-ji Temple is brilliant and lacks a solidness, and it is a dull thing losing the shine of the surrounding silver background, and the golden vapor deposition layer has failed the above peel test. became.

[0026]

According to the present invention, it is possible to industrially easily produce a plated body having a strong and colorful gold or silver-based colored metal plating layer on a partial surface or on the entire surface with a frequent adhesion. Further, in the first step of the present invention, the background color of the non-plated portion can be made to be a tasteful color by applying the sulfurizing treatment not only to the portion on which the object to be plated is subjected to vapor deposition plating, but also to the other surface portion or the entire surface. . By doing so, a high-quality plated body in which the background color tone and the metal plating are in harmony can be manufactured by the present invention.

Claims (8)

[Claims] 1. A first step in which at least a surface layer of a body to be plated, which is formed of a material containing silver and / or copper, is sulfurized, and gold, silver and At least one selected from gold and silver
A second step of plating one or more kinds of colored metals made of an alloy containing seeds by vapor deposition, and a method for producing a plated body. 2. The method for producing a plated body according to claim 1, wherein a surface other than the surface on which the object to be plated is subjected to vapor deposition plating is subjected to a sulfurating treatment. 3. The method according to claim 1, wherein the object to be plated has a pattern drawn by unevenness of a surface layer, and the first step and the second step are performed on at least a part of the pattern. Manufacturing method of plated body. 4. The method for producing a plated body according to claim 1, wherein a rough surface treatment is performed before the sulfurization treatment in the first step. 5. The method for producing a plated body according to claim 4, wherein the roughening is sandblasting. 6. The method for producing a plated body according to claim 1, wherein the degree of buffing is adjusted after the sulfurizing treatment in the first step to adjust the surface color of the plated object after the sulfurizing treatment. . 7. The method for producing a plated body according to claim 1, wherein the outer periphery of a portion requiring vapor deposition and the vicinity of the outside thereof are masked by applying an ink that is easily removed. 8. The method for producing a plated body according to claim 1, wherein at least two kinds of colored metals are used, and a plating portion is plated in two or more colors.