JPH09296283A - Formation of metallic pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming metallic patterns which have a good adhesion property to a base material. SOLUTION: A colored layer 2 is formed on the base material 1 consisting of silver or silver alloy and thereafter, a resin layer 3 contg. at least black oil-soluble dyes is formed on this colored layer 3. The resin layer 3 is then scanned by using a YAG laser beam, by which the resin layer 3 is removed to prescribed patterns. The surface of the base material 1 of the removed parts is subjected to an etching treatment and, thereafter, metallic layers 5 are formed in the etched parts. The remaining resin layers 3 are then removed. At the time of forming the metallic patterns on the silver or silver alloy, the colored layer 2 is formed on the surface of the silver or silver alloy and the resin layer 3 is formed by using the coating material or screen ink contg. the black oil- soluble dyes, by which the removal of the resin layer 3 by the laser beam is made possible without allowing the resin films to remain. In addition, the formation of the distinct patterns is made possible without the peeling of the resin layer 3 at the time of forming the metallic patterns.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an arbitrary metal pattern on the surface of a base material made of silver or a silver alloy, which is suitable for decorating writing instruments, watches, cosmetic containers, etc. It is a thing.

[0002]

2. Description of the Related Art Conventionally, the decoration of silver or silver alloy has been carried out by using a technique which is practiced in traditional crafts such as silverwork. The method is carried out by forming irregularities of milliorder on the surface, performing black dyeing by sulfurization treatment, and then polishing the entire surface. The effect of decoration by repeating the black dyeing and polishing many times is that the convex blackened layer is removed and the concave blackened layer remains, thereby emphasizing the three-dimensional effect of unevenness. In addition, there is a method of forming a concave pattern such as a character by a method such as engraving, and in this method, a method of pouring black paint into the concave portion and then wiping off unnecessary paint is used,
It is known that the pattern becomes clearer. As described above, decoration on silver or silver alloy is generally performed by a traditional method such as blackening or black ink. Further, the method of forming the metal pattern on the metal substrate, the resist pattern is formed by a method such as screen printing, a method of forming a metal pattern by plating, using a metal mask,
A method of forming a metal pattern by physical vapor deposition, a resist is formed by a coating method, then the resist layer is removed in a pattern by a YAG laser, and a metal pattern is plated on the removed portion. There was a method of forming.

[0003]

When a resist is formed on silver or a silver alloy by a screen printing or painting method, the silver or the silver alloy discolors in air and forms an unstable layer on the surface. Therefore, the resist cannot be firmly adhered. Also, when trying to form a resist by removing the unstable layer and exposing a clean metal surface,
Silver or a silver alloy has poor reactivity with the resist and cannot firmly adhere the resist. If etching or plating is performed in this state, the resist is peeled off, so that the pattern cannot be formed. Further, in order to form a metal pattern, since it is placed under an etching treatment for removing an altered layer on the surface and an electrolytic treatment condition for precipitating a metal, it is highly resistant to etching and electrolytic treatment. The resist material and the resist forming conditions have to be set, which results in a complicated forming process and an increase in cost. Further, when the resin layer formed on silver or a silver alloy is removed by a YAG laser and the metal pattern is not formed in the removed portion, the formation of the metal pattern is hindered or the metal pattern is not formed. The peeling may occur even if the core is formed. When the surface where the peeling occurred was observed carefully, it was confirmed that a thin transparent film remained on the surface of the base material. This is because the laser light is reflected on the silver or silver alloy surface, so that the resin layer cannot be completely removed, and the remaining thin transparent film adversely affects the electrolysis and etching processes in the subsequent steps. I found out. Further, when the output (energy) of the laser is increased to completely remove the resin layer, the surface of the base metal is roughened, and the resin layer is melted by heat, resulting in a change in pattern. There was a problem that caused it.

[0004]

[Means for Solving the Problems] As a result of various investigations in view of the above problems, the formation of the metal pattern is positive because the resin layer serving as a resist needs to be well adhered to the substrate. Considering a method to form an adhesive layer that helps the resin layer adhere closely, after removing the altered layer on the surface of silver and silver alloy,
It was found that the resin layer is firmly adhered by forming the colored layer and that the resin layer can be completely removed without leaving a thin transparent film by absorbing the laser beam by the colored layer. The present invention has been completed. That is, according to the present invention, therefore, a colored layer is formed on a substrate made of silver or a silver alloy, and then a resin layer containing at least a black oil-soluble dye is formed on the colored layer, and then a YAG laser beam is formed. The resin layer is removed in a predetermined pattern by scanning over the resin layer with a glass, and then the surface of the base material of the removed portion is subjected to etching treatment, and then a metal layer is formed in the etching treated portion, and then the remaining portion is left. The gist is a method of forming a metal pattern in which the resin layer is removed.

Hereinafter, the present invention will be described in detail with reference to the drawings. Reference numeral 1 is a base material made of silver or a silver alloy. Reference numeral 2 is a colored layer. The coloring layer 2 forms silver sulfide, black chrome plating, black nickel plating, and chromium coating. The thickness of the colored layer 2 is preferably 0.5 μm or less, and a film which allows the substrate surface to be exposed in a short time by a simple operation such as dipping after removing the resin layer 3 described later is preferable. When the thickness is thicker than 0.5 μm, the removal time of the colored layer 2 after removing the resin layer 3 becomes long, and the removal time makes the edge portion of the pattern of the resin layer 3 which is the resist peel off. Or, the resin layer 3 may be damaged and pinholes may be easily formed, which is not preferable. Reference numeral 3 in the figure denotes a resin layer which becomes a resist. The resin layer 3 is formed by painting or screen printing. The color tone of the resin layer 3 is not particularly limited, but black is preferable because it has good absorption of the laser beam. The paint or ink that forms the resin layer 3 is one that is dried or reaction-cured at room temperature, or one that is heat-cured. Specifically, acrylic-based, polyester-based, epoxy-based, urethane-based, alkyd-based, vinyl-based Materials including resins such as phenol, phenol, silicon, and fluorine are used.

The black oil-soluble dye contained in the resin layer is preferably a nigrosine dye, specifically, C.I.
I. Acid Black 2, C.I. I. Solvent
Black5, C.I. I. Solvent Black
7, C.I. I. SolventBlack3, C.I. I. S
olvent Black22, C.I. I. Solve
nt Black 23, C.I. I. Acid Black
123 and other commercially available products are Oil Bla.
ck BY, Oil Black BS, Oil Bl
ack 803, Oil Black HBB, Special Black EB, Spirit Black AB
(Above, manufactured by Orient Chemical Industry Co., Ltd.), Aizen
Spilon Black BH, Aizen Spi
lonBlack GSH Special (above, Hodogaya Chemical Co., Ltd. product) etc. are mentioned. The addition amount of the oil-soluble dye is preferably 5 to 40% by weight based on the solid content of the paint or the screen ink resin. A coloring material that absorbs a wavelength around 1060 nm may be added as needed. Reference numeral 4 is a portion where the resin layer has been removed by the laser beam. Reference numeral 5 is a metal layer, but the metal layer 5 may be formed by known electroplating or electroless plating.

Next, a method of forming a metal pattern will be described. The colored layer 2 is removed by immersing it in the liquid. The liquid used is selected depending on the type of the colored layer 2 formed. The silver sulfide can be removed by using a liquid such as nitric acid, a mixed liquid of hydrogen peroxide and ammonia water, or a liquid such as hydrochloric acid or nitric acid for black chromium, black nickel or the like. Further, the removal of the colored layer 2 can be performed simultaneously with the etching of the base material by appropriately selecting the liquid composition and the treatment time. By this etching process, it is possible to form irregularities on the substrate without performing mechanical processing such as engraving. After etching the portion where the resin layer was removed by the laser beam,
A metal layer is formed on the etched portion. The resin layer, which is the resist in the final step, may be removed using a commercially available release agent.

[0008]

According to the present invention, a metal pattern is formed on silver or a silver alloy.
A coating or screen containing a black oil-soluble dye, which forms a colored layer on the surface of a silver or silver alloy base material when forming a resin.
By forming the resin layer using a resin ink, the resin layer can be removed without leaving the resin film by the laser beam, and the resin layer does not peel off when forming the metal pattern. A clear pattern can be formed.

[0009]

【Example】

Example 1 A silver alloy shaft having an outer diameter of 10 mm and a length of 100 mm was used as a test piece. The shaft was buffed and subjected to known plating pretreatments of immersion and electrolytic degreasing. Then, the shaft was immersed in a 0.2% ammonium sulfide solution for 60 seconds to form a colored layer. Drying was performed at 60 ° C. for 10 minutes. Next, Nigrosine EX (Orient Chemical Industry Co., Ltd.)
Acrylic thermosetting paint (Magical Black, manufactured by Kansai Paint Co., Ltd.) in which 6 parts of the above product was dispersed was diluted to 2 times with a dedicated thinner, and a spray gun was applied. Drying is 160 ℃,
It was carried out under the condition of 20 minutes to form a 10 μm resin layer.
Next, the resin layer was partially removed in a lattice pattern with a line width of 1 mm using a YAG laser. Next, it is immersed in a 1: 1 mixture of 5% hydrogen peroxide water and 15% ammonia water at room temperature for 10 minutes to remove the colored layer and etch the base material, and apply bright nickel plating at 2 A / dm ² It was performed for 5 minutes to form a gold plating of 0.5 μm. After washing and drying with water, a commercially available paint stripper R-4ZK (manufactured by Great-Toll Co., Ltd.)
Then, the resin layer as a resist was peeled off. Then, it was immersed in a commercially available silver discoloration layer remover Lister-Ag (manufactured by Nikko Eisei Co., Ltd.) for 1 minute to remove the colored layer, followed by washing and drying. Gloss,
A silver shaft with a concave gold grid pattern was obtained.

Example 2 Outer diameter 10 mm, length 100 m
A silver alloy shaft of m was used as a test piece. The shaft was buffed and subjected to known plating pretreatments of immersion and electrolytic degreasing. After that, black chrome plating is performed at 10 A / dm ² for 3 minutes,
A colored layer was formed. After washing with water, drying was performed at 60 ° C. for 10 minutes. Next, an acrylic thermosetting paint (Magicalon Black, Kansai Paint Co., Ltd.) in which 6 parts of Nigrosine EX (Orient Chemical Co., Ltd.) is dispersed is diluted twice with a dedicated thinner, and then spray gun is used. Painted. Drying is
It was carried out under the conditions of 160 ° C. for 20 minutes to form a resin layer of 10 μm. Next, the resin layer was partially removed in a lattice pattern with a line width of 1 mm using a YAG laser. Then 3
The colored layer was removed by immersing it in a 5.5% hydrochloric acid solution at room temperature for 1 minute, and satin nickel plating was performed at 4 A / dm ² ,
It was performed under the condition of 5 minutes to form a gold plating of 0.5 μm.
After washing and drying, a commercially available paint remover R-4ZK (Great-
The resin layer as a resist was peeled off. Then, it was immersed in a 35.5% hydrochloric acid solution at room temperature for 1 minute to remove the colored layer, washed with water and dried. A silver shaft having a pallet-like, convex gold lattice pattern was obtained.

<Embodiment 3> Outer diameter 10 mm, length 100 m
A silver alloy shaft of m was used as a test piece. The shaft was buffed and subjected to known plating pretreatments of immersion and electrolytic degreasing. Then, black nickel plating was formed to a thickness of 0.3 μm to form a colored layer.
After washing with water, drying was performed at 60 ° C. for 10 minutes. Next, use Nigrosine EX (manufactured by Orient Chemical Industry Co., Ltd.)
Partially dispersed acrylic thermosetting paint (Magicalon Black, Kansai Paint Co., Ltd.) is diluted twice with a dedicated thinner,
Painted with a spray gun. Drying was performed at 160 ° C. for 20 minutes to form a 10 μm resin layer. Then YA
Using a G laser, the resin layer was partially removed in a grid pattern with a line width of 1 mm. Next, 5% hydrogen peroxide and 15%
The colored layer was removed and the substrate was etched by immersing in a 1: 1 mixed solution of ammonia water at room temperature for 5 minutes. After that, gold plating was formed to 0.5 μm. After washing with water and drying, the resin layer as a resist was peeled by immersing it in a commercially available coating film peeling agent R-4ZK (manufactured by Great Tol Co., Ltd.). Then 30.0
% Nitric acid solution at room temperature for 1 minute to remove the colored layer, followed by washing with water and drying. A silver shaft with a matt, concave gold grid pattern was obtained.

<Embodiment 4> Outer diameter 10 mm, length 100 m
A silver alloy shaft of m was used as a test piece. The shaft was buffed and subjected to known plating pretreatments of immersion and electrolytic degreasing. Then, the shaft was immersed in a 0.2% ammonium sulfide solution for 30 seconds to form a colored layer. Drying was performed at 60 ° C. for 10 minutes. Next, an acrylic thermosetting paint (Magicalon Black, Kansai Paint Co., Ltd.) in which 6 parts of Nigrosine EX (Orient Chemical Co., Ltd.) is dispersed is diluted twice with a dedicated thinner, and then spray gun is used. Painted. Drying is
It was carried out under the conditions of 160 ° C. for 20 minutes to form a resin layer of 10 μm. Next, the resin layer was partially removed in a lattice pattern with a line width of 1 mm using a YAG laser. Then 5%
Immersion in a 1: 1 mixture of hydrogen peroxide water and 15% ammonia water at room temperature for 5 minutes to remove the colored layer and etch the base material, and apply bright nickel plating to 2 A / dm ² , 15
It was performed for 1 minute to form a gold plating of 0.5 μm. After washing with water and drying, the resist was peeled off by immersing it in a commercially available coating film peeling agent R-4ZK (manufactured by GREATOL Co., Ltd.). Then, add 1 to the commercially available silver discoloration layer remover Lister-Ag
After dipping for a minute, the colored layer was removed, washed with water and dried. A silver shaft with a glossy, convex gold grid pattern was obtained.

<Comparative Example 1> Outer diameter 10 mm, length 100 m
A silver alloy shaft of m was used as a test piece. The shaft was buffed and subjected to known plating pretreatments of immersion and electrolytic degreasing. Then, it was washed with water and dried, and a grid pattern was formed by screen printing using PROTOCOAT 185 BLACK (manufactured by Yoshikawa Kako Co., Ltd.). Drying was performed at 130 ° C. for 20 minutes to form a 10 μm resist layer. Next, add 1: 1 mixture of 5% hydrogen peroxide and 15% ammonia water at room temperature for 5
After immersing under the condition of minutes and etching the base material,
Bright nickel plating was performed under the conditions of 2 A / dm ² and 5 minutes to form gold plating of 0.5 μm. After washing with water and drying, the resist was peeled off by immersing it in a commercially available coating film peeling agent R-4ZK (manufactured by GREATOL Co., Ltd.). The resist peeled off during the etching, and mottled gold plating was formed.

<Comparative Example 2> Outer diameter 10 mm, length 100 m
A silver alloy shaft of m was used as a test piece. The shaft was buffed and subjected to known plating pretreatments of immersion and electrolytic degreasing. After that, black chrome plating is performed at 10 A / dm ² for 3 minutes,
A colored layer was formed. After washing with water, drying was performed at 60 ° C. for 10 minutes. Next, an acrylic thermosetting paint (Magical Black, manufactured by Kansai Paint Co., Ltd.) was diluted twice with a dedicated thinner, and a spray gun was applied. Drying is 160
This was carried out under the conditions of 20 ° C. and 20 minutes to form a 10 μm resin layer. Next, the resin layer was partially removed in a lattice pattern with a line width of 1 mm using a YAG laser. Next, the colored layer was removed by immersing in a 35.5% hydrochloric acid solution at room temperature for 1 minute, bright nickel plating was performed at 2 A / dm ² for 5 minutes, and gold plating was formed to 0.5 μm. . After washing and drying with water, a commercially available paint stripper R-4ZK (manufactured by Great-Toll Co., Ltd.)
And the resist was peeled off. Then, it is immersed in a 35.5% hydrochloric acid solution at room temperature for 1 minute to remove the colored layer, and then washed with water.
Dried. There were spots where the plating did not deposit, resulting in a mottled pattern.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a metal pattern of the present invention.

[Explanation of symbols]

 1 base material 2 colored layer 3 resin layer 4 resin layer portion removed by laser beam 5 metal layer

Claims (1)

[Claims] 1. A colored layer is formed on a base material made of silver or a silver alloy, a resin layer containing at least a black oil-soluble dye is formed on the colored layer, and then a YAG laser beam is formed. The resin layer is removed in a predetermined pattern by scanning over the resin layer, and then the base material surface of the removed portion is subjected to etching treatment, and then a metal layer is formed in the etching treated portion, and then the remaining resin A method for forming a metal pattern with a layer removed.