JP3232652B2 - Method of manufacturing decorative body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for directly forming a natural, old-fashioned (rusty feeling) colored pattern on a member having copper or a copper alloy at least on the surface thereof. The present invention relates to a method for forming a continuous shaded colored pattern on the above member.

[0002]

2. Description of the Related Art Coloring metals includes plating, painting, printing, and chemical treatment. However, in order to embody a natural old-fashioned design, a method capable of forming a tinted colored pattern is required. As a conventional technique, a method of dropping a corrosive liquid (etching liquid) on a material (member) and a method of forming a composite surface by lamination such as plating, painting, and printing are known.

[0003]

The former has a problem that it requires a high degree of skill in a manual method, has poor reproducibility and is not suitable for mass production, and the latter has a clear boundary and a natural There was a problem that it was impossible to express an old-fashioned feeling.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method of forming a continuous dark and light colored pattern directly on a member having copper or a copper alloy on at least the surface by using a paint or ink-based colored liquid. Forming a continuous pattern of light and shade by coloring only the pattern-forming portion, thereby completing the present invention and providing a member having copper or a copper alloy at least on the surface. Then, a colored liquid made into paint or ink is applied in a pattern
The coloring liquid contained therein is reacted with the substrate, and the coloring liquid
An oxide film with a thickness proportional to the thickness of the included pattern is formed.
In this way, a continuous dark and light colored pattern is formed only in the pattern forming portion by the thickness gradient of the oxide film, and thereafter, the patterned paint or ink-colored liquid is removed, and the surface is further protected. The gist of the present invention is a method for manufacturing a decorative body provided with a clear layer.

As a member to be processed, copper or a copper alloy is used, and a metal such as titanium, iron, nickel, nickel-tin alloy, cobalt, and stainless steel is treated with copper or a copper alloy. Or synthetic resin such as acrylonitrile / butadiene / styrene resin, acrylonitrile / styrene resin, polycarbonate resin, nylon resin, etc., whose surface is treated with copper or copper alloy, or ceramics such as alumina, zirconia, silica, etc. Various types such as those having a surface treated with copper or a copper alloy can be used.

A method of using a member other than copper or a copper alloy as a member and subjecting the surface of the member to a copper or copper alloy treatment will be briefly described. The surface treatment includes known wet treatment and dry treatment. The wet treatment is performed in the order of degreasing, etching, sensitization, activation, electroless plating, and electroplating. In the dry treatment, after performing a degreasing treatment, a treatment is performed by a physical vapor deposition method (PVD), and the treatment is performed in the order of electroplating. This member is then polished and cleaned before use.

Next, a coating or ink-based coloring liquid is applied in a pattern by an appropriate method such as screen printing, and the coloring liquid may be a water-soluble resin such as an acrylic resin, a urethane resin, a polyester resin, or an epoxy resin. Or a superabsorbent resin such as hectorite, and an oxidizing agent such as potassium persulfate, sodium perchlorate, sodium nitrite, potassium chlorite, ammonium sulfate, selenite, and sodium hydroxide, hydroxide A mixed solution of a basic salt such as potassium or sodium carbonate or a commercially available coloring solution is used. The amount of the water-soluble resin or the superabsorbent resin used is,
Considering that if the amount is too small, the thickening effect may not be obtained, and if the amount is too large, gelling may not be possible. .
1% to 10% is preferred.

[0008] If necessary, these coloring liquids include bronzing copper,
A film-forming aid (which assists the oxidizing action) made of a metal salt such as lead peroxide, sodium hydrogen phosphate, or ammonium nitrate may be added, or silica having an average particle diameter of 5 to 20 μm for imparting thixotropic properties. May be added from several% to several tens%. The colored film is a composite oxide film of copper, which exhibits a color due to the formation of the oxide film. However, the colored liquid is thick at the center due to surface tension and thin at the part near the boundary with the non-coated part. Therefore, a continuous dark and light colored pattern is formed.

Next, the coloring liquid formed as a paint or ink is removed, and various methods can be adopted as the removing method, but the simplest method is washing with water.

[0010] Thereafter, a clear layer is formed on the surface for protection, using a known clear paint such as an acrylic paint, a urethane paint, or an epoxy paint, and applying it by an appropriate means such as spraying. It may be dried.

[0011]

The present invention provides an oxide film having a thickness gradient without forming a composite surface by lamination such as plating, painting, printing, etc., that is, the film thickness of a pattern of a coloring liquid made into a paint or ink. The thicker part has a thicker oxide film, and the thinner part has a thinner oxide film, which naturally forms a continuous dark and light colored pattern (old-fashioned design). A decorative body having a good old-fashioned design can be obtained.

[0012]

【Example】

Embodiment 1 FIG. As the metal member, a member having a chemical component of JIS H3100 was used, and a cylindrical shaft (writing tool shaft) formed by press working was buff-polished, washed, and pretreated. The above member was degreased and acid-activated by a known method and then dried. Next, sodium polyacrylate 20%, potassium persulfate 60 g / l, sodium hydroxide 40 g /
1 was applied in the form of a spot by spraying using a mask as a mask, and the member was colored only at the pattern forming portion to obtain a continuous shaded colored pattern. Thereafter, the colored liquid applied in the form of spots was removed by washing with water and dried. Next, Unipar Clear (acrylic paint, manufactured by Ohashi Chemical Co., Ltd.) was applied by spraying to a thickness of 5 μm.
By drying at 60 ° C. for 20 minutes, a decorative body having a continuous colored pattern of black to brown was obtained.

Embodiment 2 FIG. Using the same members as in Example 1,
The member subjected to the same preliminary treatment was degreased and acid-activated by a known method and then dried. Next, a colored liquid made into a paint consisting of 10 g / l of Laponite RD (synthetic hectorite, manufactured by Nippon Silica Industry Co., Ltd.), 50 g / l of potassium chlorite, and 50 g / l of sodium hydroxide was subjected to a stitch pattern. Using a screen as a mask, apply it in spots by spraying
The member was colored only in the pattern forming portion to obtain a continuous dark and light colored pattern. Thereafter, the member was washed with water to remove the colored liquid applied in spots, and dried. Next, a unicolor clear (acrylic paint, manufactured by Ohashi Chemical Co., Ltd.) is applied to a thickness of 5 μm by spraying and dried at 160 ° C. for 20 minutes to form a black to brown continuous colored pattern. Was obtained.

Embodiment 3 FIG. A cylindrical shaft (writing tool shaft) formed by pressing stainless steel was buffed, washed and dried. The above members were pretreated by a known method, and strike copper plating was formed to a thickness of 10 μm and dried. Next, 1.0 g / l of Sumikagel NP-1010 (a sodium acrylate polymer, manufactured by Sumitomo Chemical Co., Ltd.) and 10 g of ammonium sulfate 10
5 g / l, sodium hydroxide 10 g / l, copper sulfate 3.5 g / l, and aqueous ammonia (specific gravity 0.88) 1.7
A coating solution of 0.1 ml / l was partially applied by a spray method using a mask as a mask, and only the pattern forming portion was colored to obtain a continuous dark and light colored pattern. Thereafter, the member was washed with water to remove the partially applied coloring liquid, and dried. Next, a unicolor clear (acrylic paint, manufactured by Ohashi Chemical Co., Ltd.) is applied by spraying to a thickness of 5 μm and dried at 160 ° C. for 20 minutes to form a black to brown continuous colored pattern. Was obtained.

Embodiment 4 FIG. Using the same members as in Example 1,
The member subjected to the same preliminary treatment was degreased and acid-activated by a known method and then dried. Next, 10 g / l of Laponite RD (synthetic hectorite, manufactured by Nippon Silica Industry Co., Ltd.) and an aqueous solution of 10 g / l of selenous acid (pH 3 with sodium hydroxide).
0), and Aerosil 200 (silica particles, Nippon Aerosil Co., Ltd.) as a thixotropic agent.
(A) was added to 4%, and the colored liquid formed into an ink was subjected to pattern printing by a screen printing method. Next, the member was subjected to a pattern edge blurring treatment, and the member was colored to obtain a colored pattern of continuous shading. Thereafter, the member was washed with water to remove the partially applied coloring liquid, and dried. Next, a unicolor clear (acrylic paint, manufactured by Ohashi Chemical Co., Ltd.) is applied to a thickness of 5 μm by spraying and dried at 160 ° C. for 20 minutes to form a black to brown continuous colored pattern. Was obtained.

Table 1 shows the evaluation results of colors, pattern boundaries, and appearances of the decorative bodies obtained by the above examples.

[Table 1]

[0017]

As is clear from the above table, according to the present invention, there is an effect that it is easy to form a natural continuous shaded colored pattern.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-54-93642 (JP, A) JP-A-57-47878 (JP, A) JP-A-51-47021 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B41M 1/28 B41M 3/00 B05D 5/06 101 B05D 7/14 B44D 5/00 B44C 1/22 B44C 5/04 C23C 22/00-22/86

Claims (2)

(57) [Claims] A coating liquid or an ink-based coloring liquid is applied in a pattern to a member having copper or a copper alloy on at least the surface to react the coloring liquid contained in the pattern with the substrate.
A thickness proportional to the thickness of the pattern containing the coloring liquid.
By forming only the oxide film, a continuous shaded colored pattern is formed only in the pattern forming portion by the thickness gradient of the oxide film, and thereafter, the colored paint or ink in the form of a pattern is removed. A method for producing a decorative body provided with a protective clear layer on the surface. 2. The production of a decorative body according to claim 1, wherein a paint or ink is used, wherein a water-soluble resin or a superabsorbent resin is used as a dispersant, and a mixed aqueous solution of an oxidizing agent and a basic salt is used as a solvent. Method.