JP2630344B2 - Method for producing multicolor surface articles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a multicolor surface formed by forming at least two kinds of films having different colors and / or tones and visually distinguishable on at least one surface of a substrate. More particularly, the present invention relates to a method for manufacturing a multicolor surface article for decoration or display on decorative articles, sporting goods, tools or various parts.

2. Description of the Related Art Conventionally, mirror polishing of the surface of a base material such as stainless steel, cemented carbide, and cermet has been used for decorative parts such as a watch case, a band, and a dial. But,
This method is monotonous due to the color of the substrate itself, which limits its decorative value. Also, even if this is engraved or engraved by means such as etching, a clear image cannot be obtained.

To solve this problem, dry plating methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) methods on the surface of the substrate; or wet plating methods such as anodizing, electrolytic plating, and electroless plating Accordingly, many proposals have been made regarding decorative components formed by forming a coating exhibiting a plurality of hues in combination of gold, silver, black, and the like. Representative proposals for these multicolor decorative parts are disclosed in Japanese Patent Application Laid-Open Nos. 58-100682 and 64-75659.

(Problems to be Solved by the Invention) Among the proposals relating to multicoloring of decorative parts described above,
No. 58-100682 discloses that a sprayed material composed of Al ₂ O ₃ and TiO ₂ is coated on a surface of low carbon austenitic stainless steel by 0.1 to 1 m.
A method of manufacturing a watch external part is disclosed in which after spraying to a thickness of m, the mirror surface is formed by lapping, and the remaining stainless steel part is plated with gold or coated with TiN. However, the timepiece exterior part produced by this method causes distortion between the stainless steel and the sprayed coating due to heating and cooling at the time of thermal spraying, resulting in small cracks in the sprayed coating surface, reducing the aesthetic effect and masking. In addition, there is a problem in that a thin line pattern cannot be formed by thermal spraying, so that the shape of the pattern is limited, and in the case of gold plating, a gold film is easily peeled off.

JP-A-61-157673 also discloses that after forming a hard color layer on the surface of a base material by ion plating, an arbitrary portion of the hard color layer is masked, and then the hard color layer is formed by ion plating. A method for manufacturing a multicolor hard film that forms a layer having a color different from the color layer is disclosed. However, the multicolor hard film article obtained by this method is difficult to form a fine pattern, and furthermore, Au or Pt
However, there is a problem that even if a noble metal is formed, it can be easily peeled off and cannot be put to practical use.

Furthermore, Japanese Patent Application Laid-Open No. 64-75659 discloses that after forming a colored film on the surface of a base metal by ion plating, a part of the film is removed by laser processing, and the metal surface is exposed to multiple colors. A law is disclosed. However, the multicolored articles obtained by this method are difficult to form a fine pattern by the noble metal, in that the material and color of the coating are limited, especially when forming a coating of a noble metal such as Au or Pt. In addition, there is a problem that the adhesiveness to the substrate is poor and the film cannot be practically peeled off.

The present invention has solved the above-mentioned problems, and basically, at least one side of at least one surface of the substrate is Au.
Noble metal or Cu-based metal coatings with good adhesion, such as Pt or Pt, have a line portion of noble metal color or Cu-based metal color, and have a different color and / or color tone and can be visually distinguished By forming a surface part, it is possible to configure fine patterns, characters and symbols with these multiple colors,
It is an object of the present invention to provide a practical method for producing a multicolor surface article having improved adhesion of a film.

(Means for Solving the Problems) The present invention provides the following steps (a), (b), (c) and (d), in that order, on the whole or a part of the surface of the base material, The present invention relates to a method for producing an article having:

(A) metals having low affinity for the second coating; metals; alloys; carbides, nitrides, carbonates and nitrides of metals of Groups 4a, 5a, and 6a; oxides and carbides of Al and Si; At least one of nitride; these mutual solid solutions; and hard carbon
Forming a first coating comprising a single-layer film or a multi-layer film of a kind;
forming a line portion having a width of m to 2 mm; (c) Cu, Ag, Au, Pt, Ir, Os, P are formed on the line portion and the surface of the remaining first coating by a wet plating method.
forming a second coating of at least one of a single layer or a multilayer of d, Rh, Ru and alloys containing them; and (d) a second coating on the surface of the remaining first coating. A step of removing and removing only the coating.

The substrate used in the present invention is not particularly limited as long as it is suitable for the purpose of use of the article of the present invention, and is not particularly limited, for example, mild steel, nickel, stainless steel, high-speed steel,
Metal materials such as Cr-Al-Ni alloy, brass and bronze; glass,
Inorganic materials such as ceramics and artificial sapphire; composites of inorganic materials and metals such as cermets and cemented carbides; and
A composite of an inorganic material and an organic material such as FRP is exemplified. For use, those suitable for materials such as decorative articles, tools, and nameplates are preferable.

A first coating and a second coating are formed on the surface of the base material as a single-layer film or a plurality of films, respectively.

In the present invention, the materials constituting the first coating include Ti, Z
metals such as r, Hf, V, Nb, Ta, Cr, Mo, W, Co, Ni, Zn, Sn; alloys containing at least one of these metals; TiC, ZrC, HfC, NbC, TaC, _{cr 3 C 2, MoC, WC} , W 2 C such as 4a, 5a, 6a group metal of the carbide; TiN, ZrN, HfN, VN ,
Nitrides of Group 4a, 5a, 6a metals such as NbN, TaN; and Ti
(CO), Ti (NO), Zr (CO), Zr (NO)
Metal oxides and nitrides in the above range, such as O).

Further, metals mentioned as a second coating described later and alloys containing at least one of them are different from those actually used as the second coating and exhibit different colors and / or colors. If used, it can be used as the first coating.

In the above description, an alloy containing a specific metal, even if the alloy is a two-component or multi-component,
There is no particular limitation as long as the alloy has a low affinity between the second coating and the first coating.

Another group of substances constituting the first coating is a transition metal element Al, and among compounds of Si, oxides such as Al ₂ O ₃ and SiO ₂ ; carbides such as SiC;
It is a nitride such as AlN or Si ₃ N ₄ . Further, the mutual solid solutions of metals and inorganic compounds mentioned above as the material of the first coating can also be used as the material of the first coating. Further, hard carbon can also be used for the first coating.

One of these may be used as a single-layer film, or two or more may be used as a multi-layer film or partially multi-layered so that the coating itself is divided into two colors or more. Is also good.

The materials constituting the first coating include Ti, Zr, Cr and alloys containing them; their carbides, nitrides, carbonates and nitrides (especially TiC and TiN); and their mutual solid solutions. Desirably, at least one kind is used.

Although the thickness of the first coating can be arbitrarily selected depending on the purpose,
Preferably 10 μm or less, more preferably 1 μm or less, further preferably 0.1 to 0.5 μm, particularly preferably 0.2 to 0.5 μm
0.4 μm.

In the present invention, Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru, and Pt are used as substances constituting the second coating. Also, alloys based on these metals as defined above can be used. Examples of such alloys include Au-Ag alloys, Au-Ni alloys, Au-Ni-
In alloy, Au-Cu alloy, Au-Cu-Cd alloy, Pt-Rh alloy, Cu
-Zn alloy, Cu-Sn alloy and the like.

Of these, Cu, Ag, A
It is desirable to use at least one of u, Pt and alloys containing these. In particular, Au, Pt, and alloys containing these can be firmly adhered to the substrate only when the method of the present invention is used, and are therefore preferable as the substance of the second coating of the present invention.

One of these may be used as a single layer film,
By forming the coating a plurality of times, a plurality of second coatings having different colors and / or tones may be formed. In this case, a part of the second coating may be formed by dry plating a metal such as Ti.

As described above, the substances used for the first coating and the second coating must be different from each other and have different colors and / or tones, and must be visually distinguishable. A combination in which the color tone is symmetric is preferred.

Although the thickness of the second coating is not particularly limited, it is preferably about 0.01 to 20 μm, more preferably about 0.1 to 5 μm at a portion formed on the substrate. If the thickness is too large, not only is the material wasted, but also a large external force is required to cut the boundary portion when removing the portion formed on the first coating as described later.

The second coating according to the present invention is generally formed on a substrate, but may be formed on the first coating remaining at the bottom in the form of a groove.

Further, the color and / or color tone of the base material may be the first color used.
If it can be visually distinguished from any of the coating and the second coating, an effect as the third hue may be given by leaving a part of the substrate exposed.

The multicolor surface article of the present invention is manufactured as follows.

(A) Formation of First Coating First, a first coating is formed on a surface of a substrate to be multicolored. If necessary, the surface may be subjected to a pretreatment such as polishing, lapping, or washing.

As a method of forming the first film, any dry plating method such as ion plating, vacuum evaporation, electron beam evaporation, thermal spraying, sputtering, CVD, etc., and anodic oxidation, electrolytic plating, and electroless plating are used, depending on the material. Although a wet plating method such as that described above is used and is selected according to the material, the wet plating method is generally preferred. The film may be formed on the entire surface of the article, or may be formed only on a part of the article, for example, on a part where a multicolor surface is required, depending on the shape and purpose of the article.

(B) Laser treatment After forming the first coating in this way, the coating is locally removed by laser treatment. That is, from the surface on which the coating is applied, a pattern, a pattern, a character, a symbol, etc., is irradiated with laser light only on a portion where the second coating is to be applied later, and the first coating on the portion is melted and removed. To expose.

As the laser Ne-the He, argon, a gas laser such as CO _2; ruby, YAG, but such a semiconductor laser such as a solid laser or GaAs, such as glass can be exemplified, it may be carried out easily continuous oscillation at room temperature, and YAG lasers are preferred because of their good controllability in the low irradiation energy range. Irradiation conditions vary depending on the material and thickness of the coating B, and irradiation may be performed while controlling irradiation energy.

The width at which the first coating is destroyed by such laser irradiation is 0.1 μm to 2 mm.

(C) Formation of the second coating The surface irradiated with the laser is washed with water or an organic solvent, and then the second coating is formed. The formation of the coating can be performed by a usual wet plating method such as anodic oxidation, electrolytic plating, and electroless plating.

In the step of laser irradiation, the grooves generated by the laser generally penetrate the first coating and reach the substrate, and the main part of the second coating is generally formed on the surface of the substrate. However, depending on the intensity of the laser irradiation, the groove may further penetrate into the substrate. Further, the groove may only reach the middle of the first film, and the main part of the second film may be formed on the first film remaining at the bottom of the groove. This is performed by appropriately controlling the laser irradiation according to the purpose, and any of them is included in the present invention without departing from the spirit of the present invention.

(D) Finishing The present inventors have found that the second coating film thus formed has a property that the portion formed on the base material or in the groove formed by the laser treatment has poor adhesion to the base material. Excellent, firmly bonded to the substrate. On the other hand, the second coating formed on the first coating exhibits releasability from the first coating.

Therefore, in the present invention, the next step of forming the second film is performed on the first film by any method such as washing with water, alcohol, ketone or the like or a mixed solvent thereof, or rubbing with a cloth or leather. This is to peel off and remove the second coating of the formed portion. The material of the removed second coating can be recovered and reused.

The above description is for the case of forming a two-color surface using a single first coating and a second coating, respectively. The first coating is multicolored by any known method, or the laser irradiation and the formation of the second coating are performed a plurality of times, and the material used for the second coating is changed to a material having a different color and / or color tone each time. By doing so, it is possible to form a multicolor surface of three or more colors.

(Function) According to the present invention, a multicolor surface including a fine pattern, pattern, character and / or symbol can be formed by the first coating and the second coating. After first forming the first coating,
By the laser irradiation, the first coating at the portion where the second coating is desired to be formed can be broken, and the adhesion tax of the second coating formed next to the substrate can be increased.

(Effects of the Invention) According to the present invention, it is possible to easily form a multicolor surface which is rich in decorativeness and is robust, and an article having such a surface. The multicolor surface obtained by the present invention can express a fine pattern, pattern, character, or symbol while maintaining the color tone inherent to the material.

Therefore, the present invention is a watch case, band, dial,
Formation of multicolor patterns and display of characters on decorative items such as tie pins, cufflinks, brooches, lighters, glasses, and sporting goods such as golf clubs; improvement of aesthetic effects on tools such as cutting tools and wear-resistant tools; It is extremely effective when used to display product names, trademarks, company marks, quality, etc. on products and their nameplates.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. The numbers described in the examples are the numbers of the respective parts used in FIG. 1 for explaining the steps of the present invention. The present invention is not limited by these examples.

Example 1 SUS304 mirror-finished by surface polishing and lapping
Of the plate-shaped substrate 1 made of
Was subjected to ion plating by a normal hollow cathode discharge method (HCD method) to form a titanium coating 3.
Next, a YAG laser was irradiated from above the coating at 30 W and 12 A, and a laser beam was applied in a stripe shape having a width of 1 mm, and the coating at that portion was melted and removed.

The thus obtained surface with the coating 3 remaining in a pattern on the surface 2 is washed with water and acetone, and then subjected to gold plating using potassium gold cyanide in a conventional manner to form a gold coating 4. Obtained. The coating 4 was bonded to the substrate 1 at the portion where the laser irradiation was performed earlier, and to the thin portion 3 at the other portions. This is washed with water to peel off and remove the portion bonded to 3 out of 4, and then washed and dried to obtain the article of the present invention having two surfaces of silver white and gold. Was.

When the two-color surface thus obtained was examined with a metallurgical microscope, the thickness of 3 was 0.3 μm, and the thickness of 4 was 2 μm.

Comparative Example 1 One side 2 of the same specimen as that used in Example 1 was partially masked, and Al ₂ O ₃ —TiO ₂ was spray-sprayed.
_{(2) A} mixed film 3 was formed. Next, the masking of the surface of the base material was partially removed, and the same gold plating 4 as in Example 1 was performed.
And the coating surface was polished to obtain a comparative article having a two-color surface.

When the surface was examined with a metallurgical microscope, the thickness of 3 was about 500
μm, 4 had a thickness of 2 μm.

Both the articles obtained in Example 1 and Comparative Example 1 were subjected to appearance and film peel tests. The result is the first
As shown in the table, the method of the article of Example 1 was excellent in both appearance and adhesion of the coating.

Examples 2 to 5 In the same manner as in Example 1, the material of the coating was changed.
By forming the coating 3 by ion plating, laser irradiation, and forming the coating 4 by plating,
On the surface of the SUS304 base material, a two-color surface having a coating with the coating material and thickness shown in Table 2 was formed. The colors are as shown in Table 2, each showing a beautiful appearance, and The adhesion of the coating 3 to the substrate was also excellent.

Example 6 A disc of a cemented carbide consisting of 80% by weight of WC, 18% by weight of Ni and 2% by weight of Cr was used as a substrate. After mirror-lapping this, a part was masked, and a Ti (CO) coating 3 was formed by ion plating. Next, after the masking of the surface of the Ti (C.O) film, a titanium film 3 'was provided by ion plating. A 1 mm wide parallel linear pattern was drawn on the surfaces of the discs having different colors by laser irradiation. Then, gold plating was performed in the same manner as in Example 1, and peeling and removal were performed.
The coating 4 was obtained by washing and drying.

In this way, an article having a three-color surface with high aesthetic value of metallic luster of titanium and gold of gold on a black background of Ti (CO) was obtained.

[Brief description of the drawings]

 FIG. 1 is a sectional view showing the steps of the present invention. DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Surface on which a multicolor surface is desired to be formed 3 ... First coating film 4 ... Second coating film. (A) Formation of first coating (b) Laser irradiation (c) Formation of second coating (d) Finish

Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C25D 7/00 C25D 7 / 00P (72) Inventor Daisuke Kinashi 1-7-7 Tsukagoshi Tsukagoshi, Saiwai-ku, Kawasaki-shi, Kanagawa Toshiba Inside Tungaloy Co., Ltd. (72) Inventor Kunio Shibuki 1-7-7 Tsukakoshi, Saiwai-ku, Kawasaki City, Kanagawa Prefecture Inside Toshiba Tungaloy Co., Ltd. Inside the plating factory (72) Inventor Akihiro Watanabe 2-19-1, Higashi-Tateishi, Katsushika-ku, Tokyo Inside the Daiwa plating factory (56) References JP-A-60-59073 (JP, A) JP-A-2 JP-A-77586 (JP, A) JP-A-60-33363 (JP, A) JP-A-63-53267 (JP, A) JP-A-63-1483 (JP, A) JP-A-64-75659 (JP, A) )

Claims (1)

(57) [Claims] 1. A method for producing an article having a multicolor surface on all or a part of the surface of a base material through the following steps (a), (b), (c) and (d) in that order. (A) a metal having low affinity for the second coating; a metal; an alloy; carbides, nitrides, carbonates, and nitrides of metals belonging to periodic table 4a, 5a, and 6a; At least one of nitride; these mutual solid solutions; and hard carbon
Forming a first coating comprising a single-layer film or a multi-layer film of a kind;
forming a line portion having a width of m to 2 mm; (c) Cu, Ag, Au, Pt, Ir, Os, P are formed on the line portion and the surface of the remaining first coating by a wet plating method.
forming a second coating comprising at least one monolayer or multilayer of d, Rh, Ru and alloys containing them; and (d) forming a second coating on the surface of the remaining first coating. A step of removing and removing only the coating.