KR960008013B1 - Multi-colored product and process for producing the same - Google Patents

Abstract

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Description

Multicolored article and its manufacturing method

1 to 5 are cross-sectional views showing representative shapes of the concave surface or the concave line of the substrate surface of the article according to the invention.

6 is a sectional view of a representative article of the present invention.

7 is a front view of a letter inscribed slow away chip achieved in Example 4. FIG.

8 is a cross-sectional view of one embodiment of the method (second embodiment) of the present invention.

9 is a perspective view of a tool achieved in Example 11;

10 is a cross-sectional view of one embodiment of the method of the present invention.

* Explanation of symbols for main parts of the drawings

DESCRIPTION OF SYMBOLS 1: Base material 2: Multi-colored surface (surface type surface or indented line)

3: 1st film (temporary film) 4: 2nd film (film)

The present invention relates to a multi-colored product in which at least one kind of film having a different color and / or color tone from a base material is formed on at least one surface of the substrate and a method of manufacturing the same. . More specifically, decorative parts such as watch cases, watch bands or belts, dials, brooch, cufflinks, tie pins and lighters, golf clubs, sporting goods of equipment, spectacle frames or carved seals The present invention relates to a multi-colored article used for decorative or marking markings, such as a product, and a manufacturing method thereof.

Surfaces of substrates such as stainless steel, cemented carbide and cermet have been conventionally mirror polished, and their products have been put into practical use as decorative parts, particularly represented by watch cases, bands or belts and dials. However, according to this method, the ornament is monotonous by the intrinsic color of the substrate, and the decorative value is lowered. In addition, even when the engraving or character is realized by means such as etching, it is impossible to obtain a clear one.

In order to solve the above problem, the film is mixed with gold, silver and black according to dry plating methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) or wet plating methods such as anodizing, electroplating and electroless plating. Various proposals have been made for decorative parts exhibiting a hue of a kind. Among these proposals, representative of multicolor decorative parts are disclosed in Japanese Patent Application Publication Nos. 100682/1985, 157673/1986, and 75659/1989.

Japanese Patent Laid-Open Publication No. 100682/1983 discloses a spray coating material of Al ₂ O ₃ and TiO _{2 on} the surface of low carbon austenitic stainless steel. After spraying to a thickness of 0.1 to 1 mm, the surface is mirrored by lapping, and a method for producing a watch exterior part in which gold plating or TiN coating is applied to the remaining stainless steel part is described. However, the watch exterior parts manufactured by this method are deformed between the stainless steel and the thermal spray coating due to heating and cooling during thermal spraying, so that small cracks are generated on the surface of the thermal spray coating, and the aesthetic effect is lowered. Since it cannot be formed by masking and thermal spraying, the design shape or pattern is limited, and in the case of gold plating, the gold film is easily peeled off.

Japanese Unexamined Patent Application Publication No. 157,673 / 1986 discloses that after a hard color layer is formed on the surface of a substrate by an ion plating method, an arbitrary surface of the hard color layer is masked, and a color different from the hard color layer is obtained by ion plating treatment. A method of forming a multicolor hard film is described. However, in the multicolored article achieved by this method, it is difficult to form a fine pattern or a design, and even if a noble metal such as Au or Pt is formed into a film, there is a problem that it cannot be easily peeled off and put into practical use.

In addition, Japanese Patent Laid-Open No. 75,659 / 1989 describes a method of multicoloring a metal surface in which a colored film is formed on the surface of the base metal by ion plating, and then a part of the film is removed by laser processing so as to expose the base metal. It is. However, the multi-colored article obtained by the above method is limited in the material or color of the coating, and especially when a precious metal coating such as Au and Pt is formed, it is difficult to fine pattern or design by the precious metal and easily peels off the adhesiveness to the substrate. It cannot be put to practical use.

The present invention solves the above problems and, for the purpose, a surface portion of a precious metal color formed with good adhesion by a precious metal film such as Au or Pt and Cu on at least one surface or at least one surface thereof, and a different color from the precious metal color. And / or a plurality of colors are formed as the surface portion of the film, which is a color tone, to provide a practical multi-color article and a method of manufacturing the same, which enable fine patterns or designs, letters and marks, as well as increase the adhesion of the film.

The inventors of the present invention propose to form a fine pattern of a noble metal film having a multicolor by coating a noble metal film such as Au, Ag and Pt and another film having a different color and / or color tone from the noble metal film with good adhesion to the surface of the substrate. As a result, after the surface portion of the substrate is removed by irradiating the surface of the substrate with a laser beam locally, a wet metal coating method is used to form a noble metal film, and the adhesion between the substrate and the noble metal film is remarkably excellent. It was found that those formed on the coatings other than the substrate to be treated are easily peeled off. The present invention is accomplished by the above finding.

That is, the multicolored article of the present invention includes a substrate and a coating formed on a specific portion of one surface of the substrate, and the coating includes copper (Cu), silver (Ag), gold (Au), platinum (Pt), and iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Rh) and a monolayer or multilayer film consisting essentially of at least one of the alloys containing these metals, on a heat-melt surface And a concave-shaped surface or line provided on the surface of the substrate.

In one of the preferred embodiments of the present invention (first embodiment), an article has a second surface in which at least one side of the substrate differs in color and / or color tone from (i) the first coating surface portion and the first coating surface portion; A substrate having a multi-color surface consisting of the surface portion of the coating, or (ii) the surface portion of the first coating, the second coating surface, and the surface portion of the substrate, wherein the second coating is Cu, Ag, Au, Pt, Ir, Os, Pd, It consists of a single layer film or a multilayer film consisting essentially of at least one of Ru and the alloy containing the metal (s), and is formed of a concave surface or line provided on the surface of the substrate on a heat-melt surface. .

In another embodiment (second embodiment) of the present invention, the article has at least one side of the substrate (i) a first coating surface portion and a second coating surface portion that is different in color and / or color tone from the first coating surface portion, or ( ii) a substrate which is a multicolor coating surface composed of a first coating surface portion, a second coating surface portion and a surface of the substrate, wherein the first coating is a metal; alloy; Periodic Tables Group 4a (Titanium (Ti), Zirconium (Zr) and Hafnium (Hf)), Group 5a (Vanadium (V), Niobium (Nb) and Tantalum (Ta)) or Group 6a (Chrome (Cr), Molybdenum (Mo) ) And tungsten (W)] carbides, nitrides, carbides or nitrides of metals; oxides, carbides or nitrides of aluminum (Al) or silicon (Si); a solid solid solution of the above; and at least one of hard carbon It is essentially a single layer film or a multilayer film, and the second film is configured as at least one of alloys containing Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and the metal (s). It is a monolayer film or multilayer film.

In addition, the method for producing an article of the present invention comprises the steps of: (a) forming a hypothetically-provided coating composed of a material having a low affinity for the coating to be provided in the steps to be described later; (b) forming a heat-melt surface by a concave surface or a line on the surface of the substrate by irradiating a laser onto the surface of the temporary coating to melt and remove the surface of the temporary film and the substrate of the part; step; (c) forming a film consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and an alloy containing the metal (s); (d) removing the coating formed in step (c) remaining on the temporary coating; And (e) removing the hypothesis coating.

In one of the preferred embodiments of the present invention (first embodiment), a method for producing an article comprises (a) forming a first coating on one surface or part of a substrate by dry plating or wet plating. step; (b) applying a concave shape on the surface of the substrate by irradiating a laser beam onto the surface of the first coating to partially remove the first coating and to finely remove the surface of the substrate corresponding to the first coating. Forming a surface or line; (c) forming a single or multiple layers of a second coating consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and the alloy containing the metal (s). ; And (d) treating the article such that the second coating remains only on the concave surface or line formed in step (b), so that the first coating differs in color and / or color tone from those of the second coating formed in step (c). Forming a surface portion of the and a surface portion of the second coating.

In another preferred embodiment (second embodiment) of the present invention, a method for producing an article comprises: (a) a metal; alloy; Carbides, nitrides, carbonates, nitrates of metals 4a, 5a, or 6a of the periodic table; Oxides, carbides or nitrides of aluminum (Al) or silicon (Si); Mutual solid solution of the materials; And forming a first layer consisting essentially of at least one of the hard carbons in a single layer and a plurality of layers, (b) irradiating a laser beam on the surface of the first film to partially remove the first film. Doing; (c) forming a second film consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and alloys containing the above metals in a single layer or a multilayer by the wet plating method. step; And (d) removing the second film formed on the portion other than the portion where the first film is removed in step (b).

The substrate used in the multicolored article of the present invention is not particularly limited, but for example, a watch case, a watch band or a belt, a dial, a bleach, a cuff button, a tie pin and a lighter, a golf club, equipment, an eyeglass frame, a tool part, and the like. Metal materials such as mild steel, nickel, stainless steel, high speed steel, Cr-Al-Ni alloys, brass and bronze; Inorganic material composites such as ceramic alloys and cemented carbides; Inorganic materials such as glass, ceramic and artificial sapphire; And a material including a composite of an organic material and an inorganic material, such as a fiber reinforced polymer (FRP).

Of these, the preferred ones are stainless steel, heat resistant alloy, high speed steel, cemented carbide, Cr-Al-Ni-alloy, ceramic alloy, brass, bronze, Al alloy and ceramic, and stainless steel, ceramic alloy and cemented carbide are the color and / or color of the film. Particularly good because of the fine contrast of the hue. In terms of use, those suitable for decorative parts, tools and inscription materials are preferred.

The concave surface or the concave line may be provided locally on the surface of the substrate as a heat-melt surface to vary depending on the design or appearance of the desired decoration or display. More specifically, it consists of a width of at least 0.1 [mu] m and a depth of at least 0.5 [mu] m, with a width of at least 0.5 [mu] m and a depth of at least 0.1 [mu] m being particularly good in order to make foolish lines or shapes. The shape of the concave surface or the concave line is, for example, a staircase shape shown in FIGS. 1 and 2, a circle shape shown in FIG. 3, a square shape shown in FIG. 4, and a shape shown in FIG. It can include a V-shaped. Among these, the step shape is particularly good for forming beautiful lines and shapes and for improving the adhesion of the film to the substrate. The step shape may include the shape of one step shown in FIG. 1 or the shape of multiple steps as illustrated by FIG. 2, depending on the width of the concave surface or the concave line. The depth of the concave surface or line is good when it is at least 1 μm deeper than this reference value, based on the minimum value (maximum depth of the substrate surface) generated in the roughness of the substrate surface, and the depth of the film to the substrate. Particularly good is 3 to 100 mu m deeper than the standard value because of the adhesion and the amount of coating used. Otherwise surfaced, the concave surface or concave line is a heat-melt line formed by heating, melting and removing the substrate.

As a material used to form a film consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and an alloy containing the metal (s) (first and first Second film of the second embodiment), Cu, Ag, Au, Pt, Ir, Os, Pd, Rh and Ru, and alloys mainly composed of these metals may be included. Examples of these alloys include Au-Ag alloys, Au-Ni alloys, Au-Ni-In alloys, Au-Cu alloys, Au-Cu-Cd alloys, Pt-Rh alloys, Cu-Zn alloys and Cu-Sn alloys. Can be.

Among them, the use of at least one of Cu, Ag, Au, Pt and alloys containing the metals is particularly good in aesthetics and fastness. Also when Au, Pt and alloys containing these metals are used, these materials are firmly adhered to the substrate preferentially only when the method of the invention is used.

One of these may be used as a single layer film, or a film of a color and / or color tone different from each other or a substrate may be formed by forming a film a plurality of times.

In this case, the coating portion can be formed using a metal such as Ti by the dry plating method.

The thickness of the coating is not particularly limited, but is preferably 0.01 to 20 µm so as to exert the color possessed by the coating material and not to be peeled off internally, and more preferably 0.1 due to color tone, gloss and production cost. To 5 µm. If it is too thick, excessive external power is required to cut the boundary part when the raw material is damaged or when removing a part of the film formed on the temporary film as described below. It is particularly preferable to form the film in a state lower than the surface of the substrate. More specifically, when observing a partial view of the article, for example, it is preferable to form the film with the concave surface or the concave line on the surface of the substrate shown in Fig. 6, wherein reference numeral 1 denotes the substrate, 2 is a concave surface or a concave line, 3 is a first film and 4 is a second film. That is, when an article is observed as a partial view, it is preferable to form a film lower than the following 2nd film.

In a preferred embodiment of the present invention, the (second) film is generally formed on the surface of the substrate (heat-melt portion of the substrate), but it may be formed on the surface of the first film remaining on the substrate.

In the preferred embodiments (1 and 2) of the present invention, the first film can be formed on the surface of the substrate as a single layer film or a multilayer film. The material used to form the first coating is not particularly limited so long as it is different from the viewpoint of adhesion and glossiness to the substrate in color and / or color tone with the second coating, for example, titanium (Ti) ), Zirconium (Zr), Hafnium (Hf), Vanadium (V), Niobium (Nb), Tantalum (Ta), Chromium (Cr), Molybdenum (Mo), Tungsten (W), Cobalt (Co), Nickel (Ni ), Metals such as zinc (Zn) and tin (Sn); Ti-Zr alloys, Ti-Al alloys, Ti-Ni alloys, Ti-Cr alloys and Ti-V alloys; Carbides of metals belonging to Periodic Tables 4a, 5a or 6a, such as Tic, ZrC, Hfc, Nbc, TaC, Cr ₃ C ₂ , MoC, WC, W ₂ C, TiN, ZrN, HfN, VN, NbN and TaN, Nitrides, oxides, borides, or silicates; Metals such as Ti (C, O), Ti (C, N), Ti (N, O), Ti (C, N, O), (Ti, Zr) C and (Ti, Zr) (C, O) Carbonate or nitrate; Oxides, carbides or nitrides of Al or Si (transition metal) such as Al ₂ O ₃ , SiO ₂ , SiC, AlN and Si ₃ N ₄ ; Mutual solid solutions of the above; Or light carbon including diamond-like carbon. Among these, at least one of Ti, Zr, Cr or alloys containing these metals or components thereof; Carbides, nitrides, carbonates and nitrides (particularly TiC and TiN); And its mutual solid solution are particularly good.

In addition, the metals used in the second coating as described above, or alloys containing at least one of them, differ from the second coating in which they are substantially used, provided they provide different colors and / or tints. It may be used as one film.

In the description, the alloy containing the specific metal is not particularly limited as long as the alloy has a low affinity for the second coating in either the two-component system alloy or the multi-component system alloy.

One type of them may be used as a single layer film, and the film may be formed by using two or more types as a multilayer film or by partially forming a multilayer structure so that the film itself may have two or more colors.

The thickness of the first coating may be selectively selected depending on the object, but preferably 10 μm or less, more preferably 1 μm or less, even more preferably 0.1 to 0.5 μm, particularly preferably 0.2 to 0.4 μm. to be.

This first coating can be used as the temporary coating described in the method of making the article.

These first and second films include a single layer film or a multilayer film, and among these, the multilayer film may be formed of two or more kinds of laminates formed parallel to the surface of the substrate or perpendicular to the surface of the substrate.

When the color and / or hue of the substrate is different from either of the first or second coatings, the effect as a third color tone can be exerted on the substrate by exposing a portion of such substrate.

In the present invention, at least one selected from nickel (Ni), cobalt (Co), chromium (Cr), zinc (Zn), cadmium (Cd), aluminum (Al), tin (Sn) and lead (Pb), The precious metal film or the second film can be formed on the metal or alloy film (as the lower layer) formed on the base material or the first film.

The multicolored article may be a dry plating method represented by a physical vapor deposition method or a chemical vapor deposition method such as ion plating, sputtering, electron beam deposition, etc., which have been conventionally performed; Or it can be produced by applying the wet plating method represented by electroplating, non-electroplating and anodizing treatment, but in order to form a beautiful appearance and fine pattern, it is preferable to use the method of the present invention described below.

(a) Formation of the first or temporary film

First, a first film or a temporary film is formed on the multicolored surface of the substrate, and if necessary, pre-treatment such as polishing, lapping or washing may be performed.

Since the temporary film is removed by an acid treatment or other method after forming the film of the present invention, the material can be easily formed and easily removed from the metals and alloys, except for those used in the film formation of the present invention. It should be chosen from the materials possible. In order to easily remove the multicolor coating formed on the temporary coating, a material having a low affinity for the material forming the multicolor coating should be selected. That is, Ti, Zr, Cr, Ti-Zr alloys, Ti-Al alloys, Ti-Ni alloys and Ti-V alloys are good, but metals or alloys different from those actually used for the substrate should be used. In the case where the adhesiveness to the substrate is poor, other substitute layers such as Ni layers are preferably provided.

As a method for forming a first film or a temporary film, selective dry plating such as ion plating, electrodeposition, electron beam deposition, metal spraying, sputtering and CVD depending on the film composition material and method; And wet plating methods such as anodizing, electroplating, and non-electroplating may be used, and may be selected according to the film composition materials and methods, but wet plating is generally preferred. The formation of the coating may be carried out on the entire surface of the substrate or may be carried out only on the parts necessary to form a multicolored surface, for example.

The thickness of the temporary coating may be selectively selected depending on the purpose, but is preferably 10 µm or less, more preferably 1 µm or less, and more preferably 0.1 to 0.5 µm.

(b) laser beam treatment

After forming the first film or the temporary film as described above, the film is locally removed according to the laser beam treatment, and the substrate corresponding to the film portion is melted to a depth of at least 0.5 μm and is also well removed. That is, on the coated surface, the laser beam is irradiated only to the site where the film is later deposited in the shape of a pattern, a pattern, a letter, a mark, or a symbol, so that the first film or the temporary installation film and the substrate (surface portion only) ) Is melted away to expose the substrate.

Examples of the laser include gas lasers such as Ne-He, argon and Co ₂ ; Solid lasers such as ruby, yttrium-aluminum-galium (YAG), and glass; And a semiconductor laser such as GaAs, but YAG laser is good because it is easy to continuously oscillate at room temperature and has good controllability in a low radiation energy region. Irradiation conditions differ depending on the material and the film thickness of the first film or the temporary film and can be irradiated by adjusting the irradiation energy by heating and melting the surface of the film and the substrate to form a heat-melt surface.

The width of destroying the first coating by laser irradiation or by heating and removing the surface of the temporary coating and the substrate varies depending on the purpose and it can be selectively set within a range of 0.1 μm or more, but using the appearance of a multicolored surface. For this purpose, the range of 0.1 to 2 mm is good.

(c) formation of the coating (including the second coating)

Essentially at least one of the alloys containing Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and the metal (s) after washing the surface subjected to laser irradiation with water or an organic solvent. The film | membrane comprised is formed. The formation of the film is carried out by conventional wet plating methods such as anodizing electroplating and non-electroplating.

In the laser beam irradiation step, the grooves formed by the laser beam generally pass through the first coating or the temporary coating to reach the surface of the substrate. In some cases, it penetrates the substrate at a depth of at least 0.5 μm. In the latter case, the film is formed penetrating into the substrate at the depth of the groove. Within the formed film, the film formed on the heat-melt surface is better formed below the surface of the substrate. That is, in this part, the film is well formed on the concave surface or the inner surface of the concave line. In addition, since the grooves reach only the first film and do not reach the basic film, the main portion of the second film may sometimes be formed in the first film remaining at the bottom of the groove. This can be done according to the purpose by selectively adjusting the laser beam irradiation, which is included in the invention as long as it does not depart from the summary of the invention.

(d) Removal of the film (or the second film) from the first or temporary film

According to the discovery by the present inventors, the film (or second film) formed on the substrate or the groove formed by the laser beam treatment is excellent in adhesion to the substrate and firmly adhered to the substrate. In contrast, the coating (or the second coating) formed on the temporary coating (or the first coating) exhibits a peeling property with respect to the coating (or the second coating).

Therefore, after forming the film (or the second film) of the present invention, the next step is to select a method such as washing with water, alcohol, ketone, or a mixture thereof or rubbing with cloth or leather, or the like. Peeling or removing the coating (or the second coating) of the site formed in the coating). The material of the removed film (or second film) is recovered and can be reused.

The above description relates to the case where the two-color surface using the first film and the second film, each of which is a single film or a single layer, is formed on the substrate. By multiplying the first coating or forming the laser beam irradiation and the second coating many times by selection and conventionally known methods, and replacing the materials used for the formation of the second coating with ones of different color and / or color tone, Articles with more than one or more multicolored surfaces can be formed.

(e) Removal of temporary coatings

After the temporary coating is formed, the metal or alloy used as the temporary coating is removed. It can remove it by selecting the conditions which do not damage the film of this invention according to the material of temporary film, such as an acid treatment.

In a second embodiment of the method for producing an article according to the invention, step (a) is processable although it may vary depending on the substrate and the material of the first coating. Ion plating, sputtering or plasma CVD methods are feasible at relatively low temperatures and have little effect on the substrate, resulting in excellent adhesion between the substrate and the first coating, good adhesion of the first coating, and easy adjustment of small amounts of film thickness. Therefore, it is used well. In addition, the laser used in step (b) can be used as described above, among which a solid laser is good for easy melting and removal of fine portions of the substrate surface, and YAG is easy to control pulse width and low energy irradiation. This is especially good. The formation of the second coating in step (C) can be carried out by electrolytic plating or non-electrolytic plating, but in order to densely adhere with good adhesion to the concave surface or the concave line of the substrate on which the fine portion is to be melted away. The electroplating is good. As a post-treatment as in step (c), washing and drying are carried out, and in the washing process, almost all of the second coating attached to the surface of the first coating is removed and restored. When the second film remains on the surface of the first film, the first film is removed by rubbing the film with cloth, leather or paper.

The steps (a), (b) and (c) can be carried out by carrying out (a), (b) and (c) once, but especially when the first film or the second film consists of a multilayered film, When one film forms a multilayered film to produce an article having at least one surface of three or more colors and / or hues, the entirety or part thereof in steps (a), (b) and (c) It is preferable to execute repeatedly. In addition, when the color of the substrate is used to locally expose it, to multicolor, or not to be laminated on the coating portion, it is preferable to partially use masking conventionally performed if necessary.

According to the present invention, fine patterns, patterns, letters, marks and / or symbols may be formed of a multi-colored surface as a first film and a second film or a substrate and a film. First, after forming the first film, the laser beam is irradiated to destroy the first film portion on which the second film is to be formed, thereby improving the adhesion of the second film to be formed on the substrate. In addition, by irradiating the laser beam, not only the portion of the temporary coating film on which the film is to be formed is destroyed, but also the substrate in the portion is melted and removed to a selected depth so that the adhesion of the film formed on the substrate can be improved.

More specifically, in the multicolored article (second embodiment) of the present invention, the adhesion between the substrate and the second coating is formed by forming the second coating on the concave surface or the concave line provided locally on the surface of the substrate. Is improved.

In addition, when Au or a platinum group metal is used as the second coating, it is easily peeled off between the first coating and the second coating, and the adhesion of the second coating to the concave surface or the concave line on the surface of the substrate is good. Thus, at the surface of the article, beautiful and fine patterns, patterns, letters, marks and / or symbols are formed.

The method for producing the multicolored article of the present invention is easy during the pretreatment process, in particular when the Au or platinum group metal is used as the second coating since the second coating is hardly laminated to the surface of the first coating in step (c).

According to the present invention, a multicolored surface having good decorative properties and firmness, and an article having such a surface can be easily formed. The multicolored surface obtained by the present invention can express fine patterns, patterns, letters, marks and / or symbols as long as the material has its own color tone.

Accordingly, the present invention provides the character display in the formation of multicolored patterns or decorative parts such as watch cases, watch bands or belts, dials, bleaches, cuff buttons, tie pins, lighters and sporting goods such as glasses and golf clubs; Improving aesthetic effects such as cutting tools and flame retardant tools; And product names, trademarks, company seals and indications of the quality of the goods or their imprints.

In the following, description will be made with reference to examples and comparative examples of the present invention.

Reference numerals described in the examples are numbers of respective parts used in FIGS. 8 and 9 to describe the method of the present invention. The invention is not limited by these examples.

[Example 1]

The mirror-surfaced SUS 304 substrate by polishing and lapping is treated by a hollow cathode discharging method which has been conventionally practiced to form a Ti film on the surface of the substrate as a first film.

A laser beam is then irradiated from the Ti film surface using a YAG laser processor LAY-603 special type (trade name, produced by K.K. Toshiba) to form a line designed with a width of 0.5 μm to 1 mm. This laser irradiation was performed at an output density of 200 KW / cm 2 and a 0.7 kW pulse width, and it was confirmed that the substrate surface was melted and / or removed. Next, the designed line processed substrate was washed with water and an organic solvent, and then the gold plating treatment conventionally performed was carried out using potassium cyanide gold. After this gold plating treatment, washing and drying were performed to obtain the article 1. When the end view of the article 1 was observed with a metal microscope, the gold film having a film thickness of 3 μm as the second film had a thickness of 0.5 μm to 1 mm and a depth of 10 μm from the surface of the substrate to the inside thereof. It is formed with the concave-surface surface and the concave-shaped line which has, and the Ti film is formed in the thickness of 0.3 micrometer on the surface of a base material and the other surface of a base material. Therefore, the metallic designed lines due to the gold film are clearly highlighted by the metallic luster of the Ti film, and thus appear in two beautiful colors.

Comparative Example 1

By comparison, the surface of the substrate as described above is locally masked and the mixed film of Al ₂ O ₃ -TiO ₂ is formed by the metal spray method. Thus, the gold plating treatment as described above was applied after the masking of the substrate surface was removed, and the coated film surface was wrapped to obtain the comparative article 1. Comparative article (1) comprises an Al ₂ O ₃ -TiO ₂ film thickness of about 500 μm and a gold film of 3 μm thick, and fine cracks are formed on the surface of the Al ₂ O ₃ -TiO ₂ film, resulting in poor surface gloss. The aesthetic value of this is lowered.

The adhesion between the substrate and the gold coating of the article 1 and the comparative article 1 thus obtained was tested by attaching a cellophane tape to the surface of the gold coating and detaching the tape. Peeled off with one cellophane tape. In contrast, the gold film of the present article 1 was not peeled off even though the cellophane tape adhered and detached five times.

[Example 2]

Surface treatment of the surface of the SUS 304 substrate by ion plating or sputtering, laser beam irradiation, and electrolytic plating was carried out in the same manner as the article (1) of Example 1 to form the surface portion of the first film and the surface portion of the second film. The articles 2-5, which had been used, were manufactured. The articles 2-5 thus obtained were tested as in Example 1 to obtain the results shown in Table 1. In addition, when the peeling endogenous test of the second coating by cellophane tape was carried out on the articles 2-5, all the articles 2-5 withstood five times of the subsequent tests. In addition, the concave surface and the concave line of the substrate surface were measured as the depth of the partial surface of the substrate, and the result (depth) is also shown in Table 1. The article 5 was prepared by masking the periphery of the surface to be treated prior to treatment and formed a design from the metal color of the substrate and the color of the coating.

Example 3

After using WC-18 wt% Ni-1 wt% Cr cemented carbide as the substrate, the substrate was mirror-wrapped, and half of the mirror surface was masked and then ion plated to form a film of TiIC, O). Then, masking was first removed and the film surface of Ti (C, O) was masked, and then a Ti film was formed by ion plating. Subsequently, masking was removed, and laser beam was irradiated to the coating surface of Ti (C, O) and the coating film of Ti, and the shape line was formed in 20 micrometers-1 mm width. Next, the gold plating treatment, washing and drying are performed in the same manner as in Example 1, and a gold shape line is highlighted in the Ti metal gloss surface and the black surface of Ti (C, O) to obtain the article 6.

When the thus obtained article 6 was tested in the same manner as in Example 1, a 3 μm thick gold film, a 1 μm thick Ti film, and a 2 μm thick Ti (C, O) film were formed. The substrate surface is concave-shaped with a depth of 5 to 30 탆 toward the interior of the substrate. The gold film adhesion of the article 6 was peeled off using a cellophane tape. When tested by the endogenous test, no peeling occurred even after 5 repetitions.

Example 4

A material corresponding to JIS standard P20 is formed on the surface of a substrate having a slow away chip TNMN 220408 shape for cutting tools, and a TiC film is formed as a CVD process that has been conventionally performed, and then irradiated with a laser beam on the TiC surface. [Tangaroi] characters shown in FIG. 7 were formed by a line having a width of 0.5 µm-0.1 mm, where 1 is the base material, 3 is the first film, and 4 is the second film. Then, the article 7 is obtained after washing and drying by electrolytic plating. In this article (7), Japanese characters having a brass color including Cu-Zn, tangaroi letters are clearly engraved with an gray-black TiC coating, and are beautiful. In addition, when the cross section of the article 7 was examined in the same manner as in Example 1, the base material on which the Cu-Zn film was formed had a concave shape at a depth of 10 μm from the surface of the base material on which the TiC film was formed, A 5 μm thick Cu—Zn film and a 2 μm thick TiC film were included. Moreover, when the endurance test which peeled off the Cu-Zn film of this article 7 using the cellophane tape for adhesive force, peeling did not occur even after 5 repetitions.

Example 5

Ion-plating on a surface 2 on which a multicolored surface of a plate-shaped substrate 1 including SUS 304 mirrored by surface polishing and lapping is formed by a conventional holo-cathode discharge method (HCD method) Was carried out to form a titanium film (3). Next, the YAG laser was irradiated and traveled as 30 W and 12 A on this film, the laser was irradiated in the strip | belt shape of a 1 mm line width, and the film of the said part was melted off.

The surface remaining on the surface 2 in the pattern shape thus obtained was washed with water and acetone, and then gold-plated by a conventional method using gold cyanide and potassium to obtain a gold film 4. This film 4 was thinly bonded to the base material 1 at the portion where the laser beam irradiation was performed in advance, and to (3) at other portions. The product was washed with water, peeled off from the coating 3 to remove the portion of the coating 4 bonded to the coating 3, and then washed and dried to obtain an article having a two-color surface of white or gold color.

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

Comparative Example 2

On one surface of the substrate as used in Example 5, it was locally masked, and the mixed film 3 of AlO-TiO was formed by a metal spray method. Then, after partially masking the surface of the substrate, gold coating treatment 4 as described in Example 5 was carried out, and the coated surface was polished to obtain a comparative article 2 having a two-color surface. . When the surface of the comparative article 2 was examined with a metal microscope, the thickness of the coating 3 was about 500 µm, and the thickness of the coating 4 was 3 µm.

With respect to both articles obtained in Example 5 and Comparative Example 2, when the coating appearance and peeling inspection were performed, the results are shown in Table (2). As can be seen from Table (2), the article of Example (5) is superior to that of Comparative Example 2 in the appearance and adhesion of the coating.

(Note) * Attach cellophane tape on the surface of multi-colored surface and then detach it strongly and repeat this process 5 times and observe whether the gold film is peeled off.

[Examples 6 to 9]

In the same manner as in Example 5 except that the material of the film was changed, the film 3 was formed by ion plating, and the film 4 was formed by laser beam irradiation and plating, thereby including SUS 304. On the surface of the substrate to be formed, a two-color surface having the coating material and thickness shown in Table 3 was formed. The color is shown in Table 3, each of which is excellent in appearance and adhesion of the film 3 to the substrate.

Example 10

A disc of cemented carbide containing 80 wt% WC, 18 wt% Ni and 2 wt% Cr was used as the substrate. After mirror-wrapping this base material, a part was masked and the Ti (C, O) coating film 3 was formed by ion plating. Next, after masking the Ti (C, O) film surface in reverse, the titanium film 3 was formed by ion plating. A laser beam was irradiated on the surface of the disc with different colors to draw a parallel pattern with a width of 1 mm. This material was subjected to gold plating in the same manner as in Example 5, then peeled off, washed and dried to obtain a coating (4). Thus, an article having a three-color surface having a high aesthetic value due to metallic gloss of titanium and gold by gold on a black background of Ti (C, O) can be obtained.

Example 11

The TiC film (B) was formed on the base material of the slow-away chip 120412 for cutting tools of JIS standard P30 using the chemical vapor deposition method. This material was irradiated with a laser beam to print the Japanese tangerine shown in FIG. 9, and then Cu-Zn plating. Then, stripping and removal, washing and drying were performed to obtain a tool engraved with letters.

This tool is as shown in FIG. 9, and the Japanese tangaroy with brass color including Cu-Zn is clearly highlighted on the black TiC film, and has a high aesthetic effect.

Example 12

In order to form the plate-like substrate 1 including the surface of the SUS 304 which is mirror-polished and wrapped on the surface by mirror polishing, a temporary film is formed on the surface 2 which is a multi-colored surface by ion plating by a conventional holographic discharge method (HCD). To form a 0.3 μm thick titanium film 3. Then, the film was irradiated and scanned with a YAG laser at a 2.0 ㎳ pulse width and an output density of 400 KW / cm 2, and the laser beam was irradiated in a band with a 1 mm wide line to cover the film of the part and the substrate part of the part. It was melted off to form a heated melt surface of 30 mu m depth.

The surface where the temporary film 3 of the surface 2 in the pattern state thus obtained remained was washed with water and acetone and gold plated by a conventional method using gold potassium cyanide to obtain a gold film 4 having a thickness of 2 μm. . This film 4 was bonded to the base material 1 of the site where the laser beam irradiation was performed in advance, and was thinly bonded to the film 3 except for this area. After washing with water, the portion of the film 4 bonded to the film 3 was peeled off from the film 3, and then washed and dried. Then, the film 4 partially remaining in the film 3 is wiped off with a cloth.

Next, the gold film remains even if the material is placed in a fluorinated acid solution to remove the titanium film. Then, the material was washed with water and alcohol to obtain the present invention. According to the above steps, the article having the metallic luster and gold color of the two-color surface was obtained.

When the two-color surface thus obtained was examined with a metal microscope, the thickness of the film was 15 µm. In addition, the cellophane tape was affixed to the surface of the article, and the tape was strongly detached to observe whether the film was peeled off. This process was repeated five times but did not peel off.

Example 13

Using the same substrate as in Example 12, Ni plating was performed on the surface of the substrate with a thickness of 2 µm by a known electrolytic plating method, and then Cr plating was performed on the surface of the Ni coating so that the thickness of the coating was 2 µm. It was. Next, a laser beam is irradiated and scanned at a pulse width of 1.7 GHz and an output density of 600 KW / cm 2 from the surface side of the film to form a groove having a depth of 20 µm, and the film and the substrate at the site are melted and removed. A hot melt surface was formed on the surface. Next, in the same manner as in Example 1, a gold plated layer having a thickness of 1 μm was formed, and then washed, dried and washed with a cloth.

Thereafter, the Cr and Ni coatings were removed using hydrochloric acid and a commercially available Ni coating dissolving agent to obtain the present article having a gold coating formed on the surface of the substrate.

Comparative Example 3

By comparison, using the same base material as Examples 12 and 13, gold was plated on the surface of the base material so as to have a film thickness of 2 μm to obtain a comparative article. With respect to the articles obtained in Examples 12, 13 and Comparative Example 3, the adhesion between the gold coating and the substrate was examined by scraping the surface with a wire brush, respectively. As a result, in the article of Comparative Example 3, the gold coating was peeled off at the first trial, but in the articles of Examples 2 and 3 of the present invention, the gold coating was not peeled off even after three trials, and only the scratched line was added.

Claims (11)

Substrate, a coating formed on a specific portion of the surface described above, wherein the coating is copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os), palladium ( Pd), rhodium (Rh), ruthenium (Rh), and a monolayer or multilayer film consisting essentially of at least one of the alloys containing the metal (s) and provided on the surface of the substrate on a heat-melt surface. A multicolored article, characterized in that it is formed into a mold surface or a line. The multicolor article of claim 1, wherein the hot melt surface is formed to a depth of 0.5 μm from the surface of the substrate. at least one surface of a multicolored surface comprising (i) a first coating surface portion and a second coating surface portion that is different in color or color tone from the first coating surface portion, or (ii) a first coating surface portion, the second coating surface portion, and the surface of the substrate. Wherein the second coating includes copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), A monolayer or multilayer film consisting essentially of at least one of ruthenium (Ru) and an alloy containing the metal (s) and formed of a concave surface or a concave line provided on the surface of the substrate on a heat-melt surface. Multicolored article characterized in that. 4. The multicolor article according to claim 3, wherein the second coating has a coating thickness of 0.05 to 20 mu m. The method of claim 3, wherein the first coating is a metal; alloy; Periodic Tables Groups 4a [Titanium ITi, Zirconium (Zr) and Hafnium (Hf)], Group 5a [Vanadium (V), Niobium (Nb) and Tantalum (Ta)] or Group 6a [Chromium (Cr), Molybdenum (Mo) And tungsten (W)] carbides, nitrides, carbonates or nitrides of metals; Oxides, carbides or nitrides of aluminum (Al) or silicon (Si); Mutual solid solution of the materials; And a monolayer film or a multilayer film, which is essentially constituted as one or more of hard carbons. The multicolor article of claim 4, wherein the concave surface or concave line is at least 0.1 μm wide and at least 0.5 μm deep. at least one surface of (i) the first coating surface portion and the second coating surface portion that is different in color or color tone from the first coating surface portion, or (ii) the first coating surface portion, the second coating surface portion and the surface of the substrate. A base material, wherein the first coating is made of metal; alloy; Periodic Tables Group 4a [Titanium (Ti), Zirconium (Zr) and Hafnium (Hf)], Group 5a [Vanadium (V), Niobium (Nb) and Tantalum (Ta)] or Group 6a [Chrome (Cr), Molybdenum (Mo) ) And tungsten (W)] carbides, nitrides, carbonates or nitrides of metals; Oxides, carbides or nitrides of aluminum (Al) or silicon (Si); Mutual solid solution of the materials; And a monolayer or multilayer film consisting essentially of at least one of hard carbons, wherein the second film is copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os). ), Palladium (Pd), rhodium (Rh), ruthenium (Ru), and a multi-colored article characterized in that it is a monolayer film or a multilayer film consisting essentially of at least one of the alloys containing the metal (s). 8. The multicolor article according to claim 7, wherein the hot melt surface is formed to a depth of 0.5 mu m from the surface of the substrate. A method for producing a multicolored article, the method comprising: (a) forming a hypothetical coating made of a material having a low affinity for a coating to be provided in a step described later on a surface of a substrate; (b) forming a heat-melt surface with a concave surface or a line on the surface of the substrate by irradiating a laser beam on the surface of the temporary coating to melt and remove the surface of the temporary coating and the portion of the substrate; ; (c) Copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru) and the metal Forming a film consisting essentially of at least one of the alloys containing (s); (d) removing the coating formed in step (c) remaining on the temporary coating; and (e) removing the temporary coating. CLAIMS 1. A method for producing a multicolor article, the method comprising: (a) forming a first coating on one surface or part of a substrate by dry plating or wet plating; (b) a concave surface on the surface of the substrate by irradiating a laser beam on the surface of the first coating to partially remove the first coating and to finely remove the surface of the substrate corresponding to the first coating. Or forming a line; (c) Copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru) and the metal Forming a second film composed essentially of one or more of the alloys containing (s) in a single layer or a plurality of layers; And (d) treating the article such that the second coating remains only on the concave surface or line formed in step (b), so that the surface of the first coating differs in color or color tone from those of the second coating formed in step (c). Forming a portion and a surface portion of the second coating. CLAIMS 1. A method for producing a multicolored article, comprising: (a) a metal; alloy; Group 4a [Titanium (Ti), Zirconium (Zr) and Hafnium (Hf)], Period 5a [Vanadium (V), Niobium (Nb) and Tantalum (Ta)] or Group 6a (Chrome (Cr), Molybdenum ( Mo) and tungsten (W)] carbides, nitrides, carbonates, or nitrides of metals; Oxides, carbides or nitrides of aluminum (Al) or silicon (Si); Mutual solid solution of the materials; And forming a first film composed essentially of at least one of hard carbons in a single layer and a plurality of layers. (b) irradiating a laser beam onto the surface of the first coating to partially remove the first coating to partially remove the first coating; (c) Copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru) and the metal Forming a second film consisting essentially of at least one of the alloys containing (s) as a single layer or a plurality of layers by a wet plating method, and (d) a portion other than the portion where the first film is removed in step (b). Removing the second coating formed on the substrate.