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EP0459461B1 - Mehrfarbiges Produkt und Verfahren zur Herstellung desselben - Google Patents

Mehrfarbiges Produkt und Verfahren zur Herstellung desselben Download PDF

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Publication number
EP0459461B1
EP0459461B1 EP91108822A EP91108822A EP0459461B1 EP 0459461 B1 EP0459461 B1 EP 0459461B1 EP 91108822 A EP91108822 A EP 91108822A EP 91108822 A EP91108822 A EP 91108822A EP 0459461 B1 EP0459461 B1 EP 0459461B1
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EP
European Patent Office
Prior art keywords
film
base material
concave
product
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91108822A
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English (en)
French (fr)
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EP0459461A1 (de
Inventor
Yoshiyuki C/O Toshiba Tungaloy Co. Ltd. Sato
Daisuke C/O Toshiba Tungaloy Co. Ltd. Kinashi
Kunio C/O Toshiba Tungaloy Co. Ltd. Shibuki
Noriko C/O Yamato Plating Co. Ltd. Watanabe
Akihiro C/O Yamato Plating Co. Ltd. Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YAMATO PLATING CO Ltd
Tungaloy Corp
Original Assignee
YAMATO PLATING CO Ltd
Toshiba Tungaloy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2142160A external-priority patent/JPH0762257B2/ja
Priority claimed from JP2141611A external-priority patent/JP2630344B2/ja
Priority claimed from JP2144547A external-priority patent/JPH0765194B2/ja
Application filed by YAMATO PLATING CO Ltd, Toshiba Tungaloy Co Ltd filed Critical YAMATO PLATING CO Ltd
Publication of EP0459461A1 publication Critical patent/EP0459461A1/de
Application granted granted Critical
Publication of EP0459461B1 publication Critical patent/EP0459461B1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1605—Process or apparatus coating on selected surface areas by masking
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/024—Electroplating of selected surface areas using locally applied electromagnetic radiation, e.g. lasers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated

Definitions

  • This invention relates to a multi-colored product in which at least one kind of a film different in color and/or color tone from a base material is formed on at least one surface of the base material and a process for producing the same. More specifically, it relates to a multi-colored product used for decoration or ornamentation, display and carved seal such as ornament parts including watch cases, watch bands or belts, dials, brooches, cuff buttons, tiepins and lighters, sports goods including golf clubs, tools, flames of glasses or goods with various carved seal, and a process for producing the same.
  • this process involves the problems that the exterior parts for a watch produced by this process causes strain between the stainless steel and the flame coated film due to heat and cool during flame coating and fine cracks cause on the surface of the flame coated film so that aesthetic value becomes low, that shape of design or pattern is restricted since fine line design or pattern cannot be formed by masking and flame coating, and that a film of gold easily peels off in the case of gold plating.
  • Japanese Provisional Patent Publication No. 75659/1989 there is disclosed the multi-coloration process of a metal surface in which a colored film is formed on the surface of a fundamental metal by ion plating method, then a part of the film is removed by laser working to develop the metal.
  • the multi-colored product obtained by the above method has problems that a material of the film or color thereof is restricted, formation of fine pattern or design by a noble metal is difficult particularly when a film of a noble metal such as Au or Pt is to be formed, and adhesiveness to the base material is bad and easily peeled off so that it cannot be practically used.
  • EP-A-0337658 discloses a selective plating method involving laser ablation. A thin polymeric plating resist is placed on a substrate and selectively removed to expose portions of the substrate for metal plating.
  • the present invention has solved the above problems and an object thereof is to provide a multi-colored product having practical value in which plural colors are formed with a surface portion of a noble metal color formed by a film of a noble metal such as Au or Pt and copper series metal with good adhesiveness on at least whole or a part of one surface of the base material, and a surface portion of a film(s) different in color and/or color tone from the noble metal color whereby enabling fine pattern or design, letter and mark as well as heightening adhesiveness of the film, and a process for producing the same.
  • a noble metal color formed by a film of a noble metal such as Au or Pt and copper series metal with good adhesiveness on at least whole or a part of one surface of the base material
  • a surface portion of a film(s) different in color and/or color tone from the noble metal color whereby enabling fine pattern or design, letter and mark as well as heightening adhesiveness of the film, and a process for producing the same.
  • the present inventors have investigated to form a fine pattern with a noble metal film with plural colors by coating a film of a noble metal such as Au, Ag, Pt on the surface of a base material with good adhesiveness and other film different in color and/or color tone from the noble metal film, and as the results, they have found that a film of a noble metal formed by the wet plating method, which is formed after removing the surface portion of a base material by locally irradiating a laser beam to the surface of the base material, shows markedly excellent adhesiveness to the base material and it easily peels off formed on other than the base material processed by the laser beam.
  • the present invention has accomplished by the above findings.
  • the multi-colored product of the present invention comprises a base material and a film formed at a specific portion of one surface of the base material, and said film being a single layer film or plural layered films consisting essentially of at least one of copper (Cu), silver (Ag), gold (Au), platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru) and an alloy containing the above metal(s) and being formed on a heat-fused surface with concave-shaped surface or concave-shaped line provided on the surface of said base material.
  • the product comprises a base material at least one surface of which being a multi-colored surface constituted by (i) a first film surface and a second film surface which is different in color and/or tone from the first film surface, or (ii) the first film surface, the second film surface and a surface of the base material, and said second film being a single layer film or plural layered films consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and an alloy containing the above metal(s) and being formed on a heat-fused surface with a concave-shaped surface or concave-shaped line provided on the surface of said base material.
  • the product comprises a base material at least one surface of which being a multi-colored surface constituted by (i) a first film surface and a second film surface which is different in color and/or tone from the first film surface, or (ii) the first film surface, the second film surface and a surface of the base material, said first film being a single layer film or plural layered films consisting essentially of at least one of a metal; an alloy; a carbide, nitride, carboxide or oxynitride of a metal of group 4a (titanium (Ti), zirconium (Zr) and hafnium (Hf)), 5a (vanadium (V), niobium (Nb) and tantalum (Ta)) or 6a (chromium (Cr), molybdenum (Mo) and tungsten (W)) of the periodic table; an oxide, carbide or nitride of aluminum (Al) or silicon
  • the process for producing the product of the present invention comprises the steps of
  • the process for producing the product comprises the steps of:
  • the process for producing the product comprises the steps of:
  • Fig.s 1 to 5 are sectional views showing representative shapes of concave-shaped surface or concave-shaped line of the surface of the base material in the product according to the present invention wherein reference numeral 1 is a base material and 2 is a concave-shaped surface or concave-shaped line;
  • Fig. 6 is a sectional view showing the representative product of the present invention wherein reference numeral 1 is a base material, 2 is a concave-shaped surface or concave-shaped line, 3 is a first film and 4 is a second film;
  • Fig. 7 is a perspective view of a slow-away chip with letter inscription obtained in Example 4; Fig.
  • FIG. 8 shows one example the process of the present invention (second embodiment) with sectional views wherein reference numeral 1 is a base material, 2 is a surface on which multi-colored surface is to be formed, 3 is a first film and 4 is a second film;
  • Fig. 9 is a perspective view of a tool obtained in Example 11;
  • Fig. 10 shows one example of the process of the present invention with sectional views wherein reference numeral 1 is a base material, 2 is a surface on which multi-colored surface is to be formed, 3 is a temporarily-provided film and 4 is a film.
  • a base material to be used for the multi-colored product in the present invention is not particularly limited and may include, for example, a material to be used for a watch case, watch bands or belts, dials, brooches, cuff buttons, tiepins and lighters, sports goods such as golf clubs, tools, flames of glasses and tool parts, including metal materials such as mild steel, nickel, stainless steel, high speed steel, Cr-Al-Ni alloy, brass and bronze; inorganic materials such as glass, ceramics and artificial sapphire; complexes of an inorganic material and metal such as cermet and hard alloy; and complexes of an inorganic material and organic material such as fiber reinforced polymer (FRP).
  • metal materials such as mild steel, nickel, stainless steel, high speed steel, Cr-Al-Ni alloy, brass and bronze
  • inorganic materials such as glass, ceramics and artificial sapphire
  • complexes of an inorganic material and metal such as cermet and hard alloy
  • complexes of an inorganic material and organic material such as
  • stainless steel heat-resistant alloy, high speed steel, hard alloy, Cr-Al-Ni alloy, cermet, brass, bronze, Al alloy and ceramics
  • stainless steel, cermet and hard alloy since they provide extraordinar contrast to the color and/or tone of the film. In view of use, those which are suitable for materials for ornament parts, tool and inscription are preferred.
  • the concave-shaped surface or concave-shaped line which is heat-fused surface to be locally provided on the surface of the base material may vary depending on design or figure for desired ornament or display. More specifically, it comprises with a width of at least 0.1 »m and a depth of at least 0.5 »m, and for creating beautiful line or shape, a width of at least 0.5 »m and a depth of at least 1 »m are particularly preferred.
  • the shape of the concave-shaped surface or concave-shaped line may include, for example, the shape with steps as shown in Fig.s 1 and 2, circular shape as shown in Fig. 3, rectangular shape as shown in Fig. 4, and V-letter shape as shown in Fig. 5.
  • the shape with steps is particularly preferred for creation of beautiful line and shape, and enhancing adhesion strength of the film to the base material.
  • the shape with steps may include the shape with one step as shown in Fig. 1 or the shape with plural number of steps as exemplified by Fig. 2 depending on the width of the concave-shaped surface or concave-shaped line.
  • the depth of the concave-shaped surface or line is preferred when it becomes at least 1 »m deeper than the standard value which is the minimum value (maximum depth of the surface of the base material) occurred from surface roughness of the base material, particularly preferably 3 to 100 »m deeper than the standard value because of adhesion strength of the film to the substrate and used amount of the film.
  • the concave-shaped surface or concave-shaped line is heat-fused surface or line formed by melting and removing the base material with heat.
  • the materials to be used for forming the film consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and an alloy containing the above metal(s) there may include Cu, Ag, Au, Pt, Ir, Os, Pd, Rh and Ru, and alloys mainly composed of these metals.
  • alloys may include Au-Ag alloy, Au-Ni alloy, Au-Ni-In alloy, Au-Cu alloy, Au-Cu-Cd alloy, Pt-Rh alloy, Cu-Zn alloy and Cu-Sn alloy.
  • One kind of these may be used as a single layer film or else plural number of or layered films different in color and/or tone from each other or from the base material may be formed by effecting formation of the film with plural number of times.
  • part of films may be formed by using a metal such as Ti according to the dry plating method.
  • the thickness of the film is not particularly limited, but preferably 0.01 to 20 »m in order to develop a color possessed by the material for the film and not causing internal peel off, more preferably 0.1 to 5 »m because of color tone, gloss and production cost. If it is too thick, the raw material is spoiled or external power is much required for cutting border portion when removing a portion of the film formed on a temporarily-provided film as described below. It is particularly preferred to form the film in the state of lower than the base material surface. More specifically, when observed by the sectional view of the product, it is preferred to form the film, for example, in the concave-shaped surface or concave-shaped line of the surface of the base material as shown in Fig.
  • reference numeral 1 is the base material
  • 2 is the concave-shaped surface or concave-shaped line
  • 3 is the first film
  • 4 is the second film.
  • it is preferred to form the film lower than the second film mentioned below.
  • the above (second) film is generally formed on the surface of the base material (heat-fused portion of the base material), but it may be formed on the surface of the first film remained on the base material.
  • the first film may be formed with a single layer film or plural layered films on the surface of the substrate.
  • the material to be used for forming the first film is not particularly limited so long as it is different in color and/or tone from those of the second film, and in view of adhesiveness to the base material and beauty of gloss, there may be mentioned, for example, metals such as titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), cobalt (Co), nickel (Ni), zinc (Zn) and tin (Sn); alloys containing at least one of the above metals such as Ti-Zr alloy, Ti-Al alloy, Ti-Ni alloy, Ti-Cr alloy and Ti-V alloy; a carbide, nitride, oxide, boride or silicate of
  • At least one of Ti, Zr, Cr or an alloy containing these metals or a compound thereof; a carbide, nitride, carboxide and oxynitride (particularly TiC and TiN); and mutual solid solutions thereof are particularly preferred.
  • metals used for the second film as mentioned above or alloys containing at least one of these may be used as the first film so long as it is different from the second film actually used and provides different color and/or tone.
  • an alloy containing a specific metal is not particularly limited so long as the alloy has low affinity to the second film in either of the two-component system alloy or multiple-component system alloy.
  • One kind of them may be used as a single layer film or the film may be formed by using two kinds or more as a plural layered film or partially making plural layered structure so that the film itself may have two or more colors.
  • the thickness of the first film may be optionally selected depending on the object thereof, but preferably 10 »m or less, more preferably 1 »m or less, further preferably 0.1 to 0.5 »m, particularly preferably 0.2 to 0.4 »m.
  • This first film may be used as the temporarily-provided film mentioned in the process for producing the product.
  • first and second films comprise a single layer film or plural layered film, and of these, the plural layered film can be made laminated layer of two kinds or more formed in parallel on the surface of the base material or two kinds or more layers formed perpendicularly on the surface of the base material.
  • an effect as the third color hue may be provided to the base material by exposing part of the base material as such.
  • the film of a noble metal or the second film may be formed on a metal or alloy film (as a subbing layer) which is at least one selected from nickel (Ni), cobalt (Co), chromium (Cr), zinc (Zn), cadmium (Cd), aluminum (Al), tin (Sn) and lead (Pb), which is formed on the base material or the first film.
  • a metal or alloy film which is at least one selected from nickel (Ni), cobalt (Co), chromium (Cr), zinc (Zn), cadmium (Cd), aluminum (Al), tin (Sn) and lead (Pb), which is formed on the base material or the first film.
  • the multi-colored product can be produced by applying the dry plating method represented by the physical vapor deposition method or chemical vapor deposition method such as ion plating, sputtering, electron beam deposition, which are conventionally carried out; or the wet plating method represented by electrolytic plating, non-electrolytic plating and anodic oxidation treatment, but for forming a figure with beautiful and fine pattern, it is preferred to employ the process of the present invention as mentioned below (see Fig. 8 and Fig. 10).
  • the dry plating method represented by the physical vapor deposition method or chemical vapor deposition method such as ion plating, sputtering, electron beam deposition, which are conventionally carried out
  • the wet plating method represented by electrolytic plating, non-electrolytic plating and anodic oxidation treatment, but for forming a figure with beautiful and fine pattern, it is preferred to employ the process of the present invention as mentioned below (see Fig. 8 and Fig. 10).
  • a first film or a temporarily-provided film is formed on the surface of the base material to be multicolored. If necessary, pre-treatment such as polishing, lapping or washing may be provided on the surface thereof.
  • the temporarily-provided film is removed after formation of the film of the present invention by an acid treatment or other method.
  • the material of the temporarily-provided film should be selected from materials which are capable of forming a film and easily removable such as a metal and an alloy which are other than those used for formation of the film of the present invention. Selected are those having less affinity to the materials for forming the multi-colored film so as to easily remove the multi-colored film formed on the temporarily-provided film. That is, Ti, Zr, Cr, Ti-Zr alloy, Ti-Al alloy, Ti-Ni alloy and Ti-V alloy are preferred, provided that a metal or an alloy which is different from that actually used for the base material should be used. When adhesiveness to the base material is poor, other subbing layer such as a layer of Ni is preferably provided.
  • optional dry plating method such as ion plating, vacuum vapor deposition, electron beam deposition, metal spraying, sputtering and CVD; and wet plating method such as anodic oxidation treatment, electrolytic plating and non-electrolytic plating depending on the material of the film composition and the method can be selected depending on the same, but generally the wet plating method is preferred.
  • Formation of the film may be carried out on the whole surface of the base material or may be carried out only on part thereof, for example, only on part necessary for forming multi-colored surface.
  • the thickness of the temporarily-provided film may be optionally selected depending on the object, but preferably 10 »m or less, more preferably 1 »m or less, further preferably 0.1 to 0.5 »m.
  • said film is locally removed by the laser beam treatment and the base material corresponding to said film portion is also preferably removed by melting with a depth of at least 0.5 »m. That is, the laser beam is irradiated only to the portion on which a film (including a second film) is to be coated at the later stage with a shape of a design, pattern, letter, mark or symbol to remove by melting the first film, or the temporarily-provided film and the base material (only the surface portion) at the said portion whereby the base material is exposed.
  • the laser there may be exemplified by a gas laser such as Ne-He, argon and CO2; a solid laser such as ruby, YAG (yttrium-aluminum-galium) and glass; and a semiconductor laser such as GaAs (galium-arseinic), but YAG laser is preferred since continuous oscillation can be easily carried out at room temperature and controllability at the low irradiation energy region is good.
  • the irradiation conditions are different depending on the material and film thickness of the first film or temporarily-provided film, and irradiation may be carried out by controlling the irradiation energy so as to form a heat-fused surface by melting the film and the surface of the base material with heat.
  • the width of destroying the first film or removing the temporarily-provided film and the surface of the base material with heat according to the laser irradiation varies depending on the object and it can be set optionally within the range of 0.1 »m or more, but for the use of an appearance of multi-colored surface, it is preferred in the range of 0.1 to 2 mm.
  • a film consisting essentially of at least one of Cu, Ag, Au, Pt, Ir, Os, Pd, Rh, Ru and an alloy containing the above metal(s) is formed. Formation of the film can be carried out by the conventional wet plating method such as anodic oxidation treatment, electrolytic plating and non-electrolytic plating.
  • the groove formed by the laser beam generally reaches to the surface of the base material penetrating the first film or temporarily-provided film, and in some case, it penetrates into the base material with a depth of at least 0.5 »m. And thus, at the portion of the latter case, the film is formed by penetrating into the base material with the depth of the groove.
  • a film formed on the heat-fused surface is preferably formed at the portion lower than the surface of the base material. That is, at this portion, the film is preferably formed at the inside of the concave-shaped surface or concave-shaped line.
  • the groove reaches only in the first film and not reaches to the base film, and thus the main part of the second film may be sometimes formed on the first film remained at the bottom of the groove. This can be made depending on the object by optionally controlling the laser beam irradiation, and is included in the present invention so long as it does not deviate the summary of the present invention.
  • the film (or the second film) thus formed on the base material or the groove formed by the laser beam treatment is excellent in adhesiveness to the base material and firmly adhered to the same.
  • the film (or the second film) formed on the temporarily-provided film (or the first film) shows peel-off property to the film (or the second film).
  • the next step after forming the film (or the second film) of the present invention is to peel off or remove the film (or the second film) at the portion formed on the temporarily-provided film (or the first film) by optional methods such as washing with water, an alcohol, a ketone or a mixed solvent of these or rubbing with a cloth or a leather.
  • the material of the film (or the second film) removed can be recovered and utilized again.
  • the above explanation relates to the case where two-colored surface using the first film and the second film each of which is a single film or layer is formed on the base material.
  • the metal or alloy used as the temporarily-provided film is removed. Removal thereof can be carried out by selecting the conditions which do not impair the film of the present invention depending on the material of the temporarily-provided film such as an acid treatment.
  • the step (a) can be processed while it may vary depending on the material of the base material and that of the first film. It is preferred to use the ion plating, sputtering or plasma CVD method since these methods can be carried out at a relatively low temperature so that there is a little effect to the base material, adhesion between the base material and the first film is excellent, attachment of the first film is good and a minute amount of film thickness can be easily controlled.
  • the laser used in the step (b) may be used as those mentioned above, and of these, the solid laser is preferred since melting and removal at fine portion of the surface of the base material are easy, and YAG is particularly preferred since adjustment of a pulse width and control of low energy irradiation are easy.
  • formation of the second film in the step (c) can be carried out by electrolytic plating or non-electrolytic plating, but electrolytic plating is preferred in order to adhere densely with good adhesiveness to the concave-shaped surface or concave-shaped line of the base material in which fine portion is melted and removed.
  • the post-treatment as the step (c) washing and drying are carried out, and at the washing procedure, almost all the second film attached on the surface of the first film are removed and recovered.
  • the first film can be removed by rubbing the film with a cloth, leather or paper.
  • steps (a), (b) and (c) can be carried out by effecting each step of (a), (b) and (c) with one time.
  • the first film or the second film is made plural layered film, particularly when the first film is made plural layered film to produce a product having at least one surface with colors and/or tones of three or more, it is preferred to carry out the whole steps (a), (b) and (c) or a part thereof repeatedly.
  • the color of the base material is used for multi-coloring by locally exposing it, or not laminating on part of the film, it is preferred, if necessary, to partially use masking which has conventionally carried out.
  • multi-colored surface containing fine design, pattern, letter, mark and/or symbol can be formed by the first film and the second film or the base material and the film.
  • first film by irradiating the laser beam, a portion of the first film, at which the second film is to be formed, is destroyed and adhesiveness of the second film then formed to the base material can be enhanced.
  • a portion of the temporarily-provided film at which the film is to be formed is destroyed as well as the base material at the said portion is fused and removed to an optional depth whereby adhesiveness of the formed film to the base material can be enhanced.
  • the second film in the multi-colored product of the present invention (second embodiment), by forming the second film in the concave-shaped surface or concave-shaped line provided locally on the surface of the base material, adhesiveness between the base material and the second film is enhanced. Also, in the case where Au or platinum group metal is used as the second film, peel off between the first film and the second film easily occurs and adhesiveness of the second film to the concave-shaped surface or concave-shaped line of the surface of the base material is good. Thus, on the surface of the product, beautiful and fine design, pattern, letter, mark and/or symbol are formed.
  • the process for producing the multi-colored product of the present invention is easy in post-treatment particularly when Au or platinum group metal is used as the second film since the second film is scarcely laminated on the surface of the first film at the step (c).
  • a multi-colored surface which is rich in ornamental property and fastness, and a product having such a surface can be easily formed.
  • the multi-colored surface obtained according to the present invention retains inherent color tone possessed by the material itself and is capable of expressing fine design, pattern, letter, mark and/or symbol.
  • the present invention is extremely useful for formation of multi-colored pattern or display of letters of ornament parts such as watch cases, watch bands or belts, dials, brooches, cuff buttons, tiepins, lighters and glasses, sports goods such as golf clubs; improvement in aesthetic effect of tools such as cutting tools and wear-resistant tools; and display of product name, trade mark, company seal and quality of the product in various products or their carved seals.
  • SUS 304 base material which is mirror-surfaced by polishing and lapping was processed by the hollow cathode discharging (HCD) method which has conventionally been carried out to form a film of Ti on the surface of the base material as the first film.
  • HCD hollow cathode discharging
  • a laser beam was irradiated from the film surface of Ti by using YAG laser processor LAY-603 special type (trade name, manufactured by K.K. Toshiba) to form designed lines with a width of 0.5 »m to 1 mm.
  • This laser irradiation was carried out with a power density of 200 kw/cm2 and a puls width of 0.7 ms, and it was confirmed that the surface of the base material had been fused and/or removed.
  • the base material on which designed lines had been processed was washed with water and an organic solvent, and then gold plating treatment which has been conventionally carried out was carried out by using potassium aurous cyanide. After this gold plating treatment, washing and drying were carried out to obtain the present product 1.
  • a gold film as the second film with a film thickness of 3 »m was formed in the concave-shaped surface and concave-shaped line with a width of 0.5 »m to 1 mm and a depth from the surface of the base material to the inside of the same of 10 »m at the surface of the base material, and at the other surface of the base material, the film of Ti was formed with a thickness of 0.3 »m.
  • the film surface showed two-colored beautiful color since gold colored-designed line due to the film of gold was clearly embossed in the metallic luster of the Ti film.
  • the surface of the base material which is the same one as mentioned above was locally masked and a mixed film of Al2O3-TiO2 was formed by metal spraying method. Then, after removing the masking on the surface of the base material, the same gold plating treatment as mentioned above was applied to, and the coated film surface was subjected to lapping treatment to obtain comparative product 1.
  • the comparative product 1 comprises an Al2O3-TiO2 film thickness of about 500 »m and a gold film thickness of 3 »m, and fine cracks were present at the Al2O3-TiO2 film surface whereby gloss of the surface was poor and its aesthetic value was low.
  • the concave-shaped surface and concave-shaped line of the surface of the base material were measured as a depth from the sectional surface of the base material and the results (depths) are also shown in Table 1.
  • the present product 5 was produced by masking the peripheral portions of the surface to be treated before the treatment and formed a design from the metallic color of the base material and a color of the film.
  • a film of TiC was formed on the surface of a base material with slow away chip TNMN 220408 shape for cutting tool with a material corresponding to P20 of JIS standard by CVD treatment which has been conventionally carried out, and then letters of "TUNGALOY" in Japanese character as shown in Fig. 7 were formed by a line with a width of 0.5 »m to 0.1 mm by irradiating a laser beam on the surface of TiC film, wherein 1 is the base material, 3 is the first film and 4 is the second film. Then, Cu-Zn film treatment according to electrolytic plating, washing and drying were carried out to obtain the present product 7.
  • Titanium film 3 was formed on the surface 2 in which multi-colored surface is to be formed of the plate-shaped base material 1 comprising SUS 304 the surface of which had been mirror surfaced according to polishing and lapping of the surface, by subjecting to the ion plating according to the conventional hollow cathode discharging (HCD method) method. Then, on said film, YAG laser was irradiated and scanned with 30 W and 12 A whereby the laser beam was irradiated to striped shape with a line width of 1 mm to melt and remove the film at the said portion.
  • HCD method hollow cathode discharging
  • the surface in which the film 3 was remained on the surface 2 with pattern state thus obtained was washed with water and acetone, and subjected to gold plating by the conventional method using potassium aurous cyanide to obtain a film 4 of gold.
  • This film 4 was joined to the base material 1 at the portion in which the laser beam irradiation had been previously carried out and thinly joined to 3 at the portion other than the above.
  • the portion of the film 4 joined to the film 3 peel off and removed from the film 3, followed by washing and drying to obtain the present product 8 having two colored surface of silver white and gold colors.
  • a thickness of the film 3 was 0.3 »m and a thickness of the film 4 was 2 »m.
  • Example 5 On one surface of the base material which is the same with that used in Example 5 was locally masked and a mixed film 3 of Al2O3-TiO2 was formed by metal spraying method. Then, after partially removing the masking on the surface of the base material, the same gold plating treatment 4 as mentioned in Example 5 was applied to, and the coated film surface was polished to obtain comparative product 2 having two-colored surface.
  • a thickness of the film 3 was about 500 »m and a thickness the film 4 was 2 »m.
  • Example 5 In the same manner as in Example 5 except for changing the material of the film, two-colored surfaces having film materials and thicknesses as shown in Table 3 were formed on the surface of the base material comprising SUS 304 by subjecting to formation of the film 3 according to the ion plating, laser beam irradiation and formation of the film 4 according to plating.
  • the colors thereof are shown in Table 3, each of which showed beautiful appearance and excellent in adhesiveness of the film 3 to the base material.
  • a disc of hard alloy comprising 80 % by weight of WC, 18 % by weight of Ni and 2 % by weight of Cr was used as the base material. After this base material was subjected to mirror surface lapping, part thereof was masked and a film 3 of Ti(C, O) was formed by the ion plating. Then, after masking the Ti(C, O) film surface reversely, a film 3' of titanium was formed by the ion plating. To the disc plate surface having different color was drawn parallel line-shaped pattern with a width of 1 mm by a laser beam irradiation. To the material was subjected to gold plating in the same manner as in Example 5, followed by peel off and removal, washing and drying to obtain a film 4.
  • This tool is as shown in Fig. 9, letters of "TUNGALOY” in Japanese character comprising Cu-Zn having a brass color were clearly embossed in black colored TiC film and it has high aesthetic effects.
  • Titanium film 3 with a thickness of 0.3 »m was formed as a temporarily-provided film on the surface 2 in which multi-colored surface is to be formed of the plate-shaped base material 1 comprising SUS 304 the surface of which had been mirror surfaced according to polishing and lapping of the surface, by subjecting to the ion plating according to the conventional hollow cathode discharging (HCD method) method.
  • HCD method hollow cathode discharging
  • YAG laser was irradiated and scanned with a pulse width of 2.0 ms and a power density of 400 kW/cm2 whereby the laser beam was irradiated to striped shape with a line width of 1 mm to melt and remove the film at the said portion and part of the base material at the said portion whereby a heat-fused surface with a depth of 30 »m was formed.
  • the surface in which the temporarily-provided film 3 was remained on the surface 2 with pattern state thus obtained was washed with water and acetone, and subjected to gold plating by the conventional method using potassium aurous cyanide to obtain a film 4 of gold with a thickness of 2 »m.
  • This film 4 was joined to the base material 1 at the portion in which the laser beam irradiation had been previously carried out and thinly joined to 3 at the portion other than the above.
  • the portion of the film 4 joined to the film 3 peel off and removed from the film 3, followed by washing and drying. Then, the film 4 remained partially on the film 3 was wiped off and removed with a cloth.
  • the titanium film was removed by dipping the material in a hydrofluoric acid solution whereby the gold film was remained. Then, the material was washed with water and alcohol to obtain the product of the present invention.
  • the product of the present invention having two-colored surface of metallic luster and gold color was obtained.
  • Ni plating with a thickness of 2 »m was carried out on the surface of the base material according to the conventionally known electrolytic plating method, and then Cr plating was subjected on the surface of the Ni film so as to become the film thickness of 2 »m.
  • a laser with a pulse width of 1.7 ms and a power density of 600 kW/cm2 was irradiated and scanned to form groove with a depth of 20 »m whereby the film at the said portion and the base material of the same were fused and removed to form a heat-fused surface on the surface of the base material.
  • a gold plating layer with a thickness of 1 »m was formed, and then washing, drying and wiping with a cloth were carried out.

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  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
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  • Laminated Bodies (AREA)

Claims (11)

  1. Mehrfarbiges Produkt, das ein Basismaterial und einen Film umfaßt, welcher auf einem spezifischen Bereich von einer Oberfläche des Basismaterials gebildet ist,
    dadurch gekennzeichnet, daß
    der genannte Film ein Einzelschichtfilm ist oder aus Filmen in mehreren Schichten zusammengesetzt ist, welche im wesentlichen aus mindestens einem Material aus Kupfer (Cu), Silber (Ag), Gold (Au), Platin (Pt), Iridium (Ir), Osmium (Os), Palladium (Pd), Rhodium (Rh), Ruthenium (Ru) und aus einer die obigen Metalle enthaltenden Legierung bestehen und auf einer Hitze-geschmolzenen Oberfläche gebildet sind, wobei eine konkav-geformte Oberfläche oder konkav-geformte Linie auf der Oberfläche des genannten Basismaterials bereitgestellt sind.
  2. Produkt gemäß Anspruch 1,
    worin die genannte Hitze-geschmolzene Oberfläche in einer Tiefe von 0,5 »m von der Oberfläche des genannten Basismaterials aus gebildet ist.
  3. Produkt gemäß Anspruch 1,
    worin mindestens eine Oberfläche des Basismaterials mehrfarbig ist und
    (i) eine erste Filmoberfläche und eine zweite Filmoberfläche, die sich bezüglich Farbe und/oder Farbton von der ersten Filmoberfläche unterscheidet, oder
    (ii) die erste Filmoberfläche, die zweite Filmoberfläche und eine Oberfläche des Basismaterials umfaßt,
    worin die zweite Filmoberfläche eine in Anspruch 1 für die Filme definierte Zusammensetzung aufweist.
  4. Produkt gemäß Anspruch 3,
    worin der genannte zweite Film eine Filmdicke von 0,05 bis 20 »m aufweist.
  5. Produkt gemäß Anspruch 3,
    worin der genannte erste Film ein Einzelschichtfilm ist oder aus Filmen aus mehreren Schichten zusammengesetzt ist, welche im wesentlichen aus mindestens einem Material aus einem Metall, einer Legierung, einem Carbid, Nitrid, Carboxid oder Oxinitrid eines Metalls der Gruppe 4a (Titan (Ti), Zirkon (Zr) und Hafnium (Hf)), 5a (Vanadin (V), Niob (Nb) und Tantal (Ta)) oder 6a (Chrom (Cr), Molybdän (Mo) und Wolfram (W)) des Periodensystems, aus einem Oxid, Carbid oder Nitrid von Aluminium (Al) oder Silizium (Si), aus einer gegenseitigen festen Lösung der obigen Materialien und aus Hartkohlenstoff bestehen.
  6. Produkt gemäß Anspruch 4,
    worin genannte konkav-geformte Oberfläche oder konkavgeformte Linie eine Breite von mindestens 0,1 »m und eine Tiefe von mindestens 0,5 »m aufweisen.
  7. Produkt gemäß jedem der Ansprüche 1 , 3 oder 5,
    worin der genannte zweite Film ein Einzelschichtfilm oder aus einem Film oder Filmen aus mehreren Schichten zusammengesetzt ist, welche im wesentlichen aus mindestens einem Material aus Kupfer (Cu), Silber (Ag), Gold (Au), Platin (Pt), Iridium (Ir), Osmium (Os), Palladium (Pd), Rhodium (Rh), Ruthenium (Ru) und aus einer die obigen Metalle enthaltenden Legierung bestehen.
  8. Produkt gemäß Anspruch 7,
    worin die genannte Hitze-geschmolzene Oberfläche in einer Tiefe von 0,5 »m von der Oberfläche des genannten Basismaterials aus gebildet ist.
  9. Verfahren zur Herstellung eines mehrfarbigen Produkts, gekennzeichnet durch die Stufen, in denen man:
    (a) auf der Oberfläche eines Basismaterials einen temporär aufgebrachten Film aus einer Substanz bereitstellt, die eine niedrigere Affinität zu einem in der späteren Stufe aufzubringenden Film aufweist,
    (b) auf die Oberfäche des genannten temporär aufgebrachten Films mit einem Laserstrahl strahlt, um den genannten temporär aufgebrachten Film und die Oberfläche des Basismaterials des genannten Bereichs zu schmelzen und zu beseitigen, wodurch eine Hitze-geschmolzene Oberfläche mit einer konkav-geformten Oberfläche oder konkav-geformten Linie auf der Oberfläche des Basismaterials gebildet wird,
    (c) einen Film, bestehend im wesentlichen aus mindestens einem Metall aus Kupfer (Cu), Silber (Ag), Gold (Au), Platin (Pt), Iridium (Ir), Osmium (Os), Palladium (Pd), Rhodium (Rh), Ruthenium (Ru) und aus einer die obigen Metalle enthaltenden Legierung, auf der genannten behandelten Oberfläche bildet,
    (d) den in der obigen Stufe (c) gebildeten Film entfernt, der auf dem genannten temporär aufgebrachten Film verblieben ist, und gegebenenfalls
    (e) den genannten temporär aufgebrachten Film entfernt.
  10. Verfahren gemäß Anspruch 9,
    worin der Film in Stufe (a) durch ein Trocken- oder Naßplattierverfahren gebildet, die Bestrahlung in Stufe (b) örtlich durchgeführt werden, um den genannten ersten Film zu beseitigen, wobei der zweite Film von Stufe (c) ein einzelner sein kann oder mehrere Schichten aufweist und Stufe (d) darauf beruht, daß das Produkt so verarbeitet wird, daß der zweite Film nur auf der in Stufe (b) gebildeten konkav-geformten Oberfläche oder Linie verbleibt, und daß man einen Oberflächenteilbereich des ersten Films, der sich in Farbe und/oder Farbton vom zweiten Film unterscheidet, auf dem Substrat zurückläßt, indem man Stufe (e) wegläßt.
  11. Verfahren gemäß Anspruch 9 oder 10,
    wobei der Film in Stufe (a) im wesentlichen aus mindestens einem Metall, einer Legierung, einem Carbid, Nitrid, Carboxid oder Oxinitrid eines Metalls der Gruppe 4a (Titan (Ti), Zirkon (Zr) und Hafnium (Hf)), 5a (Vanadin (V), Niob (Nb) und Tantal (Ta)) oder 6a (Chrom (Cr), Molybdän (Mo) und Wolfram (W)) des Periodensystems, einem Oxid, Carbid oder Nitrid von Aluminium (Al) oder Silizium (Si), aus einer gegenseitigen festen Lösung der obigen Materialien und aus Hartkohlenstoff in einer Einzel- oder Mehrfachschicht besteht, die Bestrahlung in Stufe (b) den genannten ersten Film teilweise beseitigt und der oder die zweiten Film(e) in Stufe (c) durch ein Naßplattier-Verfahren hergestellt sind.
EP91108822A 1990-05-31 1991-05-29 Mehrfarbiges Produkt und Verfahren zur Herstellung desselben Expired - Lifetime EP0459461B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2142160A JPH0762257B2 (ja) 1990-05-31 1990-05-31 多色被覆表面物品及びその製造方法
JP142160/90 1990-05-31
JP141611/90 1990-06-01
JP2141611A JP2630344B2 (ja) 1990-06-01 1990-06-01 多色表面物品の製造方法
JP144547/90 1990-06-04
JP2144547A JPH0765194B2 (ja) 1990-06-04 1990-06-04 有色表面物品及びその製造方法

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EP0459461B1 true EP0459461B1 (de) 1995-08-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9611412B2 (en) 2009-02-11 2017-04-04 Element Six (Production) (Pty) Ltd Process for coating diamond with refractory metal carbide and metal

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI92112C (fi) * 1992-11-09 1994-09-26 Partek Cargotec Oy Menetelmä taustastaan tummempina erottuvien alueiden muodostamiseksi kirkkaaseen metallipintaan ja tällä tavoin värjättyjä alueita käsittävä metallipinta
US5801356A (en) * 1995-08-16 1998-09-01 Santa Barbara Research Center Laser scribing on glass using Nd:YAG laser
GB9522484D0 (en) * 1995-11-02 1996-01-03 Solicitors Of The Affairs Of H Coins
US7578921B2 (en) * 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
EP1477589A4 (de) * 2002-01-25 2007-12-12 Showa Denko Kk Metallverbundmaterial und herstellungsverfahren dafür, geätztes metallmaterial und herstellungsverfahren dafür und elektrolytkondensator
US6855408B2 (en) 2002-01-25 2005-02-15 Showa Denko K.K. Composite metal material and method for manufacturing the same, etched metal material and method for manufacturing the same and electrolytic capacitor
DE10214330A1 (de) * 2002-03-28 2003-10-16 Giesecke & Devrient Gmbh Sicherheitselement und Verfahren zu seiner Herstellung
KR20040035530A (ko) * 2002-10-22 2004-04-29 송오성 위에서 아래방향으로 선택적 제거에 의한 티타늄 발색
US8828213B2 (en) * 2011-02-09 2014-09-09 Dai Nippon Printing Co., Ltd. Stainless substrate having a gold-plating layer, and process of forming a partial gold-plating pattern on a stainless substrate
KR101594723B1 (ko) * 2011-08-18 2016-02-16 애플 인크. 양극 산화 및 도금 표면 처리
US9683305B2 (en) 2011-12-20 2017-06-20 Apple Inc. Metal surface and process for treating a metal surface
EP3708384A1 (de) * 2019-03-14 2020-09-16 Omega SA Verkleidungselement oder zifferblatt einer uhr oder eines schmuckstücks aus leitendem material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0337658A1 (de) * 1988-04-12 1989-10-18 The Whitaker Corporation Selektive Plattierung durch Abtragen mittels eines Lasers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6148570A (ja) * 1984-08-10 1986-03-10 Mitsubishi Electric Corp 樹脂への導体層形成方法
DE3770896D1 (de) * 1986-09-15 1991-07-25 Gen Electric Verfahren zur photoselektiven metallisierung.
JP2820451B2 (ja) * 1988-11-22 1998-11-05 シチズン時計株式会社 装身具

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0337658A1 (de) * 1988-04-12 1989-10-18 The Whitaker Corporation Selektive Plattierung durch Abtragen mittels eines Lasers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9611412B2 (en) 2009-02-11 2017-04-04 Element Six (Production) (Pty) Ltd Process for coating diamond with refractory metal carbide and metal

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DE69112277D1 (de) 1995-09-28
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DE69112277T2 (de) 1996-03-07
HK1000088A1 (en) 1997-11-21
EP0459461A1 (de) 1991-12-04

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