JP4131386B2 - Method for forming electroplating film on article surface - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a uniform and dense electroplating film on a surface of the article with excellent adhesion without depending on the surface material and surface properties of the article.
[0002]
[Prior art]
For the purpose of imparting surface conductivity, electromagnetic wave shielding properties, antibacterial properties, impact resistance, and the like for decorativeness, weather resistance, antistatic properties, etc., a metal film has been conventionally formed on the surface. Yes. There are various methods for forming a metal film, and among them, an electroplating film forming method by electroplating is widely used because it is suitable for mass production.
[0003]
However, in order to form an electroplated film on the article surface, the article surface needs to be conductive. Therefore, it is not possible to directly form an electroplating film on the surface of an article made of a nonconductive material such as plastic, wood, paper, glass, ceramics, rubber, or concrete. In addition, there is a case where it is desired to form a metal film on the surface of an article made of a metal material such as magnesium, aluminum or titanium (such as a case of a mobile phone or a notebook personal computer). Magnesium is a particularly base metal among metals. . Therefore, even if an electroplating film is to be formed on the surface, an abrupt displacement plating reaction occurs as soon as it is immersed in the plating bath, and it is difficult to form a high-quality electroplating film. Aluminum and titanium are highly oxidizable metals, and their surfaces are usually covered with a very dense metal oxide film. Therefore, although these metals have a low ionization tendency, the surface potential is high, and it is difficult to perform electroplating. If the metal oxide film on the surface is removed, an electroplated film can be formed. However, a special etching technique is required, and after the metal oxide film is removed, the metal oxide film is formed again. Since there is a time restriction that the electroplating process must be performed before the generation, it must be said that there is a problem in practical use. By soaking in a solution containing sodium hydroxide and zinc hydroxide, etching is performed in a strong alkaline environment, and at the same time, a so-called zincate treatment is performed to form a zinc replacement plating film, and then an electroless plating film is formed. There is a method of performing electroplating treatment through the process, but the whole process is complicated.
In addition, when a uniform electroplating film is formed on the surface of an article having pores, fine grooves or irregularities on the surface, such as a wooden bat, brick, or die-cast product, the surface of the article is made conductive. It must be solved how to ensure smoothness of the article surface as well as how to impart it.
In addition, since an article made of a highly corrosive material such as a metal such as magnesium may corrode when an electroplating process is performed, it is necessary to form an electroplating film on such an article. There are difficulties.
[0004]
[Problems to be solved by the invention]
When trying to solve the above problem using a known technique, after forming a resin film made of a resin in which metal powder is dispersed on the surface of an article, described in JP-A-61-210183, A method of forming an electroless plating film on the surface of the resin film and a method of forming an electroplating film on the surface of the electroless plating film thus formed can be considered. However, since the electroless plating film is a film formed by reducing metal ions in the plating solution by the action of a reducing agent and depositing metal on the surface of the object to be plated, it has poor adhesion to the object to be plated. At the same time, the film formation efficiency is poor. There is a method of improving the film formation efficiency using a palladium catalyst or a platinum catalyst, but this method cannot avoid an increase in cost. Moreover, it cannot be denied that impurities derived from the reducing agent contained in the electroless plating film adversely affect the formation of the electroplating film on the surface.
Therefore, an object of the present invention is to provide a method for forming a uniform and dense electroplated film on the surface with excellent adhesion without depending on the surface material or surface property of the article.
[0005]
[Means for Solving the Problems]
  In view of the above points, the method for forming an electroplated film on the surface of an article of the present invention, which has been completed through various studies by the present inventors, is as follows.The average particle size is 2 μm to 30 μmMade of resin in which powder of first metal is dispersedVolume resistivity is 1 × 10 ⁴ Non-conductive more than Ω · cmAfter forming the film, thisNon-conductiveBy immersing the film-forming article in a solution containing ions of the second metal having a potential more noble than the first metalNon-conductiveA replacement plating film of a second metal is formed on the surface of the coating, and an electroplating film of a third metal is further formed on the surface of the replacement plating film.(However, rare earth permanent magnets are excluded as articles).
MaClaim2The forming method according to claim 1, wherein the dispersion amount of the powder of the first metal in the resin film is 50 wt% to 99 wt% in the forming method according to claim 1..
MaClaim3The forming method according to claim 1 is characterized in that in the forming method according to claim 1, the film thickness of the resin film is 1 μm to 100 μm.
  Claims4The forming method according to claim 1 to claim 1.3In the forming method according to any one of the above, the first metal is zinc and the second metal is nickel.
  Claims5The forming method according to claim 1 to claim 1.3In the forming method according to any one of the above, the first metal is nickel and the second metal is copper.
  Claims6The forming method according to claim 1 to claim 1.5In the forming method according to any one of the above, the second metal and the third metal are the same metal.
  Claims7The forming method described in claim6The forming method described above is characterized in that the step of forming the displacement plating film and the step of forming the electroplating film are performed in one plating bath.
  Claims8The forming method according to claim 1 to claim 1.7In the forming method according to any one of the above, the thickness of the displacement plating film is 0.05 μm to 2 μm.
  The article of the present invention is also claimed9As described, claims 1 to8An electroplated film is formed on the surface by the forming method according to any one of(Excluding rare earth permanent magnets).
  Further, the method for forming a displacement plating film on the surface of the article of the present invention is as follows.10As stated, on the surface of the articleThe average particle size is 2 μm to 30 μmMade of resin in which powder of first metal is dispersedVolume resistivity is 1 × 10 ⁴ Non-conductive more than Ω · cmAfter forming the film, thisNon-conductiveBy immersing the film-forming article in a solution containing ions of the second metal having a potential more noble than the first metalNon-conductiveForming a replacement plating film of a second metal on the surface of the film;(Excluding rare earth permanent magnets as articles).
  The article of the present invention is also claimed11As described, a displacement plating film is formed on the surface by the forming method according to claim 13.(Excluding rare earth permanent magnets).
[0006]
DETAILED DESCRIPTION OF THE INVENTION
According to the method of forming an electroplated film on the surface of an article of the present invention, a resin film made of a resin in which a powder of a first metal is dispersed is formed on the surface of the article, and then the resin film-formed article has a higher potential than the first metal. A second metal displacement plating film is formed on the surface of the resin film by immersing in a solution containing ions of the second metal having a metal, and a third metal electroplating film is further formed on the surface of the replacement plating film. To do.
[0007]
In the method for forming an electroplated film on the surface of an article of the present invention, a resin film made of a resin in which a powder of the first metal is dispersed is formed on the article surface, and then exists on or near the resin film surface. By using a displacement plating reaction starting from the powder of the first metal, a displacement plating film of the second metal having excellent adhesion is formed on the entire surface of the resin film. As a result, since conductivity is imparted to the entire surface of the article, it is possible to form a uniform and dense third metal electroplating film on the surface of the displacement plating film with excellent adhesion. Therefore, it has excellent adhesion to the surface of the article made of any material such as plastic, wood, paper, glass, ceramics, rubber, concrete, metal, etc. without depending on the surface material and surface properties of the article. It can be formed with sex.
Hereinafter, the method for forming an electroplated film on the surface of the article of the present invention will be described in order.
[0008]
Step 1:
First, a resin film made of a resin in which a first metal powder is dispersed is formed on the surface of an article. For example, a thermosetting resin can be used as the resin that is the main component of the resin coating. Specific examples include phenol resins, epoxy resins, melamine resins, acrylic resins, polyester resins, urethane resins, polyimide resins, styrene acrylic resins, and mixed resins thereof.
[0009]
There is no particular restriction on the type of the first metal powder dispersed in the resin coating, but the first metal has a lower potential than the second metal in order to cause a displacement plating reaction in a later step. Is essential. Therefore, the first metal is appropriately selected in consideration of the potential difference with the second metal. Specific examples of the combination of the first metal and the second metal include a combination of the first metal being zinc and the second metal being nickel, and the first metal being nickel and the second metal being copper.
[0010]
  The resin film made of resin in which the powder of the first metal is dispersed is,Non-conductive coatingAndThe resin film formed on the surface of an article made of a highly corrosive material such as a metal such as magnesium is preferably a non-conductive film. Even if the surface of the resin film corrodes during the displacement plating process or electroplating process, defects such as pinholes and scratches occur in the electroplated film formed on the resin film surface via the displacement plating film, This is because even if the surface of the resin coating corrodes through the defect or the like, it is possible to prevent the corrosion from proceeding to the surface of the article through the resin coating.
[0011]
The non-conductive film made of a resin in which the powder of the first metal is dispersed is, for example, the non-conductive resin itself in which the powder of the first metal is dispersed, and if necessary, such a resin is used as an organic solvent. After the solution prepared by diluting with is spray-coated on the surface of the article as a treatment liquid, or the article is immersed in the treatment liquid for dip-coating, it is formed by drying. Some non-conductive resins in which metal powder is dispersed are commercially available and can be easily obtained. Even if the resin in which the powder of the first metal is dispersed is conductive, the treatment liquid can be made non-conductive by adding an organic dispersion medium to uniformly disperse and isolate the individual metal powder. You can also. In this case, as an organic dispersion medium, an anionic dispersion medium (aliphatic polyvalent carboxylic acid, polyether polyester carboxylate, polymer polyester acid polyamine salt, high molecular weight polycarboxylic acid long chain amine salt, etc.), nonionic -Soluble dispersion media (carboxylates such as polyoxyethylene alkyl ethers and sorbitan esters, sulfonates, and ammonium salts), polymer dispersion media (carboxylates, sulfonates, and ammonium salts of water-soluble epoxies, styrene- Acrylic acid copolymer, glue, etc.) are preferably used from the viewpoint of affinity with metal powder and cost. Moreover, as long as it is a process liquid which can form a nonelectroconductive film, itself may be electroconductive. In preparing the treatment liquid, a dispersing machine such as a ball mill, an attritor or a sand mill can be used as appropriate.
[0012]
  The non-conductive coating made of resin in which the powder of the first metal is dispersed prevents the corrosion from proceeding to the surface of the article through the inside of the coating even if the coating surface is corroded. On the other hand, it has the effect of imparting corrosion resistance. This effect includes the self-repairing action of the coating (corrosion compound of the first metal (ZnCl when the first metal is zinc).₂・ 4Zn (OH)₂Or ZnO, etc.) and the effect of burying the defects even if defects such as pinholes and scratches are present in the coating due to the increase in volume due to the generation of the resin and swelling of the resin) and the sacrificial anticorrosive action of the first metal Etc. are also considered to contribute. To make this effect more certainIn addition,The volume resistivity of the non-conductive coating is 1 × 10⁴Ω · cm or moreTheThe above-mentioned organic dispersion medium may be added to the treatment liquid to suppress the aggregation and sedimentation of the metal powder in the treatment liquid, thereby increasing the volume resistivity by increasing the dispersibility of the metal powder.
[0013]
  In order for the metal powder in the resin film to be the starting point for the displacement plating reaction and to form the displacement plating film on the entire surface of the resin film, it is advantageous that the metal powder be present uniformly and richly on the resin film surface or in the vicinity thereof. It is. Therefore, from this viewpoint, it is desirable to prepare the treatment liquid so that the dispersion amount of the metal powder in the resin coating is 50% by weight or more. The upper limit of the dispersion amount of the metal powder in the resin coating is not limited, but it is usually difficult to prepare a treatment liquid for forming a resin coating in which the dispersion amount of the metal powder exceeds 99% by weight. (Since the problem that the metal powder aggregates and settles in the processing solution and the viscosity of the processing solution increases and the handling property is inferior). Therefore, the upper limit of the amount of dispersion of the metal powder in the resin coating is 99% by weight in production.
  In order to prepare a treatment liquid in which metal powder is uniformly dispersedIn addition,The average particle size of the metal powder is2μm-30μmBut,2It should be μm-12μmHopePreferably, it should be 2 μm to 10 μmThandesirable.
[0014]
The surface of the resin film made of resin in which the powder of the first metal is dispersed is made smooth, and the metal powder is uniformly and richly present on the surface of the resin film and in the vicinity thereof. Excellent adhesion to the entire surface of the resin film In order to form a uniform displacement plating film having a thickness, the film thickness of the resin film is preferably 1 μm to 100 μm. However, an increase in the thickness of the resin coating may adversely affect the formation of a uniform electroplating coating. Therefore, considering this point, the upper limit of the film thickness of the resin coating is more preferably 30 μm.
[0015]
In addition, before performing the process for forming the resin film which consists of resin which disperse | distributed the 1st metal powder, in order to improve the adhesiveness of the interface of an article surface and a resin film, itself by degreasing of the article surface etc. You may perform the giving of the throwing effect by well-known cleaning or barrel polishing.
[0016]
Step 2:
Next, the second metal displacement plating film is formed on the surface of the resin film by immersing the article in which the resin film is formed on the surface in Step 1 in a solution containing ions of the second metal having a higher potential than the first metal. Form. The displacement plating film of the second metal has a function of imparting conductivity to the entire surface of the article, and prevents the powder of the first metal from degranulating from the resin film, thereby contributing to improvement of the article surface cleanliness. This step may be carried out in accordance with a conventional method for forming a displacement plating film, but from the viewpoint of ensuring sufficient conductivity to form a uniform and dense third metal electroplating film in a later step. It is desirable to form a film having a film thickness of 0.05 μm or more. Prior to forming the displacement plating film, an article having a resin film formed on the surface for the purpose of smoothing the surface of the resin film and exposing the active surface of the first metal powder uniformly dispersed in the resin film Barrel polishing may be applied to the surface. In addition, although the upper limit of the film thickness of a displacement plating film is not specifically limited, when it considers the point of manufacturing cost, it is desirable to set it as 2 micrometers or less. In addition, for the purpose of imparting surface conductivity, etc. for decoration and antistatic properties to the article, a practically satisfactory effect can be obtained even at this stage where a displacement plating film is formed on the surface. be able to.
[0017]
Step 3:
Finally, an electroplating film of a third metal is formed on the surface of the displacement plating film formed in step 2. This step may be performed according to a conventional method for forming an electroplated film. As described above, for the combination of the first metal and the second metal, the potential difference between the two must be considered, but for the third metal there is no particular reason to consider in relation to the second metal, For example, a metal usually formed as an electroplating film such as Ni, Cu, Sn, Co, Zn, Cr, Ag, Au, Pb, Pt, etc. is applied as the third metal. Therefore, there is no problem even if the second metal and the third metal are the same metal.
[0018]
When the second metal and the third metal are the same metal, that is, when the metal that constitutes the displacement plating film and the metal that constitutes the electroplating film are the same metal, the step 2 and the electric forming the displacement plating film It is convenient to perform step 3 of forming the plating film in one plating bath. That is, for example, when an article having a resin film made of a resin in which a first metal powder is dispersed on the surface is immersed in a plating bath, the displacement plating reaction is allowed to proceed by applying no voltage to the displacement plating film. After forming, an electroplated film can be formed by applying a voltage. Further, even when a voltage is applied from the beginning of immersing an article in which a resin film made of a resin in which the first metal powder is dispersed on the surface is immersed in a plating bath, the volume resistance of the resin film is in the initial stage of immersion. Since the rate is high, a replacement plating film is first formed on the surface of the resin film by a displacement plating reaction due to a potential difference between the first metal and the second metal. As a result, conductivity is imparted to the entire surface of the article, and a uniform and dense electroplating film is formed on the surface of the displacement plating film. What is necessary is just to set the film thickness of an electroplating film suitably according to the objective.
[0019]
For example, in the case where the replacement Ni plating film and the electric Ni plating film are formed on the surface of the article in one plating bath, various baths can be used as the plating bath depending on the shape of the article. As the plating bath, a known plating bath such as a watt bath, a sulfamic acid bath, or a wood bath may be used. In order to form a substituted Ni plating film having excellent adhesion on the surface of the non-conductive film made of a resin in which the powder of the first metal is dispersed, for example, a low nickel high sulfate bath is used, and the first metal It is desirable to suppress excessive substitution efficiency (deposition rate of substitutional Ni plating film) between nickel and nickel. Suitable low nickel high sulfate baths include nickel sulfate pentahydrate 100 g / L to 170 g / L, sodium sulfate 160 g / L to 270 g / L, ammonium chloride 8 g / L to 18 g / L, boric acid 13 g / L. A plating bath composed of L to 23 g / L can be mentioned. The pH of the plating bath is preferably 4.0 to 8.0. This is because if it is less than 4.0, there is a risk of adversely affecting an article that is unstable in acidic conditions, while if it exceeds 8.0, the adhesion of the formed substituted Ni plating film may be inferior. In addition, when the pH of the plating bath is set to 4.0 to 8.0, the first metal having a base potential lower than that of Ni is rapidly eluted to form a rough substituted Ni plating film on the surface. There is also an object of effectively suppressing adverse effects on the adhesion with the formed electric Ni plating film. The bath temperature of the plating bath is desirably 30 ° C to 70 ° C. If the temperature is lower than 30 ° C., the surface of the formed substituted Ni plating film may become rough. On the other hand, if it exceeds 70 ° C., bath temperature management is difficult, and a uniform replacement Ni plating film may not be formed. It is. When an electric Ni plating film is formed after forming a replacement Ni plating film using such a plating bath, the current density is 0.2 A / dm.²~ 20A / dm²Is desirable. 0.2 A / dm²On the other hand, if it is less than 20A / dm, the film formation rate is slow and the productivity may be inferior.²This is because the surface of the formed electric Ni plating film becomes rough when it exceeds the range, and a large number of pinholes may be generated. Although an electrolytic Ni plate is used for the anode, it is desirable to use a nickel tip containing S as the electrolytic Ni plate in order to stabilize the elution of Ni.
[0020]
For example, even when the substitution Cu plating film and the electric Cu plating film are formed on the surface of the article in one plating bath, various baths can be used as the plating bath depending on the shape of the article. The pH of the plating bath is desirably 5.0 to 8.5. This is because if it is less than 5.0, it may adversely affect articles that are unstable in acidic conditions, while if it exceeds 8.5, the adhesion of the formed substituted Cu plating film may be inferior. The bath temperature of the plating bath is preferably 25 ° C to 70 ° C. If the temperature is lower than 25 ° C., the surface of the formed substituted Cu plating film may become rough. On the other hand, if it exceeds 70 ° C., bath temperature management is difficult, and a uniform replacement Cu plating film may not be formed. It is. When forming an electric Cu plating film after forming a replacement Cu plating film using such a plating bath, the current density is 0.1 A / dm.²~ 5.0A / dm²Is desirable. 0.1 A / dm²On the other hand, if it is less than 5.0A / dm, the film formation rate is slow and the productivity may be inferior.²This is because the surface of the formed electric Cu plating film becomes rough and the number of pinholes may be generated. As the plating bath, a neutral Cu plating bath having low corrosiveness and low permeability is desirable, and in particular, a neutral Cu-EDTA bath mainly composed of copper sulfate, ethylenediaminetetraacetic acid and sodium sulfite is desirable.
[0021]
In addition, another electroplating film or the like may be laminated on the electroplating film formed as described above. By adopting such a configuration, it is possible to enhance / complement the characteristics of the electroplated film or to impart further functionality.
[0022]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0023]
Example 1 (Formation of electroplated film on transparent acrylic plate surface)
A small vibrating barrel (Chipton: VM-10) is loaded with 5 liters of transparent acrylic plate 60mm long x 20mm wide x 2mm thick and 2L of alumina media (Chipton: PSφ4) in volume. Surface polishing of the acrylic plate was performed for 30 minutes. Next, the surface-polished transparent acrylic plate was immersed in acetone for 1 minute to degrease the surface, and then naturally dried.
Epoloval (trade name made by Roval: the average particle diameter of zinc powder is 4 μm) is used as a non-conductive zinc powder dispersion resin, and diluted with an epovalar thinner (trade name, made by Roval) (weight) A non-conductive zinc powder-dispersed resin solution was prepared by stirring uniformly at a ratio of Epoval: Thinner = 1: 0.7). The obtained solution was sprayed on the entire surface of the transparent acrylic plate under a spray pressure of 0.2 MPa using an air spray device having a gun diameter of 1.2 mm, sprayed, and then heated at room temperature (20 ° C.). Non-conductive film (volume resistivity 2 × 10) having a thickness of 15 μm (according to cross-sectional observation) in which the amount of zinc powder dispersed is 96% by weight.^FiveΩ · cm: according to JIS-H0505) was formed on the surface of the transparent acrylic plate.
A small vibrating barrel (made by Chipton: VM-10), 5 transparent acrylic plates with a non-conductive coating formed on the surface obtained in step 1 and alumina media for 2 L in volume (made by Chipton: PSφ4) The surface of the non-conductive coating was polished for 30 minutes.
A transparent acrylic plate having a non-conductive film that has been subjected to surface polishing, contains nickel sulfate pentahydrate 240 g / L, nickel chloride pentahydrate 45 g / L, boric acid 35 g / L, The substrate was immersed in a watt bath having a liquid temperature of 55 ° C. adjusted to pH 4.2 with nickel, and a substituted Ni plating film was formed on the surface of the non-conductive film without applying a voltage for 30 minutes. Two of the five transparent acrylic plates were taken out of the watt bath at this point and the thickness of the formed substituted Ni plating film was examined. The average value was 1 μm (according to cross-sectional observation). The substituted Ni plating film thus formed exhibits surface properties as metallic Ni and has a volume resistivity of 5 × 10 5.^-6It was Ω · cm. Therefore, it has been found that even at this stage, it is sufficient to be practically satisfactory for the purpose of imparting decorativeness and surface conductivity for antistatic purposes.
The remaining three transparent acrylic plates were then subjected to a voltage and a current density of 1.5 A / dm.²The electric Ni plating treatment was performed for 90 minutes under the above conditions to form an electric Ni plating film on the surface of the replacement Ni plating film.
The transparent acrylic plate having the electric Ni plating film on the outermost surface obtained as described above was ultrasonically washed with water for 3 minutes and then dried at 100 ° C. for 60 minutes.
When the appearance of the electric Ni plating film on the outermost surface of three transparent acrylic plates was inspected with a magnifying glass (× 4), there was no defective product with pinholes, protrusions, foreign matter adhesion, etc., and all the films were homogeneous. It was evaluated as a good product. Since the average value (n = 3) of the total thickness of the Ni plating film formed on the surface of the non-conductive film was 25 μm (according to cross-sectional observation), the average value of the thickness of the electric Ni plating film (n = 3) ) Was found to be 24 μm.
[0024]
Example 2 (Formation of electroplated film on the surface of a wooden mascot bat)
A uniform and dense electric Ni plating film was formed on the surface of a wooden mascot bat having a length of 240 mm and a diameter of about 10 mm in the same manner as in Example 1 with excellent adhesion.
[0025]
Example 3 (Formation of electroplated film on corrugated paper surface)
Similar to Example 1 (corresponding to the surface polishing step using a small vibration barrel is omitted) on a corrugated cardboard having a length of 60 mm, a width of 20 mm, and a thickness of 2 mm. A coating was formed with excellent adhesion.
[0026]
Example 4 (Formation of electroplated film on transparent glass plate surface)
A uniform and dense electric Ni plating film was formed on the surface of a transparent glass plate 60 mm long × 20 mm wide × 2 mm thick in the same manner as in Example 1 with excellent adhesion.
[0027]
Example 5 (Formation of electroplated film on aluminum plate surface)
In the same manner as in Example 1, a uniform and dense electric Ni plating film was formed on the surface of an aluminum plate 60 mm long × 20 mm wide × 2 mm thick with excellent adhesion.
[0028]
Example 6 (Formation of electroplated film on the surface of magnesium alloy plate)
A uniform and dense electric Ni plating film was formed on the surface of a magnesium alloy plate 60 mm long × 20 mm wide × 2 mm thick in the same manner as in Example 1 with excellent adhesion.
[0029]
【The invention's effect】
According to the present invention, there is provided a method of forming a uniform and dense electroplated film on the surface with excellent adhesion without depending on the surface material and surface properties of the article.

Claims (11)

A non-conductive film having a volume resistivity of 1 × 10 ⁴ Ω · cm or more is formed on the surface of the article , which is made of a resin in which a powder of a first metal having an average particle diameter of 2 μm to 30 μm is dispersed . By immersing the film-forming article in a solution containing ions of the second metal having a higher potential than the first metal, a replacement plating film of the second metal is formed on the surface of the non-conductive film, and the second plating film is further formed on the surface of the replacement plating film. 3. A method of forming an electroplated film on the surface of an article, wherein an electroplated film of three metals is formed (except for rare earth permanent magnets as an article). 2. The forming method according to claim 1, wherein the dispersion amount of the powder of the first metal in the non-conductive coating is 50 wt% to 99 wt% . The formation method according to claim 1, wherein the film thickness of the non-conductive coating is 1 μm to 100 μm. Forming method according to any one of claims 1 to 3 first metal and the second metal in zinc and wherein the nickel. Forming method according to any one of claims 1 to 3 first metal, wherein the second metal nickel is copper. A method according to any one of claims 1 to 5 second metal and the third metal is characterized in that the same metal. 7. The forming method according to claim 6 , wherein the step of forming the displacement plating film and the step of forming the electroplating film are performed in one plating bath. A method according to any one of claims 1 to 7 the thickness of the displacement plating coating is characterized in that it is a 0.05Myuemu～2myuemu. Article, characterized in that the electric plating film on the surface by forming method according to any one of claims 1 to 8 is formed (except rare earth metal-based permanent magnets). A non-conductive film having a volume resistivity of 1 × 10 ⁴ Ω · cm or more is formed on the surface of the article , which is made of a resin in which a powder of a first metal having an average particle diameter of 2 μm to 30 μm is dispersed . To a surface of an article characterized in that a displacement plating film of a second metal is formed on the surface of a non-conductive film by immersing the film-formed article in a solution containing ions of a second metal having a noble potential than the first metal. (1) Except for rare earth permanent magnets as an article . An article having a displacement plating film formed on the surface by the forming method according to claim 10 (excluding rare earth permanent magnets) .