WO2022191167A1 - Plating method, and plated product - Google Patents

Plating method, and plated product Download PDF

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Publication number
WO2022191167A1
WO2022191167A1 PCT/JP2022/009900 JP2022009900W WO2022191167A1 WO 2022191167 A1 WO2022191167 A1 WO 2022191167A1 JP 2022009900 W JP2022009900 W JP 2022009900W WO 2022191167 A1 WO2022191167 A1 WO 2022191167A1
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Prior art keywords
resin
plating
minutes
solution
ions
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PCT/JP2022/009900
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French (fr)
Japanese (ja)
Inventor
泰望 山本
翔 櫻井
雄斗 森川
康輔 若田
涼 相澤
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株式会社Jcu
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Publication of WO2022191167A1 publication Critical patent/WO2022191167A1/en

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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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • 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
    • C23C18/31—Coating with metals

Definitions

  • the present invention relates to plating methods and plated products.
  • Electroless plating is a technique for plating resin, etc., without electrolysis. In recent years, its use has expanded to various applications such as semiconductor materials, automobile parts, and faucet fittings.
  • Patent Documents 3 and 4 and Non-Patent Document 1 are processes that use a catalyst containing copper ions without using a catalyst containing a noble metal in performing electroless copper plating, but the composition of the solution used for this is It is complicated, and moreover, the object to be plated is a printed circuit board or a film, and as a pretreatment process, modification by UV is required, and the process is complicated. Furthermore, it is not known at all whether this technology can be applied to electroless plating other than electroless copper plating.
  • the object of the present invention is to provide a new plating technique that does not use a catalyst containing precious metals such as palladium and silver when performing electroless plating on resin.
  • the present invention provides the following steps (a) to (d) (a) step of etching or surface-modifying the resin (b) step of allowing the etched or surface-modified resin to adsorb autocatalytic metal ions (c) adsorbing the autocatalytic metal ions adsorbed on the resin
  • the plating method is characterized by including a step of reducing (d) a step of performing electroless plating on the resin.
  • the present invention is a plated product characterized by providing an electroless plated layer on a resin, wherein the plated layer does not substantially contain a noble metal.
  • the plating method of the present invention does not use a catalyst containing precious metals such as palladium and silver when performing electroless plating on resin, so problems such as agglomeration of the catalyst do not occur and plating can be performed well.
  • the plating layer of the plated product of the present invention does not substantially contain precious metals, costs can be kept down when the price of precious metals rises.
  • FIG. 1 is an appearance photograph of a test piece after electroless nickel plating obtained in Example 1.
  • FIG. 1 is an appearance photograph of a test piece after electrolytic chromium plating obtained in Example 1.
  • the plating method of the present invention including the following steps (a) to (d) is as follows.
  • (a) step of etching or surface-modifying the resin (b) step of allowing the etched or surface-modified resin to adsorb autocatalytic metal ions (c) adsorbing the autocatalytic metal ions adsorbed on the resin
  • a plating method comprising a step of reducing (d) a step of performing electroless plating on the resin.
  • the resin used in step (a) of the method of the present invention is not particularly limited, but examples include acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polycarbonate (PC), PC/ Resins such as ABS, polypropylene (PP), polyamide (PA), and carbon fiber reinforced plastic (CFRP) can be used. Among these, ABS, PC/ABS, etc. are preferable.
  • degreasing, washing, etc. may be performed in accordance with conventional methods.
  • the shape of this resin is not particularly limited, but a three-dimensional shape is preferred.
  • the method for etching the resin is not particularly limited, but examples include a method using an acid solution containing an oxidizing agent such as chromic acid, permanganic acid, or persulfuric acid.
  • an oxidizing agent such as chromic acid, permanganic acid, or persulfuric acid.
  • an acidic solution containing chromic acid, permanganic acid or persulfuric acid from the viewpoint of plating deposition.
  • Persulfuric acid peroxosulfuric acid
  • electrolytic sulfuric acid is preferably generated by electrolytic oxidation of sulfuric acid (so-called electrolytic sulfuric acid).
  • Etching conditions are not particularly limited as long as the surface of the resin can be roughened appropriately.
  • the method of surface-modifying the resin includes, in addition to the method using the acid solution as described above, for example, ozone treatment, sulfuric acid immersion, ultraviolet irradiation, plasma treatment, and the like. be done. Among these, immersion in sulfuric acid is preferable because even a three-dimensional shape can be sufficiently surface-modified.
  • the concentration of sulfuric acid is not particularly limited as long as it can modify the surface of the resin, but is preferably 75% by mass or more, more preferably 90% by mass or more.
  • Conditions for surface modification are not particularly limited as long as the surface of the resin can be appropriately hydrophilized.
  • the method for causing the etched or surface-modified resin to adsorb autocatalytic metal ions is not particularly limited, but for example, a solution containing autocatalytic metal ions
  • a solution containing autocatalytic metal ions Another example is a method of treating a resin that has been etched or surface-modified.
  • metal ions having self-catalytic properties include copper ions, nickel ions, iron ions, and cobalt ions. One or more of these can be used, but at least copper ions are preferably used. Using copper ions and nickel ions is more preferable in the case of electroless nickel plating. Further, examples of the above treatment include immersion, spraying, and the like.
  • the metal ion concentration in the solution containing the self-catalytic metal ions is not particularly limited, but is, for example, 0.001 MOL/L or more, preferably 0.005 MOL/L.
  • the solution containing the metal ions is preferably adjusted to pH 2-12, preferably 4-9.
  • Conditions for adsorbing the metal ions are not particularly limited, but include conditions such as 25 to 50° C., preferably 35 to 45° C. for 0.5 to 10 minutes.
  • the metal ion source used in the solution containing the metal ions having self-catalytic properties is not particularly limited.
  • copper ion sources include copper acetate, copper chloride, copper sulfate, copper amidosulfate, copper pyrophosphate, and the like. is mentioned. Among these, copper acetate is preferred.
  • Nickel ion sources include nickel sulfate, nickel chloride, nickel acetate, and nickel amidosulfate. Among these, nickel acetate is preferred.
  • iron (II) sulfate and the like can be used as an iron ion source.
  • cobalt sources include cobalt sulfate and the like. These metal ion sources are appropriately dissolved in a solvent such as water to prepare a solution containing the metal ions having self-catalytic properties.
  • the solution containing the metal ions having self-catalytic properties may contain a stabilizer such as ascorbic acid or a derivative thereof to prevent oxidation of the metal ions.
  • the solution containing the metal ions may contain a complexing agent such as citric acid or gluconic acid.
  • the content of the stabilizer and complexing agent in the solution containing the metal ions is not particularly limited, but is, for example, 1 to 100 g/L.
  • the solution containing the metal ions having self-catalytic properties may contain bromide from the viewpoint of improving the adsorption amount.
  • Bromide is not particularly limited, but examples of bromide include sodium bromide and the like.
  • the bromide content in the solution containing the metal ions is not particularly limited, but is, for example, 0.5 to 5 g/L.
  • the solution containing the self-catalytic metal ions preferably contains a surfactant for adjusting the surface potential.
  • the surfactant is not particularly limited, and examples thereof include polyethylene glycol.
  • the content of polyethylene glycol in the solution containing the metal ions is not particularly limited, but is 0.5 to 5 g/L when the molecular weight is 6000, for example.
  • one or more metal ions selected from the group consisting of Group 3 to Group 12 transition metals can be adsorbed together with the self-catalytic metal ions. It is preferable because the deposition condition of the plating is improved.
  • the transition metal include niobium, molybdenum, titanium, tungsten, vanadium, and the like.
  • the method of adsorbing metal ions selected from the group consisting of group 3 to group 12 transition metals together with self-catalytic metal ions to the etched or surface-modified resin is not particularly limited, but for example , a method of immersing an etched or surface-modified resin in a solution containing metal ions selected from the group consisting of autocatalytic metal ions and group 3 to group 12 transition metals; and a method of immersing etched or surface-modified resin in a solution containing metal ions selected from the group consisting of Group 3 to Group 12 transition metals.
  • the content of metal ions selected from the group consisting of Group 3 to Group 12 transition metals in the solution may be appropriately set.
  • a solution containing metal ions selected from the group consisting of Group 3 to Group 12 transition metals can also be prepared in the same manner as the solution containing metal ions having self-catalytic properties. agents, bromides, surfactants, polymer compounds, and the like.
  • the concentration of metal ions in the solution containing metal ions selected from the group consisting of Group 3 to Group 12 transition metals is not particularly limited, but is preferably 0.005 MOL/L or more, for example.
  • the solution containing the metal ions is preferably adjusted to pH 2-12, preferably 4-9.
  • Conditions for adsorbing the metal ions are not particularly limited, but include conditions such as 25 to 50° C., preferably 35 to 45° C. for 0.5 to 10 minutes.
  • Example 1 Copper ion 0.001-1.0MOL/L Nickel ion 0.001-1.0MOL/L
  • Example 3 Copper ion 0.001-1.0MOL/L
  • Example 1 is suitable for electroless copper plating and electroless nickel plating
  • Example 3 is suitable for electroless copper plating.
  • the etched or surface-modified resin is adsorbed with self-catalytic metal ions (metal ions selected from the group consisting of Group 3 to Group 12 transition metals in the step (b), these metal ions Considering the life of the reducing agent, it is preferable that washing is not necessary after adsorption.
  • self-catalytic metal ions metal ions selected from the group consisting of Group 3 to Group 12 transition metals in the step (b)
  • the metal ions having self-catalytic properties adsorbed on the resin (when the metal ions selected from the group consisting of the group 3 to group 12 transition metals are adsorbed in the step (b), (including these metal ions) is not particularly limited.
  • a method of immersing the resin in a reducing solution containing a derivative thereof and the like to reduce the resin may be used.
  • These reducing agents may be used singly or in combination of two or more.
  • the pH of the solution containing the reducing agent may be in the weakly acidic to alkaline range.
  • the conditions for reduction are not particularly limited. Conditions such as 5 minutes can be mentioned. When sodium borohydride is used, conditions such as 20° C. to 30° C. for 0.5 to 10 minutes, preferably 1 to 5 minutes, etc. can be mentioned.
  • a chelating agent to the reducing solution as described in JP-A-4-26773.
  • the chelating agent include dicarboxylic acids such as N-hydroxyethyliminodiacetic acid and monocarboxylic acids such as glycolic acid and 3-hydroxypropionic acid.
  • the content of the chelating agent in the reducing solution is not particularly limited, it is, for example, 0.1 g/L to 10 g/L.
  • the method of electroless plating the resin includes, for example, a method of immersion in an electroless plating solution such as an electroless nickel plating solution or an electroless copper plating solution.
  • an electroless plating solution such as an electroless nickel plating solution or an electroless copper plating solution.
  • electroless plating conditions are not particularly limited, but include conditions such as 30 to 50° C., preferably 35 to 40° C., and 5 to 15 minutes, preferably 8 to 10 minutes.
  • Electroless nickel plating solutions such as Ni--P type using hypophosphite as a known reducing agent, Ni--B type using alkylamine borane, and Ni--N type using hydrazine as a reducing agent can be used.
  • a commercially available product can also be used as the electroless nickel plating solution.
  • electroless nickel plating solutions include amine borane reduction type ENIPAC BN-II (manufactured by JCU Corporation), hypophosphite reduction type ENILEX NI-100 and NI-5 (manufactured by JCU Corporation), and the like. mentioned.
  • hypophosphite reduction type electroless plating solution of ENILEX NI-100 it is preferable to use a hypophosphite reduction type electroless plating solution of ENILEX NI-100 from the viewpoint of bath stability.
  • ⁇ Electroless copper plating solution> for copper plating, for example, formaldehyde reduction type EBASHIELD EC-II (manufactured by JCU Co., Ltd.) can be used.
  • each step may be repeated as necessary.
  • a plated product having an electroless plating layer provided on a resin can be obtained by the method of the present invention described above.
  • the plated layer does not substantially contain precious metals.
  • “substantially not contained” means, for example, that precious metals such as gold (Au), silver (Ag), platinum (Pt), and palladium (Pd) are below the detection limit (for example, 0.1 ppm or less) by atomic absorption spectrometry. ).
  • the plated product thus obtained can be used in the same applications as known electroless plated products, such as decorative plating substrates.
  • the plated product obtained as described above may be further subjected to electrolytic plating as step (e).
  • Electroplating is not particularly limited, and known electroplating solutions and conditions can be used.
  • the plated product thus obtained can be used for the same purposes as known electrolytic plated products, such as decorative plating.
  • Example 1 Electroless nickel plating The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • FIG. 1 shows the deposition state of the plating on the test piece after electroless nickel plating.
  • the amount of noble metal was below the detection limit.
  • electrolytic chromium plating was applied according to a standard method.
  • Fig. 2 shows the deposition of plating after electrolytic chromium plating.
  • Example 2 Electroless nickel plating: An ABS resin test piece (a flat plate with a hemisphere: about 100 cm 2 ) was immersed in a 68° C. chromic acid solution (400 g/L chromic anhydride, 400 g/L sulfuric acid, 1 mL/L MISTSHUT PF: manufactured by JCU Co., Ltd.) for 10 minutes. and etched. This was immersed in a chromium reducing agent (10 mL/L ENILEX RD: manufactured by JCU Corporation, 60 mL/L hydrochloric acid) at room temperature for 1 minute to neutralize residual Cr.
  • a chromium reducing agent 10 mL/L ENILEX RD: manufactured by JCU Corporation, 60 mL/L hydrochloric acid
  • Example 3 Electroless nickel plating: In Example 2, except replacing the copper ion solution with a solution containing copper ions and nickel ions (copper sulfate 0.01 MOL / L and nickel sulfate 0.01 MOL / L, pH 4.78). Electroless nickel plating was performed in the same manner.
  • Example 4 Precious metal-free electroless nickel plating:
  • the ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes.
  • This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C.
  • Reference example 1 Preparation of electrolytic sulfuric acid: Using a boron-doped diamond electrode prepared by a known method, sulfuric acid was electrolyzed under the following conditions to prepare electrolytic sulfuric acid. ⁇ Electrolysis conditions> 78 wt% sulfuric acid was electrolyzed at 0.5 A and 4.8 V using a pair of 1 inch diamond electrodes. The bath conditions were a bath temperature of 60° C. and an oxidizing agent concentration of 5 g/L.
  • Example 5 Electroless nickel plating: A test piece of ABS resin was immersed in a wetting agent (ENILEX WE: manufactured by JCU Co., Ltd.) at 50° C. for 10 minutes to impart wettability. This test piece was then etched by being immersed in the electrolytic sulfuric acid prepared in Reference Example 1 at 65° C. for 10 minutes. After washing it with hot water at 40° C., it was immersed in a solution containing copper ions at room temperature (0.01 MOL/L of copper sulfate, adjusted to pH 10.5 with ammonia) for 5 minutes to adsorb copper ions.
  • a wetting agent ENILEX WE: manufactured by JCU Co., Ltd.
  • a reducing aqueous solution was prepared according to the description of JP-A-4-26773. Specifically, 30 g/L of sodium borohydride is dissolved in a 25 g/L sodium hydroxide aqueous solution, and 5 g/L of N-hydroxyethyliminodiacetic acid is further dissolved and diluted 10 times with pure water. to prepare a reducing aqueous solution.
  • Example 6 Electroless nickel plating: In Example 5, instead of immersing in the reducing solution at 60 ° C. for 5 minutes to reduce the copper ions, it was immersed in the reducing aqueous solution prepared in Reference Example 2 at 25 ° C. for 5 minutes. Electroless nickel plating was performed in the same manner.
  • Example 7 Electroless nickel plating: The ABS resin test piece was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • Example 8 Electroless copper plating The ABS resin test piece was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • Example 9 Electroless nickel plating: A test piece of PP resin instead of ABS resin was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • Example 11 Precious metal-free electroless nickel plating:
  • the ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes.
  • This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C.
  • Example 12 Electroless nickel plating: The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • Example 13 Electroless nickel plating The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • the etching or surface-modified resin is immersed in a solution containing at least 0.001 MOL/L or more of self-catalytic metal ions, and then subjected to a reduction process to improve catalytic properties for electroless plating.
  • a solution containing at least 0.001 MOL/L or more of self-catalytic metal ions and then subjected to a reduction process to improve catalytic properties for electroless plating.
  • electroless plating was deposited cleanly without using a noble metal catalyst.
  • Example 14 Electroless nickel plating: The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching.
  • a permanganate solution 240 mL/L DS-250NA: manufactured by JCU Co., Ltd.
  • the present invention is a process that does not use a precious metal catalyst, so it can be used for plating various applications such as semiconductor materials, automobile parts, and faucet fittings.

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Abstract

Provided is a plating method characterized by comprising the following steps (a)-(d): (a) a step for etching or surface-modifying a resin; (b) a step for causing self-catalytic metal ions to be adsorbed onto the etched or surface-modified resin; (c) a step for reducing the self-catalytic metal ions adsorbed onto the resin; and (d) a step for performing electroless plating on the resin. Also provided is a plated product characterized in that a noble metal is substantially contained in the plating layer and in that an electroless plating layer is provided on a resin and no precious metal is substantially contained in the plating layer. Due to said plating method and said plated product, a plating technology can be achieved that does not use a catalyst containing noble metals such as palladium and silver when performing electroless plating on a resin.

Description

めっき方法およびめっき製品Plating method and plated product
　本発明は、めっき方法およびめっき製品に関する。 The present invention relates to plating methods and plated products.
　無電解めっきは電解を行わず、樹脂等にめっきをする技術である。近年では、半導体材料、自動車部品、水栓金具等の多種用途へその利用が拡大している。 　Electroless plating is a technique for plating resin, etc., without electrolysis. In recent years, its use has expanded to various applications such as semiconductor materials, automobile parts, and faucet fittings.
　しかしながら、無電解めっきは、例えば、特許文献１および２に記載の通り、貴金属であるパラジウムや銀を含むコロイド触媒を樹脂の表面に付与してから行う必要があるが、このコロイド触媒は凝集すること等があるため上手にめっきができないこともある。また、少量ではあるものの貴金属の使用量を減らすことは、コストの面でメリットがある。 However, electroless plating, for example, as described in Patent Documents 1 and 2, it is necessary to apply a colloidal catalyst containing palladium and silver, which are noble metals, to the surface of the resin, but this colloidal catalyst aggregates. There are times when it is not possible to perform plating well due to certain factors. In addition, reducing the amount of precious metal used, albeit in a small amount, is advantageous in terms of cost.
　一方、特許文献３、４および非特許文献１は、無電解銅めっきを行うに当たり、貴金属を含む触媒を用いずに銅イオンを含む触媒を用いるプロセスであるが、これに用いられる溶液の組成は複雑であり、しかも、めっき対象がプリント基板であったりフィルムであり、前処理工程としてＵＶによる改質が必要であり工程が煩雑である。更に、この技術が無電解銅めっき以外のどの無電解めっきに応用できるか等一切わからないものでもある。 On the other hand, Patent Documents 3 and 4 and Non-Patent Document 1 are processes that use a catalyst containing copper ions without using a catalyst containing a noble metal in performing electroless copper plating, but the composition of the solution used for this is It is complicated, and moreover, the object to be plated is a printed circuit board or a film, and as a pretreatment process, modification by UV is required, and the process is complicated. Furthermore, it is not known at all whether this technology can be applied to electroless plating other than electroless copper plating.
特許第６５５１６２２号Patent No. 6551622 特許第６４８２０４９号Patent No. 6482049 特許第５００４３３６号Patent No. 5004336 特許第５５７０２８５号Patent No. 5570285
　従って、本発明の課題は、樹脂に無電解めっきを行うにあたり、パラジウムや銀等の貴金属を含む触媒を用いない新しいめっき技術を提供することである。 Therefore, the object of the present invention is to provide a new plating technique that does not use a catalyst containing precious metals such as palladium and silver when performing electroless plating on resin.
　本発明者らは、上記課題を解決するために鋭意研究した結果、樹脂をエッチングあるいは表面改質した後に、自己触媒性のある金属イオンを吸着させて、更にこれを還元することにより、その後に無電解めっきが行えることを見出した。 As a result of intensive research to solve the above problems, the present inventors have found that after etching or modifying the surface of the resin, by adsorbing metal ions with self-catalytic properties and further reducing them, We found that electroless plating can be performed.
　すなわち、本発明は、以下の工程（ａ）～（ｄ）
（ａ）樹脂をエッチングあるいは表面改質する工程
（ｂ）エッチングあるいは表面改質した樹脂に、自己触媒性のある金属イオンを吸着させる工程
（ｃ）樹脂に吸着した自己触媒性のある金属イオンを還元する工程
（ｄ）樹脂に無電解めっきを行う工程
を含むことを特徴とするめっき方法である。 That is, the present invention provides the following steps (a) to (d)
(a) step of etching or surface-modifying the resin (b) step of allowing the etched or surface-modified resin to adsorb autocatalytic metal ions (c) adsorbing the autocatalytic metal ions adsorbed on the resin The plating method is characterized by including a step of reducing (d) a step of performing electroless plating on the resin.
　また、本発明は、樹脂上に、無電解めっき層を設け、前記めっき層中に貴金属が実質的に含まれないことを特徴とするめっき製品である。 Further, the present invention is a plated product characterized by providing an electroless plated layer on a resin, wherein the plated layer does not substantially contain a noble metal.
　本発明のめっき方法は、樹脂に無電解めっきを行うにあたり、パラジウムや銀等の貴金属を含む触媒を用いないため、触媒の凝集等の問題が生じず、上手にめっきができる。 The plating method of the present invention does not use a catalyst containing precious metals such as palladium and silver when performing electroless plating on resin, so problems such as agglomeration of the catalyst do not occur and plating can be performed well.
　また、本発明のめっき製品は、前記めっき層中に貴金属が実質的に含まれないため、貴金属が高騰した場合にコストがおさえられる。 In addition, since the plating layer of the plated product of the present invention does not substantially contain precious metals, costs can be kept down when the price of precious metals rises.
実施例１で得られた無電解ニッケルめっき後の試験片の外観写真である。1 is an appearance photograph of a test piece after electroless nickel plating obtained in Example 1. FIG. 実施例１で得られた電解クロムめっき後の試験片の外観写真である。1 is an appearance photograph of a test piece after electrolytic chromium plating obtained in Example 1. FIG.
　以下の工程（ａ）～（ｄ）を含む本発明のめっき方法（以下、「本発明方法」という）は以下の通りのものである。
（ａ）樹脂をエッチングあるいは表面改質する工程
（ｂ）エッチングあるいは表面改質した樹脂に、自己触媒性のある金属イオンを吸着させる工程
（ｃ）樹脂に吸着した自己触媒性のある金属イオンを還元する工程
（ｄ）樹脂に無電解めっきを行う工程
を含むことを特徴とするめっき方法。 The plating method of the present invention (hereinafter referred to as "method of the present invention") including the following steps (a) to (d) is as follows.
(a) step of etching or surface-modifying the resin (b) step of allowing the etched or surface-modified resin to adsorb autocatalytic metal ions (c) adsorbing the autocatalytic metal ions adsorbed on the resin A plating method comprising a step of reducing (d) a step of performing electroless plating on the resin.
　本発明方法の工程（ａ）で用いる樹脂としては、特に限定されないが、例えば、アクリロニトリル・ブタジエン・スチレン共重合体（ＡＢＳ）、アクリロニトリル・スチレン共重合体（ＡＳ）、ポリカーボネート（ＰＣ）、ＰＣ／ＡＢＳ、ポリプロピレン（ＰＰ）、ポリアミド（ＰＡ）、炭素繊維強化プラスチック（ＣＦＲＰ）等の樹脂が挙げられる。これらの中でもＡＢＳ、ＰＣ／ＡＢＳ等が好ましい。この樹脂は工程（ａ）でエッチングあるいは表面改質をする前に、脱脂、洗浄等を常法に従って行ってもよい。この樹脂の形状は特に限定されないが、３次元形状が好ましい。 The resin used in step (a) of the method of the present invention is not particularly limited, but examples include acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polycarbonate (PC), PC/ Resins such as ABS, polypropylene (PP), polyamide (PA), and carbon fiber reinforced plastic (CFRP) can be used. Among these, ABS, PC/ABS, etc. are preferable. Before the resin is etched or surface-modified in step (a), degreasing, washing, etc. may be performed in accordance with conventional methods. The shape of this resin is not particularly limited, but a three-dimensional shape is preferred.
　本発明方法の工程（ａ）において、樹脂をエッチングする方法は特に限定されないが、例えば、クロム酸、過マンガン酸、過硫酸等の酸化剤を含む酸性液を用いる方法が挙げられる。これらの酸化剤の中でもめっき析出性の点からクロム酸、過マンガン酸または過硫酸を含有する酸性液を用いて行うことが好ましく、特に環境面からクロム酸フリーの過マンガン酸を含有する酸性液を用いて行うことが好ましい。なお、過硫酸（ペルオキソ硫酸）は、硫酸の電解酸化により発生するもの（いわゆる電解硫酸）が好ましい。エッチングの条件は、樹脂の表面を適度に粗化できるものであれば特に限定はない。 In the step (a) of the method of the present invention, the method for etching the resin is not particularly limited, but examples include a method using an acid solution containing an oxidizing agent such as chromic acid, permanganic acid, or persulfuric acid. Among these oxidizing agents, it is preferable to use an acidic solution containing chromic acid, permanganic acid or persulfuric acid from the viewpoint of plating deposition. It is preferable to use Persulfuric acid (peroxosulfuric acid) is preferably generated by electrolytic oxidation of sulfuric acid (so-called electrolytic sulfuric acid). Etching conditions are not particularly limited as long as the surface of the resin can be roughened appropriately.
　また、本発明方法の工程（ａ）において、樹脂を表面改質する方法は、上記のように酸性液を用いる方法以外にも、例えば、オゾン処理、硫酸浸漬、紫外線照射、プラズマ処理等が挙げられる。これらの中でも３次元形状のものでも十分に表面改質できることから硫酸浸漬が好ましい。硫酸の濃度は樹脂の表面を改質できる濃度であれば特に限定されないが、７５質量％以上のものが好ましく、９０質量％以上の濃硫酸がより好ましい。表面改質の条件は、樹脂の表面を適度に親水化できるものであれば特に限定されない。 Further, in the step (a) of the method of the present invention, the method of surface-modifying the resin includes, in addition to the method using the acid solution as described above, for example, ozone treatment, sulfuric acid immersion, ultraviolet irradiation, plasma treatment, and the like. be done. Among these, immersion in sulfuric acid is preferable because even a three-dimensional shape can be sufficiently surface-modified. The concentration of sulfuric acid is not particularly limited as long as it can modify the surface of the resin, but is preferably 75% by mass or more, more preferably 90% by mass or more. Conditions for surface modification are not particularly limited as long as the surface of the resin can be appropriately hydrophilized.
　上記のようにして樹脂をエッチングあるいは表面改質をした後は、必要により洗浄等を常法に従って行ってもよい。 After etching or modifying the surface of the resin as described above, washing and the like may be carried out according to the usual methods, if necessary.
　本発明方法の工程（ｂ）において、エッチングあるいは表面改質した樹脂に、自己触媒性のある金属イオンを吸着させる方法は、特に限定されないが、例えば、自己触媒性のある金属イオンを含有する溶液にエッチングあるいは表面改質した樹脂を処理等する方法等が挙げられる。ここで自己触媒性のある金属イオンとしては、例えば、銅イオン、ニッケルイオン、鉄イオン、コバルトイオン等が挙げられる。これらは１種または２種以上を用いることができるが、少なくとも銅イオンを用いることが好ましい。銅イオンとニッケルイオンを用いることが無電解ニッケルめっきの場合はより好ましい。また、上記処理としては浸漬、噴霧等が挙げられる。 In the step (b) of the method of the present invention, the method for causing the etched or surface-modified resin to adsorb autocatalytic metal ions is not particularly limited, but for example, a solution containing autocatalytic metal ions Another example is a method of treating a resin that has been etched or surface-modified. Examples of metal ions having self-catalytic properties include copper ions, nickel ions, iron ions, and cobalt ions. One or more of these can be used, but at least copper ions are preferably used. Using copper ions and nickel ions is more preferable in the case of electroless nickel plating. Further, examples of the above treatment include immersion, spraying, and the like.
　上記自己触媒性のある金属イオンを含有する溶液における、金属イオン濃度は特に限定されないが、例えば、０．００１ＭＯＬ／Ｌ以上、好ましくは０．００５ＭＯＬ／Ｌが好ましい。前記金属イオンを含有する溶液はｐＨを２～１２、好ましくは４～９に調整することが好ましい。前記金属イオンを吸着させる条件は特に限定されないが、２５～５０℃、好ましくは３５～４５℃で０．５～１０分間等の条件が挙げられる。 The metal ion concentration in the solution containing the self-catalytic metal ions is not particularly limited, but is, for example, 0.001 MOL/L or more, preferably 0.005 MOL/L. The solution containing the metal ions is preferably adjusted to pH 2-12, preferably 4-9. Conditions for adsorbing the metal ions are not particularly limited, but include conditions such as 25 to 50° C., preferably 35 to 45° C. for 0.5 to 10 minutes.
　上記自己触媒性のある金属イオンを含有する溶液に用いられる金属イオン源は特に限定されないが、例えば、銅イオン源であれば、酢酸銅、塩化銅、硫酸銅、アミド硫酸銅、ピロリン酸銅等が挙げられる。これらの中でも酢酸銅が好ましい。また、ニッケルイオン源であれば、硫酸ニッケル、塩化ニッケル、酢酸ニッケル、アミド硫酸ニッケル等が挙げられる。これらの中でも酢酸ニッケルが好ましい。更に、鉄イオン源であれば、硫酸鉄（II）等が挙げられる。また更に、コバルト源であれば、硫酸コバルト等が挙げられる。これら金属イオン源を適宜水等の溶媒に溶解させて上記自己触媒性のある金属イオンを含有する溶液を調製する。 The metal ion source used in the solution containing the metal ions having self-catalytic properties is not particularly limited. For example, copper ion sources include copper acetate, copper chloride, copper sulfate, copper amidosulfate, copper pyrophosphate, and the like. is mentioned. Among these, copper acetate is preferred. Nickel ion sources include nickel sulfate, nickel chloride, nickel acetate, and nickel amidosulfate. Among these, nickel acetate is preferred. Furthermore, iron (II) sulfate and the like can be used as an iron ion source. Further, cobalt sources include cobalt sulfate and the like. These metal ion sources are appropriately dissolved in a solvent such as water to prepare a solution containing the metal ions having self-catalytic properties.
　上記自己触媒性のある金属イオンを含有する溶液には、必要により、前記金属イオンの酸化防止のためアスコルビン酸またはその誘導体等の安定剤を含有させてもよい。また、上記した金属イオンを含有する溶液には、必要によりクエン酸、グルコン酸等の錯化剤を含有させてもよい。前記金属イオンを含有する溶液における安定剤や錯化剤の含有量は特に限定されないが、例えば、１～１００ｇ／Ｌである。 If necessary, the solution containing the metal ions having self-catalytic properties may contain a stabilizer such as ascorbic acid or a derivative thereof to prevent oxidation of the metal ions. If necessary, the solution containing the metal ions may contain a complexing agent such as citric acid or gluconic acid. The content of the stabilizer and complexing agent in the solution containing the metal ions is not particularly limited, but is, for example, 1 to 100 g/L.
　上記自己触媒性のある金属イオンを含有する溶液には、吸着量の向上の点から、臭化物を含有させても良い。臭化物は特に限定されないが、臭化物としては、例えば、臭化ナトリウム等が挙げられる。前記金属イオンを含有する溶液における臭化物の含有量は特に限定されないが、例えば、０.５～５ｇ／Ｌである。 The solution containing the metal ions having self-catalytic properties may contain bromide from the viewpoint of improving the adsorption amount. Bromide is not particularly limited, but examples of bromide include sodium bromide and the like. The bromide content in the solution containing the metal ions is not particularly limited, but is, for example, 0.5 to 5 g/L.
　上記自己触媒性のある金属イオンを含有する溶液には、表面電位の調整のため界面活性剤を含有させることが好ましい。界面活性剤としては特に限定はされないが、例えば、ポリエチレングリコール等が挙げられる。前記金属イオンを含有する溶液におけるポリエチレングリコールの含有量は特に限定されないが、例えば、分子量６０００の場合は０.５～５ｇ／Ｌである。 The solution containing the self-catalytic metal ions preferably contains a surfactant for adjusting the surface potential. The surfactant is not particularly limited, and examples thereof include polyethylene glycol. The content of polyethylene glycol in the solution containing the metal ions is not particularly limited, but is 0.5 to 5 g/L when the molecular weight is 6000, for example.
　なお、本発明方法の工程（ｂ）においては、自己触媒性のある金属イオンと共に、３族から１２族の遷移金属からなる群から選ばれる金属イオンの１種あるいは２種以上を吸着させることがめっきの析出状況が向上することから好ましい。具体的な前記遷移金属としては、ニオブ、モリブデン、チタン、タングステン、バナジウム等が挙げられる。 In the step (b) of the method of the present invention, one or more metal ions selected from the group consisting of Group 3 to Group 12 transition metals can be adsorbed together with the self-catalytic metal ions. It is preferable because the deposition condition of the plating is improved. Specific examples of the transition metal include niobium, molybdenum, titanium, tungsten, vanadium, and the like.
　工程（ｂ）において、エッチングあるいは表面改質した樹脂に自己触媒性のある金属イオンと共に３族から１２族の遷移金属からなる群から選ばれる金属イオンを吸着させる方法は、特に限定されないが、例えば、自己触媒性のある金属イオンと３族から１２族の遷移金属からなる群から選ばれる金属イオンを含有する溶液にエッチングあるいは表面改質した樹脂を浸漬する方法、自己触媒性のある金属イオンを含有する溶液と、３族から１２族の遷移金属からなる群から選ばれる金属イオンを含有する溶液に、エッチングあるいは表面改質した樹脂をそれぞれ浸漬する方法等が挙げられる。上記溶液における３族から１２族の遷移金属からなる群から選ばれる金属イオンの含有量は、適宜設定すればよい。また、３族から１２族の遷移金属からなる群から選ばれる金属イオンを含有する溶液についても、自己触媒性のある金属イオンを含有する溶液と同様に調製することができ、安定剤、錯化剤、臭化物、界面活性剤、高分子化合物等を含有させてもよい。 In the step (b), the method of adsorbing metal ions selected from the group consisting of group 3 to group 12 transition metals together with self-catalytic metal ions to the etched or surface-modified resin is not particularly limited, but for example , a method of immersing an etched or surface-modified resin in a solution containing metal ions selected from the group consisting of autocatalytic metal ions and group 3 to group 12 transition metals; and a method of immersing etched or surface-modified resin in a solution containing metal ions selected from the group consisting of Group 3 to Group 12 transition metals. The content of metal ions selected from the group consisting of Group 3 to Group 12 transition metals in the solution may be appropriately set. In addition, a solution containing metal ions selected from the group consisting of Group 3 to Group 12 transition metals can also be prepared in the same manner as the solution containing metal ions having self-catalytic properties. agents, bromides, surfactants, polymer compounds, and the like.
　上記３族から１２族の遷移金属からなる群から選ばれる金属イオンを含有する溶液における、金属イオン濃度は特に限定されないが、例えば、０．００５ＭＯＬ／Ｌ以上が好ましい。前記金属イオンを含有する溶液はｐＨを２～１２、好ましくは４～９に調整することが好ましい。前記金属イオンを吸着させる条件は特に限定されないが、２５～５０℃、好ましくは３５～４５℃で０．５～１０分間等の条件が挙げられる。なお、自己触媒性のある金属イオンを含有する溶液に、上記３族から１２族の遷移金属からなる群から選ばれる金属イオンを含有させる場合には、自己触媒性のある金属イオンを含有する溶液の濃度や条件を採用すればよい。 The concentration of metal ions in the solution containing metal ions selected from the group consisting of Group 3 to Group 12 transition metals is not particularly limited, but is preferably 0.005 MOL/L or more, for example. The solution containing the metal ions is preferably adjusted to pH 2-12, preferably 4-9. Conditions for adsorbing the metal ions are not particularly limited, but include conditions such as 25 to 50° C., preferably 35 to 45° C. for 0.5 to 10 minutes. In addition, when the solution containing the metal ions having self-catalysis is made to contain the metal ions selected from the group consisting of the transition metals of Groups 3 to 12, the solution containing the metal ions having self-catalysis concentration and conditions of
　以下に好ましい自己触媒性のある金属イオンを含有する溶液の好ましい態様を示す。
＜例１＞
銅イオン　　　　　０．００１～１．０ＭＯＬ／Ｌ
ニッケルイオン　　０．００１～１．０ＭＯＬ／Ｌ
＜例２＞
鉄イオン　　　　　０．００１～１．０ＭＯＬ／Ｌ
ニッケルイオン　　０．００１～１．０ＭＯＬ／Ｌ
＜例３＞
銅イオン　　　　　０．００１～１．０ＭＯＬ／Ｌ Preferred embodiments of solutions containing metal ions having preferred self-catalytic properties are shown below.
<Example 1>
Copper ion 0.001-1.0MOL/L
Nickel ion 0.001-1.0MOL/L
<Example 2>
Iron ion 0.001-1.0MOL/L
Nickel ion 0.001-1.0MOL/L
<Example 3>
Copper ion 0.001-1.0MOL/L
　また、以下に自己触媒性のある金属イオンと、上記３族から１２族の遷移金属からなる群から選ばれる金属イオンを含有する溶液の好ましい態様を示す。
＜例４＞
銅イオン　　　　　０．００１～１．０ＭＯＬ／Ｌ
ニッケルイオン　　０．００１～１．０ＭＯＬ／Ｌ
モリブデンイオン　０．００１～１．０ＭＯＬ／Ｌ
＜例５＞
銅イオン　　　　　０．００１～１．０ＭＯＬ／Ｌ
ニッケルイオン　　０．００１～１．０ＭＯＬ／Ｌ
ニオブイオン　　　０．００１～１．０ＭＯＬ／Ｌ
＜例５＞
銅イオン　　　　　０．００１～１．０ＭＯＬ／Ｌ
ニッケルイオン　　０．００１～１．０ＭＯＬ／Ｌ
タングステンイオン　０．００１～１．０ＭＯＬ／Ｌ Preferred embodiments of solutions containing metal ions having self-catalytic properties and metal ions selected from the group consisting of transition metals of Groups 3 to 12 are shown below.
<Example 4>
Copper ion 0.001-1.0MOL/L
Nickel ion 0.001-1.0MOL/L
Molybdenum ion 0.001-1.0MOL/L
<Example 5>
Copper ion 0.001-1.0MOL/L
Nickel ion 0.001-1.0MOL/L
Niobium ion 0.001-1.0MOL/L
<Example 5>
Copper ion 0.001-1.0MOL/L
Nickel ion 0.001-1.0MOL/L
Tungsten ion 0.001-1.0MOL/L
　上記溶液のうち、例１は無電解銅めっき、無電解ニッケルめっきに、例３は無電解銅めっきに好適である。 Of the above solutions, Example 1 is suitable for electroless copper plating and electroless nickel plating, and Example 3 is suitable for electroless copper plating.
　なお、エッチングあるいは表面改質した樹脂に自己触媒性のある金属イオン（工程（ｂ）において上記３族から１２族の遷移金属からなる群から選ばれる金属イオンを吸着させた場合にはこれら金属イオンも含む）を吸着させた後は、還元剤の寿命を考慮すると洗浄はなくともよいがあるほうが好ましい。 In the case where the etched or surface-modified resin is adsorbed with self-catalytic metal ions (metal ions selected from the group consisting of Group 3 to Group 12 transition metals in the step (b), these metal ions Considering the life of the reducing agent, it is preferable that washing is not necessary after adsorption.
　本発明方法の工程（ｃ）において、樹脂に吸着した自己触媒性のある金属イオン（工程（ｂ）において上記３族から１２族の遷移金属からなる群から選ばれる金属イオンを吸着させた場合にはこれら金属イオンも含む）を還元する方法は、特に限定されず、例えば、ボラン錯体、アミンボラン錯体、水素化ホウ素アルカリ金属塩等の水素化ホウ素化合物、ギ酸、ホルムアルデヒド、グリオキシル酸、還元糖等のアルデヒド類、次亜リン酸ナトリウム、ヒドラジン、アスコルビン酸、アスコルビン酸の異性体であるエリソルビン酸（イソアスコルビン酸）、アスコルビン酸ナトリウム等のアスコルビン酸塩、エリソルビン酸ナトリウム等のエリソルビン酸塩等のアスコルビン酸またはその誘導体等を含有する還元溶液に、樹脂を浸漬して還元する方法等が挙げられる。これら還元剤は１種または２種以上を併用してもよい。還元剤を含有する溶液のｐＨは弱酸性からアルカリ性の範囲内にすればよい。還元の条件は特に限定されないが、例えば、ジメチルアミンボランおよびアスコルビン酸またはその誘導体を併用する場合には、２５～６５℃、好ましくは４０～６０℃で０．５～１０分間、好ましくは２～５分間等の条件が挙げられる。また、水素化ホウ素ナトリウムを用いる場合には、２０℃～３０℃で０．５～１０分間、好ましくは１～５分間等の条件が挙げられる。 In the step (c) of the method of the present invention, the metal ions having self-catalytic properties adsorbed on the resin (when the metal ions selected from the group consisting of the group 3 to group 12 transition metals are adsorbed in the step (b), (including these metal ions) is not particularly limited. Aldehydes, sodium hypophosphite, hydrazine, ascorbic acid, erythorbic acid (isoascorbic acid) which is an isomer of ascorbic acid, ascorbate such as sodium ascorbate, ascorbic acid such as erythorbate such as sodium erythorbate Alternatively, a method of immersing the resin in a reducing solution containing a derivative thereof and the like to reduce the resin may be used. These reducing agents may be used singly or in combination of two or more. The pH of the solution containing the reducing agent may be in the weakly acidic to alkaline range. The conditions for reduction are not particularly limited. Conditions such as 5 minutes can be mentioned. When sodium borohydride is used, conditions such as 20° C. to 30° C. for 0.5 to 10 minutes, preferably 1 to 5 minutes, etc. can be mentioned.
　なお、上記還元溶液には、特開平４－２６７７３号公報の記載に従って、更にキレート剤を配合することが液寿命の点から好ましい。このキレート剤としては、例えば、Ｎ－ハイドロオキシエチルイミノニ酢酸等のジカルボン酸や、グリコール酸、３－ヒドロキシプロピオン酸等のモノカルボン酸が挙げられる。還元溶液におけるキレート剤の含有量は特に限定されないが、例えば、０．１ｇ／Ｌ～１０ｇ／Ｌである。 From the standpoint of liquid life, it is preferable to further add a chelating agent to the reducing solution as described in JP-A-4-26773. Examples of the chelating agent include dicarboxylic acids such as N-hydroxyethyliminodiacetic acid and monocarboxylic acids such as glycolic acid and 3-hydroxypropionic acid. Although the content of the chelating agent in the reducing solution is not particularly limited, it is, for example, 0.1 g/L to 10 g/L.
　本発明方法の工程（ｄ）において、樹脂に無電解めっきを行う方法は、例えば、無電解ニッケルめっき液、無電解銅めっき液等の無電解めっき液に浸漬等する方法等が挙げられる。これらの無電解めっき液の中でも銅以外の無電解めっき液を用いた、銅以外の無電解めっきが好ましく、無電解ニッケルめっきが特に好ましい。無電解めっきの条件は特に限定されないが、３０～５０℃、好ましくは３５～４０℃で５～１５分間、好ましくは８～１０分間等の条件が挙げられる。 In the step (d) of the method of the present invention, the method of electroless plating the resin includes, for example, a method of immersion in an electroless plating solution such as an electroless nickel plating solution or an electroless copper plating solution. Among these electroless plating solutions, electroless plating other than copper using an electroless plating solution other than copper is preferred, and electroless nickel plating is particularly preferred. The electroless plating conditions are not particularly limited, but include conditions such as 30 to 50° C., preferably 35 to 40° C., and 5 to 15 minutes, preferably 8 to 10 minutes.
　本発明方法の工程（ｄ）において用いられる無電解めっき液の好ましい態様としては以下のものが挙げられる。
＜無電解ニッケルめっき液＞
　公知の還元剤に次亜リン酸塩を用いたＮｉ－Ｐタイプ、アルキルアミンボランを用いたＮｉ－Ｂタイプ、ヒドラジンを用いたＮｉ－Ｎタイプ等の無電解ニッケルめっき液が使用できる。無電解ニッケルめっき液としては、市販品を利用することもできる。無電解ニッケルめっき液であれば、例えば、アミンボラン還元タイプのＥＮＩＰＡＣ　ＢＮ－ＩＩ（株式会社ＪＣＵ製）、次亜リン酸塩還元タイプのＥＮＩＬＥＸ　ＮＩ－１００およびＮＩ－５（株式会社ＪＣＵ製）等が挙げられる。 Preferred embodiments of the electroless plating solution used in step (d) of the method of the present invention include the following.
<Electroless nickel plating solution>
Electroless nickel plating solutions such as Ni--P type using hypophosphite as a known reducing agent, Ni--B type using alkylamine borane, and Ni--N type using hydrazine as a reducing agent can be used. A commercially available product can also be used as the electroless nickel plating solution. Examples of electroless nickel plating solutions include amine borane reduction type ENIPAC BN-II (manufactured by JCU Corporation), hypophosphite reduction type ENILEX NI-100 and NI-5 (manufactured by JCU Corporation), and the like. mentioned.
　なお、還元溶液として、上記還元水溶液を用いる場合には、次亜リン酸塩還元タイプのＥＮＩＬＥＸ ＮＩ－１００の無電解めっき液を用いることが浴安定性の点から好ましい。 When the reducing aqueous solution is used as the reducing solution, it is preferable to use a hypophosphite reduction type electroless plating solution of ENILEX NI-100 from the viewpoint of bath stability.
＜無電解銅めっき液＞
　銅めっきであれば、例えば、ホルムアルデヒド還元タイプのＥＢＡＳＨＩＥＬＤ　ＥＣ－ＩＩ（株式会社ＪＣＵ製）等が挙げられる。 <Electroless copper plating solution>
For copper plating, for example, formaldehyde reduction type EBASHIELD EC-II (manufactured by JCU Co., Ltd.) can be used.
　上記無電解めっきをした後は、洗浄等を常法に従って行ってもよい。 After the above electroless plating, washing, etc. may be performed according to the usual method.
　なお、本発明方法においては、各工程は必要により繰り返し行ってもよい。 In addition, in the method of the present invention, each step may be repeated as necessary.
　以上説明した本発明方法により、樹脂上に、無電解めっき層を設けためっき製品が得られる。前記めっき層中には、実質的に貴金属が含まれない。ここで実質的に含まれないとは、例えば、原子吸光分析等で金（Ａｕ）、銀（Ａｇ）、白金（Ｐｔ）、パラジウム（Ｐｄ）といった貴金属が検出限界以下（例えば、０.１ｐｐｍ以下）であることをいう。 A plated product having an electroless plating layer provided on a resin can be obtained by the method of the present invention described above. The plated layer does not substantially contain precious metals. Here, "substantially not contained" means, for example, that precious metals such as gold (Au), silver (Ag), platinum (Pt), and palladium (Pd) are below the detection limit (for example, 0.1 ppm or less) by atomic absorption spectrometry. ).
　このようにして得られためっき製品は、公知の無電解めっき製品と同様の用途、例えば、装飾めっき下地等に用いることができる。 The plated product thus obtained can be used in the same applications as known electroless plated products, such as decorative plating substrates.
　また、上記のようにして得られためっき製品には、更に、工程（ｅ）として電解めっきを行ってもよい。電解めっきとしては、特に限定されず、公知の電解めっき液や条件を用いることができる。 Further, the plated product obtained as described above may be further subjected to electrolytic plating as step (e). Electroplating is not particularly limited, and known electroplating solutions and conditions can be used.
　このようにして得られるめっき製品は、公知の電解めっき製品と同様の用途、例えば、装飾めっきに用いることができる。 The plated product thus obtained can be used for the same purposes as known electrolytic plated products, such as decorative plating.
　以下、本発明を本発明の実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 The present invention will be described in detail below with reference to examples of the present invention, but the present invention is not limited to these examples.
実　施　例　１
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂液（ＥＢＡＰＲＥＰ　ＳＫ－１４４：株式会社ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。その後、室温の銅イオンおよびニッケルイオンを含有する溶液（酢酸銅０．１ＭＯＬ／Ｌおよび酢酸ニッケル０．１ＭＯＬ／Ｌ、ｐＨは５．７２）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行い、更に、これを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。無電解ニッケルめっき後の試験片のめっきの析出状況を図１に示した。なお、めっき皮膜を原子吸光分析で分析したところ、貴金属は検出限界以下であった。その後、定法に従って電解クロムめっきまで施した。電解クロムめっき後のめっきの析出状況を図２に示した。 Example 1
Electroless nickel plating:
The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After that, it was immersed in a solution containing copper ions and nickel ions at room temperature (copper acetate 0.1 MOL/L and nickel acetate 0.1 MOL/L, pH 5.72) for 5 minutes to adsorb copper ions and nickel ions. rice field. After adsorption, it was washed with water, and further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH of about 9) at 60°C for 5 minutes to remove copper ions and nickel ions. returned. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating. FIG. 1 shows the deposition state of the plating on the test piece after electroless nickel plating. When the plating film was analyzed by atomic absorption spectrometry, the amount of noble metal was below the detection limit. After that, electrolytic chromium plating was applied according to a standard method. Fig. 2 shows the deposition of plating after electrolytic chromium plating.
実　施　例　２
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片（半球つき平板：約１００ｃｍ２）を、６８℃のクロム酸溶液（４００ｇ／Ｌ無水クロム酸、４００ｇ／Ｌ硫酸、１ｍＬ／Ｌ　ＭＩＳＴＳＨＵＴ　ＰＦ：株式会社ＪＣＵ製）に１０分間浸漬してエッチングした。これを室温のクロム還元剤（１０ｍＬ／Ｌ　ＥＮＩＬＥＸ　ＲＤ：株式会社ＪＣＵ製、６０ｍＬ／Ｌ塩酸）に１分間浸漬して残留Ｃｒを中和した。次にこれを室温の銅イオンを含有する溶液（酢酸銅０．０１ＭＯＬ／Ｌ、ｐＨ５．７２に建浴時にしたもの）に５分間浸漬して銅イオンを吸着させた。吸着後、水洗を行う（実施例２－１）または行わない（実施例２－２）で、更にこれを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンを還元した。最後に、これらを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 2
Electroless nickel plating:
An ABS resin test piece (a flat plate with a hemisphere: about 100 cm 2 ) was immersed in a 68° C. chromic acid solution (400 g/L chromic anhydride, 400 g/L sulfuric acid, 1 mL/L MISTSHUT PF: manufactured by JCU Co., Ltd.) for 10 minutes. and etched. This was immersed in a chromium reducing agent (10 mL/L ENILEX RD: manufactured by JCU Corporation, 60 mL/L hydrochloric acid) at room temperature for 1 minute to neutralize residual Cr. Next, this was immersed for 5 minutes in a solution containing copper ions at room temperature (copper acetate 0.01 MOL/L, pH 5.72 when the bath was prepared) to adsorb copper ions. After adsorption, washing with water (Example 2-1) or not (Example 2-2) was performed, and this was further treated with a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, The copper ions were reduced by immersion in a pH of about 9) for 5 minutes. Finally, these were immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
実　施　例　３
　　　無電解ニッケルめっき：
　実施例２において、銅イオン溶液を銅イオンおよびニッケルイオンを含有する溶液（硫酸銅０．０１ＭＯＬ／Ｌおよび硫酸ニッケル０．０１ＭＯＬ／Ｌ、ｐＨは４．７８）に代える以外は、実施例２と同様に無電解ニッケルめっきを行った。 Example 3
Electroless nickel plating:
In Example 2, except replacing the copper ion solution with a solution containing copper ions and nickel ions (copper sulfate 0.01 MOL / L and nickel sulfate 0.01 MOL / L, pH 4.78). Electroless nickel plating was performed in the same manner.
実　施　例　４
　　　貴金属フリーの無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂液（ＥＢＡＰＲＥＰ　ＳＫ－１４４：株式会社ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを水洗した後、室温の銅イオンおよびニッケルイオンを含有する溶液（硫酸銅０．０１ｍｏｌ／Ｌおよび硫酸ニッケル０．０１ｍｏｌ／Ｌ、ｐＨは４．７８）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行わないで、更にこれらを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 4
Precious metal-free electroless nickel plating:
The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing it with water, it was immersed in a solution containing copper ions and nickel ions (0.01 mol/L of copper sulfate and 0.01 mol/L of nickel sulfate, pH was 4.78) at room temperature for 5 minutes to remove copper ions and nickel ions. ions were adsorbed. After adsorption, without washing with water, they were further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH of about 9) at 60° C. for 5 minutes to remove copper ions and nickel ions. was reduced. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
参　考　例　１
　　　電解硫酸の調製：
　公知の方法により作製したホウ素ドープダイヤモンド電極を用いて以下の条件により硫酸を電解して電解硫酸を作製した。
＜電解条件＞
　７８ｗｔ％の硫酸を１対の１ｉｎｃｈダイヤモンド電極を用いて０．５Ａかつ４．８Ｖで電解。浴条件は浴温６０℃、酸化剤濃度５ｇ／Ｌであった。 Reference example 1
Preparation of electrolytic sulfuric acid:
Using a boron-doped diamond electrode prepared by a known method, sulfuric acid was electrolyzed under the following conditions to prepare electrolytic sulfuric acid.
<Electrolysis conditions>
78 wt% sulfuric acid was electrolyzed at 0.5 A and 4.8 V using a pair of 1 inch diamond electrodes. The bath conditions were a bath temperature of 60° C. and an oxidizing agent concentration of 5 g/L.
実　施　例　５
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の湿潤剤（ＥＮＩＬＥＸ　ＷＥ：株式会社ＪＣＵ製）に１０分間浸漬して濡れ性付与を行った。この試験片を次に、６５℃にした参考例１で調製した電解硫酸に１０分間浸漬してエッチングした。これを４０℃温水で洗浄した後、室温の銅イオンを含有する溶液（硫酸銅０．０１ＭＯＬ／Ｌ、アンモニアでｐＨ１０．５に調整したもの）に５分間浸漬して銅イオンを吸着させた。吸着後、水洗を行い、更にこれを６０℃の還元溶液（３ｇ／Ｌジメチルアミンボランおよび５ｇ／Ｌアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンを還元した。最後に、これを６０℃の無電解ニッケルめっき液（ＥＮＩＰＡＣ　ＢＮ－ＩＩ（アミンボラン還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 5
Electroless nickel plating:
A test piece of ABS resin was immersed in a wetting agent (ENILEX WE: manufactured by JCU Co., Ltd.) at 50° C. for 10 minutes to impart wettability. This test piece was then etched by being immersed in the electrolytic sulfuric acid prepared in Reference Example 1 at 65° C. for 10 minutes. After washing it with hot water at 40° C., it was immersed in a solution containing copper ions at room temperature (0.01 MOL/L of copper sulfate, adjusted to pH 10.5 with ammonia) for 5 minutes to adsorb copper ions. After adsorption, it was washed with water, and further immersed in a reducing solution (3 g/L dimethylamine borane and 5 g/L sodium ascorbate, pH about 9) at 60° C. for 5 minutes to reduce copper ions. Finally, this was immersed in an electroless nickel plating solution (ENIPAC BN-II (amine borane reduction type) manufactured by JCU Co., Ltd.) at 60° C. for 10 minutes to perform electroless nickel plating.
参　考　例　２
　　　還元水溶液の調製：
　特開平４－２６７７３号公報の記載に従って還元水溶液を調製した。具体的には２５ｇ／Ｌの水酸化ナトリウム水溶液に、３０ｇ／Ｌの水素化ホウ素ナトリウムを溶解し、更に５ｇ／ＬのＮ－ハイドロオキシエチルイミノニ酢酸を溶解して純水で１０倍に希釈して還元水溶液を調製した。 Reference example 2
Preparation of reducing aqueous solution:
A reducing aqueous solution was prepared according to the description of JP-A-4-26773. Specifically, 30 g/L of sodium borohydride is dissolved in a 25 g/L sodium hydroxide aqueous solution, and 5 g/L of N-hydroxyethyliminodiacetic acid is further dissolved and diluted 10 times with pure water. to prepare a reducing aqueous solution.
　この還元水溶液は建浴後１週間たっても効果は消失せず、無電解めっきをすることができるものであった。 The effect of this reducing aqueous solution did not disappear even one week after making the bath, and electroless plating was possible.
実　施　例　６
　　　無電解ニッケルめっき：
　実施例５において、６０℃の還元溶液に５分間浸漬して銅イオンを還元していたのに代えて、２５℃の参考例２で調製した還元水溶液に５分間浸漬する以外は実施例５と同様にして無電解ニッケルめっきを行った。 Example 6
Electroless nickel plating:
In Example 5, instead of immersing in the reducing solution at 60 ° C. for 5 minutes to reduce the copper ions, it was immersed in the reducing aqueous solution prepared in Reference Example 2 at 25 ° C. for 5 minutes. Electroless nickel plating was performed in the same manner.
実　施　例　７
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂（ＥＢＡＰＲＥＰ　ＳＫ－１４４：ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。その後、室温の鉄イオンおよびニッケルイオンを含有する溶液（硫酸鉄０．１ＭＯＬ／Ｌ、硫酸ニッケル０．１ＭＯＬ／Ｌ、アスコルビン酸１０ｍｇ／Ｌ、グルコン酸１５ｍＬ、ｐＨは４．５）に５分間浸漬して鉄イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行わないで、更にこれを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して鉄イオンおよびニッケルイオンを還元した。最後に、これを４５℃の無電解ニッケルめっき液（ＥＮＩＰＡＣ　ＢＮ－II（アミンボラン還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 7
Electroless nickel plating:
The ABS resin test piece was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After that, it is immersed in a solution containing iron ions and nickel ions at room temperature (0.1 MOL/L iron sulfate, 0.1 MOL/L nickel sulfate, 10 mg/L ascorbic acid, 15 mL gluconic acid, pH 4.5) for 5 minutes. to adsorb iron and nickel ions. After adsorption, without washing with water, it is further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH is about 9) at 60° C. for 5 minutes to remove iron ions and nickel ions. was reduced. Finally, this was immersed in an electroless nickel plating solution (ENIPAC BN-II (amine borane reduction type) manufactured by JCU Co., Ltd.) at 45° C. for 10 minutes to carry out electroless nickel plating.
実　施　例　８
　　　無電解銅めっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂（ＥＢＡＰＲＥＰ　ＳＫ－１４４：ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを温水で洗浄した後、室温の銅イオンおよびニッケルイオンを含有する溶液（硫酸銅０．１ＭＯＬ／Ｌおよび硫酸ニッケル０．１ＭＯＬ／Ｌ、ｐＨは５．７２）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行わないで、更にこれを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解銅めっき液（ＥＢＡＳＨＩＥＬＤ　ＥＣ－II（ホルムアルデヒド還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 8
Electroless copper plating:
The ABS resin test piece was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing it with warm water, it was immersed in a room temperature solution containing copper ions and nickel ions (0.1 MOL/L of copper sulfate and 0.1 MOL/L of nickel sulfate, pH was 5.72) for 5 minutes to remove copper ions. and nickel ions were adsorbed. After adsorption, without washing with water, it is further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH is about 9) at 60° C. for 5 minutes to remove copper ions and nickel ions. was reduced. Finally, this was immersed in an electroless copper plating solution (EBASHIELD EC-II (formaldehyde reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
実　施　例　９
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂に替えてＰＰ樹脂の試験片を、５０℃の脱脂（ＥＢＡＰＲＥＰ　ＳＫ－１４４：ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬して水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを水洗した後、室温の銅イオンおよびニッケルイオンを含有する溶液（酢酸銅０．１ＭＯＬ／Ｌおよび酢酸ニッケル０．１ＭＯＬ／Ｌ、ｐＨは５．７２）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行い、更にこれを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 9
Electroless nickel plating:
A test piece of PP resin instead of ABS resin was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing it with water, it was immersed in a room temperature solution containing copper ions and nickel ions (0.1 MOL/L copper acetate and 0.1 MOL/L nickel acetate, pH 5.72) for 5 minutes to remove copper ions and nickel ions. ions were adsorbed. After adsorption, it is washed with water, and further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH is about 9) at 60° C. for 5 minutes to reduce copper ions and nickel ions. did. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
実　施　例　１０
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂に替えてＣＦＲＰの試験片を、５０℃の脱脂（ＥＢＡＰＲＥＰ　ＳＫ－１４４：ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを水洗した後、室温の銅イオンおよびニッケルイオンを含有する溶液（酢酸銅０．１ＭＯＬ／Ｌおよび酢酸ニッケル０．１ＭＯＬ／Ｌ、ｐＨは５．７２）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行い、更にこれを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 10
Electroless nickel plating:
Instead of the ABS resin, the CFRP test piece was degreased by immersing it in 50° C. degreasing (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing it with water, it was immersed in a room temperature solution containing copper ions and nickel ions (0.1 MOL/L copper acetate and 0.1 MOL/L nickel acetate, pH 5.72) for 5 minutes to remove copper ions and nickel ions. ions were adsorbed. After adsorption, it is washed with water, and further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH is about 9) at 60° C. for 5 minutes to reduce copper ions and nickel ions. did. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
実　施　例　１１
　　　貴金属フリーの無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂液（ＥＢＡＰＲＥＰ　ＳＫ－１４４：株式会社ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを水洗した後、室温の銅イオンおよび鉄イオンを含有する溶液（硫酸銅０．１ＭＯＬ／Ｌおよび硫酸鉄０．１ＭＯＬ／Ｌ、クエン酸３ナトリウム１４．５ｇ／Ｌ、ｐＨは２．２５）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行うまたは行わないで、更にこれらを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 11
Precious metal-free electroless nickel plating:
The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing with water, a solution containing copper ions and iron ions at room temperature (copper sulfate 0.1 MOL/L and iron sulfate 0.1 MOL/L, trisodium citrate 14.5 g/L, pH 2.25) for 5 minutes to adsorb copper ions and nickel ions. After adsorption, with or without washing with water, they are further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH is about 9) at 60° C. for 5 minutes to absorb copper ions and Nickel ions were reduced. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
実　施　例　１２
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂液（ＥＢＡＰＲＥＰ　ＳＫ－１４４：株式会社ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを水洗した後、室温のニッケルイオンを含有する溶液（酢酸ニッケル０．１ＭＯＬ／Ｌ、ｐＨは６．７２）に５分間浸漬してニッケルイオンを吸着させた。吸着後、水洗を行うまたは行わないで、更にこれらを２５℃の還元溶液（３ｇ／Ｌの水素化ホウ素ナトリウム、ｐＨは約９）に５分間浸漬してニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 12
Electroless nickel plating:
The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing this with water, it was immersed in a solution containing nickel ions at room temperature (0.1 MOL/L nickel acetate, pH 6.72) for 5 minutes to adsorb nickel ions. After adsorption, with or without water washing, they were further immersed in a reducing solution (3 g/L sodium borohydride, pH about 9) at 25° C. for 5 minutes to reduce nickel ions. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
実　施　例　１３
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂液（ＥＢＡＰＲＥＰ　ＳＫ－１４４：ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。これを水洗した後、室温の鉄イオンを含有する溶液（硫酸アンモニウム鉄０．１ＭＯＬ／Ｌおよびアスコルビン酸ナトリウム３ｇ／Ｌ、酢酸アンモニウム７．７ｇ／Ｌ、ｐＨは６．１８）に５分間浸漬して鉄イオンを吸着させた。吸着後、水洗を行うまたは行わないで、更にこれらを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのアスコルビン酸ナトリウム、ｐＨは約９）に５分間浸漬して鉄イオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 13
Electroless nickel plating:
The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After washing it with water, it was immersed in a solution containing iron ions at room temperature (0.1 MOL/L of ammonium iron sulfate, 3 g/L of sodium ascorbate, 7.7 g/L of ammonium acetate, pH of 6.18) for 5 minutes. adsorbed iron ions. After adsorption, these were further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of sodium ascorbate, pH of about 9) at 60° C. for 5 minutes with or without washing with water to remove iron ions. returned. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
　以上の結果から、少なくとも０．００１ＭＯＬ／Ｌ以上の自己触媒性のある金属イオンを含む溶液に、エッチングあるいは表面改質した樹脂を浸漬した後、還元工程を行うことで無電解めっきに対する触媒性が得られた。貴金属触媒を用いなくても無電解めっきがきれいに析出することが分かった。 From the above results, it can be concluded that the etching or surface-modified resin is immersed in a solution containing at least 0.001 MOL/L or more of self-catalytic metal ions, and then subjected to a reduction process to improve catalytic properties for electroless plating. Got. It was found that electroless plating was deposited cleanly without using a noble metal catalyst.
実　施　例　１４
　　　無電解ニッケルめっき：
　ＡＢＳ樹脂の試験片を、５０℃の脱脂液（ＥＢＡＰＲＥＰ　ＳＫ－１４４：株式会社ＪＣＵ製）に１０分間浸漬して脱脂を行った。この試験片を、６８℃の過マンガン酸溶液（２４０ｍＬ／Ｌ　ＤＳ－２５０ＮＡ：株式会社ＪＣＵ製）に４分間浸漬した後、６８℃の硫酸（１１００ｇ／Ｌ硫酸）に２分間浸漬し、水洗した後、更に、上記６８℃の過マンガン酸溶液に２分間浸漬した後、上記６８℃の硫酸に２分間浸漬してエッチングした。その後、室温の銅イオンおよびニッケルイオンを含有する溶液（酢酸銅０．１ＭＯＬ／Ｌおよび酢酸ニッケル０．１ＭＯＬ／Ｌ、ｐＨは５．７２）に５分間浸漬して銅イオンおよびニッケルイオンを吸着させた。吸着後、水洗を行い、更に、これを６０℃の還元溶液（３ｇ／Ｌのジメチルアミンボランおよび５ｇ／Ｌのエリソルビン酸、ｐＨは約９）に５分間浸漬して銅イオンおよびニッケルイオンを還元した。最後に、これを４０℃の無電解ニッケルめっき液（ＥＮＩＬＥＸ　ＮＩ－１００（次亜リン酸塩還元タイプ）：株式会社ＪＣＵ製）に１０分間浸漬して無電解ニッケルめっきを行った。 Example 14
Electroless nickel plating:
The ABS resin test piece was degreased by immersing it in a 50° C. degreasing solution (EBAPREP SK-144: manufactured by JCU Co., Ltd.) for 10 minutes. This test piece was immersed in a permanganate solution (240 mL/L DS-250NA: manufactured by JCU Co., Ltd.) at 68° C. for 4 minutes, then immersed in sulfuric acid (1100 g/L sulfuric acid) at 68° C. for 2 minutes, and washed with water. After that, it was further immersed in the permanganic acid solution at 68° C. for 2 minutes, and then immersed in sulfuric acid at 68° C. for 2 minutes for etching. After that, it was immersed in a solution containing copper ions and nickel ions at room temperature (copper acetate 0.1 MOL/L and nickel acetate 0.1 MOL/L, pH 5.72) for 5 minutes to adsorb copper ions and nickel ions. rice field. After adsorption, it is washed with water, and further immersed in a reducing solution (3 g/L of dimethylamine borane and 5 g/L of erythorbic acid, pH is about 9) at 60° C. for 5 minutes to reduce copper ions and nickel ions. did. Finally, this was immersed in an electroless nickel plating solution (ENILEX NI-100 (hypophosphite reduction type) manufactured by JCU Co., Ltd.) at 40° C. for 10 minutes to perform electroless nickel plating.
　還元溶液に、エリソルビン酸を用いてもアスコルビン酸ナトリウムを用いた場合と同様の無電解めっきが得られた。 Even when erythorbic acid was used as the reducing solution, the same electroless plating was obtained as when sodium ascorbate was used.
　本発明は、貴金属触媒を用いないプロセスのため、半導体材料、自動車部品、水栓金具等の多種用途へのめっきに利用することができる。 The present invention is a process that does not use a precious metal catalyst, so it can be used for plating various applications such as semiconductor materials, automobile parts, and faucet fittings.

Claims (11)

  1. 　以下の工程（ａ）～（ｄ）
    （ａ）樹脂をエッチングあるいは表面改質する工程
    （ｂ）エッチングあるいは表面改質した樹脂に、自己触媒性のある金属イオンを吸着させる工程
    （ｃ）樹脂に吸着した自己触媒性のある金属イオンを還元する工程
    （ｄ）樹脂に無電解めっきを行う工程
    を含むことを特徴とするめっき方法。     the following steps (a) to (d)
    (a) step of etching or surface-modifying the resin (b) step of allowing the etched or surface-modified resin to adsorb autocatalytic metal ions (c) adsorbing the autocatalytic metal ions adsorbed on the resin A plating method comprising a step of reducing (d) a step of performing electroless plating on the resin.
  2. 　工程（ｂ）で自己触媒性のある金属イオンと共に３族から１２族の遷移金属からなる群から選ばれる金属イオンの１種あるいは２種以上を吸着させ、工程（ｃ）で樹脂に吸着した自己触媒性のある金属イオンと共に３族から１２族の遷移金属からなる群から選ばれる金属イオンの１種あるいは２種以上を還元するものである請求項１記載のめっき方法。 In step (b), one or more metal ions selected from the group consisting of Group 3 to Group 12 transition metals are adsorbed together with a self-catalytic metal ion, and in step (c), the self adsorbed on the resin 2. The plating method according to claim 1, wherein one or more metal ions selected from the group consisting of Group 3 to Group 12 transition metals are reduced together with catalytic metal ions.
  3. 　工程（ｂ）において、自己触媒性のある金属イオン濃度が０．００１ＭＯＬ／Ｌ以上の溶液でエッチングあるいは表面改質した樹脂を処理してエッチングあるいは表面改質した樹脂に、自己触媒性のある金属イオンを吸着させるものである請求項１または２に記載のめっき方法。 In the step (b), the etched or surface-modified resin is treated with a solution having a self-catalytic metal ion concentration of 0.001 MOL/L or more to add the self-catalytic metal to the etched or surface-modified resin. 3. The plating method according to claim 1, wherein ions are adsorbed.
  4. 　更に（ｅ）無電解めっきした樹脂に電解めっきを行う工程を含む請求項１～３の何れか１に記載のめっき方法。 The plating method according to any one of claims 1 to 3, further comprising (e) a step of electroplating the electroless-plated resin.
  5. 　工程（ａ）で行うエッチングが、酸化剤を含む酸性液を用いたものである請求項１～４の何れか１に記載のめっき方法。 The plating method according to any one of claims 1 to 4, wherein the etching performed in step (a) uses an acid solution containing an oxidizing agent.
  6. 　酸化剤が、クロム酸、過マンガン酸、オゾン水溶液または過硫酸である請求項５記載のめっき方法。 The plating method according to claim 5, wherein the oxidizing agent is chromic acid, permanganic acid, ozone aqueous solution or persulfuric acid.
  7. 　工程（ａ）で行う表面改質が、硫酸浸漬である請求項１～６の何れか１に記載のめっき方法。 The plating method according to any one of claims 1 to 6, wherein the surface modification performed in step (a) is immersion in sulfuric acid.
  8. 　工程（ｃ）で行う還元が、水素化ホウ素化合物、アルデヒド類、次亜リン酸ナトリウム、ヒドラジン、アスコルビン酸またはその誘導体、からなる群から選ばれる還元剤の１種または２種以上を含有する還元溶液を用いたものである請求項１～７の何れか１に記載のめっき方法。 Reduction performed in step (c) contains one or more reducing agents selected from the group consisting of borohydride compounds, aldehydes, sodium hypophosphite, hydrazine, ascorbic acid or derivatives thereof. The plating method according to any one of claims 1 to 7, which uses a solution.
  9. 　樹脂が、ＡＢＳ、ＡＳ、ＰＣ／ＡＢＳ、ＰＣ、ＰＡ、ＰＰまたはＣＦＲＰからなる群から選ばれる樹脂である請求項１～８の何れか１に記載のめっき方法。 The plating method according to any one of claims 1 to 8, wherein the resin is a resin selected from the group consisting of ABS, AS, PC/ABS, PC, PA, PP and CFRP.
  10. 　樹脂上に、無電解めっき層を設け、前記めっき層中に貴金属が実質的に含まれないことを特徴とするめっき製品。 A plated product characterized in that an electroless plating layer is provided on a resin, and the plating layer does not substantially contain precious metals.
  11. 　無電解めっき層の上に、更に電解めっき層を設けたものである請求項１０記載のめっき製品。 The plated product according to claim 10, wherein an electroplated layer is further provided on the electroless plated layer.
PCT/JP2022/009900 2021-03-12 2022-03-08 Plating method, and plated product WO2022191167A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002309375A (en) * 2001-02-07 2002-10-23 Okuno Chem Ind Co Ltd Catalyst impartation method for electroless plating
JP2007262481A (en) * 2006-03-28 2007-10-11 Yoichi Haruta Surface metallizing method of polyimide resin material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002309375A (en) * 2001-02-07 2002-10-23 Okuno Chem Ind Co Ltd Catalyst impartation method for electroless plating
JP2007262481A (en) * 2006-03-28 2007-10-11 Yoichi Haruta Surface metallizing method of polyimide resin material

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