EP3633066B1 - Mehrstufiges harzoberflächenätzverfahren und plattierungsverfahren auf harz damit - Google Patents

Mehrstufiges harzoberflächenätzverfahren und plattierungsverfahren auf harz damit Download PDF

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Publication number
EP3633066B1
EP3633066B1 EP18810479.8A EP18810479A EP3633066B1 EP 3633066 B1 EP3633066 B1 EP 3633066B1 EP 18810479 A EP18810479 A EP 18810479A EP 3633066 B1 EP3633066 B1 EP 3633066B1
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Prior art keywords
resin
acid
plating
resin surface
oxidizing agent
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English (en)
French (fr)
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EP3633066A1 (de
EP3633066A4 (de
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Yasuyuki Kuramochi
Hiroshi Ishizuka
Miyoko Izumitani
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JCU Corp
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JCU Corp
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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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to a multi-stage resin surface etching method, and a plating method on a resin using the same.
  • the operation is performed at a high temperature of 60°C or higher using harmful hexavalent chromium, and therefore, there was a problem that the operation environment is deteriorated, and further, attention is needed also for a waste water treatment thereof.
  • permanganic acid may sometimes be promptly decomposed depending on use conditions, and it was sometimes problematic for industrial use.
  • a composition for an etching treatment containing permanganic acid, a specific inorganic acid, and further one component selected from a halogen oxoacid, a halogen oxoacid salt, a persulfate, and a bismuthate has also been reported (PTL 2), however, the above-mentioned component is used in a large amount, and therefore, the cost is high, and this was also problematic for industrial use.
  • EP 2657367 A1 discloses a pre-etching composition and an etching process for plastic substrates.
  • JP H08 337880 A discloses a method for roughening an adhesive layer for electroless plating made of an amino resin and a heat resistant resin.
  • An object of the present invention is to provide a novel technique that is a resin etching technique without using chromic acid and can be operated at an industrial level.
  • the present inventors made intensive studies for achieving the above object, and as a result, they unexpectedly found that by dividing an etching step using an oxidizing agent for a resin into two stages and further repeatedly performing the step, a resin surface can be sufficiently etched even without performing a resin swelling step, and therefore, by the subsequent plating, high adhesion is obtained, and thus completed the present invention.
  • the present invention relates to the subject matter of claims 1 to 3. That is, the present invention is directed to a resin surface etching method, characterized in that, in etching a resin surface, the method consists of step (a), step (b) and step (c), wherein in step (c) the set of steps (a) and (b) is repeated one or more times:
  • the present invention is directed to a plating method on a resin, characterized in that, in plating a resin, the plating is performed after the resin is etched by the above-mentioned resin surface etching method.
  • the resin surface etching method of the present invention can suppress decomposition of an oxidizing agent used for etching. Further, in the resin surface etching method of the present invention, the etching step is repeatedly performed, however, etching can be more efficiently performed in a shorter time than when the etching step is performed in one stage for a long time. In addition, by the resin surface etching method of the present invention, the resin surface can be sufficiently etched, and therefore, it is not necessary to perform a resin swelling step that was conventionally required.
  • method of the present invention In the resin surface etching method of the present invention (hereinafter referred to as "method of the present invention"), one set of the following steps (a) and (b) is performed two or more times. Incidentally, even if sufficient etching cannot be achieved by a certain number of sets, sufficient etching can be achieved by increasing the number of sets.
  • the resin may be subjected to a treatment such as degreasing, or surface conditioning, before performing the method of the present invention.
  • a treatment such as degreasing, or surface conditioning
  • a swelling step for facilitating resin etching is not performed.
  • Water washing or hot water washing may be performed before or after the treatment such as degreasing, or surface conditioning.
  • the resin that can be treated with the etching solution of the present invention is selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS), acrylonitrile-styrene-acrylate (ASA), silicon-based composite rubber-acrylonitrile-styrene (SAS), NORYL, polypropylene, polycarbonate (PC), acrylonitrile-styrene, polyacetate, polystyrene, polyethylene, polyether ketone, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyether ether sulfone, polyether imide, modified polyphenylene ether, polyphenylene sulfide, polyamide, polyimide, liquid crystal polymers, and copolymers of the above-mentioned respective polymers.
  • ABS and PC/ABS are preferred.
  • the oxidizing agent used in the step (a) of the method of the present invention is permanganic acid or a salt thereof, examples thereof include permanganates such as potassium permanganate, or sodium permanganate.
  • permanganates such as potassium permanganate, or sodium permanganate.
  • manganese salts such as manganese sulfate, manganese nitrate, manganese carbonate, manganese chloride, manganese acetate, manganese dioxide, sodium manganate, or potassium manganite may be used in addition.
  • one type or two or more types can be used.
  • the solution containing the oxidizing agent for example, a solution obtained by dissolving the oxidizing agent in a solvent such as water is exemplified.
  • the content of the oxidizing agent in this solution is not particularly limited, but is, for example, 0.0005 mol/L or more, preferably from 0.005 to 2.0 mol/L.
  • a pH buffer agent or a surfactant may be incorporated in such an amount that the performance of the pH buffer agent or the surfactant is exhibited as long as the oxidizing action of this solution is not impaired.
  • the pH of the solution containing the oxidizing agent is not particularly limited, but is preferably from 3.0 to 10.0.
  • the pH buffer agent is not particularly limited, however, examples thereof include phosphates, citrates, borates, carbonates, acetates, diethylbarbiturates, tris(hydroxymethyl)aminomethane, hydroxyethylpiperazine ethanesulfonic acid, or ethylenediaminetetraacetic acid.
  • these pH buffer agents one type or two or more types can be used.
  • the surfactant is not particularly limited, however, examples thereof include amine salt type surfactants, quaternary amine salt type surfactants, amino acid type surfactants, betaine type surfactants, carboxylate type surfactants, sulfonate type surfactants, sulfuric acid ester salt type surfactants, phosphoric acid ester salt type surfactants, ether type surfactants, ester type surfactants, nitrogen-containing type surfactants, or fluorine-containing type surfactants.
  • these surfactants one type or two or more types can be used. By using the surfactant, the throwing power of plating can be improved.
  • a method for treating the resin with a solution containing the oxidizing agent and adsorbing the oxidizing agent on the resin surface is not particularly limited, and for example, the resin may be immersed in the solution containing the oxidizing agent. Conditions for immersing the resin are also not particularly limited, and for example, the resin may be immersed in the solution at 0 to 100°C, preferably at 60 to 70°C for 30 seconds or more, preferably for 1 to 5 minutes.
  • step (a) After adsorbing the oxidizing agent on the resin surface in the step (a), water washing may be performed as needed. Thereafter, the oxidizing agent adsorbed on the resin surface is activated in the step (b) .
  • a method for activating the oxidizing agent is not particularly limited, and for example, the resin may be immersed in a solution containing one type or two or more types of activating agents.
  • the activating agents are selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, methanesulfonic acid, hydrogen peroxide, peroxodisulfate, periodic acid, perchloric acid, and perbromic acid. Among these activating agents, hydrogen peroxide, phosphoric acid, and sulfuric acid are preferred.
  • Such an activating agent is prepared as a solution by being dissolved in a solvent such as water. The content of the activating agent in this solution is 0.05 mol/L or more, preferably from 0.5 to 17 mol/L.
  • a surfactant may be incorporated in such an amount that the performance of the surfactant is exhibited as long as the activating action of this solution is not impaired.
  • the surfactant is not particularly limited, however, examples thereof include amine salt type surfactants, quaternary amine salt type surfactants, amino acid type surfactants, betaine type surfactants, carboxylate type surfactants, sulfonate type surfactants, sulfuric acid ester salt type surfactants, phosphoric acid ester salt type surfactants, ether type surfactants, ester type surfactants, nitrogen-containing type surfactants, and fluorine-containing type surfactants.
  • these surfactants one type or two or more types can be used. By using the surfactant, the throwing power of plating can be improved.
  • a method for activating the oxidizing agent adsorbed on the resin surface is not particularly limited, and for example, when a solution containing the activating agent is used, the resin may be immersed in the solution at, for example, 0 to 100°C, more preferably at 60 to 70°C for 30 seconds or more, more preferably for 1 to 5 minutes.
  • each of the steps (a) and (b) constitute one set, however, after this step (b), a neutralization and reduction treatment, or a conditioner treatment may be performed as needed. Further, each of the steps (a) and (b) is performed for preferably 30 seconds or more, more preferably 1 to 5 minutes.
  • a resin surface can be etched.
  • the method of the present invention can be used for etching a resin surface in a conventionally known plating method on a resin, and in the other steps, a conventionally known plating method on a resin can be used.
  • Examples of the conventionally known plating method on a resin include an electroless plating method and a direct plating method.
  • a catalyst is imparted using a catalyst imparting treatment solution.
  • This catalyst imparting treatment solution is not particularly limited as long as it is generally used for imparting a catalyst in a plating step, but is preferably a solution containing a noble metal, more preferably a solution containing palladium, and particularly preferably a palladium/tin mixed colloidal catalyst solution.
  • the treatment may be performed by setting the temperature of the catalyst imparting treatment solution to 10 to 60°C, preferably 20 to 50°C and immersing the resin therein for 1 to 20 minutes, preferably 2 to 5 minutes.
  • the resin surface to which the catalyst is imparted in this manner is subsequently subjected to metal plating such as electroless metal plating or metal electroplating (direct plating), thereby metallizing the resin surface.
  • metal plating such as electroless metal plating or metal electroplating (direct plating)
  • a treatment may be further performed using an activation treatment solution containing hydrochloric acid or sulfuric acid.
  • the concentration of hydrochloric acid or sulfuric acid in this activation treatment solution is 0.5 mol/L or more, preferably from 1 to 4 mol/L.
  • the treatment may be performed by setting the temperature of the activation treatment solution to 0 to 60°C, preferably 30 to 45°C and immersing the resin therein for 1 to 20 minutes, preferably 2 to 5 minutes.
  • the resin subjected to the catalyst impartment and activation treatments as described above is subsequently subjected to an electroless metal plating treatment.
  • the electroless metal plating treatment can be performed according to a usual method using a known electroless metal plating solution such as an electroless nickel plating solution, an electroless copper plating solution, or an electroless cobalt plating solution.
  • the treatment may be performed by immersing the resin in the electroless nickel plating solution at pH 8 to 10 and at a liquid temperature of 30 to 50°C for 5 to 15 minutes.
  • a treatment may be further performed using an activation treatment solution containing copper ions at pH 7 or higher, preferably 12 or higher.
  • a source of the copper ions contained in this activation treatment solution is not particularly limited, and for example, copper sulfate is exemplified.
  • the treatment may be performed by setting the temperature of the activation treatment solution to 0 to 60°C, preferably 30 to 50°C and immersing the resin therein for 1 to 20 minutes, preferably 2 to 50 minutes.
  • the resin subjected to the catalyst impartment and activation treatments as described above is subsequently immersed in a widely used copper electroplating bath such as a copper sulfate bath, and may be subjected to a treatment under usual conditions, for example, at 1 to 5 A/dm 2 for 2 to 10 minutes.
  • plastic surface metallized by subjecting the resin surface to metal plating such as electroless plating or metal electroplating as described above can also be additionally subjected to various types of copper electroplating or nickel electroplating or chromium electroplating according to need.
  • water washing or hot water washing may be performed between respective steps.
  • the thus obtained resin plating has high adhesion.
  • test piece (3001M, manufactured by UMG ABS, Ltd.) of an ABS resin of 50 ⁇ 100 ⁇ 3 mm was used.
  • This sample was immersed in degreasing washing solutions PC-1 and PC-2 (manufactured by JCU Corporation) at 60°C for 10 minutes, and subsequently immersed in a surface conditioning solution at 50°C containing 10 ml/L ENILEX WE (manufactured by JCU Corporation) for 10 minutes.
  • the sample subjected to degreasing and surface conditioning was treated in an etching step shown in Table 1, and further immersed in a conditioner (catalyst impartment enhancing) treatment solution D-POP CDV (manufactured by JCU Corporation) at 25°C for 1 minute.
  • a conditioner catalyst impartment enhancing treatment solution
  • D-POP CDV manufactured by JCU Corporation
  • the etching solution used in the etching step shown in Table 1 is as follows.
  • the sample was immersed in a palladium/tin mixed colloidal catalyst solution at 35°C containing 20 ml/L CT-580 (manufactured by JCU Corporation) and 2.5 mol/L hydrochloric acid for 4 minutes, thereby imparting the catalyst on the ABS resin.
  • the sample to which the catalyst was imparted was immersed in an activation treatment solution at 35°C composed of 1.2 mol/L hydrochloric acid for 4 minutes, thereby activating the catalyst, and subsequently immersed in an electroless nickel plating solution ENILEX NI-100 (manufactured by JCU Corporation) at pH 8.8 and 35°C for 10 minutes, thereby performing electroless nickel plating until the film thickness reached 0.5 ⁇ m on the ABS resin.
  • the above sample was subjected to a 40-cycle (cyc) or 80-cycle heat shock test in which a step of maintaining the sample at -30°C for 30 minutes and maintaining the sample at 70°C for 30 minutes was regarded as one cycle.
  • the sample in which swelling did not occur in the plating film was evaluated as "A”, and the sample in which swelling occurred was evaluated as "B".
  • the adhesion is improved by extending the treatment time in the case of chromic acid etching of the conventional method, however, the adhesion is not improved even if the treatment time is simply extended in the etching step of the method of the present invention. It was found that the adhesion is improved by repeatedly performing the etching step even in a short treatment time. Incidentally, even in the case of Example Method 1, by repeating the set of the steps (a) and (b) five times, "A" was obtained in the severer 80-cycle heat shock test.
  • Electroless nickel plating was performed in the same manner as in Example 1 except that, in Example Method 1 of Example 1, the pH of the etching solution used in the step (a) was changed as shown in Table 2, and as the pH buffer solution, a buffer solution shown in Table 3 was used according to the pH. Incidentally, in the adjustment of the pH, sodium hydroxide and sulfuric acid were used. Further, for the electroless nickel plating, peel strength measurement and a heat shock test were performed in the same manner as in Example 1. The results are shown in Table 2.
  • Electroless nickel plating was performed in the same manner as in Example 1 except that, in Example Method 1 of Example 1, the pH buffer agent was removed from the solution used in the steps (a) and (b) .
  • this electroless nickel plating was subjected to peel strength measurement and a heat shock test in the same manner as in Example 1, the same results as in Example Method 1 were obtained.
  • Electroless nickel plating was performed in the same manner as in Example 1 except that, in Example Method 1 of Example 1, a test piece (3001M, manufactured by UMG ABS, Ltd.) of an ABS resin of 50 ⁇ 180 ⁇ 3 mm in a three-dimensional shape (a shape that makes air easy to remain) was used as the sample, and a surfactant shown in Table 4 was used in the solution used in the steps (a) and (b). The appearance of the electroless nickel plating was evaluated by visual observation. The results are shown in Table 4.
  • plating was performed on the resin in a three-dimensional shape with a small number of times by using a surfactant.
  • a resin surface can be etched, and therefore, the method can be used in a conventionally known plating method on a resin.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)

Claims (3)

  1. Verfahren zum Ätzen von Harzoberflächen, dadurch gekennzeichnet, dass das Verfahren beim Ätzen einer Harzoberfläche aus Schritt (a), Schritt (b) und Schritt (c), sowie den optionalen Schritten (d), (e) und (f) besteht, wobei in Schritt (c) die Gruppe der Schritte (a) und (b) ein oder mehrere Male wiederholt wird:
    (a) einen Schritt des Behandelns der Harzoberfläche mit einer Lösung, die ein Oxidationsmittel enthält, und des Adsorbierens des Oxidationsmittels auf der Harzoberfläche, wobei das verwendete Oxidationsmittel Permangansäure oder ein Salz davon ist; und
    (b) einen Schritt des Aktivierens des Oxidationsmittels, das auf der Harzoberfläche im Schritt (a) adsorbiert wurde, wobei die Aktivierung des Oxidationsmittels durch eine Behandlung mit einer Lösung durchgeführt wird, die einen Typ oder zwei oder mehr Typen von Aktivierungsmitteln enthält, die aus der Gruppe ausgewählt sind, die aus Schwefelsäure, Phosphorsäure, Salzsäure, Salpetersäure, Methansulfonsäure, Wasserstoffperoxid, Peroxodisulfat, Perjodsäure, Perchlorsäure und Perbromsäure besteht, wobei der Gehalt des Aktivierungsmittels in der Lösung 0,05 mol/L oder mehr beträgt,
    wobei nach Schritt (a) ein Waschschritt (d) mit Wasser durchgeführt werden kann und nach Schritt (b) ein Neutralisierungs- und Reduktionsbehandlungsschritt (e) oder ein Konditionierungsbehandlungsschritt (f) durchgeführt werden kann, und
    wobei das Harz ausgewählt ist aus der Gruppe bestehend aus Acrylnitril-Butadien-Styrol (ABS), Polycarbonat/Acrylnitril-Butadien-Styrol (PC/ABS), Acrylnitril-Styrol-Acrylat (ASA), Verbundkautschuk auf Silikonbasis-Acrylnitril-Styrol (SAS), Polypropylen, Polycarbonat (PC), Acrylnitril-Styrol, Polyacetat, Polystyrol, Polyethylen, Polyetherketon, Polyethylenterephthalat, Polybutylenterephthalat, Polysulfon, Polyetherethersulfon, Polyetherimid, modifizierter Polyphenylenether, Polyphenylensulfid, Polyimid, Flüssigkristallpolymere und Copolymere dieser Polymere.
  2. Verfahren zum Ätzen von Harzoberflächen nach Anspruch 1, wobei jeder der Schritte (a) und (b) für 30 Sekunden oder länger durchgeführt wird.
  3. Verfahren zum Plattieren eines Harzes, dadurch gekennzeichnet, dass beim Plattieren eines Harzes das Plattieren durchgeführt wird, nachdem das Harz durch das Verfahren zum Ätzen der Harzoberfläche nach Anspruch 1 oder 2 geätzt worden ist.
EP18810479.8A 2017-06-01 2018-03-15 Mehrstufiges harzoberflächenätzverfahren und plattierungsverfahren auf harz damit Active EP3633066B1 (de)

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US12435273B2 (en) * 2021-02-26 2025-10-07 Atotech Deutschland GmbH & Co. KG Method for etching at least one surface of a plastic substrate

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KR20200014763A (ko) 2020-02-11
KR102591173B1 (ko) 2023-10-18
JP7036817B2 (ja) 2022-03-15
US20200087791A1 (en) 2020-03-19
EP3633066A4 (de) 2021-02-17

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