US20200190682A1 - Plating pretreatment method for abs resin surface, plating treatment method for abs resin surface, and abs resin plated product - Google Patents

Plating pretreatment method for abs resin surface, plating treatment method for abs resin surface, and abs resin plated product Download PDF

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US20200190682A1
US20200190682A1 US16/642,375 US201816642375A US2020190682A1 US 20200190682 A1 US20200190682 A1 US 20200190682A1 US 201816642375 A US201816642375 A US 201816642375A US 2020190682 A1 US2020190682 A1 US 2020190682A1
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Prior art keywords
abs resin
plating
treatment
resin surface
sulfuric acid
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Inventor
Tatsuo Nagai
Yuzuki YAMAMOTO
Taibou YAMAMOTO
Yasuo Hashimoto
Miyoko Izumitani
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JCU Corp
Kurita Water Industries Ltd
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JCU Corp
Kurita Water Industries Ltd
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Assigned to KURITA WATER INDUSTRIES LTD., JCU CORPORATION reassignment KURITA WATER INDUSTRIES LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAMAMOTO, Yuzuki, YAMAMOTO, TAIBOU, IZUMITANI, MIYOKO, HASHIMOTO, YASUO, NAGAI, TATSUO
Publication of US20200190682A1 publication Critical patent/US20200190682A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • 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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/036—Bipolar electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • 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
    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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

Definitions

  • the present invention relates to a pretreatment method performed prior to a plating treatment of an ABS resin surface.
  • the present invention further relates to a plating treatment method for an ABS resin surface that has been subjected to this pretreatment.
  • the present invention still further relates to an ABS resin plated product obtained by plating the ABS resin surface that has been subjected to this pretreatment.
  • Plastics are substituted for parts where metals are used as structural materials and component materials for advantages such as weight reduction, cost reduction, freedom of shape, ease of mass production, and the like. At present, they are widely used not only for decoration but also for exterior and interior parts of automobiles, home electric appliances, and the like. At this time, a plastic surface is often plated to improve rigidity, wear resistance, weather resistance, heat resistance, and the like.
  • plastics are non-conductive, it is necessary to first form a metal film serving as a conductor on a plastic before plating.
  • Methods therefor are roughly classified into dry methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD), and wet methods such as electroless nickel plating.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • wet methods such as electroless nickel plating.
  • the wet methods have been employed so far because the dry methods mostly involve film formation in a vacuum state and therefore are not suitable for mass production or application to large components.
  • ABS resin is widely used as the main plastic substituted for metals because it is a resin which is most easily plated.
  • surface roughening treatment as a pretreatment for plating the ABS resin, surface roughening treatment using a chromic acid/sulfuric acid solution is performed.
  • Chromic acid is represented by the chemical formula: H 2 CrO 4
  • etching liquid that is a mixed solution of chromic acid with concentrated sulfuric acid, there is an equilibrium of 2CrO 4 2 ⁇ +2H 3 O + ⁇ Cr 2 O 7 2 ⁇ +3H 2 O, but Cr is hexavalent.
  • Hexavalent chromium is subject to REACH regulations and the RoHS Directive, but hexavalent chromium itself is not regulated because it does not remain in products.
  • hexavalent chromium itself is not regulated because it does not remain in products.
  • wastewater treatment such as reduction, neutralization, and coagulation sedimentation is required for wastewater containing Cr, and the precipitate from the treatment cannot be easily disposed because it contains Cr.
  • Patent Literature 1 proposes etching using a mixed solution of permanganate and an inorganic salt.
  • Patent Literature 2 and Patent Literature 3 disclose a pretreatment method for electroless plating in which a surface of a plastic molded article is roughened using ozone-dissolved water.
  • the method of etching with the mixed solution of permanganate and an inorganic salt disclosed in Patent Literature 1 has problems that the surface treatment of the ABS resin is difficult, and adhesiveness to the metal is poor.
  • manganese (Mn) will also become subject to REACH regulations and the RoHS Directive in the future in the same manner as Cr, and therefore it is desirable not to use it.
  • Mn manganese
  • the plating pretreatment method for a plastic surface disclosed in Patent Literature 2 and Patent Literature 3 since ozone has a high decomposition rate, it is necessary to produce high-concentration ozone water and maintain a high concentration. Therefore, not only is large-scale equipment required, but there is also a problem that unevenness is likely to occur in treatment due to a local difference in ozone concentration.
  • the present invention has been made in view of the above problems, and an objective thereof is to provide a plating pretreatment method for a Cr- and Mn-free ABS resin surface which is a plating pretreatment method for an ABS resin surface by which plating sufficiently adhered to an ABS resin surface can be formed. Another objective of the present invention is to provide a plating treatment method in which plating is favorably adhered to the ABS resin surface that has been subjected to such a pretreatment method. Still another object of the present invention is to provide an ABS resin plated product obtained by plating the ABS resin surface that has been subjected to this pretreatment.
  • the present invention provides a plating pretreatment method for an ABS resin surface (Invention 1), the method including treating ABS resin with a solution obtained by electrolysis of sulfuric acid.
  • ABS resin refers to not only the case of an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) alone, but also a blend resin of this ABS resin and another resin, specifically, a mixed resin of ABS resin and polycarbonate (PC resin).
  • ABS resin also includes a PC/ABS mixed resin in which a content of PC resin is 20% to 70% by weight with respect to a total of 100% by weight of ABS resin and PC resin.
  • a concentration of sulfuric acid in the solution is preferably 60% to 87% by weight (Invention 2).
  • a specific surface area is increased by suitably roughening an ABS resin surface with a persulfate solution obtained by electrolysis of sulfuric acid at this concentration, whereby adhesiveness of plating can be improved.
  • a concentration of sulfuric acid within the above range, it is possible to adjust a degree of treatment of an ABS resin surface.
  • a temperature in the treatment is preferably 50° C. to 80° C. (Invention 3).
  • a specific surface area is increased by suitably roughening an ABS resin surface while inhibiting decomposition of persulfuric acid, whereby adhesiveness of plating can be further improved.
  • a concentration of persulfuric acid in the solution is preferably 3 g/L or more (Invention 4).
  • a specific surface area is increased by suitably roughening an ABS resin surface through a strong oxidizing action of persulfuric acid, whereby adhesiveness of plating can be still further improved.
  • the present invention provides a plating treatment method for an ABS resin surface (Invention 5), the method including subjecting an ABS resin surface to electroless plating or electroplating after treating the surface by the plating pretreatment method for the ABS resin surface according to any one of the above inventions (Inventions 1 to 4).
  • invention 5 by dissolving a butadiene component on an ABS resin surface through a strong oxidizing action of persulfuric acid generated by electrolysis of sulfuric acid, the surface is roughened, and hydrophilic functional groups are exposed. Therefore, when the ABS resin is subjected to plating treatment after this treatment, it is possible to precipitate plating such as chromium with favorable adhesiveness to an ABS resin surface.
  • the present invention provides an ABS resin plated product (Invention 6) which has been subjected to plating treatment by the plating treatment method for the ABS resin surface according to the above invention (Invention 5).
  • the ABS resin plated product is obtained by plating an ABS resin surface with chromium or the like with favorable adhesiveness.
  • the plating treatment method for an ABS resin surface of the present invention when an ABS resin surface is roughened by dissolving a butadiene component on the surface through a strong oxidizing action of persulfuric acid generated by electrolysis of sulfuric acid, a specific surface area increases and hydrophilic functional groups are exposed, and therefore, when the ABS resin is subjected to plating treatment after this treatment, a sufficiently adhered plating can be obtained.
  • FIG. 1 is a schematic diagram showing a configuration of a treatment device which is suitable for a plating pretreatment method for an ABS resin surface according to an embodiment of the present invention can be applied.
  • FIG. 1 shows a treatment device which is suitable for a plating pretreatment method for an ABS resin surface according to an embodiment of the present invention can be applied.
  • a treatment device 1 includes a treatment tank 2 provided with a constant temperature heater 3 on an outer periphery, an electrolytic cell 6 continuing from a pipe 4 having a circulation pump 5 , and a pipe 7 for supply from the electrolytic cell 6 to the treatment tank 2 .
  • the electrolytic cell 6 has an anode 6 A and a cathode 6 B formed from diamond electrodes, and a bipolar electrode 6 C disposed therebetween.
  • the treatment tank 2 may have a stirring means such as an air diffuser for stirring the inside of the tank as needed.
  • Such a treatment device 1 is configured such that the treatment tank 2 and the electrolytic cell 6 are filled with sulfuric acid of a predetermined concentration in an initial state, a sulfate solution S containing persulfuric acid (an oxidizing agent) such as peroxodisulfuric acid (hereinafter referred to as a persulfate solution in the present specification) is generated by making a predetermined current to be supplied from a direct current power supply unit to the anode 6 A and the cathode 6 B, and by electrolysis of sulfuric acid, this persulfate solution S can be supplied to the treatment tank 2 via the pipe 7 .
  • a sulfate solution S containing persulfuric acid (an oxidizing agent) such as peroxodisulfuric acid
  • the device 1 is configured such that the persulfate solution S refluxes from the treatment tank 2 to the electrolytic cell 6 via the pipe 4 by the circulation pump 5 , and thereby the persulfate solution S is circulated.
  • an ABS resin plate 8 to be treated is suspended in a vertical direction.
  • a concentration of sulfuric acid is preferably 60% to 87% by weight, particularly 70% to 83% by weight.
  • concentration of sulfuric acid is less than 60% by weight, a concentration of sulfuric acid in a resulting persulfate solution S becomes too low, a surface of the ABS resin plate 8 therefore cannot be sufficiently roughened, and an effect of improving adhesiveness of plating cannot be sufficiently obtained, whereas even when the concentration exceeds 87% by weight, not only can the effect not be further improved, but a handling property also deteriorates, which is not preferable.
  • the persulfate solution S it is preferable to heat the persulfate solution S with the constant temperature heater 3 such that a temperature of the persulfate solution S becomes 50° C. to 80° C.
  • a temperature of the persulfate solution S becomes 50° C. to 80° C.
  • a concentration of persulfuric acid such as peroxodisulfuric acid generated by the electrolysis is 3 g/L or more, particularly 3 to 20 g/L.
  • concentration of persulfuric acid is less than 3 g/L, the effect of improving adhesiveness of plating cannot be obtained sufficiently, whereas even when the concentration exceeds 20 g/L, the above effect cannot be further improved, and it is not economical.
  • the surface of the ABS resin plate 8 is treated by immersing the degreased ABS resin plate 8 in the treatment tank 2 .
  • the ABS resin plate 8 be subjected to wet treatment in advance in order to suppress air bubbles adhering to the plate when the plate is immersed in the persulfate solution S.
  • neutralization and/or reduction treatment, conditioning treatment, and the like may be performed as necessary.
  • the surface of the ABS resin plate 8 can be etched by the pretreatment method of the present embodiment described above.
  • a conventionally known plating method for a resin such as an electroless plating method and a direct plating method.
  • a catalyst is applied to the ABS resin plate 8 that has been treated by the pretreatment method of the present embodiment using a catalyst application treatment liquid.
  • the catalyst application treatment liquid is not particularly limited as long as it is a liquid generally used for applying a catalyst in a plating step, but it preferably contains a noble metal, more preferably contains palladium, and particularly preferably contains a palladium/tin mixed colloid catalyst solution.
  • a temperature of the catalyst application treatment liquid is preferably set to 10° C. to 60° C., particularly 20° C. to 50° C., and the ABS resin plate 8 is immersed therein and treated for 1 to 20 minutes, preferably 2 to 5 minutes.
  • the resin surface to which the catalyst has been applied is metallized by a metal plating treatment such as electroless plating or electroplating (direct plating).
  • treatment may be further performed with an activation treatment liquid containing hydrochloric acid or sulfuric acid after a catalyst is applied with the catalyst application treatment liquid.
  • a concentration of hydrochloric acid or sulfuric acid in this activation treatment liquid is 0.5 mol/L or more, preferably 1 to 4 mol/L.
  • a temperature of the activation treatment solution is preferably set to 0° C. to 60° C., particularly 30° C. to 45° C., and the ABS resin plate 8 is immersed therein and treated for preferably 1 to 20 minutes, particularly 2 to 5 minutes.
  • the ABS resin plate 8 to which the catalyst has been applied and which has been subjected to activation treatment as described above is then subjected to electroless plating treatment.
  • the electroless plating treatment can be performed according to a general method using electroless plating such as known electroless nickel plating liquid, electroless copper plating liquid, electroless cobalt plating liquid, or the like. Specifically, in the case of performing plating treatment to a resin surface with the electroless nickel plating liquid, the ABS resin plate 8 is immersed in the electroless nickel plating liquid at a pH of 8 to 10 and a liquid temperature of 30° C. to 50° C. for 5 to 15 minutes.
  • a catalyst is applied with a catalyst application treatment liquid, and thereafter, treatment can be further performed with an activation treatment liquid containing copper ions at a pH of 7 or more.
  • the origin of the copper ions contained in the activation treatment liquid is not particularly limited, and examples thereof include copper sulfate.
  • a temperature of the activation treatment solution is preferably set to 0° C. to 60° C., particularly 30° C. to 50° C., and the ABS resin plate 8 is immersed therein and treated for preferably 1 to 20 minutes, particularly 2 to 50 minutes.
  • the ABS resin plate 8 to which the catalyst has been applied and subjected to activation treatment as described above is subsequently immersed in a general-purpose copper electroplating bath such as a copper sulfate bath, and treated in general conditions, for example, 1 to 5 A/dm 2 for 2 to 10 minutes. In addition, sufficient washing with water or hot water is performed between treatments.
  • a general-purpose copper electroplating bath such as a copper sulfate bath
  • the surface of the ABS resin plate 8 is subjected to metal plating such as electroless plating or electroplating, and if necessary, the surface of the metallized ABS resin plate 8 may further be subjected to various plating such as copper electroplating, nickel electroplating, and chrome electroplating. It is sufficient for these metal platings to enable acquirement of a film as plating, and examples thereof include nickel, copper, chromium, cobalt, tin, zinc, iron, silver, gold, and alloys thereof.
  • Such a treatment may be performed continuously while replacing the ABS resin plate 8 , but it is desirable that the circulation pump 5 be continuously driven to continuously replenish the treatment tank 2 with fresh persulfate solution S from the electrolytic cell 6 via the pipe 7 , because persulfuric acid of the persulfate solution S in the treatment tank 2 decomposes with the progress of the treatment, which decreases a concentration of persulfuric acid.
  • the treatment tank 2 may be appropriately replenished with sulfuric acid, and when the concentration of sulfuric acid increases, the treatment tank 2 may be appropriately replenished with water.
  • a sulfuric acid concentration system can be installed in the treatment tank 2 so that this operation can be performed automatically.
  • the ABS resin plate 8 may be subjected to treatment for imparting wettability, if necessary.
  • This treatment may be performed by, for example, sufficiently immersing the ABS resin plate 8 in a wet treatment tank to impart wettability to the surface of the resin substrate.
  • a surfactant may be contained in the wet treatment tank.
  • the surfactant is not particularly limited, but for example, it is possible to use an amine salt type surfactant, a quaternary amine salt type surfactant, an amino acid type surfactant, a betaine type surfactant, a carboxylate type surfactant, a sulfonate type surfactant, a sulfate ester type surfactant, a phosphate ester type surfactant, an ether type surfactant, an ester type surfactant, a nitrogen-containing surfactant, a fluorine-containing surfactant, and the like.
  • One kind of these surfactants may be used, or two or more kinds thereof may be used.
  • ABS resin plate 8 pretreated as above can be subjected to electroless plating or electroplating by a general method. Accordingly, it is possible to obtain an ABS resin plated product in which the surface of the ABS resin plate 8 is plated with chromium or the like with favorable adhesiveness.
  • the plating treatment method for an ABS resin surface according to the present invention has been described above based on the above-described embodiment.
  • the present invention is not limited to the above-described examples, and various modifications can be made.
  • the present invention is applicable not only to batch treatment as in the present embodiment but also to continuous treatment.
  • the ABS resin plate is not limited to the plate as in the present embodiment, but can also be applied to molded articles of various shapes.
  • a concentration of a total oxidizing agent contained in a treatment liquid was measured by iodine titration.
  • This iodine titration is a method in which KI is added to the persulfate solution S to release I 2 , this I 2 is titrated with a sodium thiosulfate standard solution to determine an amount of I 2 , and a concentration of an oxidizing agent is obtained from the amount of I 2 .
  • This test is for examining adhesiveness by performing thermal shock by heating and rapidly cooling a sample, in which, after performing 40 cycles of the shock at 70° C. and ⁇ 30° C., that is, a temperature difference of 100° C., for 1 hour at each temperature, conditions such as the presence or absence of peeling, cracks, swelling, and the like on a plating surface were observed and evaluated on a three-point scale of classifications 1 to 3 below.
  • Classification 1 No peeling, cracks, wrinkles, or swelling on plating was observed.
  • Classification 2 Peeling, cracks, wrinkles, and swelling on plating were observed in less than 25% of the sample area.
  • Classification 3 Peeling, cracks, wrinkles, and swelling on plating were observed in 25% or more of the sample area.
  • a surface treatment of the ABS resin plate 8 was performed using the device shown in FIG. 1 .
  • Specifications and conditions of a treatment tank are as follows.
  • Treatment temperature 75° C.
  • Anode and cathode Diamond electrode (150 mm diameter)
  • Bipolar electrode material Same as the anode and the cathode
  • Treatment temperature 75° C.
  • the ABS resin plate 8 was first immersed in a wet treatment tank containing a surfactant for 10 minutes, and then was immersed in the treatment tank 2 filled with the persulfate solution S for 10 minutes. Thereafter, the plate was removed from the treatment tank 2 , washed with tap water, and then subjected to electroless nickel plating through an activation step and a catalyst application step. Thereafter, chromium plating was finally performed on the plate.
  • Tables 1 and 2 show the treatment conditions in the plating step. In addition, plating adhesiveness of the chrome-plated ABS resin plate 8 was evaluated by the above method. Table 3 shows results together with conditions for the electrolytic sulfuric acid treatment.
  • Chromium plating was performed in the same manner as in Example 1 except that various settings of conditions for the electrolytic sulfuric acid treatment were changed as shown in Table 3, and plating adhesiveness was evaluated. Table 3 shows results together with conditions for the electrolytic sulfuric acid treatment.
  • Chromium plating was performed in the same manner as in Example 1 except that a sulfuric acid solution having a sulfuric acid concentration of 75% by weight was used instead of the electrolytic sulfuric acid solution, and plating adhesiveness was evaluated. Table 3 shows results together with conditions for the treatment.
  • Chromium plating was performed in the same manner as in Example 1 except that a mixed solution of sulfuric acid and hydrogen peroxide was used instead of the electrolytic sulfuric acid solution, and plating adhesiveness was evaluated. Table 3 shows results together with conditions for the treatment.
  • Example 2 TABLE 3 Concentration of Treatment Concentration of Treatment Result of Example sulfuric acid temperature persulfuric acid time adhesiveness Nos. (% by weight) (° C.) (g/L) (minutes) test Example 1 75 75 10 15 Classification 1 Example 2 65 80 5 20 Classification 1 Example 3 85 50 3 7 Classification 1 Example 4 65 85 5 15 Classification 2 Example 5 60 80 10 20 Classification 2 Example 6 75 75 10 3 Classification 2 Example 7 85 75 2 20 Classification 2 Comparative 75 75 0 15 Classification 3 Example 1 Comparative 75 10 15 Classification 2 Example 2

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JP2017168258A JP2019044229A (ja) 2017-09-01 2017-09-01 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品
JP2017-168258 2017-09-01
PCT/JP2018/032342 WO2019045047A1 (fr) 2017-09-01 2018-08-31 Procédé de prétraitement de placage pour une surface de résine abs, procédé de traitement de placage pour une surface de résine abs et produit plaqué à base de résine abs

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JP7484407B2 (ja) 2020-05-18 2024-05-16 栗田工業株式会社 電解硫酸溶液製造システムの立上げ方法

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US20130186774A1 (en) * 2012-01-23 2013-07-25 Trevor Pearson Etching of Plastic Using Acidic Solutions Containing Trivalent Manganese
US8603352B1 (en) * 2012-10-25 2013-12-10 Rohm and Haas Electroncis Materials LLC Chrome-free methods of etching organic polymers
WO2017137584A1 (fr) * 2016-02-12 2017-08-17 Biconex Gmbh Procédé de prétraitement de pièces en plastique pour l'électroplacage
US20190136380A1 (en) * 2016-04-28 2019-05-09 Kurita Water Industries Ltd. Method for treating surface of plastic

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EP3677703A1 (fr) 2020-07-08

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