WO2019045047A1 - 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 - Google Patents

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 Download PDF

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WO2019045047A1
WO2019045047A1 PCT/JP2018/032342 JP2018032342W WO2019045047A1 WO 2019045047 A1 WO2019045047 A1 WO 2019045047A1 JP 2018032342 W JP2018032342 W JP 2018032342W WO 2019045047 A1 WO2019045047 A1 WO 2019045047A1
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Prior art keywords
plating
abs resin
abs
treatment
sulfuric acid
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PCT/JP2018/032342
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English (en)
Japanese (ja)
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永井　達夫
裕都喜 山本
泰望 山本
康男 橋本
美代子 泉谷
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栗田工業株式会社
株式会社Ｊｃｕ
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Application filed by 栗田工業株式会社, 株式会社Ｊｃｕ filed Critical 栗田工業株式会社
Priority to EP18849843.0A priority Critical patent/EP3677703A4/fr
Priority to CN201880055459.8A priority patent/CN111032910A/zh
Priority to US16/642,375 priority patent/US20200190682A1/en
Publication of WO2019045047A1 publication Critical patent/WO2019045047A1/fr

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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 plating of an ABS-based resin surface.
  • the present invention also relates to a plating treatment method of the surface of the ABS-based resin which has been subjected to this pretreatment.
  • the present invention relates to an ABS-based resin plated product obtained by plating the surface of the ABS-based resin subjected to the pretreatment.
  • plastics are being replaced by taking advantage of weight reduction, cost reduction, freedom of shape, ease of mass production, and the like. At present, it is widely used not only for decoration but also for exterior and interior parts of automobiles, home appliances, and the like. At that time, in order to improve the rigidity, the abrasion resistance, the weather resistance, the heat resistance and the like, the plastic surface is often plated.
  • plastic Since plastic is nonconductive, it is necessary to first form a metal film on the plastic to be a conductor in order to perform plating.
  • the methods can be broadly classified into dry methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), and wet methods of electroless nickel plating. Since the dry method is mostly film formation in a vacuum state and is not suitable for mass production or application to large parts, the wet method has been adopted so far.
  • an ABS-based resin is widely used as a resin that is most easily plated and as a main plastic for metal substitution.
  • a surface roughening treatment with a chromic acid / sulfuric acid solution is performed for the surface roughening treatment as the plating pretreatment of the ABS resin.
  • Chromic acid is represented by the chemical formula: H 2 CrO 4
  • etching solution which is a mixed solution with concentrated sulfuric acid, 2CrO 4 2- + 2H 3 O + ⁇ Cr 2 O 7 2- + 3H 2 O
  • Cr's equilibrium exists Cr is in any case hexavalent.
  • hexavalent chromium is subject to the REACH regulations and the RoHS directive, it is not restricted by itself because hexavalent chromium does not remain in the product.
  • waste water containing Cr requires waste water treatment such as reduction, neutralization, coagulation sedimentation, etc., and the precipitate also contains Cr, so that it can not be easily discarded.
  • Patent Document 1 proposes etching with a mixed solution of permanganate and an inorganic salt. Further, Patent Document 2 and Patent Document 3 disclose a pretreatment method of electroless plating in which the surface of a plastic molded product is roughened using ozone-dissolved water.
  • the present invention has been made in view of the above problems, and is a plating pretreatment method for a chromium and manganese free ABS resin surface, which is capable of forming a plating sufficiently in contact with the ABS resin surface. It aims at providing the plating pretreatment method of the resin surface. Another object of the present invention is to provide a plating method which adheres well to the surface of an ABS resin to which such pretreatment method has been applied. Another object of the present invention is to provide an ABS-based resin plated product obtained by plating on the surface of the ABS-based resin which has been subjected to this pretreatment.
  • the present invention first provides a method for pre-plating a surface of an ABS-based resin, wherein the ABS-based resin is treated with a solution obtained by electrolyzing sulfuric acid (Invention 1).
  • an ABS-based resin refers not only to acrylonitrile-butadiene-styrene copolymer resin (ABS resin) alone, but also to a blend resin of this ABS resin and another resin, specifically an ABS resin.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • PC resin polycarbonate
  • PC resin contains 20 to 70% by weight of PC / ABS mixed resin with respect to 100% by weight in total of ABS resin and PC resin.
  • the sulfuric acid concentration of the solution is preferably 60 to 87% by weight (Invention 2).
  • the specific surface area is increased by suitably roughening the surface of the ABS-based resin with a persulfuric acid solution obtained by electrolyzing sulfuric acid at this concentration, and the adhesion of plating is improved. it can. Then, by varying the concentration of sulfuric acid within the above range, the degree of treatment of the surface of the ABS-based resin can be adjusted.
  • the temperature of the treatment is preferably 50 to 80 ° C. (Invention 3).
  • the specific surface area can be increased by appropriately roughening the surface of the ABS-based resin while suppressing the decomposition of the persulfuric acid, and the adhesion of the plating can be further improved.
  • the persulfate concentration of the solution is preferably 3 g / L or more (Invention 4).
  • the specific surface area can be increased by suitably roughening the surface of the ABS-based resin by the strong oxidizing action of persulfuric acid, and the adhesion of plating can be further improved.
  • the butadiene component on the surface of the ABS-based resin is dissolved by the strong oxidizing action of the persulfuric acid generated by electrolyzing sulfuric acid to roughen the surface and at the same time the hydrophilic functional group is exposed. Since plating is performed on the ABS resin after this treatment, plating of chromium or the like with good adhesion can be deposited on the surface of the ABS resin.
  • the present invention thirdly provides an ABS-based resin plated product (invention 6), which is plated by the plating method of the surface of the ABS-based resin described in the above invention (Invention 5).
  • invention 6 it is an ABS resin-plated product in which the surface of the ABS resin is plated with chromium or the like with good adhesion.
  • the butadiene component on the surface of ABS resin is dissolved by the strong oxidizing action of the persulfuric acid generated by electrolyzing sulfuric acid, thereby roughening the surface. Since the surface area is increased and the hydrophilic functional group is exposed, plating can be performed on the ABS-based resin after this treatment to obtain sufficiently close plating.
  • FIG. 1 shows a processing apparatus to which a plating pretreatment method for an ABS-based resin surface according to an embodiment of the present invention can be applied.
  • the processing apparatus 1 includes an electrolytic cell 6 continuous from a processing tank 2 provided with a constant temperature heater 3 on the outer periphery thereof, a pipe 4 provided with a circulating pump 5, and a pipe supplying the processing cell 2 from the electrolytic cell 6.
  • the electrolysis cell 6 is provided with an anode 6A and a cathode 6B formed of diamond electrodes, and a bipolar electrode 6C disposed between the two.
  • the processing tank 2 and the electrolytic cell 6 are filled with sulfuric acid having a predetermined concentration in the initial state, and a predetermined current is supplied to the anode 6A and the cathode 6B from the DC power supply unit.
  • a sulfuric acid solution (hereinafter referred to as a persulfuric acid solution in the present specification) S containing persulfuric acid (oxidizing agent) such as peroxodisulfuric acid is produced by electrolyzing sulfuric acid, and the persulfuric acid solution S is It can be supplied to the processing tank 2 via 7.
  • the persulfuric acid solution S is configured to be circulated by circulating the persulfuric acid solution S from the treatment tank 2 to the electrolytic cell 6 by the circulation pump 5 via the pipe 4. And in the processing tank 2, the ABS-type resin board 8 which is a process target is suspended by the up-down direction.
  • the persulfuric acid solution S preferably has a sulfuric acid concentration of 60 to 87% by weight, particularly 70 to 83% by weight. If the concentration of sulfuric acid is less than 60% by weight, the concentration of sulfuric acid in the obtained persulfuric acid solution S is too thin to roughen the surface of the ABS-based resin plate 8 sufficiently, thereby improving the adhesion of plating. However, even if it exceeds 87% by weight, no further improvement of the effect can not be obtained, and the handleability is unfavorably deteriorated.
  • the constant temperature heater 3 it is preferable to heat by the constant temperature heater 3 so that the temperature of the persulfuric acid solution S becomes 50 to 80.degree.
  • the temperature of the persulfuric acid solution S is less than 50 ° C., the surface of the ABS-based resin plate 8 can not be roughened sufficiently, and while the effect of improving the adhesion of plating can not be sufficiently obtained, 80 ° C.
  • it exceeds decomposition of persulfate is promoted and processing efficiency is reduced.
  • the electrolysis of sulfuric acid in the electrolytic cell 6 may be performed under conditions such that the concentration of persulfuric acid such as peroxodisulfuric acid generated by the electrolysis is 3 g / L or more, particularly 3 to 20 g / L. If the persulfate concentration is less than 3 g / L, sufficient improvement in the adhesion of the plating can not be obtained. If the concentration is more than 20 g / L, the above effect can not be improved and it is not economical.
  • the surface of the ABS resin sheet 8 is treated by immersing the degreased ABS resin sheet 8 in the processing tank 2.
  • the ABS resin plate 8 is preferably subjected to a wet treatment in advance.
  • neutralization / reduction treatment, conditioner treatment, etc. may be performed if necessary.
  • the surface of the ABS resin plate 8 can be etched by the pretreatment method of the present embodiment described above. And the plating pre-processing method of this embodiment can apply the plating method to conventionally well-known resin, such as an electroless plating method and direct plating method, after that.
  • a catalyst is applied to the ABS resin plate 8 treated by the pretreatment method of the present embodiment using a catalyst application treatment solution.
  • the treatment liquid for applying a catalyst is not particularly limited as long as it is generally used for applying a catalyst in a plating step, but one containing a noble metal is preferable, one containing palladium is more preferable, and a mixed palladium / tin catalyst solution is particularly preferable.
  • the temperature of the catalyst application treatment solution is preferably 10 to 60 ° C., particularly 20 to 50 ° C.
  • the ABS resin plate 8 is used for 1 to 20 minutes, preferably 2 to 20 minutes. It may be treated by immersion for 5 minutes.
  • the resin surface to which the catalyst has been applied in this manner is then metallized on the resin surface by metal plating such as electroless plating and electroplating (direct plating).
  • the catalyst When electroless plating is used to metallize the resin surface, the catalyst may be applied with a catalyst application treatment solution and then treated with 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 1 to 4 mol / L.
  • the liquid temperature of the activation treatment liquid is preferably set to 0 to 60 ° C., particularly 30 to 45 ° C., and the ABS resin plate 8 is preferably 1 to 20 here. Immersion treatment may be carried out for a minute, especially for 2 to 5 minutes.
  • electroless plating is performed on the ABS-based resin plate 8 to which the catalyst has been applied and activated as described above.
  • the electroless plating treatment can be carried out according to a conventional method using electroless plating such as known electroless nickel plating solution, electroless copper plating solution, electroless cobalt plating solution and the like.
  • electroless plating such as known electroless nickel plating solution, electroless copper plating solution, electroless cobalt plating solution and the like.
  • the ABS resin plate 8 is immersed in the electroless nickel plating solution with a pH of 8 to 10 and a temperature of 30 to 50 ° C. for 5 to 15 minutes. You may do it.
  • the liquid temperature of the activation treatment liquid is preferably set to 0 to 60 ° C., particularly 30 to 50 ° C., and the ABS resin plate 8 is preferably used here for 1 to 20 minutes. In particular, it may be treated by immersion for 2 to 50 minutes.
  • the ABS resin plate 8 subjected to the catalyst application and activation treatment as described above is subsequently immersed in a general-purpose copper electroplating bath such as a copper sulfate bath under ordinary conditions, for example, 1 to 5 A / dm. 2 may be treated for 2 to 10 minutes. By the way, it is decided to carry out sufficient water washing and hot water washing between each process so far.
  • a general-purpose copper electroplating bath such as a copper sulfate bath under ordinary conditions, for example, 1 to 5 A / dm. 2 may be treated for 2 to 10 minutes.
  • the surface of the ABS resin plate 8 is plated with metal such as electroless plating or electroplating, and the surface of the metallized ABS resin plate 8 is further subjected to various kinds of electric copper plating or electricity as required. It is also possible to apply nickel plating or electrochromic plating.
  • the metal plating should just be able to obtain a film as plating, and examples thereof include nickel, copper, chromium, cobalt
  • Such treatment may be continuously performed while replacing the ABS resin plate 8, but the persulfuric acid of the persulfuric acid solution S in the processing tank 2 is decomposed with the processing, and the persulfuric acid concentration is reduced. It is desirable to continuously drive the pump 5 to continuously replenish the processing tank 2 with fresh persulfate solution S from the electrolytic cell 6 through the pipe 7. Further, when the concentration of sulfuric acid decreases, the processing tank 2 may be appropriately supplemented with sulfuric acid, and when the concentration of sulfuric acid increases, the processing tank 2 may be appropriately supplemented with water.
  • a sulfuric acid concentration system can be installed in the processing tank 2 and this operation can be performed automatically.
  • This treatment may be performed, for example, by sufficiently immersing the ABS resin plate 8 in a wet treatment tank to impart wettability to the surface of the resin substrate.
  • the wetting treatment tank may contain a surfactant.
  • the surfactant is not particularly limited.
  • an amine salt surfactant for example, an amine salt surfactant, a quaternary amine salt surfactant, an amino acid surfactant, a betaine surfactant, a carboxylate surfactant, Sulfonate surfactants, sulfate ester surfactants, phosphate surfactants, ether surfactants, ester surfactants, nitrogen-containing surfactants, fluorine-containing surfactants, etc.
  • These surfactants can be used alone or in combination of two or more.
  • Electroless plating or electroplating can be applied to the ABS-based resin plate 8 thus pretreated by a conventional method. As a result, it is possible to obtain an ABS-based resin plated product in which the surface of the ABS-based resin plate 8 is plated with chromium or the like having good adhesion.
  • the present invention is not limited to the above-mentioned example, and various modification implementation is possible.
  • it is applicable not only to batch processing like this embodiment but to continuous processing.
  • the ABS-based resin plate is applicable not only to the plate as in the present embodiment but also to molded articles of various shapes.
  • ⁇ Plating adhesion test> the adhesion is examined by thermal shock of heating and quenching the sample, and peeling of the plated surface is performed after 70 cycles and -30 ° C, that is, a temperature difference of 100 ° C is maintained for 1 hour for 40 cycles. The situation such as the presence or absence of a crack, swelling, etc. is observed and it evaluates in three steps from the following classification 1-3.
  • Category 2 Peeling, cracks, wrinkles and blisters of less than 25% of the sample area.
  • Category 3 Plating peeling, cracks, wrinkles, and blisters 25% or more of the sample area.
  • Example 1 The surface treatment of the ABS resin plate 8 was performed using the apparatus shown in FIG.
  • the specifications and conditions of the treatment tank are as follows.
  • the ABS resin plate 8 is immersed for 10 minutes in a wetting treatment tank containing a surfactant, and then immersed for 10 minutes in the treatment tank 2 filled with the persulfuric acid solution S, and then removed from the treatment tank 2 After washing with water, electroless nickel plating was applied through an activation step and a catalyst application step. Thereafter, chromium plating was finally performed.
  • the processing conditions of the plating step are shown in Tables 1 and 2. Then, the adhesion of the plating of the chromium-plated ABS-based resin plate 8 was evaluated by the above method. The results are shown in Table 3 together with electrolytic sulfuric acid treatment conditions.
  • Examples 2 to 7 Chromium plating was performed in the same manner as in Example 1 except that various settings were changed as shown in Table 3 for electrolytic sulfuric acid treatment conditions, and the adhesion of the plating was evaluated. The results are shown in Table 3 together with electrolytic sulfuric acid treatment conditions.
  • Example 1 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 the adhesion of the plating was evaluated. The results are shown in Table 3 together with the processing conditions.
  • Comparative Example 2 Chrome 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 the adhesion of the plating was evaluated. The results are shown in Table 3 together with the processing conditions.
  • processing apparatus processing tank 3 constant temperature heater 4 piping 5 circulation pump 6 electrolysis cell 6A anode 6B cathode 6C bipolar electrode 7 piping 8 ABS resin plate S persulfate solution

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un dispositif de traitement (1) comprenant : un bac de traitement (2) pourvu d'un dispositif de chauffage à température constante (3) sur la périphérie externe ; une cellule électrolytique (6) qui est dans le prolongement d'un tuyau (4) pourvu d'une pompe de circulation (5) ; et un tuyau (7) destiné à alimenter le bac de traitement (2) à partir de la cellule électrolytique (6). Dans la cellule électrolytique (6) sont disposées une électrode positive (6A) et une électrode négative (6B) formées à partir d'électrodes en diamant et une électrode bipolaire (6C) disposée entre les deux. Le bac de traitement (2) et la cellule électrolytique (6) sont remplis d'acide sulfurique à une concentration prescrite. Le dispositif de traitement est conçu de façon telle qu'une solution de persulfate (S), telle que de l'acide peroxydisulfurique, est produite par l'électrolyse de l'acide sulfurique par le fait d'amener un courant prescrit à circuler d'une unité d'alimentation en courant continu à l'électrode positive (6A) et l'électrode négative (6B) et cette solution de persulfate (S) peut être fournie au bac de traitement (2) par l'intermédiaire du tuyau (7). L'invention concerne également un procédé de prétraitement de placage pour des surfaces de résine ABS sans Cr et sans Mn, qui permet de former un placage suffisamment adhérent à une surface de résine ABS. Le procédé peut être appliqué grâce au dispositif de traitement (1) selon l'invention.
PCT/JP2018/032342 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 WO2019045047A1 (fr)

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EP18849843.0A EP3677703A4 (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
CN201880055459.8A CN111032910A (zh) 2017-09-01 2018-08-31 Abs系树脂表面的镀前处理方法、abs系树脂表面的镀敷处理方法和abs系树脂镀敷制品
US16/642,375 US20200190682A1 (en) 2017-09-01 2018-08-31 Plating pretreatment method for abs resin surface, plating treatment method for abs resin surface, and abs resin plated product

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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

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JP7484389B2 (ja) 2020-04-28 2024-05-16 栗田工業株式会社 樹脂成形体のエッチング方法及び樹脂成形体用エッチング処理システム
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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CN111032910A (zh) 2020-04-17
EP3677703A1 (fr) 2020-07-08

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