EP2360294A1 - Procédé de métallisation d'objets comportant au moins deux matières plastiques différentes sur la surface - Google Patents

Procédé de métallisation d'objets comportant au moins deux matières plastiques différentes sur la surface Download PDF

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Publication number
EP2360294A1
EP2360294A1 EP10001464A EP10001464A EP2360294A1 EP 2360294 A1 EP2360294 A1 EP 2360294A1 EP 10001464 A EP10001464 A EP 10001464A EP 10001464 A EP10001464 A EP 10001464A EP 2360294 A1 EP2360294 A1 EP 2360294A1
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EP
European Patent Office
Prior art keywords
objects
solution
metallization
treatment
articles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10001464A
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German (de)
English (en)
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EP2360294B1 (fr
Inventor
Arnaldo Pereira
Heinz Ewald
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to EP10001464.6A priority Critical patent/EP2360294B1/fr
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to ES10001464T priority patent/ES2416982T3/es
Priority to PT100014646T priority patent/PT2360294E/pt
Priority to PL10001464T priority patent/PL2360294T3/pl
Priority to KR1020127020537A priority patent/KR20120115993A/ko
Priority to US13/578,315 priority patent/US20120305406A1/en
Priority to CN201180009084.XA priority patent/CN102791907B/zh
Priority to BR112012020131A priority patent/BR112012020131A2/pt
Priority to PCT/EP2011/051757 priority patent/WO2011098428A1/fr
Priority to JP2012552355A priority patent/JP2013519786A/ja
Publication of EP2360294A1 publication Critical patent/EP2360294A1/fr
Application granted granted Critical
Publication of EP2360294B1 publication Critical patent/EP2360294B1/fr
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    • 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
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means
    • 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
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • 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
    • 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
    • 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
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • 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
    • C25D5/20—Electroplating using ultrasonics, vibrations
    • 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
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present invention is based on a conventional metallization process for articles having at least two different plastics on the surface.
  • the articles A) are pickled with a pickling solution, B) treated with a solution of a colloid or a compound of a metal of subgroup VIII of the PSE, and C) electrolytically metallized with a metallizing solution.
  • Plastic articles may be metallized by an electroless plating process or alternatively by a direct plating process. In both methods, the article is first cleaned and pickled, then treated with a precious metal and finally metallized.
  • the pickling is typically carried out by means of chromic acid.
  • pickling solutions based on organic solvents or an alkaline or acidic permanganate solution are used for certain plastics. The pickling serves to make the surface of the article susceptible to the subsequent metallization, so that the surfaces of the articles in the subsequent treatment steps with the respective solutions are good are wetted and the deposited metal finally adheres sufficiently firmly on the surface.
  • ABS copolymer acrylontrile-butadiene-styrene copolymer
  • chromosulphuric acid chromosulphuric acid
  • the plastic for electroless metallization by means of an activator containing a noble metal, activated and then electroless metallized.
  • a thicker metal layer can be applied electrolytically.
  • the pickled surface is typically treated with a palladium-collodial solution followed by an alkaline solution containing complexed copper ions with a complexing agent.
  • the article can be electrolytically metallized directly ( EP 1 054 081 B1 ).
  • Plastic parts to be metallized are generally produced by injection molding. If plastic parts are to be manufactured from two or more different plastics in order to create different surface characteristics, these can be produced in the so-called multi-shot process. In this method, a first plastic is injected into an injection mold, and then a second plastic is injected into an injection mold containing the resulting injection-molded article with a modified shape. Correspondingly, the procedure in the case of consisting of three plastics objects.
  • the objects to be treated are made of at least two different plastics to achieve metallization of only a part of the surface of the article, while the other part of the surface remains unmetallized.
  • activators are usually used, which are specially set up depending on the respective requirements, in terms of their composition or in terms of operating parameters in their use. With such activators, a maximum occupancy of the surfaces of the article with palladium or alternatively optimal selectivity of different surface regions of the article can be adjusted. If different objects are produced in a metallization, therefore, several containers for the different activators and possibly additional rinse containers must be maintained, so that a total of a comprehensive system technology and a complex system control and logistics is required.
  • the present invention is therefore based on the problem that it has not been possible with sufficient process reliability to achieve a selective, sharp edge metallization of objects on the surfaces of each at least two different plastics are exposed to a safe error-free on the one plastic Metallization and on the other plastic to achieve a completely free surface of deposited metal. It is therefore an object that it must be ensured that the surface areas which are not to be metallized are completely free from metal and the surface areas to be metallized are perfectly and completely covered with metal after the metallization step has been carried out.
  • the method according to the invention is used for the metallization of objects which are at least partially and preferably completely made of plastic, in particular to provide at least a second surface area of the article completely, that is to say completely and without uncovered areas, with a metal layer and not at least a first surface area To metallize, that is, in this area, the existing plastic surface free of metal.
  • the selectivity of the metallization is made possible by the fact that there is at least one first plastic on the surface of the article, which is not coated by the metal, and a second plastic, which is completely coated with the metal.
  • the boundary between the two surface areas is sharp, that is, the metal-coated surface area extends exactly along the surface boundary line between the first surface area and the second surface area.
  • the article may be partially made of metal or other material, and partially of the at least two types of plastics.
  • the article is made completely Plastic, wherein it consists, for example, predominantly of one or possibly more adherent metallizable second plastics, and one or optionally a plurality of first plastics that are not adherent or not metallizable.
  • the article consists of one or more adherent metallizable second plastics and one or more first plastics, which / is not adherent metallizable / are and / at least superficially applied to the one or more adherent metallizable second plastic / e.
  • Such objects can be used in the sanitary sector, in the automotive industry, as a furniture or lock fitting, for controls on electrical or electronic equipment, jewelry, glasses or the like.
  • the selective metal coating due to the different surface textures of the article is preferably utilized to achieve decorative effects.
  • process steps A), B) and C) are not necessarily carried out immediately following each other.
  • further process steps are carried out between these process steps, for example rinsing steps and optionally further treatment steps.
  • the article is treated and / or rinsed at least between process steps B) and C) in at least one further process step.
  • the specified sequence of process steps A), B) and C) is complied with.
  • the ultrasonic exposure to the article is carried out during any process step applied after treating the article with the noble metal colloidal solution or the solution of the noble metal compound according to process step B), but not during an electroless plating step.
  • this rinsing steps into consideration which are usually carried out between the two specified process steps B) and C) and after process step C).
  • the ultrasound treatment according to the invention has the effect that not even a metal layer deposits on the first surface regions of the article or that a deposited metal layer is completely removed again.
  • the conditions for the metallization on the second surface areas can be adjusted so that the metallization takes place there properly and easily, that is, the metallization conditions need not be chosen so that the metallization on the second plastic areas just takes place to ensure that no metal separates on the first plastic areas.
  • This opens up a broader window of opportunity for successful metallization without the deposition of metal on the first surface areas. This ensures a safer process management, so that no faulty metallized objects are produced more.
  • This also results in the boundary line between the first plastic, which forms the first surface region of the article, and the second plastic, which forms the second surface region of the article, being accurately imaged by the metallization boundary, so that a sharp edge selective metallization is achieved.
  • a second plastic is an acrylonitrile-butadiene-styrene copolymer (ABS copolymer) or a polyamide or a mixture of an ABS copolymer with at least one further polymer.
  • ABS copolymer acrylonitrile-butadiene-styrene copolymer
  • PC polycarbonate
  • ABSIPC blends are preferably used.
  • a first plastic is a polycarbonate or a cover lacquer (stop-off lacquer) used to prevent metallization of the article.
  • topcoats have long been used to selectively cover surface areas of workpieces that are to be electroplated to prevent metal from depositing in the covered surface areas.
  • covercoats are familiar to the person skilled in the art.
  • Masking lacquers can be any lacquer which, in particular, hampers metal deposition and also ensures that they adhere well to the plastic body, so that at the interface between the Abdecklack and the plastic body no galvanizing liquid can penetrate. Obstruction of the metallization is achieved, for example, by introducing substances which inhibit electroless metallization, for example lead compounds such as lead acetate, lead chloride or lead acetate.
  • topcoats based on solutions of tar compounds are used.
  • the process steps Ba1), Bb1), Bc1), Bd1) and Be1) are carried out in the order given, but not necessarily immediately following one another.
  • a plurality of rinsing steps may be performed instead of each of the rinsing steps Ba1), Bc1), Be1). This also applies to the rinsing step Ca1).
  • the accelerator solution is preferably used to remove constituents of the colloid of the colloid solution according to process step B), for example a protective colloid.
  • a solution of an acid is preferably used as accelerator solution, for example Sulfuric acid, hydrochloric acid, citric acid or tetrafluoroboric acid to remove the protective colloid (tin compounds).
  • the reductar solution is used when in step B) a solution of a compound of a noble metal is used, for example a hydrochloric acid solution of palladium chloride or an acidic solution of a silver salt.
  • the reducing solution is also saline and contains, for example, stannous chloride, or it contains another reducing agent, such as NaH 2 PO 2 or a borane or borohydride, such as an alkali or Erdalkaliboran or Dimethylaminoboran.
  • another reducing agent such as NaH 2 PO 2 or a borane or borohydride, such as an alkali or Erdalkaliboran or Dimethylaminoboran.
  • the objects are subjected during the treatment in at least one of the process steps Ba1), Bb1), Bc1), Be1), C), Ca1) the ultrasonic treatment, wherein the ultrasonic treatment, if instead of a rinsing step several rinsing steps that is, the articles are ultrasonically treated in one or more of the process steps, including the rinsing steps, after being treated in the colloidal solution or in the reductor solution, but not in the process step in which the objects are electrolessly metallized. This is because the electroless plating bath would not be stable to ultrasonic exposure.
  • the ultrasonic treatment can be carried out in each of the Kollold treatment or treatment with the Reduktorat subsequent process step, including in the electrolytic metallization according to process step C).
  • the process steps Ba2), Bb2) and Be2) are carried out in the order given, but not necessarily immediately following one another.
  • a plurality of rinsing steps may be performed instead of each of the rinsing steps Ba2) and Bc2). This also applies to the Spülschdtt Ca2).
  • the conversion solution is preferably used to produce a sufficiently electrically conductive layer on the surface of the articles, in order subsequently to ermnöglicen a direct electrolytic metallization, without first electroless metallized.
  • the colloid of the colloid solution according to process step B) is a palladium / tin colloid
  • the conversion solution used is preferably an alkaline solution of complexes complexed with a copper ion.
  • the conversion solution may contain an organic complexing agent such as tartaric acid or ethylenediaminetetraacetic acid and / or a salt thereof, as well as a copper salt such as copper pentoxide.
  • the articles are subjected during the treatment in at least one of the process steps Ba2), Bb2), Bc2), Ca2) of the ultrasonic treatment, wherein the ultrasonic treatment, when a plurality of rinsing steps are performed instead of a rinsing step, in a some or all of these rinsing steps may be performed, that is, the articles are ultrasonically subjected in one or more of the process steps, including rinsing steps, after treatment in the colloidal solution.
  • the ultrasonic treatment can be carried out in any process step performed after the colloid treatment, including in the electrolytic metallization according to process step C).
  • ultrasonic emitters are typically in the form of flat plates trained ultrasonic generators and resonators.
  • these generators may be arranged in a plane in the treatment vessel which is parallel to a plane in which the articles are arranged for treatment or which are arranged parallel to that plane.
  • the ultrasound generator may be placed parallel to that plane of the frame in the container. This achieves the most uniform possible treatment of all objects fastened to the frame, because the distance between the ultrasound generator and the objects is the same in each case.
  • the ultrasound emitter is arranged on one side of the objects.
  • an ultrasound reflector or another ultrasound emitter can additionally be arranged. Both the first ultrasound emitter and the second ultrasound emitter or the ultrasound reflector can each have a planar shape.
  • the ultrasonic reflector may be, for example, a metal plate, for example a stainless steel plate (reflection plate).
  • the ultrasonic emitter or ultrasonic emitters are immersed in the solution in which they are treated for treating the articles.
  • the ultrasound energy is transmitted from the ultrasound or the Ultraschallemittem on the solution as a medium on the objects.
  • an ultrasound emitter can also deliver ultrasonic energy to the objects via a holder on which the objects are held, for example a frame.
  • the ultrasound emitter can be placed, for example, on a receptacle for the mounting of the frame in the treatment container and fastened so that the ultrasound energy is transmitted to the objects via this receptacle and the holder.
  • the treatment liquids described below are preferably aqueous.
  • the pickling solution is a chromosulfuric acid solution.
  • Such solutions typically contain 300-400 g / l CrO 3 and 300-400 g / l conc. H 2 SO 4 in water. Particular preference is given to a solution containing CrO 3 in a concentration of 360-400 g / l and more preferably of 375-385 g / l and H 2 SO 4 in a concentration of 360-400 g / l and particularly preferably of 375. Contains 385 g / l.
  • the chromosulfuric acid may additionally contain a fluorosurfactant to achieve optimized wetting of the surfaces.
  • the chromosulfuric acid palladium ions for example in the form of a salt, for example Palladium chloride, included.
  • the palladium ions may be present at a concentration of, for example, 5-100 mg / L, more preferably 7-50 mg / L, and most preferably 10-30 mg / L, based on Pd 2+ .
  • the chromosulfuric acid is preferably operated at a temperature above room temperature, for example at 30-90 ° C, more preferably 60-80 ° C, and most preferably 65-75 ° C.
  • the treatment time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.
  • chromium (VI) ions still adhering to the surface of the articles become chromium (III) ions be reduced.
  • This solution is also preferably operated above room temperature, for example at 30-60 ° C, more preferably at 40-50 ° C.
  • the treatment time is preferably 0.5 to 5 minutes, more preferably 1 to 3 minutes and most preferably 1.5 to 2.5 minutes.
  • a pickling treatment in potassium or sodium permanganate solution can also be carried out.
  • This solution can be acidic or alkaline.
  • it may contain sulfuric acid, and if it is alkaline, it may particularly contain sodium hydroxide.
  • Potassium permanganate can be contained in a concentration of up to about 70 g / l and sodium permanganate in a concentration of up to about 250 g / l. The lower limit of each of these two salts is typically 30 g / l.
  • the solution is alkaline, it contains, for example, 20-80 g / l, preferably 30-60 g / l NaOH.
  • a fluorosurfactant may also be included in this case in order to improve the wetting of the surfaces of the objects.
  • a fluorosurfactant may also be included in this case in order to improve the wetting of the surfaces of the objects.
  • a fluorosurfactant may also be included in this case in order to improve the wetting of the surfaces of the objects.
  • the Chtomschwefelklad palladium ions may be present, for example in the form of a palladium salt, in particular palladium chloride, in a concentration of for example 5 -100 mg / l, more preferably from 7 to 50 mg / l and most preferably from 10 to 30 mg / l, based on Pd 2+
  • the permanganate solution is preferably operated at a temperature above room temperature, for example at 60-95 ° C, particularly preferably 80-90 ° C.
  • the treatment time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.
  • the colloidal solution may also contain another VIII subgroup metal of the PSE, for example platinum, iridium, rhodium, gold or silver, or a mixture of these metals.
  • another protective colloid is used, for example, an organic protective colloid such as polyvinyl alcohol.
  • a solution of a noble metal compound is used instead of a colloid solution, it is preferable to use a solution containing an acid, especially hydrochloric acid, and a noble metal salt.
  • the noble metal salt can, for example, be a palladium salt, preferably palladium chloride, palladium sulfate or palladium acetate, or a silver salt, for example silver acetate.
  • a noble metal complex can also be used, for example a palladium complex salt, such as a salt of a palladium-aminopyridine complex.
  • the noble metal compound is present, for example, in a concentration of 40 mg / l to 80 mg / l, based on the noble metal, for example, based on Pd 2+ , before.
  • the solution of the noble metal compound can be operated at 25 ° C or at a temperature of 25 ° C to 70 ° C.
  • the articles are first contacted with a pre-dip solution having the same composition as the colloid solution, but without the metal of the colloid solution Containing colloid and its protective colloid, that is, this solution contains in the case of a palladium / tin colloidal solution only hydrochloric acid, if the Kolloidlösurtg also contains hydrochloric acid. Without rinsing the objects, these are brought into direct contact with the colloid solution after the treatment in the pre-dipping solution.
  • the articles After treating the articles with the colloid solution, they are typically rinsed and then contacted with the accelerating solution to remove the protective colloid from the surface of the articles.
  • the articles are treated with a solution of a noble metal compound rather than a colloidal solution, they are subjected to a reductant treatment after subsequent rinsing.
  • the solution of the noble metal compound is a hydrochloric acid solution of palladium chloride
  • the reducing agent solution used therefor contains hydrochloric acid and tin (II) chloride.
  • an aqueous solution of NaH 2 PO 2 is used.
  • the objects can first be rinsed after the acceleration or treatment with the Reduktoriösung and then, for example, electroless nickel plating.
  • a conventional nickel bath containing, among other nickel sulfate, a hypophosphite, for example, sodium hypophosphite, as a reducing agent and organic complexing agents and pH adjusting agent (for example, a buffer).
  • an electroless copper bath may be employed which typically comprises a copper salt, for example, copper sulfate or copper hypophosphite, a reducing agent such as formaldehyde or a hypophosphite set, for example, an alkali or ammonium salt, or hypophosphorous acid, one or more complexing agents such as tartaric acid, and a pH adjusting agent such as sodium hydroxide.
  • a copper salt for example, copper sulfate or copper hypophosphite
  • a reducing agent such as formaldehyde or a hypophosphite set, for example, an alkali or ammonium salt, or hypophosphorous acid
  • complexing agents such as tartaric acid
  • a pH adjusting agent such as sodium hydroxide
  • any metal deposition baths can be used, for example for the deposition of nickel, copper, silver, gold, tin, zinc, iron, lead or their alloys.
  • Such deposition baths are familiar to the person skilled in the art.
  • a bright nickel bath typically a Watts nickel bath is used which contains nickel sulfate, nickel chloride and boric acid and saccharin as additive.
  • a composition comprising copper sulfate, sulfuric acid, sodium chloride and organic sulfur compounds in which the sulfur is present in a low oxidation state is used as the bright copper bath.
  • organic sulfides or disulfides as additives.
  • an electrolytic plating bath for example a stoppered nickel bath, preferably based on a wetting wire.
  • Nickel bath is composed.
  • Such baths contain, for example nickel nickel sulfate, nickel chloride and boric acid and as an additive saccharin.
  • the treatment of the articles according to the method of the invention is preferably carried out in a conventional dipping process by successively immersing the articles in solutions in containers in which the respective treatment takes place.
  • the articles can either be attached to racks or filled with drums into the solutions.
  • An attachment to racks is preferred because it allows a more targeted transmission of the ultrasonic energy to the objects.
  • the articles can also be treated in so-called continuous installations, for example by lying on trays and being conveyed continuously through the installations in a horizontal direction.
  • Fig. 1 shows a treatment tank 1 containing a treatment solution 2 which reaches to a liquid level 3 in the treatment tank 1.
  • the treatment liquid 2 may be, for example, a rinsing liquid or the colloid solution or an accelerating solution, or another treatment liquid in which objects are ultrasonically treated in accordance with the invention
  • the treatment tank 1 is designed according to the kind of the treatment liquid 2 to satisfy the functions required for the respective treatment in this treatment liquid 2.
  • the treatment tank 1 can be equipped with a heater, a filter system, an air injection, a goods movement, vibration devices for the objects, Circulating pumps, metering devices and the like may be equipped.
  • the appropriate design is known to those skilled in each case and is chosen appropriately.
  • a product support rod 5 extends over the treatment container 1.
  • a frame 10 is attached via a suspension 6, to which a plurality of objects to be treated 7 are attached.
  • the frame 10 with the objects 7 is arranged centrally and parallel to a vertical plane in the container 1.
  • an ultrasonic emitter 8 which is formed in the form of a plate. This is fixed in the present case on the ground and on the side walls of the treatment tank 1.
  • a second ultrasonic emitter 9 is arranged in the container.
  • a steel plate may be used which reflects the ultrasonic waves emitted from the first ultrasonic emitter 8.
  • the distances a and b are preferably the same. With this arrangement, a very uniform treatment of the objects 7 on the frame 10 is achieved.
  • the parts were then rinsed, activated, coated with bright nickel (10 min) and then with chromium (2 min).
  • the ultrasonic frequency was 40 kHz.
  • Example 2 the method according to Inventive Example 2 was used to treat 72 switch slide holders attached to a rack (surface 15 dm 2 ), but with an altered activator composition (Pd 2+ : 18.9 mg / l, Sn 2+ ; 40 g / l, HCl (37% by weight): 241 ml / l).
  • ultrasound was also applied in this case in a second rinse after electroless nickel plating.
  • the ultrasonic frequency was again 40 kHz.

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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)
  • Electroplating Methods And Accessories (AREA)
EP10001464.6A 2010-02-12 2010-02-12 Procédé de métallisation d'objets comportant au moins deux matières plastiques différentes sur la surface Not-in-force EP2360294B1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
ES10001464T ES2416982T3 (es) 2010-02-12 2010-02-12 Procedimiento para la metalización de objetos que presentan al menos dos plásticos distintos sobre la superficie
PT100014646T PT2360294E (pt) 2010-02-12 2010-02-12 Processo para a metalização de objectos apresentando no mínimo duas matérias plásticas diferentes à superfície
PL10001464T PL2360294T3 (pl) 2010-02-12 2010-02-12 Sposób metalizowania przedmiotów wykazujących na powierzchni co najmniej dwa różne tworzywa sztuczne
EP10001464.6A EP2360294B1 (fr) 2010-02-12 2010-02-12 Procédé de métallisation d'objets comportant au moins deux matières plastiques différentes sur la surface
US13/578,315 US20120305406A1 (en) 2010-02-12 2011-02-07 Method for Metallising Objects Which Have at Least Two Different Plastics on the Surface
CN201180009084.XA CN102791907B (zh) 2010-02-12 2011-02-07 对表面上具有至少两种不同塑料的物体进行金属化的方法
KR1020127020537A KR20120115993A (ko) 2010-02-12 2011-02-07 표면에 적어도 2 종의 상이한 플라스틱들을 갖는 대상물들을 금속화하는 방법
BR112012020131A BR112012020131A2 (pt) 2010-02-12 2011-02-07 método para metalizar objetos que têm pelo menos dois plásticos diferentes sobre a superfície
PCT/EP2011/051757 WO2011098428A1 (fr) 2010-02-12 2011-02-07 Procédé pour la métallisation d'objets qui ont au moins deux matières plastiques différentes sur la surface
JP2012552355A JP2013519786A (ja) 2010-02-12 2011-02-07 表面上に少なくとも２種の異なるプラスチックを有する対象物の金属化方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10001464.6A EP2360294B1 (fr) 2010-02-12 2010-02-12 Procédé de métallisation d'objets comportant au moins deux matières plastiques différentes sur la surface

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EP2360294A1 true EP2360294A1 (fr) 2011-08-24
EP2360294B1 EP2360294B1 (fr) 2013-05-15

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US (1) US20120305406A1 (fr)
EP (1) EP2360294B1 (fr)
JP (1) JP2013519786A (fr)
KR (1) KR20120115993A (fr)
CN (1) CN102791907B (fr)
BR (1) BR112012020131A2 (fr)
ES (1) ES2416982T3 (fr)
PL (1) PL2360294T3 (fr)
PT (1) PT2360294E (fr)
WO (1) WO2011098428A1 (fr)

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EP2639333A1 (fr) * 2012-03-15 2013-09-18 Atotech Deutschland GmbH Procédé de métallisation de surfaces en matière synthétique non conductrices
LT6070B (lt) * 2012-12-07 2014-09-25 Atotech Deutschland Gmbh Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas
EP3168326B2 (fr) 2014-07-10 2023-09-20 Okuno Chemical Industries Co., Ltd. Procédé de placage de résine
US10895015B1 (en) 2014-12-16 2021-01-19 Hrl Laboratories, Llc Thin-walled high temperature alloy structures via multi-material additive manufacturing
DE102015204912A1 (de) 2015-03-18 2016-09-22 Coventya Gmbh Verfahren zur selektiven Metallisierung von Butadien-haltigen Kunststoffbereichen in einem Bauteil und Kit zur Durchführung des Verfahrens
JP6750293B2 (ja) * 2016-04-28 2020-09-02 栗田工業株式会社 プラスチック表面の処理方法
US10525919B2 (en) 2016-05-27 2020-01-07 Srg Global Inc. Vehicle exterior components having discontinuous plated features
US9914404B2 (en) 2016-08-08 2018-03-13 Srg Global Inc. Vehicle components having deep mesh plated features
DE102021117567A1 (de) 2021-07-07 2023-01-12 Leibniz-Institut Für Polymerforschung Dresden E.V. Verfahren zur selektiven Beschichtung von Mehrkomponenten-Kunststoffverbunden und Bauteile aus selektiv beschichteten Mehrkomponenten-Kunststoffverbunden

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Also Published As

Publication number Publication date
US20120305406A1 (en) 2012-12-06
ES2416982T3 (es) 2013-08-05
BR112012020131A2 (pt) 2018-03-06
CN102791907B (zh) 2015-08-05
PL2360294T3 (pl) 2013-09-30
KR20120115993A (ko) 2012-10-19
WO2011098428A1 (fr) 2011-08-18
PT2360294E (pt) 2013-06-28
CN102791907A (zh) 2012-11-21
EP2360294B1 (fr) 2013-05-15
JP2013519786A (ja) 2013-05-30

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