EP2360294B1 - 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
EP2360294B1
EP2360294B1 EP10001464.6A EP10001464A EP2360294B1 EP 2360294 B1 EP2360294 B1 EP 2360294B1 EP 10001464 A EP10001464 A EP 10001464A EP 2360294 B1 EP2360294 B1 EP 2360294B1
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EP
European Patent Office
Prior art keywords
objects
solution
rinsing
treatment
ultrasound
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.)
Not-in-force
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EP10001464.6A
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German (de)
English (en)
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EP2360294A1 (fr
Inventor
Arnaldo Pereira
Heinz Ewald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to PT100014646T priority Critical patent/PT2360294E/pt
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to PL10001464T priority patent/PL2360294T3/pl
Priority to EP10001464.6A priority patent/EP2360294B1/fr
Priority to ES10001464T priority patent/ES2416982T3/es
Priority to JP2012552355A priority patent/JP2013519786A/ja
Priority to CN201180009084.XA priority patent/CN102791907B/zh
Priority to PCT/EP2011/051757 priority patent/WO2011098428A1/fr
Priority to KR1020127020537A priority patent/KR20120115993A/ko
Priority to BR112012020131A priority patent/BR112012020131A2/pt
Priority to US13/578,315 priority patent/US20120305406A1/en
Publication of EP2360294A1 publication Critical patent/EP2360294A1/fr
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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 also used for certain plastics.
  • the etching serves to make the surface of the object susceptible to the subsequent metallization, so that the surfaces of the objects in the subsequent treatment steps are well wetted with the respective solutions and the deposited metal finally adheres sufficiently firmly to the surface.
  • ABS copolymer acrylonitrile-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 colloid solution and then with an alkaline solution containing complexed copper ions with a complexing agent.
  • the article can be electrolytically metallized directly ( EP 1 054 081 B1 ).
  • a plastic article made in the polymer small electric non-conductive oxide particles of a base metal, such as copper.
  • the oxide particles exposed on the surface of the article are reduced to metal with a reducing agent, for example a borohydride.
  • a reducing agent for example a borohydride.
  • the article may then be electrolytically coated with metal. It is stated in this document that a copper (1) oxide-containing article is cleaned by ultrasonication in a water bath for its purification. Subsequently, the copper (I) oxide contained in the article is reduced to copper by means of sodium borohydride, so that thereafter electrolytically copper can be deposited on the surface of the article.
  • 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.
  • WO 2007/035091 A1 Further, a method for partially metallizing a product comprising a first and a second polymeric material is described.
  • the surface of the first polymer material becomes hydrophilic and the surface of the second polymer material is rendered hydrophobic.
  • the introduction to the description states that it is not possible to select a plastic or change it to such an extent, for example, by etching, irradiation or other surface treatment, that takes place at the metallization no metallization at all.
  • significant differences in the adhesion of metal layers on different plastics can be achieved.
  • mechanical removal of a metal layer for example by ultrasound, is considered difficult and does not result in the desired 100% selectivity.
  • Plastic metallization typically employs a palladium-based colloidal activator. With this activator, defects in the surface of the object, which are attributed to the injection molding, although covered and thus laminated.
  • articles produced in this way can fail in a subsequent temperature test procedure or only when the article is already in final use and, for example, installed in a device, because it may turn out that the metal layers applied after the activation are not sufficiently firmly fixed on the surface Adhere to the base.
  • 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. There is therefore the task of ensuring 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 to say in this area, the existing plastic Obernache 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. Typically, further process steps are carried out between these process steps, for example rinsing steps and optionally further treatment steps.
  • the article is treated and 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.
  • Ultrasonic exposure to the article is performed during at least one process step applied after treating the article with the precious metal colloidal solution or solution of the noble metal compound according to step B), but not during an electroless plating step.
  • this rinsing steps into consideration which are usually carried out between the two specified method steps B) and C).
  • the ultrasound treatment according to the invention has the effect that no metal layer is deposited on the first surface areas of the article.
  • 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 depositing 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 ABS / PC blend.
  • 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 reductant 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) of the ultrasonic treatment, wherein the ultrasonic treatment, if instead of a rinsing step several rinsing steps are carried out in one, carried out in some or all of these rinsing steps That is, the articles are subjected to ultrasound in one of the process steps or several process steps, including the rinsing steps, after the treatment in the colloid 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 ultrasound treatment can be carried out in each of the colloid treatment or treatment with the reductant solution subsequent process step.
  • the process steps Ba2), Bb2) and Bc2) are carried out in the order given, but not necessarily in direct succession.
  • a plurality of rinsing steps may be performed instead of each of the rinsing steps Ba2) and Bc2). This also applies to the rinsing step Ca2).
  • the conversion solution is preferably used to produce a sufficiently electrically conductive layer on the surface of the objects, in order subsequently to enable a direct electrolytic metallization, without first electrolessly 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 sulfate.
  • the articles are subjected during the treatment in at least one of the process steps Ba2), Bb2), Bc2) of the ultrasonic treatment, wherein the ultrasonic treatment, if instead of a rinsing step several rinsing steps are carried out, carried out in one, in some or all of these rinsing steps That is, the articles are ultrasonically subjected to one or more of the process steps, including the rinsing steps, after treatment in the colloidal solution.
  • the ultrasonic treatment can be carried out in any process step performed after the colloid treatment.
  • 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 handling container 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 can be 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 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.
  • a reduction treatment in a reduction solution may preferably be carried out after one, preferably several, for example three, rinsing steps, in which chromium (VI) ions still adhering to the surface of the articles are converted into chromium (III) ions be reduced.
  • an aqueous solution of sodium sulfite or a hydroxylammonium salt, for example the chloride or sulfate is used for this purpose.
  • 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.
  • 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 7-50 mg / l and most preferably 10-30 mg / l, based on Pd 2+ .
  • the permanganate solution is preferably operated at a temperature above room temperature, for example at 60-95 ° C, more preferably 80-90 ° C.
  • the treatment time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.
  • the articles are subjected to a reductone treatment in a reduction solution in order to still To reduce permanganate adhering to the surfaces of the articles to manganese (II) ions.
  • a reductone treatment in a reduction solution in order to still to reduce permanganate adhering to the surfaces of the articles to manganese (II) ions.
  • an acidic solution of hydroxylammonium sulfate or chloride is used or else an acidic solution of hydrogen peroxide.
  • the solution of the colloid of the VIII subgroup metal of the PSE is an activating solution with a palladium / tin colloid.
  • This colloidal solution preferably contains palladium chloride, stannous chloride and hydrochloric acid or sulfuric acid.
  • the concentration of palladium chloride is preferably 5-100 mg / l, more preferably 20-50 mg / l, and most preferably 30-45 mg / l, based on Pd 2+ .
  • the concentration of stannous chloride is preferably 0.5 to 10 g / l, preferably 1 to 5 g / l, and most preferably 2 to 4 g / l, based on Sn 2 + .
  • the concentration of hydrochloric acid is preferably 100-300 ml / l (37 wt.% HCl).
  • a palladium / tin colloid solution preferably additionally contains tin (IV) ions, which are formed by oxidation of the stannous ions.
  • the temperature of the colloid solution is preferably 20-50 ° C, and more preferably 30-40 ° C.
  • the treatment time is preferably 0.5-10 minutes, more preferably 2-5 minutes and most preferably 3.5-4.5 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 may, 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 / 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 colloidal solution Colloid and its protective colloid contained, that is, this solution contains in the case of a palladium / tin colloidal solution only hydrochloric acid, if the colloid solution also contains hydrochloric acid. Without rinsing the objects, they are brought into direct contact with the colloid solution after treatment in the pre-dip 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 reductant solution used for this purpose contains, when the solution of the noble metal compound is a hydrochloric acid palladium chloride solution, hydrochloric acid and stannous 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 such as copper sulfate or copper hypophosphite, a reducing agent such as formaldehyde or a hypophosphite set such as an alkali or ammonium salt, or hypophosphorous acid, one or more complexing agents such as tartaric acid, and the like a pH adjusting agent such as sodium hydroxide.
  • a copper salt such as copper sulfate or copper hypophosphite
  • a reducing agent such as formaldehyde or a hypophosphite set such as an alkali or ammonium salt, or hypophosphorous acid
  • complexing agents such as tartaric acid
  • 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 in the treatment tank 1 to a liquid level 3
  • the treatment liquid 2 may be, for example, a rinsing liquid or the colloid solution or an accelerating solution or other treatment liquid in which objects are treated according to the invention with ultrasound
  • 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.
  • ultrasound was also applied in this case in a second rinse after electroless nickel plating.
  • the ultrasonic frequency was again 40 kHz.
  • ultrasound was also applied in this case in a second rinse after electroless nickel plating.
  • the ultrasonic frequency was again 40 kHz.
  • ultrasound was also applied in this case in a second rinse after electroless nickel plating.
  • the ultrasonic frequency was again 40 kHz.
  • the parts were not metallized with bright nickel and chrome.
  • ultrasound was also applied in this case in a second rinse after electroless nickel plating.
  • the ultrasonic frequency was again 40 kHz.
  • Tab. 3 gives the conditions for the individual tests, with corresponding deviations from the conditions given in Tab. 2 being shown separately.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (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)

Claims (6)

  1. Procédé de métallisation d'objets comportant au moins deux matières plastiques différentes sur leur surface, dans lequel une première matière plastique est un polycarbonate et une deuxième matière plastique est choisie dans un groupe comprenant un copolymère d'ABS (copolymère d'acrylonitrile - butadiène - styrène), un polyamide et un mélange d'ABS avec au moins un autre polymère, comprenant les étapes de procédé comprenant :
    A) amorcer les objets avec une solution d'amorçage,
    B) traiter les objets avec une solution d'un colloïde ou d'un composé d'un métal du groupe secondaire VIII du tableau périodique des éléments,
    C) métalliser par électrolyse les objets avec une solution de métallisation, le procédé comprenant en outre les autres étapes de procédé suivantes, situées entre les étapes de procédé B) et C), comprenant :
    Ba1) rincer les objets dans une solution de rinçage,
    Bb1) traiter les objets dans une solution d'accélérateur ou une solution de réducteur,
    Bc1) rincer les objets dans une solution de rinçage,
    Bd1) métalliser sans courant les objets dans une solution de métallisation et
    Be1) rincer les objets dans une solution de rinçage, ou
    le procédé comprenant en outre les autres étapes de procédé suivantes, situées entre les étapes de procédé B) et C), comprenant :
    Ba2) rincer les objets dans une solution de rinçage,
    Bb2) traiter les objets dans une solution de transformation de sorte qu'une couche suffisamment électriquement conductrice pour une métallisation électrolytique directe soit formée, et
    Bc2) rincer les objets dans une solution de rinçage,
    caractérisé en ce que les objets sont soumis à un traitement aux ultrasons, pendant le traitement dans une autre étape de procédé réalisée après l'exécution de l'étape de procédé B), mais pas lors d'un dépôt sans courant de métal, pour empêcher la métallisation de la première matière plastique exposée sur la première surface des objets, alors que la deuxième matière plastique exposée sur la surface des objets est métallisée, et
    les objets étant soumis au traitement aux ultrasons pendant un traitement lors d'au moins une des étapes de procédé Ba1), Bb1), Bc1) ou lors d'au moins une des étapes de procédé Ba2), Bb2), Bc2).
  2. Procédé selon la revendication 1, caractérisé en ce que le au moins un autre polymère est un polycarbonate.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que les objets sont plongés dans des récipients de traitement contenant les solutions respectives pour réaliser les étapes de procédé et en ce que la solution respective dans le récipient de traitement, dans lequel un traitement aux ultrasons est réalisé, comprend au moins un émetteur d'ultrasons pour l'exposition des objets aux ultrasons.
  4. Procédé selon la revendication 3, caractérisé en ce que l'émetteur d'ultrasons est disposé sur un côté des objets et en ce qu'un réflecteur d'ultrasons ou un autre émetteur d'ultrasons est disposé de l'autre côté des objets.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que la solution d'amorçage est une solution d'acide chromosulfurique.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que la solution du colloïde du métal du groupe secondaire VIII du tableau périodique des éléments est une solution d'activateur avec un colloïde de palladium/étain.
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
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
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
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
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
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
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

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 EP2360294A1 (fr) 2011-08-24
EP2360294B1 true 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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LT6070B (lt) * 2012-12-07 2014-09-25 Atotech Deutschland Gmbh Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas
CN110344033A (zh) * 2014-07-10 2019-10-18 奥野制药工业株式会社 树脂镀敷方法以及树脂镀敷用蚀刻浴的管理方法
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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
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Also Published As

Publication number Publication date
ES2416982T3 (es) 2013-08-05
CN102791907A (zh) 2012-11-21
WO2011098428A1 (fr) 2011-08-18
EP2360294A1 (fr) 2011-08-24
JP2013519786A (ja) 2013-05-30
BR112012020131A2 (pt) 2018-03-06
PT2360294E (pt) 2013-06-28
PL2360294T3 (pl) 2013-09-30
US20120305406A1 (en) 2012-12-06
KR20120115993A (ko) 2012-10-19
CN102791907B (zh) 2015-08-05

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