EP1546435B1 - Verfahren zur vorbehandlung einer oberfläche eines mit metall zu beschichtenden nichtleitenden materials - Google Patents

Verfahren zur vorbehandlung einer oberfläche eines mit metall zu beschichtenden nichtleitenden materials Download PDF

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Publication number
EP1546435B1
EP1546435B1 EP03798083A EP03798083A EP1546435B1 EP 1546435 B1 EP1546435 B1 EP 1546435B1 EP 03798083 A EP03798083 A EP 03798083A EP 03798083 A EP03798083 A EP 03798083A EP 1546435 B1 EP1546435 B1 EP 1546435B1
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EP
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ions
metal
conducting material
manganese dioxide
conducting
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English (en)
French (fr)
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EP1546435A1 (de
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Per Moller
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INSTITUTTET FOR PRODUKTUDVIKLING
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INSTITUTTET FOR PRODUKTUDVIKLING
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Classifications

    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1889—Multistep pretreatment with use of metal 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
    • C23C18/2006—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
    • C23C18/208—Multistep pretreatment with use of metal 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
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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

Definitions

  • the present invention relates to a method for pretreating a surface of a non-conducting material to be plated by way of precipitation of metal in the presence of a catalytic metal, and optionally to be subjected to a subsequent electrolytic plating or another type of surface treatment.
  • the surface is activated by a catalytic metal, such as palladium.
  • the activating metal for instance is a metallic palladium, viz. oxidation step 0.
  • the palladium acts as an efficient catalyst for the precipitation of metal, such as copper, cobalt, silver, tin, gold or nickel.
  • metal such as copper, cobalt, silver, tin, gold or nickel.
  • an electrically conducting metal layer on the surface of a non-conducting material, on which, if desired, an additional layer of metal can be applied from an aqueous or an organic electrolyte by way of a conventional coating process, such as by way of an electrolytic plating process.
  • metals capable of being applied after the first precipitation of metal are for instance metal layers ofNi, Cu, Ag, Au, Sn and In.
  • non-conducting materials such as ceramics (a technical nomenclature for British “ceramics”, viz. ceramics), glass and plastics, can be plated when the surface is made electrically conducting. This can be carried out by way of a precipitation of metal, such as copper or nickel.
  • the precipitation of metal can for instance be an autocatalytic precipitation of metal, which is also called a chemical plating, but such a precipitation of metal requires a previous treatment of the surface in form of an etching and an activation for instance by means of palladium.
  • the etching of the non-conducting material results in formation of small pores in the surface, and the metal can be anchored in said small pores.
  • the etching can be carried out by means of an oxidant. After the etching procedure, both the excess oxidant and the reaction product resulting from the oxidizing process are removed, said substances being undesirable at the subsequent plating process.
  • oxidants for the etching are chromic sulphuric acid (CrO 3 + sulphuric acid) and potassium permanganate (KMnO 4 ).
  • CrO 3 + sulphuric acid chromic sulphuric acid
  • KMnO 4 potassium permanganate
  • the use of the latter substance has the effect that the resulting reaction product is manganese dioxide (pyrolusite; MnO 2 ).
  • a sulphuric acid solution is usually used.
  • the surface is activated by means of colloidal palladium (Pd (0) surrounded by Sn ++++ ).
  • the tin ions are then chemically removed through a complex formation with the result that the metallic palladium is left in the small pores of the surface where said tin ions catalyze a subsequent chemical plating, in particular together with nickel or copper.
  • the above known method is suitable for plating some polymeric materials, especially such materials including several phases, where one of the phases can be etched away in the surface, such as for instance the butadiene phase in ABS plastics.
  • Other types of plastics are also suitable, such as polypropylene, polyphenylene oxide, nylon (6.6) and Teflon®.
  • Teflon® Teflon®
  • the plastics capable of being plated by means of the method described are encumbered with the further draw-back that a very strong oxidative etching is necessary in order to achieve a sufficient fixation of the palladium ions, which in turn is necessary for the fixation of the chemical plating layer.
  • the oxidative etching of the polymer in question causes in connection with multi-phased, such as two-phased polymers, often a varying etching speed for the individual phases. As a result, small cavities or pores are formed in which it is possible to mechanically lock (interlock) a subsequent chemically precipitated metal layer.
  • the oxidative etching can optionally be supplemented with an advance mechanical raising (making rough) in order to achieve an improved physical adhesion.
  • US-PS No. 4 999 251 discloses a method of pretreating polyetherimide (PEI) prior to a conventional activation by means of a solution of palladium chloride in hydrochloric acid. After treatment with a degreaser, the PEI-surface is initially treated with concentrated sulphuric acid. Then follows a treatment with an aqueous base to pH 14 or higher. After treatment with permanganate, the resulting manganese dioxide is then removed by means of hydroxylamine hydrochloride, which irritates the skin and is difficult to handle. According to the publication, the method can be used for pretreatment and activation of PEI for a subsequent autocatalytic plating. However, the method is complicated and involves the use of heavily etching and irritating chemicals, and is not believed to have found industrial propagation.
  • US-PS No. 5 693 209 discloses a process for metallizing circuit boards with a non-conducting surface. After the oxidation of the surface by means of permanganate, the deposited manganese dioxide is allowed to remain on the surface after a washing away of the excess permanganate. Then the surface is treated with pyrrole monomer and pyrrole oligomer in a weak acid with the result that an electrically conducting insoluble polymer is deposited which can subsequently be subjected to a direct plating.
  • the process is suitable on epoxy resin boards, but does not present a wide-spectrum applicability on various types of plastics.
  • the metallization is carried out at a low speed involving heterogeneous metal coatings, and the process is not suitable for plating large surfaces requiring a base layer presenting a good electric conductivity. The latter requirement cannot be met by the electrically conducting polymer.
  • US-PS No. 5 078 889 discloses a specially-treated electrolytic manganese dioxide of the ⁇ -type for a selective removal of contaminants from drinking water. It is inter alia stated that the described manganese dioxide can remove small amounts of heavy metals from the drinking water by way of adsorption.
  • EP 0414 097 describes a method whereby a conducting metal layer is formed by a reduction of metal compounds so as thereby to establish an electric conductivity on the surface of a polymer.
  • an adhesive is applied onto the surface
  • This adhesive can be selected among metal oxide, metal hydroxide or metal carbonate, and can according to an embodiment be manganese dioxide resulting from reduction of permanganate.
  • a metal compound is adsorbed, said metal compound being selected among almost all such metals capable of being reduced by means of a suitable reducing agent.
  • Gold, silver, cobalt, nickel, iron and other metals have been suggested.
  • a treatment is carried out by means of a strong reducing agent so as to form a metal layer which together with manganese dioxide must be capable of forming an electrically conducting layer without the use of autocatalytic baths.
  • This step is difficult and can easily result in the entire process being unsuccessful. The process can presumably be used for plating circuit boards, but it is hardly useful for plating large areas.
  • the present invention relates to a method for pretreating a surface of a non-conducting material to be plated by way of precipitation of metal in the presence of a catalytic metal, and optionally to be subjected to a subsequent electrolytic plating or another type of surface treatment.
  • the depositing of the adsorbing metal oxide in form of manganese dioxide can be carried out by oxidizing the surface in step (a) by means of a permanganate compound while forming manganese dioxide, and by washing away the remaining permanganate compound after the oxidation without removing the formed manganese dioxide deposited in form of a layer or in form of small clusters on the surface.
  • Step (b) can according to an embodiment be carried out by treating the surface with an aqueous solution of Sn ++ ions.
  • the catalytic metal ions used in step (c) are ions of a metal catalyzing the autocatalytic precipitation, such as a metal from the platinum group, preferably Pd ++ , Rh ++ or Pt ++ .
  • the method according to the invention renders it possible to plate non-conducting materials and matrixes where a conventional electrolytic or autocatalytic treatment is unsuitable or can only be carried out with difficulties. In addition, it allows other processes requiring an electrically conducting surface, such as electrostatic powder lacquering.
  • the non-conducting material can also be a non-conducting matrix including reinforcing fibres and/or fillers based on organic and/or inorganic matter.
  • the pretreatment by the method according to the invention can activate the surface so as to obtain a uniform precipitation of metal.
  • the method according to the invention is based on the recognition that a deposited layer of a metal oxide on a non-conducting material, such as a plastic material, adsorbs in an efficient manner some metal ions when the metal oxide layer is immersed in a solution including such metal ions.
  • a deposited layer of a metal oxide on a non-conducting material such as a plastic material
  • adsorbs in an efficient manner some metal ions when the metal oxide layer is immersed in a solution including such metal ions.
  • suitable metal oxides are manganese dioxide MnO 2 and ochre (Fe 2 O 3 ).
  • the present invention utilizes the fact that the water-insoluble manganese dioxide adheres strongly to the surface of the material in combination with the capability of adsorbing some metal ions. Instead of removing the layer of manganese dioxide by means of acid, the treated material is washed with water so as only to remove the excess permanganate compound.
  • the first step (a) is a conventional etching of the surface by means of a permanganate compound, such as KMnO 4 .
  • a permanganate compound such as KMnO 4 .
  • the oxidation process results in formation of manganese dioxide (MnO 2 ).
  • the new features of this embodiment are found in the fact that it is only necessary to remove the excess KMnO 4 from the surface while MnO 2 is allowed to remain in form of deposits on the surface as a thin layer or in small clusters.
  • the latter is rendered possible by the surface being washed with water instead of with acid, such as sulphuric acid.
  • the surface is subsequently treated with a solution of a Sn ++ -compound, such as SnCl 2 , whereby Sn ++ ions are adsorbed and thereby immobilized, viz. fixed, on the deposited MnO 2 .
  • a Sn ++ -compound such as SnCl 2
  • the used solution of an Sn ++ -compound can be neutral or weak acid, but it must not be so acid that the manganese dioxide is dissolved, which can usually be ensured by a pH-value in the range of 4 to 7.
  • Sn ++ is chosen as metal ion because it is a transition metal ion capable of reducing catalytic metal ions into the metallic form, such as Pd ++ into Pd, i.e. palladium with oxidation step 0.
  • the fixed metallic palladium is subsequently used as catalyst for the precipitation of metal.
  • the new pretreatment opens up the possibility of applying metal coatings, viz. plating, even onto difficult types of plastics, which cannot or which can only with great difficulty be plated by the above known methods.
  • the adhesion is established by means of the activating metallic palladium during the chemical raising of the plastic surface, where micropores are etched away in the surface, said palladium being capable of being bound in said micropores by being introduced in finely dispersed, viz. colloidal, form.
  • the chemical raising can result in a treated material presenting a dull appearance not being so aesthetic, and the method can only be used on a limited number of plastic types.
  • the adhesion is ensured in another way, and the method according to the invention does not require the same degree of mechanical and/or chemical raising. As a result the material does not present the same dull surface characteristics, and the method opens up a possibility of treating a significantly increased number of non-conducting substrate materials.
  • the function of the metal oxide deposited on the surface is found in the adsorbing properties thereof.
  • a metal oxide viz. manganese dioxide
  • the desired adsorbing function can also be ensured through a deposition of manganese dioxide by another chemical process or through a deposition of another metal oxide presenting the corresponding adhesive and adsorbing properties, such as ochre (Fe 2 O 3 ).
  • the material is treated with a solution including transition metal ions being adsorbed on the layer of metal oxide and thereby fixed, viz. immobilized, on the surface of the material.
  • a preferred transition metal ion for this treatment is Sn ++
  • a preferred solution is a solution of SnCl 2 .
  • the solution of transition metal ions can be in any solvent in which the transition metal ions can be dissolved in a sufficiently stable form.
  • the preferred solvent is water, but other polar solvents based on organic chemistry, such as alcohols or mixtures of water and an alcohol, can also be used.
  • Suitable transition metal ions are ions presenting a low oxidation step of a transition metal which forms soluble salts with several different oxidation steps, and which through reaction with a catalytic metal ion as defined below can reduce the catalytic metal ion into the free catalytic metal, viz. oxidation step 0.
  • the material is washed with water whereafter it is treated with a solution including ions of a catalytic metal, viz. a metal catalyzing chemical plating, especially a metal from the platinum group, such as Pd ++ ions, Rh ++ ions or Pt ++ ions, such as a solution of palladium chloride (PdCl 2 ).
  • a catalytic metal viz. a metal catalyzing chemical plating
  • Pd ++ ions especially a metal from the platinum group
  • Rh ++ ions or Pt ++ ions such as a solution of palladium chloride (PdCl 2 ).
  • PdCl 2 palladium chloride
  • the fixed transition metal ions such as Sn ++ ions, reduce the catalytic metal ions into metallic form, i.e. for instance the Pd ++ ions into metallic palladium, which is subsequently fixed to the layer of metal oxide.
  • the solution of catalytic metal ions can be in any solvent in which the catalytic metal ions can be dissolved in a sufficiently stable form.
  • the preferred solvent is water, but other polar solvents based on organic chemistry, such as alcohols or mixtures of water and an alcohol, can also be used.
  • the method according to the invention renders it possible after a mild raising (making rough or rugged) of the surface of the material to provide the desired fixing of a catalyzing metal, such as Pd, which can catalyze a chemical plating by means of for instance copper or nickel, whereby in a manner known per se it is now possible to involve further chemical and/or electrolytic plating methods.
  • a catalyzing metal such as Pd
  • PC polycarbonate
  • PPO polyphenylene oxide
  • PEI polyether imide
  • ABS acrylnitrile/butadiene/styrene-terpolymer
  • thermoset and thermoplastic including plastic materials with reinforcing fibres and/or fillers, such as materials of glass, carbon, mica or titanium oxide.
  • the method according to the invention turned out to be usable for plating glass, ceramics, viz. ceramic material, and the like materials.
  • thermoset plastics capable of being activated by the method according to the invention are polyurethane (PUR), epoxy (EP), unsaturated polyester (UP) and phenolic plastic (PF).
  • PUR polyurethane
  • EP epoxy
  • UP unsaturated polyester
  • PF phenolic plastic
  • thermoplastic capable of being activated by the method according to the invention are polyacrylamide (PAA), aliphatic or aromatic polyamide (PA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polyphthalamide (PPA), polyphenylene sulphide PPS), thermoplastic polyester (PET/PBT), liquid crystal polymer (LCP), polyetherether-ketone (PEEK), polysulphone (PSU) and polyether sulphone (PES).
  • PAA polyacrylamide
  • PA aliphatic or aromatic polyamide
  • PE polyethylene
  • PP polypropylene
  • PVC polyvinyl chloride
  • PS polystyrene
  • PPA polyphthalamide
  • PPS polyphenylene sulphide PPS
  • thermoplastic polyester PET/PBT
  • LCP liquid crystal polymer
  • PEEK polyetherether-ketone
  • PSU polysulphone
  • PES polyether sulphone
  • plastic materials including reinforcing substances and/or fillers capable of being pretreated and activated by the method according to the invention are glass in a matrix of polysulphone (PSU), polyether sulphone (PES) or polyacrylamide (PAA) and glass and mineral in a polyphenylene sulfide matrix (PPS).
  • PSU polysulphone
  • PES polyether sulphone
  • PAA polyacrylamide
  • PPS polyphenylene sulfide matrix
  • the content of reinforcing substances and/or fillers in such a type of composite materials can be relatively high.
  • An example is polyacrylamide with 50% by weight of glass.
  • the activation by means of a catalytic metal has in particular been exemplified by means of palladium.
  • any catalytic metal originating from a solution including ions of said metal such as a solution of a salt thereof, which is reduced by the transition metal ions fixed in the layer or clusters of metal oxide so as subsequently to be bound in the metallic form.
  • the catalytic metal can thus be exemplified by rhodium and platinum.
  • plastic blanks such as by wey of injection moulding
  • material compositions or material structures deviating from the basic composition of the plastic blanks in the surface or in areas on said surface. Such areas can often complicate the adhesion to the surface of the plastic blank. Therefore, it can be necessary to carry out a mechanical or a chemical raising prior to the activation.
  • a mechanical raising can for instance be carried out through a mild wet blowing where the additive is selected on the basis of the matrix material and the desired surface topography.
  • a chemical raising can for instance be in form of an etching by means of permanganate which according to the above particular embodiment is used by the method according to the invention, but which is also used by the known pretreatment described in the introduction to the description of a surface on a non-conducting material to be plated.
  • the chemical raising is, however, significantly less intense by the method according to the invention.
  • the method according to the invention turned out to be suited for the production of plastic materials through a plating with a good electric conductivity.
  • a chemical plating with Cu to plate electrolytically with Cu and/or Ag, preferably with Cu first and then with Ag.
  • the method according to the invention can be used on any surface where it is at all possible to deposit a suitable layer or small clusters of the metal oxide.
  • the method has turned out to be usable not only on various problematic types of plastics, but also on glass.
  • the invention can also be used for activation of surfaces of ceramics, mineral and biological material, such as wood.
  • the method has been developed for activation in connection with a conventional, autocatalytic plating optionally followed by an electrolytic plating, but in principle it can be used for other purposes where a surface is to be made electrically conducting or where an insufficient conductivity is to be increased.
  • An example is pretreatment prior to an electrostatic powder lacquering of for instance wooden furniture.
  • An injection moulded polycarbonate article with a complicated design is initially subjected to a mechanical raising through a wet blowing by means of glass pearls.
  • Such a mild treatment involves a modest raising of the surface.
  • the object of this treatment is to increase the adhesion of the plastic surface to the metal layer.
  • the plastic article is immersed for 10 minutes in an aqueous solution of 60 g/l of KMnO 4 of a temperature of 90°C, whereafter the excess potassium pennanganate was removed through rinsing in pure water.
  • the surface activated in this manner is then treated in a commercial, chemical copper-bath (CircupositElectroless Copper 3350, Shipley Company LLC., Marlborough, Massachusetts, USA) for 30 minutes at 45 °C while forming a 2 to 3 ⁇ m thick copper layer.
  • a commercial, chemical copper-bath (CircupositElectroless Copper 3350, Shipley Company LLC., Marlborough, Massachusetts, USA) for 30 minutes at 45 °C while forming a 2 to 3 ⁇ m thick copper layer.
  • the surface is electrolytically treated in a conventional copper-electrolyte with the result that a 20 ⁇ m thick copper layer is formed atop the chemical copper layer.
  • the surface is electrolytically treated in a commercial silver electrolyte (Engbright A silver bath, Engelhard Corporation, Iselin, NJ, USA) with the result that a 5 ⁇ m thick silver layer is formed atop the electrolytic copper layer.
  • a commercial silver electrolyte Engelhard Corporation, Iselin, NJ, USA
  • scribe-grid test two or more parallel lines or a rectangular pattern are cut by means of a sharp instrument.
  • the cut is made to the substrate, and the distance between the lines should be approximately ten times the layer thickness, but at least 0.4 mm.
  • the adhesion is too poor when the coating between the lines falls off.
  • Samples produced according to the present example meet as a minimum ISO Class or ASTM Class 4B, which corresponds to the fact that only insignificant defects are found at the location where two scratches intersect one another. Quantitatively, these defects do not exceed 5% of the total area of the surface.
  • the treated polycarbonate material cannot be plated by means of the conventional method described in the introduction to the description, where a treatment is carried out by means of permanganate followed by an etching off of the manganese dioxide and then a treatment by means of colloidal palladium due to the lacking adhesion.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Catalysts (AREA)

Claims (13)

  1. Verfahren zur Vorbehandlung einer Oberfläche eines nicht leitenden Materials, das mittels einer Ausfällung von Metall in der Gegenwart eines katalytischen Metalls zu plattieren ist und optional einem anschließenden elektrolytischen Plattieren oder einer anderen Art einer Oberflächenbehandlung zu unterziehen ist, gekennzeichnet durch
    a) Abscheiden von Mangandioxid (MnO2) oder Ocker (Fe2O3) auf der Oberfläche,
    b) Behandeln der Oberfläche mit einer Lösung von Sn++-Ionen oder Co++-Ionen und anschließend
    c) Behandeln der Oberfläche mit einer Lösung von katalytischen Metallionen eines Metalls aus der Platingruppe.
  2. Verfahren nach Anspruch 1, gekennzeichnet durch Oxidieren der Oberfläche in Schritt (a) mittels einer Permanganatverbindung, während Mangandioxid gebildet wird, und durch Abwaschen der verbleibenden Permanganatverbindung nach der Oxidation ohne Entfernen des gebildeten Mangandioxids, das in der Form einer Schicht oder in der Form von kleinen Clustern auf der Oberfläche abgeschieden ist.
  3. Verfahren nach einem der vorangehenden Ansprüche, gekennzeichnet durch Behandeln der Oberfläche in Schritt (b) mit einer wäßrigen Lösung von Sn++-Ionen oder Co++-Ionen.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die katalytischen Metallionen Ionen eines Metalls aus der Platingruppe, bevorzugt Pd++, Rh++ oder Pt++, sind.
  5. Verfahren nach einem der vorangehenden Ansprüche, gekennzeichnet durch Behandeln der Oberfläche in Schritt (c) mit einer wäßrigen Lösung katalytischer Metallionen.
  6. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das nicht leitende Material ein Polymermaterial als Hauptbestandteil einschließt.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das Polymermaterial ausgewählt wird aus Polycarbonat (PC), Polyphenylenoxid (PPO), Acrylnitril/Butadieri/Styrol-Terpolymer (ABS), Polyacrylamid (PAA), aliphatischem oder aromatischem Polyamid (PA), Polyethylen (PE), Polpropylen (PP), Polyvinylchlorid (PVC), Polystyrol (PS), Polyetherimid (PEI), Polyphthalamid (PPA), Polyphenylensulphid (PPS), thermoplastischem Polyester (PET/PBT), Flüssigkristallpolymer (LCP), Polyether-Ether-Keton (PEEK), Polysulphon (PSU), Polyethersulphon (PES), Polyurethan (PUR), Epoxy (EP), ungesättigtem Polyester (UP) und phenolischem Kunststoff (PF).
  8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß das nicht leitende Material Verstärkungsfasern und/oder Füllstoffe basierend auf organischem und/oder anorganischem Material einschließt.
  9. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das nicht leitende Material ein Glas, eine Keramik oder ein biologisches Material als Hauptbestandteil einschließt.
  10. Gegenstand eines nicht leitenden Materials mit einer Oberfläche, die teilweise oder vollständig beschichtet ist mit einem autokatalytisch abgeschiedenen Kupfer, Kobalt, Silber, Zinn, Gold oder Nickel oder einer Legierung derselben, erhältlich durch eine Vorbehandlung eines nicht leitenden Gegenstands durch das Verfahren gemäß einem der vorangehenden Ansprüche und gefolgt von einer autokatalytischen Abscheidung.
  11. Gegenstand eines nicht leitenden Materials mit einer Oberfläche, die teilweise oder vollständig mit einer elektrolytischen Plattierungsschicht beschichtet ist, erhältlich durch eine Vorbehandlung eines nicht leitenden Gegenstands durch das Verfahren nach einem der Ansprüche 1 bis 9, gefolgt von einer autokatalytischen Abscheidung und dann einer herkömmlichen Elektrolyse
  12. Gegenstand nach Anspruch 11 mit einer oder mehreren elektrolytischen Plattierungsschichten.
  13. Gegenstand nach Anspruch 12 und beschichtet mit wenigstens einer elektrolytischen Plattierungsschicht mit einer hohen elektrischen Leitfähigkeit.
EP03798083A 2002-09-26 2003-09-23 Verfahren zur vorbehandlung einer oberfläche eines mit metall zu beschichtenden nichtleitenden materials Expired - Lifetime EP1546435B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK200201429 2002-09-26
DK200201429A DK175025B1 (da) 2002-09-26 2002-09-26 Fremgangsmåde til forbehandling af en overflade på et ikke-ledende materiale, der skal pletteres
PCT/DK2003/000617 WO2004029327A1 (en) 2002-09-26 2003-09-23 Method for pretreating a surface of a non-conducting material to be plated

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EP1546435A1 EP1546435A1 (de) 2005-06-29
EP1546435B1 true EP1546435B1 (de) 2007-07-25

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US (1) US20060000720A1 (de)
EP (1) EP1546435B1 (de)
AT (1) ATE368136T1 (de)
AU (1) AU2003266486A1 (de)
DE (1) DE60315170D1 (de)
DK (1) DK175025B1 (de)
WO (1) WO2004029327A1 (de)

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
US6900236B1 (en) 1999-10-18 2005-05-31 University Of Connecticut Cannabimimetic indole derivatives
US20050199587A1 (en) * 2004-03-12 2005-09-15 Jon Bengston Non-chrome plating on plastic
DE102010021553A1 (de) 2010-05-21 2011-11-24 Siemens Aktiengesellschaft Bauteil mit einer katalytischen Oberfläche, Verfahren zu dessen Herstellung und Verwendung dieses Bauteils
DE102010021554A1 (de) * 2010-05-21 2011-11-24 Siemens Aktiengesellschaft Bauteil mit einer katalytischen Oberfläche, Verfahren zu dessen Herstellung und Verwendung dieses Bauteils
CN111519226A (zh) * 2020-06-05 2020-08-11 麦德美科技（苏州）有限公司 聚醚酰亚胺化学粗化电镀工艺

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US3579428A (en) * 1967-09-30 1971-05-18 Mitsubishi Petrochemical Co Method of manufacturing plated polypropylene shaped articles
GB1404855A (en) * 1971-07-28 1975-09-03 Mitsui Mining & Smelting Co Catalytic purification of exhaust gases
GB1401600A (en) * 1972-12-13 1975-07-16 Kollmorgen Corp Composition and process for the activation of resinous bodies for adherent metallization
US4073740A (en) * 1975-06-18 1978-02-14 Kollmorgen Technologies Corporation Composition for the activation of resinous bodies for adherent metallization
DE3816494A1 (de) * 1988-05-10 1989-11-16 Schering Ag Loesung und verfahren zum aetzen und aktivieren von isolierenden oberflaechen
US5078889A (en) * 1989-02-28 1992-01-07 Csa Division, Lake Industries, Inc. Selective removal of contaminants from water sources using inorganic media
US4999251A (en) * 1989-04-03 1991-03-12 General Electric Company Method for treating polyetherimide substrates and articles obtained therefrom
DE3928435A1 (de) * 1989-08-24 1991-02-28 Schering Ag Verfahren zur direkten metallisierung eines nicht leitenden substrats
US5693209A (en) * 1989-09-14 1997-12-02 Atotech Deutschland Gmbh Process for metallization of a nonconductor surface
US5648125A (en) * 1995-11-16 1997-07-15 Cane; Frank N. Electroless plating process for the manufacture of printed circuit boards

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DE60315170D1 (de) 2007-09-06
DK175025B1 (da) 2004-05-03
US20060000720A1 (en) 2006-01-05
ATE368136T1 (de) 2007-08-15
AU2003266486A1 (en) 2004-04-19
DK200201429A (da) 2004-03-27
EP1546435A1 (de) 2005-06-29
WO2004029327A1 (en) 2004-04-08

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