WO2004029327A1 - Procede pour le pretraitement d'une surface d'un materiau non conducteur devant subir une electrodeposition - Google Patents

Procede pour le pretraitement d'une surface d'un materiau non conducteur devant subir une electrodeposition Download PDF

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Publication number
WO2004029327A1
WO2004029327A1 PCT/DK2003/000617 DK0300617W WO2004029327A1 WO 2004029327 A1 WO2004029327 A1 WO 2004029327A1 DK 0300617 W DK0300617 W DK 0300617W WO 2004029327 A1 WO2004029327 A1 WO 2004029327A1
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ions
metal
metal ions
conducting material
catalytic metal
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PCT/DK2003/000617
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English (en)
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Per MØLLER
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Instituttet For Produktudvikling
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Application filed by Instituttet For Produktudvikling filed Critical Instituttet For Produktudvikling
Priority to AU2003266486A priority Critical patent/AU2003266486A1/en
Priority to DE60315170T priority patent/DE60315170D1/de
Priority to US10/529,467 priority patent/US20060000720A1/en
Priority to EP03798083A priority patent/EP1546435B1/fr
Publication of WO2004029327A1 publication Critical patent/WO2004029327A1/fr

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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 cata- lytic 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 of Ni, 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 (Cr0 3 + sulphuric acid) and potassium permanganate (KMn0 4 ).
  • Cr0 3 + sulphuric acid chromic sulphuric acid
  • KMn0 4 potassium permanganate
  • the use of the latter substance has the effect that the resulting reaction product is manganese dioxide (pyrolusite; Mn0 2 ).
  • a sulphuric acid solution is usually used.
  • the surface is activated by means of colloidal palladium (Pd (0) surrounded by Sn "1"4 ⁇ ).
  • 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 neces- sary 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. 4999251 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 hydrochlori.de, 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 fo-ra ⁇ ig 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 method is characterised by a) depositing an adsorbing metal oxide on the surface, b) treating the surface with a solution of transition metal ions, and subsequently c) treating the surface with a solution of catalytic metal ions, where the transition metal ions used in step (b) are selected among such ions which can reduce catalytic metal ions into catalytic metal.
  • 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 w ions.
  • the catalytic metal ions used in step (c) are ions of a metal catalyzing the autocatalyt- ic 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, hi 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 0 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 KMn0 4 .
  • a permanganate compound such as KMn0 4 .
  • the oxidation process re- suits in formation of manganese dioxide (Mn0 ).
  • the bound manganese dioxide with such a metal ion, viz. Sh" " , i.e. 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 Mn0 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 "1" * 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 "1""1" 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.
  • 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 deposi- tion 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 0 3 ).
  • [Ox ] can be 0 2 or another suitable oxidant.
  • Fe 2 0 3 For precipitation and deposition of ochre, Fe 2 0 3 , a non-limiting example is correspondingly oxidation of Fe ++ at or on the surface where the reaction product Fe 2 0 3 is immobilized on the surface:
  • [Ox] can be 0 2 or another suitable oxidant.
  • the material is treated with a solu- tion 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* -1"
  • 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 4"1" ions, R-h 1""1" ions or Pt ++ ions, such as a solution of palladium chloride (PdCl 2 ).
  • a catalytic metal viz. a metal catalyzing chemical plating, especially a metal from the platinum group, such as Pd 4"1" ions, R-h 1""1” ions or Pt ++ ions, such as a solution of palladium chloride (PdCl 2 ).
  • the fixed transition metal ions such as Sn 1""1" ions, reduce the catalytic metal ions into metallic form, i.e. for instance the Pd 1""1" 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
  • AB S 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 permanga- nate 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/1 of KMn0 4 of a temperature of 90 °C, whereafter the excess potassium permanganate 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 (Eng- bright 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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Abstract

L'invention concerne un procédé pour le prétraitement d'une surface d'un matériau non conducteur devant subir une électrodéposition par le biais de la précipitation d'un métal, dans laquelle un oxyde métallique absorbant est initialement déposé, notamment MnO2 ou Fe2O3, sur la surface, puis ladite surface est traitée à l'aide d'une solution d'ions de métal de transition, notamment des ions Sn++, et ensuite à l'aide d'une solution d'ions métalliques d'un métal catalytique catalysant une électrodéposition chimique, notamment un métal du groupe platine. Les ions de métal de transition utilisés sont sélectionnés parmi des ions pouvant réduire des ions métalliques catalytiques en un métal catalytique. Grâce à cette méthode il est possible d'effectuer une électrodéposition sur des matériaux non conducteurs, notamment des matières plastiques, qui ne peuvent pas subir d'électrodéposition, ou qui peuvent subir une électrodéposition avec une grande difficulté, par le biais d'une activation classique, au moyen de palladium colloïdal.
PCT/DK2003/000617 2002-09-26 2003-09-23 Procede pour le pretraitement d'une surface d'un materiau non conducteur devant subir une electrodeposition WO2004029327A1 (fr)

Priority Applications (4)

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AU2003266486A AU2003266486A1 (en) 2002-09-26 2003-09-23 Method for pretreating a surface of a non-conducting material to be plated
DE60315170T DE60315170D1 (de) 2002-09-26 2003-09-23 Verfahren zur vorbehandlung einer oberfläche eines mit metall zu beschichtenden nichtleitenden materials
US10/529,467 US20060000720A1 (en) 2002-09-26 2003-09-23 Method for pretreating a surface of a non-conducting material to be plated
EP03798083A EP1546435B1 (fr) 2002-09-26 2003-09-23 Procede pour le pretraitement d'une surface d'un materiau non conducteur devant subir une electrodeposition

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DK200201429A DK175025B1 (da) 2002-09-26 2002-09-26 Fremgangsmåde til forbehandling af en overflade på et ikke-ledende materiale, der skal pletteres
DKPA200201429 2002-09-26

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WO2011144568A1 (fr) * 2010-05-21 2011-11-24 Siemens Aktiengesellschaft Pièce pourvue d'une surface catalytique, procédé de fabrication et utilisation de ladite pièce
US9346037B2 (en) 2010-05-21 2016-05-24 Siemens Aktiengesellschaft Component having a catalytic surface, method for producing same and use of said component

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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
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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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
US5112513A (en) * 1988-05-10 1992-05-12 Schering Ag Solution and process for etching and activating surfaces of a nonconductive substrate
EP0414097A2 (fr) * 1989-08-24 1991-02-27 Schering Aktiengesellschaft Procédé de métallisation directe d'un substrat non conducteur
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011144568A1 (fr) * 2010-05-21 2011-11-24 Siemens Aktiengesellschaft Pièce pourvue d'une surface catalytique, procédé de fabrication et utilisation de ladite pièce
CN102905775A (zh) * 2010-05-21 2013-01-30 西门子公司 具有催化剂表面的组件、其制备方法以及所述组件的用途
US9205411B2 (en) 2010-05-21 2015-12-08 Siemens Aktiengesellschaft Component having a catalytic surface, method for producing same, and use of said component
US9346037B2 (en) 2010-05-21 2016-05-24 Siemens Aktiengesellschaft Component having a catalytic surface, method for producing same and use of said component

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DE60315170D1 (de) 2007-09-06
ATE368136T1 (de) 2007-08-15
US20060000720A1 (en) 2006-01-05
EP1546435B1 (fr) 2007-07-25
AU2003266486A1 (en) 2004-04-19
EP1546435A1 (fr) 2005-06-29
DK175025B1 (da) 2004-05-03
DK200201429A (da) 2004-03-27

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