EP2440693B1 - Verwendung von ionischen flüssigkeiten zur vorbehandlung von kunststoffoberflächen zur metallisierung - Google Patents

Verwendung von ionischen flüssigkeiten zur vorbehandlung von kunststoffoberflächen zur metallisierung Download PDF

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Publication number
EP2440693B1
EP2440693B1 EP10722357.0A EP10722357A EP2440693B1 EP 2440693 B1 EP2440693 B1 EP 2440693B1 EP 10722357 A EP10722357 A EP 10722357A EP 2440693 B1 EP2440693 B1 EP 2440693B1
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EP
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Prior art keywords
methylimidazolium
butyl
dimethylimidazolium
process according
ethylimidazolium
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German (de)
English (en)
French (fr)
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EP2440693A1 (de
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Itamar Michael Malkowsky
Aurelie Alemany
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BASF SE
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BASF SE
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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
    • C23C18/1601—Process or apparatus
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a process for coating plastics with metals, which is characterized in that the plastics are pretreated with a composition which contains at least one salt with a melting point below 100 ° C. at 1 bar (hereinafter referred to as ionic liquid) ,
  • Plastic plating processes provide composites that combine the benefits of plastics and metals. Plastic can be made into almost any shape by simple processing methods such as injection molding or extrusion; subsequent electroplating of the resulting moldings takes place e.g. for decorative purposes or to achieve shielding effects, when the moldings are to serve as a housing for electronic devices.
  • a critical process step in plastic electroplating is the pretreatment of the plastic surface.
  • a pretreatment is u. a. necessary to improve the adhesion of the metal to the plastic surface.
  • the plastic surface should be roughened and also become more hydrophilic.
  • a roughening was also carried out by mechanical methods, has now prevailed for this purpose, a swelling and pickling of the plastic surface with chemicals.
  • the most frequently used pickle is the chromium-sulfuric acid pickle (chromium trioxide in sulfuric acid), in particular for ABS (acylnitrile-butadiene-styrene copolymer) or else polycarbonate.
  • Chromosulphuric acid pickling is very toxic and requires special precautions during the process, after treatment and disposal. Due to chemical processes in the pickling process, e.g. the reduction of the chromium compound used, consumes the stain and is not reusable.
  • Salts designated as ionic liquids with a melting point of less than 100 ° C. at 1 bar have hitherto been used in a wide variety of technical fields.
  • US 5145572 discloses a method wherein the surface of a substrate is catalytically activated and the catalytically activated surface is subsequently pretreated before thereafter electrochemically depositing a metal.
  • the pretreatment in US 5145572 serves to improve an already catalytically activated surface.
  • Object of the present invention was a method for coating plastic surfaces with metals in the previously used, disadvantageous pickling agent are no longer needed. By the method, the best possible adhesion between plastic and metal should be effected.
  • a pickling agent used should be as reusable as possible and suitable as a mordant for as many plastics.
  • composition used in the method according to the invention contains at least one salt with a melting point of less than 100 ° C. at 1 bar (hereinafter referred to as ionic liquid).
  • the ionic liquid has a melting point of less than 70 ° C, more preferably less than 30 ° C and most preferably less than 0 ° C at 1 bar.
  • the ionic liquid is under normal conditions (1 bar, 21 ° C), i. at room temperature, liquid.
  • Preferred ionic liquids contain at least one organic compound as cation, very particularly preferably they contain only organic compounds as cations.
  • Suitable organic cations are, in particular, organic compounds containing heteroatoms, such as nitrogen, sulfur or phosphorus, particular preference being given to organic compounds having a cationic group selected from an ammonium group, an oxonium group, a sulfonium group or a phosphonium group ,
  • the ionic liquids are ammonium cation salts, which includes non-aromatic compounds having a localized positive charge on the nitrogen atom, e.g. for tetravalent nitrogen (quaternary ammonium compounds) or else compounds with trivalent nitrogen, where one bond is a double bond, or aromatic compounds with delocalized positive charge and at least one, preferably one or two, nitrogen atoms in the ring system.
  • ammonium cation salts which includes non-aromatic compounds having a localized positive charge on the nitrogen atom, e.g. for tetravalent nitrogen (quaternary ammonium compounds) or else compounds with trivalent nitrogen, where one bond is a double bond, or aromatic compounds with delocalized positive charge and at least one, preferably one or two, nitrogen atoms in the ring system.
  • organic cations are quaternary ammonium cations having preferably four C 1 - to C 12 -alkyl groups as substituents on the nitrogen atom.
  • Organic cations which contain a heterocyclic ring system having one or two nitrogen atoms as part of the ring system are also particularly preferred.
  • Suitable compounds are monocyclic, bicyclic, aromatic or non-aromatic ring systems. Examples include bicyclic systems, as in WO 2008/043837 are described.
  • bicyclic systems of WO 2008/043837 they are diazabicyclo derivatives, preferably from a 7- and a 6 ring, which contain an amidinium group; in particular the 1,8-diazabicyclo- (5.4.0) undec-7-enium cation may be mentioned.
  • Very particularly preferred organic cations comprise a five- or six-membered heterocyclic ring system having one or two nitrogen atoms as part of the ring system.
  • Suitable cations are pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations, imidazolium cations, pyrazolium cations, pyrazolinium cations, imidazolinium cations, thiazolium cations, triazolium cations, pyrrolidinium cations and imidazolidinium. These cations are eg in WO 2005/113702 listed.
  • the nitrogen atoms are in each case by an organic group having generally not more than 20 C atoms, preferably a hydrocarbon group, in particular a C1 to C16 alkyl group, in particular a C1 to C10 , particularly preferably a C1 to C4 alkyl groups substituted.
  • the carbon atoms of the ring system can also be substituted by organic groups having generally not more than 20 C atoms, preferably a hydrocarbon group, in particular a C1 to C16 alkyl group, in particular a C1 to C10, particularly preferably a C1 to C4 alkyl groups.
  • ammonium cations are the above quaternary ammonium cations and imidazolium cations, pyrimidinium cations and pyrazolium cations, including compounds having an imidazolium, pyridinium or pyrazolium ring system and optionally any substituents on the carbon and / or nitrogen atoms of Ringsystems be understood.
  • the anion may be an organic or inorganic anion.
  • Particularly preferred ionic liquids consist exclusively of the salt of an organic cation having one of the abovementioned anions.
  • the molecular weight of the ionic liquids is preferably less than 2000 g / mol, more preferably less than 1500 g / mol, more preferably less than 1000 g / mol, and most preferably less than 750 g / mol; in a particular embodiment, the molecular weight is between 100 and 750 or between 100 and 500 g / mol.
  • R 1 and R 3 are preferably independently an organic group containing 1 to 10 C atoms. Most preferably, it is a hydrocarbon group which has no further heteroatoms, e.g. a saturated or unsaturated aliphatic group, an aromatic group or a hydrocarbon group having both aromatic and aliphatic components. Most preferably it is a C1 to C10 alkyl group, a C1 to C10 alkenyl group, e.g. an allyl group, a phenyl group, a benzyl group. In particular, it is a C1 to C4 alkyl group, e.g. a methyl group, ethyl group, propyl group, i-propyl group or n-butyl group.
  • R 2, R 4 and R 5 are preferably independently of one another an H atom or an organic group which contains 1 to 10 C atoms.
  • R 2, R 4 and R 5 are particularly preferably an H atom or a hydrocarbon group which has no further heteroatoms, for example an aliphatic group, an aromatic group or a hydrocarbon group which has both aromatic and aliphatic constituents.
  • it is an H atom or a C1 to C4 alkyl group, for example a methyl group, ethyl group, propyl group, i-propyl group or n-butyl group.
  • n is preferably 1.
  • anions in principle, all anions can be used which, in conjunction with the cation, lead to an ionic liquid.
  • R a , R b , R c and R d are each independently Hydrogen; C 1 -C 30 -alkyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO-, -CO-O- or -CO- N ⁇ substituted components such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl) , 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl 1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-butyl,
  • CqF 2 (qa) - (1-b) H 2a-b with q ⁇ 30, 0 ⁇ a ⁇ q and b 0 or 1;
  • C 2 -C 30 alkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components, such as for example, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C q F 2 (qa) - (1-b) H 2a-b with q ⁇ 30, 0 ⁇ a ⁇ q and b 0 or 1;
  • C 3 -C 12 cycloalkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components such as
  • R a , R a , R c and R d are preferably each independently a hydrogen atom or a C 1 to C 12 alkyl group.
  • Very particularly preferred anions are chloride; Bromide; iodide; thiocyanate; hexafluorophosphate; trifluoromethanesulfonate; methane; formate; Acetate; mandelate; Nitrate; Nitrite; trifluoroacetate; Sulfate; Bisulfate; Methyl sulfate; ethyl sulfate; 1-propyl sulfate; 1-butyl sulfate; 1-hexyl sulfate; 1-octyl sulfate; Phosphate; dihydrogen phosphate; Hydrogen phosphate; C 1 -C 4 dialkyl phosphates; propionate; tetrachloroaluminate; Al 2 Cl 7 -; chlorozincate; Chloroferrat; imide, bis (trifluoromethylsulfonyl); Bis (pentafluoroethylsulfonyl) im
  • Chloride bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methylsulfate, ethylsulfate, methanesulfonate, formate, acetate, dimethyl phosphate, diethyl phosphate, p-toluenesulfonate, tetrafluoroborate and hexafluorophosphate.
  • ionic liquids which have, as cation, methyltri (1-butyl) ammonium, 2-hydroxyethylammonium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethyl-imidazolium, 1-ethyl-3-methylimidazolium, 1 - (1-Butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3
  • ionic liquids 1,3-dimethylimidazolium methylsulfate, 1,3-dimethylimidazolium hydrogensulfate, 1,3-dimethylimidazolium dimethyl phosphate, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1 Ethyl 3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1- (1-butyl) -3-methylimidazolium methylsulfate, 1- (1-Butyl) -3-methylimidazolium hydrogensulfate, 1- (1-Butyl) -3-methylimidazolium hydrogensulf
  • composition according to the invention may contain further constituents in addition to the ionic liquid.
  • Additives with which a desired viscosity is set are preferred.
  • additional additives may optionally be thickeners or leveling agents.
  • the composition consists of more than 80% by weight of the ionic liquid. In a particularly preferred embodiment, more than 90% by weight, and in particular more than 95% by weight, of an ionic liquid is present. In a very particular embodiment, the composition consists exclusively of the ionic liquid.
  • the ionic liquid and composition containing or consisting of the ionic liquid are preferably liquid in the entire temperature range from 20 to 100 ° C, in particular from 0 to 100 ° C (atmospheric pressure, 1 bar).
  • plastics are coated.
  • it is thermoplastic.
  • Thermoplastics can be melted and made into the desired shape by various methods such as injection molding, extrusion thermoforming or blow molding.
  • Suitable thermoplastics include polyamides, polyolefins, polyesters, polyethers, polyacetals, in particular polyoxymethylene, polycarbonate, polyurethanes, polyacrylates, polystyrene or copolymers of styrene, in particular with acrylonitrile, e.g. Acrylonitrile / butadiene / styrene copolymer (ABS).
  • ABS Acrylonitrile / butadiene / styrene copolymer
  • polycondensates of aminocarboxylic acids e.g. of 6-amino-carboxylic acid or epsilon-caprolactam
  • polycondensates of diamino compounds and dicarboxylic acids e.g. of 1,6 hexanediamine and adipic acid, called.
  • Suitable polyolefins are polyethylene, polypropylene and copolymers of ethylene or propylene.
  • Polyesters are polycondensation products of polyhydric alcohols, e.g. Butanediol, hexanediol, glycerol or trimethylolpropane and polybasic carboxylic acids, especially phthalic acid and its isomers, adipic acid or trimellitic anhydride.
  • polyhydric alcohols e.g. Butanediol, hexanediol, glycerol or trimethylolpropane
  • polybasic carboxylic acids especially phthalic acid and its isomers, adipic acid or trimellitic anhydride.
  • Polyacetal which may be mentioned in particular polyoxymethylene (POM).
  • Polycarbonates are esters of carbonic acid and polyhydric alcohols, e.g. Bisphenol-A; Also mentioned are polyestercarbonates which contain further polybasic carboxylic acids as synthesis components.
  • Polyethers contain repeating ether groups. Of particular technical importance are e.g. Polyetherimides which contain in particular via recurring ether and imide linked aromatic ring systems, polyether ketones containing in particular via repeating ether and ketone-linked phenylene groups, polyether sulfides containing in their polymer backbone ether and thioether groups, and polyethersulfones in their polymer backbone repeating ether groups and Contain sulfone groups.
  • Polyetherimides which contain in particular via recurring ether and imide linked aromatic ring systems
  • polyether ketones containing in particular via repeating ether and ketone-linked phenylene groups
  • polyether sulfides containing in their polymer backbone ether and thioether groups
  • polyethersulfones in their polymer backbone repeating ether groups and Contain sulfone groups.
  • Polyurethanes are polyadducts of polyfunctional isocyanates and polyhydric alcohols, both aliphatic and aromatic compounds come into consideration.
  • Polyacrylates are homo- or copolymers of acrylic or methacrylic monomers; called e.g. Polymethymethacrylate (PMMA).
  • PMMA Polymethymethacrylate
  • styrene such as polystyrene, styrene / acrylonitrile copolymer and in particular acrylonitrile / butadiene / styrene copolymers (ABS).
  • ABS acrylonitrile / butadiene / styrene copolymers
  • Particularly preferred polymers are polyamides, polyesters, polyethers, polyoxymethylene and ABS.
  • the latter is e.g. sold under the trade name Terlurran® by BASF SE.
  • the objects to be coated may consist entirely of one of the above plastics.
  • Such articles may be arbitrarily colored and are e.g. obtainable by thermoplastic deformation methods such as injection molding, extrusion thermoforming and blow molding. But they can also consist of different materials; It is essential that the surface to be coated is made of plastic.
  • the plastics are coated with metals.
  • metal e.g. Nickel, aluminum, copper, chromium, tin or zinc and their alloys.
  • the metal can be applied in one or more layers or operations. It is also possible to apply layers of different metals.
  • An essential element of the process according to the invention is the claimed pretreatment of the plastics.
  • the coating with the metal and further necessary or recommended measures for implementation, preparation and follow-up can be found in various embodiments in the prior art.
  • the pretreatment according to the invention replaces the hitherto customary pickling with aggressive chemicals such as chromosulfuric acid (chromium trioxide in sulfuric acid).
  • the pretreatment according to the invention is preferably carried out at elevated temperature, preferably at temperatures of from 30 to 120 ° C., more preferably from 50 to 120 ° C.
  • the composition has the above temperature.
  • a previous separate heating of the plastic part to be coated is not necessary.
  • the article to be coated is immersed in the composition, the composition preferably having the above temperature.
  • the composition is moved to better mass transfer, which can be done according to the prior art by means of stirrers, pumps, blowing air etc.
  • the workpiece itself can also be moved by means of special devices known in electroplating in the composition.
  • the required amount of the composition is adjusted so that the workpiece is wetted to the desired extent.
  • the workpiece can be completely or partially immersed.
  • the duration of the action of the composition on the plastic surface is preferably 1-60 minutes (min), in particular 1-30 min, particularly preferably 1-15 min.
  • the composition may preferably be removed from the pretreated article by rinsing with water or an organic solvent.
  • composition can be recovered (recycled), optionally cleaned and reused.
  • the recycling of the composition may e.g. by precipitation of the dissolved plastic by means of water or an organic solvent and subsequent separation of the dissolved plastic by filtration.
  • the media used for the precipitation can subsequently be recovered by distillation. Volatile constituents of the dissolved plastic can also be removed directly from the composition by distillation. In this way, a purified and reusable composition can be obtained.
  • the pretreatment according to the invention is only one part of all measures which are referred to as pretreatment in the gawanization of plastics as a whole. Under this term of pretreatment usually all currentless running processes are summarized.
  • To this pretreatment belongs in particular a first application of metal nuclei, for example of palladium, silver or gold, preferably palladium, which also be referred to as activation. and a first coating of metals, wherein the type of activation and the first metal coating are matched.
  • metal nuclei for example of palladium, silver or gold, preferably palladium, which also be referred to as activation.
  • first coating of metals wherein the type of activation and the first metal coating are matched.
  • Known methods of activation are e.g. classical colloidal activation (application of palladium / tin colloids), ionic activation (application of palladium cations), direct metallization or processes known by the names Udique Plato®, Enplate MID select or LDS Process.
  • the first electrolessly deposited layer is a layer of nickel, copper, chromium or their alloys.
  • the adhesion of the metal layers to plastic surfaces for example of ABS
  • plastic surfaces for example of ABS
  • the achieved adhesion of the metal layers is very good, even under mechanical stress or high temperatures.
  • a platelet of dimensions 60 ⁇ 30 ⁇ mm made of ABS (AcryIn trilbutadiene terpolymer, Terluran® BASF, was used in all examples Terluran GP 35) is immersed for 2 minutes in 60 ml of ethanol at room temperature for pre-cleaning. Subsequently, the plate is immersed at 80 ° C for 10 minutes in 80 mL of stirred 1-ethyl-3-methylimidazolium acetate (EMIM acetate). After the pickling has ended, the substrate is rinsed with water and immersed for a further 5 minutes in 60 ml of stirred water (dist.) At room temperature to remove the last salts. The pickling effect of the IL is checked by means of SEM analysis and shows a new structuring of the surface.
  • a plate of dimensions 60 ⁇ 30 ⁇ 2 mm of Terluran is immersed for 2 minutes in 60 ml of ethanol at room temperature for pre-cleaning. Subsequently, the plate is immersed at 80 ° C for 5 minutes in 80 mL of stirred methyl tributylammonium methylsulfate (MTBS). After the pickling has ended, the substrate is rinsed with water and immersed for a further 5 minutes in 60 ml of stirred water (dist.) At room temperature to remove the last salts. The pickling effect of the IL is checked by means of SEM analysis and shows a new structuring of the surface.
  • MTBS stirred methyl tributylammonium methylsulfate
EP10722357.0A 2009-06-08 2010-06-01 Verwendung von ionischen flüssigkeiten zur vorbehandlung von kunststoffoberflächen zur metallisierung Active EP2440693B1 (de)

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EP10722357.0A EP2440693B1 (de) 2009-06-08 2010-06-01 Verwendung von ionischen flüssigkeiten zur vorbehandlung von kunststoffoberflächen zur metallisierung

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EP09162184 2009-06-08
PCT/EP2010/057602 WO2010142567A1 (de) 2009-06-08 2010-06-01 Verwendung von ionischen flüssigkeiten zur vorbehandlung von kunststoffoberflächen zur metallisierung
EP10722357.0A EP2440693B1 (de) 2009-06-08 2010-06-01 Verwendung von ionischen flüssigkeiten zur vorbehandlung von kunststoffoberflächen zur metallisierung

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EP2440693A1 EP2440693A1 (de) 2012-04-18
EP2440693B1 true EP2440693B1 (de) 2016-08-10

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JP5916604B2 (ja) 2016-05-11
KR20170053748A (ko) 2017-05-16
CN102459715B (zh) 2015-11-25
JP2012529566A (ja) 2012-11-22
WO2010142567A1 (de) 2010-12-16
KR102055812B1 (ko) 2019-12-13
EP2440693A1 (de) 2012-04-18
SG10201402353PA (en) 2014-10-30
AU2010257683A1 (en) 2011-12-08
KR20120027474A (ko) 2012-03-21
AU2010257683B2 (en) 2016-09-29
MY156523A (en) 2016-02-26
CA2763967A1 (en) 2010-12-16
SG176136A1 (en) 2011-12-29
CA2763967C (en) 2017-08-15
US20120073978A1 (en) 2012-03-29
US9090966B2 (en) 2015-07-28

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