EP1942207A1 - Solution de prétraitement et procédé de formation d'une couche d'un métal de revêtement sur un substrat doté d'une surface en plastique - Google Patents

Solution de prétraitement et procédé de formation d'une couche d'un métal de revêtement sur un substrat doté d'une surface en plastique Download PDF

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EP1942207A1
EP1942207A1 EP06077232A EP06077232A EP1942207A1 EP 1942207 A1 EP1942207 A1 EP 1942207A1 EP 06077232 A EP06077232 A EP 06077232A EP 06077232 A EP06077232 A EP 06077232A EP 1942207 A1 EP1942207 A1 EP 1942207A1
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Prior art keywords
treatment solution
acid
plastics
metal
substrate
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EP06077232A
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German (de)
English (en)
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Hermann-Josef Middeke
Lu Baosen
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
    • 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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/26—Roughening, e.g. by etching using organic liquids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Definitions

  • the present invention relates to a pre-treatment solution and to a method of forming a layer of a coating metal on a substrate, said substrate having a plastics surface, more specifically to a method of forming a layer of a coating metal on at least one of a polyamide and a polyoxymethylene plastics part.
  • Such solutions and methods are applied to plating polyamide or polyoxymethylene plastics substrates especially in decorative plating industry.
  • ABS plastics parts have been electroplated for many years. Nevertheless, little research effort has been made in this field because electroplating polyamide plastics parts has ever been an application having a narrow application range due to the limited market thereof.
  • a first method has been described in a publication on the 65th Conference of the American Electroplating Society (AES) in Washington (1978 ) which achieved a peel strength of the metal layer to the plastics part higher than about 1 N/mm. However, no indication was made as to specific details of this method, except for that no chromic acid was used.
  • the influence of the surface texture obtained after the first method step on the adhesion strength was described to be similar to that of acrylonitrile-butadiene-styrene-copolymer (ABS) plastics parts. With ABS plastics parts a clear correlation proves to exist between the microscopic surface texture and adhesion strength.
  • a first optional step comprises immersing the plastics part into a solution of a polar polymer thus providing the surface of the part with a very thin layer of this polymer.
  • This polymer serves to bond the catalyst more strongly, and at a higher concentration, to the surface of the polyamide plastics part.
  • the part After rinsing off adhering solution from the plastics part, the part is usually catalyzed by contacting same with a - solution containing colloidal palladium.
  • a - solution containing colloidal palladium Such solutions are acidic and contain tin chloride and are perfectly well suited to catalyze nonpolar olefinic polymers like ABS or polycarbonate.
  • Such solutions are also described to be used for the catalyzation of polyamide plastics parts ( EP 0 406 859 B1 ).
  • Ionic palladium being adsorbed to the plastics parts used will instead be reduced to the elemental palladium metal by means of reducing agents, such as by boranates (dimethylaminoborane and alkali metal borohydrides) and hypophosphites.
  • reducing agents such as by boranates (dimethylaminoborane and alkali metal borohydrides) and hypophosphites.
  • most applied methods comprise treating a polyamide plastics part using a swelling and cleansing solution, said solution containing a glycol ether, a mineral acid and a surface active agent. Residues of this solution adhering to the plastics part will be rinsed off thoroughly after it has been treated in this solution for the treatment time required. Thereafter the part is treated in a suitable conditioner and finally catalyzed in an acidic palladium salt solution. After having been exposed to a reduction solution the part is nickel plated in an electroless nickel solution, then electroplated with copper and finally electroplated with a metal desired to be the final finish, mostly nickel or chromium.
  • DE 31 37 587 C2 discloses pre-treatment of polyamide plastics parts for decorative applications with a solution containing an organic solvent, a glycol ether, for example, and an acid, such as hydrochloric acid. Subsequently, the parts are plated by electroless metal coating, the metal adhering well to the parts.
  • EP 0 406 859 B1 and EP 0 604 131 B1 disclose pre-treating polyamide plastics parts with oxidizing acids, such as chromic acid/sulfuric acid for example.
  • EP 0 604 131 B1 discloses etching the polyamide plastics part with mineral acids including hydrochloric acid, sulfuric acid, phosphoric acid, chromic acid, formic acid and acetic acid.
  • the method of both documents further comprises contacting polyamide plastics parts with a solution containing colloidal palladium and tin (II) the tin (II) being removed after the treatment by acceleration.
  • EP 0 604 131 B1 discloses treating the polyamide plastics parts applying a sensitizer-activator method or soaking the parts in a palladium solution-reduction solution.
  • the method comprises contacting the polyamide plastics part with an organic palladium complex first, then intermediate treatment of the part, comprising swelling the amorphous surface of the part, using an etchant, which contains salts of calcium und aluminium, and finally electroless nickel plating the part.
  • a method of forming a metal layer on the surface of polyamide plastics parts is described in U.S. Patent No. 5,296,020 , the method comprising treating the polyamide plastics part with an activator formulation consisting of organic noble metal, fillers, organic solvent and an aqueous dispersion of a polyurethane polymer.
  • the organic noble metals are provided by organometallic compounds of palladium with olefins, with ⁇ , ⁇ -unsaturated carbonyl compounds, with crown ethers and with nitriles.
  • the activator compounds are then reduced to metallic form, or are complexed by means of complexing agents and introduced into the aqueous dispersion of the polyurethane polymer.
  • the solvent may be glycol ethers, for example ethylene glycol monomethyl ether, diglyme or propylene glycol monomethyl ether acetate and simply serves to dissolve the organic Pd compound. Therefore, such solvent may be employed in a small amount.
  • Metallization of the plastics part, once pre-treated in this formulation, by dipping for example, will be performed by electroless metal plating, such as by electroless nickel plating. Ionic palladium may be reduced in the electroless metal plating solution directly with no further method step being required.
  • U.S. Patent No. 5,300,140 discloses a hydroprimer for metallizing substrate surfaces, polyamide surfaces for example.
  • This hydroprimer is used to be applied to the substrate surfaces by application of a thin layer thereof to the substrate surfaces for subsequent electroless metal plating, nickel plating for example.
  • the hydroprimer contains, in addition to water, a water-dispersible polymer selected from the group consisting of water-dispersible polyacrylates, polybutadienes, polyesters, melamine resins, polyurethanes and polyurethane-ureas, further an ionic noble metal, a colloidal noble metal or a covalent or complex compound of a noble metal as metallization catalyst and a filler.
  • Possible activators are organometallic complex compounds of palladium with olefins, with ⁇ , ⁇ -unsaturated carbonyl compounds, with crown ethers, with nitriles and with diketones.
  • Ionic metals in the form of salts, such as halides, may likewise be used.
  • the noble metal may be reduced in the electroless metal plating solution directly.
  • the aforementioned methods are said to yield metal layers coating the substrate surfaces at high adhesion.
  • the catalyst formulations have been shown not to be very reliable in terms of metal plating capability (uniformity of metal plating) and adhesion of a metal layer deposited.
  • Another method of electroless plating a polyamide plastics part is disclosed in U.S. Patent No. 4,554,183 .
  • This method comprises pre-treating the polyamide plastics part with a solution of a mixture of halides of elements of the 1 st and 2 nd main groups of the Periodic Table of Elements with salts of weak inorganic bases and strong inorganic acids in a non-etching organic swelling agent or solvent for polyamides and treating the plastics part with a metal-organic complex compound of palladium, for example.
  • Coordination complexes of olefins with palladium which contain functional groups, as indicated in this document, are used as the metal-organic complex compounds.
  • the metal-organic complex compounds are advantageously employed in the form of the dispersions thereof, and in particular, the solutions thereof in suitable organic solvents, these solvents being water-immiscible. Examples are given which exclusively describe solutions comprising a coordination complex of an olefin with palladium in an organic solvent. Reduction of the coordination complex compound may be performed in an electroless nickel plating bath directly.
  • inorganic ligands means any neutral or ionic inorganic chemical species which is arranged at a central atom or ion and the number of which depends on the coordination number of the central atom or ion.
  • the inorganic ligands comprise those species which do not contain C-H-bonds.
  • halogen acids means hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid.
  • pKs means the negative Brigg's logarithm of Ks, Ks being the dissociation constant of the acid in an aqueous solution, producing hydronium (H 3 O + ) ions.
  • electroless metal plating solution means a metal plating solution which contains a chemical species capable of reducing coating metal ions to elemental coating metal.
  • an electroless nickel plating solution may contain hypophosphite salts, hypophosphoric acid or dimethyl amine borane as the reducing agents.
  • substrate means any workpiece which may be coated with a metal layer, such as a plate, other moulded device or powder.
  • wt-% means a fraction of components contained in a mixture, the term indicating this fraction as parts of the component by weight per 100 parts of the mixture by weight.
  • alkyl means a chemical species with the general chemical formula C n H 2n+1 , with n being an integer > 0 and more specifically being an integer from 1 to 8, more specifically from 1 to 6 and most specifically from 1 to 4.
  • Alkyl species may be branched or unbranched and may preferably be methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl.
  • etching of plastics surface means the roughening and modifying of a plastics surface using chemical species, more specifically solutions into which the plastics substrates may be immersed. Due to this treatment the bonds of the polymers treated are either broken and/or oxidized and/or certain chemical functional groups are modified. Concurrently with chemically modifying the plastics surface it will also be hydrophilized. Such effects have not only been found out with polyamide and with polyoxymethylene substrates but also with ABS substrates.
  • ABS substrates are treated using a chromic acid etch, carboxylic acid, keto and aldehyde groups are formed from the polybutadiene moiety of the polymer whereas, in the case of polyamide and polyoxymethylene substrates, the condensation reaction performed to form the polyamide or polyoxymethylene polymer is reversed by the action of strong acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or formic acid.
  • strong acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or formic acid.
  • the amino groups formed due to this reaction in polyamide plastics are believed to cause hydrophilicity of the polyamide surface.
  • the hydroxyl groups formed due to this reaction in polyoxymethylene plastics are believed to cause hydrophilicity of this plastics material.
  • the term "swelling of plastics surface” means swelling such surfaces with polar organic species, which are believed to be incorporated into the polymer matrix, thus expanding same and slightly softening the surface thereof.
  • Very strong polar solvents are capable of completely dissolving the polymer. Such dissolution will damage the plastics surface considerably. Therefore, for the treatment of polyamide and polyoxymethylene substrates only organic solvents may be used which cause slight swelling thereof, glycol ethers for example, or strong solvents the impact thereof being reduced if they are mixed with water (propylencarbonate, ⁇ -butyrolactone for example).
  • the term "conditioner" means chemical species which are capable of influencing the surface properties of plastics substrates for the metal plating of such substrates.
  • the conditioners are organic molecules which adsorb at the plastics surface and enhance hydrophilicity of the substrate due to a plurality of identical functional groups, -OH groups or -NH groups for example.
  • the conditioner may comprise positively or negatively charged groups.
  • the term "activating" means a preparation of the plastics surface for the subsequent electroless metal plating method step, comprising depositing a noble metal, being in ionic form or in colloidal form, to the plastics surface. If the noble metal is in ionic form such noble metal ions are subsequently reduced to elemental noble metal using a reducing solution, the elemental noble metal forming noble metal catalyst nuclei. If the noble metal is in colloidal form such colloidal metal serves the starting catalyst nuclei. In general, any protective colloid surrounding the colloid particles must be removed after deposition of the particles (acceleration). In any case electroless metal plating will thereafter be initiated from a solution containing coating metal salt and reducing agent.
  • palladium and platinum as well as iridium and rhenium can be employed as the noble metal catalyst used for the oxidation of phosphite or formaldehyde reducing agents (for silver depositing for example). This can concurrently initiate autocatalytic reduction of metals like nickel, copper, iron and cobalt.
  • the pre-treatment solution and the method serve the formation of a layer of a coating metal on a substrate, the substrate preferably having at least one of a polyamide and a polyoxymethylene surface, the substrate more specifically being a polyamide or polyoxymethylene plastics substrate.
  • Such solution and method may accordingly be used to plate polyamide or polyoxymethylene plastics substrates for decorative purpose, for example for sanitary appliances, in automotive industry, as furniture fittings, for jewelry and for other applications, wherein a polyamide or polyoxymethylene plastics substrate, which is mainly used because of its mechanical, chemical, processing or thermal properties, is metal-plated.
  • the polyamide plastics substrate may be a polyamide 6, polyamide 6.6, polyamide 11 and polyamide 12 plastics substrate, but may likewise be any other polyamide plastics substrate. Further, both polyamide or polyoxymethylene plastics material being provided with filler material (for example mineral powder such as kaolin or glass fibers), and polyamide or polyoxymethylene plastics material not being provided with filler material may be treated in accordance with the method of the invention. It has been found out that polyamide 11 and polyamide 12 plastics substrates cannot be metal plated using prior art methods. Polyamide and polyoxymethylene plastics substrates are injection molded to give them a specific shape depending on their intended use.
  • the pre-treatment solution of the invention contains at least one organic solvent, at least one noble metal in ionic form being capable of reducing coating metal ions to elemental coating metal and at least one acid.
  • the method of the invention comprises: a) providing the substrate; b) contacting the substrate with the pre-treatment solution; and c) forming the layer of coating metal on the substrate by contacting the substrate with an electroless metal plating solution.
  • the solution of the invention may also be aqueous, such that the content of any organic solvent contained therein may be minimized. Therefore, TOC will be minimized, too.
  • the method of the invention can be easily performed with low effort. This again will also assure application of the method at low cost.
  • the at least one acid may preferably have a pKs at or below 5, more preferred at or below 3 and most preferred at or below 2.
  • the at least one acid is able to attack the surface of the polyamide or polyoxymethylene plastics material, thereby rendering same wettable by further treatment agents on the one side and imparts a certain roughening to the surface thereof on the other side, because acids are in general capable of dissolving polyamide and polyoxymethylene plastics material.
  • roughening of the plastics surface will, however, not be required to achieve sufficient adhesion of a metal layer formed on the plastics surface and will be minimized to avoid too much damage of the surface. It seems that surface texture does not significantly influence adhesion of the metal layer formed.
  • the acid contained in the pre-treatment solution dissolves a thin surface film of the polyamide or polyoxymethylene plastics material, thus creating a clean and polar surface.
  • acid attack was not observed to dissolve a considerable amount of polyamide or polyoxymethylene plastics material. The impact of the acid may therefore be based on another mechanism.
  • the inventors assume that the acid breaks hydrogen bonds present at the plastics surface. This would be in contrast to the breakdown (etching) mechanism of chromic acid which seems to involve breaking carbon-carbon bonds, thus chemically modifying the plastics surface.
  • a suitable acid at a suitable concentration.
  • hydrochloric acid proves to be favourable at a concentration of up to about 200 ml/l (37 wt.-% hydrochloric acid solution), whereas sulfuric acid, phosphoric acid (without hydrochloric acid) or methane sulfonic acid were not suitable.
  • C 1 - to C 4 -carboxylic acids such as formic acid and acetic acid, formic acid being preferred, likewise cause considerable adhesion of the metal layer to the plastics surface.
  • Optimum concentration of these other acids is 200 - 250 g/l. It has to be taken into consideration, however, that formic acid may reduce noble metal, more specifically Pd 2+ , to elemental noble metal, more specifically palladium.
  • the at least one acid is even more preferably selected from the group comprising halogen acids, formic acid, acetic acid and lactic acid.
  • the halogen acid is hydrochloric acid. Using these acids a very good adhesion of the metal layer formed on the surface of the polyamide or polyoxymethylene plastics substrate may be achieved.
  • the pre-treatment solution contains phosphoric acid in addition to another strong acid such as hydrochloric acid.
  • the pre-treatment solution contains in one litre about 150 ml of an aqueous solution of 37 wt.-% hydrochloric acid, about 100 ml phosphoric acid and about 50 ml organic solvent. Best adhesion values are obtained if the concentration of hydrochloric acid in the pre-treatment solution is 150 ml/l.
  • the at least one organic solvent contained in the pre-treatment solution may preferably be selected from the group comprising glycol ethers, more specifically glycol ethers having chemical formula R 1 -O-gly x -R 2 , wherein R 1 is C 1 - to C 6 -alkyl, gly is -CH 2 -CH 2 -O- or -CH 2 -CH(CH 3 )-O-, wherein further x is 1, 2, 3 or 4 and wherein R 2 is H, C 1 - to C 6 -alkyl or R 3 -CO-, with R 3 being C 1 - to C 6 -alkyl.
  • glycol ethers more specifically glycol ethers having chemical formula R 1 -O-gly x -R 2 , wherein R 1 is C 1 - to C 6 -alkyl, gly is -CH 2 -CH 2 -O- or -CH 2 -CH(CH 3 )-O-, wherein further x is 1, 2,
  • the organic solvent is selected from the group comprising diethylene glycol monoethyl ether and diethylene glycol monoethyl ether acetate.
  • concentration thereof in the pre-treatment solution may be in the range of from 1 to 990 ml/l, preferably from 15 ml/l to 150 ml/l. If concentration of the organic solvent is in a concentration range of from 50 to 200 ml/l adhesion of a metal layer on the polyamide or polyoxymethylene plastics surface drops if the acids are a mixture of hydrochloric and phosphoric acid.
  • the organic solvent proves to significantly influence the adhesion of a metal layer formed on the polyamide or polyoxymethylene plastics surface.
  • Glycol ethers have been found out to be particularly suitable.
  • the compounds mentioned explicitly prove to fulfil the requirements of not having any detrimental environmental impact, not comprising any halogens being bonded to carbon, being water-miscible, not being easily volatile, not having a low ignition point, being stable against decomposition by acid attack, having low cost and not being toxic, like mutagenic or teratogenic.
  • Both, the at least one acid and the at least one organic solvent further serve the wetting of the plastics surface in order to assure complete and reliable contacting of the plastics surface with the treatment liquids.
  • the plastics surface must be pre-treated prior to metal plating such that no contamination thereof may interfere with the electroless metal plating method.
  • pre-treatment according to the invention only comprises one method step and in addition three rinse steps, such pre-treatment step must be able to remove all contaminants in addition to wet (hydrophilize) the surface and allow the catalyst to sufficiently adsorb to the plastics surface.
  • some cleansing effect takes place if the pre-treatment solution of the invention is used. However, severe impurities adsorbed at the plastics surfaces as well as finger prints have to be avoided thoroughly.
  • the noble metal is palladium. Such metal proves to have superior catalyst properties, once it has been reduced to metallic nuclei. Its concentration in the pre-treatment solution may be in the range of from 10 mg/l to 2000 mg/l, preferably from 20 mg/l to 100 mg/l.
  • the noble metal being in ionic form may in a preferred embodiment be formed not to comprise any ligand or to exclusively comprise inorganic ligands, such as halide ligands, more specifically chloride ligands, hence not comprising any organic ligand. Most preferably the noble metal in ionic form is Pd 2+ . If nickel is subsequently electroless plated, any other metal, having an electrochemical standard potential of a few hundred mV more negative than nickel, may be used and will hence be able to initiate nickel deposition, such as iron or nickel. In an aqueous solution palladium ions will have water molecules be coordinated to the central ion.
  • Pd 2+ may be used in the form of palladium chloride, palladium nitrate or palladium sulfate.
  • concentration thereof will, in general, not be critical as to the ability of the activated plastics substrate to be metal plated. Neither too high a concentration thereof, nor too low a concentration thereof has revealed any negative effects.
  • the noble metal concentration may be selected to be at or below 100 mg/l, more specifically at or below 80 mg/l, even more specifically at or below 60 mg/l, even more preferably at or below 40 mg/l and most preferably from 20 to 40 mg/l (or at about 30 mg/l).
  • initiation of electroless metal deposition will be delayed more and more. However, such delay does not have any detrimental implication, all the more electroless metal plating is more slowly during the first plating period than in subsequent periods.
  • the pre-treatment solution is an aqueous solution.
  • the pre-treatment solution fulfils the requirement that the pre-treatment solution shall have reduced TOC and no detrimental environmental impact.
  • the pre-treatment solution may advantageously be free of any binder.
  • the present invention will preferably do without such binder, such that no film will be formed on the surface of the polyamide or polyoxymethylene plastics substrate, such film incorporating the catalyst nuclei required for initiating electroless metal plating.
  • such films would require much more catalyst metal to initiate electroless metal plating than the present method, because many catalyst nuclei in the film would be sheathed from the electroless plating solution.
  • a very favourable embodiment of the present invention comprises using an agent promoting adsorption of noble metal catalyst nuclei to the polyamide or polyoxymethylene surface (conditioner).
  • agent will preferably be contained in the pre-treatment solution.
  • the agent promoting absorption of noble metal catalyst nuclei to the polyamide or polyoxymethylene surface may be a water-soluble polymer having polar groups, for example positively or negatively charged groups, such that they are able to mediate adhesion between the plastics surface and chemical species contained in the solution. It may, for example, be a polyelectrolyte compound. In one most preferred embodiment such polyelectrolyte compound may be a polyimidazolium compound, such as polyimidazolium methosulfate.
  • Concentration of this agent in the pre-treatment solution may be in the range of from 1 mg/l to 5000 mg/l, preferably from 10 mg/l to 100 mg/l.
  • the agent promoting adsorption promotes adsorption of the noble metal catalyst nuclei to the plastics substrate but also promotes adsorption of the catalyst to any holding elements for plastics parts, a rack, for example. This adsorption will increase noble metal consumption on the one hand and further initiate coating metal deposition on the holding elements on the other hand. Thus coating metal must be stripped off either frequently.
  • the agent promoting adsorption of the noble metal catalyst nuclei will enhance adsorption of the noble metal, the concentration thereof may be minimized, to 20 mg Pd 2+ per litre pre-treatment solution for example.
  • a couple of polyamide or polyoxymethylene plastics substrates may be metal plated, which would otherwise not be accessible to plating.
  • the agent promoting adsorption of the noble metal catalyst seems to some extent enhance adhesion of a metal layer deposited on the plastics substrate if no phosphoric acid is used in the pre-treatment solution but only hydrochloric acid.
  • the pre-treatment solution of the invention may contain a surface active agent.
  • This agent will reduce surface tension of the solution such that the plastics substrate may be more easily wetted. No requirements are posed to its chemical structure and identity. Apart from an as low as possible surface tension of the pre-treatment solution to be achieved, this agent will preferably simply be easily rinsed off and be harmless, especially with respect to animals. For this reason nonylphenol derivates are not preferred.
  • any electroless metal plating solution may be employed.
  • the coating metal is nickel. Therefore, to deposit the first metal layer an electroless nickel plating solution may be used, since electroless nickel plating is cost-effective and offers the advantage of easily being performed because the nickel plating solution is essentially stable to decomposition. Further, use of any noxious compounds such as formaldehyde may be dispensed with.
  • an electroless metal plating solution contains at least one metal ion source, more specifically at least one nickel ion source, such as nickel sulfate or nickel chloride, further a reducing agent, such as at least one hypophosphite salt, hypophosphoric acid, a borane compound, such as dimethyl amine borane or sodium borohydride or, if copper is to be deposited, formaldehyde, further at least one complexing agent, such as carboxylic acids, like succinic acid, citric acid, lactic acid, malic acid, ethylene tetraacetic acid as well as the salts thereof, at least one buffer or other pH adjusting agent, like acetic acid/acetate salt or sodium hydroxide. Hypophosphite salts and hypophosphoric acid are preferred over the other reducing agents due to the cost thereof.
  • the plating solution may contain additives which act as a stabilizer to prevent spontaneous decomposition of the solution.
  • the method of the invention makes use of the fact that the reducing agent of the metal plating solution may also be employed to reduce palladium or other noble metal ions to elemental palladium or another elemental noble metal.
  • the same reducing agent may be used both for the reduction of the noble metal ions and for the deposition of the coating metal, the noble metal ions may be reduced using the reducing agent contained in the electroless metal plating solution.
  • the method may in one embodiment comprise only four method steps (pre-treatment step and three rinse steps) prior to electroless metal plating the plastics substrate.
  • hypophosphite salts and hypophosphoric acid prove to react spontaneously with Pd 2+ ions adsorbed to the polyamide or polyoxymethylene plastics surface, forming palladium catalyst nuclei which may be large enough to store hydrogen atoms to initiate nickel plating. If the temperature of the electroless nickel plating solution is about 50°C reduction of Pd 2+ is complete after less than 30 seconds. Surprisingly, there is practically no delay in reduction of Pd 2+ , compared with methods, in which Pd 2+ is reduced in a separate method step. In general, electroless nickel plating takes about 6 to 12 minutes; therefore any minor delay in nickel plating initiation cannot be detected. Electroless nickel plating proves to be reliable irrespective of which electroless nickel plating solution is employed.
  • the method of the invention comprising reducing the noble metal ions in the electroless metal plating solution, has been found out to be reliable as to metal plating capability (uniform metal plating), though treatment of the pre-treated plastics substrate with the electroless metal plating solution was assumed to strip off, by rinsing, at least partly, the noble metal ions adsorbed to the plastics surface before reduction can take place. In such event part of the noble metal adsorbed could not serve initiation of electroless metal plating, but would render the electroless coating metal plating solution unstable, since coating metal would be deposited at the stripped off noble metal. Such assumption did not turn out to take place, however. Otherwise noble metal being stripped off the plastics surface would have tended to destabilize the metal plating solution. However, such behaviour could not be verified and, likewise, increased consumption of the reducing agent contained in the metal plating solution could not be observed.
  • the substrate may be contacted additionally with a reducing solution, after method step b), and prior to method step c).
  • a reducing solution preferably contains at least one reducing agent capable of reducing the at least one noble metal in ionic form to elemental noble metal.
  • the reducing agent may preferably be selected from the group comprising hypophosphite salts and hypophosphoric acid.
  • the method may be rendered very economic since consumption of noble metal may be minimized due to less loss of noble metal as a consequence of drag-out of the pre-treatment solution from the pre-treatment bath.
  • the electroless metal plating solution will be protected by removing any species from the pre-treatment solution, eventually adhering to the plastics surface from dragging same into the electroless metal plating solution.
  • the reducing solution will preferably be operated at a pH not below 3. Further, the temperature of this solution is preferably not below 35°C.
  • the concentration of hypophosphite salt in this solution is recommended to be below 30 g/l, about 20 g/l being sufficient (sodium hypophosphite; other salts or hypophosphoric acid being at the same molar concentration).
  • Rinsing between the pre-treatment step and the electroless metal plating step proves not to be critical as to metal-plastics adhesion, uniform metal plating and other requirements.
  • the period of time used between the pre-treatment and the first rinse step has to be as short as possible, to prevent formation of draining structures on the plastics surface.
  • the first rinse should take at least 1 minute and should be performed with efficient agitation of the plastics substrate in the rinse, in order to remove any organic solvent from the substrate matrix.
  • adhesion seems to significantly depend on the extent water is absorbed into a polyamide plastics part and also being adsorbed on the surface thereof.
  • Such assumption may, for example, be derived from the fact that caustic will not be able to pre-treat the surface of the polyamide or polyoxymethylene plastics substrate such that sufficient adhesion of a metal layer thereon will be attained.
  • Caustic is assumed to break the amide bonds or polyamide plastics material, too, but it will also introduce much water into the polymer matrix due to its strong hydrophilization properties and thus impedes sufficient adhesion of the metal layer. Similar effects will be brought about with polyoxymethylene.
  • Adhesion of the metal layer to the polyamide or polyoxymethylene plastics substrate may be higher than a metal layer to an ABS substrate, though roughness of the polyamide and polyoxymethylene plastics surfaces is much lower than that of an ordinarily pre-treated ABS plastics surface. This observation may be attributed to electrostatic interactions between the metal layer and the polyamide or polyoxymethylene plastics surface, which is more polar than the ABS plastics surface. Such higher adhesion will be obtained with polyamide or polyoxymethylene plastics surfaces after any water being adsorbed to the interface between the metal layer and the plastics surface and absorbed into the plastics material has been distributed all over the plastics material. Such distribution may be brought forward by the porosity of the polyamide and polyoxymethylene plastics material.
  • the plastics substrates are brought into contact with the pre-treatment solution, optionally the reducing solution, the electroless metal plating solution and the rinse liquids by immersing them into these liquids or by spraying or splashing the solutions to the plastics substrate surfaces.
  • the plastics parts may either be secured to racks, or contained in a drum, or be conveyed through a treatment apparatus, which may for holding the parts be equipped with baskets on which the parts are deposited.
  • a pre-treatment solution To prepare a pre-treatment solution, to 1 litre of an aqueous solution containing 200 ml/l diethylene glycol monomethyl ether and 40 ml/l 37 wt.-% hydrochloric acid 250 ⁇ l of a solution of palladium dichloride, which contained the palladium salt at a concentration of 10 wt.-%, referring to the palladium content, 0.5 ml of a 30 wt.-% solution of the conditioner Lugalvan ® (trade mark of BASF, Germany) PVI and 0.1 g sodium lauryl sulfonate were added. Thus, the concentration of Pd 2+ was 25 mg/l in the pre-treatment solution.
  • the pre-treatment solution formed was clear and slightly yellowish. This solution was heated and held at a temperature of 40°C.
  • the nickel layer deposited was subsequently copper electroplated (Cupracid ® (trade mark of Atotech, Germany) Ultra), with 2.5 A/dm 2 cathodic current density, until a metal layer thickness of about 30 ⁇ m was attained. After rinsing, the plate was stored for 1 hour at 70°C. Then a stripe having a width of 1 cm was cut from each plate and copper peeled off the strip using a tensile testing machine (Instron ® (trade mark of Instron Corp., USA)). The adhesion of metal to the polyamide plastics part was measured to be 1.10 N/mm.
  • Example 1 the concentration of Pd 2+ in the pre-treatment solution was varied and the amount of Pd [mg/m 2 ] measured depending on the Pd 2+ concentration (dissolution of Pd from a plate having a defined surface area using nitric acid and determination of Pd amount in the nitric acid solution by AAS (atomic absorption spectrometry)).
  • the amount of Pd adsorbed on the polyamide plastics parts is given in Table 1.
  • Table 1 Amount of Pd on polyamide plastics plates Palladium Concentration [mg/l] Palladium Amount Adsorbed [mg/m 2 ] 40 12.7 60 18.0 80 23.2 100 25.2 120 30.7
  • Example 1 Further experiments have been performed to evaluate maximum temperature of the pre-treatment solution. For this purpose Example 1 was repeated. An upper temperature of 40°C was considered appropriate to assure that no streaks formed if the polyamide plastics parts treated were transferred from a container containing the pre-treatment solution to a first rinse tank. If temperature was selected to be higher than 40°C too much solvent proved to be evaporated during the transfer so that the components of the pre-treatment solution contained in the liquid film adhering to the plastics surface concentrated, further reacted with the plastics surface and thus uneven conditions occurred at the plastics surface (formation of relief-like structure).
  • Example 1 The procedure of Example 1 was repeated. Instead of hydrochloric acid 40 ml/l formic acid (about 98 wt.-%) were used. After copper electroplating adhesion of the metal layer on the plastics strip was found to amount to 1.85 N/mm.
  • Example 1 The procedure of Example 1 was repeated. Instead of Durethan ® BM240 Minlon ® (trade mark of E.I. Du Pont de Nemours, USA) 73M40 (polyamide 6.6) was used. The dimensions of the plastics part were the same as before. Adhesion of the metal layer to the plastics surface was determined to be 0.97 N/mm.
  • a pre-treatment solution To prepare a pre-treatment solution, to 1 litre of an aqueous solution containing 150 ml/l diethylene glycol monoethyl ether acetate and 100 ml/l 98 wt.-% formic acid 0.50 ml of a palladium sulfate solution, which contained the palladium salt at a concentration of 4 wt.-%, referring to the palladium content, and 0.1 g sodium lauryl sulfonate were added. Thus concentration of Pd 2+ was 20 mg/l in the pre-treatment solution. The pre-treatment solution formed was heated and held at a temperature of 40°C.
  • a 3 mm thick plate made from Durethan ® BM 420 which had a width of 5 cm and a length of 7 cm was treated in the pre-treatment solution for 10 minutes while slightly agitating the plate in the solution. Thereafter, the plate was rinsed with cold tap water and afterwards held in the water for another 2 minutes while slightly agitating same. Then the plate was nickel-plated for 10 minutes at a temperature of 45°C in a commercial electroless nickel-plating bath which contained 3 g/l nickel and 20 g/l sodium hypophosphite. The nickel layer deposited was subsequently copper electroplated. After rinsing, the plate was stored for 1 hour at 70°C. As described previously, adhesion between the plastics surface and the metal layer was tested and measured to be 1.64 N/mm.
  • Example 1 was repeated with the palladium ion concentration in the pre-treatment solution being, in this case, 50 mg/l, different acids and acid combinations as well as the organic solvent (diethylene glycol monoethyl ether) being used at different concentrations.
  • the temperature of the pre-treatment solution was 30°C. Duration of treatment in the pre-treatment solution was 6 minutes. Adhesion values measured are shown in a graph in Fig. 1 .
  • Fig. 1 shows that best results with respect to adhesion of the nickel/copper layer on the polyamide strip were obtained using 150 ml/l hydrochloric acid (37 wt.-%) and 100 ml/l phosphoric acid. Best adhesion was achieved if the organic solvent concentration was set to a relatively low value (50 ml/l for example). Further, if the concentration of the acids used is rather low, concentration of the solvent has preferably to be increased to a concentration higher than 50 ml/l. Some difference in adhesion values was in fact observed on either side of the plates. This was attributed to different moulding conditions on the two sides of the plate.

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EP06077232A 2006-12-08 2006-12-18 Solution de prétraitement et procédé de formation d'une couche d'un métal de revêtement sur un substrat doté d'une surface en plastique Withdrawn EP1942207A1 (fr)

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EP2639332A1 (fr) * 2012-03-15 2013-09-18 Atotech Deutschland GmbH Procédé de métallisation de surfaces en matière synthétique non conductrices
US9364822B2 (en) 2013-06-28 2016-06-14 Rohm And Haas Electronic Materials Llc Catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds
WO2022207559A1 (fr) * 2021-03-29 2022-10-06 Hso Herbert Schmidt Gmbh & Co. Kg Décapage de polyamide
EP3144414B1 (fr) * 2015-09-21 2022-11-23 Airbus Defence and Space GmbH Traitement enzymatique d'objets en polyamide à des fins de métallisation

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EP2639333A1 (fr) * 2012-03-15 2013-09-18 Atotech Deutschland GmbH Procédé de métallisation de surfaces en matière synthétique non conductrices
CN108890940A (zh) * 2012-05-14 2018-11-27 汽车专利管理和利用有限公司 塑料制复合材料组件
LT6070B (lt) * 2012-12-07 2014-09-25 Atotech Deutschland Gmbh Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas
CN107923043A (zh) * 2015-07-30 2018-04-17 巴斯夫欧洲公司 将塑料表面金属化的方法
US10822703B2 (en) * 2015-07-30 2020-11-03 Basf Se Process for pretreatment of plastic surfaces for metallization
CN109778152A (zh) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 一种高比表面积钯/聚合物复合膜的改进化学镀方法
CN108251874B (zh) * 2018-01-24 2019-08-16 永星化工(上海)有限公司 适于电镀的功能性树脂组合物上涂布金属层的预处理溶液
US20220213600A1 (en) * 2019-05-17 2022-07-07 Fundación Cidetec Light permeable metallic coatings and method for the manufacture thereof
CN113293362B (zh) * 2021-05-25 2022-02-11 吉安宏达秋科技有限公司 一种化学镀铜膨松液及其制备方法和应用

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EP2639332A1 (fr) * 2012-03-15 2013-09-18 Atotech Deutschland GmbH Procédé de métallisation de surfaces en matière synthétique non conductrices
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EP3144414B1 (fr) * 2015-09-21 2022-11-23 Airbus Defence and Space GmbH Traitement enzymatique d'objets en polyamide à des fins de métallisation
WO2022207559A1 (fr) * 2021-03-29 2022-10-06 Hso Herbert Schmidt Gmbh & Co. Kg Décapage de polyamide

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