WO2022043241A1 - Procédé de métallisation d'un substrat non métallique et composition de prétraitement - Google Patents

Procédé de métallisation d'un substrat non métallique et composition de prétraitement Download PDF

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Publication number
WO2022043241A1
WO2022043241A1 PCT/EP2021/073224 EP2021073224W WO2022043241A1 WO 2022043241 A1 WO2022043241 A1 WO 2022043241A1 EP 2021073224 W EP2021073224 W EP 2021073224W WO 2022043241 A1 WO2022043241 A1 WO 2022043241A1
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Prior art keywords
manganese
treatment composition
composition
species
ions
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PCT/EP2021/073224
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English (en)
Inventor
Brigitte Dyrbusch
Franziska Finn
Carl Christian Fels
Original Assignee
Atotech Deutschland GmbH & Co. KG
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Application filed by Atotech Deutschland GmbH & Co. KG filed Critical Atotech Deutschland GmbH & Co. KG
Priority to CA3190838A priority Critical patent/CA3190838A1/fr
Priority to CN202180052417.0A priority patent/CN116134175A/zh
Priority to EP21766456.4A priority patent/EP4204601A1/fr
Priority to US18/042,852 priority patent/US20230357932A1/en
Priority to JP2023513484A priority patent/JP2023539605A/ja
Priority to KR1020237009607A priority patent/KR20230054853A/ko
Priority to BR112023003111A priority patent/BR112023003111A2/pt
Publication of WO2022043241A1 publication Critical patent/WO2022043241A1/fr

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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
    • C23C18/18—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
    • C23C18/2053—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 only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • 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
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • 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
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—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
    • C23C18/31—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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 metallizing a non-metallic substrate, the method comprising the steps (A) to (C), wherein step (A) is a pre-treatment step for etching and step (C) the metallization step.
  • step (A) a pre-treatment composition is utilized comprising individual manganese (II), (III), and (IV) species.
  • the present invention furthermore relates to a specific pre-treatment composition.
  • Metallizing non-metallic substrates such as plastic substrates has a long history in modern technology. Typical applications are found in automotive industry as well as for sanitary articles.
  • compositions comprising environmentally questionable chromium species, such as hexavalent chromium species. Although these compositions usually provide very strong and acceptable etching results, environmentally friendly alternatives are more and more demanded and to a certain extent already provided in the art.
  • WO 2018/095998 A1 refers to a chrome free etch for plating on plastic processes, wherein plastic surfaces are contacted in a first step with an etching solution at least comprising Mn(IV)-ions and, in a second etching step, with a solution at least comprising Mn(lll)- and Mn(VII)-ions prior to the plating step.
  • EP 3 584 352 A1 refers to a pretreatment composition for electroless plating and a respective pretreatment method exhibiting high plating deposition performance without using harmful chromic acid and expensive palladium, while reducing the number of steps.
  • EP 0 913 498 A1 refers to a process combining surface treatment and metal deposition.
  • a respective aqueous solution comprises a metal activator, such as an oxidized species of silver, cobalt, ruthenium, cerium, iron, manganese, nickel, rhodium, or vanadium.
  • the activator can be suitably oxidized to a higher oxidation state electrochemically.
  • EP 2 025 708 A1 refers to an etching solution comprising Mn(VII) ions.
  • EP 2 937 446 B1 refers to a composition for etching treatment of a resin material, the composition comprising permanganate ions.
  • US 2017/159183 A1 refers to a resin plating method using an etching bath containing manganese as an active ingredient.
  • US 8,603,352 B1 refers to a chrome-free composition of an acidic suspension of manganese compounds and manganese ions are applied to an organic polymer surface to etch the surface.
  • the suspension comprises one or more undissolved Mn(ll) compounds, or one or more undissolved Mn(lll) compounds, or mixtures thereof, dissolved Mn(ll) ions and dissolved Mn(lll) ions, and one or more acids.
  • CN 110172684 A refers to the formulation and preparation of a chromium-free roughening solution for ABS plastics.
  • manganese species are utilized instead of chromium ions.
  • certain manganese species inherently have specific disadvantages.
  • manganese (VII) species typically form difficult to handle manganese dioxide, which often adsorbs on the surface of the substrate and needs to be chemically reduced in order to dissolve it.
  • the etching process additionally affects the overall quality of the subsequently deposited outermost metal layer, in particular in terms of glance/brightness and surface roughness. This is in particular observed if the outermost metal layer is a chromium layer. Since the optical appearance of the outermost metal layer is desired to be as perfect as possible, a suitable method for metallizing starts with a well-balanced etching step.
  • the total concentration of manganese (IV) species is higher than the combined concentration of manganese (II) and (III) species,
  • step (A) contacting said substrate with manganese species is carried out in a single step.
  • the present invention is primarily based on a specifically designed pre-treatment composition utilized in step (A); most preferably in combination with a metalizing composition comprising nickel for nickel plating in step (C).
  • Said specifically designed pre-treatment composition comprises individual manganese (II), (III), and (IV) species. This means that throughout the method, the pre-treatment composition comprises at least three distinct manganese species, which are different from each other. All three species are simultaneously present.
  • the term “manganese (II), (III), and (IV)” denotes the element manganese with the oxidation numbers +2, +3, and +4, respectively, in respective compounds and/or ions.
  • Preferred is a method of the present invention, wherein the individual manganese (II), (III), and (IV) species are present in a steady state in the pre-treatment composition during step (A).
  • the method of the present invention results in a unique, fine sponge-like etch pattern/struc- ture leading to a sufficient roughening of the substrate without causing too deep or large cavities (i.e. soft etching).
  • deep and/or large cavities are typically desired in order to obtain a strong adhesion to a metal layer, our own investigations show that such deep/strong cavities often negatively affect the optical appearance of the final decorative layer (e.g. a chromium layer), in particular in terms of brightness and uniformity.
  • Such deep/strong cavities (which are undesired in the context of the present invention) are typically obtained if the substrate is contacted with a composition comprising suitable amounts of manganese (VII) species, in particular permanganate ions.
  • said fine spongelike etch pattern/structure which is seemingly a disadvantage, is in fact a great advantage of the present invention.
  • the substrates are of varying manufacturing quality; a problem sometimes observed for substrates comprising butadiene moi- eties, preferably polybutadiene.
  • Often such defects are a result of varying manufacturing parameters during a casting process, typically leading to an inhomogeneous material distribution or other manufacturing defects.
  • Such defects are not necessarily outwardly seen right from the beginning but often become obvious or at least pronounced during the pretreatment step.
  • the pre-treatment step pronounces such defects, the optical quality of a respective metallized substrate is in many cases deteriorated particularly at such areas of the substrate.
  • the method of the present invention did not only produced fine results with high quality substrates but still very acceptable results for substrates with manufacturing defects, i.e. lower manufacturing quality. In most cases a still very homogeneous optical appearance of the metallized substrate was obtained due to the less pronounced manufacturing defects. As a result, the method of the present invention allows a metallization of substrates that otherwise would be discarded.
  • an electrical current is applied to the pre-treatment composition such that manganese (II) species are oxidized to manganese (III) species, preferably continually.
  • step (A) no strongly adhering particulate manganese dioxide is formed during step (A) which otherwise must be chemically reduced by contacting the substrate with a composition comprising a reducing agent. Instead, it is easily removed by a simple rinsing, which is typically anyways applied (preferably with water). Since it does not strongly adhere to the substrate (i.e. they are not incorporated onto the substrate), removal is quickly and easily accomplished.
  • the electrical current allows to keep the individual manganese (II), (III), and (IV) species in individual and comparatively constant concentration ranges, which would be not achievable without an electrical current. Furthermore, some manganese species, in particular the manganese (III) species, would not be present without the applied electrical current. As a result, without wishing to be bound to any theory, the presence of the individual manganese (II), (III), and (IV) species in the pre-treatment composition, caused by the electrical current, are essential to achieve the advantages mentioned above. The manganese species primarily needed for the excellent pre-treating result is believed to be the manganese (IV) species.
  • the electrical current preferably decomposes water that typically accumulates in the pre-treatment composition, e.g. due to hygroscopic effects.
  • the quality of the pretreatment composition maintains stable (e.g. in terms of density).
  • the method of the present invention primarily includes a contacting with a specific pretreatment composition in order to obtain a particularly pre-treated substrate.
  • step (A) is a method of the present invention, wherein in step (A) the pre-treatment composition is an etching-composition for etching the non-metallic substrate, preferably a non- metallic substrate as defined as being preferred throughout the present text.
  • the non-metallic substrate is a substrate for forming the non-metallic substrate.
  • the non-metallic substrate comprises, preferably is, a non-conductive substrate.
  • the non-metallic substrate comprises, preferably is, a plastic substrate.
  • the non-metallic substrate (and the non-conductive substrate, respectively) comprises butadiene moieties, preferably polybutadiene.
  • non-metallic substrate and the non-conductive substrate, respectively
  • the non-metallic substrate comprises nitrile moieties.
  • non-metallic substrate and the non-conductive substrate, respectively
  • the non-metallic substrate comprises acryl moieties
  • the non-metallic substrate comprises styrene moieties.
  • the non-metallic substrate comprises, preferably is, acrylonitrile-butadiene-styrene (ABS) and/or acrylonitrile-butadi- ene-styrene-polycarbonate (ABS-PC).
  • ABS acrylonitrile-butadiene-styrene
  • ABS-PC acrylonitrile-butadi- ene-styrene-polycarbonate
  • the pre-treatment composition :
  • the pre-treatment composition utilized in the method of the present invention comprises water.
  • the pre-treatment composition comprises less than 50 wt.-% water, based on the total weight of the pre-treatment composition, preferably 45 wt.-% or less, more preferably 40 wt.-% or less, even more preferably 35 wt.-% or less, yet even more preferably 30 wt.-% or less, most preferably 25 wt.-% or less.
  • the pre-treatment composition comprises water ranging from 0 wt.-% to 25 wt.-%, based on the total weight of the pre-treatment composition, preferably from 0.1 wt.-% to 21 wt.-%, more preferably from 1 wt.-% to 18 wt.-%, even more preferably from 2 wt.-% to 16 wt.-%, yet even more preferably from 5 wt.-% to 14 wt.-%, most preferably from 8 wt.-% to 12 wt.-%. Most preferably, water is the only solvent in the pre-treatment composition.
  • the pre-treatment composition comprise specific manganese species.
  • Other manganese species are less preferred or are most preferably to be avoided entirely.
  • step (A) the pre-treatment composition is substantially free of, preferably does not comprise, manganese (VII) species, or only up to a total concentration of 100 mg/L, based on the total volume of the pre-treatment composition and on the element manganese, preferably only up to a total concentration of 75 mg/L, more preferably only up to a total concentration of 50 mg/L, even more preferably only up to a total concentration of 35 mg/L, most preferably only up to a total concentration of 20 mg/L, even most preferably only up to a total concentration of 10 mg/L. Own experiments indicate that an insignificant low amount (e.g.
  • the pre-treatment composition comprises manganese (VII) species in a concentration from 0 mg/L to 10 mg/L, based on the total volume of the pre-treatment composition.
  • manganese (VII) species are preferably formed (preferably only) in situ, most preferably up to a concentration range as defined above. This means that manganese (VII) species, are preferably not intentionally/purposely added to the pre-treatment composition.
  • Preferred is a method of the present invention, wherein in step (A) the pre-treatment composition is substantially free of, preferably does not comprise, permanganate ions, or only up to a total concentration of 100 mg/L, based on the total volume of the pre-treatment composition and the element manganese, preferably only up to a total concentration of 75 mg/L, more preferably only up to a total concentration of 50 mg/L, even more preferably only up to a total concentration of 35 mg/L, most preferably only up to a total concentration of 20 mg/L, even most preferably only up to a total concentration of 10 mg/L.
  • the aforementioned regarding manganese (VII) species preferably applies likewise.
  • permanganate ions are preferably formed (preferably only) in situ, most preferably up to a concentration range as defined above. This means, that permanganate ions are preferably not intentionally/purposely added to the pre-treatment composition.
  • the pre-treatment composition is substantially free of, preferably does not comprise, a methane sulfonic acid and salts thereof, preferably is substantially free of, preferably does not comprise, a C1 to C4 alkyl sulfonic acid and salts thereof, most preferably is substantially free of, preferably does not comprise, a C1 to C4 sulfonic acid and salts thereof. It appears that such compounds negatively affect the water balance in a respective pre-treatment composition.
  • the pre-treatment composition is substantially free of, preferably does not comprise, bromide and iodide anions, preferably is substantially free of, preferably does not comprise, chloride, bromide, and iodide anions, most preferably is substantially free of, preferably does not comprise, halide anions.
  • the pre-treatment composition is substantially free of, preferably does not comprise, trivalent chromium ions and hexavalent chromium compounds, preferably is substantially free of, preferably does not comprise, any compounds and ions comprising chromium.
  • the pre-treatment composition is substantially free of, preferably does not comprise, manganese (V) species, or only up to a total concentration of 100 mg/L, based on the total volume of the pre-treatment composition and the element manganese, preferably only up to a total concentration of 75 mg/L, more preferably only up to a total concentration of 50 mg/L, even more preferably only up to a total concentration of 35 mg/L, most preferably only up to a total concentration of 20 mg/L, even most preferably only up to a total concentration of 10 mg/L.
  • manganese (V) species are not detectable, preferably via UV/VIS spectroscopy.
  • the pre-treatment composition is substantially free of, preferably does not comprise, manganese (VI) species, or only up to a total concentration of 100 mg/L, based on the total volume of the pre-treatment composition and the element manganese, preferably only up to a total concentration of 75 mg/L, more preferably only up to a total concentration of 50 mg/L, even more preferably only up to a total concentration of 35 mg/L, most preferably only up to a total concentration of 20 mg/L, even most preferably only up to a total concentration of 10 mg/L.
  • manganese (VI) species are not detectable, preferably via UV/VIS spectroscopy.
  • they are not intentionally/purposely added to the pre-treatment composition.
  • the pre-treatment composition comprises individual manganese (II), (III), and (IV) species.
  • Preferred is a method of the present invention, wherein during step (A) in the pre-treatment composition the total amount of all manganese species is more than 5.0 g/L, based on the total volume of the pre-treatment composition and the element manganese, preferably is 5.4 g/L or more, even more preferably is 5.8 g/L or more, most preferably is 6.0 g/L or more.
  • a preferred maximum concentration is up to 7.5 g/L, based on the total volume of the pre-treatment composition and the element manganese, preferably up to 7.2 g/L, more preferably up to 7.0 g/L, even more preferably up to 6.8 g/L, yet even more preferably up to 6.6 g/L, most preferably up to 6.3 g/L.
  • the manganese (II) species comprise, preferably are, Mn(ll) ions.
  • the manganese (II) species have a total concentration in a range from 0.1 g/L to 0.8 g/L, based on the total volume of the pre-treatment composition and the element manganese, preferably from 0.15 g/L to 0.7 g/L, more preferably from 0.2 g/L to 0.6 g/L, most preferably from 0.25 g/L to 0.5 g/L.
  • This preferably includes all manganese species as long as the element manganese has the oxidation number +2.
  • a preferred source of manganese (II) species is manganese (II) sulfate.
  • manganese (III) species comprise, preferably are, Mn(lll) ions.
  • step (A) in the pre-treatment composition the manganese (III) species have a total concentration in a range from 0.2 g/L to 1.9 g/L, based on the total volume of the pre-treatment composition and the element manganese, preferably from 0.3 g/L to 1.5 g/L, more preferably from 0.4 g/L to 1.2 g/L, even more preferably from 0.5 g/L to 1.0 g/L, most preferably from 0.6 g/L to 0.8 g/L.
  • the manganese (III) species have a higher total concentration than the manganese (II) species.
  • concentrations in g/L based on the total volume of the pre-treatment composition and the element manganese in these manganese species.
  • the manganese (IV) species comprise colloidal manganese (IV) species, preferably comprise a mixture of colloidal manganese (IV) species and manganese (IV) ions.
  • the manganese (IV) species have a total concentration in a range from 1.5 g/L to 5.0 g/L, based on the total volume of the pre-treatment composition and the element manganese, preferably from 1.8 g/L to 4.5 g/L, more preferably from 2.0 g/L to 4.0 g/L, even more preferably from 2.2 g/L to 3.5 g/L, most preferably from 2.4 g/L to 3.0 g/L.
  • the colloidal manganese (IV) species comprises manganese dioxide.
  • the total concentration of manganese (IV) species is higher than the combined concentration of manganese (II) and (III) species.
  • manganese (IV) species based on the total weight of all manganese species and the element manganese, preferably 59 wt.-% or more, more preferably 63 wt.-% or more, even more preferably 67 wt.-% or more, most preferably 70 wt.-% or more.
  • the pre-treatment composition is acidic, preferably has a pH of 3.0 or below, more preferably of 2.1 or below, even more preferably of 1.5 or below, most preferably of 1.0 or below, even most preferably of 0.7 or below.
  • the strong acidic condition is a result of acids being present in the pretreatment composition.
  • the pre-treatment composition additionally comprises
  • the pre-treatment composition comprises sulfuric acid in a total concentration of 10 mol/L or less, based on the total volume of the pre-treatment composition, preferably of 9.6 mol/L or less, more preferably of 9.1 mol/L or less, most preferably of 8.6 mol/L or less.
  • the pre-treatment composition comprises sulfuric acid in a total concentration of at least 3.0 mol/L, based on the total volume of the pre-treatment composition, preferably of at last 3.5 mol/L, more preferably of at least 4.0 mol/L, most preferably of at least 4.5 mol/L.
  • the pre-treatment composition comprises at least a combination of sulfuric acid and phosphoric acid, wherein the phosphoric acid has a higher concentration than the sulfuric acid, preferably the molar ratio of phosphoric acid to sulfuric acid is in a range from 1.1 : 1 to 3 : 1 , more preferably is in a range from 1.3 : 1 to 2.6 : 1 , even more preferably is in a range from 1.4 : 1 to 2.4 : 1 , yet even more preferably is in a range from 1.5 : 1 to 2.1 : 1 , most preferably is in a range from 1.6 : 1 to 2.0 : 1.
  • the phosphoric acid has a higher concentration than sulfuric acid.
  • sulfuric acid incorporates a comparatively high amount of water due to hygroscopic effects. This leads to an undesired dilution of the pre-treatment composition. If the concentration of sulfuric acid is minimized to the best extent possible, such a dilution is minimized too. Own experiments have shown that the concentrations and molar ratios as defined above for sulfuric acid result in an excellent balance between water accumulation on the one hand and water decomposition by means of the electrical current on the other hand. This allows to keep the pre-treatment composition under stable condition (stable water-balance).
  • the pre-treatment composition has an absorbance of more than 1 .0, referenced to a wavelength of 400 nm and preferably a path length of 1 cm, preferably in a range from 1.1 to 2.1 , more preferably from 1.2 to 2.0, most preferably from 1.3 to 1.7. If the absorbance is significantly below 1.0, typically an undesired low adhesion between the non-metallic substrate and the metal layers applied in step (C) is often observed (e.g. ⁇ 0.5 N/cm). In contrast, if the absorbance is above 1.0, more particularly in the preferred ranges as mentioned above, typically a good adhesion (e.g. >1.0 N/cm) is even observed. This parameter is a preferred quality parameter to evaluate whether the three manganese species are properly present in the pre-treatment composition.
  • the absorbance (also named extinction) is determined via LIV/VIS spectroscopy with a path length of 1 cm at 400 nm (Beer-Lambert law).
  • the pre-treatment composition additionally comprises
  • the one or more than one species of additional transition metal ions different from manganese comprise silver ions, said silver ions preferably having a total concentration in a range from 4 mmol/L to 25 mmol/L, based on the total volume of the pre-treatment composition, preferably from 6 mmol/L to 20 mmol/L, more preferably from 8 mmol/L to 17 mmol/L, most preferably from 10 mmol/L to 14 mmol/L.
  • said silver ions are the only additional transition metal ions.
  • the aforementioned total concentration of silver ions includes silver ions with any oxidation number.
  • silver ions are preferably present, halide ions, in particular chloride ions, are to be avoided to prevent precipitation.
  • the pre-treatment composition additionally comprises
  • the one or more than one wetting agent preferably the fluorinated wetting agent
  • the pre-treatment composition in a total concentration in a range from 0.001 g/L to 1.0 g/L, based on the total volume of the pre-treatment composition, preferably in a range from 0.005 g/L to 0.7 g/L, more preferably in a range from 0.01 g/L to 0.5 g/L, even more preferably in a range from 0.02 g/L to 0.3 g/L, most preferably in a range from 0.03 g/L to 0.15 g/L.
  • the fluorinated wetting agent is partly or fully fluorinated or a mixture thereof (if e.g. more than one wetting agent is present).
  • the pre-treatment composition additionally comprises
  • (A-e) peroxomonosulfate anions and/or peroxodisulfate anions preferably in a total concentration in a range from 0.01 g/L to 10.0 g/L, based on the total volume of the pre-treatment composition, preferably from 0.05 g/L to 7.0 g/L, more preferably from 0.1 g/L to 4.0 g/L, even more preferably from 0.2 g/L to 2.0 g/L, most preferably from 0.1 g/L to 0.5 g/L.
  • the pre-treatment composition additionally comprises
  • (A-f) peroxomonophosphate anions and/or peroxodiphospate anions preferably in a total concentration in a range from 0.01 g/L to 10.0 g/L, based on the total volume of the pre-treatment composition, preferably from 0.05 g/L to 9.0 g/L, more preferably from 0.07 g/L to 8.0 g/L, even more preferably from 0.09 g/L to 7.0 g/L, most preferably from 0.1 g/L to 5.0 g/L.
  • the pre-treatment composition additionally comprises
  • (A-g) nitrate anions preferably in a total concentration in a range from 0.01 g/L to 20.0 g/L, based on the total volume of the pre-treatment composition, preferably from 0.05 g/L to 17.0 g/L, more preferably from 0.1 g/L to 13.0 g/L, even more preferably from 0.25 g/L to 9.0 g/L, most preferably from 0.5 g/L to 5.0 g/L.
  • the source of nitrate anions is silver nitrate.
  • the total concentration of nitrate anions corresponds to the total concentration of silver ions.
  • the only source of silver ions and nitrate anions is silver nitrate.
  • aforementioned components (A-c), (A-e), (A-f), and (A-g) support the electrochemical reactions in the pre-treatment composition.
  • the pre-treatment composition has a density in a range from 1.50 g/cm 3 to 1.90 g/cm 3 , referenced to a temperature of 25°C, preferably from 1.55 g/cm 3 to 1.80 g/cm 3 , more preferably from 1.60 g/cm 3 to 1.70 g/cm 3 , most preferably from 1.61 g/cm 3 to 1.68 g/cm 3 .
  • a density range indicates that a suitable water-balance is provided.
  • step (A) primarily polybutadiene is pre-treated, preferably etched, if the substrate comprises, preferably is, acrylonitrile-bu- tadiene-styrene (ABS) and/or acrylonitrile-butadiene-styrene-polycarbonate (ABS-PC), most preferably polybutadiene is more pre-treated, preferably etched, than the acrylonitrile styrene.
  • ABS acrylonitrile-bu- tadiene-styrene
  • ABS-PC acrylonitrile-butadiene-styrene-polycarbonate
  • a composition comprising permanganate ions preferably is additionally not contacted with a composition comprising manganese (VII) species.
  • a method of the present invention wherein the substrate and pre-treated substrate, respectively, is not contacted with any composition comprising permanganate ions in a total concentration of 2 g/L or more, based on the total volume of said composition, preferably of 1 g/L or more, even more preferably of 500 mg/L or more, yet even more preferably of 250 mg/L or more, most preferably of 150 mg/L or more.
  • step (A) substantially no, preferably no, manganese dioxide (MnC>2) is incorporated onto the pre-treated substrate.
  • MnC>2 manganese dioxide
  • step (A) substantially no, preferably no, manganese dioxide (MnC>2) is incorporated onto the pre-treated substrate.
  • no step is needed (and therefore not applied) in order to reduce manganese dioxide on the pre-treated substrate; i.e. in order to dissolve MnC>2 by chemical reduction through a reducing agent.
  • the pre-treated substrate obtained after step (A) is not contacted with a respective composition comprising a reducing agent.
  • step (A) or prior to step (B) manganese dioxide adsorbed on the pre-treated substrate (preferably if present) is removed by rinsing, preferably by rinsing with water, more preferably by rinsing with water free of a reducing agent capable to chemically reduce manganese dioxide.
  • step (A) or prior to step (B) the pre-treated substrate is not contacted with a composition comprising a reducing agent capable to chemically reduce manganese dioxide, preferably is not contacted with a composition comprising any reducing agent.
  • step (A) the pre-treatment composition has a temperature in a range from 15°C to 60°C, preferably from 20°C to 55°C, more preferably from 27°C to 50°C, even more preferably from 34°C to 46°C, most preferably from 38°C to 43°C.
  • step (A) is carried out for a time ranging from 1 minute to 25 minutes, preferably from 5 minutes to 20 minutes, most preferably from 10 minutes to 18 minutes.
  • step (A) Preferred is a method of the present invention, wherein during step (A) the electrical current is continuously applied.
  • step (A) the manganese (III) species is continuously formed through the electrical current.
  • the electrical current has an anodic current density in a range from 0.1 A/dm 2 to 20 A/dm 2 , preferably from 0.8 A/dm 2 to 15 A/dm 2 , more preferably from 1 .5 A/dm 2 to 10 A/dm 2 , most preferably from 2.1 A/dm 2 to 5.0 A/dm 2 .
  • step (A) the pre-treatment composition is exposed to a current load by the electrical current ranging from 0.5 Ah/L to 100 Ah/L, based on the total volume of the pre-treatment composition, preferably ranging from 1.0 Ah/L to 70 Ah/L, more preferably ranging from 2.0 Ah/L to 50 Ah/L, most preferably ranging from 4.0 Ah/L to 30 Ah/L.
  • step (A) is carried out in a pretreatment compartment comprising at least one cathode and at least one anode, preferably comprising at least one cathode, at least one anode, and at least one membrane, such that said manganese (II) species are oxidized to said manganese (III) species in the pre-treat- ment compartment.
  • step (A) is carried out in a pre-treatment compartment fluidically connected with an oxidizing compartment, the oxidizing compartment comprising at least one cathode and at least one anode, preferably comprising at least one cathode, at least one anode, and at least one membrane, such that said manganese (II) species are oxidized to said manganese (III) species in the oxidizing compartment.
  • the pre-treatment compartment preferably does not comprise a cathode and an anode.
  • the pre-treatment composition preferably circulates continually or semi-continually between the pre-treatment compartment and the oxidizing compartment.
  • Preferred is a method of the present invention, wherein the electrical current is applied in the oxidizing compartment.
  • the at least one anode comprises a mixed metal anode or a graphite anode.
  • a preferred mixed metal anode comprises at least two of lead, tin, silver, titanium, and platinum.
  • a more preferred mixed metal anode comprises at least lead and tin, even more preferably at least lead, tin, and silver.
  • Our own experiments have shown that the preparation of a respective pre-treatment composition while using anodes comprising lead, tin, and silver, is significantly shorter than using anodes comprising lead and tin but without silver.
  • a mixed metal anode comprising lead, 0.1 wt.-% to 3.0 wt.-% silver, and 1 .0 wt.-% to 10.0 wt.-% tin, based on the total weight of the mixed metal anode.
  • the balance to 100 wt.-% is lead.
  • the at least one cathode is a mixed metal cathode or a graphite cathode, preferably is a mixed metal cathode, even more preferably comprising at least lead and tin, most preferably is a mixed metal cathode comprising at least lead and 1.0 wt.-% to 10.0 wt.-% tin, based on the total weight of the at least one cathode.
  • step (B) of the method of the present invention the pre-treated substrate is contacted with an activation composition.
  • Step (A) includes all steps carried out prior to step (B), preferably including a rinsing and further optional steps carried out prior to and/or after step (A), e.g. a swelling and/or a conditioning step.
  • a method of the present invention comprising prior to step (B) but after the contacting with the pre-treatment composition a conditioning step with a conditioning composition, i.e. a contacting with a conditioning composition. Own experiments have shown that such a conditioning step significantly increases (and thereby improves) the adsorption of palladium in step (B). In other words, the total amount of palladium adsorbed and attached, respectively, on the non-metallic substrate after step (B) is finished, is significantly increased compared to a method of the present invention without such a conditioning step. In some cases, the adsorbed, respectively attached, total amount is sufficient for a subsequent so-called direct metallization. Generally, such a conditioning step reduces the amount of wasted palladium due to the increased adsorption (and therefore increased efficiency) in step (B).
  • the non-metallic substrate is rinsed in a rinse step, preferably is at least once rinsed with water.
  • the conditioning composition is alkaline, preferably has a pH ranging from 9 to 14, more preferably from 10 to 13.5, even more preferably from 11 to 13, most preferably from 11.5 to 12.5.
  • the conditioning composition comprises an amine-compound, preferably a diamine-compound. More preferred is a method of the present invention, wherein the conditioning composition comprises at least two amine-compounds, preferably at least two diamine-compounds.
  • a preferred amine-compound and diamine-compound, respectively, comprises an alkyl moiety, preferably an alkyl moiety having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, most preferably 2 to 6 carbon atoms. Most preferably this denotes an alkylene, i.e. a divalent, moiety if it relates to a diamine.
  • a very preferred diamine-compound comprises hexane diamine, i.e. hexamethylene diamine (most preferably hexane-1 ,6-diamine) and/or ethane diamine, i.e. ethylene diamine (most preferably ethane-1 ,2-diamine).
  • the conditioning composition has a temperature ranging from 25°C to 50°C, preferably from 28°C to 46°C, more preferably from 30°C to 42°C, even more preferably from 32°C to 39°C, most preferably from 34°C to 37°C.
  • step (B) is a step separated and independently from step (A).
  • the pre-treatment composition utilized in step (A) is not the activation composition utilized in step (B).
  • step (B) the activation composition comprises palladium, preferably dissolved palladium ions or colloidal palladium, most preferably colloidal palladium.
  • the colloidal palladium comprises tin.
  • the activation composition comprises palladium in a total concentration ranging from 20 mg/L to 200 mg/L, based on the total volume of the activation composition, preferably ranging from 40 mg/L to 150 mg/L, even more preferably from 50 mg/L to 110 mg/L, most preferably from 55 mg/L to 80 mg/L.
  • this total concentration includes both dissolved palladium ions and colloidal palladium. Above concentrations are based on the element palladium.
  • step (B) the activation composition has a temperature ranging from 25°C to 70°C, preferably from 30°C to 60°C, even more preferably from 36°C to 50°C, most preferably from 39°C to 46°C.
  • step (B) is a method of the present invention, wherein in step (B) the contacting is carried out for a time ranging from 1 minute to 15 minutes, preferably from 2 minutes to 12 minutes, even more preferably from 3 minutes to 9 minutes, most preferably from 4 minutes to 7 minutes.
  • step (B) comprises step
  • step (B) the activation composition comprises colloidal palladium, or
  • step (B) a reducing agent for reducing palladium ions to metallic palladium, if in step (B) the activation composition comprises palladium ions but no colloidal palladium.
  • step (B-1) the accelerator composition comprises no reducing agent but at least one complexing agent for tin ions and is acidic, preferably comprising in addition sulfuric acid.
  • step (B-1) as defined above is carried out after contacting the pre-treated substrate with an activation composition such that an activated substrate is obtained.
  • step (C) of the method of the present invention the activated substrate is metallized.
  • step (C) comprises a contacting with at least one metalizing composition comprising nickel ions, preferably comprises a contacting with at least two distinct metalizing compositions each comprising nickel ions, most preferably prior to a contacting with a metalizing composition comprising copper ions.
  • the at least one, preferably the at least two, metalizing compositions are for depositing a nickel and/or a nickel alloy metal layer, respectively.
  • step (C) comprises step
  • (C-1) contacting the activated substrate with a first metalizing composition for electroless plating to obtain a metalized substrate having a first nickel/nickel alloy metal layer, wherein the first metalizing composition comprises nickel ions and a reducing agent for nickel ions.
  • step (C-1) the first metalizing composition is alkaline, preferably has a pH ranging from 8.0 to 11.0, preferably from 8.2 to 10.2, more preferably from 8.4 to 9.3, most preferably from 8.6 to 9.0.
  • step (C-1) the first metalizing composition has a temperature ranging from 18°C to 60°C, preferably from 20°C to 55°C, even more preferably from 23°C to 50°C, most preferably from 26°C to 45°C.
  • step (C) comprises after step (C-1) step
  • C-2 contacting the metalized substrate having the first nickel/nickel alloy metal layer with a second metalizing composition for electrolytic plating to obtain a metalized substrate with a second nickel/nickel alloy metal layer, wherein the second metalizing composition comprises nickel ions and is preferably substantially free of, preferably does not comprise, a reducing agent for nickel ions.
  • step (C-2) the second metalizing composition is acidic, preferably has a pH ranging from 1.0 to 5.0, preferably from 2.0 to 4.5, more preferably from 2.8 to 4.0, most preferably from 3.3 to 3.7.
  • step (C-2) the second metalizing composition has a temperature ranging from 25°C to 70°C, preferably from 35°C to 65°C, even more preferably from 45°C to 61 °C, most preferably from 52°C to 58°C.
  • step (C-2) the contacting is carried out for a time ranging from 1 minute to 10 minutes, preferably from 2 minutes to 8 minutes, most preferably from 2.5 minutes to 5.5 minutes.
  • step (C-2) an electrical current is applied, preferably ranging from 0.3 A/dm 2 to 10.0 A/dm 2 , preferably ranging from 0.5 A/dm 2 to 8.0 A/dm 2 , more preferably ranging from 0.8 A/dm 2 to 6.0 A/dm 2 , even more preferably ranging from 1.0 A/dm 2 to 4.0 A/dm 2 , most preferably ranging from 1 .3 A/dm 2 to 2.5 A/dm 2 .
  • step (C-2) the second metalizing composition comprises chloride ions and/or (preferably and) boric acid.
  • step (C-2) the second metalizing composition is a Watts Nickel composition.
  • the second metalizing composition comprises chloride ions, sulfate ions, and boric acid.
  • step (C) comprises after step (C-1) step
  • C-2 contacting the metalized substrate having the first nickel/nickel alloy metal layer with a second metalizing composition to obtain a metalized substrate with a copper/ copper alloy metal layer on the first nickel/nickel alloy metal layer, wherein the second metalizing composition comprises copper ions and is preferably an immersion copper metallization composition.
  • step (C) comprises after step (C-2), most preferably if (C-2) involves nickel, step
  • step (C) at least one metalizing composition of the one or more than one metalizing composition comprises trivalent chromium ions such that a chromium or chromium alloy metal layer, respectively, is deposited.
  • the chromium or chromium alloy metal layer, respectively is the outermost metallic layer.
  • the method of the present invention is for metalizing a non-metallic substrate, wherein the metalizing comprises a chromium deposition, preferably a decorative chromium deposition.
  • step (C) comprises after step (C-3) a further step
  • step (C-x) contacting the metalized substrate obtained after a step prior to step (C-x) with a further metalizing composition to obtain a metalized substrate with a chro- mium/chromium alloy metal layer, wherein the further metalizing composition comprises trivalent chromium ions.
  • the present invention furthermore refers to a specific pre-treatment composition comprising
  • (A-c) silver ions wherein the pre-treatment composition has - a density in a range from 1 .50 g/cm 3 to 1 .90 g/cm 3 , referenced to a temperature of 25°C, and
  • - is substantially free of, preferably does not comprise, methane sulfonic acid, salts thereof, and chloride ions,
  • - is substantially free of, preferably does not comprise, permanganate ions, or comprises permanganate ions only up to a total concentration of 100 mg/L, based on the total volume of the pre-treatment composition and the element manganese, preferably only up to a total concentration of 75 mg/L, more preferably only up to a total concentration of 50 mg/L, even more preferably only up to a total concentration of 35 mg/L, most preferably only up to a total concentration of 20 mg/L, even most preferably only up to a total concentration of 10 mg/L.
  • the following method for metallizing a non-metallic substrate was repeatedly carried out for at least 3 months with parameters as described below.
  • a respective pre-treatment composition was prepared as follows in an oxidizing compartment comprising all together 6 tin/lead/silver anodes, 12 lead/tin (97 wt.-% I 3 wt.-%) anodes, and 9 tin/lead cathodes with a total cathodic surface to a total anodic surface of approximately 1 :2:
  • Manganese (II) sulfate and silver nitrate were added and dissolved in the acid mixture such that the concentration of Mn(ll) ions (i.e. the manganese (II) species) is exceeding 5 g/L but below 6 g/L.
  • the silver concentration was about 12 mmol/L.
  • a current in a range from 1.2 A/dm 2 to 1.5 A/dm 2 was applied in order to oxidize Mn(ll) ions to manganese (III) species.
  • the pre-treatment composition reached an absorbance at 400 nm of about 1 .0.
  • the absorbance was measured via LIV/VIS spectroscopy with a path length of 1 cm.
  • the so obtained pre-treatment composition utilized in the method of the present invention does not comprise methane sulfonic acid and no intentionally added compounds/ions comprising chromium; in particular no hexavalent chromium compounds. Furthermore, the pretreatment composition is free of chloride ions and free of intentionally added permanganate compounds/ions.
  • the oxidizing compartment was fluidically connected with a pre-treatment compartment (tank volume approximately 5400 liters) such that the pre-treatment composition was allowed to constantly circulate between the pre-treatment compartment and the oxidizing compartment.
  • a pre-treatment compartment tank volume approximately 5400 liters
  • no anodes and no cathodes were installed in the pre-treatment compartment.
  • step (A) of the method of the present invention a plurality of non-metallic plastic substrates (ABS or ABS-PC having surface dimensions ranging from 0.1 dm 2 to 10 dm 2 with varying production qualities) was used. Prior to contacting with the prepared pre-treatment composition in the pre-treatment compartment, the substrates were cleansed with Uniclean 151 (product of Atotech) and afterwards air dried.
  • Uniclean 151 product of Atotech
  • composition and pre-treatment parameters during step (A) denotes: determined by LIV/VIS spectroscopy
  • Concentrations of manganese species are in g/L, based on the total volume of the pretreatment composition and based on the element manganese.
  • step (A) an electrical current of 1.2 - 1.5 A/dm 2 was constantly applied to the pre- treatment composition in the oxidizing compartment.
  • step (A) is a one-step contacting with manganese species and the only con- tacting step with manganese species throughout the entire method. This is a general and important feature of the method of the present invention as a whole.
  • step (A) pre-treated substrates were obtained with an etch pattern, showing an exceptionally fine sponge-like structure after removal of polybutadiene spheres contained in the surface of the ABS and ABS-PC, respectively, substrates. Own analysis confirmed that in the substrates primarily the polybutadiene frame work was etched wherein the acrylonitrile styrene of the substrates remained primarily intact. As a result, a very fine-pored surface was obtained after step (A), which was significantly less strongly etched compared to substrates contacted with e.g. permanganate ions but still providing sufficient adhesion. It was therefore an excellent balance obtained between etching and adhesion.
  • step (B) Prior to step (B) a rinsing was carried out with water. If any manganese dioxide particles are present on the substrate, they are simply rinsed away with water since no strong adherence of manganese dioxide is observed.
  • step (B) the pre-treated substrates were contacted with an activation composition comprising colloidal palladium (approximately: 55 mg/L to 80 mg/L Pd, temperature 42°C, contact time 5 minutes).
  • step (B) comprises step (B-1), wherein the pre-treated substrate was contacted with an acidic accelerator composition to modify the activated substrate, the accelerator composition comprising at least one complexing agent for tin ions, since in step (B) the activation composition comprises colloidal palladium.
  • step (C) Prior to step (C) a rinsing was carried out with water.
  • step (C) the activated substrate is contacted with more than one metalizing composition in order to obtain a metalized substrate.
  • step (C) included step (C-1), wherein the activated substrate was contacted with an alkaline (pH approximately 8.6 to 9.0) first metalizing composition (having a temperature of approximately 26°C to 45°C; contact time about 10 minutes) for electroless nickel plating.
  • the first metalizing composition comprised approximately 3.5 g/L nickel ions and approximately 15 g/L hypophosphite ions as a reducing agent for nickel ions to obtain a metalized substrate having a first nickel alloy metal layer.
  • step (C) included after step (C-1) step (C-2), wherein the metallized substrate having the first nickel alloy metal layer was contacted for approximately 2.5 to 5 min with an acidic second metalizing composition (pH approximately 3.3 to 3.7; temperature 55°C, current density approximately 1.5 A/dm 2 ) comprising nickel sulfate, nickel chloride, and boric acid (Watts-Nickel composition).
  • step (C-2) is an electrolytic deposition of nickel.
  • the metalized substrate with the second nickel metal layer was rinsed with water.
  • the respective substrates were contacted in a step (C-3) with a third metalizing composition (acidic pH) in order to obtain a metalized substrate having a copper layer with a layer thickness of more than 30 pm (contact time about 45 min, 32.5°C, 40 g/L copper ions).
  • a third metalizing composition acidic pH
  • a final metallization step (C-x) the respective substrates were contacted with a further metalizing composition in order to obtain a metalized substrate having a chromium layer, the further metalizing composition comprising 15 g/L to 30 g/L trivalent chromium and boric acid (acidic pH, 25°C to 60°C).
  • the optical quality of the chromium layer was evaluated by analyzing coverage and optical defects. As a result, no haze and no other optical defects were observed. In particular, the chromium layer showed a very homogeneous optical distribution.
  • the substrates obtained after contacting with the third metalizing composition i.e. plated with copper
  • the adhesion for ABS was above 1 .0 N/mm and for ABS-PC in a range from 0.5 to 0.8 N/mm.
  • the method of the present invention showed a significantly higher adhesion (at least 10%) and in addition a reduced tendency to form blisters. This was particularly observed for substrates, wherein in step (C-2) a copper layer was deposited by immersion plating.
  • the method of the present invention includes basically a single-step pre-treatment sequence, which significantly reduces the time for the entire pre-treatment procedure because no contacting with a composition comprising a reducing agent and/or no second contacting step with a second or further manganese species is needed.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • ing And Chemical Polishing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention concerne un procédé de métallisation d'un substrat non métallique, le procédé comprenant les étapes (A) à (C), l'étape (A) étant une étape de prétraitement pour l'attaque et l'étape (C) étant l'étape de métallisation. Dans l'étape (A), une composition de prétraitement est utilisée comprenant des espèces individuelles de manganèse (II), (III) et (IV). La présente invention concerne en outre une composition de prétraitement spécifique.
PCT/EP2021/073224 2020-08-25 2021-08-23 Procédé de métallisation d'un substrat non métallique et composition de prétraitement WO2022043241A1 (fr)

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Application Number Priority Date Filing Date Title
CA3190838A CA3190838A1 (fr) 2020-08-25 2021-08-23 Procede de metallisation d'un substrat non metallique et composition de pretraitement
CN202180052417.0A CN116134175A (zh) 2020-08-25 2021-08-23 非金属衬底的金属化方法和预处理组合物
EP21766456.4A EP4204601A1 (fr) 2020-08-25 2021-08-23 Procédé de métallisation d'un substrat non métallique et composition de prétraitement
US18/042,852 US20230357932A1 (en) 2020-08-25 2021-08-23 Method for metallizing a non-metallic substrate and pre-treatment composition
JP2023513484A JP2023539605A (ja) 2020-08-25 2021-08-23 非金属基板のメタライズ方法及び前処理組成物
KR1020237009607A KR20230054853A (ko) 2020-08-25 2021-08-23 비금속 기재의 금속화 방법 및 전처리 조성물
BR112023003111A BR112023003111A2 (pt) 2020-08-25 2021-08-23 Método para metalizar um substrato não metálico e composição de pré-tratamento

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EP20192718.3 2020-08-25

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BR (1) BR112023003111A2 (fr)
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EP2025708A1 (fr) 2007-08-10 2009-02-18 Enthone Inc. Décapage sans chrome pour surfaces en matière synthétique
US20130186774A1 (en) * 2012-01-23 2013-07-25 Trevor Pearson Etching of Plastic Using Acidic Solutions Containing Trivalent Manganese
US8603352B1 (en) 2012-10-25 2013-12-10 Rohm and Haas Electroncis Materials LLC Chrome-free methods of etching organic polymers
US20170159183A1 (en) 2014-07-10 2017-06-08 Okuno Chemical Industries Co., Ltd. Resin plating method
WO2018095998A1 (fr) 2016-11-22 2018-05-31 Macdermid Enthone Gmbh Gravure sans chrome pour placage sur plastique
EP2937446B1 (fr) 2013-10-22 2018-06-13 Okuno Chemical Industries Co., Ltd. Composition pour le traitement par gravure d'un matériau résineux
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EP3584352A1 (fr) 2017-05-23 2019-12-25 Okuno Chemical Industries Co., Ltd. Composition de prétraitement pour déposition autocatalytique, procédé de prétraitement pour déposition autocatalytique, et procédé de déposition autocatalytique

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EP2025708A1 (fr) 2007-08-10 2009-02-18 Enthone Inc. Décapage sans chrome pour surfaces en matière synthétique
US20130186774A1 (en) * 2012-01-23 2013-07-25 Trevor Pearson Etching of Plastic Using Acidic Solutions Containing Trivalent Manganese
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EP2937446B1 (fr) 2013-10-22 2018-06-13 Okuno Chemical Industries Co., Ltd. Composition pour le traitement par gravure d'un matériau résineux
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WO2018095998A1 (fr) 2016-11-22 2018-05-31 Macdermid Enthone Gmbh Gravure sans chrome pour placage sur plastique
EP3584352A1 (fr) 2017-05-23 2019-12-25 Okuno Chemical Industries Co., Ltd. Composition de prétraitement pour déposition autocatalytique, procédé de prétraitement pour déposition autocatalytique, et procédé de déposition autocatalytique
CN110172684A (zh) 2019-06-06 2019-08-27 南通柏源汽车零部件有限公司 一种abs无铬粗化液及其制备方法与应用

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BR112023003111A2 (pt) 2023-04-04
CN116134175A (zh) 2023-05-16
US20230357932A1 (en) 2023-11-09
JP2023539605A (ja) 2023-09-15
KR20230054853A (ko) 2023-04-25
CA3190838A1 (fr) 2022-03-03

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