EP4204600A1 - Procédé d'activation d'une surface d'un substrat non-conducteur ou contenant des fibres de carbone destiné à la métallisation - Google Patents

Procédé d'activation d'une surface d'un substrat non-conducteur ou contenant des fibres de carbone destiné à la métallisation

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Publication number
EP4204600A1
EP4204600A1 EP21762062.4A EP21762062A EP4204600A1 EP 4204600 A1 EP4204600 A1 EP 4204600A1 EP 21762062 A EP21762062 A EP 21762062A EP 4204600 A1 EP4204600 A1 EP 4204600A1
Authority
EP
European Patent Office
Prior art keywords
preferred
present
ions
species
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21762062.4A
Other languages
German (de)
English (en)
Inventor
André Beyer
Laurence John GREGORIADES
Stefan Kempa
Julia Lehmann
Yvonne Welz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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Filing date
Publication date
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP4204600A1 publication Critical patent/EP4204600A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—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
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
    • C23C18/1601—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
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
    • C23C18/31—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
    • C23C18/38—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
    • 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
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • the present invention relates to the activation of surfaces of typically non-conductive or carbon-fibres containing substrates for subsequent metallization.
  • the present invention relates to a method for activating a surface of a non- conductive or carbon-fibres containing substrate for metallization, a method for metallizing an activated surface of a non-conductive or carbon-fibres containing substrate, a method for preparing an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization, and an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon- fibres containing substrate for metallization.
  • a metallization of typically such substrates is commercially of high interest.
  • such substrates are covered with structures or layers of metal, either for decorative or functional applications.
  • typically non-conductive plastic substrates are used to manufacture sanitary articles with a shiny chromium layer.
  • chromium covered plastic substrates are used in the automotive industry.
  • a functional metallization is essential in for example manufacturing printed circuit boards.
  • a non-conductive resin-containing laminate is used as a base material usually harboring a circuitry of copper lines.
  • Carbon-fibres containing substrates experience an increasing potential as catalytically active surfaces in e.g. power-to-gas, power-to-fuel, and power-to-chemicals applications, and batteries.
  • a cleaning of the surface of the non-conductive or carbon-fibres containing substrate is carried out, e.g. to remove grease or impurities.
  • a conditioning also called pre-treatment
  • a conditioning for example includes in some cases an etching in order to create pores and to enlarging the surface.
  • the important activation is carried out.
  • a very thin seed or activation layer is deposited/anchored on the surface of the non-conductive or carbon-fibres containing substrate, serving as starting point for a subsequent first metallization layer.
  • the seed or activation layer usually serves as mediator between said surface of the non-conductive or carbon- fibres containing substrate and the one or more following metallization layers.
  • the seed/activation layer is formed by depositing metal nanoparticles on said surface, for example from a colloidal activation composition.
  • said first metallization layer is deposited on the seed/activation layer, most commonly by electroless plating.
  • this electroless plating includes an immersion-type plating, i.e. a deposition of a more noble metal on the seed/activation layer by means of exchange reaction and in absence of a reducing agent.
  • it includes a deposition of a metal or metal alloy through autocatalytic deposition, which means a deposition facilitated by means of a reducing agent.
  • a second metallization layer is deposited on the first metallization layer, either again by autocatalytic deposition or by electrolytic deposition.
  • noble metal nanoparticles are utilized very often as palladium nanoparticles.
  • noble metals are generally expensive and wastewater treatment is of high concern in order to recycle remaining noble metals.
  • less expensive metal ions are more and more utilized in respective activation compositions.
  • CN 107460459 A relates to simple nano-copper activation liquid utilizing stabilizers and reducing agents to prevent agglomeration and oxidation, respectively, of the nanoparticles.
  • CN 109295442 A relates to a method for preparing an electroless copper-nickel bimetal layer, wherein the method uses a colloidal copper activation.
  • US 4,278,712 discloses a method for the activation of a weakly active colloidal dispersion useful in the preparation of non-conductors prior to electroless plating. The method is based upon controlled oxidation of otherwise weakly active colloids by treatment with suitable gases and/or chemical agents, which render said controlled oxidation. However, the presence of at least one colloid stabilizer is mandatory. In this way a reversible equilibrium is not maintained.
  • WO 2020/201387 A1 discloses a method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization and a respective activation composition, which is on the one hand simple and highly effective, and on the other hand is in particular insensitive to agglomeration and precipitation to ensure a long service life.
  • step (c) contacting the substrate (substrate treated according to step (I)) with the selector composition;
  • step (a) providing the substrate treated according to step (II);
  • the metal particles are formed from the dissolved transition metal ions through a continuous or semi-continuous reduction through the one or more than one reducing agent
  • the dissolved transition metal ions are formed from the metal particles through continuous or semi-continuous oxidation of said particles, and
  • step (c) contacting the substrate (substrate treated according to step (II)) with said activation composition such that a transition metal or a transition metal alloy is deposited on the surface of said substrate and an activated surface for metallization is obtained.
  • the present invention relies on the fact, that the particles are formed again and again in situ, which renders any stabilization or stabilizer compounds obsolete.
  • the dissolved transition metal ions and the metal particles thereof are present in a reversible equilibrium.
  • a very effective and strong activation can be achieved because fresh particles without a shell of stabilizer compounds around them are formed with a relatively short lifetime.
  • they are reacted back into their ionic form by oxidation.
  • fresh particles are formed again, i.e. in situ.
  • a transition metal or a transition metal alloy is deposited on the surface of said substrate and an activated surface for subsequent metallization is obtained.
  • concentration of dissolved metal ions of the first species decreases over time due to deposition.
  • replenishment of the first species is easily achieved by simply adding ions of that species. Therefore, replenishment is extremely easy and simple. This furthermore, significantly increases the lifetime of a respective activation composition and a thereto related method.
  • the respective method and activation composition does not necessarily require expensive noble metals but can be carried out with low-priced transition metals.
  • “semi-continuous”, “semi-continuously”, and, “semi- continually”, respectively, denote a doing of a respective action with one or more than one even significant interruption of the action while e.g. a respective method or aspect of the invention is carried out.
  • the interruptions are in some cases longer than the time during the action is carried out. It includes even only temporary and brief actions.
  • species e.g. first species or second species
  • a first species of dissolved transition metal ions denotes dissolved metal ions of a transition metal element of groups 3 to 12 of the periodic table, e.g. copper.
  • a first species of dissolved transition metal ions and additionally metal particles thereof denotes dissolved metal ions of this first species and additionally metal particles of this first species, e.g. in the aqueous, palladium-free activation composition.
  • the substrate is a first layer of the substrate.
  • step (l)(a) of the method of the present invention a non-conductive or carbon-fibres containing substrate with a surface is provided.
  • activating means to modify the surface of the non- conductive or carbon-fibres containing substrate in such a way that it comprises the transition metal or transition metal alloy after the respective activation step with sufficient adhesion for subsequent metallization.
  • the deposited transition metal and transition metal alloy, respectively is sufficiently adherent to the surface such that a subsequent metallization layer (i) can be deposited thereon and (ii) is altogether also sufficiently adherent to the surface of the non-conductive or carbon-fibres containing substrate.
  • the non-conductive substrate comprises, preferably is, selected from the group consisting of plastics, resin-containing laminates, glasses, ceramics, semi-conductors, and mixtures thereof.
  • Preferred plastics comprise, preferably are, thermoplastics, more preferably comprise, preferably are, polyacrylates, polyamides, polyimides, polyesters, polycarbonates, polyalkylenes, polyphenylenes, polystyrenes, polyvinyls, or mixtures thereof.
  • Preferred polyacrylates comprise poly(methyl methacrylate) (PMMA).
  • Preferred polyimides comprise polyetherimide (PEI).
  • Preferred polyesters comprise polylactic acid (PLA).
  • Preferred polycarbonates comprise polycarbonate obtained with bisphenol A (PC).
  • Preferred polyalkylenes comprise polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyoxymethylene (POM), or mixtures thereof.
  • Preferred polyphenylenes comprise poly(phenylene oxide) (PPO), poly(phenylene ether) (PPE), or mixtures thereof.
  • Preferred polystyrenes comprise polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene/butadiene rubber (SBR), styrene-acrylonitrile (SAN).
  • PS polystyrene
  • ABS acrylonitrile butadiene styrene
  • SBR styrene/butadiene rubber
  • SAN styrene-acrylonitrile
  • Preferred polyvinyls comprise polyvinyl chloride (PVC), poly(ethylene-vinyl acetate) (PEVA), polyvinylidene difluoride (PVDF), or mixtures thereof.
  • PVC polyvinyl chloride
  • PEVA poly(ethylene-vinyl acetate)
  • PVDF polyvinylidene difluoride
  • Preferred resin-containing laminates comprise, preferably are, fiber-enforced resin-containing laminates, most preferably glass-fiber-enforced laminates.
  • the resin-containing laminates comprise as resin one or more than one polymer of epoxys, vinylesters, polyesters, amides, imides, phenols, alkylenes, sulfones, or mixtures thereof, most preferably epoxy, imides, or mixtures thereof.
  • a very preferred resin-containing laminate comprises, preferably is, FR4.
  • Preferred glasses comprise, preferably are, silica glass, soda-lime glass, float glass, fluoride glass, aluminosilicate glass, phosphate glass, borate glass, borosilicate glass, chalcogenide glass, aluminium oxide glass, or mixtures thereof.
  • Preferred ceramics comprise, preferably are, glass-ceramics, aluminium oxide ceramics, or mixtures thereof.
  • Preferred semi-conductors comprise, preferably are, silicon-based semi-conductors, more preferably silicon-based semi-conductors comprising silicon dioxide and/or silicon.
  • Very preferred semi-conductors are wafers.
  • the carbon-fibres containing substrate comprise, preferably are, carbon-fibre composites and/or arrangements of carbon- fibre filaments.
  • Preferred carbon-fibre composites comprise, preferably are, carbon-fibre reinforced polymers and/or carbon-fibre containing fabrics, more preferably carbon-fibre reinforced polymers and/or woven carbon-fibre containing fabrics.
  • Preferred arrangements of carbon-fibre filaments comprise, preferably are, fabrics made of carbon-fibres, most preferably woven fabrics made of carbon-fibres.
  • An in particularly preferred carbon-fibres containing substrate is a carbon-fibre containing felt.
  • the conditioning solution has an alkaline pH, preferably a pH in a range from 9.0 to 14.0, more preferably in a range from 10.0 to 13.5, even more preferably in a range from 10.5 to 13.0, most preferably in a range from 11.0 to 12.5.
  • the ni- trogen-containing compound is a polymer, preferably a water-soluble polymer.
  • the nitrogen-containing compound is a polymer comprising pyrrolidine moieties.
  • the polymer is cationic.
  • the nitrogen-containing compound consists of carbon atoms, nitrogen atoms, and hydrogen atoms.
  • the nitrogen-containing compound comprises, preferably is, Polyquaternium 6.
  • the nitrogen-con- taining compound comprises, preferably is, a polymer which results from the polyaddition and/or polycondensation of at least one nitrogen-containing compound.
  • the nitrogen-containing compound comprises, preferably is, a polymer of methylamine and epichlorohydrin.
  • the concentration of the nitrogencontaining compound is of from 0.1 g/L to 4 g/L, preferred of from 0.2 g/L to 2 g/L, more preferred of from 0.25 g/L to 1.5 g/L, more preferred of from 0.3 g/L to 1 g/L.
  • (I)(c) has a temperature in a range from 20°C to 90°C, preferably in a range from 25°C to 80°C, more preferably in a range from 30°C to 70°C, most preferably in a range from 40°C to 60°C.
  • step (l)(c) is carried out for 1 minute to 10 minutes, preferably for 2 minutes to 8 minutes, more preferably for 3 minutes to 6 minutes, most preferably for 3.5 minutes to 5 minutes.
  • Step (II) of the method of the present invention is a selector treatment of the surface of a non-conductive or carbon-fibres containing substrate, the selector treatment method comprising the steps of
  • the selector composition has an alkaline pH, preferably a pH in a range from 9.0 to 14.0, more preferably in a range from 10.0 to 13.5, even more preferably in a range from 10.5 to 13.0, most preferably in a range from 11.0 to 12.5.
  • ni- trogen-containing compound is an amine of the formula
  • guanidine derivates are understood as guanidine compounds, which are preferably guanidine in which one or more hydrogen is substituted by functional groups preferably as hydroxy, halogen, amino or C1-C4 alkyl and/or wherein these guanidine compounds are chosen from guanidinium salts.
  • the concentration of the nitrogen-containing compound is of from 1 g/L to 50 g/L, preferred of from 2 g/L to 40 g/L, more preferred of from 3 g/L to 35 g/L, more preferred of from 5 g/L to 30 g/L.
  • (i) comprises a) a first nitrogen-containing compound which is selected from ammonia, monoethanolamine, triethanolamine or mixtures thereof; and b) a second nitrogen-containing compound which is selected from guanidine, guanidine compounds such as guanidinium salts, or mixtures thereof; and
  • (ii) has a pH of from 9 to 12.
  • (i) comprises a) a first nitrogen-containing compound which is selected from ammonia, monoethanolamine, triethanolamine or mixtures thereof; and b) a second nitrogen-containing compound which is selected from guanidine, guanidine compounds such as guanidinium salts, or mixtures thereof; and
  • (ii) has a pH of from 9 to 12, wherein in the selector composition the concentration of the first nitrogen-containing compound is of from 1 g/L to 50 g/L, preferred of from 2 g/L to 40 g/L, more preferred of from 3 g/L to 35 g/L, more preferred of from 5 g/L to 30 g/L, and in the selector composition the concentration of the second nitrogen-containing compound is of from 1 g/L to 10 g/L, preferred of from 2 g/L to 8 g/L, more preferred of from 3 g/L to 7 g/L, more preferred of from 4 g/L to 6 g/L.
  • (i) comprises a) a first nitrogen-containing compound which is selected from ammonia, monoethanolamine, triethanolamine or mixtures thereof; and b) a second nitrogen-containing compound which is selected from guanidine, guanidine compounds such as guanidinium salts, or mixtures thereof; and
  • (ii) has a pH of from 9 to 12, wherein in the selector composition the concentration of the first nitrogen-containing compound is of from 1 g/L to 50 g/L, preferred of from 2 g/L to 40 g/L, more preferred of from 3 g/L to 35 g/L, more preferred of from 5 g/L to 30 g/L, and in the selector composition the concentration of the second nitrogen-containing compound is of from 1 g/L to 10 g/L, preferred of from 2 g/L to 8 g/L, more preferred of from 3 g/L to 7 g/L, more preferred of from 4 g/L to 6 g/L..
  • step (I l)(c) has a temperature in a range from 20°C to 90°C, preferably in a range from 25°C to 80°C, more preferably in a range from 30°C to 70°C, most preferably in a range from 40°C to 60°C.
  • step (I l)(c) is carried out for 1 minute to 10 minutes, preferably for 2 minutes to 8 minutes, more preferably for 3 minutes to 7 minutes, even more preferably for 3.5 minutes to 6 minutes, most preferably for 4 minutes to 5.5 minutes.
  • step (lll)(b) of the method of the present invention an aqueous, palladium-free activation composition is provided.
  • the aqueous composition utilized in the method of the present invention is an aqueous composition, which means that water is the primary component.
  • more than 50 wt.-% of the composition is water, based on the total weight of the aqueous composition, preferably at least 70 wt.-%, even more preferably at least 90 wt.-%, most preferably 95 wt.-% or more.
  • the composition comprises one or more than one solvent (other than water) that is miscible with water.
  • most preferred is a method, wherein water is the only solvent, and, thus, most preferably the composition is substantially free of or does not comprise organic solvents at all.
  • the term “substantially free of or does not comprise” of a subject-matter independently denotes that said subject-matter is not present at all (“does not comprise”) or is present only in (to) a very little and non-disturbing amount (extent) without affecting the intended purpose of the invention (“substantially free of”).
  • a subject-matter e.g. a compound, a chemical, a material, etc.
  • substantially free of e.g. a compound, a chemical, a material, etc.
  • the activation composition preferably 0 ppm to 3 ppm, more preferably 0 ppm to 1.5 ppm, even more preferably 0 ppm to 1 ppm, most preferably 0 ppm to 0.5 ppm, even most preferably 0 ppm to 0.1 ppm.
  • This principle applies likewise to other subject-matters, e.g. to the total weight of the transition metal or transition metal alloy obtained in step (I I l)(c) of the method of the present invention.
  • the activation composition has an acidic pH, a neutral pH, or an alkaline pH, preferably an acidic or neutral pH, most preferably an acidic pH.
  • the pH of the activation composition is in a range from > 2.0 to ⁇ 13.0, preferably in a range from > 3.0 to ⁇ 12.0, more preferably in a range from > 4.0 to ⁇ 11.0, most preferably in a range from > 4.5 to ⁇ 10.0.
  • a method of the present invention is preferred, wherein the pH of the activation composition is in a range from > 3.0 to ⁇ 6.5, preferably in a range from > 4.0 to ⁇ 6.0.
  • the one or more than one reducing agent comprises a borohydride.
  • the pH in the activation composition is typically a result of the presence of (i) to (iv). If an adjustment of the pH is necessary, it is carried out by typical means.
  • Preferred acids are mineral acids and organic acids.
  • a preferred mineral acid is sulfuric acid.
  • a preferred organic acid is the acid form of the one or more than one complexing agent.
  • a preferred alkaline compound is an alkaline hydroxide, preferably NaOH, an alkaline carbonate, preferably sodium carbonate, and ammonia.
  • the pH is determined at a temperature of 20°C, i.e. the defined pH is referenced to 20°C.
  • the activation composition has a temperature of 20°C. This does not mean that the activation composition in itself is limited to the specific temperature of 20°C. For preferred temperatures of the activation composition see below.
  • the aqueous composition utilized in the method of the present invention is palladium-free. Therefore, the activation composition is substantially free of or does not comprise palladium ions. This means that neither compounds comprising palladium are present nor palladium atoms/particles or palladium ions.
  • the present invention is an excellent alternative to palladium-containing activation processes with identical or at least almost identical results in terms of activation.
  • the activation composition is substantially free of or does not comprise platinum ions, gold ions, silver ions, rhodium ions, ruthenium ions, and iridium ions, preferably is substantially free of or does not comprise platinum, gold, silver, rhodium, ruthenium, and iridium.
  • the aqueous composition utilized in the method of the present invention comprises (i) a first species of dissolved transition metal ions and additionally metal particles thereof.
  • the metal particles are nanoparticles.
  • the metal particles comprise one or more than one elemental metal (Me 0 ), preferably (essentially) consist of one or more than one elemental metal (Me 0 ).
  • the metal particles of the first species have a particle diameter in a range from 0.1 nm to 500 nm, preferably in a range from 0.5 nm to 200 nm, more preferably in a range from 1.0 nm to 100 nm, most preferably in a range from 3 nm to 50 nm, even most preferably in a range from 5 nm to 15 nm.
  • the metal particles of the first species in the activation composition are colloidal metal particles.
  • the activation composition is a colloid, preferably a colloidal suspension.
  • the activation composition is still a clear but colored solution depending on the coloring effect caused by the dissolved ions, primarily of the first species.
  • said dissolved transition metal ions of the first species and said metal particles thereof form together a total amount of the metal of the first species.
  • the method of the present invention can be basically carried out with comparatively high concentrations of the first species, it turned out that surprisingly very low concentrations are already sufficient to obtain very efficient and excellent results (see examples). This is in particular advantageous in terms of waste-water treatment and is thus cost- and ecofriendly.
  • the first species is copper or cobalt, preferably copper.
  • Copper and cobalt are cost efficient metals compared to commonly used palladium but achieve sufficient activation on the surface of the non-conductive or carbon- fibres containing substrate.
  • concentrations most preferably apply to copper and cobalt, most preferably to copper.
  • the source of dissolved copper ions is selected from the group consisting of copper sulfate, copper chloride, copper nitrate, copper fluoroborate, copper acetate, copper citrate, copper phenyl sulfonate, copper para-tolu- ene sulfonate, and copper alkyl sulfonates.
  • a preferred copper alkyl sulfonate is copper methane sulfonate.
  • the most preferred copper source is copper sulfate, most preferably CuSC * 5 H 2 O.
  • the aqueous, palladium-free activation composition comprises (iv) one or more than one second species of dissolved metal ions being different from the first species.
  • the second species is substantially free of or does not comprise alkali metals.
  • the one or more than one second species is selected from the group consisting of transition metals and magnesium, preferably nickel, cobalt, iron, and magnesium, preferably nickel and cobalt, more preferably nickel.
  • transition metals and magnesium preferably nickel, cobalt, iron, and magnesium, preferably nickel and cobalt, more preferably nickel.
  • the aqueous, palladium-free activation composition comprises (ii) one or more than one complexing agent.
  • the one or more than one complexing agent is suitable to form complexes with the dissolved transition metal ions of at least the first species.
  • the one or more than one complexing agent comprises or is an organic complexing agent, preferably a carboxylic acid and/or salts thereof, more preferably a di- or tricarboxylic acid and/or salts thereof, even more preferably a tricarboxylic acid and/or salts thereof, most preferably a hydroxy tricarboxylic acid and/or salts thereof, even most preferably citric acid, structural isomers, and/or salts thereof.
  • a preferred structural isomer is iso-citric acid and salts thereof.
  • the one or more than one complexing agent defined above is the only complexing agent in the activation composition.
  • the one or more than on complexing agent in a total concentration are present in a molar ratio in a range from 1.0 : 0.2 to 1.0 : 100.0, preferably in a range from 1.0 : 0.5 to 1.0 : 50.0, more preferably in a range from 1.0 : 0.85 to 1.0 : 25.0, even more preferably in a range from 1.0 : 0.95 to 1.0 : 15.0, yet even more preferably in a range from 1.0 : 1.0 to 1.0 : 10.0, most preferably in a range from 1.0 : 1.1 to 1.0 : 5.0.
  • the one or more than one complexing agent comprises a tricarboxylic acid and/or salts thereof, more preferably a hydroxy tricarboxylic acid and/or salts thereof, most preferably citric acid, structural isomers, and/or salts thereof.
  • the aqueous, palladium-free activation composition comprises permanently or temporarily (iii) one or more than one reducing agent.
  • the one or more than one reducing agent is essential for forming the metal particles from the dissolved transition metal ions of at least the first species.
  • the dissolved transition metal ions are chemically reduced, continuous or semi-continuous, in order to form said particles.
  • said particles are either formed continually or semi-continually, respectively, depending on the presence of the one or more than one reducing agent in the activation composition, which is permanent or temporary.
  • the one or more than one reducing agent typically said particles will be formed until said reducing agent is used up or insufficiently present.
  • oxidation affects said particles and is in constant competition with the reduction.
  • oxidation starts as soon as the one or more than one reducing agent is used up, which is explicitly desired in the context of the present invention.
  • Said oxidation is furthermore very relevant if in the method of the present invention after one or more than one first step (c) the method is interrupted for a comparatively long time.
  • said oxidation is carried out until no particles are any longer present but rather only dissolved transition metal ions.
  • the oxidation is accelerated by adding an oxidizing agent, more preferably a peroxide, most preferably hydrogen peroxide.
  • particles are formed by adding continually or semi-continually the one or more than reducing agent to re-form particles. Afterwards, the method of the present invention is resumed.
  • the one or more than one reducing agent is suitable for reducing the dissolved transition metal ions of at least the first species.
  • the one or more than one reducing agent comprises one or more than one hydrogen atom such that hydrogen is released upon reducing said transition metal ions, which at least partly adsorbs on said activated surface.
  • a preferred borohydride comprises an inorganic borohydride and/or an organic borohydride.
  • a preferred organic borohydride comprises an alkylaminoborane, most preferably dimethylaminoborane.
  • a preferred inorganic borohydride comprises an alkali borohydride, most preferably sodium borohydride. In the method of the present invention, most preferred is an alkali borohydride, preferably sodium borohydride.
  • step (c) of the method of the present invention allows a slightly acidic pH and a temperature in step (c) of the method of the present invention, in a moderate range, preferably from 15°C to 30°C. These are excellent room temperature conditions. Thus, no additional and cost-intensive heating is necessarily required. Furthermore, hydrogen is generated.
  • the boron-containing reducing agent preferably a borohydride, more preferably an alkali borohydride and/or an alkylaminoborane, most preferably sodium borohydride and/or dimethylaminoborane is the only reducing agent in the activation composition.
  • a borohydride in the activation composition as one of the one or more than one reducing agent, typically boric acid and/or salts thereof are formed.
  • a method of the present invention is preferred, wherein the one or more than one reducing agent comprises an aldehyde, preferably formaldehyde, glyoxylic acid, salts of glyoxylic acid, or mixtures thereof, most preferably as the only reducing agent. In such a case formation of boric acid is avoided.
  • a method of the present invention is preferred, wherein the one or more than one reducing agent comprises hydrazine, most preferably as the only reducing agent. Also, in such a case formation of boric acid is avoided.
  • the activation composition comprises the one or more than one reducing agent in a total concentration in a range from 0.2 mmol/L to 500.0 mmol/L, based on the total volume of the activation composition, preferably in a range from 0.4 mmol/L to 350.0 mmol/L, more preferably in a range from 0.6 mmol/L to 250.0 mmol/L, even more preferably in a range from 0.8 mmol/L to 150.0 mmol/L, most preferably in a range from 1.0 mmol/L to 80.0 mmol/L.
  • An in particular preferred total concentration is in a range from 0.9 mmol/L to 50.0 mmol/L, very preferably in a range from 1.0 mmol/L to 30.0 mmol/L, most preferably in a range from 1.1 mmol/L to 10.0 mmol/L. Most preferably, this applies to the aforementioned preferred, more preferred, etc. reducing agents, most preferably to a borohydride.
  • the metal ions of the first species and the metal particles thereof forming together a total concentration based on the total volume of the activation composition and based on an ionic, non-particular form, and the one or more than on reducing agent (if semi-continually added, in the moment of addition) in a total concentration are present in a molar ratio of more than 0.5, preferably of 1 or more, more preferably of 2 or more, even more preferably of 3 or more, most preferably of 3.5 or more. Very preferred is a molar ratio in the range from 1 to 20.
  • the one or more than one reducing agent is preferably present (either permanently or temporarily) in such a total concentration that the dissolved transition metal ions of the first species are not quantitatively reduced into the respective particles.
  • a method of the present invention is preferred, wherein the activation composition does not predominantly exhibit a reductive environment to prevent oxidation of the metal particles.
  • oxidation is required and desired.
  • a method of the present invention wherein the activation composition is predominantly kept in oxidizing condition to allow oxidation of the metal particles.
  • the one or more than on reducing agent (if semi-continually added, in the moment of addition) in a total concentration are present in a molar ratio in a range from 0.3 to 60.0, preferably in a range from 0.5 to 30.0, more preferably in a range from 1 .0 to 20.0, even more preferably in a range from 1 .5 to 10.0, most preferably in a range from 1 .8 to 3.0.
  • a method of the present invention is preferred, wherein in the aqueous, palladium-free activation composition the one or more than one reducing agent is permanently present.
  • the one or more than one reducing agent is added to the activation composition continually, preferably by a permanent flow of a respective liquid containing said one or more than one reducing agent.
  • oxidation and reduction are taking place simultaneously over the time during step (c) of the method of the present invention is carried out.
  • the metal particles are present in a comparatively constant concentration.
  • a method of the present invention is preferred, wherein in the aqueous, palladium-free activation composition the one or more than one reducing agent is temporarily present.
  • the one or more than one reducing agent is added semi-continuously; e.g. in consecutive portions with time-wise interruptions between each portion. This means that when the one or more than one reducing agent is added fresh particles are formed.
  • the oxidation, creating the dissolved transition metal ions is very dominant.
  • the metal particles are present in a basically varying concentration.
  • the reversible equilibrium is not only a side reaction or an undesired side reaction.
  • the total concentration of the dissolved transition metal ions basically increases as a result of the reversible equilibrium, wherein the total amount of said metal particles decreases.
  • This reversible equilibrium is preferably monitored for a better process control. Therefore, preferred is a method of the present invention, wherein the reversible equilibrium is monitored by UV/VIS inspection.
  • said dissolved transition metal ions are monitored at a wavelength within a range from 700 nm to 800 nm, preferably within a range from 710 nm to 780 nm, more preferably within a range from 720 nm to 760 nm, most preferably within a range from 730 nm to 750 nm.
  • said metal particles are monitored at a wavelength within a range from 400 nm to 600 nm, preferably within a range from 450 nm to 550 nm. This allows determining when to add one of the one or more than one reducing agent in order to form, preferably re-form, said metal particles in order to increase their total amount.
  • the one or more than one reducing agent is continually or semi-continually added to the activation composition such that further metal particles are continually or semi-continually, respectively, formed from the dissolved transition metal ions of the first species, preferably added after one or more than one step (c) is carried out.
  • step (c) is carried out more than one time, preferably the method, including step (c), is carried out repeatedly.
  • metal particles are freshly formed by said reduction. This is possible because said oxidation is allowed and desired, leading, preferably continually but at least semi-continually, to fresh dissolved transition metal ions ready for re-reduction. This is contrary to common approaches, wherein metal particles are formed (and stabilized) before the activation is carried out, which afterwards typically last as long as possible by particle stabilization until the respective activation composition is unstable and inoperable.
  • a reducing agent used for said reduction reacts with the dissolved transition metal ions and leads to a reducing agent degradation product, preferably boric acid and/or salts thereof.
  • a reducing agent degradation product preferably boric acid and/or salts thereof.
  • degradation products accumulate in the activation composition, which is not preferred in the context of the present invention. Therefore, a method of the present invention is preferred, wherein the method is performed by bleed and feed. In such an approach, a certain volume of the activation composition is removed (e.g. by drag out; thereby removing also degradation products) and replaced by a replacement volume (e.g.
  • the replacement volume typically does not comprise boric acid and/or salts thereof, preferably does not comprise the reducing agent degradation product. This is also beneficial for stabilizing the pH to a basically constant pH.
  • the activation composition comprises boric acid and/or salts thereof in a total concentration of 5 g/L or less, based on the total volume of the activation composition, preferably of 3 g/L or less, more preferably of 2 g/L or less, most preferably of 1.2 g/L or less.
  • the one or more than one reducing agent comprises a borohydride and (2) step (c) is carried out more than one time.
  • Majority preferably denotes more than 50% of the particles.
  • the one or more than one reducing agent is substantially free of or does not comprise hypophosphite ions, preferably is substantially free of or does not comprise a phospho- rous-containing reducing agent. Own experiments have shown that in some cases the activation with such reducing agents is too weak or even incomplete.
  • the activation composition does not additionally require stabilizing compounds. Therefore, preferred is a method of the present invention, wherein the activation composition is substantially free of or does not comprise a compound preventing the oxidation of the metal particles and/or is substantially free of or does not comprise a stabilizer compound to stabilize the metal particles. Preferably, the activation composition is substantially free of or does not comprise a stabilizer compound to stabilize the metal particles by preventing agglomeration of the metal particles.
  • the one or more than one reducing agent (temporarily or permanently present in the activation composition) and compounds involved in the oxidation, preferably ambient air and/or oxygen gas (i.e. most preferably molecular oxygen), are not considered to be such a compound.
  • the one or more than one reducing agent is rather required in order to form the metal particles, which includes re-forming the particles.
  • the activation composition is substantially free of or does not comprise in addition to said one or more than one reducing agent and compounds involved in the oxidation a stabilizer compound and/or a compound preventing the oxidation of the metal particles.
  • the one or more than one reducing agent is not present in a total amount to prevent the oxidation, preferably is not present in a total amount to prevent the oxidation after or during one or more than one step (c) is carried out.
  • the oxidation most preferably through ambient air, is needed to re-form the dissolved transition metal ions such that no precipitating agglomerates of said metal particles are formed.
  • a method of the present invention is preferred, wherein the activation composition is substantially free of or does not comprise a compound encapsulating fully or partly the metal particles or which fully or partly adsorbs onto the surface of the particles. It is believed that some stabilizer compounds are based on such a function. In the context of the present invention this is not desired.
  • the activation composition is substantially free of or does not comprise a compound preventing the equilibrium from being reversible and/or is substantially free of or does not comprise a compound in order to shift the equilibrium entirely towards the metal particles.
  • the one or more than one reducing agent is not considered to be such a compound for the reasons outlined above.
  • the activation composition is substantially free of or does not comprise tin ions, preferably is substantially free of or does not comprise tin ions, lead ions, germanium ions, gallium ions, antimony ions, bismuth ions, and aluminium ions, more preferably is substantially free of or does not comprise metal ions of main groups III, IV, and V of the periodic table of elements.
  • metal ions of main group III does not include respective boron-containing ions.
  • tin ions are very well known to prevent oxidation of for example copper particles in respective palladium-free copper-tin activation compositions, thereby preventing the equilibrium from being reversible. Such tin ions typically form a reductive environment, which is by no means desired in the context of the present invention.
  • the activation composition is substantially free of or does not comprise polyvinylpyrrolidone, preferably is substantially free of or does not comprise a polyvinyl compound, more preferably is substantially free of or does not comprise an organic polymer comprising a vinyl moiety, most preferably is substantially free of or does not comprise a dissolved organic polymer.
  • Preferred is a method of the present invention, wherein the activation composition is substantially free of or does not comprise gelatin.
  • the activation composition is substantially free of or does not comprise thiourea, preferably is substantially free of or does not comprise sulfur-containing compounds with divalent sulfur, more preferably is substantially free of or does not comprise sulfur-containing compounds with sulfur in an oxidation number of +5 or below.
  • the activation composition is substantially free of or does not comprise a compound comprising an aromatic ring and a sulfonic acid group (including salts thereof), preferably is substantially free of or does not comprise a sulfonic acid or salts thereof.
  • the activation composition is substantially free of or does not comprise polyethylenimine, preferably is substantially free of or does not comprise polyalkylenimine, most preferably is substantially free of or does not comprise an organic polymer comprising an imine moiety.
  • polymers as mentioned above are commonly used as stabilizer compounds in order to stabilize the metal particles.
  • polymers are not necessary in the context of the present invention.
  • the metal particles are significantly more effective I more active if no such molecules are forming a shell around the particles.
  • the activation composition is substantially free of or does not comprise sodium dodecyl sulfate, preferably is substantially free of or does not comprise an alkyl sulfate with 8 to 20 carbon atoms, more preferably is substantially free of or does not comprise an alkyl sulfate, most preferably is substantially free of or does not comprise a surfactant.
  • the activation composition is substantially free of or does not comprise a hydroquinone, pyrogallol, and/or resorcinol, preferably is substantially free of or does not comprise a hydroxy benzene.
  • hydroxy benzenes are commonly used as anti-oxidizing agents, thereby preventing the equilibrium from being reversible, which are not needed in the activation composition.
  • the activation composition is substantially free of or does not comprise an alkylene glycol, preferably is substantially free of or does not comprise a glycol.
  • the activation composition does not comprise a stabilizing compound and/or a compound preventing the oxidation of the metal particles
  • a method of the present invention is preferred, wherein the activation composition is substantially free of or does not comprise precipitating agglomerates of said metal particles. This is achieved because the oxidation is not suppressed (i.e. is not avoided) but rather the dissolved transition metal ions of at least the first species and the metal particles thereof, respectively, are repeatedly involved in said reduction and said oxidation.
  • a method of the present invention is preferred, wherein the continuous or semi-continuous oxidation is additionally or solely achieved through an oxidizing agent, which is not molecular oxygen, more preferably through a peroxide, most preferably hydrogen peroxide.
  • an oxidizing agent which is not molecular oxygen, more preferably through a peroxide, most preferably hydrogen peroxide.
  • this preferably accelerates the oxidation of the particles if this is required, e.g. if an activation composition must be inactivated and stored for longer times.
  • the activation composition In order to sufficiently facilitate the oxidation in the activation composition, preferred is a method of the present invention, wherein the activation composition continually or semi-con- tinually circulates, preferably by shaking, stirring and/or pumping. This is preferred to ensure that the oxidation is equally distributed in the entire activation composition. In other words, this ensures that the metal particles are equally contacted with an oxidizing agent, which facilitates the oxidation.
  • the activation composition is a colloidal suspension
  • the metal particles are formed from the dissolved transition metal ions through a continuous or semi-continuous reduction through the one or more than one reducing agent
  • the dissolved transition metal ions are formed from the metal particles through continuous or semi-continuous oxidation of said particles through oxidation by ambient air,
  • step (c) contacting the substrate with said activation composition such that a transition metal or a transition metal alloy is deposited on the surface of said substrate and an activated surface for metallization is obtained, wherein the metal particles are continually or semi-continually formed in situ in the activation composition by said reduction after and/or during one or more than one step (c) is carried out.
  • the present invention is also directed to a method for preparing an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization (preferably an activation composition as utilized in the method of the present invention), the method comprising the steps
  • this method for preparing an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres is used for providing an aqueous, palladium-free activation composition according to the present invention.
  • the present invention is also directed to the use of continuous or semi-continuous reduction of dissolved transition metal ions of a first species in combination with continuous or semi- continuous oxidation of metal particles of the first species in a reversible equilibrium to continually or semi-continually form in situ metal particles in an aqueous, palladium-free activation composition.
  • the present invention is also directed to an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization, the composition comprising
  • the metal particles are formed from the dissolved transition metal ions through a continuous or semi-continuous reduction through the one or more than one reducing agent
  • the dissolved transition metal ions are formed from the metal particles through continuous or semi-continuous oxidation of said particles, and
  • the activation composition of the present invention is obtained at and/or has a temperature in a range from 10°C to 90°C, preferably in a range from 14°C to 75°C, more preferably in a range from 16°C to 65°C, most preferably in a range from 18°C to 45°C, even most preferably in a range from 20°C to 32°C.
  • a temperature in a range from 18°C to 45°C preferably in a range from 20°C to 32°C, with the proviso that the one or more than one reducing agent is a borohydride, preferably sodium borohydride.
  • the activation composition of the present invention is not obtained at and/or has not a temperature above 110°C, preferably above 100°C, more preferably above 95°C. Most preferably the activation composition of the present invention is not obtained at a temperature above 110°C. This likewise preferably applies to the method of the present invention (for preparing said activation composition) and the method of the present invention.
  • step (I ll)(c) of the method of the present invention the substrate is contacted with the aqueous, palladium-free activation composition in order to obtain an activated surface for metallization by depositing the metal or metal alloy, i.e. depositing a seed or activation layer.
  • a method of the present invention wherein in step (lll)(c) the contacting is carried out at a temperature in a range from 10°C to 90°C, preferably in a range from 14°C to 75°C, more preferably in a range from 16°C to 65°C, most preferably in a range from 18°C to 45°C, even most preferably in a range from 20°C to 32°C.
  • a temperature in step (I ll)(c) in a range from 18°C to 45°C, preferably in a range from 20°C to 32°C, and wherein the reduction through the one or more than one reducing agent is a borohydride, preferably sodium borohydride.
  • step (lll)(c) the contacting is carried out for a time in a range from 1 minute to 10 minutes, preferably for 2 minutes to 8 minutes, more preferably for 3 minutes to 6 minutes, most preferably for 3.5 minutes to 5 minutes.
  • step (I ll)(c) a rinsing step is carried out.
  • a rinsed, activated surface for metallization is obtained.
  • the rinsing is carried out with water.
  • the present invention furthermore refers to a method for metallizing an activated surface of a non-conductive or carbon-fibres containing substrate, the method comprising the steps
  • step (A) of the method of the present invention for metallizing
  • the non-conductive or carbon-fibres containing substrate with the activated surface is provided as obtained by the method of the present invention; for details see text above.
  • the aforementioned, regarding the method of the present invention preferably applies to the method of the present invention for metallization, most preferably as described as being preferred.
  • Preferred is a method of the present invention (for metallizing), wherein in step (B) the first metallization layer is a distinct layer deposited on the transition metal or transition metal alloy obtained in step (I I l)(c) of the method of the present invention.
  • step (B) is a method of the present invention (for metallizing), wherein in step (B) the first metallization solution is essentially free of or does not comprise a reversible equilibrium between metal ions and particles thereof; more preferably is essentially free of or does not comprise metal/metal alloy particles, most preferably is essentially free of or does not comprise any particles.
  • step (B) is a method of the present invention (for metallizing), wherein in step (B) the first metallization solution comprises a reducing agent or does not comprise a reducing agent.
  • step (B) is carried out at a temperature in a range from 10°C to 95°C, preferably in a range from 15°C to 85°C, more preferably in a range from 20°C to 65°C, even more preferably in a range from 25°C to 55°C, most preferably in a range from 30°C to 45°C.
  • step (B) is carried out for 30 seconds to 180 minutes, preferably for 45 seconds to 120 minutes, more preferably for 1 minutes to 60 minutes, most preferably for 1 .5 minutes to 45 minutes.
  • the first metallization solution does not comprise a reducing agent and is an immersion type metallization solution, preferably comprising one or more than one species of ions selected from the group consisting of palladium ions, platinum ions, silver ions, gold ions, and mercury ions, more preferably comprising palladium ions, most preferably comprising palladium ions in a total concentration in a range from 0.05 mg/L to 20 mg/L.
  • step (B) More preferred is a method of the present invention (for metallizing), wherein in step (B) the first metallization solution is an acidic palladium immersion type metallization solution.
  • the first metallization solution is an immersion type metallization solution comprising palladium ions in a total concentration in a range from 0.09 mg/L to 10.0 mg/L, based on the total volume of the metallization solution, preferably in a range from 0.1 mg/L to 5.0 mg/L, more preferably in a range from 0.12 mg/L to 3.0 mg/L, even more preferably in a range from 0.15 mg/L to 2.0 mg/L, most preferably in a range from 0.2 mg/L to 1 mg/L, even most preferably in a range from 0.22 mg/L to 0.75 mg/L.
  • the metallization solution is acidic.
  • such a metallization solution surprisingly requires a significantly low concentration of palladium ions compared to conventional prior art metallization solutions but in the context of the present invention without compromising the metallization result/quality.
  • the first metallization solution comprises a reducing agent and is an autocatalytic type metallization solution, preferably comprising one or more than one species of transition metal ions, more preferably comprising copper ions and/or nickel ions.
  • the first metallization solution is, preferably it is a clear solution without particles.
  • a first metallizing solution being an autocatalytic type metallization solution comprising copper ions and a reducing agent such that a first metallization layer comprising copper or a copper alloy is deposited on the activated surface.
  • metallizing the activated surface by contacting the activated surface with a first metallizing solution being an immersion type metallization solution comprising palladium ions (preferably as described before) such that a first metallization layer comprising palladium is at least partly deposited on the activated surface, and subsequently
  • step (C) Preferred is a method of the present invention (for metallizing), wherein in step (C) the second metallizing solution comprises a reducing agent, preferably comprises a reducing agent and nickel ions.
  • the second metallization layer comprises nickel; preferably is a nickel or a nickel alloy layer.
  • step (C) the second metallizing solution comprises a reducing agent, preferably comprises a reducing agent and copper ions.
  • step (C) the second metallization layer comprises copper; preferably is a copper or a copper alloy layer.
  • step (C) the second metallizing solution comprises a reducing agent, preferably comprises a reducing agent and cobalt ions.
  • step (C) the second metallization layer comprises cobalt; preferably is a cobalt or a cobalt alloy layer.
  • step (C) the second metallization layer starts deposition within 8 seconds to 30 seconds, preferably within 10 seconds to 25 seconds, most preferably within 12 seconds to 20 seconds.
  • the second metallization layer comprises nickel; preferably is a nickel or a nickel alloy layer.
  • the coverage is evaluated using an industry standard Backlight test, in which the respective substrate is sectioned, so as to allow areas of incomplete coverage to be detected as bright spots when viewed over a strong light source (compare US 2008/0038450 A1 and WO 2013/050332).
  • the quality of the coverage is determined by the amount of light that is observed under a conventional optical microscope. The results are given on a scale from D1 to D10, wherein D1 (little, incomplete coverage) means the worst result and D10 (complete, strong coverage) the best result.
  • Solder shock test :
  • the electrical reliability coupons were immersed for 10 s in a 10% H2SO4 solution at room temperature and then 40 pm of copper were electrolytically plated onto the coupons.
  • the coupons were then annealed for 6 hours at 140 °C and, after cooling to room temperature, were subjected to a solder shock test, in which the coupons were floated for 10 s on molten solder at 288 °C and then allowed to cool to room temperature again. This floating and cooling procedure was repeated a further five times.
  • the electrolessly plated ABF coupons were immersed for 10 s in a 10% H2SO4 solution at room temperature and then electrolytically plated with 35 pm of copper. After plating, the coupons were fully cured according to the Ajinomoto recommendations. The coupons were then cut into strips of 1 cm width using a routing machine. The force required to peel the copper film from these strips was measured using an Erichsen Unimat Plus 050-2kN material testing machine equipped with a 20 N load cell, at a peeling speed of 50.8 mm/min while ensuring a peeling angle of 90° at all times.
  • ABS Acrylonitrile butadiene styrene
  • FR4 FR4
  • ABSF laminated Ajinomoto build-up film
  • GX- 92R test coupons Table 1 were used for the assessment of the quality of the electroless copper deposit. The parameters tested were appearance, blistering, deposit thickness, coverage, electrical reliability and peel strength.
  • ABF GX-92R prepregs were laminated onto Bondfilm®-treated copper-clad FR4 panels using a Dynachem VA 7124-HP6 vacuum laminator (lamination conditions: 30 s vacuum time, 30 s dynamic slap-down time, 20 s static slap-down time, 2.0 mbar vacuum set point, 5.0 kg/cm 2 pressure).
  • the laminated panels were then semi-cured in an air-circulated oven according to the Ajinomoto recommendations.
  • Table 2 a Tap water rinse of approximately 60 s between each step.
  • Coupons were processed according to the conditions detailed in Table 4, which are representative of a commercially used palladium-based process.
  • Table 6 a Tap water rinse of approximately 60 s between each step, except between steps 5 and 6. b Operating parameters are known to the one skilled in the art.

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Abstract

La présente invention concerne un procédé pour traiter une surface d'un substrat non-conducteur ou contenant des fibres de carbone, le procédé comprenant les étapes de conditionnement, de traitement sélecteur et d'activation.
EP21762062.4A 2020-08-27 2021-08-26 Procédé d'activation d'une surface d'un substrat non-conducteur ou contenant des fibres de carbone destiné à la métallisation Pending EP4204600A1 (fr)

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EP20193047 2020-08-27
PCT/EP2021/073578 WO2022043417A1 (fr) 2020-08-27 2021-08-26 Procédé d'activation d'une surface d'un substrat non-conducteur ou contenant des fibres de carbone destiné à la métallisation

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US (1) US20230340673A1 (fr)
EP (1) EP4204600A1 (fr)
JP (1) JP2023539602A (fr)
KR (1) KR20230054852A (fr)
CN (1) CN116137875A (fr)
CA (1) CA3190848A1 (fr)
TW (1) TW202208681A (fr)
WO (1) WO2022043417A1 (fr)

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US4278712A (en) 1978-08-31 1981-07-14 Surface Technology, Inc. Method for activating non-noble metal colloidal dispersion by controlled oxidation for electroless plating
EP1876262A1 (fr) 2006-07-07 2008-01-09 Rohm and Haas Electronic Materials, L.L.C. Compositions de dépôt autocatalytique sans danger pour lýenvironnement
WO2013050332A2 (fr) 2011-10-05 2013-04-11 Atotech Deutschland Gmbh Solution pour cuivrage autocatalytique exempte de formaldéhyde
EP3181724A3 (fr) * 2015-12-14 2017-08-16 Rohm and Haas Electronic Materials LLC Catalyseurs écologiques stables pour la métallisation autocatalytique de cartes de circuits imprimés et de trous traversants
CN107460459A (zh) 2017-06-29 2017-12-12 深圳安德万斯新材料科技有限公司 一种纳米铜活化液及其制备方法
CN109295442A (zh) 2018-10-15 2019-02-01 河北工业大学 胶体铜活化碳纤维并一步制备化学镀铜-镍双金属层的方法
EP3947772A1 (fr) 2019-04-04 2022-02-09 ATOTECH Deutschland GmbH Procédé d'activation d'une surface d'un substrat contenant des fibres non conductrices ou de carbone destiné à la métallisation

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JP2023539602A (ja) 2023-09-15
CN116137875A (zh) 2023-05-19
US20230340673A1 (en) 2023-10-26
CA3190848A1 (fr) 2022-03-03
KR20230054852A (ko) 2023-04-25
WO2022043417A1 (fr) 2022-03-03
TW202208681A (zh) 2022-03-01

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