WO2011035921A1 - Procédé d'application de revêtement métallique sur un substrat non conducteur - Google Patents

Procédé d'application de revêtement métallique sur un substrat non conducteur Download PDF

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Publication number
WO2011035921A1
WO2011035921A1 PCT/EP2010/005851 EP2010005851W WO2011035921A1 WO 2011035921 A1 WO2011035921 A1 WO 2011035921A1 EP 2010005851 W EP2010005851 W EP 2010005851W WO 2011035921 A1 WO2011035921 A1 WO 2011035921A1
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WIPO (PCT)
Prior art keywords
metal
substrate
process according
foregoing
solution
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PCT/EP2010/005851
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English (en)
Inventor
Wei Jie Wu
Ke Liang Pan
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Atotech Deutschland Gmbh
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Filing date
Publication date
Application filed by Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Priority to EP10759590A priority Critical patent/EP2483443A1/fr
Priority to US13/394,165 priority patent/US20120160697A1/en
Priority to CN201080043209.6A priority patent/CN102549196B/zh
Publication of WO2011035921A1 publication Critical patent/WO2011035921A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the invention relates to a process for applying a metal coating to a non- conductive substrate and to a composition used in this process which is electrically treated to enhance its performance.
  • the surfaces to be metallised are, after an appropriate preliminary treatment, either firstly catalysed and then metallised in an electroless manner and thereafter, if necessary, metallised electrolytically, or are directly electrolyti- cally metallised.
  • Electroless copper depositing solutions to which the invention described in US 4,938,853 relates are those of the type comprised of aqueous solutions of a bath-soluble source of copper ions (e.g., copper sulfate), a reducing agent (e.g., formaldehyde or a soluble source of hypophosphite such as sodium hypophophite), a complexing agent for copper ions (e.g., the hydroxy acids and their metal salts such as the tartrates, gluconates, glycolates, lactates and the like, amine-type agents such as N-hydroxyethyl ethylenediamine triace- tic acid (HEEDTA), ethylenediamine tetraacetic acid (EDTA), and the like).
  • a bath-soluble source of copper ions e.g., copper sulfate
  • a reducing agent e.g., formaldehyde or a soluble source of hypophosphite such as sodium hypophophit
  • the bath generally will further comprise pH adjusting agents (acids, bases, buffers) to attain optimum operating pH, and typically will contain further additives for brightening, levelling or other like functions.
  • the baths may also contain additional metal species, such as bath-soluble nickel and/or cobalt compounds which may be required to render the bath autocatalytic.
  • planar anode surfaces are not critical as such, so long as adequate current density can be achieved to effect the oxidation of a substantial portion of the copper metal fines in the vessel and bath and, most preferably, the dimensions of the overall planar anode surface should be such as to occupy (or reside over) most (i.e., greater than about 50%, and preferably greater than about 75%) if not substantially all of the vessel bottom area such that the majority of fines which drop to the vessel bottom will fall upon the anode surface.
  • the equipment and process disclosed in US 4,938,853 serves to redissolve metal copper particles.
  • US 2002/0079226 A1 discloses an electroless plating method, comprising oxidizing first metal ions of a redox system of a plating bath from a lower oxidation state to a higher oxidation state, and second metal ions of said redox system are reduced and deposited onto the surface of an object to be plated, wherein a process is provided in which by supplying an electrical current to the plating bath, the first metal ions are reduced from said higher oxidation state to said lower oxidation state to thereby activate the plating bath.
  • EP 0 616 053 A1 there is disclosed a method for direct metallisation of non- conductive surfaces, in which the surfaces are firstly treated with a cleaner/conditioner solution, thereafter with an activator solution, for example a palladium colloidal solution, stabilised with tin compounds, and are then treated with a solution which contains compounds of a metal which is more noble than tin, as well as an alkali hydroxide and a complex former. Thereafter the surfaces can be treated in a solution containing a reducing agent, and can finally be elec- trolytically metallised.
  • an activator solution for example a palladium colloidal solution
  • stabilised with tin compounds stabilised with tin compounds
  • a solution which contains compounds of a metal which is more noble than tin as well as an alkali hydroxide and a complex former.
  • WO 96/29452 concerns a process for the selective or partial electrolytic metallisation of surfaces of substrates made from electrically non-conducting materials which for the purpose of the coating process are secured to plastic-coated holding elements.
  • the proposed process involves the following steps: a) preliminary treatment of the surfaces with an etching solution containing chromium (VI) oxide; followed immediately by b) treatment of the surfaces with a colloidal acidic solution of palladiunWtin compounds, care being taken to prevent prior contact with adsorption-promoting solutions; c) treatment of the surfaces with a solution containing a soluble metal compound capable of being reduced by tin (II) compounds, an alkali or alkaline earth metal hydroxide, and a complex forming agent for the metal in a quantity sufficient at least to prevent precipitation of metal hydroxides; d) treatment of the surfaces with an electrolytic metallisation solution.
  • This object is achieved by a process for applying a metal coating to a non- conductive substrate comprising the steps of
  • composition comprising a solution of:
  • step (iii) a complexing agent for an ion of the metal of said metal salt comprising an organic material having a cumulative formation constant log K of from about 0.73 to about 21.95 for an ion of the metal of said metal salt, characterised in that the composition according to step (b) is treated with an electrical current for a period of time prior to or during contacting said solution with the substrate.
  • the process according to the present invention does not apply an electroless coating process.
  • the method applied according to the present invention is directed to a two step process consisting of the steps (a) and (b) described above in which the conductivity of the initially non-conductive substrate is increased by means of an immersion metal composition (b) as described above. After such treatment the substrate is sufficiently conductive to be directly elec- trolytically coated with a metal.
  • composition according to 1 (b) does not require an added reducing agent like formaldehyde or hypophosphite.
  • Figure 1 shows a typical set up of a system according to the present invention having a current source to provide an electrical current to compositions according to step (b) for treatment of substrates.
  • the current density preferably ranges between 0.01 and 10 A/dm 2 as measured on the cathode, more preferred between 0.05 and 1 A/dm 2 and even more preferred between 0.1 and 0.5 A/dm 2 .
  • the electrical current can be applied continuously while contacting the substrate with a composition according to step (b).
  • the electrical current can be applied prior to contacting the substrate with a composition according to step (b) and be stopped during immersion of the substrate.
  • the electrical current can be applied prior to contacting the substrate with a composition according to step (b) and additionally during immersion of the substrate.
  • the electrical current is usually applied for a time between 30 s and 120 minutes, more preferred between 10 and 60 minutes and even more preferred between 20 - 40 minutes.
  • the electrical current can be applied once to a composition according to step (b)described herein and thereafter several substrates may be treated in such treated composition. Alternatively, the electrical current may be applied before each treatment in the composition.
  • the electrical current When the electrical current is applied continuously while contacting the substrate with a composition according to step (b) this can preferably be done during the entire immersion of the substrate into the solution. Alternatively, the current may be discontinued at some point during the immersion of the substrate.
  • the anode material used preferably is stainless steel, copper, a copper alloy like brass, titanium, platinized titanium, graphite, iridium or rhodium.
  • the cathode material can be the same or different as the anode material.
  • Preferably used is stainless steel, copper, a copper alloy like brass, titanium, platinized titanium, graphite, iridium or rhodium. Because of the mechanism to employ a metal layer to an initially non-conductive substrate by treating the substrate with compositions (a) and (b) as described above, the substrate cannot serve as a cathode.
  • the dimensions of the anode and cathode may vary according to the current applied, geometry of the work pieces (substrates), concentrations of compounds in a composition according to step (b), temperature of the solution etc.
  • the anode and cathode can have dimensions from 90 cm x 300 cm to 10 cm x 10 cm, preferred from 90 cm x 30 cm to 30 cm x 30 cm.
  • the dimensions of the anode and the cathode can be the same or different. This depends on the tank size and the facility limitation e.g. maximum current which can be applied. Optimum dimensions of cathode and anode can be determined in routine experiments.
  • the standard shape of the anodes and cathodes is rectangular or square.
  • a typical set up of a system (1) according to the present invention is shown in Figure 1.
  • the treatment liquid (2) is a composition according to step (b) as described above.
  • a substrate (4) is immersed into such treatment liquid using a holding device (5).
  • a set up for supplying an electrical current (3) comprises a source of an electrical current, rectifier (3a), an anode (3b) and a cathode (3c).
  • the electrical treatment of the composition according to step (b) results in reduced chemical consumption, less drag-out of precious metals and higher production reliability.
  • the non-conductive substrates to be coated according to the process of the present invention are not particularly limited. These substrates include plastic parts which are intensely structured, such for example as combs or articles designed with a substantial extension in the third dimension, e.g. coffee pots, telephone handsets, water pipe fittings, etc. However, also other non-conductive substrates such as ceramic substrates or other metal oxide non-conductive substrates can be coated according to the present invention. In addition, small surfaces such as through-hole walls of printed circuit boards can be coated.
  • the non-conductive substrates can be a polymer, selected from the group consisting of polyolefins like polystyrene, polystyrene copolymers such as poly(styrene-butadiene-styrene, SBS), polypropylene, polyethylene; polyam- ides; copolymers of acrylonitrile and methyl acrylate, acrylonitrile and methyl- methacrylate, vinyl chloride and styrene (SAN), butadiene and styrene (ABS), butadiene, styrene (ABS) and polycarbonate (PC); polyimides, polyesters, phenolic resins, and epoxides.
  • the non-conductive substrate can be a glass substrate.
  • the non-conductive substrate Prior to treating the non-conductive substrate with an activator according to step (a), it may be immersed in a commercial pre-dip containing NaCI, SnC ⁇ and HCI, the pH of which is below about 0.5.
  • the substrate is then treated with an activator according to step (a) comprising a noble metal/Group IVA metal sol.
  • Noble metals comprise Ag or Au or Group VIII noble metals including Ru, Rh, Pd, Os, Ir, Pt, or various mixtures of such noble metals.
  • the preferred noble metals are the Group VIII noble metals and especially palladium.
  • the activator of the present invention is prepared in such a fashion that there is excess Group IVA metal compound reducing agent present, i.e., a stoichiometric excess of reducing agent (e.g., divalent tin) compared to the noble metal compound (e.g., divalent Pd) from which the activator is made.
  • reducing agent e.g., divalent tin
  • the noble metal compound e.g., divalent Pd
  • the Group IVA metals that may be employed include, for example, Ge, Sn and Pb, or mixtures thereof Sn being preferred.
  • the activator preferably will contain a stoichiometric excess of the Group IVA metal as compared to the noble metal.
  • the Group IVA metal is substantially in its lowest oxidation state so that it will be available to reduce the more noble metal salts that are employed in forming the activator. Because it is also employed in a stoichiometric excess based on the salts of the noble metal that are employed to form the activator, the excess of the Group IVA metal in combination with the activator will also be substantially in its lowest oxidation state.
  • the activator thus prepared with the excess of the Group IVA metal in its lowest oxidation state will also be available to reduce the Group IB or other more noble metal salts that are subsequently brought into contact with the activator in step (b) as described above, such as the salts of copper as described herein.
  • the Group IVA metal is preferably employed as a salt, such as a halide and especially a chloride, but in any event, will be present in an amount so that the molar ratio of the Group IVA metal to the noble metal of the activator is from 4:1 to 95:1 , especially 10:1 to 55:1 and preferably from 15:1 to 50:1.
  • Some specific Group IVA metal salts that may be used in this regard comprise PbC , SnC ⁇ or a mixture of GeC and GeCU dissolved in dilute hydrochloric acid.
  • the preferred Group IVA metal comprises tin and especially tin in the form of stannous chloride.
  • the activator comprises at least 10 mg/l of palladium and usually not more than 400 mg/l as noble metal. Preferred is a range between preferably 30 - 130 mg/l. The higher the palladium concentration the higher the palladium drag out, which is disadvantageous. Therefore, it is an aim to reduce the palladium concentration in the activator. If the palladium concentration is too small, though, subsequent metallisation of the activated substrate remains incomplete.
  • the preparation of the activator is conventional and is disclosed in United States Patent No. 3,011 ,920 and United States Patent No. 3,682,671.
  • the treated substrate after the activator solution has been applied in step (a), is rinsed and then treated with the above mentioned composition according to step (b) comprising the Cu(ll), Ag, Au or Ni soluble metal salt, the group IA metal hydroxide and the complexing agent for the ions of the metal of the aforementioned metal salts, comprising Ag + , Ag 2+ , Au ⁇ Au 2+ and Ni 2+ salts.
  • the metal salt is a Cu(ll) salt, e.g. copper sulfate.
  • anywhere from 0.0002 to 0.2 mol/l and especially from 0.004 to 0.01 mol/l of the said metal salt may be employed in the bath where the solvent preferably comprises water.
  • the temperature of the composition may vary from 40°C to 85°C. Treatment time ranges from 4 to 12 minutes or more which is typical for production purposes, however, may vary out of this range depending on the temperature and condition of the bath. The time used is actually the time necessary to provide the best metal coverage for the formation of the conductive coating or to provide minimum required coverage.
  • the composition according to step (b) includes a source of hydroxide ions.
  • the source of hydroxide ions is a Group IA metal hydroxide in an amount from 0.05 to 5 mol/l, preferably 1 to 3 mol/l and most preferred 1.5 to 2 mol/l.
  • the Group IA metals in this regard comprise Li, Na, K, Rb, Cs or mixtures thereof, especially Li, Na, K and mixtures thereof and preferably a metal comprising Li.
  • the complexing agent is employed in an amount sufficient for the bath to form a thin, dense metal-rich catalytic coating on the substrate with sufficient electrical conductivity for subsequent electroplating and at the same time produce relatively clean metal surfaces.
  • the complexing agent is used in an amount of 0.005 to 1.5 mol/l, preferably 0.05 to 1 mol/l and most preferably 0.2 to 0.5 mol/l.
  • Suitable complexing agents include complexing agents selected from the group consisting of acetate, acetylacetone, citric acid, 1 ,2-diaminocyclohexane- ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetic acid, dimethylglyoxime (50% dioxane), 2,2'-dipyridyl, etha- nolamine, ethylenediamine, ethylenediamine ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetic acid, glycine, N'-(2-hydroxyethyl)ethylenediamine-N,N,N'-triacetic acid, 8-hydroxy-2-methyl- quinoline (50% dioxane), 8-hydroxyquinoline-5-sulfonic acid, lactic acid, ni- trilotriacetic acid, 1-nitroso-2-naphthol (75% dioxane), oxalate, 1 ,10- phenanthroline, phthalic acid, piperidine, prop
  • alkanolamines comprising for example monoethanolamine.
  • Alkanolamines in addition to monoethanolamine include the following lower alkanolamines: diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, mono-sec-butanolamine, di-sec-butanolamine, 2-amino-2- methyl-1 -propanediol, 2-amino-2-ethyl-1 ,3-propanediol, 2-dimethylamino-2- methyl-1-propanol, tris(hydroxymethyl)aminomethane, and various mixtures of the alkanolamines.
  • weak complexing agents can be used such as other amines, including aliphatic and cyclic, e.g., aromatic amines having up to 10 carbon atoms all of which are described in Kirk-Othmer, Encyclopedia of Chemical Technology under "Amines”. Additionally, mono and poly carboxylic acids having up to 8 carbon atoms and their salts can be used and include amino acids. These acids are also defined in Kirk-Othmer, Id. under “Carboxylic Acids” and "Amino Acids”. The preferred acids in this regard include gluconic acid, lactic acid, acetic acid and tartaric acid.
  • Another preferred complexing agent is iminosuccinic acid or a derivative thereof. This group of complexing agents further helps to reduce the amount of noble metal such as palladium in the activator.
  • Suitable iminosuccinic acid derivatives for use in the present invention include those having the formula (I) shown below:
  • Ri is selected from the group consisting of H, Na, K, NH 4 , Ca, Mg, Li and Fe,
  • R 2 is selected from the group consisting of
  • R 3 is selected from the group consisting of H, -CH2-COOR1 , -CH 2 -CH 2 -COORi , -CH2-CH2-OH, -CH2-CHOH-CH3 and -CH2-CHOH-CH2OH.
  • WO 00/26398 describes a method of producing compounds of formula (I) and their mixtures on the basis of carbohydrates by fermentation in the presence of microorganisms.
  • the iminosuccinic acid derivative is the iminosuccinic acid sodium salt having the following structural formula:
  • the various anions of the above mentioned water-soluble metal salts include inorganic acid anions or mixtures thereof such as the halogen anions, i.e., F “ , CI “ , Br “ or I “ , CI “ being especially preferred, sulfate or carbonate anions, lower molecular weight organic acid anions such as formate or acetate anions or sali- cylate anions and the like. Additionally, mixtures of the foregoing anions can be employed as well as salt-like anions such as CUCI 2 2KCI.2H 2 O, CuCl 2 2NaCI.2H 2 0 and the various art known equivalents thereof.
  • the composition according to step (b) does not contain an added reducing agent like formaldehyde or hypophosphite suitable to reduce the metal ions of the composition, i.e. Cu 2+ , Ag + , Au 2+ or Ni 2+ . It also does not contain a metal redox system suitable to reduce metal ions.
  • the reduction of metal ions present in the composition according to step (b), e.g. Cu(ll) ions, is by the activator employed to the non-conductive substrate in preceding step (a) as described herein before.
  • no additional reducing agent in the composition according to step (b) is required.
  • the method according to the present invention is different from electroless plating methods.
  • the composition according to step (b) only serves to provide a first very thin conductive coating of the respective metal, e.g. a copper layer in case the composition according to step (b) contains Cu(ll) ions.
  • the conductive coating is then electrolytically coated by methods well known in the art to obtain a metal coating of sufficient thickness.
  • step (b) Subsequent electroplating is best achieved if the conductive coating is micro- etched in an acidic oxidising medium so that the adhesion and morphology of the electrolytically applied metal coating (e.g. copper) as formed in step (b) is optimised.
  • Microetching is effected by an acidic oxidising agent which is conventional in the art, however, it has been found that even short exposures of the metal coating (e.g. about one-half minute) to the microetch solution causes a loss in conductivity and if microetching is carried out over a period of time for about two minutes the coating loses substantially all of its conductivity which indicates it is most likely entirely removed from the substrate.
  • the substrate after the substrate has been treated with the composition according to step (b) it is then preferably rinsed with water and subjected to a neutrali- sation and reducing bath to eliminate this problem.
  • the neutralisation and reducing bath neutralises the residual alkali on the treated surfaces and also improves the resistance of the conductive metal coating to oxidising chemical mi- cro-etchants.
  • the neutralisation and reducing steps may be conducted separately, i.e., in separate steps employing a first acid neutralisation bath and a second reducing bath.
  • Reducing agents that may be employed in this regard are generally disclosed in United States Patent No. 4,005,051 and EP-A-0 616 053.
  • the present invention is directed to a two-step process wherein the conductivity is increased initially by applying a very thin metal coating.
  • a very thin metal coating is made of copper.
  • at least one metal layer is deposited electrolytically on the conductive coating to obtain a finally coated substrate having a sufficient metal layer thickness.
  • Example 1 The present invention is further illustrated by the following examples.
  • Example 1 The present invention is further illustrated by the following examples.
  • Example 1
  • compositions (A) and (B) were prepared as shown below:
  • composition (A) was 4.1.
  • the pH of composition (B) was 13.
  • composition (A) 90 ml/I of composition (A) and 13 ml/l of composition (B) were mixed to obtain a bath comprising the above mentioned components and ingredients and to be employed as a composition according to step (b) described above.
  • the substrates were treated in a solution for four minutes at 40°C, the solution being composed as follows (to be employed as an activator according to step (a) described above): Colloidal solution containing 120 ppm palladium as palladium chloride, 35 g/l stannous chloride (18.5 g/l Sn) and 350 ml/l hydrochloric acid with a pH of 1 or less for 4 minutes.
  • the substrates were again rinsed. After the rinsing treatment, the substrate was immersed into the bath obtained from compositions (A) and (B), composition according to step (b). The temperature applied was 60°C, treatment time was 3 minutes.
  • Substrate Sample 1 (Table 1), comparative: No electrical current was applied either prior or during immersion of the substrate.
  • Substrate Sample 2 (Table 1): An electrical current of 0.2 A/dm 2 was applied (as measured on the cathode) to such composition during immersion of the substrate.
  • the anode material used was copper, the cathode material brass.
  • the treatment tank containing a solution according to step (b) had the dimensions of 20 cm x 20 cm x 20 cm and a volume of 8 I of treatment liquid.
  • the anode and cathode had dimensions of 10 cm x 19 cm.
  • Example 1 The results obtained in Example 1 are summarised in Table 1 below.
  • the amount of palladium absorbed on the surface of the treated substrates is about the same for Sample 1 (0.35 mg/dm 2 ) and Sample 2 (0.36 mg/dm 2 ) since the same solution is used for activation.
  • the substrates treated according to Example 1 were washed with water and then subjected to a subsequent copper electroplating step.
  • a commercially available copper electroplating bath Cupracid® Ultra (Atotech Deutschland GmbH) was used, which contains 250 g/l copper sulfate, 50 g/l sulphuric acid, 50 ppm chloride ions and a brightening agent.
  • Sample 1 no electrical treatment: incomplete metal coverage of the surface, voids remaining.
  • Sample 2 electrical treatment: complete metal coverage of the surface, no voids remaining, very good plating result.
  • the higher amount of metallic Cu (0) absorbed on the substrate surface as treated with a process according to the present invention results in an excellent final metal coating deposited thereon.
  • a treatment not applying an electrical current does not result in a completely metallised surface of the non-conductive surface.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
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  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention porte sur un nouveau procédé d'application d'un revêtement métallique sur un substrat non conducteur qui comporte les étapes consistant (a) à mettre en contact le substrat avec un activateur qui comporte un sol de métal noble/métal du groupe IVA pour obtenir un substrat traité, (b) à mettre en contact ledit substrat traité avec une composition qui comporte une solution composée : (i) d'un sel métallique soluble de Cu(II), d'Ag, d'Au ou de Ni ou des mélanges de ceux-ci, (ii) de 0,05 à 5 mol/l d'un hydroxyde de métal du groupe IA et (iii) d'un agent complexant pour un ion du métal dudit sel métallique comportant une matière organique ayant une constante de formation cumulée log K d'environ 0,73 à environ 21,95 pour un ion du métal dudit sel métallique, le procédé étant caractérisé en ce que la composition selon l'étape (b) est traitée par un courant électrique pendant un certain temps avant et/ou pendant la mise en contact de ladite solution avec le substrat.
PCT/EP2010/005851 2009-09-28 2010-09-22 Procédé d'application de revêtement métallique sur un substrat non conducteur WO2011035921A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10759590A EP2483443A1 (fr) 2009-09-28 2010-09-22 Procédé d'application de revêtement métallique sur un substrat non conducteur
US13/394,165 US20120160697A1 (en) 2009-09-28 2010-09-22 Process for applying a metal coating to a non-conductive substrate
CN201080043209.6A CN102549196B (zh) 2009-09-28 2010-09-22 用于将金属涂层施加到非电导性基体上的方法

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CN102549196A (zh) * 2009-09-28 2012-07-04 安美特德国有限公司 用于将金属涂层施加到非电导性基体上的方法
CN104169465A (zh) * 2012-03-15 2014-11-26 安美特德国有限公司 将非电导塑料表面金属化的方法

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EP3271964A4 (fr) * 2015-03-19 2018-10-17 Primus Power Corporation Compositions d'électrolyte de batterie de type flux contenant un agent chélateur et un amplificateur de placage de métal
WO2018033461A1 (fr) * 2016-08-15 2018-02-22 Atotech Deutschland Gmbh Composition acide aqueuse pour cuivrage électrolytique
FR3061601B1 (fr) * 2016-12-29 2022-12-30 Aveni Solution d'electrodeposition de cuivre et procede pour des motifs de facteur de forme eleve
CN110952118A (zh) * 2019-11-20 2020-04-03 中电国基南方集团有限公司 一种陶瓷电路无氰镀铜溶液、配制方法及电镀工艺

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CN102549196A (zh) * 2009-09-28 2012-07-04 安美特德国有限公司 用于将金属涂层施加到非电导性基体上的方法
CN102549196B (zh) * 2009-09-28 2015-07-22 安美特德国有限公司 用于将金属涂层施加到非电导性基体上的方法
CN104169465A (zh) * 2012-03-15 2014-11-26 安美特德国有限公司 将非电导塑料表面金属化的方法

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CN102549196B (zh) 2015-07-22
TW201120254A (en) 2011-06-16
CN102549196A (zh) 2012-07-04
EP2483443A1 (fr) 2012-08-08
EP2305856A1 (fr) 2011-04-06
US20120160697A1 (en) 2012-06-28

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