EP2639334A1 - Procédé de métallisation de surfaces en matière synthétique non conductrices - Google Patents

Procédé de métallisation de surfaces en matière synthétique non conductrices Download PDF

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Publication number
EP2639334A1
EP2639334A1 EP20120159659 EP12159659A EP2639334A1 EP 2639334 A1 EP2639334 A1 EP 2639334A1 EP 20120159659 EP20120159659 EP 20120159659 EP 12159659 A EP12159659 A EP 12159659A EP 2639334 A1 EP2639334 A1 EP 2639334A1
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EP
European Patent Office
Prior art keywords
solution
pickling
plastic
acid
alkaline
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.)
Withdrawn
Application number
EP20120159659
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German (de)
English (en)
Inventor
Dr. Hermann Middeke
Enrico Kuhmeiser
Steve Schneider
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to EP20120159659 priority Critical patent/EP2639334A1/fr
Priority to BR112014021969-9A priority patent/BR112014021969B1/pt
Priority to CA2866769A priority patent/CA2866769C/fr
Priority to PT137094421T priority patent/PT2825688T/pt
Priority to KR1020147028905A priority patent/KR101872066B1/ko
Priority to CN201380014402.0A priority patent/CN104169466A/zh
Priority to EP13709442.1A priority patent/EP2825688B1/fr
Priority to JP2014561462A priority patent/JP6246139B2/ja
Priority to ES13709442.1T priority patent/ES2587730T3/es
Priority to PCT/EP2013/055357 priority patent/WO2013135863A1/fr
Priority to US14/379,497 priority patent/US9051643B2/en
Priority to PL13709442.1T priority patent/PL2825688T3/pl
Priority to CN201910131690.7A priority patent/CN109913860A/zh
Publication of EP2639334A1 publication Critical patent/EP2639334A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the present invention relates to a method of metallizing electrically non-conductive plastic surfaces of articles using pickling solutions that are free of hexavalent chromium.
  • the pickling solutions are based on permanganate solutions. After treatment with the pickling solutions, the articles can be metallized by known methods.
  • Articles of electrically non-conductive plastic may be metallized by an electroless plating process or alternatively by a direct plating process. In both methods, the article is first cleaned and pickled, then treated with a precious metal and finally metallized. The pickling is typically carried out by means of chromic acid. The etching serves to make the surface of the object susceptible to the subsequent metallization, so that the surfaces of the objects in the subsequent treatment steps are well wetted with the respective solutions and the deposited metal finally adheres sufficiently firmly to the surface.
  • the surface of articles of, for example, acrylonitrile-butadiene-styrene copolymer (ABS copolymer) is etched using chromosulfuric acid, so that superficially microcaverns form, in which metal is deposited and subsequently adheres firmly there.
  • ABS copolymer acrylonitrile-butadiene-styrene copolymer
  • the plastic for electroless metallization by means of an activator containing a noble metal, activated and then electroless metallized. Subsequently, a thicker metal layer can be applied electrolytically.
  • the pickled surface is typically treated with a palladium colloid solution.
  • the surface is brought into contact with an alkaline solution containing complexed copper ions complexed to increase the conductivity.
  • This step results in the formation of a copper layer and thus a metal layer on the surface of the article of increased conductivity.
  • the article can be electrolytically metallized directly ( EP 1 054 081 B1 ).
  • pickling solutions based on chromosulfuric acid are toxic and should therefore be replaced as far as possible.
  • EP 1 0010 52 is an acidic permanganate solution which is said to be suitable for use in plastic plating.
  • the solutions described therein differ in many respects from the present invention, for example because they use very high acid concentrations and very low permanganate concentrations (eg 15 MH 2 SO 4 and 0.05 M KMnO 4 ).
  • EP 1 0010 52 does not report the bond strengths achievable with this pickling treatment. Our own tests have shown that the adhesive strengths are below a value of 0.4 N / mm.
  • the in EP 1 0010 52 not stable solutions described. A constant quality of the metallization can therefore not be achieved.
  • chromic acid As an alternative to chromic acid are in WO 2009/023628 A2 strongly acidic solutions containing an alkali permanganate salt proposed.
  • the solution contains about 20 g / l alkali permanganate salt in 40-85% by weight phosphoric acid.
  • Such solutions form colloidal manganese (IV) species that are difficult to separate.
  • the WO 2009/023628 A2 lead the colloids after a short time to a coating of sufficient quality is no longer possible.
  • the WO 2009/023628 A2 to use sources of manganese (VII) that contain no alkali or alkaline earth ions.
  • the preparation of such manganese (VII) sources is expensive. Therefore, the toxic chromosulfuric acid is still used for the pickling treatment of plastics.
  • the present invention is therefore based on the problem that it has not been possible to achieve a metallization of objects made of electrically non-conductive plastic in an ecologically safe manner with sufficient process reliability and adhesion of the subsequently applied metal layers. Furthermore, it has hitherto not been possible to obtain an adherent, large-area metallization of objects made of electrically non-conductive plastic by direct electroplating, if the plastic was not pickled with chromic-sulfuric acid prior to the metallization.
  • articles are understood to mean objects which are made of at least one electrically non-conductive plastic or which are covered with at least one layer of at least one electrically non-conductive plastic.
  • the objects thus have surfaces of at least one electrically non-conductive plastic.
  • plastic surfaces are understood as meaning said surfaces of the objects.
  • process steps of the present invention are carried out in the order given, but not necessarily immediately consecutively. It is possible to carry out further process steps and, in each case, additional rinsing steps, preferably with water, between the steps.
  • the pickling according to the invention results in the plastic surface with pickling solutions which at least one acid pickling solution and at least one alkaline pickling solution comprise (method step A)) to a significantly higher coverage of the plastic surfaces with a metal during activation of the plastic surfaces with a solution of a colloid or a compound of a metal.
  • pickling solutions which at least one acid pickling solution and at least one alkaline pickling solution comprise (method step A)) to a significantly higher coverage of the plastic surfaces with a metal during activation of the plastic surfaces with a solution of a colloid or a compound of a metal.
  • the plastic surfaces are made of at least one electrically non-conductive plastic.
  • the at least one electrically nonconducting plastic is selected from the group comprising an acrylonitrile-butadiene-styrene copolymer (ABS copolymer), a polyamide (PA), a polycarbonate (PC) and a mixture of an ABS copolymer with at least one other polymer.
  • the electrically non-conductive plastic is an ABS copolymer or a mixture of an ABS copolymer with at least one further polymer.
  • the at least one further polymer is particularly preferably polycarbonate (PC), that is to say particularly preferred are ABS / PC mixtures.
  • the treatment of the rack with a solution containing a source of iodate ions is also referred to below as protecting the rack.
  • the protection of the frame can take place at different times during the method according to the invention.
  • the articles are not yet secured in the frame.
  • the frame alone, without the objects, is treated with the solution containing a source of iodate ions.
  • the attachment of the articles in racks allows the simultaneous treatment of a large number of articles with the successive solutions of the individual process steps as well as the electrical contacting during the last steps to produce electrolytic deposition of one or more metal layers.
  • the treatment of the articles according to the method of the invention is preferably carried out in a conventional dipping process by successively immersing the articles in solutions in containers in which the respective treatment takes place.
  • the articles can either be attached to racks or filled with drums into the solutions.
  • the articles can also be treated in so-called continuous installations, for example by lying on trays and being conveyed continuously through the installations in a horizontal direction.
  • An attachment to racks is preferred.
  • the racks are usually self-coated with plastic.
  • the plastic is usually polyvinyl chloride (PVC).
  • the protection of the frame may be performed prior to the attachment step.
  • This further method step is referred to below as a pretreatment step.
  • this pretreatment step the adhesion between the plastic and the metal layer is increased.
  • the pretreatment step is carried out between the fastening step and method step A).
  • a glycol compound is understood as meaning compounds of the following general formula (I): wherein n is an integer between 1 and 4; and R 1 and R 2, independently of one another, denote -H, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -CH 2 -CH 2 - CH 3 , -CH (CH 3 ) -CH 2 -CH 3 , -CH 2 -CH (CH 3 ) -CH 3 , -CH 2 -CH 2 -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 2 -CH 2 -CH 3 , -CH 2 -CH (CH 3 ) -CH 2 -CH 3 , -CH 2 -CH (CH 3 ) -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH 2 -CH
  • the glycol compounds include the glycols themselves as well as glycol derivatives.
  • the glycol derivatives, the glycol esters and the glycol ether esters are calculated as glycol derivatives.
  • the glycol compounds are solvents.
  • Preferred glycol compounds are ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, butyl glycol, ethylene glycol monobutyl ether, ethylene glycol diacetate and mixtures thereof.
  • Particularly preferred are diethylene glycol monoethyl ether acetate, ethylene glycol acetate, ethylene glycol diacetate, butyl glycol and mixtures thereof.
  • glycol esters and glycol ether esters it is useful to keep the pH of the aqueous solution of the glycol compound in the neutral range by suitable measures in order to force back the hydrolysis to the alcohol and the carboxylic acid as much as possible.
  • An example is the hydrolysis of diethylene glycol monoethyl ether acetate: CH 3 -CO-O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 3 + H 2 O ⁇ CH 3 -COOH + HO-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 3
  • the water concentration of the solution containing a glycol compound also has a Influence on the hydrolysis of the glycol esters and glycol ether esters.
  • the solution must contain water for two reasons: on the one hand to obtain a non-flammable treatment solution and on the other hand to adjust the strength of the attack on the plastic surface can.
  • a pure solvent, ie 100% of a glycol compound would dissolve most uncrosslinked polymers or leave at least one unacceptable surface. It has therefore been found to be very advantageous to buffer the solution of a glycol ester or glycol ether ester and thus to keep it in the neutral pH range, which means to trap the protons produced by hydrolysis of the solvent.
  • a phosphate buffer mixture has proven to be sufficiently suitable for this purpose.
  • the well-soluble potassium phosphates allow sufficiently high concentrations with good buffering capacity at solvent concentrations up to 40% vol.
  • the optimal treatment time of the plastic surface depends on the plastic used, the temperature and the type and concentration of the glycol compound.
  • the treatment parameters have an influence on the adhesion between the treated plastic surface and the metal layer applied in subsequent process steps. Higher temperatures or concentrations of the glycol compounds also affect the texture of the plastic surface. In any case, it should be possible for the subsequent pickling step A) to remove the solvent from the plastic matrix again, because otherwise the subsequent steps of the process, in particular the activation according to process step B), are disturbed.
  • the treatment time in the pretreatment step is between 1 and 30 minutes, preferably between 5 and 20 minutes, and more preferably between 7 to 15 minutes.
  • Example 8 the influence of the treatment duration (residence time) of the plastic surfaces with a glycol solution on the adhesion of the subsequently applied metal layer was investigated for an ABS / PC mixture.
  • the results are in FIG. 2 shown graphically.
  • the term "normalized values" in FIG. 2 means: For the bond strengths, the original measured values were plotted. Values were plotted for the manganese values which were normalized to the highest manganese value. Values were plotted for the palladium values, which were normalized to the highest palladium value. All original measurements are summarized in Table 10.2.
  • the treatment temperature is between 20 ° C and 70 ° C, depending on the type of solvent or solvent mixture used.
  • a treatment temperature between 20 ° C and 50 ° C, more preferably a treatment temperature between 20 ° C and 45 ° C.
  • the treatment of the plastic surfaces in the pretreatment step may be carried out in an aqueous solution containing a glycol compound or in an aqueous solution containing two or more different glycol compounds.
  • the total concentration of glycol compounds in the aqueous solution is 5% vol. - 50% vol., Preferably 10% vol. - 40% vol., And more preferably 20% vol. - 40% vol. If said solution contains a glycol compound corresponds the total concentration of the concentration of this one glycol compound. When said solution contains two or more different glycol compounds, the total concentration equals the sum of the concentrations of all the glycol compounds contained.
  • the concentration data for the glycol compound / glycol compounds in% always means a concentration in% vol.
  • the first solvent serves to produce the adhesive strength
  • the second solvent as a nonionic surfactant, increases the wettability and helps to remove possibly existing contaminants from the plastic surface.
  • the protection of the frame between the fastening step and the pretreatment step can be performed.
  • the protection of the frame between the pretreatment step and the process step A) can be performed. At these times, the items are already mounted in the rack. The frame is therefore treated together with the objects with the solution containing a source of iodate ions. Regardless of whether the protection of the rack takes place on its own or together with the objects, it protects the plastic casing of the racks from metal deposition while metallizing the objects which are mounted in the racks during the mounting step.
  • the protection of the frame ensures that the plastic coating of the frames in the later steps B) to C) is not metallized, that is, the racks remain free of metal. This effect is particularly pronounced on a PVC sheathing of the racks.
  • the pickling treatment according to the invention in process step A) is carried out with pickling solutions which comprise at least one acid pickling solution and at least one alkaline pickling solution.
  • the acidic and the alkaline pickling solution thus contain a source of permanganate ions.
  • the source of permanganate ions is selected from the group of alkali metal permanganates containing potassium permanganate and sodium permanganate.
  • the source of permanganate ions is selected independently for the acidic and alkaline pickling solution, that is, both pickling solutions may contain the same source of permanganate, or the two pickling solutions may contain different sources of permanganate.
  • the source of permanganate ions is present in the acidic and alkaline pickling solution in a concentration between 30 g / l and 250 g / l, preferably between 30 g / l and 180 g / l, more preferably between 90 g / l and 180 g / l. and more preferably between 90 g / l and 110 g / l. Due to its solubility, potassium permanganate can be contained in a pickling solution at a concentration of up to 70 g / l. Sodium permanganate can be contained in a pickling solution at a concentration of up to 250 g / l. The lower concentration limit each of these two salts is typically 30 g / l.
  • the content of the permanganate source is preferably between 90 g / l and 180 g / l.
  • the content of the permanganate source is preferably between 30 g / l and 100 g / l.
  • the concentration of the permanganate source is selected independently for the acid and alkaline pickle solution, that is, both pickle solutions may contain the same concentration of the permanganate source or the two pickle solutions may contain different concentrations of the permanganate source.
  • the acids used in the acid pickling solution are preferably inorganic acids.
  • the inorganic acid in the acidic pickling solution according to process step A) is selected from the group comprising sulfuric acid, nitric acid and phosphoric acid.
  • the acid concentration must not be too high, otherwise the acidic pickling solution will not be stable.
  • the acid concentration is between 0.02-0.6 mol / l based on a monobasic acid. It is preferably between 0.06 and 0.45 mol / l, more preferably between 0.07 and 0.30 mol / l in each case based on a monobasic acid.
  • Sulfuric acid is preferably used in a concentration between 0.035 and 0.15 mol / l, which corresponds to an acid concentration between 0.07 and 0.30 mol / l based on a monobasic acid.
  • the acid pickling solution can be operated at temperatures between 30.degree. C. and 90.degree. C., preferably between 55.degree. C. and 75.degree. Although it has been found that sufficiently high bond strengths between metal layers and plastic surfaces can be achieved even at low temperatures between 30 ° C and 55 ° C. However, it can then not be ensured that all the solvent of the treatment with glycol compound in the pretreatment step is removed from the plastic surface. This is especially true for pure ABS. Thus, if the pretreatment step is carried out in the process according to the invention, the temperatures in the subsequent process step A) are to be selected higher, namely in the range of 55 ° C to 90 ° C, preferably in the range of 55 ° C to 75 ° C.
  • the optimal treatment time with acidic pickling solution depends on the treated plastic surface and the selected temperature of the pickling solution.
  • a longer treatment time than 30 minutes usually does not lead to an improvement in the adhesive strength or the metal coverage.
  • An acidic permanganate solution is very reactive at elevated temperatures, for example at 70 ° C. It then form by the oxidation reaction with the plastic surface much manganese (IV) species, which precipitate out. These manganese (IV) species are predominantly manganese (IV) oxides or oxide hydrates and are referred to below simply as manganese dioxide.
  • the manganese dioxide precipitate interferes with the subsequent metallization when it remains on the plastic surface. During activation according to method step B), it ensures that areas of the plastic surface are not covered with metal colloid or generates unacceptable roughness of the metal layer to be applied in later method steps.
  • the manganese dioxide also catalyzes the reaction of the permanganate with water and can lead to the instability of the pickling solution.
  • the pickling solution should therefore advantageously be kept free of manganese dioxide.
  • the hydroxide ion source in the alkaline pickling solution according to process step A) is selected from the group of alkali metal hydroxides containing sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the hydroxide ion source is sodium hydroxide.
  • the hydroxide ion source is selected in the alkaline pickle solution, regardless of the source of permanganate ions, that is, the alkaline pickle solution may contain a source of hydroxide ion and source of permanganate ions with the same alkali metal ion or the alkaline pickle solution may contain a source of hydroxide ion and source of permanganate ions with various alkali metal ions.
  • the concentration of the hydroxide ion source is between 1 g / l and 100 g / l, preferably between 5 g / l and 50 g / l and particularly preferably between 10 g / l and 30 g / l.
  • the alkaline pickling solution may be at temperatures between 20 ° C and 90 ° C, preferably be operated between 30 ° C to 75 ° C and more preferably between 30 ° C and 60 ° C.
  • the temperature of the alkaline pickling solution has almost no influence on the extent of the coverage of the plastic surfaces with the metal of the activator.
  • the treatment of the plastic surfaces with alkaline pickling solution in the temperature range between 30 ° C and 60 ° C leads to higher adhesive strengths.
  • the stability of the alkaline permanganate solution decreases somewhat at elevated temperatures. But in general, the alkaline permanganate solution is much more stable than the acidic permanganate solution.
  • the stability of the alkaline permanganate solution is not critical in the range between 40 ° C and 60 ° C.
  • the optimal treatment time with the alkaline pickling solution also depends on the treated plastic surface and the selected temperature of a pickling solution.
  • the best adhesion between plastic surface and subsequently applied metal layer and the best occupancy of the plastic surface with metal of the activator is achieved at a treatment time with the alkaline pickling solution between 1 and 20 minutes, preferably between 1 and 15 minutes and more preferably between 1 and 5 minutes.
  • a longer treatment time than 20 minutes usually does not lead to an improvement in the coverage of the plastic surface with metal of the activator or the adhesive strength more.
  • Example 9 the influence of the temperature and the treatment time (residence time) in the alkaline permanganate solution on the adhesion between the plastic and the plated metal layer (by direct electroplating) and the amount of palladium bound during the activation step are exemplified for ABS / PC mixture plastic surfaces Service.
  • the adhesive strengths obtained after the pickling step in the alkaline permanganate solution at various temperatures are in FIG. 3A shown.
  • ABS / PC blends achieve the best bond strengths of the electrodeposited metal layer after 2 to 5 minutes residence time in the alkaline permanganate solution. Looking at the temperatures of the alkaline permanganate solution gives the best adhesion in the range of 30 ° C and 50 ° C.
  • the treatment with alkaline permanganate solution at about 50 ° C at a treatment time between one and five minutes proves to be particularly advantageous.
  • FIG. 3B are the adhesive strengths and amounts of palladium bound on the surfaces obtained in Example 9 after treatment with alkaline permanganate solution shown at 50 ° C.
  • the amounts of palladium found were divided by the factor 50 for the graph. From about one minute residence time in alkaline permanganate solution, the maximum amount of bound palladium is already reached; Longer residence times in alkaline permanganate solution lead to no significant change in the amount of palladium bound on the plastic surface.
  • the treatment with alkaline permanganate solution at about 50 ° C between 1 and 5 minutes is therefore well suited also in view of the amount of palladium bound for plastic surfaces of ABS / PC blends.
  • Example 1 describes the effects of the two embodiments.
  • a plastic plate was first treated with an acidic pickling solution (acidic permanganate solution) and then with an alkaline pickling solution (alkaline permanganate solution), then activated with a palladium colloid and provided with a copper layer by direct electroplating.
  • the plastic plate could be completely and evenly coated with a copper layer by direct electroplating.
  • Example 2 plastic sheets were treated in both of the above orders with an acidic and an alkaline pickling solution. Subsequently, the plates were activated with a palladium colloid, electrolessly nickel-plated and electroplated copper. Plastic plates, which had been pickled with an acid and an alkaline pickling solution in both of the above orders, could be provided with a copper layer. The plates, which were first stained with an alkaline and subsequently with an acidic pickling solution, could also be coated with a copper layer, although this was not completely complete. The adhesive strength of the resulting metal layers on the plastic panels was determined according to the standard ASTM B 533 1985 Reapproved 2009 with the stripping test as described in Example 2.
  • the achieved bond strengths of the deposited metal layers were significantly higher than those which could be achieved after treatment with a single acid pickling solution or a single alkaline pickling solution or a chromosulfuric acid solution of the prior art (see Comparative Example 3).
  • plastic plates that had been first stained with an acidic and subsequently with an alkaline pickling solution higher adhesive strengths than the plastic plates, which had been first stained with an alkaline and subsequently with an acidic pickling solution.
  • process step A) more than two steps for treating the plastic surfaces with pickling solutions can be carried out.
  • the first two steps in method step A) may each comprise treating the plastic surfaces with acid pickling solutions, and a third step comprises treating the plastic surfaces with an alkaline pickling solution.
  • the first two steps in process step A) each comprise treating the plastic surfaces with alkaline pickling solutions and a third step comprises treating the plastic surfaces with an acid pickling solution.
  • process step A) comprises three steps for treating the plastic surfaces with pickling solutions, wherein in each case acidic and alkaline pickling solutions are used alternately.
  • Process step A) may also comprise more than three steps for treating the plastic surfaces with pickling solutions.
  • process step A) always at least one step for treating the plastic surfaces with an acidic pickling solution and at least one step for treating the plastic surfaces with an alkaline pickling solution includes.
  • step A) the respective first step in treating the plastic surfaces with an acid pickling solution and the last step in treating the plastic surfaces with an alkaline pickling solution are particularly preferred.
  • Regular - usually daily - analysis of the constituents of the pickling solutions is advantageous in order to optimize process reliability.
  • This includes the titration of the acid or the base to obtain the original acid concentration or hydroxide ion concentration and the photometric determination of the permanganate concentration.
  • the latter can be done with a simple photometer.
  • the consumptions are then to be completed according to the analytical data.
  • the pickling solutions according to the invention contain no chromium or chromium compounds; the pickling solutions contain neither chromium (III) ions nor chromium (VI) ions.
  • the pickling solutions according to the invention are thus free of chromium or chromium compounds; the pickling solutions are free of chromium (III) ions and chromium (VI) ions.
  • a pickling solution For the treatment of the plastic surfaces with an acidic pickling solution, a pickling solution is used whose acid concentration is low and whose permanganate concentration is high. As a result, the formation of manganese dioxide species can be adjusted so that the stability of the pickling solution is ensured and yet a significant contribution to higher adhesion is achieved.
  • the sole or sole treatment of the plastic surfaces with alkaline permanganate solutions, as routinely used in the printed circuit board industry as a pickling solution, is not suitable for the present task since it does not provide sufficient adhesion between the plastic surface and the metal layer.
  • the process step A) comprises treating the plastic surface with pickling solutions which comprise at least one acid pickling solution and at least one alkaline pickling solution, and thus represents a combination of steps for treating plastic surfaces with different pickling solutions.
  • pickling solutions which comprise at least one acid pickling solution and at least one alkaline pickling solution
  • the process step A) comprises treating the plastic surface with pickling solutions which comprise at least one acid pickling solution and at least one alkaline pickling solution, and thus represents a combination of steps for treating plastic surfaces with different pickling solutions.
  • Example 2 adhesive strengths were determined for metal layers on plastic surfaces which were produced according to two preferred embodiments of the metallization method according to the invention.
  • ABS / PC plastic sheets were pickled differently: a group of plastic sheets with an acid pickling solution of the present invention, a group with an alkaline pickling solution of the present invention and a group with chromic acid (known in the prior art) , Subsequently, all plates were activated with palladium-colloid, then electroless nickel-plated, then electroplated copper and determined the adhesion of the metal layers on the plastic plates, as described in Example 2.
  • Table 1 The adhesive strength values obtained in Examples 2 and 3 for electrolessly metallised plastic plates are summarized in Table 1.
  • Example 5 plastic sheets of an ABS / PC mixture were treated with the pickling treatments I., III., IV. And V., activated with a palladium colloid, then provided with a copper layer by direct electroplating, and then the adhesion strength of the deposited copper layer was determined as described in Example 2.
  • the adhesion values for direct galvanized metallized plastic sheets obtained in Example 5 are summarized in Table 8.2.
  • Example 5 The resulting peel strengths after direct plating in Example 5 were lower than the peel strengths for all stain treatments for the metal layers applied in Examples 2 and 3 by electroless plating. It is a known effect that the bond strengths of metal layers on plastic surfaces after direct metallization are generally lower than for electroless metallization. This effect can also be observed here.
  • the adhesive strengths in Example 5 showed qualitatively the same behavior as in Examples 2 and 3.
  • the best adhesion strengths were obtained for the plastic sheets which were pickled with the inventive pickling treatment I. (first acid pickling solution, then alkaline pickling solution) (Table 8.2 ).
  • Adhesive strengths of at least 0.8 N / mm are obtained with the method according to the invention when the metal layers are applied to the plastic surfaces with the aid of electroless metallization.
  • adhesion strengths of at least 0.6 N / mm are obtained by the method according to the invention.
  • the adhesive strengths achieved by the method according to the invention are well above the required minimum value of 0.4 N / mm.
  • the pickling according to the invention of the plastic surface with pickling solutions which comprise at least one acid pickling solution and at least one alkaline pickling solution leads to a significantly higher coverage of the plastic surfaces with a metal during the activation of the plastic surfaces with a solution of a colloid or a compound of one metal. This effect is especially pronounced when activation is performed with a metal colloid.
  • the direct electroplating of the plastic surfaces that is, the plastic surfaces are not metallized without external current but directly metallized by an electrolytic process.
  • this can reduce the concentration of the metal in the metal colloid or in the solution of a compound of a metal become.
  • electroless plating of the plastic surfaces or direct electroplating of the plastic surfaces is subsequently possible.
  • Example 4 plastic sheets of ABS and an ABS / PC mixture with the pickling treatments I. (only acid pickling solution, then alkaline pickling solution), III. (only acidic pickling solution) and V. (chromosulfuric acid) pickled and activated with solutions of a colloidal activator with different palladium concentrations. After activation, the palladium bound to the surface of the plates was dissolved in a defined volume of aqua regia and the concentration of palladium therein was determined by inductively coupled plasma optical emission spectrometry (ICP-OES).
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • the combined pickling with an acidic and an alkaline pickling solution thus surprisingly leads to significantly more palladium being deposited from the activator on the plastic surfaces. Therefore, the combined pickling with an acidic and an alkaline pickling solution allows activation of the plastic surfaces on the one hand for a subsequent electroless metallization.
  • a direct subsequent galvanic metallization (direct electroplating) by the combined pickling with an acidic and an alkaline pickling solution is possible. As described initially, direct electroplating generally requires higher coverage of the plastic surfaces with metal, e.g. Palladium, as the electroless metallization of plastic surfaces.
  • the surfaces of the various plastics were treated with activators having different concentrations of palladium.
  • the observed advantageous effect of the higher palladium coverage of the plastic surfaces was tested and observed in the concentration range of 50 ppm or above 50 ppm to 200 ppm of palladium in the activator.
  • the concentration of palladium in the activator can thus be reduced to a range between 50 ppm and 100 ppm. In spite of this low palladium concentration in the activator, subsequent electroless metallization of the plastic surfaces or even direct electroplating of the plastic surfaces possible.
  • Example 6 in addition, the uptake of palladium on surfaces of plates of an ABS / PC mixture after various pickling treatments was measured.
  • the ABS / PC boards were pickled with pickling treatment 1. (first acid pickling solution, then alkaline pickling solution) and pickling treatment IV. (Alkaline pickling solution only), then treated with a colloidal palladium activator, then the plastic material pickled on the surface. Palladium bound palladium again dissolved by aqua regia and the concentration of palladium in the resulting solution determined, as described in Example 4. The results obtained are given in Example 6.
  • Example 4 significantly higher amounts of palladium per unit area were found on ABS / PC boards for all palladium concentrations in the activator when the boards had been treated with the inventive pickling treatment I than when the boards were treated with a single acid pickling step according to pickling treatment III , had been pickled. This results in a similar effect as with the achieved bond strengths, which have already been discussed. Neither a single acid pickling step nor a single alkaline pickling step can result in increased metal coverage of the plastic surfaces from the activator. Only the combination of an acidic pickling step with an alkaline pickling step results in the advantageous effect of the significantly higher metal coverage of the plastic surfaces after activation. It turns out that a first acidic pickling step in the pickling treatment I.
  • the articles become subsequent to the permanganate treatment according to process step A) by rinsing off excess permanganate solution.
  • the rinsing takes place in one or more, preferably three, rinsing steps with water.
  • the further process step A iii) is also referred to as reduction treatment.
  • reduction treatment By means of this reduction treatment, manganese dioxide adhering to the plastic surfaces is reduced to water-soluble manganese (II) ions.
  • the reduction treatment is carried out after the permanganate treatment according to process step A) and optionally after rinsing off.
  • an acidic solution of a reducing agent is used.
  • the reducing agent is selected from the group consisting of hydroxylammonium sulfate, hydroxylammonium chloride and hydrogen peroxide.
  • Preferred is an acidic solution of hydrogen peroxide because hydrogen peroxide is neither toxic nor complexing.
  • the content of hydrogen peroxide in the solution of reduction treatment is between 25 ml / l and 35 ml / l of a 30% hydrogen peroxide solution (wt%), preferably 30 ml / l of a 30% hydrogen peroxide solution (wt. -%).
  • the acid used in the reduction solution is an inorganic acid, preferably sulfuric acid.
  • the acid concentration is 0.4 mol / l to 5.0 mol / l, preferably 1.0 mol / l to 3.0 mol / l, particularly preferably 1.0 mol / l to 2.0 mol / l in each case based on a monobasic acid.
  • concentrations of 50 g / l of 96% sulfuric acid to 100 g / l of 96% sulfuric acid are particularly preferred, resulting in an acid concentration of 1.0 mol / l to 2.0 mol / l based on a monobasic Acid corresponds.
  • the reduction treatment removes the manganese dioxide precipitate, which has a disruptive effect on the metallization of the objects.
  • the reduction treatment of process step A iii) thereby promotes the uniform continuous coverage of the articles with the desired metal layer and promotes the adhesive strength and smoothness of the metal layer applied to the articles.
  • the reduction treatment according to process step A iii) also has an advantageous effect on the metallization of the plastic coating of the frame.
  • the unwanted occupancy of the plastic coating with palladium during process step B) is suppressed.
  • This effect is particularly pronounced when the reducing solution contains a strong inorganic acid, preferably sulfuric acid.
  • Hydrogen peroxide is also preferred over hydroxylammonium sulfate or chloride in the reducing solution because it better suppresses framework metallization.
  • the reduction treatment according to process step A iii) is carried out at a temperature between 30 ° C and 50 ° C, preferably at 40 ° C to 45 ° C.
  • the reduction treatment is carried out for a period between 1 and 10 minutes, preferably between 3 to 6 minutes.
  • the reducing agent hydrogen peroxide used must be replenished from time to time.
  • the consumption of hydrogen peroxide can be calculated from the amount of manganese dioxide bound on the plastic surfaces. In practice, it is sufficient to observe the evolution of gas in the reduction reaction during process step A iii) and to meter the original amount of hydrogen peroxide, for example 30 ml / l of a 30% solution, as the gas evolution subsides.
  • elevated operating temperature of the reducing solution for example at 40 ° C, the reaction is completed quickly and after one minute at the latest.
  • Example 8 shows the influence of the residence time of plastic surfaces in solutions of glycol compounds on adhesion strengths, as well as on deposited manganese dioxide and bound palladium amounts.
  • the results from Example 8 are in FIG. 2 shown graphically.
  • the term "normalized values" in FIG. 2 has already been explained above. All original measurements are summarized in Table 10.2.
  • the amount of manganese found on the plastic surface is a measure of the amount of manganese dioxide bound during activation.
  • FIG. 2 It can be seen that with increasing residence time of the plastic surfaces in glycol solutions, the amount of manganese dioxide deposited on the plastic surface also increases. The amounts of manganese deposited on the plastic surface are also the quantities of palladium bound on the plastic surfaces assigned from a palladium activator. FIG. 2 clearly shows that as the amount of deposited manganese dioxide increases, so does the amount of palladium bound on the plastic surfaces.
  • the objects are usually attached to racks.
  • racks These are metal carrier systems that allow the simultaneous treatment of a large number of objects with the successive solutions of the individual process steps and last steps for the electrolytic deposition of one or more metal layers.
  • the racks are usually self-coated with plastic. Therefore, the racks in principle also represent a substrate for metallization processes on plastic surfaces.
  • the additional metallization of the racks is undesirable because the metal layers must be removed from the racks after the articles have been coated. This means an additional expense for the removal associated with additional consumption of chemicals. Furthermore, the productivity of the metallization system is lower in this case, since the racks must first be demetallised before re-loading with objects.
  • chromic acid stains significantly reduces this problem.
  • the chromic acid also penetrates during the pickling in the plastic coating of the racks and diffuses during the subsequent process steps out of this and thus prevents the metallization of the frame. If you want to replace the toxic chromosulfuric acid for pickling of plastics by ecologically safe process steps, it is advantageous to prevent the unwanted metallization of the racks.
  • the protection of the frame between process step A) and process step B) can be carried out, preferably between the process steps A iii) and A iv).
  • the treatment with iodate ions is particularly advantageous if the process step B ii) according to one embodiment of the invention consists of an electroless plating of the objects in a metallization solution.
  • Protecting the rack with a solution containing a source of iodate ions is carried out at a temperature of from 20 ° C to 70 ° C, more preferably from 45 ° C to 55 ° C.
  • Suitable sources of iodate ions are selected from the group of metal iodates containing sodium iodate, potassium iodate, magnesium iodate, calcium iodate and their hydrates.
  • the concentration of the metal iodates is between 5 g / l and 50 g / l, preferably from 15 g / l to 25 g / l.
  • the duration of treatment of the frame with iodate ions is between 1 to 20 minutes, preferably between 2 to 15 minutes and particularly preferably between 5 to 10 minutes.
  • the solution containing a source of iodate ions may further contain an acid.
  • inorganic acids which are selected from the group comprising sulfuric acid and phosphoric acid, preferably sulfuric acid.
  • the acid concentration is 0.02 mol / l to 2.0 mol / l, preferably 0.06 mol / l to 1.5 mol / l, particularly preferably 0.1 mol / l to 1.0 mol / l in each case based on a monobasic acid.
  • concentrations of 5 g / l of 96% sulfuric acid to 50 g / l of 96% sulfuric acid are particularly preferred, resulting in an acid concentration of 0.1 mol / to 1.0 mol / l based on a monobasic acid equivalent.
  • the process of the present invention further includes process step B), wherein a plastic surface is treated with a solution of a metal colloid or a compound of a metal.
  • the metal of the metal colloid or of the metal compound is selected from the group comprising the metals of subgroup I of the Periodic Table of the Elements (PSE) and subgroup VIII of the PSE.
  • the VIII subgroup metal of the PSE is selected from the group consisting of palladium, platinum, iridium, rhodium and a mixture of two or more of these metals.
  • the metal of the 1st subgroup of the PSE is selected from the group containing gold, silver and a mixture of these metals.
  • the metal of the metal colloid palladium is preferred.
  • the metal colloid is stabilized with a protective colloid.
  • the protective colloid is selected from the group consisting of metallic protective colloids, organic protective colloids and other protective colloids.
  • metallic Protective colloid are preferred tin ions.
  • the organic protective colloid is selected from the group comprising polyvinyl alcohol, polyvinylpyrrolidone and gelatin, polyvinyl alcohol is preferred.
  • the solution of the metal colloid in process step B) is an activator solution with a palladium / tin colloid.
  • This colloid solution is generated from a palladium salt, a stannous salt and an inorganic acid.
  • palladium salt palladium chloride is preferred.
  • stannous salt tin (II) chloride is preferred.
  • the inorganic acid may consist of hydrochloric acid or sulfuric acid, preferably hydrochloric acid.
  • the colloid solution is formed by reduction of the palladium chloride to palladium with the aid of stannous chloride. The conversion of the palladium chloride into the colloid is complete, therefore the colloid solution no longer contains palladium chloride.
  • the concentration of palladium in the colloid solution is 5 mg / l - 100 mg / l, preferably 20 mg / l - 50 mg / l and more preferably 30 mg / l - 45 mg / l , based on Pd 2+ .
  • the concentration of palladium in the colloid solution is 50 mg / l-200 mg / l, preferably 75 mg / l-150 mg / l, more preferably 100 mg / l-150 mg / l. l, and more preferably 80 mg / l - 120 mg / l based on Pd 2+ .
  • the concentration of tin (II) chloride is 0.5 g / l - 10 g / l, preferably 1 g / l - 5 g / l and more preferably 2 g / l - 4 g / l, based on Sn 2+ .
  • the concentration of hydrochloric acid is 100 ml / l - 300 ml / l (37 wt% HCl).
  • a palladium / tin colloidal solution additionally contains tin (IV) ions, which are formed by oxidation of tin (II) ions.
  • the temperature of the colloid solution during process step B) is 20 ° C-50 ° C and preferably 35 ° C-45 ° C.
  • the treatment time with the activator solution is 0.5 min-10 min, preferably 2 min-5 min and particularly preferably 3 min-5 min.
  • the solution of a compound of a metal is used instead of the metal colloid.
  • a solution of a metal compound a solution containing an acid and a metal salt is used.
  • the metal of the metal salt consists of one or more of the above listed metals of the I. and VIII. Subgroup of the PSE.
  • the metal salt may be a palladium salt, preferably palladium chloride, palladium sulfate or palladium acetate, or a silver salt, preferably silver acetate.
  • the acid is preferably in hydrochloric acid.
  • a metal complex can also be used, for example a palladium complex salt, such as a salt of a palladium-aminopyridine complex.
  • the metal compound is present in process step B) in a concentration of 40 mg / l to 80 mg / l, based on the metal.
  • the solution of the metal compound can be operated at a temperature of 25 ° C to 70 ° C, preferably at 25 ° C.
  • the treatment time with the solution of a metal compound is 0.5 min - 10 min, preferably 2 min - 6 min and more preferably 3 min - 5 min.
  • Process step A iv) is preferably carried out between process steps A iii) and B). If in the process according to the invention process step A iii) was followed by protecting the racks, process step A iv) is particularly preferably carried out between protecting the racks and process step B).
  • the treatment of the plastic surfaces according to process step A iv) is also referred to as pretreatment and the aqueous acidic solution used as a pre-dip solution.
  • the pre-dip solution has the same composition as the colloid solution in step B), without containing the metal of the colloid and its protective colloid.
  • the pre-dip solution contains exclusively hydrochloric acid if the colloid solution also contains hydrochloric acid. For pre-dipping a brief immersion in the pre-dipping solution at ambient temperature is sufficient. Without rinsing the plastic surfaces, they are further treated directly with the colloid solution of process step B) after treatment in the pre-dip solution.
  • Process step A iv) is preferably carried out if process step B) consists of treating a plastic surface with a solution of a metal colloid. Process step A iv) can also be carried out if process step B) consists of treating a plastic surface with a solution of a compound of a metal.
  • Table 2 Embodiment of plastic metallization step ingredients duration temperature A) pickling: A i) 100 g / l sodium permanganate, 10 g / l 96% sulfuric acid 5-15 min 70 ° C A ii) 30 g / l NaMnO 4 , 20 g / l NaOH 10-25 min 30-90 ° C A iii) Reduce 100 g / l 96% sulfuric acid, 30 ml / l hydrogen peroxide, 30% by weight 1 min 45 ° C A iv) Prelude Hydrochloric acid, about 10% by weight 1 min 20 ° C B) Activate Hydrochloric acid palladium / tin colloid, 5 mg / l - 100 mg / l Pd 3-6 min 20-45 ° C B i) Accelerate Sulfuric acid (5%) 2-6 min 40-50 ° C B ii) electrolessly deposit metal Chemically reductive nickel plating or copper plat
  • the plastic surfaces are treated with an accelerator solution in order to remove constituents of the colloid of the colloid solution, for example a protective colloid, from the plastic surfaces.
  • an aqueous solution of an acid is preferably used as accelerator solution.
  • the acid for example selected from the group comprising sulfuric acid, hydrochloric acid, citric acid and tetrafluoroboric acid.
  • the accelerator solution is used to remove the tin compounds which serve as a protective colloid.
  • step B i) a reduction treatment is carried out if in step B) a solution of a metal compound has been used instead of a metal colloid for the activation.
  • the reducing agent solution used therefor contains hydrochloric acid and stannous chloride.
  • the reductant solution may also contain another reducing agent, such as NaH 2 PO 2 or else a borane or borohydride, such as an alkali or alkaline earth borane or dimethylaminoborane.
  • NaH 2 PO 2 is used in the reductor solution.
  • the plastic surfaces can first be rinsed.
  • Process step B i) and, if appropriate, one or more rinsing steps are followed by process step B ii), in which the plastic surfaces are electrolessly metallized.
  • electroless nickel plating for example, a conventional nickel bath containing, among others, nickel sulfate, a hypophosphite, for example, sodium hypophosphite, as a reducing agent, and organic chelating agents and pH adjusting agents (for example, a buffer) is used.
  • Dimethylaminoborane or a mixture of hypophosphite and dimethylaminoborane can likewise be used as the reducing agent.
  • the plastic surface can be copper-plated without current.
  • an electroless copper bath may be employed which is typically a copper salt, for example, copper sulfate, copper chloride, copper EDTA or copper hypophosphite, a reducing agent such as formaldehyde or a hypophosphite salt such as an alkali or ammonium salt, or hypophosphorous acid, and one or more Complexing agents, such as tartaric acid, and a pH adjusting agent, such as sodium hydroxide.
  • the surface thus rendered conductive can then be metallized further electrolytically to obtain a functional or decorative surface.
  • Table 3 Another embodiment of plastic metallization step ingredients length of stay temperature
  • B i) Convert Alkaline solution with copper ions 1 min > 55 ° C
  • Electrolytically deposit metal For example, electrochemical copper plating or nickel plating 15-70 min 20-
  • the treatment of the plastic surfaces in a conversion solution results in that a sufficiently electrically conductive layer is formed on the plastic surfaces for a direct electrolytic metallization, without first electrolessly metallized.
  • the colloid of the colloid solution according to process step B) is a palladium / tin colloid
  • the conversion solution used is preferably an alkaline solution of complexes complexed with a copper ion.
  • the conversion solution may contain an organic complexing agent such as tartaric acid, ethylenediaminetetraacetic acid (EDTA) or ethanolamine and / or a salt thereof, and a copper salt such as copper sulfate.
  • the plastic surfaces can first be rinsed.
  • the thus rendered plastic surface can then be electrolytically metallized further to obtain a functional or decorative surface.
  • Step C) of the process according to the invention is the metallization of the plastic surface with a metallization solution.
  • the metallization according to process step C) can be carried out electrolytically.
  • any metal deposition baths can be used, for example for the deposition of nickel, copper, silver, gold, tin, zinc, iron, lead or their alloys. Such deposition baths are familiar to the person skilled in the art.
  • As a bright nickel bath typically a Watts nickel bath is used, which contains nickel sulfate, nickel chloride and boric acid and saccharin as an additive.
  • a composition which contains copper sulfate, sulfuric acid, sodium chloride, and organic sulfur compounds in which the sulfur is in a low oxidation state, for example, organic sulfides or disulfides, as additives.
  • step C) results in the plastic surface being coated with metal, the metal being selected from the metals listed above for the deposition baths.
  • the adhesion strength between metal and plastic substrate increases in the first time after the application of the metal layer. At room temperature, this process is completed in about three days. This can be significantly accelerated by storage at elevated temperature. The process is completed at 80 ° C after about an hour. It is believed that the initial low adhesion is caused by a thin layer of water located at the interface between metal and nonconductive substrate and hindering the formation of electrostatic forces.
  • the pickling according to the invention with acidic and alkaline permanganate solution produces a structure of the plastic surface which allows a larger contact surface of the plastic with the metal layer than, for example, a conventional pretreatment with chromic acid. This is also the reason that higher adhesion strengths are achieved compared to the treatment with chromic acid (see Examples 2, 3 and 5).
  • the smoother surface sometimes provides even lower initial adhesion immediately after metallization than does chromosulfuric acid.
  • the galvanic Nickel plating and, more particularly, when the deposited metal layers have high internal stresses or when the thermal expansion coefficients of metal and plastic are widely different and the composite is exposed to rapidly changing temperatures the initial bond strength may not be sufficient.
  • Such a step may be to treat a metallized article of ABS plastic for a period between 5 minutes and 60 minutes at elevated temperature in the range of 50 ° C to 80 ° C, preferably at a temperature of 70 ° C, in a water bath so that the water can be distributed at the boundary layer of metal - plastic in the plastic matrix.
  • the treatment or storage of the metallized plastic surfaces at elevated temperature leads to an initial, lower adhesive strength is further enhanced, so that after the process step C i) an adhesion of the applied to the plastic surface metal layer is achieved in the desired range of at least or greater is 0.6 N / mm.
  • the method according to the invention thus makes it possible to achieve metallization of electrically non-conductive plastic surfaces of objects with good process reliability and excellent adhesion of the subsequently applied metal layers. Not only planar plastic surfaces are metallized by the method according to the invention with high adhesion, but also unevenly shaped plastic surfaces are provided with a uniform and adherent metal coating.
  • the pickling according to the invention of the plastic surface with pickling solutions which comprise at least one acid pickling solution and at least one alkaline pickling solution leads to a significantly higher coverage of the plastic surfaces with a metal during the activation of the plastic surfaces with a solution of a colloid or a compound of one metal.
  • the plate was treated for ten minutes in an acidic permanganate solution (100 g / l NaMnO 4 , 10 g / l 96% H 2 SO 4 ), which was heated to 70 ° C. Thereafter, the plate was treated for ten minutes in an alkaline permanganate solution (30 g / l NaMnO 4 and 20 g / l NaOH) (Pickling I., Step A)).
  • an acidic permanganate solution 100 g / l NaMnO 4 , 10 g / l 96% H 2 SO 4
  • alkaline permanganate solution 30 g / l NaMnO 4 and 20 g / l NaOH
  • the plate then had a uniformly brown surface.
  • a reducing solution of 25 ml / l 96% sulfuric acid and 30 ml / l 30% hydrogen peroxide at 40 ° C was replaced from the plate, the manganese dioxide (step A iii)).
  • step A iv After subsequent rinsing and brief immersion in a solution of 300 ml / l 36% hydrochloric acid (step A iv)), the plate was five minutes in a colloidal activator based on a palladium colloid (Adhemax activator PL Fa. Atotech, 125 mg / l palladium) at 40 ° C activated (step B)).
  • Adhemax activator PL Fa. Atotech, 125 mg / l palladium at 40 ° C activated
  • the plate was copper plated by placing it at room temperature in a galvanic copper bath (Cupracid HT, Atotech, process step C)) and applying about 2.5 A current.
  • a galvanic copper bath Cupracid HT, Atotech, process step C
  • the plate was completely and evenly copper-plated after two minutes.
  • the two plates were labeled P1 and P2.
  • Plate P1 was treated for ten minutes in an acidic permanganate solution (100 g / l NaMnO 4 , 10 g / l 96% H 2 SO 4 ), which was heated to 70 ° C.
  • Plate P2 was treated for ten minutes in the alkaline permanganate solution (30 g / l NaMnO 4 and 20 g / l NaOH) kept at 50 ° C. Thereafter, plate P1 was treated for ten minutes in the alkaline permanganate solution described (pickling treatment I, step A)) and plate P2 for ten minutes in the acidic permanganate solution described (pickling treatment II, step A)).
  • the two plates as described in Example 1, treated with reducing solution and pre-immersed. Subsequently, the plates were activated for five minutes in a colloidal activator based on a palladium colloid (Adhemax activator PL from Atotech, 23 ppm palladium) at 40 ° C (step B)).
  • a colloidal activator based on a palladium colloid Adhemax activator PL from Atotech, 23 ppm palladium
  • the plates were rinsed and then the protective covers of the palladium particles were removed for five minutes at 40 ° C (Adhemax accelerator ACC1 Fa. Atotech, step B i)).
  • the plates were then electroless nickel-plated for ten minutes (Adhemax LFS, Atotech, process step B ii)) at 45 ° C. While plate P1 then had a uniform, matte, light gray nickel layer, plate P2 had some open spots on which no nickel had been deposited.
  • Both plates were then rinsed and coppered for one hour at 3.5 A / dm 2 at room temperature (Cupracid HT, Fa. Atotech, process step C)). After rinsing, the plates were stored for one hour at 80 ° C (step C i)). Subsequently, the adhesive strength of the applied metal layers was determined by cutting out with a knife about 1 cm wide strip of metallized plastic plates and its precise width was measured. Subsequently, the metal layer was removed from the plastic with a tensile testing machine (Instron) and the necessary force registered (according to ASTM B 533 1985 Reapproved 2009).
  • a tensile testing machine Instron
  • Plate P1 had a bond strength of the copper layer of 1.41 N / mm and 1.24 N / mm (average: 1.32 N / mm) and plate P2 1.01 N / mm and 0.95 N / mm (average: 0.98 N / mm). mm).
  • Pickling III Two of the pretreated plates were then treated with a warm (70 ° C.) acidic permanganate solution containing 100 g / l sodium permanganate and 10 g / l 96% sulfuric acid (final concentration: 0.1 mol / l sulfuric acid).
  • Pickling IV The other two pretreated plates were treated with alkaline permanganate solution consisting of 30 g / l sodium permanganate and 20 g / l sodium hydroxide. The pickling treatment was carried out at 70 ° C for ten minutes.
  • Example 3 The sequence of the process steps in Example 3 is summarized in Table 6.
  • Pickling treatment I One of the two sets of plates was then further treated in an alkaline permanganate solution consisting of 30 g / l sodium permanganate and 20 g / l sodium hydroxide in a second pickling step for 10 minutes at 50 ° C.
  • Pickling V A third set of plastic and dimensional plates as described above were treated in a chromosulfuric acid solution and then rinsed as described in Example 3.
  • the dry plates were placed horizontally in a suitable crystallizing dish and covered with exactly 25 ml of aqua regia diluted 1: 1 with water. After one minute reaction time, the liquid from each plate was collected and the concentration of palladium therein determined by ICP-OES.
  • the measured values were evaluated with the aid of the ICP Expert software belonging to the device and output directly as concentration values in mg / l.
  • the palladium concentration found was then converted into the amount of palladium per unit area.
  • the values obtained for the palladium bound to the plastic surfaces are summarized in Table 7 and are shown in FIG FIG. 1 shown graphically. The results are discussed in the description.
  • Bayblend T45PG (5,2cm x 14,9cm x 0,3cm, ABS / PC Blend) boards used for pickling treatments I., III. and IV. were treated in a solution of 2- (2-ethoxyethoxy) ethyl acetate (pretreatment step) and rinsed as described in Example 1.
  • Pickling treatment I (Pickling treatment according to the invention): Two of the plates already pickling III. (permanganate acid solution) were then further treated with an alkaline permanganate solution for two minutes as described in Example 4.
  • step A iii) In a reducing solution of deposited manganese dioxide purified (step A iii)), as indicated in Example 3.
  • the plates were immersed for three minutes in a conversion solution based on copper ions (Futuron Plus CuLink from Atotech, process step B i)).
  • Copper plating (Cupracid HT, 3A / dm 2 ) 70 min 25 ° C To store 60 min 70 ° C *
  • pickling pickling solutions Adhesive strength [N / mm] individual measurements Average I. Acid and alkaline permanganate solution 0.78 / 0.75 / 0.90 / 0.84 0.82 III. acidic permanganate solution 0.72 / 0.74 / 0.70 / 0.82 0.75 IV. alkaline permanganate solution 0.12 / 0.16 / 0.11 / 0.12 0.13 V. chromic acid 0.52 / 0.53 / 0.55 / 0.59 12:55
  • the plates were pretreated in a solution of 2- (2-ethoxyethoxy) ethyl acetate (pretreatment step) for ten minutes and rinsed for about one minute as described in Example 1.
  • Pickling treatment I. (pickling treatment according to the invention): Two plates after pretreatment were first treated with a warm (70 ° C.) acidic permanganate solution containing 100 g / l sodium permanganate and 10 g / l 96% sulfuric acid for 10 minutes (Final concentration: 0.1 mol / l sulfuric acid). Thereafter, the plates were treated for two minutes at 50 ° C with alkaline permanganate solution consisting of 30 g / l sodium permanganate and 20 g / l sodium hydroxide.
  • the pickling treatment according to the invention results in significantly more palladium being bound to plastic surfaces than if the surfaces were treated only with an alkaline pickling solution.
  • Table 9 Amount of manganese on plastic surfaces after various pickling treatments plates pickling Mn / g / m 2 SECTION only acid permanganate (III.) 0.895 first acid permanganate, then alkaline permanganate (I.) 1,044 ABS / PC only acid permanganate (III.) 0,695 first acid permanganate, then alkaline permanganate (I.) 0.793
  • the amount of manganese found on the plastic surface is a measure of the amount of manganese dioxide bound during activation.
  • the combination of pickling the plastic surfaces in an acidic permanganate solution and in an alkaline permanganate solution further increases the amount of manganese dioxide deposited on the plastic surfaces over plastic surfaces which have been pickled with a single acid pickling step (Pickling III.).
  • Sheets of Bayblend T45PG (ABS / PC blend) were treated in a 40% solution of 2- (2-ethoxyethoxy) ethyl acetate for various periods of time at 25 ° C (residence times see Table 10.2).
  • Manganese dioxide was removed with a solution of 30 ml / l of 30% hydrogen peroxide in 5% sulfuric acid.
  • the amount of manganese deposited was determined by ICP-OES as described in Examples 4 and 7.
  • the obtained values of the manganese adhering to the plastic surfaces are summarized in Table 10.2 and are given in FIG. 2 shown.
  • the amount of manganese found on the plastic surface is a measure of the amount of manganese dioxide bound during activation.
  • step A iv After subsequent rinsing and brief immersion in a solution of 300 ml / l 36% hydrochloric acid (step A iv)), the remaining plates were for five minutes in a colloidal activator based on a palladium colloid (Adhemax activator PL Fa. Atotech, 140 mg / l palladium) at 45 ° C activated (step B)).
  • Adhemax activator PL Fa. Atotech, 140 mg / l palladium at 45 ° C activated
  • Example 8 The sequence of the process steps in Example 8 is summarized in Table 10.1.
  • Table 10.1 Sequence of process steps in Example 8 step length of stay temperature 40% by volume of 2- (2-ethoxyethoxy) ethyl acetate 2 to 10 min 25 ° C Acid permanganate solution 10 min 70 ° C alkaline permanganate solution 2 min 50 ° C Removing the manganese dioxide 1 min 40 ° C Activate 5 min 45 ° C Convert (Futuron Plus CuLink) 3 min 60 C.
  • Copper plating (Cupracid HT, 3A / dm 2 ) 70 min 25 ° C To store 60 min 70 ° C length of stay Mn Pd Adhesive strength [N / mm] [Min] [mg / m 2 ] [mg / m 2 ] individual values means 0 112.7 15.2 --- * --- 2 268.0 29.9 0.48 / 0.60 0.54 4 347.2 37.5 0.77 / 0.87 0.82 6 366.3 42.8 0.95 / 1:03 0.99 8th 417.3 49.1 1.00 / 1.10 1.05 10 423.4 43.3 0.93 / 0.91 0.92 *: not electroplated
  • the residence time of the plastic surfaces in the solution of the glycol compounds has an influence on the adhesive strength of the applied metal layers. Without treatment with glycol compounds (residence time 0 min in FIG. 2 ) no metal could be deposited by direct electroplating on the plastic surface. After only 4 minutes of treatment with glycol compounds, however, a good adhesive strength of 0.8 N / mm was already achieved, which continues to increase with longer treatment time.
  • Bayblend T45PG (14.9 cm x 5.1 cm x 3 mm, surface: 1.64 dm 2 , ABS / PC blend) plates were treated in a solution of 2- (2-ethoxyethoxy) ethyl acetate (pretreatment step) and rinsed, such as described in Example 1.
  • the copper-plated plates were stored for one hour at 70 ° C and then determined with an Instron tensile tester, the adhesion of the copper layer to the plastic substrate, as described in Example 2.

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BR112014021969-9A BR112014021969B1 (pt) 2012-03-15 2013-03-15 Processo para metalizar superfícies de plástico não condutoras
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PT137094421T PT2825688T (pt) 2012-03-15 2013-03-15 Processo para a metalização de superfícies plásticas não condutoras
KR1020147028905A KR101872066B1 (ko) 2012-03-15 2013-03-15 비전도성 플라스틱 표면의 금속화 방법
CN201380014402.0A CN104169466A (zh) 2012-03-15 2013-03-15 将非电导塑料表面金属化的方法
EP13709442.1A EP2825688B1 (fr) 2012-03-15 2013-03-15 Procédé de métallisation de surfaces en matière synthétique non conductrices
JP2014561462A JP6246139B2 (ja) 2012-03-15 2013-03-15 非導電性プラスチック表面の金属化方法
ES13709442.1T ES2587730T3 (es) 2012-03-15 2013-03-15 Procedimiento para metalizar superficies de plástico no conductor
PCT/EP2013/055357 WO2013135863A1 (fr) 2012-03-15 2013-03-15 Procédé pour la métallisation de surfaces plastiques non conductrices
US14/379,497 US9051643B2 (en) 2012-03-15 2013-03-15 Process for metallizing nonconductive plastic surfaces
PL13709442.1T PL2825688T3 (pl) 2012-03-15 2013-03-15 Sposób metalizowania powierzchni nieprzewodzących tworzyw sztucznych
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