EP0815292B1 - Procede de metallisation electrolytique selective ou partielle de surfaces de substrats composes de materiaux non conducteurs - Google Patents

Procede de metallisation electrolytique selective ou partielle de surfaces de substrats composes de materiaux non conducteurs Download PDF

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Publication number
EP0815292B1
EP0815292B1 EP96907505A EP96907505A EP0815292B1 EP 0815292 B1 EP0815292 B1 EP 0815292B1 EP 96907505 A EP96907505 A EP 96907505A EP 96907505 A EP96907505 A EP 96907505A EP 0815292 B1 EP0815292 B1 EP 0815292B1
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Prior art keywords
metal
plastics material
solution
metallization
moulded plastics
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EP96907505A
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German (de)
English (en)
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EP0815292A1 (fr
Inventor
Hermann Middeke
John Mc Caskie
Nayan H. Joshi
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the invention relates to a method for selective or partial electrolytic Metallizing surfaces of molded plastic parts made of electrically non-conductive Materials which are coated with plastics for the following treatment Holding elements are attached.
  • a number of metallization processes have therefore been developed with which the non-conductive surfaces without electroless metallization directly with metal can be coated.
  • such methods are particularly described for the metallization of the borehole walls in printed circuit boards.
  • the direct electrolytic metallization in borehole metallization is opposite a metal coating of other plastic parts, such as Sanitary fittings or with three-dimensional in comparison to plates Contour, but much easier, because smaller areas can be metallized are.
  • the distances of the non-conductive to be overcome in the metallization Sustrat surface is shorter in the case of borehole metallization on printed circuit boards and therefore easier to reach.
  • EP 0 298 298 A2 describes a method for electrolytic metallization described a non-conductor in which the non-conductor surface to be metallized is coated with a metal chalcogenide.
  • the metal chalcogenide is obtained by treating the surfaces with a palladium colloid Tin compounds as a protective colloid, and subsequent treatment with a soluble metal chalcogenide compound, preferably a metal sulfide, educated.
  • EP 0 320 601 A2 describes a method for metallizing non-conductors, in which the non-conductor surfaces first with a permanganate solution are treated, referring to this insoluble manganese dioxide forms.
  • the manganese dioxide layer is then treated with a chalcogen compound, preferably containing sulfur compounds Solution converted.
  • a metal layer can then be deposited electrolytically become.
  • a chalcogenide layer can be sufficient high electrical conductivity by means of a special pretreatment for subsequent metallization of drill holes in printed circuit boards become.
  • the conductivity of such a layer is not sufficient for that Metallization of large-area non-conductive substrates, because there too large bridged non-conductive paths from the contact points of the power supply Need to become.
  • US-A-39 84 290 discloses a method in which the borehole walls a circuit board first in a solution containing the connection of one nobler metal than copper, is treated, whereby a metal layer on the copper surfaces of the circuit board and the non-conductor surfaces. Subsequently, the metal layer from the copper surfaces again removed, and then the metal layer on the non-conductive surfaces and electrolytically metallized the copper surfaces.
  • Non-metallic objects to be metallized are first with a solution containing a noble metal, for example treated with a palladium activator stabilized with tin compounds and then electrolytically coated in a metallization bath.
  • Suitable organic additives are contained in the metallization bath, with which a preferred metal deposition on the previous process step Formed metal layers promoted on the non-conductive areas becomes.
  • EP 0 456 982 A1 describes a method for the electrolytic metallization of a Disclosed substrate, in which the substrate surfaces first, for example catalyzed in a solution containing a palladium colloid solution stabilized with tin compounds are then the tin compounds in a known manner are removed from the substrate surface, the one used for this Solution additionally contains the connection of a metal that is more noble than tin and the surfaces are subsequently electrolytically metallized.
  • German laid-open specification 39 07 789 A1 there is a process for the deposition an electrically conductive layer on an electrically non-conductive Surface specified, in which the surface is initially an electrical conductive base layer, which is characterized by an electroless chemical polymerization at least one conductive polymer is produced on the surface, is generated and then another electrically conductive layer, for example another conductive polymer layer or a metal layer, is deposited.
  • This process can also be used for substrates with larger sizes non-conductive surfaces can be directly electrolytically metallized if the the aforementioned procedure is repeated several times. However, this is not practical because it leads to extremely long process times.
  • the conductive polymer layers formed on the surfaces have A sufficiently high conductivity only a short time after their manufacture on. After that, it quickly falls off, so that large-area metallization is not possible anyway.
  • EP 0 616 053 A1 describes a method for the direct metallization of non-conductive Surfaces disclosed, in which the surfaces first with a Cleaner / conditioning solution, then with an activator solution, for example a palladium colloid solution, stabilized with tin compounds, and then treated with a solution containing compounds of a metal, which is nobler than tin, as well as an alkali hydroxide and a complexing agent. Thereafter, the surfaces can be in a containing a reducing agent Solution treated and finally metallized.
  • an activator solution for example a palladium colloid solution
  • tin compounds of a metal which is nobler than tin
  • an alkali hydroxide and a complexing agent an alkali hydroxide and a complexing agent
  • the present invention is therefore based on the problem, the disadvantages to avoid the prior art and a method for selective or partial electrolytic metallization of surfaces of substrates (plastic molded parts) Made of electrically non-conductive materials on the outside with plastic coated holding elements, for example support frames, are attached Find.
  • the substrate surfaces can be between some or all process steps be rinsed.
  • adsorption-promoting solutions are in particular So-called conditioning solutions used in the manufacture of printed circuit boards used. These are usually aqueous solutions in which in particular Polyelectrolytes, such as polycationic polymers, with a molecular weight above 10,000 g / mol are included. After treating the non-conductive surfaces with such a conditioning solution not only those that are to be metallized, as desired Plastic surfaces coated with metal, but also - unnecessarily - The holding elements coated on the outside with plastics.
  • the holding elements it is not necessary to Free the holding elements from the metal after use, as the substrates not be brought into contact with a conditioning solution. Rather, the holding elements after metallizing the substrate surfaces and removing the metallized substrates without further treatment be immediately returned to the production cycle and immediately for the metallization of further non-conductive substrates become. Should be on the contact tips / metal tips during the Metallization has deposited metals, they must be removed from time to time, to avoid contact problems and contamination of the bathroom.
  • Another advantage of the method is that the surfaces of the metallizing substrates can also be partially metallized by Parts of the surfaces are covered with a suitable material. There this material also when carrying out the method according to the invention is not coated, a subsequent removal of the material is very easily possible without selective treatment if necessary Removal of the metal deposited there the metal layers on the damage metallized substrate.
  • the method is particularly electrical for three-dimensionally structured non-conductive molded parts, their enveloping surface, that is the smallest possible surface an envelope of an object, is significantly smaller than its surface, for example for plastic parts for the sanitary area, automobile construction, or suitable for electrically shielded housings, because their disadvantage, the Exploiting treatment solutions from the baths is often only in practice unsatisfactory can be avoided.
  • direct electrolytic metallization in the method according to the invention without preceding electroless Metallization drops smaller amounts of toxic and complexing agents Sewage on than with conventional processes for plastic metallization.
  • the method according to the invention is therefore less expensive overall, less complex and environmentally friendly than the state of the art known methods.
  • an organic solvent such as one Diethylene glycol or ethylene glycol derivative, dimethylformamide or others polar or non-polar solvents to swell the substrate.
  • organic solvent such as one Diethylene glycol or ethylene glycol derivative, dimethylformamide or others polar or non-polar solvents to swell the substrate.
  • solvents can also be used in a mixture with water.
  • Especially preferred treatment agents additionally contain alkalizing agents, such as for example alkali hydroxides or tetraalkylammonium hydroxides.
  • the solutions can vary depending on the type of substrate to be treated at room temperature or used at an elevated temperature.
  • the surfaces to be metallized pretreated in an etching solution containing chromium (VI) oxide pretreated in an etching solution containing chromium (VI) oxide.
  • a solution containing chromic acid which also contains sulfuric acid may contain.
  • the Treatment time from 2 to 16 minutes.
  • Chromium (VI) compounds reduced to chromium (III) compounds adhering to the substrate surfaces Chromium (VI) compounds reduced to chromium (III) compounds.
  • an acidic aqueous solution of sodium hydrogen sulfite be used.
  • other reducing agents such as hydroxylamine.
  • the substrate can be dissolved 300 ml / l of concentrated hydrochloric acid or another mineral acid, such as concentrated sulfuric acid, are treated in aqueous solution.
  • This treatment is useful to the activator solution with which the substrate subsequently treated, not continuously by rinse water dilute. Since the activator also contains tin compounds in addition to palladium, the mineral acid treatment solution can also add these tin compounds contain. This will partially compensate for the carryover losses.
  • the treatment time in this pre-immersion solution can vary widely can be varied. It is only important that the surfaces of the substrate are complete be wetted. Any bath temperature can be set.
  • the success of the process is probably due to the fact that the adsorption of palladium particles from a colloid solution is used to make the non-conductive surface with a large number of palladium particles too occupy. Because the palladium particles come from a colloidal solution after adsorption, surround it with a protective colloid cover that covers the electrical Prevents conductivity of the deposited palladium layer.
  • the activator usually consists of a mineral acid and preferably hydrochloric acid aqueous solution of a palladium colloid.
  • the palladium content in the Solution can range from about 50 mg / l to about 500 mg / l solution, in particular between about 150 mg / l and 250 mg / l solution.
  • a palladium salt is used to make the colloid.
  • tin (II) salt is added to the solution, which in the reaction of the tin (II) salt is partially oxidized with palladium salt to tin (IV) compounds.
  • the Tin content of the solution can range from 2 g / l to 50 g / l, preferably between 10 g / l and 25 g / l solution.
  • the colloid solutions are described in US-A-30 11 920 and US-A-36 82 671 Method made.
  • the concentration range is the hydrochloric acid between 2 wt .-% and 30 wt .-%, preferably between 5 wt% and 15 wt% in water.
  • hydrochloric acid content below 0.5 mol / l solution, there is no longer enough palladium from the activator adsorbed on the surface to allow rapid metal growth during to achieve the metallization.
  • the substrate is rinsed again.
  • the reduction ability of the tin (II) compounds is used, order in the subsequent treatment step from a metal, preferably Solution containing copper ions the ions to metal, preferably to metallic copper, and in this way between the To deposit palladium particles of metal, for example copper. Moreover the disruptive tin (II) / tin (IV) layer is removed in this way.
  • this solution is used as a metal compound used a copper compound.
  • a metal compound used a copper compound for example, silver Gold, palladium and other precious metals are suitable.
  • copper compounds come all compounds that are particularly soluble in aqueous media, for example Salts such as copper sulfate and copper acetate.
  • the concentration of the metal is in the range of 0.1 g / l to 50 g / l aqueous solution and preferably adjusted from 0.5 g / l to 15 g / l solution.
  • the solution containing metal ions is preferably alkaline.
  • the solution contains an alkali or alkaline earth metal hydroxide and also a complexing agent for the metal.
  • Lithium hydroxide in particular, has been found to be the alkali metal hydroxide turned out to be cheap.
  • other hydroxides are basically such as sodium, potassium, magnesium, calcium or barium hydroxide suitable.
  • Their concentration is in the range from 0.1 mol / l to 3 mol / l aqueous solution, preferably in the range of 0.5 mol / liter to 1.5 mol / liter Solution.
  • the complexing agent also contained serves to the metal in the alkaline Keep solution solved. Therefore, this must be sufficiently large Have complexation constants for the metal and are present in an amount, to at least prevent the precipitation of metal hydroxides.
  • suitable complexing agents have in particular compounds such as ethanolamine, Ethylenediaminetetraacetic acid and its salts, tartaric acid and its Salts, citric acid and their salts as well as N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, proven.
  • the operating temperature of the solution containing the metal ions can be as a whole practical range, but preferably in the range of 30 ° C to 65 ° C and in a preferred embodiment between 50 ° C and 60 ° C can be set.
  • the substrate rinsed again.
  • the first reduction of the metal ions can be done by a further reduction step get supported.
  • boron / hydrogen compounds have been found found to be the cheapest.
  • the substrate is then rinsed again to remove residues of the reducing agent completely removed from the substrate surface.
  • the extremely thin layer shows a sufficient high electrical conductivity for the subsequent electrolytic metallization on.
  • All electrodepositable metals can be used on the after Process pretreated substrate surface without further electroless metallization be directly put down.
  • copper Nickel, palladium and other precious metals are suitable. Can on these metals other metals are deposited. It is also possible that to partially cover the first metal layer with dielectric layers in order to make decorative To produce effects or functional properties.
  • Such dielectric layers can also be placed in front of any of the above Treatment steps applied to the surface of the substrate to prevent metallization at this point.
  • bodies made of acrylonitrile / butadiene / styrene copolymers are used as substrates or their mixtures metallized with other non-conductive materials.
  • chromium (VI) ions containing pretreatment solutions substrates made of polyvinyl chloride in particular are hardly attacked. Therefore, holding elements, such as support frames, are used in electrolytic Metallizing plastics coated with this material, to avoid their metallization during the electrolytic treatment.
  • the substrates are treated with the treatment solutions by immersion, spraying, Contacted gushes or splashes.
  • a uniformly shiny copper layer was deposited exclusively on the ABS molded parts within one hour at a current density of 2 A / dm 2 . No copper deposits were found on the supports covered with polyvinyl chloride.
  • the metal layers had an adhesive strength of more than 1 N / mm in the peel test according to the DE standard DIN.
  • Example 1 The process described in Example 1 was repeated, but in process step 6 with a nickel bath (Watts type) instead of the sulfuric acid Copper bath. The same result was obtained with regard to the selectivity of the process as well as the adhesive strength of the deposited metal layer reached.
  • a nickel bath Watts type
  • An ABS sample was partially coated with a polyester layer and then treated as described in Example 1.
  • the polyester layer was not metallized.
  • a molded part (telephone housing), which in a so-called two-shot process in the injection molding process partially made of ABS-containing plastic (Cycoloy C1100 from General Electric Plastics, Ruesselsheim, Germany) and partly from a polyamide (Noryl GTX924 from General Electric Plastics) was treated as described in Example 1. Only the ABS-containing plastic was covered with metal, while the Polyamide surface was completely metal-free.
  • Example 2 Analogously to Example 1, a frame with attached ABS molded parts was immersed in a solution heated to 45 ° C. for two minutes before conditioning after process step 3 (pre-immersion) to condition the ABS surfaces 1 g of the polymer Luresin KNU (product from BASF, Ludwigshafen, Germany) per liter of aqueous solution contained. After this treatment step, both the ABS surfaces and the tegumite surface of the frame were metallized.
  • the surface conductivity of the layer formed before the metallization was measured. After the treated molded part has been rinsed and dried, a resistance measurement with two measuring electrodes took place, which were at a distance of 1 cm were pressed onto the treated surface of the molded part.
  • the lateral progression of the copper layer was also determined.
  • a surface conductivity of approximately 50 pSiemens ( ⁇ S) was measured.
  • Fig. 1 shows the conductivity in ⁇ S and the growth of the metal front in cm after 1.5 minutes (process step 6) the concentration of hydrochloric acid (mol / l) in the activator (process step 4).
  • the empirical values indicate that the conductivity is almost increasing linearly with the acid concentration, while the metal deposition rate, after a steep rise above a minimum concentration cannot be increased in proportion to the concentration.
  • Example 7 was repeated and the samples were examined depending on different parameters.
  • Table 1 shows the spread of the metal front of two samples up to a metallization time of 2.5 minutes at a galvanizing voltage of 0.6 volts.
  • Table 2 shows the calculated growth rate (cm / min) from a large number of samples metallized at different electroplating voltages at different times since the start of metallization. It is striking that the maximum growth rate is reached about 2 minutes after the start of the coating and then remains approximately constant.
  • Table 3 and Figure 2 show that the growth rate is dependent on the bath temperature during the treatment according to process step c) in claim 1 and step 5 in examples 1 and 8, respectively.
  • This bath Cu-LINK
  • With a low and / or short dwell time a low conductivity is set on the substrate, which results in correspondingly long metallization times.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)

Claims (7)

  1. Procédé pour la métallisation électrolytique sélective de pièces moulées en matière plastique constituées de matériaux ne conduisant pas l'électricité, lesquels sont fixés à des éléments de support revêtus de matière plastique qui ne sont pas à métalliser, en vue du traitement suivant, comprenant les étapes de procédé consistant à :
    a) choisir un polychlorure de vinyle pour le revêtement des éléments de support,
    b) pré-traiter les pièces moulées en matière plastique au moyen d'une solution d'attaque chimique contenant un oxyde de chrome (VI).
    c) traiter ensuite les pièces moulées en matière plastique avec une solution acide colloïdale à base de composés palladium/étain, en évitant un contact prématuré du matériau utilisé pour les éléments de support avec des solutions favorisant l'adsorption,
    d) traiter les pièces moulées en matière plastique avec une solution contenant un composé métallique soluble pouvant être réduit au moyen de composés de l'étain(II) un hydroxyde de métal alcalin ou alcalino-terreux et un agent complexant pour le métal en au moins une quantité empêchant la précipitation d'hydroxydes métalliques,
    e) métalliser par voie électrolytique les pièces moulées en matière plastique.
  2. Procédé selon la revendication 1, caractérisé en ce que les pièces moulées en matière plastique sont partiellement métallisées en recouvrant des parties des surfaces des pièces moulées en matière plastique d'un matériau choisi dans le groupe du polychlorure de vinyle, du polyester ou du polyamide, avant la mise en oeuvre du procédé.
  3. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les pièces moulées en matière plastique sont rincées entre quelques unes ou toutes les étapes de procédé.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé par un composé du cuivre en tant que composé métallique soluble.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé par l'hydroxyde de lithium en tant qu'hydroxyde de métal alcalin.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé par l'acide tartrique et/ou un tartrate en tant qu'agent complexant.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que des pièces moulées en matière plastique à base de copolymères acrylonitrile / butadiène /styrène ou leurs mélanges avec d'autres matériaux non conducteurs ou constitués de polycarbonate sont métallisées.
EP96907505A 1995-03-17 1996-03-15 Procede de metallisation electrolytique selective ou partielle de surfaces de substrats composes de materiaux non conducteurs Revoked EP0815292B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19510855 1995-03-17
DE19510855A DE19510855C2 (de) 1995-03-17 1995-03-17 Verfahren zum selektiven oder partiellen elektrolytischen Metallisieren von Substraten aus nichtleitenden Materialien
PCT/EP1996/001190 WO1996029452A1 (fr) 1995-03-17 1996-03-15 Procede de metallisation electrolytique selective ou partielle de surfaces de substrats composes de materiaux non conducteurs

Publications (2)

Publication Number Publication Date
EP0815292A1 EP0815292A1 (fr) 1998-01-07
EP0815292B1 true EP0815292B1 (fr) 2000-01-26

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EP96907505A Revoked EP0815292B1 (fr) 1995-03-17 1996-03-15 Procede de metallisation electrolytique selective ou partielle de surfaces de substrats composes de materiaux non conducteurs

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EP (1) EP0815292B1 (fr)
JP (1) JPH11502263A (fr)
KR (1) KR19980703108A (fr)
AT (1) ATE189274T1 (fr)
BR (1) BR9607848A (fr)
CA (1) CA2210883A1 (fr)
DE (2) DE19510855C2 (fr)
ES (1) ES2142572T3 (fr)
HK (1) HK1008552A1 (fr)
WO (1) WO1996029452A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006042269A1 (de) * 2006-09-08 2008-03-27 Gerhardi Kunststofftechnik Gmbh Verfahren zum galvanischen Beschichten von Bauteilen aus Kunststoffen
US9951433B2 (en) 2014-01-27 2018-04-24 Okuno Chemical Industries Co., Ltd. Conductive film-forming bath
US10036097B2 (en) 2012-12-21 2018-07-31 Okuno Chemical Industries Co., Ltd. Conductive coating film forming bath

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19857290C2 (de) * 1998-12-14 2001-02-01 Lpw Chemie Gmbh Verfahren zur direkten Metallisierung der Oberfläche eines Kunststoffgegenstandes
US6541080B1 (en) 1998-12-14 2003-04-01 Enthone Inc. Double-dip Pd/Sn crosslinker
DE10208674B4 (de) * 2002-02-28 2011-07-07 BIA Kunststoff- und Galvanotechnik GmbH & Co. KG, 42655 Verfahren zur Herstellung galvanisch beschichteter Elemente mit hinterleuchtbaren Symbolen und nach dem Verfahren hergestellte Elemente
DE10223081A1 (de) * 2002-05-17 2003-12-04 Hansgrohe Ag Verfahren zur Herstellung von galvanisierten Sanitärgegenständen aus Kunststoff
KR100913265B1 (ko) * 2002-07-30 2009-08-21 엘지전자 주식회사 전원 공급 단자
DE102005026633A1 (de) 2005-06-03 2006-12-28 Hansgrohe Ag Verfahren zur Herstellung von galvanisierten Sanitärgegenständen aus Kunststoff
DE102005031454A1 (de) * 2005-07-04 2007-01-11 Huf Hülsbeck & Fürst Gmbh & Co. Kg Türgriff, Türgriff-Gehäuse und Verfahren zum Herstellen des Türgriff-Gehäuses
DE102005051632B4 (de) * 2005-10-28 2009-02-19 Enthone Inc., West Haven Verfahren zum Beizen von nicht leitenden Substratoberflächen und zur Metallisierung von Kunststoffoberflächen
EP1988192B1 (fr) 2007-05-03 2012-12-05 Atotech Deutschland GmbH Procédé d'application d'un revêtement métallique sur un substrat non conducteur
EP2305856A1 (fr) 2009-09-28 2011-04-06 ATOTECH Deutschland GmbH Processus d'application d'un revêtement métallique sur un substrat non conducteur
EP2602357A1 (fr) 2011-12-05 2013-06-12 Atotech Deutschland GmbH Nouveaux agents de promotion d'adhésion pour la métallisation des surfaces de substrats
EP2639332A1 (fr) 2012-03-15 2013-09-18 Atotech Deutschland GmbH Procédé de métallisation de surfaces en matière synthétique non conductrices
EP2639333A1 (fr) 2012-03-15 2013-09-18 Atotech Deutschland GmbH Procédé de métallisation de surfaces en matière synthétique non conductrices
EP2644744A1 (fr) 2012-03-29 2013-10-02 Atotech Deutschland GmbH Procédé pour favoriser l'adhésion entre des substrats diélectriques et de couches métalliques
WO2015044091A1 (fr) 2013-09-26 2015-04-02 Atotech Deutschland Gmbh Nouveau procédé promoteur d'adhésion pour la métallisation de surfaces de substrats
ES2727075T5 (es) 2015-02-23 2022-05-27 Macdermid Enthone Inc Composición inhibidora para bastidores cuando se utilizan mordientes exentos de cromo en un proceso de galvanizado sobre materiales plásticos

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5376248A (en) * 1991-10-15 1994-12-27 Enthone-Omi, Inc. Direct metallization process
DE4206680C1 (de) * 1992-02-28 1994-01-27 Schering Ag Verfahren zur Metallisierung von Nichtleiteroberflächen und die Verwendung von Hydroxymethansulfinsäure im Verfahren
DK0616053T3 (da) * 1993-03-18 2001-06-18 Atotech Usa Inc Selvaccelererende og genopfyldende neddypningsovertræksfremgangsmåde uden formaldehyd
GB2277745A (en) * 1993-04-20 1994-11-09 Enthone Omi Post activator solution for use in electroplating non-conductive substrates e.g in plating through holes in PCB,s

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006042269A1 (de) * 2006-09-08 2008-03-27 Gerhardi Kunststofftechnik Gmbh Verfahren zum galvanischen Beschichten von Bauteilen aus Kunststoffen
DE102006042269B4 (de) * 2006-09-08 2014-08-28 Automobile Patentverwaltungs- und -verwertungsgesellschaft mbH Verfahren zum galvanischen Beschichten von Trägerteilen aus Kunststoffen
US10036097B2 (en) 2012-12-21 2018-07-31 Okuno Chemical Industries Co., Ltd. Conductive coating film forming bath
US9951433B2 (en) 2014-01-27 2018-04-24 Okuno Chemical Industries Co., Ltd. Conductive film-forming bath

Also Published As

Publication number Publication date
ATE189274T1 (de) 2000-02-15
EP0815292A1 (fr) 1998-01-07
BR9607848A (pt) 1998-07-14
DE19510855A1 (de) 1996-09-19
JPH11502263A (ja) 1999-02-23
DE19510855C2 (de) 1998-04-30
WO1996029452A1 (fr) 1996-09-26
ES2142572T3 (es) 2000-04-16
DE59604301D1 (de) 2000-03-02
CA2210883A1 (fr) 1996-09-26
KR19980703108A (ko) 1998-10-15
HK1008552A1 (en) 1999-05-14

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