EP0043485A1 - Method of activating surfaces for electroless plating - Google Patents

Method of activating surfaces for electroless plating Download PDF

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Publication number
EP0043485A1
EP0043485A1 EP81104782A EP81104782A EP0043485A1 EP 0043485 A1 EP0043485 A1 EP 0043485A1 EP 81104782 A EP81104782 A EP 81104782A EP 81104782 A EP81104782 A EP 81104782A EP 0043485 A1 EP0043485 A1 EP 0043485A1
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EP
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Prior art keywords
organic solvent
organometallic
nickel
metallic
metallized
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EP81104782A
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German (de)
French (fr)
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EP0043485B1 (en
Inventor
Henning Dr. Giesecke
Gerhard Dieter Dr. Wolf
Harold Dr. Ebneth
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Bayer AG
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Bayer AG
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Priority to AT81104782T priority Critical patent/ATE13319T1/en
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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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to a method for activating metallic and non-metallic surfaces for the purpose of electroless metal deposition.
  • the previously usual method for the currentless production of metal coatings on non-conductive or semiconductive supports consists in cleaning the support surface, successively in a bath containing stannous chloride or another stannous salt, and in a bath of a metal salt catalyzing the deposition of the desired metal, for example S- Silver nitrate or gold chloride, palladium chloride or platinum chloride is immersed so as to form catalytic nucleus centers, the metal ions of the salt being reduced to centers of the catalytic metal by the ion ions absorbed on the support and / or by reducing agents contained in the electroless metal salt bath, and that then the desired metal, for example copper, nickel or cobalt, by treating the catalyzed surface with the solution of the desired metal in the presence of a reduction by means of deposits; (e.g. G. Müller: electroplating of plastics, Eugen G. Leutze Verlag, Saulgau (1966)).
  • a metal salt catalyzing the deposition of the desired metal for example S- Silver
  • both activation methods have the disadvantage that several process steps (activation, sensitization, rinsing, etc.) are required to carry them out, which make the electroless metallization very cumbersome and therefore expensive.
  • both methods are not universally applicable, but primarily limited to substrates whose surfaces can be pretreated by chemical or mechanical processes.
  • the invention therefore relates to a method for activating metallic and non-metallic surfaces for the purpose of electroless metal deposition, characterized in that the surface to be metallized is wetted with an organometallic compound distributed in an organic solvent by elements of the 1st and 8th subgroups of the Periodic Table of the Elements , the organic solvent is removed and the organometallic compound adhering to the surface to be metallized is reduced.
  • the organometallic compound can, for example, be dissolved or dispersed in the organic solvent, or it can also be a rubbing of the organometallic compounds in the solvent.
  • the surface can then be electrolessly metallized in a known manner.
  • An organometallic compound of elements of the 1st and 8th subgroups of the periodic table in particular of Cu, Ag, Au, Co, Ni, Pd and Pt, olefins, nitriles or 1,3-dicarbonyl compounds being used as organic constituents, very particularly compounds of the divalent Palladium and platinum with olefins, e.g. Butadiene palladium dichloride, with nitriles, e.g.
  • the concentration of organometallic compound should be between 0.01 g and 10 g per liter, but in special cases can also be below or above.
  • Particularly suitable organic solvents are polar protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol, dioxane and tetrahydrofuran.
  • polar protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol, dioxane and tetrahydrofuran.
  • Suitable substrates for the process according to the invention are: steels, titanium, glass, quartz, ceramic, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters, polyamides, polycarbonates and textile fabrics, threads and fibers made of polyamide, polyester, Polyalkylene, polyacrylonitrile, polyvinyl halides, cotton and wool, and their mixtures or copolymers.
  • the organic solvent is removed.
  • Low boiling solvents are preferred by evaporation, e.g. removed in vacuum.
  • other methods such as extraction with a solvent in which the organometallic compounds are insoluble, are appropriate.
  • the reductions customary in electroplating can preferably be used agents such as hydrazine hydrate, formaldehyde, hypophosphite or boranes can be used. Of course, other reducing agents are also possible.
  • the reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.
  • the surfaces activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surfaces of the reducing agent residues.
  • a very particularly preferred embodiment of the method according to the invention consists in that the reduction in the metallization bath is carried out immediately with the reducing agent of the electroless metallization.
  • This version represents a simplification of the electroless metallization that has not been possible until now.
  • This very simple embodiment only consists of the three operations. Immersing the substrate in the solution of the organic compound, evaporating the solvent and immersing the surfaces thus impregnated in the metallization bath (reduction and Metallization).
  • This embodiment is very particular for nickel baths containing amine borane or copper containing formalins suitable for baths.
  • Metallization baths which can be used in the process according to the invention are preferably baths with nickel salts, cobalt salts, iron salts or mixtures thereof with copper salts, gold and silver salts. Such metallization baths are known in the electroless metallization art.
  • ABS plastic part with a structured surface is sprayed evenly with a solution of 0.1 g butadiene palladium dichloride per 1 chloroform (blowing agent Frigen).
  • a 13 x 13 cm square of a polyester / cotton fabric (plain weave) is immersed in a solution of 0.3 g of dicyclopentadiene-gold (I) chloride in 1 l of chloroform for 30 seconds, dried at room temperature and then in one alkaline nickel plating bath nickel-plated according to Example 1.
  • a shiny metallic piece of fabric with a metal coating of 12% by weight of nickel is obtained.
  • the electrical resistance is 1.7 ohms in the warp direction and 3.5 ohms in the weft direction.
  • a 13 x 13 cm square of a polyacrylonitrile fabric (copolymer on 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methalylsulfonate;) plain weave is immersed in a solution of 0.01 g diacetronitrile palladium dichloride in 100 ml methylene chloride for 30 seconds, dried at room temperature and then nickel-plated for 10 minutes in an alkaline nickel plating bath according to Example 1. This gives a shiny metallic piece of fabric with a metal coating of 10% by weight of nickel, the resistance of which is 2.8 ohms in the warp direction and 6.7 ohms in the weft direction.
  • a 13 x 13 cm square made of a polyacrylonitrile fabric (copolymer as in Example 3) is immersed in a solution of 0.1 g of acetylacetonatoplatinum (II) chloride in 100 ml of methylene chloride for 20 seconds, dried and then 1 minute in a 1% -reduced aqueous sodium borohydride solution.
  • the piece of fabric is then metallized for 10 minutes in an alkaline nickel plating bath which contains 25 g / 1 nickel sulfate, 20 g / 1 citric acid and 24 g / 1 sodium hyphosphite and the pH of which has been adjusted to 8.8 with ammonia.
  • a piece of shiny metallic fabric with a nickel coating of 12% by weight is obtained.
  • a knitted fabric made from a fiber yarn (Nm 40) made from a polyester polymer (100% polyethylene terephthalate) is immersed in an activation solution according to Example 3 at room temperature for 30 seconds. The solvent is allowed to evaporate at room temperature and then the knitted fabric is immersed for 1 minute in a solution containing 0.5 g / 1 sodium borohydride. The goods are then rinsed with water. The product is then introduced into an aqueous solution of 0.2 mol / 1 nickel (II) chloride, 0.15 mol / 1 citric acid, 0.2 mol / 1 sodium hypophosphite, which is brought to pH 9 at 25 ° C. with ammonia. 0 is set. After approx. 15 seconds the surface of the textile fabric begins to discolor. After only 30 seconds, the goods are covered with a fine layer of nickel metal and discolored darkly.
  • the nickel layer After about 10 minutes the nickel layer has a thickness of 0.2 ⁇ m.
  • the goods are removed from the bath, rinsed with water and dried.
  • the weight gain was 23% based on the raw weight of the knitted fabric.
  • the surface resistance of a 10 x 10 cm square cut out of the material was 3.6 ohms in the direction of the rods and 4.2 ohms across.
  • a fabric made of a polyacrylonitrile multifilament yarn (100% polyacrylonitrile) is immersed in an activation solution according to Example 1 for 1 minute.
  • the sample is then dried at 40 ° C. and placed in an alkaline copper bath composed of 10 g / 1 copper sulfate, 15 g / 1 Seignette salt and 20 ml / 1 35% by weight formaldehyde solution, which is brought to pH 12-13 with sodium hydroxide solution was discontinued.
  • the surface of the fabric begins to turn dark, after about 2 minutes metallic copper luster develops. After about 20 minutes, the sample was removed from the metallization bath, rinsed thoroughly and air-dried. The layer thickness of the copper was approx. 0.2 ⁇ m.
  • the surface resistance was 0.6 ohms, measured as the resistance of a square of 10 ⁇ 10 cm in the warp direction.
  • a 10 x 10 cm square of carbon fiber fabric is immersed in a solution of 0.05 g of butadiene palladium dichloride per 1 methylene chloride for 30 seconds, dried at room temperature and then in an alkaline nickel plating for 20 minutes Bad nickel plated according to Example 1. This gives a shiny metallic piece of material with a metal coating of 16.9 wt .-%, the resistance 0.3. Is ohms.
  • a glass plate of 30 ⁇ 30 cm is sprayed uniformly with an activation solution according to Example 1, dried and then immersed in an alkaline nickel plating bath according to Example 1 for 7 minutes. After 80 seconds the surface turns dark and after 5 minutes a shiny metallic layer is observed. The glass pane washed and dried after metallization is covered with a reflective metal layer.
  • a 30 x 30 cm polyethylene film is degreased with methylene chloride and then sprayed on one side with an activation solution according to Example 1. After drying, the films are metallized in a nickel plating bath according to Example 1 for 20 minutes. A film nickel-plated on one side with a nickel content of 10.8 g / m 2 is obtained .
  • the fabric web is then drawn through a metallization bath containing 25 g / 1 nickel sulfate, 3 g / 1 dimethylamine borane and 14 g / 1 citric acid at a speed of 25 m / h.
  • the bath time is 10 minutes.
  • the pH value, nickel concentration and reducing agent concentration are kept constant by continuous addition.
  • the goods are then washed and dried.
  • a uniformly nickel-plated fabric web with a nickel coating of 30.5 g / m 2 is obtained .
  • a stamp pad is wetted with 1 gram of dibenzonitrile palladium dichloride in 20 ml of ethylene glycol. Letters are then stamped onto a polyethylene film using a stamp. The film is immersed in a water bath for 30 seconds and then nickel-plated in a metallization bath as in Example 1. After 5 minutes the letters were clearly recognizable as shiny metallic surfaces.
  • a 30 x 26 cm steel plate is degreased with 1,1,1-trichloroethane, then sprayed on one side with an activation solution according to Example 1 and dried. The plate is then immersed in a metallization bath according to Example 1 for 20 minutes.
  • a steel plate evenly coated with a nickel layer of approximately 2 gm is obtained.
  • a 14 cm x 14 cm polypropylene part is sprayed uniformly from one side with a solution of 0.1 g of butadiene palladium dichloride per liter of methylene chloride (blowing agent Frigen), dried at room temperature and then nickel-plated in an alkaline nickel bath according to Example 1 for 15 minutes.
  • a shiny metallic, well adhering nickel layer is obtained on the polypropylene part, which has an electrical resistance of 7 cm ohms.
  • An 8 cm x 11 cm polypropylene network is sprayed uniformly with a solution of 0.1 g of butadiene palladium dichloride per liter of methylene chloride (blowing agent Frigen), dried at room temperature and then nickel-plated in an alkaline nickel bath as in Example 1 for 15 minutes. A glossy, well-nickel-plated polypropylene network with an electrical resistance of 3 ohms is obtained.
  • a 4 cm x 6 cm polyamide sheet is sprayed with an activation solution according to Example 1. After drying, the plate is immersed in a nickel plating bath according to Example 1 for 10 minutes. A plate nickel-plated on one side with a nickel content of 4.2 g / m 2 and a resistance of 5 ohms is obtained.
  • a 15 cm x 15 cm polycarbonate sheet is sprayed with an activation solution according to Example 1. After drying, the plate is immersed in a nickel plating bath according to Example 1 for 15 minutes. After washing and drying, the polycarbonate plate is coated with a reflective metal layer that has a resistance of 4 ohms.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
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  • Electrolytic Production Of Metals (AREA)

Abstract

1. Process for activating metallic and non-metallic surfaces for the purpose of currentless metal deposition, characterized in that a) the surface to be metallized is wetted with an organometallic compound from the series comprising butadiene palladium dichloride, diacetonitrile palladium dichloride, diacetonitrile platinum dichloride and dibenzonitrile palladium dichloride, which compound is stable towards air and moisture and is dispersed in an organic solvent, b) the organic solvent is removed and c) the organometallic compound adhering to the surface to be metallized is reduced.

Description

Die Erfindung betrifft ein Verfahren zur Aktivierung von metallischen und nicht-metallischen Oberflächen zum Zweck der stromlosen Metallabscheidung.The invention relates to a method for activating metallic and non-metallic surfaces for the purpose of electroless metal deposition.

Die bisher übliche Methode zur stromlosen Erzeugung von Metallüberzügen auf nichtleitenden oder halbleitenden Trägern besteht darin, daß man die Trägeroberfläche reinigt, nacheinander in ein Stannochlorid oder ein anderes Stannosalz enthaltendes Bad, und in ein Bad eines die Abscheidung des gewünschten Metalls katalysierenden Metallsalzes, z.B. S-ilbernitrat oder Goldchlorid, Palladiumchlorid oder Platinchlorid, eintaucht, um so katalytische Keimzentren zu bilden, wobei die Metallionen des Salzes zu Zentren des katalytischen Metalls durch die auf dem Träger absorbierten Stannoionen und/oder durch in dem stromlosen Metallsalzbad enthaltene Reduktionsmittel reduziert werden, und daß man dann das gewünschte Metall, z.B. Kupfer, Nickel.oder Kobalt, durch Behandlung der katalysierten Oberfläche mit der Lösung des gewünschten Metalls in Gegenwart eines Reduktionsmittels abscheidet; (z.B. G. Müller: Galvanisieren von Kunststoffen, Eugen G. Leutze Verlag, Saulgau (1966)).The previously usual method for the currentless production of metal coatings on non-conductive or semiconductive supports consists in cleaning the support surface, successively in a bath containing stannous chloride or another stannous salt, and in a bath of a metal salt catalyzing the deposition of the desired metal, for example S- Silver nitrate or gold chloride, palladium chloride or platinum chloride is immersed so as to form catalytic nucleus centers, the metal ions of the salt being reduced to centers of the catalytic metal by the ion ions absorbed on the support and / or by reducing agents contained in the electroless metal salt bath, and that then the desired metal, for example copper, nickel or cobalt, by treating the catalyzed surface with the solution of the desired metal in the presence of a reduction by means of deposits; (e.g. G. Müller: electroplating of plastics, Eugen G. Leutze Verlag, Saulgau (1966)).

Diese und ähnliche Methoden werden im allgemeinen als ionische Aktivierung bezeichnet.These and similar methods are commonly referred to as ionic activation.

Eine andere Möglichkeit zum Aktivieren von Polymeroberflächen bei deren Galvanisierung ist in DE-AS 1 197 720 beschrieben. Dieser Methode liegt die Vereinigung der Arbeitsgänge Sensibilisieren und Aktivieren durch Einbringen von Zin(II)-chlorid in eine Salzsäure-Palladiumchlorid-Lösung zugunde.Another possibility for activating polymer surfaces during their galvanization is described in DE-AS 1 197 720. This method is based on the combination of the steps of sensitizing and activating by introducing zin (II) chloride into a hydrochloric acid-palladium chloride solution.

Es ist anzunehmen, daß dabei eine Kolloidallösung aus metallischem Palladium entsteht, die durch Zinnsäure und Zinn(IV)-oxychlorid stabilisiert wird. Daher wird diese Methode im allgemeinen auch als kolloidale Aktivierung bezeichnet. Bei dem nachfolgenden Arbeitsgang - Beschleunigung in Säuren, Laugen oder Salzen von geeigneter Konzentration - wird das Schutzkolloid beseitigt und die Palladiumteilchen können katalytisch im Elektrolyt für chemische Vernickelung einwirken.It can be assumed that a colloidal solution of metallic palladium is formed which is stabilized by tin acid and tin (IV) oxychloride. For this reason, this method is generally referred to as colloidal activation. In the subsequent work step - acceleration in acids, bases or salts of a suitable concentration - the protective colloid is removed and the palladium particles can act catalytically in the electrolyte for chemical nickel plating.

Beide Aktivierungsmethoden haben den Nachteil, daß zu ihrer Durchführung mehrer Verfahrensschritte (Aktivieren, Sensibilisieren, Spülen, usw.) erforderlich sind, die die stromlose Metallisierung sehr umständlich und damit teuer machen. Außerdem sind beide Verfahren nicht universell anwendbar, sondern vornehmlich auf Substrate beschränkt, deren Oberflächen sich durch chemische oder mechanische Verfahren vorbehandeln lassen.Both activation methods have the disadvantage that several process steps (activation, sensitization, rinsing, etc.) are required to carry them out, which make the electroless metallization very cumbersome and therefore expensive. In addition, both methods are not universally applicable, but primarily limited to substrates whose surfaces can be pretreated by chemical or mechanical processes.

Es wurde nun überraschenderweise eine neue, schondende und verfahrenstechnisch einfache Methode zur Aktivierung von metallischen und nicht metallischen Oberflächen mit der außerdem auch schwer zu metallisierende Oberflächen ohne Vorbehandlung mit einem gut haftenden Metallüberzug versehen werden können, gefunden.Surprisingly, a new, gentle and process-technically simple method for activating metallic and non-metallic surfaces has now been found, with which even surfaces that are difficult to metallize can be provided with a well-adhering metal coating without pretreatment.

Die Erfindung betrifft daher ein Verfahren zum Aktivieren von metallischen und nichtmetallischen Oberflächen zum Zwecke der stromlosen Metallabscheidung, dadurch gekennzeichnet, daß die zu metallisierende Oberfläche mit einer in einem organischen Lösungsmittel verteilten organometallischen Verbindungen von Elementen der 1. und 8. Nebengruppe des Periodensystems der Elemente benetzt, das organische Lösungsmittel entfernt und die an der zu metallisierenden Oberfläche haftende organometallische Verbindung reduziert wird.The invention therefore relates to a method for activating metallic and non-metallic surfaces for the purpose of electroless metal deposition, characterized in that the surface to be metallized is wetted with an organometallic compound distributed in an organic solvent by elements of the 1st and 8th subgroups of the Periodic Table of the Elements , the organic solvent is removed and the organometallic compound adhering to the surface to be metallized is reduced.

Die organometallische Verbindung kann in dem organischen Lösungsmittel beispielsweise gelöst oder dispergiert sein, es kann sich auch um eine Anreibung der organometallischen Verbindungen in dem Lösungsmittel handeln.The organometallic compound can, for example, be dissolved or dispersed in the organic solvent, or it can also be a rubbing of the organometallic compounds in the solvent.

Anschließend kann dann die Oberfläche in bekannter Weise stromlos metallisiert werden.The surface can then be electrolessly metallized in a known manner.

Es kommen grundsätzliche alle organometallischen Verbindungen in Frage, mit denen zum Zwecke der stromlosen Metallisierung die Substrate hinreichend aktiviert werden können. Ohne den Umfang der Erfindung einzuschränken, empfiehlt sich jedoch bei der Durchführung des Verfahrens im technischen Maßstab, folgende Bedingungen einzuhalten:

  • 1. die verwendeten metallorganischen Verbindungen sollten an der Luft und gegenüber Feuchtigkeit stabil sein. Sie sollten in organischen Lösungsmittel gut löslich, in Wasser aber schwer löslich sein. Sie sollten außerdem mit gebräuchlichen Reduktionsmitteln zu einer bei der stromlosen Metallisierung katalytisch wirksamen Verbindung reduzierbar sein.
  • 2. Die Lösungen der metallorganischen Verbindungen in organischen Lösungsmitteln sollten an der Luft und gegenüber Feuchtigkeit stabil sein.
  • 3. Das organische Lösungsmittel sollte leicht entfernbar sein.
  • 4. Bei der Reduktion der organometallischen Verbindung dürfen keine Liganden frei werden, die die Metallisierungsbäder vergiften.
  • 5. Die reduzierten aktiven Keime sollten in wässriger Lösung fest an der Oberfläche haften, um eine Zersetzung der Bäder durch eingeschleppte Metalle zu verhindern.
Basically all organometallic come Compounds in question with which the substrates can be sufficiently activated for the purpose of electroless metallization. However, without restricting the scope of the invention, it is advisable to comply with the following conditions when carrying out the process on an industrial scale:
  • 1. The organometallic compounds used should be stable to air and moisture. They should be readily soluble in organic solvents, but poorly soluble in water. They should also be reducible with customary reducing agents to a compound which is catalytically active in the electroless metallization.
  • 2. The solutions of the organometallic compounds in organic solvents should be stable to air and moisture.
  • 3. The organic solvent should be easily removable.
  • 4. When reducing the organometallic compound, no ligands that poison the metallization baths must be released.
  • 5. The reduced active germs should adhere firmly to the surface in aqueous solution to prevent decomposition of the baths by imported metals.

Das erfindungsgemäß neue Verfahren wird im allgemeinen folgenderweise durchgeführt:The process according to the invention is generally carried out as follows:

Eine metallorganische Verbindung von Elementen der 1. und 8. Nebengruppe des Periodensystems, insbesondere von Cu, Ag, Au, Co, Ni, Pd und Pt, wobei als organischer Bestandteil Olefine, Nitrile oder 1.3-Dicarbonylverbindungen Verwendung finden, ganz besonders Verbindungen des zweiwertigen Palladiums und Platins mit Olefinen, z.B. Butadienpalladiumdichlorid, mit Nitrilen, z.B. Diacetonitrilpalladiumdichlorid, Diacetonitrilplatindichlorid oder Dibenzonitrilpalladiumdichlorid, ferner Acetylacetonate des zweiwertigen Palladiums und Platins sowie Olefinkomplexe-des einwertigen Golds, z.B. Dicyclopentadien-Gold(I)-chlorid, werden in einem organischen Lösungemittel gelöst. Selbstverständlich können auch Mischungen der oben genannten Verbindungen eingesetzt werden. Die Konzentration an metallorganischer Verbindung soll zwischen 0,01 g und 10 g pro Liter betragen, kann aber in besonderen Fällen auch darunter oder darüber liegen.An organometallic compound of elements of the 1st and 8th subgroups of the periodic table, in particular of Cu, Ag, Au, Co, Ni, Pd and Pt, olefins, nitriles or 1,3-dicarbonyl compounds being used as organic constituents, very particularly compounds of the divalent Palladium and platinum with olefins, e.g. Butadiene palladium dichloride, with nitriles, e.g. Diacetonitrile palladium dichloride, diacetonitrile platinum dichloride or dibenzonitrile palladium dichloride, also acetylacetonates of divalent palladium and platinum and olefin complexes - of monovalent gold, e.g. Dicyclopentadiene gold (I) chloride, are dissolved in an organic solvent. Mixtures of the abovementioned compounds can of course also be used. The concentration of organometallic compound should be between 0.01 g and 10 g per liter, but in special cases can also be below or above.

Als organische Lösungsmittel sind besonders polare protische und aprotische Lösungsmittel wie Methylenchlorid, Chloroform, 1,1,1-Trichlorethan, Trichlorethylen, Perchlorethylen, Aceton, Methylethylketon, Butanol, Ethylenglykol, Dioxan und Tetrahydrofuran geeignet.Particularly suitable organic solvents are polar protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol, dioxane and tetrahydrofuran.

Selbstverständlich können auch Gemische obiger Lösungsmittel und-Verschnitte mit anderen Lösungsmitteln, wie Benzin, Ligroin, Toluol, usw. verwendet werden. Mit diesen Lösungen werden bei dem erfindungsgemäßen Verfahren die Oberflächen der zu metallisierenden Substrate benetzt, wobei die Einwirkungsdauer vorzugsweise 1 Sekunde bis 1 Minute beträgt. Besonders geeignet sind dazu Verfahren wie das Eintauchen des Substrats in die Lösungen oder das Besprühen von Substratoberflächen mit den Aktivierungslösungen. Selbstverständlich ist es bei dem neuen Verfahren auch möglich, die Aktivierungslösungen durch Stempeln oder durch Druckverfahren aufzubringen.Mixtures of the above solvents and blends with other solvents such as gasoline, ligroin, toluene, etc. can of course also be used. With the solutions according to the invention, the surfaces of the substrates to be metallized are wetted with these solutions, the duration of action preferably being 1 second to 1 minute. Methods such as immersing the substrate in the solutions or spraying substrate surfaces with the activation solutions are particularly suitable for this purpose. Of course, with the new process it is also possible to apply the activation solutions by stamping or by printing processes.

Als Substrate für das erfindungsgemäße Verfahren eignen sich: Stähle, Titan, Glas, Quarz, Keramik, Kohlenstoff, Papier, Polyethylen, Polypropylen, ABS-Kunststoffe, Epoxyharze, Polyester, Polyamide, Polycarbonate und textile Flächengebilde, Fäden und Fasern aus Polyamid, Polyester, Polyalkylen, Polyacrylnitril, Polyvinylhalogeniden, Baumwolle und Wolle, sowie deren Mischungen oder Mischpolymerisaten.Suitable substrates for the process according to the invention are: steels, titanium, glass, quartz, ceramic, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters, polyamides, polycarbonates and textile fabrics, threads and fibers made of polyamide, polyester, Polyalkylene, polyacrylonitrile, polyvinyl halides, cotton and wool, and their mixtures or copolymers.

Nach der Benetzung wird das organische Lösungsmittel entfernt. Dabei werden niedrig siedene Lösungsmittel bevorzugt durch Verdampfen, z.B. im Vakuum entfernt. Bei höher siedenden Lösungsmitteln sind andere Verfahren, wie Extraktion mit einem Lösungsmittel, in dem die organometallischen Verbindungen unlöslich sind, angebracht.After wetting, the organic solvent is removed. Low boiling solvents are preferred by evaporation, e.g. removed in vacuum. For higher boiling solvents, other methods, such as extraction with a solvent in which the organometallic compounds are insoluble, are appropriate.

Die so imprägnierten Oberflächen müssen anschließend durch Reduktion aktiviert werden. Dazu können bevorzugt die in der Galvanotechnik üblichen Reduktionsmittel, wie Hydrazinhydrat, Formaldehyd, Hypophosphit oder Borane verwendet werden. Natürlich sind auch andere Reduktionsmittel möglich. Bevorzugt wird die Reduktion in wässriger Lösung durchgeführt. Es sind aber auch andere Lösungsmittel wie Alkohole, Ether, Kohlenwasserstoffe einsetzbar. Selbstverständlich können auch Suspensionen oder Aufschlämmungen der Reduktionsmittel verwendet werden.The surfaces impregnated in this way must then be activated by reduction. For this purpose, the reductions customary in electroplating can preferably be used agents such as hydrazine hydrate, formaldehyde, hypophosphite or boranes can be used. Of course, other reducing agents are also possible. The reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.

Die so aktivierten Oberflächen können direkt zur stromlosen Metallisierung eingesetzt werden. Es kann aber auch erforderlich sein, die Oberflächen durch Spülen von den Reduktionsmittelresten zu reinigen.The surfaces activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surfaces of the reducing agent residues.

Eine ganz besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß die Reduktion im Metallisierungsbad gleich mit dem Reduktionsmittel der stromlosen Metallisierung durchgeführt wird. Diese Ausführung stellt eine bisher nicht mögliche Vereinfachung der stromlosen Metallisierung dar. Diese ganz einfache Ausführungsform besteht nur noch aus den drei.Arbeitsgängen Eintauchen des Substrates in die Lösung der organischen Verbindung, Verdampfen des Lösungsmittels und Eintauchen der so imprägnierten Oberflächen in das Metallisierungsbad (Reduktion und Metallisierung).A very particularly preferred embodiment of the method according to the invention consists in that the reduction in the metallization bath is carried out immediately with the reducing agent of the electroless metallization. This version represents a simplification of the electroless metallization that has not been possible until now. This very simple embodiment only consists of the three operations. Immersing the substrate in the solution of the organic compound, evaporating the solvent and immersing the surfaces thus impregnated in the metallization bath (reduction and Metallization).

Diese Ausführungsform ist ganz besonders für aminboranhaltige Nickelbäder oder formalinhaltige Kupferbäder geeignet.This embodiment is very particular for nickel baths containing amine borane or copper containing formalins suitable for baths.

Als in dem erfindungsgemäßen Verfahren einsetzbare Metallisierungsbäder kommen bevorzugt Bäder mit Nickelsalzen, Cobaltsalzen, Eisensalzen oder deren Gemische mit Kupfersalzen, Gold- und Silbersalzen in Betracht. Derartige Metallisierungsbäder sind in der Technik der stromlosen Metallisierung bekannt.Metallization baths which can be used in the process according to the invention are preferably baths with nickel salts, cobalt salts, iron salts or mixtures thereof with copper salts, gold and silver salts. Such metallization baths are known in the electroless metallization art.

Beispiel 1example 1

Ein ABS-Kunststoffteil mit einer struktuierten Oberfläche wird gleichmäßig mit einer Lösung von 0,1 g Butadienpalladiumdichlorid pro 1 Chloroform besprüht (Treibmittel Frigen).An ABS plastic part with a structured surface is sprayed evenly with a solution of 0.1 g butadiene palladium dichloride per 1 chloroform (blowing agent Frigen).

Anschließend wird es bei Raumtemperatur getrocknet und dann in ein alkalisches Vernickelungsbad getaucht, das 30 g/1 Nickelchlorid, 3 g/1 Dimethylaminboran und 10 g/1 Citronensäure enthält und mit Ammoniak auf pH 8,1 eingestellt wurde. Nach etwa 30 Sekunden beginnt sich die Oberfläche dunkel zu färben und nach 10 Minuten war eine gut haftende, metallisch glänzende Nickelschicht abgeschieden worden.It is then dried at room temperature and then immersed in an alkaline nickel plating bath which contains 30 g / 1 nickel chloride, 3 g / 1 dimethylamine borane and 10 g / 1 citric acid and was adjusted to pH 8.1 with ammonia. After about 30 seconds the surface begins to turn dark and after 10 minutes a well adhering, shiny metallic nickel layer had been deposited.

Beispiel 2Example 2

Ein 13 x 13 cm großes Quadrat eines Polyester/Baumwoll-Gewebes (Leinwandbindung) wird 30 Sekunden in eine Lösung von 0,3 g Dicyclopentadien-Gold(I)-chlorid in 1 1 Chloroform getaucht, bei Raumtemperatur getrocknet und dann 20 Minuten in einem alkalischen Vernicklungsbad gemäß Beispiel 1 vernickelt. Man erhält ein metallisch glänzendes Stoffstück mit einer Metallauflage von 12 Gew.-% Nickel. Der elektrische Widerstand beträgt in Kettrichtung 1,7 Ohm und in Schußrichtung 3,5 Ohm.A 13 x 13 cm square of a polyester / cotton fabric (plain weave) is immersed in a solution of 0.3 g of dicyclopentadiene-gold (I) chloride in 1 l of chloroform for 30 seconds, dried at room temperature and then in one alkaline nickel plating bath nickel-plated according to Example 1. A shiny metallic piece of fabric with a metal coating of 12% by weight of nickel is obtained. The electrical resistance is 1.7 ohms in the warp direction and 3.5 ohms in the weft direction.

Beispiel 3Example 3

Ein 13 x 13 cm großes Quadrat eines Polyacrylnitrilgewebes (Copolymerisat auf 93,6 % Acrylnitril, 5,7 % Methylacrylat und 0,7 % Natriummethalylsulfonat;) Leinwandbindung wird 30 Sekunden in eine Lösung von 0,01 g Diacetronitrilpalladiumdichlorid in 100 ml Methylenchlorid getaucht, bei Raumtemperatur getrocknet und dann 10 Minuten in einem alkalischen Vernicklungsbad gemäß Beispiel 1 vernickelt. Man erhält ein metallisch glänzendes Stoffstück mit einer Metallauflage von 10 Gew.-% Nickel, dessen Widerstand 2,8 Ohm in Kettrichtung und 6,7 Ohm in Schußrichtung beträgt.A 13 x 13 cm square of a polyacrylonitrile fabric (copolymer on 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methalylsulfonate;) plain weave is immersed in a solution of 0.01 g diacetronitrile palladium dichloride in 100 ml methylene chloride for 30 seconds, dried at room temperature and then nickel-plated for 10 minutes in an alkaline nickel plating bath according to Example 1. This gives a shiny metallic piece of fabric with a metal coating of 10% by weight of nickel, the resistance of which is 2.8 ohms in the warp direction and 6.7 ohms in the weft direction.

Beispiel 4Example 4

Ein 13 x 13 cm großes Quadrat aus einem Polyacrylnitrilgewebe (Copolymerisat wie in Beispiel 3) wird 20 Sekunden in eine Lösung von 0,1 g Acetylacetonato- platin(II)chlorid in 100 ml Methylenchlorid getaucht, getrocknet und anschließend 1 Minute in einer 1 %-igen wäßrigen Natriumborhydridlösung reduziert. Anschließend wird das Stoffstück 10 Minuten in einem alkalischen Vernickelungsbad metallisiert, das 25 g / 1 Nickelsulfat, 20 g / 1 Citronensäure und 24 g / 1 Natriumhyphosphit enthält und dessen pH mit Ammoniak auf 8,8 eingestellt wurde. Man erhält ein metallisch glänzendes Stoffstück mit einer Nickelauflage von 12 Gew.-%.A 13 x 13 cm square made of a polyacrylonitrile fabric (copolymer as in Example 3) is immersed in a solution of 0.1 g of acetylacetonatoplatinum (II) chloride in 100 ml of methylene chloride for 20 seconds, dried and then 1 minute in a 1% -reduced aqueous sodium borohydride solution. The piece of fabric is then metallized for 10 minutes in an alkaline nickel plating bath which contains 25 g / 1 nickel sulfate, 20 g / 1 citric acid and 24 g / 1 sodium hyphosphite and the pH of which has been adjusted to 8.8 with ammonia. A piece of shiny metallic fabric with a nickel coating of 12% by weight is obtained.

Beispiel 5Example 5

Ein Gestrick (Wevenit) aus einem Fasergarn (Nm 40) aus einem Polyesterpolymerisat (100 % Polyethylenterephthalat) wird bei Raumtemperatur 30 Sekunden in eine Aktivierungslösung gemäß Beispiel 3 getaucht. Man läßt das Lösungsmittel bei Raumtemperatur verdampfen und taucht anschließend das Gestrick 1 Minute in eine Lösung, die 0,5 g/1 Natriumborhydrid enthält. Das Gut wird dann mit Wasser gespült. Anschließend trägt man das Gut in eine wäßrige Lösung von 0,2 mol/1 Nickel-II-chlorid, 0,15 mol/1 Citronensäure, 0,2 mol/1 Natriumhypophosphit ein, die bei 25°C mit Ammonaik auf pH 9,0 eingestellt ist. Nach ca. 15 Sekunden beginnt sich die Oberfläche des textilen Flächengebildes dunkel zu verfärben. Bereits nach 30 Sekunden ist das Gut mit einer feinen Nickelmetallschicht bedeckt und dunkel verfärbt.A knitted fabric (Wevenit) made from a fiber yarn (Nm 40) made from a polyester polymer (100% polyethylene terephthalate) is immersed in an activation solution according to Example 3 at room temperature for 30 seconds. The solvent is allowed to evaporate at room temperature and then the knitted fabric is immersed for 1 minute in a solution containing 0.5 g / 1 sodium borohydride. The goods are then rinsed with water. The product is then introduced into an aqueous solution of 0.2 mol / 1 nickel (II) chloride, 0.15 mol / 1 citric acid, 0.2 mol / 1 sodium hypophosphite, which is brought to pH 9 at 25 ° C. with ammonia. 0 is set. After approx. 15 seconds the surface of the textile fabric begins to discolor. After only 30 seconds, the goods are covered with a fine layer of nickel metal and discolored darkly.

Nach ca. 10 Minuten hat die Nickelschicht eine Dicke von 0,2 µm. Das Gut wird dem Bad entnommen, mit Wasser gespült und getrocknet.After about 10 minutes the nickel layer has a thickness of 0.2 µm. The goods are removed from the bath, rinsed with water and dried.

Die Gewichtszunahme betrug 23 % bezogen auf das Rohgewicht des Gestricks.The weight gain was 23% based on the raw weight of the knitted fabric.

Der Oberflächenwiderstand eines Quadrats von 10 x 10 cm, das aus dem Gut ausgeschnitten wurde, betrug 3,6 Ohm in Stäbchenrichtung und 4,2 Ohm quer dazu.The surface resistance of a 10 x 10 cm square cut out of the material was 3.6 ohms in the direction of the rods and 4.2 ohms across.

Beispiel 6Example 6

Ein Gewebe aus einem Polyacrylnitril-Multifilamentgarn (100 %-iges Polyacrylnitril) wird 1 Minute in eine Aktivierungslösung gemäß Beispiel 1 getaucht. Anschließend wird die Probe bei 40°C getrocknet und in ein alkalisches Kupferbad aus 10 g/1 Kupfersulfat, 15 g/1 Seignette-Salz und 20 ml/1 35 Gew.-%ige Formaldehydlösung gebracht, das mit Natronlauge auf pH 12 - 13 eingestellt wurde.A fabric made of a polyacrylonitrile multifilament yarn (100% polyacrylonitrile) is immersed in an activation solution according to Example 1 for 1 minute. The sample is then dried at 40 ° C. and placed in an alkaline copper bath composed of 10 g / 1 copper sulfate, 15 g / 1 Seignette salt and 20 ml / 1 35% by weight formaldehyde solution, which is brought to pH 12-13 with sodium hydroxide solution was discontinued.

Nach etwa 45 Sekunden beginnt sich die Oberfläche des Gewebes dunkel zu verfärben, nach etwa 2 Minuten entwickelt sich bereits metallischer Kupferglanz. Nach ca. 20 Minuten wurde die Probe dem Metallisierungsbad entnommen, gründlich gespült und an der Luft getrocknet. Die Schichtdicke des Kupfers betrug ca. 0,2 µm.After about 45 seconds, the surface of the fabric begins to turn dark, after about 2 minutes metallic copper luster develops. After about 20 minutes, the sample was removed from the metallization bath, rinsed thoroughly and air-dried. The layer thickness of the copper was approx. 0.2 µm.

Der Oberflächenwiderstand betrug 0,6 Ohm, gemessen als Widerstand eines Quadrats von 10 x 10 cm in Kettrichtung.The surface resistance was 0.6 ohms, measured as the resistance of a square of 10 × 10 cm in the warp direction.

Beispiel 7Example 7

Ein 10 x 10 cm großes Quadrat eines Kohlenstoff-Fasergewebes wird 30 Sekunden in eine Lösung von 0,05 g Butadienpalladiumdichlorid pro 1 Methylenchlorid getaucht, bei Raumtemperatur getrocknet und dann 20 Minuten in einen alkalischen Vernicklungsbad gemäß Beispiel 1 vernickelt. Man erhält ein metallisch glänzendes Stoff stück mit einer Metallauflage von 16,9 Gew.-%, dessen Widerstand 0,3. Ohm beträgt.A 10 x 10 cm square of carbon fiber fabric is immersed in a solution of 0.05 g of butadiene palladium dichloride per 1 methylene chloride for 30 seconds, dried at room temperature and then in an alkaline nickel plating for 20 minutes Bad nickel plated according to Example 1. This gives a shiny metallic piece of material with a metal coating of 16.9 wt .-%, the resistance 0.3. Is ohms.

Beispiel 8Example 8

Eine Glasplatte von 30 x 30 cm wird mit einer Aktivierungslösung gemäß Beispiel 1 gleichmäßig besprüht, getrocknet und anschließend 7 Minuten in ein alkalisches Vernicklungsbad gemäß Beispiel 1 getaucht. Nach 80 Sekunden färbt sich die Oberfläche dunkel und nach 5 Minuten wird eine metallisch glänzende Schicht beobachtet. Die nach der Metallisierung gewaschene und getrocknete Glasscheibe ist mit einer spiegelnden Metallschicht überzogen.A glass plate of 30 × 30 cm is sprayed uniformly with an activation solution according to Example 1, dried and then immersed in an alkaline nickel plating bath according to Example 1 for 7 minutes. After 80 seconds the surface turns dark and after 5 minutes a shiny metallic layer is observed. The glass pane washed and dried after metallization is covered with a reflective metal layer.

Beispiel 9Example 9

Eine Polyethylenfolie von 30 x 30 cm wird mit Methylenchlorid entfettet und anschließend einseitig mit einer Aktivierungslösung gemäß Beispiel 1 besprüht. Nach dem Trocknen wird die Folien 20 Minuten in einem Vernickelungsbad gemäß Beispiel 1 metallisiert. Man erhält eine einseitig vernickelte Folie mit einem Nickelgehalt von 10,8 g/m2.A 30 x 30 cm polyethylene film is degreased with methylene chloride and then sprayed on one side with an activation solution according to Example 1. After drying, the films are metallized in a nickel plating bath according to Example 1 for 20 minutes. A film nickel-plated on one side with a nickel content of 10.8 g / m 2 is obtained .

Beispiel 10Example 10

In einer Klotzvorrichtung wird eine 10 m lange und 15 cm breite Stoffbahn bei einer Geschwindigkeit von 160 m/h durch eine Lösung von 0,1 g Butadienpalladiumdichlorid pro 1 Methylenchlorid gezogen und spannungsfrei bei 40°C getrocknet. Anschließend wird die Stoffbahn mit einer Geschwindigkeit von 25 m/h durch ein Metallisierungsbad gezogen, das 27 g/1 Nickelsulfat, 3 g/1 Dimethylaminboran und 14 g/1 Citronensäure enthält. Die Badverweilzeit beträgt 10 Minuten. Während der Metallisierung werden pH-Wert, Nickelkonzentration und Reduktionsmittelkonzentration durch kontinuierliche Ergänzung konstant gehalten. Das Gut wird anschließend gewaschen und getrocknet. Man erhält eine gleichmäßig vernickelte Stoffbahn mit einer Nickelauflage von 30,5 g/m2.A 10 m long and 15 cm wide fabric at a speed of 160 m / h through a solution of 0.1 g of butadiene palladium dichloride per 1 methylene chloride and dried stress-free at 40 ° C. The fabric web is then drawn through a metallization bath containing 25 g / 1 nickel sulfate, 3 g / 1 dimethylamine borane and 14 g / 1 citric acid at a speed of 25 m / h. The bath time is 10 minutes. During the metallization, the pH value, nickel concentration and reducing agent concentration are kept constant by continuous addition. The goods are then washed and dried. A uniformly nickel-plated fabric web with a nickel coating of 30.5 g / m 2 is obtained .

Beispiel 11Example 11

Ein Stempelkissen wird mit einer Anreibung von 1 g Dibenzonitrilpalladiumdichlorid in 20 ml Ethylenglykol benetzt. Anschließend werden dann mit einem Stempel Buchstaben auf eine Polyethylenfolie gestempelt. Die Folie wird 30 Sekunden in ein Wasserbad getaucht und anschließend in einem Metallisierungsbad gemäß Beispiel 1 vernickelt. Nach 5 Minuten waren die Buchstaben als metallisch glänzende Flächen klar erkennbar.A stamp pad is wetted with 1 gram of dibenzonitrile palladium dichloride in 20 ml of ethylene glycol. Letters are then stamped onto a polyethylene film using a stamp. The film is immersed in a water bath for 30 seconds and then nickel-plated in a metallization bath as in Example 1. After 5 minutes the letters were clearly recognizable as shiny metallic surfaces.

Beispiel 12Example 12

Eine 30 x 26 cm große Stahlplatte wird mit 1,1,1-Trichlorethan entfettet, anschließend einseitig mit einer Aktivierungslösung gemäß Beispiel 1 besprüht und getrocknet. Dann wird die Platte 20 Minuten in ein Metallisierungsbad gemäß Beispiel 1 getaucht.A 30 x 26 cm steel plate is degreased with 1,1,1-trichloroethane, then sprayed on one side with an activation solution according to Example 1 and dried. The plate is then immersed in a metallization bath according to Example 1 for 20 minutes.

Man erhält eine gleichmäßig mit einer Nickelschicht von ca. 2gm beschichtete Stahlplatte.A steel plate evenly coated with a nickel layer of approximately 2 gm is obtained.

Beispiel 13Example 13

Ein 14 cm x 14 cm großes Polypropylenteil wird von einer Seite gleichmäßig mit einer Lösung von 0,1 g Butadienpalladiumdichlorid pro Liter Methylenchlorid besprüht (Treibmittel Frigen), bei Raumtemperatur getrocknet und dann 15 Minuten in einem alkalischen Nickelbad gemäß Beispiel 1 vernickelt. Man erhält eine metallisch glänzende, gut haftende Nickelschicht auf dem Polypropylenteil, die einen elektrischen Widerstand von 7 cm Ohm aufweist.A 14 cm x 14 cm polypropylene part is sprayed uniformly from one side with a solution of 0.1 g of butadiene palladium dichloride per liter of methylene chloride (blowing agent Frigen), dried at room temperature and then nickel-plated in an alkaline nickel bath according to Example 1 for 15 minutes. A shiny metallic, well adhering nickel layer is obtained on the polypropylene part, which has an electrical resistance of 7 cm ohms.

Beispiel 14Example 14

Ein 8 cm x 11 cm großes Polypropylennetz wird gleichmäßig mit einer Lösung von 0,1 g Butadienpalladiumdichlorid pro Liter Methylenchlorid besprüht (Treibmittel Frigen), bei Raumtemperatur getrocknet und dann 15 Minuten in einem alkalischen Nickelbad gemäß Beispiel 1 vernickelt. Man erhält ein metallisch glänzendes, gut vernickeltes Polypropylennetz, das einem elektrischen Widerstand von 3 Ohm aufweist.An 8 cm x 11 cm polypropylene network is sprayed uniformly with a solution of 0.1 g of butadiene palladium dichloride per liter of methylene chloride (blowing agent Frigen), dried at room temperature and then nickel-plated in an alkaline nickel bath as in Example 1 for 15 minutes. A glossy, well-nickel-plated polypropylene network with an electrical resistance of 3 ohms is obtained.

Beispiel 15Example 15

Eine 4cm x 6cm große Polyamidplatte wird mit einer Aktivierungslösung gemäß Beispiel 1 besprüht. Nach dem Trocknen wird die Platte 10 Minuten in ein Vernickelungsbad gemäß Beispiel 1 getaucht. Man erhält eine einseitig vernickelte Platte mit einem Nickelgehalt von 4,2 g/m2 und einem Widerstand von 5 Ohm.A 4 cm x 6 cm polyamide sheet is sprayed with an activation solution according to Example 1. After drying, the plate is immersed in a nickel plating bath according to Example 1 for 10 minutes. A plate nickel-plated on one side with a nickel content of 4.2 g / m 2 and a resistance of 5 ohms is obtained.

Beispiel 16Example 16

Eine 15cm x 15cm große Polycarbonatplatte wird mit einer Aktivierungslösung gemäß Beispiel 1 besprüht. Nach dem Trocknen wird die Platte 15 Minuten in ein Vernickelungsbad gemäß Beispiel 1 getaucht. Nach dem Waschen und Trocknen ist die Polycarbonatplatte mit einer spiegelnden Metallschicht überzogen, die einen Widerstand von 4 Ohm aufweist.A 15 cm x 15 cm polycarbonate sheet is sprayed with an activation solution according to Example 1. After drying, the plate is immersed in a nickel plating bath according to Example 1 for 15 minutes. After washing and drying, the polycarbonate plate is coated with a reflective metal layer that has a resistance of 4 ohms.

Claims (9)

1. Verfahren zum Aktivieren von metallischen und nichtmetallischen Oberflächen zum Zwecke der stromlosen Metallabscheidung, dadurch gekennzeichnet, daß die zu metallisierende Oberfläche mit einer in einem organischen Lösungsmittel verteilten organometallischen Verbindung von Elementen der 1. und 8. Nebengruppe des Periodensystems der Elemente benetzt, das organische Lösungsmittel entfernt und die an der zu metallisierenden Oberfläche haftende organometallische Verbindung reduziert wird.1. A method for activating metallic and non-metallic surfaces for the purpose of electroless metal deposition, characterized in that the surface to be metallized is wetted with an organometallic compound of elements of the 1st and 8th subgroups of the Periodic Table of Elements distributed in an organic solvent, the organic Solvent is removed and the organometallic compound adhering to the surface to be metallized is reduced. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als organometallische Verbindungen Komplexe der Elemente Cu, Ag, Au, Co, Ni, Pd und Pt mit Olefinen 1,3-Dicarbonylverbindungen oder Nitrilen verwendet werden.2. The method according to claim 1, characterized in that complexes of the elements Cu, Ag, Au, Co, Ni, Pd and Pt with olefins 1,3-dicarbonyl compounds or nitriles are used as organometallic compounds. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als organometallische Verbindungen Komplexe des zweiwertigen Palladiums oder Platins mit Olefinen, Nitrilen oder Acetylaceton verwendet werden.3. The method according to claim 1, characterized in that complexes of divalent palladium or platinum with olefins, nitriles or acetylacetone are used as organometallic compounds. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als organometallische Verbindungen Komplexe des einwertigen Golds mit Olefinen verwendet werden.4. The method according to claim 1, characterized in that complexes of monovalent gold with olefins are used as organometallic compounds. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Konzentrationen der organometallischen Verbindungen zwischen 0,01 g und 10 g pro Liter organischen Lösungsmittels betragen.5. The method according to claim 1, characterized in that the concentrations of the organometallic compounds are between 0.01 g and 10 g per liter of organic solvent. 6. Verfahren zur Aktivierung von metallischen und nichtmetallischen Oberflächen, dadurch gekennzeichnet, daß die organometallischen Aktivierungslösung durch Eintauchen der Substrate, Besprühen, Bestempeln oder Bedrucken der Substrate aufgebracht wird.6. A method for activating metallic and non-metallic surfaces, characterized in that the organometallic activation solution is applied by immersing the substrates, spraying, stamping or printing on the substrates. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß als Reduktionsmittel Hydrazine, Formaldehyd, Hypophosphit oder Borane verwendet werden.7. The method according to claim 6, characterized in that hydrazines, formaldehyde, hypophosphite or boranes are used as reducing agents. 8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß als Substrate Stähle, Titan, Glas, Quarz, Keramik, Papier, Kohlenstoff, Polyethylen, Polypropylen, ABS-Kunststoffe, Epoxyharze, Polyester, Polyamide, Polycarbonate und textile Flächengebilde, Fäden und Fasern aus Polyamid, Polyester, Polyalkylen, Polyacrylnitril, Polyvinylhalogeniden, Baumwolle und Wolle, sowie deren Mischungen oder Mischpolymerisaten, verwendet werden.8. The method according to claim 6, characterized in that as substrates steels, titanium, glass, quartz, ceramics, paper, carbon, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters, polyamides, polycarbonates and textile fabrics, threads and fibers Polyamide, polyester, polyalkylene, polyacrylonitrile, polyvinyl halides, cotton and wool, as well as their mixtures or copolymers, can be used. 9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die organometallische Verbindung im organischen Lösungsmittel gelöst ist.9. The method according to claim 1, characterized in that the organometallic compound is dissolved in the organic solvent.
EP81104782A 1980-07-04 1981-06-22 Method of activating surfaces for electroless plating Expired EP0043485B1 (en)

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EP0163805A1 (en) * 1984-06-07 1985-12-11 Bayer Ag Composite material
US4575467A (en) * 1983-07-08 1986-03-11 Bayer Aktiengesellschaft Process for activating substrates for electroless metallization
EP0214097A1 (en) * 1985-08-23 1987-03-11 Ciba-Geigy Ag Mixture of an olefin and dibenzal acetone palladium complex and its use
US4657786A (en) * 1982-10-22 1987-04-14 Bayer Aktiengesellschaft Black-metallized substrate surfaces
US4659592A (en) * 1982-11-13 1987-04-21 Bayer Aktiengesellschaft Process for the production of laminated materials
US4668533A (en) * 1985-05-10 1987-05-26 E. I. Du Pont De Nemours And Company Ink jet printing of printed circuit boards
DE3938710A1 (en) * 1989-11-17 1991-05-23 Schering Ag COMPLEX CONNECTIONS WITH OLIGOMEREM TO POLYMERIC CHARACTER
US5183611A (en) * 1987-11-30 1993-02-02 Nisshinbo Industries, Inc. Method of producing polymer article having metallized surface

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EP0082438B1 (en) * 1981-12-23 1985-10-09 Bayer Ag Process for the activation of surfaces for electroless metallization
US4657786A (en) * 1982-10-22 1987-04-14 Bayer Aktiengesellschaft Black-metallized substrate surfaces
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DE3938710A1 (en) * 1989-11-17 1991-05-23 Schering Ag COMPLEX CONNECTIONS WITH OLIGOMEREM TO POLYMERIC CHARACTER

Also Published As

Publication number Publication date
ES503645A0 (en) 1982-06-01
JPS6354791B2 (en) 1988-10-31
EP0043485B1 (en) 1985-05-15
DE3170482D1 (en) 1985-06-20
JPS5743977A (en) 1982-03-12
CA1169720A (en) 1984-06-26
ES8205269A1 (en) 1982-06-01
DE3025307A1 (en) 1982-01-28
ATE13319T1 (en) 1985-06-15

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