EP0142691B1 - Process for activating substrates for electroless plating - Google Patents

Process for activating substrates for electroless plating Download PDF

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Publication number
EP0142691B1
EP0142691B1 EP84112030A EP84112030A EP0142691B1 EP 0142691 B1 EP0142691 B1 EP 0142691B1 EP 84112030 A EP84112030 A EP 84112030A EP 84112030 A EP84112030 A EP 84112030A EP 0142691 B1 EP0142691 B1 EP 0142691B1
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EP
European Patent Office
Prior art keywords
silver
process according
compound
soluble
nickel
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EP84112030A
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German (de)
French (fr)
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EP0142691A3 (en
EP0142691A2 (en
Inventor
Henning Dr. Giesecke
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Bayer AG
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Bayer AG
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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

Definitions

  • the invention relates to a gentle method for activating non-conductive or semiconductive substrate surfaces for chemogalvanic metal deposition.
  • the adhesion of the noble metal nuclei to the substrate surfaces is so low that a number of rinsing processes are necessary to prevent the introduction of noble metal nuclei into the metallization baths.
  • the object of the present invention was therefore to avoid these disadvantages as far as possible, i.e. To develop an inexpensive activation process which, in a simple manner and without organic solvents if possible, brings about a good adhesive strength of the activators on the surfaces to be metallized.
  • Preferred complexing agents for dissolving the sparingly soluble silver compounds are nitrogen-containing compounds which, by the action of heat and / or acids, provide complexes which are easily split.
  • Aqueous ammonia is particularly preferred.
  • Amines can also be used, but their boiling point should preferably be below 100.degree.
  • other complexing agents can be used, such as. B. cyanide ions or thiosulfate ions.
  • Germination - as already mentioned - is preferably carried out from an aqueous solution.
  • water-like compounds such.
  • wetting agents e.g. B. Mersolate, Texapon add.
  • the concentration of silver compounds is generally between 0.01 g and 10 g / l, in special cases also above or below.
  • Preferred silver I compounds are e.g. B. silver chloride, silver bromide, silver cyanide. Silver isothiocyanate, silver chromate, silver nitrite, Silver metaphosphate and silver diphosphate.
  • the surfaces of the substrates to be metallized are wetted with the complex solutions, the exposure time preferably being 1 second to 1 minute. Methods such as immersing the substrate in the solutions or spraying or brushing the substrate surfaces are particularly suitable for this purpose. Furthermore, it is also possible to apply the activation solutions by stamping or by printing processes.
  • the wetting is carried out at temperatures between 0 ° C and 90 ° C. In special cases, the temperature can also be below or above. Working at 15-40 ° C. is very particularly preferred.
  • any organic solvents used are removed and the complexes applied are cleaved. This is preferably done by the action of heat, the temperature and drying conditions having to be chosen such that the surfaces of the substrates are not attacked. In general, temperatures of 0 to 200 ° C, preferably 50 to 150 ° C are used; in special cases (freeze drying, baking) these temperatures can also be exceeded or fallen below.
  • Another variant of the process is that the poorly soluble silver salt is precipitated on the moistened surface by a chemical reaction.
  • An example is the acidification of a silver amine chloride solution with mineral acid, which leads to the precipitation of silver chloride. In these cases, removal of the complexing agent is no longer necessary.
  • the surfaces germinated according to one of the process variants described must then be activated by reduction.
  • the reducing agents customary in electroplating such as hydrazine hydrate, formaldehyde, hypophosphite, boranes or borohydrides, can preferably be used.
  • the reduction is preferably carried out in aqueous solution.
  • solvents such as alcohols, ethers, hydrocarbons can also be used.
  • Suitable substrates for the process according to the invention are: glass, quartz, ceramic, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters, polycarbonates, polyamides, polyethylene fluoride and textile fabrics, threads and fibers made of polyamide. Polyester, polyalkylene, polyacrylonitrile, polyvinyl halide, cotton and wool as well as their blends or copolymers, graphite fibers, flock and whiskers made of aluminum oxide etc. Textile materials are preferred.
  • the surfaces activated according to the invention can be used directly for electroless metallization.
  • 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 variant only consists of three work steps, for example: immersing the substrate in the solution of the silver compound, drying the substrate surfaces and immersing the surfaces activated in this way in the metallization bath.
  • This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
  • Metallization baths which can be used in the process according to the invention are preferably baths with nickel salts, cobalt salts, copper salts or their mixtures with iron salts, gold and silver salts. Such metallization baths are known in the electroless metallization art.
  • the silver salts according to the invention only detach from the germinated substrate surfaces to such an extent that the surfaces are metallized without the metallization baths being destroyed by noble metal nuclei.
  • a 15 cm x 15 cm square of a cotton fabric (satin) is immersed in a solution of 0.7 g of silver chloride in one liter of aqueous ammonia for 10 seconds, then dried at 90 ° C. and then in an alkaline nickel-plating bath containing 30 g / 1 contains nickel chloride, 10 g / I dimethylamine borane and 10 g / I citric acid and was adjusted to pH 8 with ammonia, nickel-plated.
  • a shiny metallic piece of fabric with a metal coating of 44 g nickel / m 2 is obtained .
  • the electrical resistance of a 10 cm x 10 cm square area is 2 ohms in the warp direction and 3 ohms in the weft direction.
  • a 15 cm x 15 cm square of a polyamide fabric (polyamide-6) is immersed in a solution of 1.3 g of silver chloride in one liter of aqueous ammonia for 1 minute.
  • the fabric is then dried at 80 ° C. and then nickel-plated for 30 minutes in an alkaline nickel-plating bath in accordance with Example 1.
  • a shiny metallic piece of fabric is obtained with a metal coating of 37 g nickel / m 2 .
  • the resistance measured on a 10 cm x 10 cm square area is 0.2 ohms in the warp direction and 0.4 ohms in the weft direction.
  • a 15 cm x 15 cm square of carbon fabric (plain weave) is immersed for 1 minute in an activation solution containing 0.5 g silver chloride / l aqueous ammonia.
  • the fabric is dried at 120 ° C. and then metallized in an alkaline nickel plating bath according to Example 1 for one hour.
  • a shiny metallic fabric with a metal coating of 55 g nickel / m2 is obtained.
  • the resistance of a 10 cm x 10 cm square area is 0.2 ohms in the warp direction and 0.3 ohms in the weft direction.
  • a 15 cm x 15 cm network of aromatic polyamide is immersed in an activation solution containing 7 g / l ammoniacal aqueous solution of silver chloride for 30 seconds.
  • the fabric is then dried at 100 ° C.
  • a shiny metallic mesh with a metal coating of 10 g / m 2 is obtained .
  • the resistance of a square area of 10 cm x 10 cm is 16 ohms or 18 ohms.
  • a knitted fabric made of a polyester fiber yarn (Nm 40) (100% polyethylene terephthalate) is immersed in an activation solution according to Example 4 at room temperature for 1 minute.
  • the knitted fabric is dried at 100 ° C. and then nickel-plated in an alkaline nickel-plating bath according to Example 1 for 45 minutes.
  • a shiny metallic knitted fabric with a metal coating of 76 g nickel / m2 is obtained.
  • a glass plate of 20 cm x 8 cm is sprayed uniformly with an activation solution according to Example 4, dried and then metallized in an alkaline nickel plating bath according to Example 1 for 5 minutes. After 1 minute 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 cm x 8 cm polyester film is degreased with 20% sodium hydroxide solution at 70 ° C. (10 minutes) and then sprayed on one side with an activation solution containing 3.5 g of silver chloride / l ammoniacal water.
  • the film is dried at 120 ° C. and then immersed in a solution of 1 g of sodium borohydride in one liter of water for 2 minutes.
  • the film is then rinsed with water and then metallized at 70 ° C. in an alkaline cobalt bath containing 35 g / l cobalt sulfate, 140 g / l potassium sodium tartate and 20 g / 1 sodium hypophosphite.
  • a cobalt-coated film with a cobalt content of 8.3 g / m 2 is obtained on one side.
  • a cotton fabric according to Example 1 is immersed for 30 seconds in an activation solution which contains 1.5 g of silver rhodanide / l of aqueous ammonia.
  • the sample is dried at 120 ° C. and then nickel-plated in an alkaline nickel bath according to Example 1 for 40 minutes.
  • a shiny metallic piece of fabric with a nickel coating of 88 g / m 2 is obtained .
  • a polyamide fabric according to Example 2 is immersed for 1 minute in a solution of 1 g of silver bromide in one liter of aqueous ammonia, then dried at 80 ° C. and then nickel-plated in an alkaline nickel bath according to Example 1 for 80 minutes. A shiny metallic piece of fabric with a nickel coating of 60 g / m 2 is obtained .
  • the resistance of a 10 cm x 10 cm area is 0.1 ohm in the warp direction and 0.2 ohm in the weft direction.
  • a piece of paper measuring 15 cm ⁇ 15 cm is immersed in an activation solution according to Example 1, dried according to Example 1 and then reduced in a 2% aqueous dimethylamine borane solution. After rinsing with water, the activated piece of paper is placed in an alkaline Nickel plating bath containing 30 g / l nickel chloride, 20 g / l citric acid and 8 g / l sodium hypophosphite and adjusted to pH 9 with ammonia, nickel plated for 25 minutes at room temperature. A shiny metallic piece of paper with a metal coating of 41 g / m 2 is obtained . The resistance of a 10 cm x 10 cm square area is 2 ohms in both directions.
  • a 15 cm x 15 cm square of a cotton fabric (satin) is immersed in a solution of 1.6 g of silver chloride in one liter of aqueous ammonia for 30 seconds. The piece of fabric is then immersed in a 3% hydrochloric acid solution for one minute, washed and then nickel-plated in an alkaline nickel-plating bath according to Example 1 for 15 minutes. A shiny metallic piece of fabric with a nickel coating of 48 g / m 2 is obtained .
  • the electrical resistance of a 10 cm x 10 cm square area is 0.9 ohms in the chain direction and 1.3 ohms in the weft direction.
  • ABS piece preheated with chromic acid is immersed in a solution of 3 g of silver chloride in one liter of aqueous ammonia, then dried at 80 ° C. and then metallized in an alkaline nickel plating bath according to Example 1 for 10 minutes. After 30 seconds the surface begins to turn dark and after 10 minutes a well adhering, shiny metallic nickel layer had been deposited.
  • a 15 cm x 15 cm piece of fabric made of polyamide 6 is immersed for one minute in an ammoniacal aqueous solution of 2.5 g of silver chloride / l, then dried at 130 ° C. and then in an alkaline copper bath made of 10 g / l of copper sulfate, 14 g / I Seignette salt and 20 ml / I 35 wt .-% formaldehyde solution brought, which was adjusted to pH 12.5 to 13 with sodium hydroxide solution. After one minute, the surface of the fabric begins to discolor and after 20 minutes a shiny metallic, copper-colored fabric with 12 g / m 2 copper is obtained.
  • the resistance of a 10 cm x 10 cm square area is 3.5 ohms in the warp direction and 5 ohms in the weft direction.

Description

Gegenstand der Erfindung ist ein schonendes Verfahren zur Aktivierung von nichtleitenden oder halbleitenden Substratoberflächen für die chemogalvanische Metallabscheidung.The invention relates to a gentle method for activating non-conductive or semiconductive substrate surfaces for chemogalvanic metal deposition.

Es ist allgemein bekannt, daß die Metallisierung derartiger Oberflächen eine relativ aufwendige Vorbehandlung erfordert. Dazu gehören beispielsweise das Aufrauhen der Oberfläche durch mechanische Einwirkung oder Beizen mit starken Oxidationsmitteln, das Imprägnieren mit ionischen oder kolloidalen Edelmetallösungen, die Reduktion der Edelmetallionen zum Metall sowie mehrere Spüllvorgänge.It is generally known that the metallization of such surfaces requires a relatively complex pretreatment. These include, for example, roughening the surface by mechanical action or pickling with strong oxidizing agents, impregnating with ionic or colloidal noble metal solutions, reducing the noble metal ions to the metal and several rinsing processes.

Die verfahrenstechnischen Nachteile dieser vielstufigen und z.T. sehr drastischen Maßnahmen sind offensichtlichThe procedural disadvantages of this multi-stage and sometimes very drastic measures are obvious

Es sind daher vor allem in der Patentliteratur diverse materialschonende und verfahrenstechnische einfacher durchzuführende Aktivierungsverfahren vorgeschlagen worden, bei denen die zu metallisierenden Substrate mit Lösungen oder Disperionen von Komplexverbindungen von Elementen der 1. und 8. Nebengruppe des Periodensystems in zumeist organischen Lösungsmitteln behandelt werden (vgl. DE-A-1 696 603, DE-A-2451 217, DE-A-2 116 389, DE-A-3 025 307, DE-A-3 148 280 u.a.m.)Therefore, especially in the patent literature, various material-saving and procedural, easier to carry out activation processes have been proposed, in which the substrates to be metallized are treated with solutions or dispersions of complex compounds of elements of the 1st and 8th subgroup of the periodic table in mostly organic solvents (cf. DE-A-1 696 603, DE-A-2451 217, DE-A-2 116 389, DE-A-3 025 307, DE-A-3 148 280 and many others)

Aber auch diese an sich sehr eleganten Verfahren konnten nicht voll befriedigen.But even these processes, which are very elegant in themselves, were not fully satisfactory.

Abgesehen davon, daß man optimale Aktivierungseffekte praktisch nur mit den Vebindungen des relativ teueren Palladiums erzielen kann, weisen nämlich auch diese Verfahren verschiedene von Fall zu Fall mehr oder weniger schwerwiegende Nachteile auf.Apart from the fact that optimal activation effects can practically only be achieved with the compounds of the relatively expensive palladium, these processes also have various disadvantages which are more or less serious from case to case.

Neben der bisweilen geringen Lagerungsstabilität der Aktivierungsbäder und der manchmal ungenügenden Haftfestigkeit der Aktivatoren an der Substratoberfläche sind die Flüchtigkeit, Brennbarkeit und Toxizität der organischen Lösungsmittel sowie insbesondere der hohe Preis der Metallkomplexverbindungen zu nennen.In addition to the sometimes poor storage stability of the activation baths and the sometimes insufficient adhesive strength of the activators on the substrate surface, the volatility, flammability and toxicity of the organic solvents and, in particular, the high price of the metal complex compounds should be mentioned.

Bei den bisher beschriebenen Aktivierungsverfahren mit Edelmetallkomplexen aus wäßriger Lösung ist die Haftung der Edelmetallkeime an den Substratoberflächen so gering, daß eine Reihe von Spülvorgängen erforderlich sind, um ein Einschleppen von Edelmetallkeimen in die Metallisierungsbäder zu verhindern.In the activation processes described so far with noble metal complexes from aqueous solution, the adhesion of the noble metal nuclei to the substrate surfaces is so low that a number of rinsing processes are necessary to prevent the introduction of noble metal nuclei into the metallization baths.

Die Aufgabe der vorliegenden Erfindung bestand daher darin, diese Nachteile weitestgehend zu vermeiden, d.h. ein preiswerteres Aktivierungsverfahren zu entwickeln, das auf einfache Weise auch möglichst unter Verzicht auf organische Lösungsmittel, eine gute Haftfestigkeit der Aktivatoren auf den zu metallisierenden Oberflächen bewirkt.The object of the present invention was therefore to avoid these disadvantages as far as possible, i.e. To develop an inexpensive activation process which, in a simple manner and without organic solvents if possible, brings about a good adhesive strength of the activators on the surfaces to be metallized.

Erfindungsgemäß wird nun eine solche "Bekeimung" dadurch erzielt, daß man

  • a) die zu metallisierende Oberfläche mit einer Aktivierungslösung benetzt, die eine mit Hilfe von Komplexbildnern in eine lösliche Form überführte an sich in Wasser schwer lösliche Silber-I-Verbindung enthält,
  • b) nach dieser Benetzung die lösliche Komplexverbindung in die schwerlösliche Silber-I-Verbindung rückspaltet und
  • c) die auf der Substratoberfläche zurückbleibende Silber-I-Verbindung reduziert.
According to the invention, such "germination" is now achieved in that
  • a) the surface to be metallized is wetted with an activation solution which contains a silver I compound which is inherently difficult to dissolve in water with the aid of complexing agents,
  • b) after this wetting, the soluble complex compound is split back into the poorly soluble silver I compound and
  • c) the silver I compound remaining on the substrate surface is reduced.

Die Vorteile dieses Verfahrens gegenüber der bisher bekannten Aktivierungsmethoden liegen auf der Hand:

  • 1. Anstelle des teueren Palladiums wird das wesentlich preiswertere Silber als Aktivator eingesetzt.
  • 2. Das Verfahren wird vorzugsweise in wäßrigem Medium - also in Abwesenheit von organischen Lösungsmitteln - durchgeführt.
The advantages of this method compared to the previously known activation methods are obvious:
  • 1. Instead of the expensive palladium, the much cheaper silver is used as an activator.
  • 2. The process is preferably carried out in an aqueous medium, ie in the absence of organic solvents.

Aus DE-A-2 116 385 ist zwar bereits ein Verfahren zur Aktivierung von Substratoberflächen mittels wäßriger Lösungen von Silberkomplexsalzen bekannt, wobei jedoch die "Bekeimung" durch einfaches Tauchen, d.h. ohne Rückspaltung in eine wasserunlösliche Silberverbindung erfolgt, wie es das erfindungsgemäße Verfahren zwingend vorschreibt Durch diese Rückspaltung ist die Ablösung der Silbermetallkeime von der Substratoberfläche so gering, daß auf die üblichen Spülgänge verzichtet werden kann und daher sogar in einer besonderen Ausführungsform des Verfahrens die Reduktion der Silberverbindung im stromlosen Metallisierungsbad durchgeführt werden kann, ohne eine Vergiftung des Metallisierungsbades befürchten zu müssen.From DE-A-2 116 385 a method for activating substrate surfaces by means of aqueous solutions of silver complex salts is already known, but the "seeding" by simple dipping, i.e. without cleavage into a water-insoluble silver compound, as prescribed by the process according to the invention.This cleavage means that the detachment of the silver metal nuclei from the substrate surface is so small that the usual rinsing steps can be dispensed with and, therefore, even in a special embodiment of the process, the reduction of the silver compound can be carried out in the electroless metallization bath without fear of poisoning the metallization bath.

Bevorzugte Komplexbildner zum Lösen der schwerlöslichen Silberverbindungen sind stickstoffhaltige Verbindungen, die.durch Einwirkung von Wärme und/oder Säuren leichtspaltbare Komplexe liefern. Besonders bevorzugt ist wäßriger Ammoniak. Darüber hinaus können auch Amine eingesetzt werden, deren Siedepunkt sollte aber bevorzugt unter 100°C liegen. Grundsätzlich sind auch andere Komplexbildner einsetzbar, wie z. B. Cyanidionen oder Thiosulfationen.Preferred complexing agents for dissolving the sparingly soluble silver compounds are nitrogen-containing compounds which, by the action of heat and / or acids, provide complexes which are easily split. Aqueous ammonia is particularly preferred. Amines can also be used, but their boiling point should preferably be below 100.degree. Basically, other complexing agents can be used, such as. B. cyanide ions or thiosulfate ions.

Die Bekeimung wird - wie bereits erwähnt - bevorzugt aus wäßriger Lösung durchgeführt. Selbstverständlich können auch wasserähnliche Verbindungen, wie z. B. aliphatische Alkohole oder Verschnitte von organischen Lösungsmitteln mit Wasser oder Alkoholen eingesetzt werden. Für Substrate, deren Oberflächen von den Aktivierungslösungen kaum oder nur sehr schlecht benetzt werden, kann es erforderlich sein, den Lösungen Netzmittel, wie z. B. Mersolate, Texapon zuzusetzen.Germination - as already mentioned - is preferably carried out from an aqueous solution. Of course, water-like compounds such. B. aliphatic alcohols or blends of organic solvents with water or alcohols. For substrates, the surfaces of which are hardly or only very poorly wetted by the activation solutions, it may be necessary to add wetting agents, e.g. B. Mersolate, Texapon add.

Die Konzentration an Silber-Verbindungen liegt im allgemeinen zwischen 0,01 g und 10 g/I, in besonderen Fällen auch darüber oder darunter. Bevorzugte Silber-I-Verbindungen sind z. B. Silberchlorid, Silberbromid, Silbercyanid. Silberisothiocyanat, Silberchromat, Silbernitrit, Silbermetaphosphat und Silberdiphosphat.The concentration of silver compounds is generally between 0.01 g and 10 g / l, in special cases also above or below. Preferred silver I compounds are e.g. B. silver chloride, silver bromide, silver cyanide. Silver isothiocyanate, silver chromate, silver nitrite, Silver metaphosphate and silver diphosphate.

Zweckmäßigerweise wird das erfindungsgemäße Verfahren wie folgt durchgeführt:The method according to the invention is expediently carried out as follows:

Die Oberflächen der zu metallisierenden Substrate werden mit den Komplexlösungen 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 oder Bepinseln der Substratoberflächen. Weiterhin ist es auch möglich, die Aktivierungslösungen durch Stempeln oder durch Druckverfahren aufzubringen.The surfaces of the substrates to be metallized are wetted with the complex solutions, the exposure time preferably being 1 second to 1 minute. Methods such as immersing the substrate in the solutions or spraying or brushing the substrate surfaces are particularly suitable for this purpose. Furthermore, it is also possible to apply the activation solutions by stamping or by printing processes.

Die Benetzung wird bei Temperaturen zwischen 0°C und 90° C durchgeführt. In besonderen Fällen kann die Temperatur auch darunter oder darüber liegen. Ganz besonders bevorzugt wird bei 15 - 40° C gearbeitet.The wetting is carried out at temperatures between 0 ° C and 90 ° C. In special cases, the temperature can also be below or above. Working at 15-40 ° C. is very particularly preferred.

Nach der Benetzung werden gegebenenfalls eingesetzte organische Lösungsmittel entfernt und die aufgebrachten Komplexe gespalten. Bevorzugt geschieht dies durch Wärmeeinwirkung, wobei Temperatur und Trockenbedingungen so gewählt werden müssen, daß die Oberflächen der Substrate nicht angegriffen werden. Im allgemeinen werden dabei Temperaturen von 0 bis 200° C, vorzugsweise 50 bis 150°C angewandt; in besonderen Fällen (Gefriertrocknung, Einbrennen) können diese Temperaturen auch unter- oder überschritten werden.After wetting, any organic solvents used are removed and the complexes applied are cleaved. This is preferably done by the action of heat, the temperature and drying conditions having to be chosen such that the surfaces of the substrates are not attacked. In general, temperatures of 0 to 200 ° C, preferably 50 to 150 ° C are used; in special cases (freeze drying, baking) these temperatures can also be exceeded or fallen below.

Eine andere Variante des Verfahrens besteht darin, daß man auf der befeuchteten Oberfläche durch eine chemische Reaktion das schwer lösliche Silbersalz ausfällt. Als Beispiel sei das Ansäuern einer Silberaminchlorid-Lösung mit Mineralsäure genannt, das zum Ausfallen von Silberchlorid führt. In diesen Fällen ist die Entfernung des Komplexbildners nicht mehr erforderlich.Another variant of the process is that the poorly soluble silver salt is precipitated on the moistened surface by a chemical reaction. An example is the acidification of a silver amine chloride solution with mineral acid, which leads to the precipitation of silver chloride. In these cases, removal of the complexing agent is no longer necessary.

Die nach einem der beschriebenen Verfahrensvarianten bekeimten Oberflächen müssen anschließend durch Reduktion aktiviert werden. Dazu können bevorzugt die in der Galvanotechnik üblichen Reduktionsmittel, wie Hydrazinhydrat, Formaldehyd, Hypophosphit, Borane oder Borhydride verwendet werden. Bevorzugt wird die Reduktion in wäßriger Lösung durchgeführt. Es sind aber auch andere Lösungsmittel wie Alkohole, Ether, Kohlenwasserstoffe einsetzbar.The surfaces germinated according to one of the process variants described must then be activated by reduction. For this purpose, the reducing agents customary in electroplating, such as hydrazine hydrate, formaldehyde, hypophosphite, boranes or borohydrides, can preferably be used. The reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used.

Als Substrate für das erfindungsgemäße Verfahren eignen sich: Glas, Quarz, Keramik, Kohlenstoff, Papier, Polyethylen, Polypropylen, ABS-Kunststoffe, Epoxyharze, Polyester, Polycarbonate, Polyamide, Polyethylenfluorid und textile Flächengebilde, Fäden und Fasern aus Polyamid. Polyester, Polyalkylen, Polyacrylnitril, Polyvinylhalegonide, Baumwolle und Wolle sowie deren Mischungen oder Mischpolymerisate, Graphitfasern, Flock und Whisker aus Aluminiumoxid u.a.m. Bevorzugt sind textile Materialien.Suitable substrates for the process according to the invention are: glass, quartz, ceramic, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters, polycarbonates, polyamides, polyethylene fluoride and textile fabrics, threads and fibers made of polyamide. Polyester, polyalkylene, polyacrylonitrile, polyvinyl halide, cotton and wool as well as their blends or copolymers, graphite fibers, flock and whiskers made of aluminum oxide etc. Textile materials are preferred.

Die erfindungsgemäß aktivierten Oberflächen können in den meisten Fällen direkt zur stromlosen Metallisierung eingesetzt werden.In most cases, the surfaces activated according to the invention can be used directly for electroless metallization.

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 Variante besteht nur noch aus den drei Arbeitsgängen, beispielsweise: Eintauchen des Substrates in die Lösung der Silberverbindung, Trocknen der Substratoberflächen und Eintauchen der so aktivierten Oberflächen in das Metallisierungsbad.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 variant only consists of three work steps, for example: immersing the substrate in the solution of the silver compound, drying the substrate surfaces and immersing the surfaces activated in this way in the metallization bath.

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

Als in dem erfindungsgemäßen Verfahren einsetzbare Metallisierungsbäder kommen bevorzugt Bäder mit Nickelsalzen, Cobaltsalzen, Kupfersalzen oder deren Gemische mit Eisensalzen, 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, copper salts or their mixtures with iron salts, gold and silver salts. Such metallization baths are known in the electroless metallization art.

Es ist überraschend, daß auch in alikalischen Metallisierungsbädern, die Ammoniak enthalten, sich die erfindungsgemäßen Silbersalze nur so gering von den bekeimten Substratoberflächen ablösen, daß eine Metallisierung der Oberflächen ohne Zerstörung der Metallisierungsbäder durch Edelmetallkeime stattfindet.It is surprising that even in alkaline metallization baths which contain ammonia, the silver salts according to the invention only detach from the germinated substrate surfaces to such an extent that the surfaces are metallized without the metallization baths being destroyed by noble metal nuclei.

BeispieleExamples Beispiel 1example 1

Ein 15 cm x 15 cm großes Quadrat eines Baumwollgewebes (Satin) wird 10 Sekunden in eine Lösung von 0,7 g Silberchlorid in einem Liter wäßrigem Ammoniak getaucht, anschließend bei 90°C getrocknet und dann 10 Minuten in einem alkalischen Vernickelungsbad, das 30 g/1 Nickelchlorid, 10 g/I Dimethylaminboran und 10 g/I Zitronensäure enthält und mit Ammoniak auf pH 8 eingestellt wurde, vernickelt. Man erhält ein metallisch-glänzendes Stoffstück mit einer Metallauflage von 44 g Nickel/m2. Der elektrische Widerstand einer 10 cm x 10 cm großen quadratischen Fläche beträgt in Kettrichtung 2 Ohm und in Schußrichtung 3 Ohm.A 15 cm x 15 cm square of a cotton fabric (satin) is immersed in a solution of 0.7 g of silver chloride in one liter of aqueous ammonia for 10 seconds, then dried at 90 ° C. and then in an alkaline nickel-plating bath containing 30 g / 1 contains nickel chloride, 10 g / I dimethylamine borane and 10 g / I citric acid and was adjusted to pH 8 with ammonia, nickel-plated. A shiny metallic piece of fabric with a metal coating of 44 g nickel / m 2 is obtained . The electrical resistance of a 10 cm x 10 cm square area is 2 ohms in the warp direction and 3 ohms in the weft direction.

Beispiel 2Example 2

Ein 15 cm x 15 cm großes Quadrat eines Polyamidgewebes (Polyamid-6) wird 1 Minute in eine Lösung von 1,3 g Silberchlorid in einem Liter wäßrigen Ammoniak getaucht. Anschließend wird das Gewebe bei 80°C getrocknet und dann 30 Minuten in einem alkalischen Vernickelungsbad gemäß Beispiel 1 vernickelt. Man erhält ein metallisch-glänzendes Stoffstück mit einer Metallauflage von 37 g Nickel/m2. Der Widerstand gemessen an einer 10 cm x 10 cm großen quadratischen Fläche berägt 0,2 Ohm in Kettrichtung und 0,4 Ohm in Schußrichtung.A 15 cm x 15 cm square of a polyamide fabric (polyamide-6) is immersed in a solution of 1.3 g of silver chloride in one liter of aqueous ammonia for 1 minute. The fabric is then dried at 80 ° C. and then nickel-plated for 30 minutes in an alkaline nickel-plating bath in accordance with Example 1. A shiny metallic piece of fabric is obtained with a metal coating of 37 g nickel / m 2 . The resistance measured on a 10 cm x 10 cm square area is 0.2 ohms in the warp direction and 0.4 ohms in the weft direction.

Beispiel 3Example 3

Ein 15 cm x 15 cm großes Quadrat eines Kohlenstoffgewebes (Leinwandbindung) wird 1 Minute in eine Aktivierungslösung getaucht, die 0,5 g Silberchlorid/I wäßriges Ammoniak enthält. Das Gewebe wird bei 120°C getrocknet und anschließend in einem alkalischen Vernickelungsbad gemäß Beispiel 1 eine Stunde metallisiert. Man erhält ein metallisch-glänzendes Gewebe mit einer Metallauflage von 55 g Nickel/m2. Der Widerstand einer 10 cm x 10 cm großen quadratischen Fläche beträgt in Kettrichtung 0,2 Ohm und in Schußrichtung 0,3 Ohm.A 15 cm x 15 cm square of carbon fabric (plain weave) is immersed for 1 minute in an activation solution containing 0.5 g silver chloride / l aqueous ammonia. The fabric is dried at 120 ° C. and then metallized in an alkaline nickel plating bath according to Example 1 for one hour. A shiny metallic fabric with a metal coating of 55 g nickel / m2 is obtained. The resistance of a 10 cm x 10 cm square area is 0.2 ohms in the warp direction and 0.3 ohms in the weft direction.

Beispiel 4Example 4

Ein 15 cm x 15 cm großes Netz aus aromatischem Polyamid wird in einer Aktivierungslösung, die 7 g/I ammoniakalisch wäßriger Lösung Silberchlorid enthält, 30 Sekunden eingetaucht. Anschließend wird das Gewebe bei 100°C getrocknet. Nach zehnminütigem Metallisieren in einem alkalischen Vernickelungsbad gemäß Beispiel 1 erhält man ein metallisch-glänzendes Netz mit einer Metallauflage von 10 g/m2. Der Widerstand einer quadratischen Fläche von 10 cm x 10 cm beträgt 16 Ohm bzw. 18 Ohm.A 15 cm x 15 cm network of aromatic polyamide is immersed in an activation solution containing 7 g / l ammoniacal aqueous solution of silver chloride for 30 seconds. The fabric is then dried at 100 ° C. After metallizing for ten minutes in an alkaline nickel plating bath according to Example 1, a shiny metallic mesh with a metal coating of 10 g / m 2 is obtained . The resistance of a square area of 10 cm x 10 cm is 16 ohms or 18 ohms.

Beispiel 5Example 5

Ein Gestrick aus einem Polyester-Fasergarn (Nm 40) (100 % Polyethylenterephthalat) wird bei Raumtemperatur 1 Minute in eine Aktivierungslösung gemäß Beispiel 4 getaucht. Das Gestrick wird bei 100° C getrocknet und anschließend in einem alkalischen Vernickelungsbad gemäß Beispiel 1 45 Minuten vernickelt. Man erhält ein metallisch-glänzendes Gestrick mit einer Metallauflage von 76 g Nickel/m2.A knitted fabric made of a polyester fiber yarn (Nm 40) (100% polyethylene terephthalate) is immersed in an activation solution according to Example 4 at room temperature for 1 minute. The knitted fabric is dried at 100 ° C. and then nickel-plated in an alkaline nickel-plating bath according to Example 1 for 45 minutes. A shiny metallic knitted fabric with a metal coating of 76 g nickel / m2 is obtained.

Beispiel 6Example 6

Eine Glasplatte von 20 cm x 8 cm wird mit einer Aktivierungslösung gemäß Beispiel 4 gleichmäßig gesprüht, getrocknet und anschließend 5 Minuten in einem alkalischen Vernickelungsbad gemäß Beispiel 1 metallisiert. Nach 1 Minute 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 20 cm x 8 cm is sprayed uniformly with an activation solution according to Example 4, dried and then metallized in an alkaline nickel plating bath according to Example 1 for 5 minutes. After 1 minute 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 7Example 7

Eine Polyesterfolie von 30 cm x 8 cm wird mit 20 %-iger Natronlauge bei 70° C entfettet (10 Minuten) und anschließend mit einer Aktivierungslösung, die 3,5 g Silberchlorid/I ammoniakalischen Wasser enthält, einseitig besprüht. Die Folie wird bei 120°C getrocknet und anschließend 2 Minuten in eine Lösung von 1 g Natriumborhydrid in einem Liter Wasser getaucht. Anschließend wird die Folie mit Wasser gespült und dann in einem alkalischen Cobaltbad, das 35 g/1 Cobaltsulfat, 140 g/I Kalium-Natriumtatrat und 20 g/1 Natriumhypophosphit enthält, bei 70° C metallisiert. Man erhält eine einseitig vercobaltete Folie mit einem Cobaltgehalt von 8,3 g/m2.A 30 cm x 8 cm polyester film is degreased with 20% sodium hydroxide solution at 70 ° C. (10 minutes) and then sprayed on one side with an activation solution containing 3.5 g of silver chloride / l ammoniacal water. The film is dried at 120 ° C. and then immersed in a solution of 1 g of sodium borohydride in one liter of water for 2 minutes. The film is then rinsed with water and then metallized at 70 ° C. in an alkaline cobalt bath containing 35 g / l cobalt sulfate, 140 g / l potassium sodium tartate and 20 g / 1 sodium hypophosphite. A cobalt-coated film with a cobalt content of 8.3 g / m 2 is obtained on one side.

Beispiel 8Example 8

Ein Baumwollgewebe gemäß Beispiel 1 wird 30 Sekunden in eine Aktivierungslösung getaucht, die 1,5 g Silberrhodanid/I wäßrigem Ammoniak enthält. Die Probe wird bei 120°C getrocknet und anschließend in einem alkalischen Nickelbad gemäß Beispiel 1 40 Minuten vernickelt. Man erhält ein metallisch-glänzendes Stoffstück mit einer Nickelauflage von 88 g/m2.A cotton fabric according to Example 1 is immersed for 30 seconds in an activation solution which contains 1.5 g of silver rhodanide / l of aqueous ammonia. The sample is dried at 120 ° C. and then nickel-plated in an alkaline nickel bath according to Example 1 for 40 minutes. A shiny metallic piece of fabric with a nickel coating of 88 g / m 2 is obtained .

Beispiel 9Example 9

Ein Polyamidgewebe gemäß Beispiel 2 wird 1 Minute in eine Lösung von 1 g Silberbromid in einem Liter wäßrigen Ammoniak getaucht, anschließend bei 80°C getrocknet und dann in einem alkalischen Nickelbad gemäß Beispiel 1 80 Minuten vernickelt. Man erhält ein metallisch-glänzendes Stoffstück mit einer Nickelauflage von 60 g/m2. Der Widerstand einer 10 cm x 10 cm großen Fläche beträgt 0,1 Ohm in Kettrichtung und 0,2 Ohm in Schußrichtung.A polyamide fabric according to Example 2 is immersed for 1 minute in a solution of 1 g of silver bromide in one liter of aqueous ammonia, then dried at 80 ° C. and then nickel-plated in an alkaline nickel bath according to Example 1 for 80 minutes. A shiny metallic piece of fabric with a nickel coating of 60 g / m 2 is obtained . The resistance of a 10 cm x 10 cm area is 0.1 ohm in the warp direction and 0.2 ohm in the weft direction.

Beispiel 10Example 10

Ein Papierstück von 15 cm x 15 cm wird in eine Aktivierungslösung gemäß Beispiel 1 getaucht, gemäß Beispiel 1 getrocknet und anschließend in einer 2 %-igen wäßrigen Dimethylaminboranlösung reduziert. Nach Spülen mit Wasser wird das aktivierte Papierstück in einem alkalischen Vernickelungsbad, das 30 g/I Nickelchlorid, 20 g/I Zitronensäure und 8 g/I Natriumhypophosphit enthält, und mit Ammoniak auf pH 9 eingestellt wurde, 25 Minuten bei Raumtemperatur vernickelt. Man erhält ein metallisch-glänzendes Papierstück mit einer Metallauflage von 41 g/m2. Der Widerstand einer 10 cm x 10 cm großen quadratischen Fläche beträgt in beiden Richtungen 2 Ohm.A piece of paper measuring 15 cm × 15 cm is immersed in an activation solution according to Example 1, dried according to Example 1 and then reduced in a 2% aqueous dimethylamine borane solution. After rinsing with water, the activated piece of paper is placed in an alkaline Nickel plating bath containing 30 g / l nickel chloride, 20 g / l citric acid and 8 g / l sodium hypophosphite and adjusted to pH 9 with ammonia, nickel plated for 25 minutes at room temperature. A shiny metallic piece of paper with a metal coating of 41 g / m 2 is obtained . The resistance of a 10 cm x 10 cm square area is 2 ohms in both directions.

Beispiel 11Example 11

Ein 15 cm x 15 cm großes Quadrat eines Baumwollgewebes (Satin) wird 30 Sekunden in eine Lösung von 1,6 g Silberchlorid in einem Liter wäßrigem Ammoniak getaucht. Anschließend wird das Stoffstück eine Minute in eine 3 %-ige Salzsäurelösung getaucht, gewaschen und dann in einen alkalischen Vernickelungsbad gemäß Beispiel 1 15 Minuten vernickelt. Man erhält ein metallisch-glänzendes Stoffstück mit einer Nickelauflage von 48 g/m2. Der elektrische Widerstand einer 10 cm x 10 cm großen quadratischen Fläche beträgt in Kettenrichtung 0,9 Ohm und in Schußrichtung 1,3 Ohm.A 15 cm x 15 cm square of a cotton fabric (satin) is immersed in a solution of 1.6 g of silver chloride in one liter of aqueous ammonia for 30 seconds. The piece of fabric is then immersed in a 3% hydrochloric acid solution for one minute, washed and then nickel-plated in an alkaline nickel-plating bath according to Example 1 for 15 minutes. A shiny metallic piece of fabric with a nickel coating of 48 g / m 2 is obtained . The electrical resistance of a 10 cm x 10 cm square area is 0.9 ohms in the chain direction and 1.3 ohms in the weft direction.

Beispiel 12Example 12

Ein mit Chromsäure vorgebeiztes ABS-Stück wird in eine Lösung von 3 g Silberchlorid in einem Liter wäßrigen Ammoniak getaucht, anschließend bei 80° C getrocknet und dann in einem alkalischen Vernickelungsbad gemäß Beispiel 1 10 Minuten lang metallisiert. Nach 30 Sekunden beginnt sich die Oberfläche dunkel zu färben und nach 10 Minuten war eine gut haftende, metallisch-glänzende Nickelschicht abgeschieden worden.An ABS piece preheated with chromic acid is immersed in a solution of 3 g of silver chloride in one liter of aqueous ammonia, then dried at 80 ° C. and then metallized in an alkaline nickel plating bath according to Example 1 for 10 minutes. After 30 seconds the surface begins to turn dark and after 10 minutes a well adhering, shiny metallic nickel layer had been deposited.

Beispiel 13Example 13

Ein 15 cm x 15 cm großes Gewebestück aus Polyamid-6 wird eine Minute lang in eine ammoniakalisch wäßrige Lösung von 2,5 g Silberchlorid/I eingetaucht, anschließend bei 130°C getrocknet und dann in einem alkalischen Kupferbad aus 10 g/I Kupfersulfat, 14 g/I Seignette-Salz und 20 ml/I 35 Gew.-%-ige Formaldehydlösung gebracht, das mit Natronlauge auf pH 12,5 bis 13 eingestellt wurde. Nach einer Minute beginnt sich die Oberfläche des Gewebes dunkel zu verfärben und nach 20 Minuten wird ein metallisch-glänzendes, kupferfarbenes Gewebe mit 12 g/m2 Kupfer erhalten. Der Widerstand einer 10 cm x 10 cm großen quadratischen Fläche beträgt in Kettrichtung 3,5 Ohm und in Schußrichtung 5 Ohm.A 15 cm x 15 cm piece of fabric made of polyamide 6 is immersed for one minute in an ammoniacal aqueous solution of 2.5 g of silver chloride / l, then dried at 130 ° C. and then in an alkaline copper bath made of 10 g / l of copper sulfate, 14 g / I Seignette salt and 20 ml / I 35 wt .-% formaldehyde solution brought, which was adjusted to pH 12.5 to 13 with sodium hydroxide solution. After one minute, the surface of the fabric begins to discolor and after 20 minutes a shiny metallic, copper-colored fabric with 12 g / m 2 copper is obtained. The resistance of a 10 cm x 10 cm square area is 3.5 ohms in the warp direction and 5 ohms in the weft direction.

Claims (10)

1. Process for activating non-conductive or semi- conductive substrate surfaces for the purpose of electroless metallisation, where
a) the surface to be metallised is wetted with an activating solution containing a silver-I compound which is sparingly soluble in water and has been converted into a soluble form with the aid of complexing agents,
b) after this wetting, the soluble complex compound is split back into the sparingly soluble silver-I compound and
c) the silver-I compound remaining on the surface of the substrate is reduced.
2. Process according to Claim 1, characterised in that silver chloride, silver bromide, silver cyanide, silver isothiocyanate, silver chromate, silver nitrite, silver metaphosphate or silver diphosphate is used as the silver-I compound.
3. Process according to Claim 1, characterised in that ammonia or amines with a boiling point below 100°C are used as complexing agents.
4. Process according to Claim 1, characterised in that the concentration of the silver complex solution is 0.01 to 10 %.
5. Process according to Claim 1, characterised in that activating solutions which are free from organic solvents are used.
6. Process according to Claim 1, characterized in that the customary rinsing processes are dispensed with.
7. Process according to Claim 1, characterised in that the soluble silver complexes are split back by drying.
8. Process according to Claim 1, characterised in that the silver complexes are split back by heating to 50 - 150° C.
9. Process according to Claim 1, characterised in that the soluble silver complexes are split back by the action of mineral acids.
10. Process according to Claim 1, characterised in that the silver compound which has been split back is reduced in the metallisation bath, preferably in nickel baths containing aminoborane or copper baths containing formalin.
EP84112030A 1983-10-18 1984-10-08 Process for activating substrates for electroless plating Expired EP0142691B1 (en)

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DE19833337856 DE3337856A1 (en) 1983-10-18 1983-10-18 METHOD FOR ACTIVATING SUBSTRATES FOR CURRENT METALIZATION
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DE3419755A1 (en) * 1984-05-26 1985-11-28 Bayer Ag, 5090 Leverkusen Chemical silvering bath
DE3571545D1 (en) * 1984-09-19 1989-08-17 Bayer Ag Method of partially activating a substrate surfaces
JPH079069B2 (en) * 1986-03-12 1995-02-01 ブラザー工業株式会社 Method for forming copper coating with excellent mechanical properties
US4900618A (en) * 1986-11-07 1990-02-13 Monsanto Company Oxidation-resistant metal coatings
DE3840199C2 (en) * 1988-11-29 1994-12-01 Heraeus Noblelight Gmbh Process for structuring metal layers that are catalytically active in electroless metallization by means of UV radiation
FI95816C (en) * 1989-05-04 1996-03-25 Ad Tech Holdings Ltd Antimicrobial article and method of making the same
JP2524436B2 (en) * 1990-09-18 1996-08-14 インターナショナル・ビジネス・マシーンズ・コーポレイション Surface treatment method
US6544397B2 (en) 1996-03-22 2003-04-08 Ronald Redline Method for enhancing the solderability of a surface
US5733599A (en) * 1996-03-22 1998-03-31 Macdermid, Incorporated Method for enhancing the solderability of a surface
US6905587B2 (en) 1996-03-22 2005-06-14 Ronald Redline Method for enhancing the solderability of a surface
GB9722028D0 (en) * 1997-10-17 1997-12-17 Shipley Company Ll C Plating of polymers
USRE45842E1 (en) 1999-02-17 2016-01-12 Ronald Redline Method for enhancing the solderability of a surface
GB0118870D0 (en) * 2001-08-02 2001-09-26 Shipley Co Llc A combined adhesion promotion and direct metallization process
US6645557B2 (en) 2001-10-17 2003-11-11 Atotech Deutschland Gmbh Metallization of non-conductive surfaces with silver catalyst and electroless metal compositions
TWI526573B (en) * 2011-08-17 2016-03-21 羅門哈斯電子材料有限公司 Stable catalysts for electroless metallization

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US3880580A (en) * 1971-01-11 1975-04-29 Polymer Research Corp Of Ameri Method of activating polymeric materials
DE2116389C3 (en) * 1971-03-30 1980-04-03 Schering Ag, 1000 Berlin Und 4619 Bergkamen Solution for activating surfaces for metallization
US3959547A (en) * 1971-07-29 1976-05-25 Photocircuits Division Of Kollmorgen Corporation Process for the formation of real images and products produced thereby
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CA1232498A (en) 1988-02-09
EP0142691A2 (en) 1985-05-29

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