EP0508265B1 - Process for activating substrates surfaces for electrolysis - Google Patents

Process for activating substrates surfaces for electrolysis Download PDF

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Publication number
EP0508265B1
EP0508265B1 EP92105453A EP92105453A EP0508265B1 EP 0508265 B1 EP0508265 B1 EP 0508265B1 EP 92105453 A EP92105453 A EP 92105453A EP 92105453 A EP92105453 A EP 92105453A EP 0508265 B1 EP0508265 B1 EP 0508265B1
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Prior art keywords
weight
parts
activator
gew
palladium
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EP92105453A
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German (de)
French (fr)
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EP0508265A2 (en
EP0508265A3 (en
Inventor
Günther Dr. Reichert
Frank Dipl.-Ing. Kobelka
Gerhard-Dieter Dr. Wolf
Ulrich Dr. Von Gizycki
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—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

  • formulations according to the invention are adhesive Effect metallization.
  • Preferred spray activator formulations contain 0.05 to 1.5 parts by weight of component a) and 10 to 20 parts by weight of component b).
  • Organometallic activators come in the formulations according to the invention Compounds of subgroups 1 and 8 of the periodic table (especially Pd, Pt, Au, Ag). Organometallic ones are particularly suitable Complex compounds of palladium with olefins (dienes), with ⁇ , ⁇ -unsaturated Carbonyl compounds, with crown ethers and with nitriles. Particularly suitable are bisacetonitrile palladium dichloride, butadiene palladium dichloride, 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride, Mesityl oxide palladium dichloride, 3-hepten-2-one-palladium chloride and 5-methyl-3-hexan-2-one palladium chloride.
  • mixtures of these compounds can also be used be used.
  • the activators or mixtures thereof are according to the process according to the invention in the aqueous dispersion brought in. This is generally done through Mixing the ingredients. Incorporation of the formulation components can also be done in separate steps be performed. For example, you can use the activator first in a solvent of the total formulation, e.g. pre-dissolve or disperse in ethanol and then filler, e.g. Add Aerosil®.
  • the activator is reduced to the metallic form by adding formalin or complexed by means of complexing agents and introduced into the aqueous dispersion of the binder. This is done by stirring or dispersing. Chlorides, thiosulfates, rhodanides, cyanides, ammonia or amines are used as complexing agents.
  • Examples of complex compounds are Pd (NH 3 ) 2 Cl 2 , Pd (NH 3 ) 4 Cl 2 , Pd (NH 3 ) 4 (NO 3 ) 2 , K 2 PdCl 4 , K 2 Pd (CN) 4 , [NH 4 ] 2 PdCl 6 , [NH 4 ] 2 PdCl 4 , PL (NH 3 ) 4 Cl 2 , K 2 PtCl 4 , KAg (CN) 2 , KAg (S 2 O 3 ), KAu (CN) 2 , NaAuCl 4 .
  • colloidal precious metal systems also as Pd, Ag, Au, Pt can serve as activators Activated carbon, on aluminum oxide, on calcium carbonate Barium carbonate, on activated alumina and Palladium black, called platinum black.
  • the fillers come from printing and painting technology known auxiliaries such as pigments, disperse Silicas, carbon blacks, silicates, oxides, rheological Additives and clay minerals are considered.
  • Silicates, bentonites and talc are preferred and chalk.
  • the amount of filler can range from 0.5 to 3 parts by weight, based on the mass of the formulation, vary.
  • Activators and fillers In addition to the dispersible polymers, Activators and fillers other ingredients, such as Surfactants, leveling agents, defoamers, dyes and Metal dyes in low concentrations up to 10 % By weight, preferably up to 2% by weight, is admixed become.
  • a solvent in the formulations according to the invention come well-known in printing or painting technology
  • ketones for example Methyl ethyl ketone, cyclohexanone
  • esters for example Butyl acetate, dioctyl phthalate, butyl glycolate, Glycol ethers, for example ethylene glycol monomethyl ether, Diglyme, propylene glycol monomethyl ether acetate
  • Alcohols such as ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol
  • Diacetone alcohol Diacetone alcohol. Mixtures of these solvents can of course also be used and their blends with other solvents be used.
  • the solvents used only serve to dissolve the organic Pd compound and can optionally after reduction of the precious metal activator by Evaporation can be removed.
  • the binders of the aqueous dispersion according to the invention with a polymer content of 10-60, preferably 20-55, particularly preferably 30-50% by weight are known from polyurethane chemistry. They are produced, for example, by reacting polyesters and / or polyethers with aromatic or aliphatic polyisocyanates (Angew. Chemie 82 (1970), 53-63; DE-OS 23 14 512; DE-OS 23 14 513; DE-OS 26 51 506 ).
  • polyurethanes which contain no free isocyanate groups, optionally blocked isocyanate groups and / or anionic groups, for example SO 3 groups.
  • Linear, aliphatic have been found to be particularly suitable Proven polyurethanes, such as those made from hexanediol, Neopentyl glycol and polyisocyanates become.
  • fillers, binders and solvents contain the formulations optionally surfactants, leveling agents and / or dyes.
  • Suitable as substrates for the process according to the invention paper, enamel, ceramic, polyethylene, polypropylene, Epoxy resins, polyesters, polycarbonates, polyamides, Polyimides, polyhydantoins, ABS plastics, silicones, Polyvinyl halides and polyvinylidene fluoride in the form of Foils, plates, papers and nonwovens.
  • substrates like those used in the electronics industry can be used as a housing, e.g. ABS and polycarbonate plastics or their blends, polyphenylene sulfide, Polybutylene terephthalate and its blends and polypropylene oxide.
  • the solvents are removed. This happens through Drying or tempering at substrate-specific temperatures, for example between room temperature and 240 ° C under normal pressure, increased pressure or vacuum.
  • the Drying time can be varied.
  • the surfaces treated in this way then only have to in the case of the complexed activator by reduction be activated, e.g. through reducing agents such as Formaldehyde, hypophosphites, rongalite and boranes.
  • reducing agents such as Formaldehyde, hypophosphites, rongalite and boranes.
  • One form of the process is therefore that the Reduction, e.g. in the case of complex activators, in the metallization bath with the reducing agent the electroless metallization is carried out.
  • a preferred form of the method exists in the fact that formulations are used in which the activator already in active form by reduction is present.
  • the formulations according to the invention are particularly suitable for the partial activation geometrically more complicated Surfaces, especially for the production of or moldings metallized on both sides or by Metallized housing parts on the inside for the electronics industry for the purpose of electromagnetic Shielding. By using this procedure, of course also structured metal surfaces using a suitable mask.
  • the formulation can be prepared, for example, by dissolving the Pd compound in 200 ml of ethanol. it is then diluted with 200 ml of H 2 O, and 15 g of Aerosil® 380 (380 m 2 / g according to BET) are stirred or dispersed in the preliminary solution. Then 1.4 ml of fresh aqueous formalin is added with stirring using a syringe.
  • the spray activator formulation so prepared was using a spray gun with air support (4 bar) sprayed on injection molded test panels (molded parts).
  • the spraying distance was approx. 40 cm; the nozzle cross-section was 1.5 mm; the air metering (2-6 bar) could can be varied.
  • a blend was used as the test plate substrate made of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbon dioxide used.
  • the plate was annealed at 70 ° C. for 1 hour, in a metal bath at 23 ° C for 4 h in a commercially available metallized copper bath and then annealed at 70 ° C for 1 h. You got a coherent layer of metal.
  • Adhesive strength according to DIN 53494 30 N / 25 mm.
  • Blend panels made of polyamide or one Polyurethane so will be comparable results receive.
  • the formulation was applied using a spray gun Air support on an injection molded test plate from a polycarbonate from 4,4'-dihydroxydiphenyl-2,2-propane and aerated, the plate Annealed at 100 ° C for 1 h, after cooling the plate in Metallized metal bath at 23 ° C for 2 h. Subsequently was annealed at 100 ° C for 1 h.
  • Adhesive strength according to DIN 53494 18 N / 25 mm.
  • the formulation was applied using a spray gun Air support on an injection molded test plate (Molded part) made of an ABS polymer (acrylonitrile-butadiene-styrene copolymer) sprayed the air metering was set to 4 bar.
  • the plate was Annealed at 70 ° C for 1 h after the plate has cooled to room temperature in a metal bath at 23 ° C for 4.5 h metallized. A coherent metal layer was obtained.
  • Adhesive strength according to DIN 53494 29 N / 25 mm.
  • the formulation was prepared by pre-dissolving the palladium compound in 200 ml of ethanol. The mixture was then diluted with 200 ml of water and 15 g of Aerosil® 380 (380 m 2 / g according to BET) were stirred or dispersed in this preliminary solution. Then 1.4 ml of fresh aqueous formalin was added with stirring using a syringe.
  • the spray activator formulation so prepared was using a spray gun with air support (4 bar) sprayed on injection molded test panels (molded parts).
  • the spraying distance was approx. 40 cm; the nozzle cross-section was 1.5 mm; the air metering (2-6 bar) could be varied.
  • ABS polymer was used as the test plate substrate (Acrylonitrile-butadiene-styrene copolymer) and a polycarbonate made from 4,4'-dihydroxydiphenyl-2,2-propane and carbon dioxide used.
  • the plate was dried for 24 hours at room temperature dried long, in metal bath at 23 ° C for 3 hours metallized in a commercially available formalin-containing copper bath and then annealed at 70 ° for 1 h. Man received a coherent metal layer.
  • Adhesive strength according to DIN 53494 25 N / 25 mm.
  • the formulation was applied using a spray gun Air support on an injection molded test plate from polycarbonate from 4,4'-dihydroxydiphenyl-2,2-propane and aerated, the plate was dried after dried at room temperature for 24 h, in Metal bath at 23 ° C for 1.5 hours in a commercially available metallized copper bath and then metallized annealed at 100 ° C for 1 h. A coherent was obtained Metal layer.
  • Adhesive strength according to DIN 53494 20 N / 25 mm.
  • the formulation was prepared by pre-dissolving the palladium compound in 200 ml of ethanol, then diluting with 200 ml of water and stirring or dispersing 15 g of Aerosil® 380 (380 m 2 / g by BET) in this preliminary solution. Then 0.7 ml of fresh aqueous formalin was added with stirring using a metering device (syringe).
  • the spray activator formulation so prepared was using a spray gun with air support (4 bar) sprayed on injection molded test panels (molded parts).
  • the spraying distance was approx. 40 cm; the nozzle cross-section was 1.5 mm; the air metering (2-6 bar) could can be varied.
  • ABS polymer was used as the test plate substrate.
  • the plate was dried for 24 hours at room temperature dried long, at 23 ° C for 3 h in a commercial metallized copper bath and then metallized annealed at 70 ° C for 1 h. You got one coherent metal layer.
  • Adhesive strength according to DIN 53494 28 N / 25 mm.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemically Coating (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Mixtures containing an organometallic activator, a filler, a solvent and an aqueous dispersion of a polyurethane polymer are eminently suitable for activating plastic surfaces in order to electrolessly metallise them. <??>After metallisation, the plastic parts activated in this way are preferably used for screening electromagnetic waves.

Description

Es ist allgemein bekannt. daß polymere Werkstoffe vor dem chemischen Metallisieren vorbehandelt werden müssen, z.B. durch Ätzen der Polymeroberfläche mit Chromschwefelsäuren. Dieses Verfahren ist jedoch nur auf solche Polymeren anwendbar. deren Oberfläche sich oxidativ unter Bilduna von Kavernen und Vakuolen verändern läßt.It's commonly known. that polymeric materials before have to be pretreated for chemical metallization, e.g. by etching the polymer surface with chromic sulfuric acids. However, this procedure is only for such Polymers applicable. whose surface is oxidative can be changed under image of caverns and vacuoles.

Ferner ist bekannt. daß das Arbeiten mit Chromschwefelsäure; SO3-Dampf oder anderen Oxidantien mit einer Verschlechterung der physikalischen Eigenschaften, wie der Kerbschlagzähigkeit und des elektrischen Oberflächenwiderstands des polymeren Werkstoffs, einhergeht. Darüber hinaus stören oftmals Spuren von sechswertigem Chrom, die rasch zu einer Vergiftung der Metallbäder führen.It is also known. that working with chromic sulfuric acid; SO 3 vapor or other oxidants is accompanied by a deterioration in the physical properties, such as the notched impact strength and the electrical surface resistance of the polymeric material. In addition, traces of hexavalent chromium often interfere, which quickly lead to poisoning of the metal baths.

Die bekannten Verfahren zur stromlosen Metallisierung von Werkstoffen bestehen im übrigen aus mehreren Verfahrensstufen und haben den Nachteil, daß sie nicht direkt auf alle Polymeren anwendbar sind. Oftmals muß eine chemische oder physikalische Aufrauhung durchgeführt werden.The known methods for electroless metallization materials consist of several process stages and have the disadvantage that they are not are directly applicable to all polymers. Often must chemical or physical roughening can be carried out.

Es ist deshalb bereits vorgeschlagen worden, die Polymeroberflächen sehr schonen mit metallorganischen Katalysatoren zu aktivieren (vgl. z.B. US-A 3 560 257 und EP-A 81 129). Diese an sich sehr elegante Methode ist indessen ebenfalls nicht universell anwendbar. Darüber hinaus führt der Einsatz von Lösungsmitteln häufig zur Auslösung der Spannungsrißkorrosion des unter Zug- oder Druckspannung stehenden Polymerspritzgußteiles.It has therefore already been proposed that the polymer surfaces be very careful with to activate organometallic catalysts (see, for example, US-A 3 560 257 and EP-A 81 129). However, this very elegant method is also not universal applicable. In addition, the use of solvents often leads to Triggering of stress corrosion cracking of the tensile or compressive stress Polymer injection molded part.

Andere Verfahren, wie sie in US-A 3 560 257 und 4 017 265 sowie DE-A 3 627 256 beschrieben werden, haben den Nachteil, daß sie relativ größere Mengen an teuren Edelmetallaktivatoren erfordern.Other processes such as those in US Pat. Nos. 3,560,257 and 4,017,265 and DE-A 3,627,256 have the disadvantage that they are relatively large amounts of expensive Precious metal activators require.

Es wurde nun überraschenderweise gefunden, daß man ohne die genannten Nachteile gut haftende Metallschichten auf Kunststoffoberflächen erzeugen kann, wenn man diese ohne vorheriges Beizen mit einer Aktivatorformulierung auf der Basis von organischen Edelmetallverbindungen, Füllstoffen, eines Lösungsmittels und einer wäßrigen Dispersion eines Polyurethanpolymeren als Bindemittel behandelt. Die Formulierungen sind dadurch gekennzeichnet, daß sie eine wäßrige Dispersion eines Polyurethanpolymeren enthalten.It has now surprisingly been found that one does not have the disadvantages mentioned can create well adhering metal layers on plastic surfaces if one this without prior pickling with an activator formulation based on organic precious metal compounds, fillers, a solvent and one treated aqueous dispersion of a polyurethane polymer as a binder. The Formulations are characterized in that they are an aqueous dispersion of a Contain polyurethane polymers.

Die Erfindung betrifft demnach Aktivatorformulierungen zur Aktivierung von Substratoberflächen für deren stromlose Metallisierung auf der Basis von organischen Edelmetallverbindungen, Füllstoffen, Lösungsmitteln und eines Bindemittels, die dadurch gekennzeichnet sind, daß das Bindemittel eine wäßrige Dispersion eines Polyurethanpolymern ist und die Aktivatorformulierungen

a) 0,03 bis 3,0 Gew.-Teile
einer organischen Edelmetallverbindung als Aktivator, die durch Reduktion in die metallische oder kolloide Form oder durch Komplexbildner in die komplexierte Form übergeführt werden kann,
b) 10 bis 30 Gew.-Teile
eines Lösungsmittels mit einem Flammpunkt > 20°C und Siedepunkt ≥70°C,
c) 0,5 bis 3,0 Gew.-Teile
eines Füllstoffs,
und
d) 12 bis 28 Gew.-Teile
eines Polyurethanpolymeren
enthalten.The invention accordingly relates to activator formulations for activating substrate surfaces for their electroless metallization based on organic noble metal compounds, fillers, solvents and a binder, which are characterized in that the binder is an aqueous dispersion of a polyurethane polymer and the activator formulations
a) 0.03 to 3.0 parts by weight
an organic noble metal compound as an activator, which can be converted into the metallic or colloidal form by reduction or into the complexed form by means of complexing agents,
b) 10 to 30 parts by weight
a solvent with a flash point> 20 ° C and boiling point ≥70 ° C,
c) 0.5 to 3.0 parts by weight
a filler,
and
d) 12 to 28 parts by weight
of a polyurethane polymer
contain.

Es ist überraschend, daß die erfindungsgemäßen Formulierungen eine haftfeste Metallisierung bewirken. Bevorzugte Sprühaktivatorformulierungen enthalten 0,05 bis 1,5 Gew.-Teile an Komponente a) und 10 bis 20 Gew.-Teile an Komponente b).It is surprising that the formulations according to the invention are adhesive Effect metallization. Preferred spray activator formulations contain 0.05 to 1.5 parts by weight of component a) and 10 to 20 parts by weight of component b).

Als Aktivatoren kommen in den erfindungsgemäßen Formulierungen organometallische Verbindungen der 1. und 8. Nebengruppe des Periodensystems (insbesondere Pd, Pt, Au, Ag) in Betracht. Besonders geeignet sind organometallische Komplex-Verbindungen des Palladiums mit Olefinen (Dienen), mit α, β-ungesättigten Carbonylverbindungen, mit Kronenethern und mit Nitrilen. Ganz besonders geeignet sind Bisacetonitrilpalladiumdichlorid, Butadienpalladiumdichlorid, 4-Cyclohexen-1,2-dicarbonsäureanhydridpalladiumdichlorid, Mesityloxidpalladiumdichlorid, 3-Hepten-2-on-palladiumchlorid und 5-Methyl-3-hexan-2-on-palladiumchlorid. Organometallic activators come in the formulations according to the invention Compounds of subgroups 1 and 8 of the periodic table (especially Pd, Pt, Au, Ag). Organometallic ones are particularly suitable Complex compounds of palladium with olefins (dienes), with α, β-unsaturated Carbonyl compounds, with crown ethers and with nitriles. Particularly suitable are bisacetonitrile palladium dichloride, butadiene palladium dichloride, 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride, Mesityl oxide palladium dichloride, 3-hepten-2-one-palladium chloride and 5-methyl-3-hexan-2-one palladium chloride.

Falls gewünscht, können auch Gemische dieser Verbindungen eingesetzt werden.If desired, mixtures of these compounds can also be used be used.

Die Aktivatoren oder die Gemische derselben werden gemäß dem erfindungsgemäßen Verfahren in die wäßrige Dispersion eingebracht. Dies geschieht im allgemeinen durch Vermischen der Bestandteile. Das Einarbeiten der Formulierungskomponenten kann auch in getrennten Schritten durchgeführt werden. Beispielsweise kann man den Aktivator zuerst in einem Lösungsmittel der Gesamtformulierung, z.B. in Ethanol vorlösen bzw. dispergieren und anschließend den Füllstoff, z.B. Aerosil® zugeben.The activators or mixtures thereof are according to the process according to the invention in the aqueous dispersion brought in. This is generally done through Mixing the ingredients. Incorporation of the formulation components can also be done in separate steps be performed. For example, you can use the activator first in a solvent of the total formulation, e.g. pre-dissolve or disperse in ethanol and then filler, e.g. Add Aerosil®.

Dann wird der Aktivator mittels Zugabe von Formalin reduziert zur metallischen Form oder mittels Komplexbildnern komplexiert und in die wäßrige Dispersion des Bindemittels eingebracht. Dies erfolgt durch Rühren oder Dispergieren. Als Komplexbildner werden z.B. Chloride, Thiosulfate, Rhodanide, Cyanide, Ammoniak oder Amine eingesetzt. Beispiele komplexer Verbindungen sind Pd(NH3)2Cl2, Pd(NH3)4Cl2, Pd(NH3)4(NO3)2, K2PdCl4, K2Pd(CN)4, [NH4]2PdCl6, [NH4]2PdCl4, PL(NH3)4Cl2, K2PtCl4, KAg(CN)2, KAg(S2O3), KAu(CN)2, NaAuCl4.Then the activator is reduced to the metallic form by adding formalin or complexed by means of complexing agents and introduced into the aqueous dispersion of the binder. This is done by stirring or dispersing. Chlorides, thiosulfates, rhodanides, cyanides, ammonia or amines are used as complexing agents. Examples of complex compounds are Pd (NH 3 ) 2 Cl 2 , Pd (NH 3 ) 4 Cl 2 , Pd (NH 3 ) 4 (NO 3 ) 2 , K 2 PdCl 4 , K 2 Pd (CN) 4 , [NH 4 ] 2 PdCl 6 , [NH 4 ] 2 PdCl 4 , PL (NH 3 ) 4 Cl 2 , K 2 PtCl 4 , KAg (CN) 2 , KAg (S 2 O 3 ), KAu (CN) 2 , NaAuCl 4 .

Dadurch wird erreicht, daß bei Zugabe der komplexierten Aktivatoren zu der wäßrigen Dispersion eine Koagulation vermieden oder herabgesetzt wird.This ensures that when adding the complexed Activators to coagulate the aqueous dispersion is avoided or reduced.

Das Vorliegen des Aktivators in der komplexierten wie auch in der reduzierten metallischen Form führt zu besonders guten Ergebnissen bezüglich störungsfreier Oberflächen bei der Beschichtung mit den erfindungsgemäßen Formulierungen. The presence of the activator in the complexed like even in the reduced metallic form leads to special good results with regard to trouble-free surfaces when coating with the invention Wording.

Auch kommen nullwertige Komplexverbindungen wie Palladium(O)-tetrakis(triphenylphosphin), Bis[bis-(1,2-diphenylphosphino)-ethan]-palladium(O) oder Bis(dibenzylidenaceton)-palladium(O) in Betracht.Also zero-valued complex compounds like Palladium (O) tetrakis (triphenylphosphine), bis [bis- (1,2-diphenylphosphino) ethane] palladium (O) or bis (dibenzylidene acetone) palladium (O) into consideration.

Als Kolloidale Edelmetallsysteme, die ebenfalls als Aktivatoren dienen können, seien Pd, Ag, Au, Pt auf Aktivkohle, auf Aluminiumoxid, auf Calciumcarbonat, auf Bariumcarbonat, auf aktiviertem Aluminiumoxid und Palladium-Schwarz, Platinmohr genannt.As colloidal precious metal systems, also as Pd, Ag, Au, Pt can serve as activators Activated carbon, on aluminum oxide, on calcium carbonate Barium carbonate, on activated alumina and Palladium black, called platinum black.

Als Füllstoffe kommen aus der Druck- bzw. Lackierungstechnik bekannte Hilfsstoffe wie Pigmente, disperse Kieselsäuren, Ruße, Silikate, Oxide, rheologische Additive und Tonmineralien in Betracht.The fillers come from printing and painting technology known auxiliaries such as pigments, disperse Silicas, carbon blacks, silicates, oxides, rheological Additives and clay minerals are considered.

Insbesondere sei auf die Oxide der Elemente Mn, Ti, Mg, Al, Bi, Cu, Ni, Sn, Zn, Si, sowei deren Mischoxide hingewiesen.In particular, the oxides of the elements Mn, Ti, Mg, Al, Bi, Cu, Ni, Sn, Zn, Si and their mixed oxides pointed out.

Bevorzugten Einsatz finden Silikate, Bentonite, Talkum und Kreide.Silicates, bentonites and talc are preferred and chalk.

Die Menge des Füllstoffs kann im Bereich 0,5 - 3 Gew.-Teilen, bezogen auf die Masse der Formulierung, variieren. The amount of filler can range from 0.5 to 3 parts by weight, based on the mass of the formulation, vary.

Es können auch neben den dispergierbaren Polymeren, Aktivatoren und Füllstoffen weitere Bestandteile, wie Tenside, Verlaufsmittel, Entschäumer, Farbstoffe und Metallfarbstoffe in geringen Konzentrationen bis zu 10 Gew.-%, vorzugsweise bis zu 2 Gew.-%, zugemischt werden.In addition to the dispersible polymers, Activators and fillers other ingredients, such as Surfactants, leveling agents, defoamers, dyes and Metal dyes in low concentrations up to 10 % By weight, preferably up to 2% by weight, is admixed become.

Als Lösungsmittel in den erfindungsgemäßen Formulierungen kommen in der Druck- bzw. Lackiertechnik bekannte Substanzen in Betracht wie Ketone, beispielsweise Methylethylketon, Cyclohexanon, Ester, beispielsweise Essigsäurebutylester, Phthalsäuredioctylester, Glykolsäurebutylester, Glykolether, beispielsweise Ethylenglykolmonomethylether, Diglyme, Propylenglykolmonomethyletheracetat; Alkohole wie Ethanol, n-Propanol, iso-Propanol, n-Butanol, iso-Butanol; Diacetonalkohol. Selbstverständlich können auch Gemische dieser Lösungsmittel und ihrer Verschnitte mit anderen Lösungsmitteln eingesetzt werden.As a solvent in the formulations according to the invention come well-known in printing or painting technology Consider substances such as ketones, for example Methyl ethyl ketone, cyclohexanone, esters, for example Butyl acetate, dioctyl phthalate, butyl glycolate, Glycol ethers, for example ethylene glycol monomethyl ether, Diglyme, propylene glycol monomethyl ether acetate; Alcohols such as ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol; Diacetone alcohol. Mixtures of these solvents can of course also be used and their blends with other solvents be used.

Die eingesetzten Lösungsmittel dienen nur zur Lösung der organischen Pd-Verbindung und können gegebenenfalls nach erfolgter Reduktion des Edelmetall-Aktivators durch Abdampfen entfernt werden.The solvents used only serve to dissolve the organic Pd compound and can optionally after reduction of the precious metal activator by Evaporation can be removed.

Deshalb brauchen nur geringe Mengen an Lösungsmittel eingesetzt zu werden. Ferner kann durch den Einsatz von Lösungsmitteln die Korngröße des erzeugten metallischen Edelmetalls bei der Reduktion beeinflußt werden. Therefore only small amounts of solvent are needed to be used. Furthermore, by using Solvents the grain size of the generated metallic Precious metal can be influenced in the reduction.

Die erfindungsgemäßen Bindemittel der wäßrigen Dispersion mit einem Polymergehalt von 10-60, bevorzugt 20-55, besonders bevorzugt 30-50 Gew.-%, sind aus der Polyurethanchemie bekannt. Sie werden beispielsweise hergestellt durch Umsetzung von Polyestern und/oder Polyethern mit aromatischen oder aliphatischen Polyisocyanaten (Angew. Chemie 82 (1970), 53-63; DE-OS 23 14 512; DE-OS 23 14 513; DE-OS 26 51 506).The binders of the aqueous dispersion according to the invention with a polymer content of 10-60, preferably 20-55, particularly preferably 30-50% by weight are known from polyurethane chemistry. They are produced, for example, by reacting polyesters and / or polyethers with aromatic or aliphatic polyisocyanates (Angew. Chemie 82 (1970), 53-63; DE-OS 23 14 512; DE-OS 23 14 513; DE-OS 26 51 506 ).

Zur Herstellung einer lagerstabilen, versprühbaren und toxikologisch unbedenklichen Formulierung ist es vorteilhaft, Polyurethane einzusetzen, die keine freien Isocyanatgruppen, gegebenenfalls verkappte Isocyanatgruppen und/oder anionische Gruppen z.B. SO3-Gruppen enthalten.To produce a storage-stable, sprayable and toxicologically harmless formulation, it is advantageous to use polyurethanes which contain no free isocyanate groups, optionally blocked isocyanate groups and / or anionic groups, for example SO 3 groups.

Als besonders geeignet haben sich lineare, aliphatische Polyurethane erwiesen, wie sie beispielsweise aus Hexandiol, Neopentylglykol und Polyisocyanaten hergestellt werden.Linear, aliphatic have been found to be particularly suitable Proven polyurethanes, such as those made from hexanediol, Neopentyl glycol and polyisocyanates become.

Neben den Aktivatoren und Salzen, Füllstoffen, Bindemitteln und Lösungsmitteln enthalten die Formulierungen gegebenenfalls Tenside, Verlaufsmittel und/oder Farbstoffe.In addition to the activators and salts, fillers, binders and solvents contain the formulations optionally surfactants, leveling agents and / or dyes.

Vorzugsweise durch Aufsprühen der erfindungsgemaßen Formulierungen mittels aus der Lackindustrie bekannten Verfahren können Oberflächen zum Zwecke einer haftfesten chemischen Metallisierung aktiviert werden. Selbstverstandlich kann das Aufsprühen der Formulierungen durch Tauchen, Aufpinseln und Aufrollen ersetzt werden. Preferably by spraying on the formulations according to the invention by means of processes known from the paint industry can use surfaces for the purpose of adherent chemical metallization can be activated. Of course can by spraying the formulations Diving, brushing and rolling up can be replaced.

Als Substrate für das erfindungsgemäße Verfahren eignen sich Papier, Emaille, Keramik, Polyethylen, Polypropylen, Epoxidharze, Polyester, Polycarbonate, Polyamide, Polyimide, Polyhydantoine, ABS-Kunststoffe, Silikone, Polyvinylhalogenide und Polyvinylidenfluorid in Form von Folien, Platten, Papieren und Vliesen. Besonders bevorzugt sind Substrate, wie sie in der Elektronikindustrie als Gehäuse eingesetzt werden, z.B. ABS- und Polycarbonat-Kunststoffe bzw. deren Blends, Polyphenylensulfid, Polybutylenterephthalat und deren Blends und Polypropylenoxid.Suitable as substrates for the process according to the invention paper, enamel, ceramic, polyethylene, polypropylene, Epoxy resins, polyesters, polycarbonates, polyamides, Polyimides, polyhydantoins, ABS plastics, silicones, Polyvinyl halides and polyvinylidene fluoride in the form of Foils, plates, papers and nonwovens. Particularly preferred are substrates like those used in the electronics industry can be used as a housing, e.g. ABS and polycarbonate plastics or their blends, polyphenylene sulfide, Polybutylene terephthalate and its blends and polypropylene oxide.

Nach dem Aufbringen der erfindungsgemäßen Formulierungen auf die Oberfläche, z.B. die Innenseite eines Gehäuses, werden die Lösungsmittel entfernt. Dies geschieht durch Trocknen oder Tempern bei substratspezifischen Temperaturen, beispielsweise zwischen Raumtemperatur und 240°C unter Normaldruck, erhöhtem Druck oder Vakuum. Die Trocknungszeit kann dabei variiert werden.After application of the formulations according to the invention on the surface, e.g. the inside of a case, the solvents are removed. This happens through Drying or tempering at substrate-specific temperatures, for example between room temperature and 240 ° C under normal pressure, increased pressure or vacuum. The Drying time can be varied.

Die so behandelten Oberflächen müssen anschließend nur im Fall des komplexierten Aktivators durch Reduktion aktiviert werden, z.B. durch Reduktionsmittel wie Formaldehyd, Hypophosphite, Rongalit und Borane.The surfaces treated in this way then only have to in the case of the complexed activator by reduction be activated, e.g. through reducing agents such as Formaldehyde, hypophosphites, rongalite and boranes.

Es sei ausdrücklich erwähnt, daß im Fall der erfindungsgemäßen Formulierungen, in denen der Aktivator bereits vollständig reduziert vorliegt, die Oberflächen keinen weiteren Behandlungschritt erfordern. Ferner unterbleibt ein Auftreten von Spannungen und Störungen bei der Metallabscheidung. It should be expressly mentioned that in the case of the invention Formulations in which the activator is already completely reduced, the surfaces none require further treatment step. Also omitted an occurrence of tension and disturbances in the Metal deposition.

Eine Form des Verfahrens besteht deshalb darin, daß die Reduktion, z.B. im Fall der komplexierten Aktivatoren, im Metallisierungsbad gleich mit dem Reduktionsmittel der stromlosen Metallisierung durchgeführt wird. Dies gilt für geeignete Nickel- und Kupferbäder.One form of the process is therefore that the Reduction, e.g. in the case of complex activators, in the metallization bath with the reducing agent the electroless metallization is carried out. This applies to suitable nickel and copper baths.

Eine bevorzugt ausgeführte Form des Verfahrens besteht darin, daß Formulierungen eingesetzt werden, in denen der Aktivator bereits durch Reduktion in aktiver Form vorliegt.A preferred form of the method exists in the fact that formulations are used in which the activator already in active form by reduction is present.

Die mit den erfindungsgemäßen Formulierungen behandelten Oberflächen können direkt stromlos metallisiert werden. Die dafür in Frage kommenden Metallisierungsbäder sind in der Technik der stromlosen Metallisierung bekannt.Those treated with the formulations according to the invention Surfaces can be metallized without current. The metallization baths in question are known in the art of electroless metallization.

Die erfindungsgemäßen Formulierungen eignen sich besonders für die partielle Aktivierung geometrisch komplizierter Oberflächen, besonders zur Herstellung von ein- oder beidseitig metallisierten Formkörpern bzw. von innenseitig metallisierten Gehäuseteilen für die Elektronikindustrie zum Zwecke der elektromagnetischen Abschirmung. Durch dieses Verfahren können selbstverständlich auch strukturierte Metallflächen mittels einer geeigneten Maske hergestellt werden.The formulations according to the invention are particularly suitable for the partial activation geometrically more complicated Surfaces, especially for the production of or moldings metallized on both sides or by Metallized housing parts on the inside for the electronics industry for the purpose of electromagnetic Shielding. By using this procedure, of course also structured metal surfaces using a suitable mask.

Bei den in den nachfolgenden Beispielen mit dem Buchstaben "®" gekennzeichneten Produkten handelt es sich um eingetragene Warenzeichen. In the following examples with the letter "®" marked products for registered trademarks.

Beispiel 1example 1

Als 40%ige wäßrige Dispersion eines linearen, leicht verzweigten und emulgatorfreien Polyurethans wurden solche auf Basis von linearen Polyestern und aliphatischen Polyisocyanaten eingesetzt, die SO3-Gruppen enthalten. Die mittlere Teilchengröße lag bei 100-300 µm. Die Dichte (DIN 51 757) bei 20°C lag bei ca. 1:0 g/cm3.As a 40% aqueous dispersion of a linear, slightly branched and emulsifier-free polyurethane, those based on linear polyesters and aliphatic polyisocyanates containing SO 3 groups were used. The average particle size was 100-300 µm. The density (DIN 51 757) at 20 ° C was approx. 1: 0 g / cm 3 .

Die Rezeptur einer Sprühaktivatorformulierung bestand aus folgenden Komponenten:

1 Gew.-Teil
Bis-(benzonitril)-palladium(II)-dichlorid
500 Gew.-Teilen
einer 40%igen wäßrigen Dispersion des Polyurethans
300 Gew.-Teilen
Wasser
15 Gew.-Teilen
Aerosil® 380 (380 m2/g nach BET)
1,4 Gew.-Teilen
37%iges frisches wäßriges Formalin
200 Gew.-Teilen
Ethanol
The formulation of a spray activator formulation consisted of the following components:
1 part by weight
Bis (benzonitrile) palladium (II) dichloride
500 parts by weight
a 40% aqueous dispersion of the polyurethane
300 parts by weight
water
15 parts by weight
Aerosil® 380 (380 m 2 / g according to BET)
1.4 parts by weight
37% fresh aqueous formalin
200 parts by weight
Ethanol

Die Herstellung der Formulierung kann z.B. so erfolgen, daß die Pd-Verbindung in 200 ml Ethanol gelöst wird. anschließend wird mit 200 ml H2O verdünnt, 15 g Aerosil® 380 (380 m2/g nach BET) in die Vorlösung eingerührt bzw. dispergiert. Dann wird mittels einer Spritze 1,4 ml frisches wäßriges Formalin unter Rühren zugefügt. The formulation can be prepared, for example, by dissolving the Pd compound in 200 ml of ethanol. it is then diluted with 200 ml of H 2 O, and 15 g of Aerosil® 380 (380 m 2 / g according to BET) are stirred or dispersed in the preliminary solution. Then 1.4 ml of fresh aqueous formalin is added with stirring using a syringe.

Nach 2-stündiger Rührzeit wird die Suspension unter Rühren mit der 40%igen wäßrigen Dispersion des Polyurethans vermischt. Zuletzt wird mit 100 ml Wasser nachverdünnt.After stirring for 2 hours, the suspension is added Stir with the 40% aqueous dispersion of the polyurethane mixed. Finally, with 100 ml of water post-diluted.

Die so hergestellte Sprühaktivatorformulierung wurde mittels einer Sprühpistole mit Luftunterstützung (4 bar) auf spritzgegossenen Testplatten (Formteilen) versprüht. Der Spritzabstand betrug ca. 40 cm; der Düsenquerschnitt betrug 1,5 mm; die Luftzudosierung (2-6 bar) konnte variiert werden. Als Testplattensubstrat wurde ein Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure eingesetzt.The spray activator formulation so prepared was using a spray gun with air support (4 bar) sprayed on injection molded test panels (molded parts). The spraying distance was approx. 40 cm; the nozzle cross-section was 1.5 mm; the air metering (2-6 bar) could can be varied. A blend was used as the test plate substrate made of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbon dioxide used.

Die Platte wurde nach Abtrocknen bei 70°C 1 h lang getempert, im Metallbad bei 23°C 4 h lang in einem handelsüblichen formalinhaltigen Kupferbad metallisiert und anschließend bei 70°C 1 h lang getempert. Man erhielt eine zusammenhängende Metallschicht.After drying, the plate was annealed at 70 ° C. for 1 hour, in a metal bath at 23 ° C for 4 h in a commercially available metallized copper bath and then annealed at 70 ° C for 1 h. You got a coherent layer of metal.

Haftfestigkeit nach DIN 53494: 30 N/25 mm.Adhesive strength according to DIN 53494: 30 N / 25 mm.

Setzt man anstelle der Testplatte aus den oben beschriebenen Blend Platten aus Polyamid oder aus einem Polyurethan ein, so werden vergleichbare Ergebnisse erhalten. If you replace the test plate from the ones described above Blend panels made of polyamide or one Polyurethane, so will be comparable results receive.

Beispiel 2Example 2

Die Herstellung der Sprühaktivatorformulierung und die Durchführung des Verfahrens erfolgte wie in Beispiel 1, nur daß 2 Gew.-Teile Bis-(benzonitril)-palladium(II)-dichlorid in der Sprühaktivatorformulierung eingesetzt wurden.The preparation of the spray activator formulation and the The procedure was carried out as in Example 1, only that 2 parts by weight of bis (benzonitrile) palladium (II) dichloride used in the spray activator formulation were.

Die Rezeptur der Sprühaktivatorformulierung bestand aus folgenden Komponenten:

2 Gew.-Teilen
Bis-(benzonitril)-palladium(II)-dichlorid
500 Gew.-Teilen
einer 40%igen wäßrigen Dispersion des Polyurethans wie in Beispiel 1
300 Gew.-Teilen
Wasser
15 Gew.-Teilen
Aerosil® 380 (380 m2/g nach BET)
1,4 Gew.-Teilen
37%iges frisches wäßriges Formalin
200 Gew.-Teilen
Ethanol.
The formulation of the spray activator formulation consisted of the following components:
2 parts by weight
Bis (benzonitrile) palladium (II) dichloride
500 parts by weight
a 40% aqueous dispersion of the polyurethane as in Example 1
300 parts by weight
water
15 parts by weight
Aerosil® 380 (380 m 2 / g according to BET)
1.4 parts by weight
37% fresh aqueous formalin
200 parts by weight
Ethanol.

Die Formulierung wurde mittels einer Sprühpistole mit Luftunterstützung auf einer spritzgegossenen Testplatte aus einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure versprüht, die Platte bei 100°C 1 h lang getempert, nach Abkühlen der Platte im Metallbad bei 23°C 2 h lang metallisiert. Anschließend wurde bei 100°C 1 h lang getempert. Man erhielt zusammenhängende Metallschicht.The formulation was applied using a spray gun Air support on an injection molded test plate from a polycarbonate from 4,4'-dihydroxydiphenyl-2,2-propane and aerated, the plate Annealed at 100 ° C for 1 h, after cooling the plate in Metallized metal bath at 23 ° C for 2 h. Subsequently was annealed at 100 ° C for 1 h. One received coherent Metal layer.

Haftfestigkeit nach DIN 53494: 18 N/25 mm. Adhesive strength according to DIN 53494: 18 N / 25 mm.

Beispiel 3Example 3

Die Herstellung der Sprühaktivatorformulierung und die Durchführung erfolgte wie in Beispiel 1, nur daß 0,7 ml Formalin eingesetzt wurden.The preparation of the spray activator formulation and the The procedure was as in Example 1, except that 0.7 ml Formalin were used.

Die Rezeptur der Sprühaktivatorformulierung bestand aus folgenden Komponenten:

1 Gew.-Teil
Bis-(benzonitril)-palladium(II)-dichlorid
500 Gew.-Teilen
einer 40%igen wäßrigen Dispersion des Polyurethans wie im Beispiel 1
300 Gew.-Teilen
Wasser
15 Gew.-Teilen
Aerosil® 380 (380 m2/g nach BET)
0,7 Gew.-Teilen
37%iges frisches wäßriges Formalin
200 Gew.-Teilen
Ethanol.
The formulation of the spray activator formulation consisted of the following components:
1 part by weight
Bis (benzonitrile) palladium (II) dichloride
500 parts by weight
a 40% aqueous dispersion of the polyurethane as in Example 1
300 parts by weight
water
15 parts by weight
Aerosil® 380 (380 m 2 / g according to BET)
0.7 parts by weight
37% fresh aqueous formalin
200 parts by weight
Ethanol.

Die Formulierung wurde mittels einer Sprühpistole mit Luftunterstützung auf einer spritzgegossenen Testplatte (Formteil) aus einem ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) versprüht, die Luftzudosierung wurde dabei auf 4 bar eingestellt. Die Platte wurde bei 70°C 1 h lang getempert, nach Abkühlen der Platte auf Raumtemperatur im Metallbad bei 23°C 4,5 h lang metallisiert. Man erhielt eine zusammenhängende Metallschicht.The formulation was applied using a spray gun Air support on an injection molded test plate (Molded part) made of an ABS polymer (acrylonitrile-butadiene-styrene copolymer) sprayed the air metering was set to 4 bar. The plate was Annealed at 70 ° C for 1 h after the plate has cooled to room temperature in a metal bath at 23 ° C for 4.5 h metallized. A coherent metal layer was obtained.

Haftfestigkeit nach DIN 53494: 29 N/25 mm. Adhesive strength according to DIN 53494: 29 N / 25 mm.

Beispiel 4Example 4

Es wurde die gleiche 40%-ige wäßrige Dispersion eines Polyurethans wie in Beispiel 1 eingesetzt.The same 40% aqueous dispersion of one Polyurethane as used in Example 1.

Die Rezeptur der Sprühaktivatorformulierung bestand aus folgenden Komponenten:

1 Gew.-Teil
Bis-(benzonitril)-palladium(II)-dichlorid
500 Gew.-Teilen
der 40%igen wäßrigen Dispersion des Polyurethans
500 Gew.-Teilen
Wasser
15 Gew.-Teilen
Aerosil® 380 (380 m2/g nach BET)
1,4 Gew.-Teilen
37%iges frisches wäßriges Formalin
200 Gew.-Teilen
Ethanol.
The formulation of the spray activator formulation consisted of the following components:
1 part by weight
Bis (benzonitrile) palladium (II) dichloride
500 parts by weight
the 40% aqueous dispersion of the polyurethane
500 parts by weight
water
15 parts by weight
Aerosil® 380 (380 m 2 / g according to BET)
1.4 parts by weight
37% fresh aqueous formalin
200 parts by weight
Ethanol.

Die Herstellung der Formulierung erfolgte so, daß die Palladiumverbindung in 200 ml Ethanol vorgelöst wurde. Anschließend wurde mit 200 ml Wasser verdünnt, 15 g Aerosil® 380 (380 m2/g nach BET) in diese Vorlösung eingerührt bzw. dispergiert. Dann wurde mittels einer Spritze 1,4 ml frisches wäßriges Formalin unter Rühren zugefügt.The formulation was prepared by pre-dissolving the palladium compound in 200 ml of ethanol. The mixture was then diluted with 200 ml of water and 15 g of Aerosil® 380 (380 m 2 / g according to BET) were stirred or dispersed in this preliminary solution. Then 1.4 ml of fresh aqueous formalin was added with stirring using a syringe.

Nach zweistündiger Rührzeit wurde die Suspension mit 300 ml Wasser verdünnt und anschließend unter weiterem Rühren auf ca. 80°C-100°C erwärmt, bis Ethanol restlos entfernt war. Verluste an verdampftem Wasser wurden durch Nachfüllen ausgeglichen. After two hours of stirring, the suspension with Diluted 300 ml of water and then under further Stirring heated to approx. 80 ° C-100 ° C until ethanol is completely was removed. Evaporated water losses compensated by refilling.

Nach Abkühlen der Suspension auf Raumtemperatur wurde die Suspension unter Rühren mit der 40%igen wäßrigen Dispersion des Polyurethans vermischt.After cooling the suspension to room temperature the suspension with stirring with the 40% aqueous Dispersion of the polyurethane mixed.

Die so hergestellte Sprühaktivatorformulierung wurde mittels einer Sprühpistole mit Luftunterstützung (4 bar) auf spritzgegossenen Testplatten (Formteilen) versprüht. Der Spritzabstand betrug ca. 40 cm; der Düsenquerschnitt betrug 1,5 mm; die Luftzudosierung (2-6 bar) konnte variiert werden.The spray activator formulation so prepared was using a spray gun with air support (4 bar) sprayed on injection molded test panels (molded parts). The spraying distance was approx. 40 cm; the nozzle cross-section was 1.5 mm; the air metering (2-6 bar) could be varied.

Als Testplattensubstrat wurde ein Blend aus ABS-Polymerisat (Acrylnitril-Butadien-Styrol-Copolymerisat) und einem Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure eingesetzt.A blend of ABS polymer was used as the test plate substrate (Acrylonitrile-butadiene-styrene copolymer) and a polycarbonate made from 4,4'-dihydroxydiphenyl-2,2-propane and carbon dioxide used.

Die Platte wurde nach Abtrocknen bei Raumtemperatur 24 h lang getrocknet, im Metallbad bei 23°C 3 Std. lang in einem handelsüblichen formalinhaltigen Kupferbad metallisiert und anschließend bei 70° 1 h lang getempert. Man erhielt eine zusammenhängende Metallschicht.The plate was dried for 24 hours at room temperature dried long, in metal bath at 23 ° C for 3 hours metallized in a commercially available formalin-containing copper bath and then annealed at 70 ° for 1 h. Man received a coherent metal layer.

Haftfestigkeit nach DIN 53494:25 N/25 mm.Adhesive strength according to DIN 53494: 25 N / 25 mm.

Beispiel 5Example 5

Es wurde die gleiche 40%-ige wäßrige Dispersion eines Polyurethans wie in Beispiel 1 eingesetzt.The same 40% aqueous dispersion of one Polyurethane as used in Example 1.

Die Rezeptur der Sprühaktivatorformulierung bestand aber aus folgenden Komponenten:

1 Gew.-Teil
Bis-(benzonitril)-palladium(II)-dichlorid
500 Gew.-Teilen
der 40%igen wäßrigen Dispersion des Polyurethans wie in Beispiel 1
500 Gew.-Teilen
Wasser
15 Gew.-Teilen
Aerosil® 380 (380 m2/g nach BET)
1,4 Gew.-Teilen
37%iges frisches wäßriges Formalin
200 Gew.-Teilen
Ethanol.
The formulation of the spray activator formulation consisted of the following components:
1 part by weight
Bis (benzonitrile) palladium (II) dichloride
500 parts by weight
the 40% aqueous dispersion of the polyurethane as in Example 1
500 parts by weight
water
15 parts by weight
Aerosil® 380 (380 m 2 / g according to BET)
1.4 parts by weight
37% fresh aqueous formalin
200 parts by weight
Ethanol.

Die Herstellung der Formulierung erfolgt wie in Beispiel 4.The formulation is prepared as in Example 4th

Die Formulierung wurde mittels einer Sprühpistole mit Luftunterstützung auf einer spritzgegossenen Testplatte aus Polycarbonat aus 4,4'-Dihydroxydiphenyl-2,2-propan und Kohlensäure versprüht, die Platte wurde nach Abtrocknen bei Raumtemperatur 24 h lang getrocknet, im Metallbad bei 23°C 1,5 h lang in einem handelsüblichen formalinhaltigen Kupferbad metallisiert und anschließend bei 100°C 1 h lang getempert. Man erhielt eine zusammenhängende Metallschicht.The formulation was applied using a spray gun Air support on an injection molded test plate from polycarbonate from 4,4'-dihydroxydiphenyl-2,2-propane and aerated, the plate was dried after dried at room temperature for 24 h, in Metal bath at 23 ° C for 1.5 hours in a commercially available metallized copper bath and then metallized annealed at 100 ° C for 1 h. A coherent was obtained Metal layer.

Haftfestigkeit nach DIN 53494: 20 N/25 mm.Adhesive strength according to DIN 53494: 20 N / 25 mm.

Beispiel 6Example 6

Es wurde die gleiche 40%ige wäßrige Dispersion eines Polyurethans wie in Beispiel 1 eingesetzt.The same 40% aqueous dispersion of one Polyurethane as used in Example 1.

Die Rezeptur der Sprühaktivatorformulierung bestand aber aus folgenden Komponenten:

1 Gew.-Teil
Bis-(benzonitril)-palladium(II)dichlorid
500 Gew.-Teilen
einer 40%igen wäßrigen Dispersion des Polyurethans wie in Beispiel 1
300 Gew.-Teilen
Wasser
15 Gew.-Teilen
Aerosil® 380 (380 m2/g nach BET)
0,7 Gew.-Teilen
37%iges wäßriges frisches Formalin
200 Gew.-Teilen
Ethanol.
The formulation of the spray activator formulation consisted of the following components:
1 part by weight
Bis (benzonitrile) palladium (II) dichloride
500 parts by weight
a 40% aqueous dispersion of the polyurethane as in Example 1
300 parts by weight
water
15 parts by weight
Aerosil® 380 (380 m 2 / g according to BET)
0.7 parts by weight
37% aqueous fresh formalin
200 parts by weight
Ethanol.

Die Herstellung der Formulierung erfolgte so, daß die Palladiumverbindung in 200 ml Ethanol vorgelöst wurde, anschließend wurde mit 200 ml Wasser verdünnt, 15 g Aerosil® 380 (380 m2/g nach BET) in diese Vorlösung eingerührt bzw. dispergiert. Dann wurde mittels einer Dosiereinrichtung (Spritze) 0,7 ml frisches wäßriges Formalin unter Rühren zugefügt.The formulation was prepared by pre-dissolving the palladium compound in 200 ml of ethanol, then diluting with 200 ml of water and stirring or dispersing 15 g of Aerosil® 380 (380 m 2 / g by BET) in this preliminary solution. Then 0.7 ml of fresh aqueous formalin was added with stirring using a metering device (syringe).

Nach 2-stündiger Rührzeit wurde die Suspension mit 300 ml Wasser verdünnt und anschließend unter weiterem Rühren auf ca. 80°C-100°C erwärmt, bis Ethanol restlos entfernt war. Verluste an verdampftem Wasser wurden durch Nachfüllen mit Wasser ausgeglichen.After 2 hours of stirring, the suspension with Diluted 300 ml of water and then under further Stirring heated to approx. 80 ° C-100 ° C until ethanol is completely was removed. Evaporated water losses compensated by refilling with water.

Nach Abkühlen der Suspension auf Raumtemperatur wurde die Suspension unter Rühren mit der 40%igen wäßrigen Dispersion des Polyurethans vermischt.After cooling the suspension to room temperature the suspension with stirring with the 40% aqueous Dispersion of the polyurethane mixed.

Die so hergestellte Sprühaktivatorformulierung wurde mittels einer Sprühpistole mit Luftunterstützung (4 bar) auf spritzgegossenen Testplatten (Formteilen) versprüht. Der Spritzabstand betrug ca. 40 cm; der Düsenquerschnitt betrug 1,5 mm; die Luftzudosierung (2-6 bar) konnte variiert werden.The spray activator formulation so prepared was using a spray gun with air support (4 bar) sprayed on injection molded test panels (molded parts). The spraying distance was approx. 40 cm; the nozzle cross-section was 1.5 mm; the air metering (2-6 bar) could can be varied.

Als Testplattensubstrat wurde ein ABS-Polymerisat eingesetzt.An ABS polymer was used as the test plate substrate.

Die Platte wurde nach Abtrocknen bei Raumtemperatur 24 h lang getrocknet, bei 23°C 3 h lang in einem handelsüblichen formalinhaltigen Kupferbad metallisiert und anschließend bei 70°C 1 h lang getempert. Man erhielt eine zusammenhängende Metallschicht.The plate was dried for 24 hours at room temperature dried long, at 23 ° C for 3 h in a commercial metallized copper bath and then metallized annealed at 70 ° C for 1 h. You got one coherent metal layer.

Haftfestigkeit nach DIN 53494: 28 N/25 mm.Adhesive strength according to DIN 53494: 28 N / 25 mm.

Claims (6)

  1. Activator formulation for activating substrate surfaces for the electroless metallisation thereof based on organic noble metal compounds, fillers, solvents and a binder, characterised in that the binder is an aqueous dispersion of a polyurethane polymer and the activator formulation contains
    a) 0.03 to 3.0 parts by weight
    of an organic noble metal compound as activator, which compound may be converted into the metallic or colloidal form by reduction or into the complexed form by a complexing agent,
    b) 10 to 30 parts by weight
    of a solvent having a flash point of >20°C and a boiling point of ≥70°C,
    c) 0.5 to 3.0 parts by weight
    of a filler and
    d) 12 to 28 parts by weight
    of a polyurethane polymer.
  2. Activator formulation according to claim 1,
    characterised in that the activators a) are complex palladium compounds or palladium in metallic form or colloidal form.
  3. Activator formulation according to claim 1,
    characterised in that the solvent is an alcohol, ketone, ether ester or ketone alcohol.
  4. Activator formulation according to claim 1,
    characterised in that the solvent is ethanol, propanol or methyl ethyl ketone.
  5. Activator formulation according to claim 1,
    characterised in that the polyurethane polymer is synthesised from a polyester or polyether having terminal OH groups and a polyisocyanate.
  6. Process for activating substrate surfaces for the
    electroless metallisation thereof, characterised in that said surfaces are treated with a formulation according to claim 1.
EP92105453A 1991-04-11 1992-03-30 Process for activating substrates surfaces for electrolysis Expired - Lifetime EP0508265B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4111817 1991-04-11
DE4111817A DE4111817A1 (en) 1991-04-11 1991-04-11 FORMULATION FOR ACTIVATING SUBSTRATE SURFACES FOR THEIR CURRENT METALIZATION

Publications (3)

Publication Number Publication Date
EP0508265A2 EP0508265A2 (en) 1992-10-14
EP0508265A3 EP0508265A3 (en) 1994-03-09
EP0508265B1 true EP0508265B1 (en) 2000-01-12

Family

ID=6429353

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92105453A Expired - Lifetime EP0508265B1 (en) 1991-04-11 1992-03-30 Process for activating substrates surfaces for electrolysis

Country Status (7)

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US (1) US5296020A (en)
EP (1) EP0508265B1 (en)
JP (1) JP2515463B2 (en)
AT (1) ATE188750T1 (en)
CA (1) CA2065605C (en)
DE (2) DE4111817A1 (en)
ES (1) ES2141712T3 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4319759A1 (en) * 1993-06-15 1994-12-22 Bayer Ag Powder mixtures for metallizing substrate surfaces
US5674606A (en) * 1995-04-06 1997-10-07 Parker-Hannifin Corporation Electrically conductive flame retardant materials and methods of manufacture
DE19812880A1 (en) 1998-03-24 1999-09-30 Bayer Ag Shaped part and flexible film with protected conductor track and process for its production
US20040031404A1 (en) * 2002-08-19 2004-02-19 John Dixon Seamless embossing shim
CN101195911B (en) * 2006-12-08 2011-06-22 埃托特克德国有限公司 Preprocessing solution and method for forming coating metal layer on substrate with plastic surface
JP2010138475A (en) * 2008-12-15 2010-06-24 Fujifilm Corp Plating catalyst liquid, plating method, method for producing laminated body having metal film
EP2835446A1 (en) * 2013-08-08 2015-02-11 FRANZ Oberflächentechnik GmbH & Co KG Metallisation method with protective layer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930109A (en) * 1971-03-09 1975-12-30 Hoechst Ag Process for the manufacture of metallized shaped bodies of macromolecular material
DE2635457C2 (en) * 1976-08-04 1985-06-05 Schering AG, 1000 Berlin und 4709 Bergkamen Catalytic varnish and its use in the manufacture of printed circuits
DE3627256A1 (en) * 1986-08-12 1988-02-18 Bayer Ag METHOD FOR IMPROVING THE ADHESIVITY OF ELECTRICALLY DEPOSED METAL LAYERS ON PLASTIC SURFACES
IT1217328B (en) * 1988-02-01 1990-03-22 Donegani Guido Ist PROCESS FOR THE METALLIZATION OF FIBROUS MATERIALS

Also Published As

Publication number Publication date
DE4111817A1 (en) 1992-10-15
CA2065605A1 (en) 1992-10-12
ATE188750T1 (en) 2000-01-15
JPH05125550A (en) 1993-05-21
EP0508265A2 (en) 1992-10-14
DE59209793D1 (en) 2000-02-17
EP0508265A3 (en) 1994-03-09
US5296020A (en) 1994-03-22
ES2141712T3 (en) 2000-04-01
JP2515463B2 (en) 1996-07-10
CA2065605C (en) 2002-03-26

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