EP0508265A2 - Procédé d'activation des surfaces de substrats en vue d'une métallisation par voie chimique - Google Patents

Procédé d'activation des surfaces de substrats en vue d'une métallisation par voie chimique Download PDF

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Publication number
EP0508265A2
EP0508265A2 EP92105453A EP92105453A EP0508265A2 EP 0508265 A2 EP0508265 A2 EP 0508265A2 EP 92105453 A EP92105453 A EP 92105453A EP 92105453 A EP92105453 A EP 92105453A EP 0508265 A2 EP0508265 A2 EP 0508265A2
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EP
European Patent Office
Prior art keywords
weight
parts
gew
activator
palladium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92105453A
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German (de)
English (en)
Other versions
EP0508265A3 (fr
EP0508265B1 (fr
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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Publication date
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Publication of EP0508265A3 publication Critical patent/EP0508265A3/xx
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Publication of EP0508265B1 publication Critical patent/EP0508265B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

  • metal layers which adhere well to plastic surfaces can be produced without the disadvantages mentioned, if they are treated without a prior pickling with an activator formulation based on organic noble metal compounds, fillers, a solvent and an aqueous dispersion of a polyurethane polymer as a binder.
  • the formulations are characterized in that they contain an aqueous dispersion of a polyurethane polymer.
  • 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).
  • Suitable activators in the formulations according to the invention are organometallic compounds of the 1st and 8th subgroups of the periodic table (in particular Pd, Pt, Au, Ag), as are described, for example, in EP-A 34 485, 81 438, 131 198.
  • Organometallic complex compounds of palladium with olefins (dienes), with ⁇ , ⁇ -unsaturated carbonyl compounds, with crown ethers and with nitriles are particularly suitable.
  • Bisacetonitrile palladium dichloride, butadiene palladium dichloride, 4-cyclohexane-1,2-dicarboxylic acid anhydride palladium dichloride, mesityl oxide palladium dichloride, 3-hepten-2-one palladium chloride and 5-methyl-3-hexane-2-one palladium chloride are very particularly suitable.
  • mixtures of these compounds can also be used.
  • the activators or the mixtures thereof are introduced into the aqueous dispersion in accordance with the process according to the invention. This is generally done by mixing the ingredients.
  • the incorporation of the formulation components can also be carried out in separate steps.
  • the activator can first be in a solvent of the overall 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.
  • complexing agents e.g. Chlorides, thiosulfates, rhodanides, cyanides, ammonia or amines are used.
  • complex compounds are Pd (NH3) 2Cl2, Pd (NH3) 4Cl2, Pd (NH3) 4 (NO3) 2, K2PdCl4, K2Pd (CN) 4, [NH4] 2PdCl6, [NH4) 2PdCl4, Pt (NH3) 4Cl2, K2PtCl4, KAg (CN) 2, KAg (S2O3), KAu (CN) 2, NaAuCl4.
  • Zero-valent complex compounds such as palladium (O) tetrakis (triphenylphosphine), bis [bis- (1,2-diphenylphosphino) ethane] palladium (O) or bis (dibenzylidene acetone) palladium (O) are also suitable.
  • Pd, Ag, Au, Pt on activated carbon, on aluminum oxide, on calcium carbonate, on barium carbonate, on activated aluminum oxide and palladium black platinum black may be mentioned as colloidal noble metal systems which can also serve as activators.
  • Auxiliaries known from printing or coating technology such as pigments, disperse silicas, carbon blacks, silicates, oxides, rheological additives and clay minerals, are suitable as fillers.
  • Silicates bentonites, talc and chalk are preferred.
  • the amount of filler can vary in the range from 0.5 to 3 parts by weight, based on the mass of the formulation.
  • further constituents such as surfactants, leveling agents, defoamers, dyes and metal dyes, can also be mixed in at low concentrations of up to 10% by weight, preferably up to 2% by weight.
  • Suitable solvents in the formulations according to the invention are substances known in printing or coating technology, such as ketones, for example methyl ethyl ketone, cyclohexanone, esters, for example butyl acetate, diacctate of 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 and their blends with other solvents can of course also be used.
  • ketones for example methyl ethyl ketone, cyclohexanone
  • esters for example butyl acetate, diacctate of phthalate, butyl glycolate, glycol ethers, for example ethylene glycol monomethyl ether, diglyme, propylene glycol monomethyl ether
  • the solvents used only serve to dissolve the organic Pd compound and, if necessary, can be removed by evaporation after the noble metal activator has been reduced.
  • the grain size of the metallic noble metal produced can be influenced during the reduction by the use of solvents.
  • 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 do not contain any free isocyanate groups, optionally blocked isocyanate groups and / or anionic groups, e.g. Contain SO3 groups.
  • Linear, aliphatic polyurethanes such as those made, for example, from hexanediol, neopentyl glycol and polyisocyanates, have proven particularly suitable.
  • the formulations may contain surfactants, leveling agents and / or dyes
  • Surfaces can be activated for the purpose of adhesive chemical metallization, preferably by spraying on the formulations according to the invention by means of processes known from the paint industry.
  • spraying on the formulations can be replaced by dipping, brushing and rolling up.
  • Suitable substrates for the process according to the invention are paper, enamel, ceramics, polyethylene, polypropylene, epoxy resins, polyesters, polycarbonates, polyamides, polyimides, polyhydantoins, ABS plastics, silicones, polyvinyl halides and polyvinylidene fluoride in the form of films, sheets, papers and nonwovens.
  • Substrates such as are used as housings in the electronics industry are particularly preferred, e.g. ABS and polycarbonate plastics or their blends, polyphenylene sulfide, polybutylene terephthalate and their blends and polypropylene oxide.
  • the solvents are removed. This is done by 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 be activated by reduction in the case of the complexed activator, 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 the complexed activators, is carried out in the metallization bath with the reducing agent of the electroless metallization. This applies to suitable nickel and copper baths.
  • a preferred form of the method consists in using formulations in which the activator is already in active form by reduction.
  • the surfaces treated with the formulations according to the invention can be metallized directly without current.
  • the metallization baths that are suitable for this are known in the art of electroless metallization.
  • the formulations according to the invention are particularly suitable for the partial activation of geometrically complicated surfaces, in particular for the production of molded bodies metallized on one or both sides or of housing parts metallized on the inside for the electronics industry for the purpose of electromagnetic shielding.
  • This method can of course also be used to produce structured metal surfaces using a suitable mask.
  • the spray activator formulation thus produced was sprayed on an injection-molded test plate (molded parts) using an air-assisted spray gun (4 bar).
  • the spraying distance was approx. 40 cm; the nozzle cross section was 1.5 mm; the air metering (2-6 bar) could be varied.
  • a blend of ABS polymer (acrylonitrile-butadiene-styrene copolymer) and a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid was used as the test plate substrate.
  • the plate was annealed at 70 ° C for 1 h, metallized in a metal bath at 23 ° C for 4 h in a commercially available formalin-containing copper bath and then annealed at 70 ° C for 1 h. A coherent metal layer was obtained.
  • the spray activator formulation was prepared and the process carried out as in Example 1, except that 2 parts by weight of bis (benzonitrile) palladium (II) dichloride were used in the spray activator formulation.
  • the formulation was sprayed using an air-assisted spray gun on an injection-molded test plate made of a polycarbonate composed of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid, the plate was annealed at 100 ° C. for 1 hour, after the plate had cooled in a metal bath Metallized at 23 ° C for 2 h. The mixture was then heated at 100 ° C for 1 h. A coherent metal layer was obtained.
  • the spray activator formulation was prepared and carried out as in Example 1, except that 0.7 ml of formalin was used.
  • the formulation was sprayed by means of a spray gun with air support on an injection-molded test plate (molded part) made of an ABS polymer (acrylonitrile-butadiene-styrene copolymer), the air metering was adjusted to 4 bar.
  • the plate was annealed at 70 ° C for 1 h, after cooling the plate to room temperature in a metal bath at 23 ° C for 4.5 h. A coherent metal layer was obtained.
  • Example 1 The same 40% aqueous dispersion of a polyurethane as in Example 1 was used.
  • 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 suspension was diluted with 300 ml of water and then heated to about 80 ° C.-100 ° C. with continued stirring until ethanol was completely removed. Losses of evaporated water were compensated for by refilling.
  • the suspension was mixed with the 40% strength aqueous dispersion of the polyurethane with stirring.
  • the spray activator formulation thus produced was sprayed on an injection-molded test plate (molded parts) using an air-assisted spray gun (4 bar).
  • 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 acrylonitrile-butadiene-styrene copolymer
  • polycarbonate 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid
  • the plate was dried at room temperature for 24 hours, metallized in a metal bath at 23 ° C. for 3 hours in a commercially available formalin-containing copper bath and then annealed at 70 ° C. for 1 hour. A coherent metal layer was obtained.
  • Adhesive strength according to DIN 53494 25 N / 25 mm.
  • Example 1 The same 40% aqueous dispersion of a polyurethane as in Example 1 was used.
  • the formulation is prepared as in Example 4.
  • the formulation was sprayed using an air-assisted spray gun on an injection-molded test plate made of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid, the plate was dried after drying at room temperature for 24 hours, in a metal bath at 23 ° C 1 , Metallized for 5 hours in a commercially available formalin-containing copper bath and then annealed at 100 ° C. for 1 hour. A coherent metal layer was obtained.
  • Example 1 The same 40% aqueous dispersion of a polyurethane as in Example 1 was used.
  • 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 suspension was diluted with 300 ml of water and then heated to about 80 ° C.-100 ° C. with continued stirring until ethanol was completely removed. Losses of evaporated water were compensated for by adding water.
  • the suspension was mixed with the 40% strength aqueous dispersion of the polyurethane with stirring.
  • the spray activator formulation thus produced was sprayed on an injection-molded test plate (molded parts) using an air-assisted spray gun (4 bar).
  • 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.
  • the plate was dried at room temperature for 24 hours, metallized at 23 ° C. for 3 hours in a commercially available formalin-containing copper bath and then annealed at 70 ° C. for 1 hour. A coherent metal layer was obtained.
  • Adhesive strength according to DIN 53494 28 N / 25 mm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemically Coating (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP92105453A 1991-04-11 1992-03-30 Procédé d'activation des surfaces de substrats en vue d'une métallisation par voie chimique Expired - Lifetime EP0508265B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4111817A DE4111817A1 (de) 1991-04-11 1991-04-11 Formulierung zum aktivieren von substratoberflaechen fuer deren stromlose metallisierung
DE4111817 1991-04-11

Publications (3)

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

Family

ID=6429353

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92105453A Expired - Lifetime EP0508265B1 (fr) 1991-04-11 1992-03-30 Procédé d'activation des surfaces de substrats en vue d'une métallisation par voie chimique

Country Status (7)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633298A1 (fr) * 1993-06-15 1995-01-11 Bayer Ag Mélange de poudres pour la métallisation de substrats
EP1942207A1 (fr) * 2006-12-08 2008-07-09 Atotech Deutschland Gmbh Solution de prétraitement et procédé de formation d'une couche d'un métal de revêtement sur un substrat doté d'une surface en plastique

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674606A (en) * 1995-04-06 1997-10-07 Parker-Hannifin Corporation Electrically conductive flame retardant materials and methods of manufacture
DE19812880A1 (de) 1998-03-24 1999-09-30 Bayer Ag Formteil und flexible Folie mit geschützter Leiterbahn und Verfahren zu ihrer Herstellung
US20040031404A1 (en) * 2002-08-19 2004-02-19 John Dixon Seamless embossing shim
JP2010138475A (ja) * 2008-12-15 2010-06-24 Fujifilm Corp めっき用触媒液、めっき方法、金属膜を有する積層体の製造方法
EP2835446A1 (fr) * 2013-08-08 2015-02-11 FRANZ Oberflächentechnik GmbH & Co KG Procédé de métallisation avec couche de protection

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2635457A1 (de) * 1976-08-04 1978-02-09 Schering Ag Katalytischer lack zur herstellung von gedruckten schaltungen
EP0327057A1 (fr) * 1988-02-01 1989-08-09 TEXMET S.p.A. Procédé pour métalliser les matériaux fibreux
EP0256395B1 (fr) * 1986-08-12 1992-07-01 Bayer Ag Procédé pour améliorer l'adhérence des couches de métaux déposées par voie chimique sur des surfaces en matière plastique

Family Cites Families (1)

* 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2635457A1 (de) * 1976-08-04 1978-02-09 Schering Ag Katalytischer lack zur herstellung von gedruckten schaltungen
EP0256395B1 (fr) * 1986-08-12 1992-07-01 Bayer Ag Procédé pour améliorer l'adhérence des couches de métaux déposées par voie chimique sur des surfaces en matière plastique
EP0327057A1 (fr) * 1988-02-01 1989-08-09 TEXMET S.p.A. Procédé pour métalliser les matériaux fibreux

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633298A1 (fr) * 1993-06-15 1995-01-11 Bayer Ag Mélange de poudres pour la métallisation de substrats
US5487964A (en) * 1993-06-15 1996-01-30 Bayer Aktiengesellschaft Powder mixtures for metallization of substrate surfaces
EP1942207A1 (fr) * 2006-12-08 2008-07-09 Atotech Deutschland Gmbh Solution de prétraitement et procédé de formation d'une couche d'un métal de revêtement sur un substrat doté d'une surface en plastique

Also Published As

Publication number Publication date
DE59209793D1 (de) 2000-02-17
ATE188750T1 (de) 2000-01-15
CA2065605C (fr) 2002-03-26
US5296020A (en) 1994-03-22
EP0508265A3 (fr) 1994-03-09
JPH05125550A (ja) 1993-05-21
JP2515463B2 (ja) 1996-07-10
ES2141712T3 (es) 2000-04-01
CA2065605A1 (fr) 1992-10-12
DE4111817A1 (de) 1992-10-15
EP0508265B1 (fr) 2000-01-12

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