EP0508265B1 - 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
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
Authority
EP
European Patent Office
Prior art keywords
weight
parts
activator
gew
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.)
Expired - Lifetime
Application number
EP92105453A
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German (de)
English (en)
Other versions
EP0508265A3 (fr
EP0508265A2 (fr
Inventor
Günther Dr. Reichert
Frank Dipl.-Ing. Kobelka
Gerhard-Dieter Dr. Wolf
Ulrich Dr. Von Gizycki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Filing date
Publication date
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Publication of EP0508265A2 publication Critical patent/EP0508265A2/fr
Publication of EP0508265A3 publication Critical patent/EP0508265A3/xx
Application granted granted Critical
Publication of EP0508265B1 publication Critical patent/EP0508265B1/fr
Anticipated expiration legal-status Critical
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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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Claims (6)

  1. Formulation d'activateur pour l'activation de surfaces de substrats en vue de leur métallisation chimique, à base de composés organiques de métaux nobles, de charges, de solvants et d'un liant, caractérisée en ce que le liant est une dispersion aqueuse d'un polymère polyuréthane et en ce que la formulation d'activateur contient
    a) 0,03 à 3,0 parties en masse
    d'un composé organique de métal noble comme activateur, pouvant être transformé en la forme métallique ou colloïdale par réduction, ou en une forme complexée au moyen d'agents complexants,
    b) 10 à 30 parties en masse
    d'un solvant ayant un point d'éclair supérieur à 20°C et un point d'ébullition supérieur ou égal à 70°C ;
    c) 0,5 à 3,0 parties en masse
    d'une charge,
    et
    d) 12 à 28 parties en masse
    d'un polymère polyuréthane.
  2. Formulation d'activateur selon la revendication 1, caractérisée en ce que les activateurs a) sont des composés complexes du palladium ou du palladium sous forme métallique ou sous forme colloïdale.
  3. Formulation d'activateur selon la revendication 1, caractérisée en ce que le solvant est un alcool, une cétone, un étherester ou un cétone-alcool.
  4. Formulation d'activateur selon la revendication 1, caractérisée en ce que le solvant est l'éthanol, le propanol ou la méthyléthylcétone.
  5. Formulation d'activateur selon la revendication i, caractérisée en ce que le polymère polyuréthane est synthétisé à partir d'un polyester ou d'un polyéther à groupes OH terminaux et d'un polyisocyanate.
  6. Procédé d'activation de surfaces de substrats pour leur métallisation chimique, caractérisé en ce qu'on les traite avec une formulation selon la revendication 1.
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 EP0508265A2 (fr) 1992-10-14
EP0508265A3 EP0508265A3 (fr) 1994-03-09
EP0508265B1 true 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)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4319759A1 (de) * 1993-06-15 1994-12-22 Bayer Ag Pulvermischungen zum Metallisieren von Substratoberflächen
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
CN101195911B (zh) * 2006-12-08 2011-06-22 埃托特克德国有限公司 在具有塑料表面的基底上形成涂布金属层的预处理溶液和方法
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

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 (de) * 1976-08-04 1985-06-05 Schering AG, 1000 Berlin und 4709 Bergkamen Katalytischer Lack und seine Verwendung zur Herstellung von gedruckten Schaltungen
DE3627256A1 (de) * 1986-08-12 1988-02-18 Bayer Ag Verfahren zur verbesserung der haftfestigkeit von stromlos abgeschiedenen metallschichten auf kunststoffoberflaechen
IT1217328B (it) * 1988-02-01 1990-03-22 Donegani Guido Ist Processo per la metallizzazione di materiali fibrosi

Also Published As

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

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