EP0131195B1 - Verfahren zur Aktivierung von Substraten für die stromlose Metallisierung - Google Patents

Verfahren zur Aktivierung von Substraten für die stromlose Metallisierung Download PDF

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Publication number
EP0131195B1
EP0131195B1 EP84107302A EP84107302A EP0131195B1 EP 0131195 B1 EP0131195 B1 EP 0131195B1 EP 84107302 A EP84107302 A EP 84107302A EP 84107302 A EP84107302 A EP 84107302A EP 0131195 B1 EP0131195 B1 EP 0131195B1
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EP
European Patent Office
Prior art keywords
activation
complex
process according
alkyl
baths
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
Application number
EP84107302A
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German (de)
English (en)
French (fr)
Other versions
EP0131195A2 (de
EP0131195A3 (en
Inventor
Kirkor Dr. Sirinyan
Rudolf Dr. Merten
Henning Dr. Giesecke
Gerhard Dieter Dr. Wolf
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Bayer AG
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Bayer AG
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Publication date
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Publication of EP0131195A2 publication Critical patent/EP0131195A2/de
Publication of EP0131195A3 publication Critical patent/EP0131195A3/de
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Publication of EP0131195B1 publication Critical patent/EP0131195B1/de
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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

  • the invention relates to a gentle method for activating non-conductive or semiconductive substrate surfaces for chemogalvanic metal deposition by means of solutions or dispersions of complex compounds of elements of the 1st and 8th subgroups of the periodic table.
  • complex compounds include those of amines, amides, carboxylic acids, ketones, olefins and others. to use.
  • the palladium-O complexes mentioned have the disadvantage that they only partially very toxic aromatics and not sufficiently soluble in the other common solvents such as 1,1-dichloroethane, trichlorethylene, ethanol and cyclohexane.
  • the activation baths need constant, careful monitoring. They have to be supplemented with solvents and / or concentrate in order to ensure a constant production process.
  • the object of the present invention was therefore to develop activators which are stable in storage and whose continuous monitoring is possible with simple physical and / or chemical methods.
  • the complexes of the compounds of the formula are notable for good solubility in all organic solvents customary in the industry. They can be used in concentration ranges from 0.001 g / I up to the respective solubility limit. It is preferable to work with 0.1-3.0 g / l of these substances.
  • the sorption properties of the complex compounds to be used according to the invention can be increased further by introducing special substituents (in particular NO 2 and CN) into the radicals R i and R 4 .
  • the complexes of the compounds of the formula are partly known or obtainable by methods known per se (cf. Parshal and Wilkinson, "Inorganic Chemistry” 1, (1962), p. 896) by, for. B. a suitable aqueous solution of the noble metal salt to an excess compound of formula I and at temperatures of 20-150 ° C preferably 60-120 ° C, the complex formation leads to the end.
  • the complex separates out in solid form. It is washed, dried, optionally recrystallized and dissolved in a suitable solvent.
  • Suitable metals for the preparation of the complexes are e.g. B. Pd, Pt, Ag and Au, of which the palladium in the oxidation states 1 and 2 is particularly preferred.
  • Suitable compounds of the formula are, above all, those in which "alkyl” stands for C, -C 2o-alkyl radicals, "cycloalkyl” for cyclohexyl and "aryl” for benzene radicals, the alkyl radicals being represented by Cl, CN, N0 2 , C l -C 4 alkoxy or C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, the cycloalkyl radicals by CH 3 and the aryl radicals by Cl, N0 2 , C l -C 4 - Alkyl or C, -C 4 alkoxy may be substituted.
  • R 1 and R 4 are C 1 -C 20 alkyl, preferably C 1 -C 6 alkyl, R 2 and R 3 are hydrogen or C, -C 4 alkyl, preferably methyl.
  • Examples include: mesityl oxide, n-buten-3-one-2, n-hepten-3-one-2, n-hexen-3-one-2, n-decen-4-one-3,5-chloro penten-3-one-2, ethyl vinyl ketone, 3-methyl-octen-5-one-4, 3-methyl-penten-3-one-2, 7-methoxy-hepten-3-one-2 and cyclohexen-2- on.
  • the new activation process is generally carried out by wetting the substrate surfaces to be metallized with a dispersion or - preferably - a solution of the metal complex in a suitable organic solvent, removing the solvent and, if appropriate, sensitizing it with a suitable reducing agent.
  • the substrate pretreated in this way can then be metallized in a conventional metallization bath.
  • Suitable reducing agents for the sensitization are aminoboranes, alkali hypophosphites and alkali borohydrides.
  • the substrates can be wetted by spraying, printing, impregnation or impregnation.
  • those solvents or solvent mixtures which lead to dissolution or swelling of the plastic surface to be metallized are particularly preferably used to carry out the method according to the invention.
  • the solvents are removed from the wetted substrates simply by evaporation or, in the case of higher-boiling compounds, by extraction.
  • the activation baths are monitored with a photometer as a detector.
  • the wavelength of the filter should correspond to the absorption maxima of the solution.
  • the measurement signal is recorded by a compensation recorder and called up by a clock generator at intervals of 0.1 seconds to several minutes. With the help of a computer, the missing components (solvent, activator) can be added.
  • a very particularly preferred embodiment of the method according to the invention consists in that the reduction in the metallization bath is carried out immediately with the reducing agent of the electroless metallization.
  • This embodiment is particularly suitable for nickel baths containing amine borane or copper baths or silver baths containing formalin.
  • Metallization baths which can be used in the processes according to the invention are preferably baths with Ni, Co, Cu, Au, Ag salts or their mixtures with one another or with iron salts. Such baths are known in the art of electroless metallization of plastics.
  • Suitable substrates for the process according to the invention are: steels, titanium, glass, aluminum, textiles and flat structures based on natural and / or synthetic polymers, ceramics, carbon, paper, thermoplastics such as polyamide types, ABS (acrylonitrile butadiene styrene) polymers, polycarbonates, Polypropylene, polyester, polyethylene, polyhydantoin and thermosets such as epoxy resins, melamine resins, and their mixtures or copolymers.
  • thermoplastics such as polyamide types, ABS (acrylonitrile butadiene styrene) polymers, polycarbonates, Polypropylene, polyester, polyethylene, polyhydantoin and thermosets such as epoxy resins, melamine resins, and their mixtures or copolymers.
  • a 20 x 20 cm square of a 0.2 mm thick polyester film (100% polyethylene terephthalate) is at room temperature for 30 seconds in an activation bath, which is made from 0.6 g according to Parshal and Wilkinson (see page 2), mesityl oxide-palladium chloride complex and 1 technical trichlorethylene is prepared, activated, dried at room temperature and then for 15 minutes in an aqueous alkaline nickel plating bath, which in 1 l 30 g NiS0 4 . 6H 2 0 11.5 g of citric acid, 18 ml of 2N DMAB (dimethylamine borane) solution, 2 g of boric acid and adjusted to pH 8.5 with 25% ammonia solution, electroless nickel-plated. After about 45 seconds the polymer surface begins to turn gray and after about 12 minutes the specimen is covered with a shiny - 0.15 ⁇ m thick nickel layer.
  • an activation bath which is made from 0.6 g according to Parshal and Wilkinson (see page 2), mesityl
  • a 140 x 250 mm injection-molded ABS plate (acrylonitrile-butadiene-styrene graft copolymer from Bayer AG) is activated in a solution of 500 ml of technical methanol, 50 ml of technical trichloroethene and 0.4 g of mesityl oxide-palladium complex for 5 minutes at room temperature , dried at RT, sensitized for 3 minutes in a reduction bath of 500 ml of ethanol and 50 ml of 2N DMAB solution and then nickel-plated at 33 ° C. in a conventional metallization bath from Blasberg GmbH and KG, 5650 Solingen. The test specimen is covered with a very fine nickel coating after only 4 minutes.
  • the chemical nickel layer has an average thickness of approximately 0.20 ⁇ m.
  • the test specimen is removed from the chemical metallization bath and rinsed with distilled water, it is switched as the cathode in a conventional acidic galvanic copper plating bath and is amplified to a thickness of approx. 40 1 1m at 1.1 A / dm 2 .
  • a 150x200 mm injection molded polyethylene terephthalate plate is activated at room temperature for 30 seconds in an activation bath which is made up of 0.4 g mesityl oxide platinum complex and 650 ml tetrachlorethylene, dried at RT and then nickel-plated according to Example 1. You get a shiny metallic polymer plate with a - 0.15 1 1m thick electrically conductive nickel coating.
  • a 150 ⁇ 300 mm rectangle of a cotton fabric is immersed for 30 seconds in a solution of 0.5 g of mesityl oxide palladium chloride in 600 ml of methylene chloride, dried at room temperature and then nickel-plated in a reductive nickel bath according to Example 1 for 22 minutes.
  • a 120x120 mm square of a conventional polyester-cotton blend is activated for 20 seconds in accordance with Example 1, sensitized in a reduction bath in accordance with Example 2, rinsed with distilled water and then coppered in a chemical copper bath from Schering AG, Berlin (West) for 20 minutes .
  • a well-adhering, electrically conductive copper layer was deposited after only 5 minutes.
  • ABS plate is activated at RT for 5 min in a bath which is prepared from 500 ml of ethanol, 25 ml of 2,4-pentanedione and 0.4 g of n-3-hepten-2-one-palladium chloride, at 35 ° C. Dried for 5 minutes and then nickel-plated according to Example 1 over a period of 20 minutes. After galvanic reinforcement, the pull-off force of the metal layer is higher than the tensile strength of the metal layer.
  • a polyamide 6,6 plate is activated according to example 6 in an activation bath which is adjusted to pH 2.5 with concentrated hydrochloric acid, washed with distilled water and then sensitized according to example 2 and then metallized for 20 minutes. A shiny metallic sample with an adherent metal coating is obtained.
  • a 100x200 mm rectangle of a 2 mm thick with through holes, glass fiber reinforced epoxy resin plate laminated on both sides, is immersed in 1 I CH 2 C1 2 in air in an activation bath of 0.5 g n-3-hepten-2-one-palladium chloride dried, sensitized according to Example 2 and then copper-coated according to Example 5 for 25 minutes. You get a plate through-plated with an electrically conductive Cu layer, which can be used for the production of electrical circuit boards.
  • the heptenone complex is made as follows.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84107302A 1983-07-08 1984-06-26 Verfahren zur Aktivierung von Substraten für die stromlose Metallisierung Expired EP0131195B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833324767 DE3324767A1 (de) 1983-07-08 1983-07-08 Verfahren zur aktivierung von substraten fuer die stromlose metallisierung
DE3324767 1983-07-08

Publications (3)

Publication Number Publication Date
EP0131195A2 EP0131195A2 (de) 1985-01-16
EP0131195A3 EP0131195A3 (en) 1985-10-23
EP0131195B1 true EP0131195B1 (de) 1987-08-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107302A Expired EP0131195B1 (de) 1983-07-08 1984-06-26 Verfahren zur Aktivierung von Substraten für die stromlose Metallisierung

Country Status (5)

Country Link
US (1) US4575467A (enrdf_load_stackoverflow)
EP (1) EP0131195B1 (enrdf_load_stackoverflow)
JP (1) JPS6039166A (enrdf_load_stackoverflow)
CA (1) CA1234134A (enrdf_load_stackoverflow)
DE (2) DE3324767A1 (enrdf_load_stackoverflow)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3423457A1 (de) * 1984-06-26 1986-01-02 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von leiterplatten
DE3424065A1 (de) * 1984-06-29 1986-01-09 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung
DE3667800D1 (de) * 1985-08-23 1990-02-01 Ciba Geigy Ag Mischung aus olefin und dibenzalaceton-palladiumkomplex und deren verwendung.
JPH0613808B2 (ja) * 1986-02-14 1994-02-23 株式会社大井製作所 自動車用窓ガラス開閉装置
DE3612822A1 (de) * 1986-04-14 1987-10-15 Schering Ag Verfahren zur haftfesten metallisierung von polyetherimid
DE3625587A1 (de) * 1986-07-29 1988-02-04 Bayer Ag Verfahren zur verbesserung der haftfestigkeit von stromlos abgeschiedenen metallschichten auf kunststoffoberflaechen
US5182135A (en) * 1986-08-12 1993-01-26 Bayer Aktiengesellschaft Process for improving the adherency of metallic coatings deposited without current on plastic surfaces
DE3627256A1 (de) * 1986-08-12 1988-02-18 Bayer Ag Verfahren zur verbesserung der haftfestigkeit von stromlos abgeschiedenen metallschichten auf kunststoffoberflaechen
DE3901029A1 (de) * 1989-01-14 1990-07-19 Bayer Ag Verfahren zum metallisieren von formkoerpern aus polyarylensulfiden
US5200272A (en) * 1988-04-29 1993-04-06 Miles Inc. Process for metallizing substrate surfaces
US5238702A (en) * 1988-10-27 1993-08-24 Henning Giesecke Electrically conductive patterns
JPH0334186U (enrdf_load_stackoverflow) * 1989-08-08 1991-04-03
FR2656493A1 (fr) * 1989-12-21 1991-06-28 Bull Sa Procede d'interconnexion de couches metalliques du reseau multicouche d'une carte electronique, et carte en resultant.
DE4209708A1 (de) * 1992-03-25 1993-09-30 Bayer Ag Verfahren zur Verbesserung der Haftfestigkeit von stromlos abgeschiedenen Metallschichten
US5419954A (en) * 1993-02-04 1995-05-30 The Alpha Corporation Composition including a catalytic metal-polymer complex and a method of manufacturing a laminate preform or a laminate which is catalytically effective for subsequent electroless metallization thereof
US5705463A (en) * 1993-02-24 1998-01-06 Tech Spray, Inc. Composition and process for removal of ionic salt deposits
US5604191A (en) * 1993-02-24 1997-02-18 Tech Spray, Inc. Composition for removal of ionic salt deposits
DE19624071A1 (de) * 1996-06-17 1997-12-18 Bayer Ag Verfahren zur Herstellung von bahnförmigen metallbeschichteten Folien
US7011738B2 (en) * 2000-07-06 2006-03-14 Akzo Nobel N.V. Activation of a cathode
JP2017138164A (ja) * 2016-02-02 2017-08-10 大日本印刷株式会社 電極構造の製造方法、センサ電極の製造方法、電極構造およびセンサ電極

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1471135A (fr) * 1965-03-17 1967-02-24 Shell Int Research Procédé de production de complexes de pi-allyle
NL6503362A (enrdf_load_stackoverflow) * 1965-03-17 1966-09-19
DE2451217C2 (de) * 1974-10-29 1982-12-23 Basf Ag, 6700 Ludwigshafen Aktivierung von Substraten für die stromlose Metallisierung
DE3025307A1 (de) * 1980-07-04 1982-01-28 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von oberflaechen fuer die stromlose metallisierung
DE3202484A1 (de) * 1982-01-27 1983-08-04 Bayer Ag, 5090 Leverkusen Metallisierte halbleiter und verfahren zu ihrer herstellung

Also Published As

Publication number Publication date
US4575467A (en) 1986-03-11
EP0131195A2 (de) 1985-01-16
DE3324767A1 (de) 1985-01-17
EP0131195A3 (en) 1985-10-23
JPS6039166A (ja) 1985-02-28
JPH0416548B2 (enrdf_load_stackoverflow) 1992-03-24
CA1234134A (en) 1988-03-15
DE3465344D1 (en) 1987-09-17

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