EP0043485B1 - Verfahren zur Aktivierung von Oberflächen für die stromlose Metallisierung - Google Patents

Verfahren zur Aktivierung von Oberflächen für die stromlose Metallisierung Download PDF

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Publication number
EP0043485B1
EP0043485B1 EP81104782A EP81104782A EP0043485B1 EP 0043485 B1 EP0043485 B1 EP 0043485B1 EP 81104782 A EP81104782 A EP 81104782A EP 81104782 A EP81104782 A EP 81104782A EP 0043485 B1 EP0043485 B1 EP 0043485B1
Authority
EP
European Patent Office
Prior art keywords
nickel
palladium dichloride
organic solvent
minutes
bath
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
EP81104782A
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German (de)
English (en)
French (fr)
Other versions
EP0043485A1 (de
Inventor
Henning Dr. Giesecke
Gerhard Dieter Dr. Wolf
Harold Dr. Ebneth
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Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT81104782T priority Critical patent/ATE13319T1/de
Publication of EP0043485A1 publication Critical patent/EP0043485A1/de
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Publication of EP0043485B1 publication Critical patent/EP0043485B1/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
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to a method for activating metallic and non-metallic surfaces for the purpose of electroless metal deposition.
  • the previously common method for the currentless production of metal coatings on non-conductive or semiconductive supports is that the support surface is cleaned, successively in a stannous chloride or other stannous salt containing bath, and in a bath of a metal salt catalyzing the deposition of the desired metal, z. B. silver nitrate or gold chloride, palladium chloride or platinum chloride, so as to form catalytic nucleus centers, wherein the metal ions of the salt to centers of the catalytic metal by the Stannoions absorbed on the support and / or by reducing agents contained in the electroless metal salt bath are reduced, and that then the desired metal, e.g. B.
  • both activation methods have the disadvantage that several process steps (activation, sensitization, rinsing, etc.) are required to carry them out, which make the electroless metallization very cumbersome and therefore expensive.
  • both processes are not universally applicable, but are primarily restricted to substrates whose surfaces can be pretreated by chemical or mechanical processes.
  • the organometallic compound can, for example, be dissolved or dispersed in the organic solvent; it can also be a rubbing of the organometallic compounds in the solvent.
  • the concentration of organometallic compound should be between 0.01 g and 10 g per liter, but can also be lower in special cases.
  • the organic solvent should be easily removable.
  • the surface can then be electrolessly metallized in a known manner.
  • Particularly suitable organic solvents are polar protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol, dioxane and tetrahydrofuran.
  • polar protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol, dioxane and tetrahydrofuran.
  • mixtures of the above solvents and blends with other solvents such as gasoline, ligroin, toluene, etc. can also be used.
  • the surfaces of the substrates to be metallized are wetted with these solutions, the duration of action preferably being 1 second to 1 minute.
  • Methods such as immersing the substrate in the solutions or spraying substrate surfaces with the activation solutions are particularly suitable for this purpose.
  • the activation solutions it is also possible to apply the activation solutions by stamping or by printing processes.
  • Suitable substrates for the process according to the invention are: steels, titanium, glass, quartz, ceramic, carbon, paper, polyethylene, Po lypropylene, ABS plastics, epoxy resins, polyesters, polyamides, polycarbonates and textile fabrics, threads and fibers made of polyamide, polyester, polyalkylene, polyacrylonitrile, polyvinyl halides, cotton and wool, and their mixtures or copolymers.
  • the organic solvent is removed.
  • Low-boiling solvents are preferred by evaporation, e.g. B. removed in vacuo.
  • other methods such as extraction with a solvent in which the organometallic compounds are insoluble, are appropriate.
  • the surfaces impregnated in this way must then be activated by reduction.
  • the reducing agents customary in electroplating such as hydrazine hydrate, formaldehyde, hypophosphite or boranes, can preferably be used for this purpose. Of course, other reducing agents are also possible.
  • the reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.
  • the surfaces activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surfaces of the reducing agent residues.
  • 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 version represents a simplification of the electroless metallization that has not been possible until now.
  • This very simple embodiment only consists of the three operations of immersing the substrate in the solution of the organic compound, evaporating the solvent and immersing the surfaces thus activated in the metallization bath (reduction and metallization ).
  • This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
  • Metallization baths which can be used in the process according to the invention are preferably baths with nickel salts, cobalt salts, iron salts or mixtures thereof with copper salts, gold and silver salts. Such metallization baths are known in the electroless metallization art.
  • ABS plastic part with a structured surface is sprayed evenly with a solution of 0.1 g butadiene palladium dichloride per 1 chloroform (blowing agent Frigen (R) ).
  • a 13 x 13 cm square of a polyacrylonitrile fabric (copolymer on 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methalyl sulfonate); Plain weave is immersed in a solution of 0.01 g of diacetonitrile palladium dichloride in 100 ml of methylene chloride for 30 seconds, dried at room temperature and then nickel-plated in an alkaline nickel-plating bath according to Example 1 for 10 minutes. This gives a shiny metallic piece of fabric with a metal coating of 10% by weight of nickel, the resistance of which is 2.8 ohms in the warp direction and 6.7 ohms in the weft direction.
  • a knitted fabric made from a fiber yarn (Nm 40) made from a polyester polymer ( 100% polyethylene terephthalate) is immersed in an activation solution according to Example 2 at room temperature for 30 seconds.
  • the solvent is allowed to evaporate at room temperature and then the knitted fabric is immersed in a solution containing 0.5 g / l of sodium borohydride for 1 minute.
  • the goods are then rinsed with water.
  • the product is then introduced into an aqueous solution of 0.2 mol / l nickel-II chloride, 0.15 mol / 1 citric acid, 0.2 mol / l sodium hypophosphite, which is brought to pH 9 with ammonia at 25 ° C. 0 is set. After approx. 15 seconds the surface of the textile fabric begins to discolor. After only 30 seconds, the goods are covered with a fine layer of nickel metal and discolored darkly.
  • the nickel layer After about 10 minutes the nickel layer has a thickness of 0.2 ⁇ m.
  • the goods are removed from the bath, rinsed with water and dried.
  • the weight gain was 23% based on the raw weight of the knitted fabric.
  • the surface resistance of a 10 x 10 cm square cut out of the material was 3.6 ohms in the direction of the rods and 4.2 ohms across.
  • a fabric made of a polyacrylonitrile multifilament yarn (100% polyacrylonitrile) is immersed in an activation solution according to Example 1 for 1 minute.
  • the sample is then dried at 40 ° C. and placed in an alkaline copper bath composed of 10 g / l copper sulfate, 15 g / l Seignette salt and 20 ml / l 35% by weight formaldehyde solution, which is brought to pH 12-13 with sodium hydroxide solution was discontinued.
  • the surface of the fabric begins to turn dark, after about 2 minutes metallic copper luster develops.
  • the sample was removed from the metallization bath, rinsed thoroughly and air-dried.
  • the layer thickness of the copper was approximately 0.2 wm.
  • the surface resistance was 0.6 ohms, measured as the resistance of a square of 10 ⁇ 10 cm in the warp direction.
  • a 10 x 10 cm square of a carbon fiber fabric is immersed in a solution of 0.05 g of butadiene palladium dichloride per 1 methylene chloride for 30 seconds, dried at room temperature and then nickel-plated in an alkaline nickel-plating bath according to Example 1 for 20 minutes. This gives a shiny metallic piece of fabric with a metal coating of 16.9% by weight, the resistance of which is 0.3 ohms.
  • a glass plate of 30 ⁇ 30 cm is sprayed uniformly with an activation solution according to Example 1, dried and then immersed in an alkaline nickel plating bath according to Example 1 for 7 minutes. After 80 seconds the surface turns dark and after 5 minutes a shiny metallic layer is observed. The glass pane washed and dried after metallization is covered with a reflective metal layer.
  • a 30 x 30 cm polyethylene film is degreased with methylene chloride and then sprayed on one side with an activation solution according to Example 1. After drying, the films are metallized in a nickel plating bath according to Example 1 for 20 minutes. A film nickel-plated on one side with a nickel content of 10.8 g / m 2 is obtained.
  • a 10 m long and 15 cm wide fabric web is drawn at a speed of 160 m / h through a solution of 0.1 g butadiene palladium dichloride per liter methylene chloride and dried stress-free at 40 ° C.
  • the fabric web is then drawn through a metallization bath containing 25 g / l nickel sulfate, 3 g / l dimethylamine borane and 14 g / l citric acid at a speed of 25 m / h.
  • the bath time is 10 minutes.
  • the pH value, nickel concentration and reducing agent concentration are kept constant by continuous addition.
  • the goods are then washed and dried. A uniformly nickel-plated sheet of material with a nickel coating of 30.5 gm 2 is obtained .
  • a stamp pad is wetted with 1 gram of dibenzonitrile palladium dichloride in 20 ml of ethylene glycol. Letters are then stamped onto a polyethylene film using a stamp. The film is immersed in a water bath for 30 seconds and then nickel-plated in a metallization bath as in Example 1. After 5 minutes the letters were clearly recognizable as shiny metallic surfaces.
  • a 30 x 26 cm steel plate is degreased with 1,1,1-trichloroethane, then sprayed on one side with an activation solution according to Example 1 and dried. The plate is then immersed in a metallization bath according to Example 1 for 20 minutes.
  • a steel plate is uniformly coated with a nickel layer of approx. 2 f Lm.
  • a 14 cm x 14 cm polypropylene part is uniformly sprayed from one side with a solution of 0.1 g butadiene palladium dichloride per liter methylene chloride (blowing agent Frigen (R) ), dried at room temperature and then nickel-plated in an alkaline nickel bath according to Example 1 for 15 minutes.
  • a shiny metallic, well adhering nickel layer is obtained on the polypropylene part, which has an electrical resistance of 7 cm ohms.
  • An 8 cm x 11 cm polypropylene network is sprayed uniformly with a solution of 0.1 g of butadiene palladium dichloride per liter of methylene chloride (blowing agent Frigen (R » dried at room temperature and then nickel-plated for 15 minutes in an alkaline nickel bath as in Example 1) shiny, well-nickel-plated polypropylene mesh with an electrical resistance of 3 ohms.
  • Blowing agent Frigen R » dried at room temperature and then nickel-plated for 15 minutes in an alkaline nickel bath as in Example 1 shiny, well-nickel-plated polypropylene mesh with an electrical resistance of 3 ohms.
  • a 4 cm x 6 cm polyamide sheet is sprayed with an activation solution according to Example 1. After drying, the plate is immersed in a nickel plating bath according to Example 1 for 10 minutes. A plate nickel-plated on one side with a nickel content of 4.2 g / m 2 and a resistance of 5 ohms is obtained.
  • a 15 cm x 15 cm polycarbonate sheet is sprayed with an activation solution according to Example 1. After drying, the plate is immersed in a nickel plating bath according to Example 1 for 15 minutes. After washing and drying, the polycarbonate plate is coated with a reflective metal layer that has a resistance of 4 ohms.

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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)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
EP81104782A 1980-07-04 1981-06-22 Verfahren zur Aktivierung von Oberflächen für die stromlose Metallisierung Expired EP0043485B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81104782T ATE13319T1 (de) 1980-07-04 1981-06-22 Verfahren zur aktivierung von oberflaechen fuer die stromlose metallisierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3025307 1980-07-04
DE19803025307 DE3025307A1 (de) 1980-07-04 1980-07-04 Verfahren zur aktivierung von oberflaechen fuer die stromlose metallisierung

Publications (2)

Publication Number Publication Date
EP0043485A1 EP0043485A1 (de) 1982-01-13
EP0043485B1 true EP0043485B1 (de) 1985-05-15

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ID=6106372

Family Applications (1)

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EP81104782A Expired EP0043485B1 (de) 1980-07-04 1981-06-22 Verfahren zur Aktivierung von Oberflächen für die stromlose Metallisierung

Country Status (6)

Country Link
EP (1) EP0043485B1 (enrdf_load_stackoverflow)
JP (1) JPS5743977A (enrdf_load_stackoverflow)
AT (1) ATE13319T1 (enrdf_load_stackoverflow)
CA (1) CA1169720A (enrdf_load_stackoverflow)
DE (2) DE3025307A1 (enrdf_load_stackoverflow)
ES (1) ES8205269A1 (enrdf_load_stackoverflow)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3146235A1 (de) * 1981-11-21 1983-05-26 Bayer Ag, 5090 Leverkusen Selbstklebende metallisierte textile flaechenmaterialien
DE3150985A1 (de) * 1981-12-23 1983-06-30 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung
JPS58189365A (ja) * 1982-04-28 1983-11-05 Okuno Seiyaku Kogyo Kk 化学メッキ用アンダーコート組成物
DE3239090A1 (de) * 1982-10-22 1984-04-26 Bayer Ag, 5090 Leverkusen Schwarz-metallisierte substratoberflaechen
DE3242162A1 (de) * 1982-11-13 1984-05-17 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von verbundwerkstoffen
DE3324767A1 (de) * 1983-07-08 1985-01-17 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substraten fuer die stromlose metallisierung
JPS6079604A (ja) * 1983-10-05 1985-05-07 株式会社村田製作所 ポリアクリロニトリル導電性フイルムの製造方法
DE3337941A1 (de) * 1983-10-19 1985-05-09 Bayer Ag, 5090 Leverkusen Passive radarreflektoren
DE3421123A1 (de) * 1984-06-07 1985-12-12 Bayer Ag, 5090 Leverkusen Verbundmaterial
US4668533A (en) * 1985-05-10 1987-05-26 E. I. Du Pont De Nemours And Company Ink jet printing of printed circuit boards
DE3667800D1 (de) * 1985-08-23 1990-02-01 Ciba Geigy Ag Mischung aus olefin und dibenzalaceton-palladiumkomplex und deren verwendung.
US5182135A (en) * 1986-08-12 1993-01-26 Bayer Aktiengesellschaft Process for improving the adherency of metallic coatings deposited without current on plastic surfaces
JPH0826462B2 (ja) * 1987-11-30 1996-03-13 龍徳 四十宮 表面金属化重合体成形物の製造方法
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
DE3914726A1 (de) * 1989-05-04 1990-11-08 Deutsche Automobilgesellsch Vorrichtung zur chemischen metallisierung von offenporigen schaeumen, vliesstoffen, nadelfilzen aus kunststoff- oder textilmaterial
DE3938710A1 (de) * 1989-11-17 1991-05-23 Schering Ag Komplexverbindungen mit oligomerem bis polymerem charakter
DE4209708A1 (de) * 1992-03-25 1993-09-30 Bayer Ag Verfahren zur Verbesserung der Haftfestigkeit von stromlos abgeschiedenen Metallschichten
DE4418016A1 (de) * 1994-05-24 1995-11-30 Wilfried Neuschaefer Nichtleiter-Metallisierung
US7166152B2 (en) 2002-08-23 2007-01-23 Daiwa Fine Chemicals Co., Ltd. Pretreatment solution for providing catalyst for electroless plating, pretreatment method using the solution, and electroless plated film and/or plated object produced by use of the method
GB2395365B8 (en) * 2002-11-13 2006-11-02 Peter Leslie Moran Electrical circuit board
JP4605074B2 (ja) * 2006-03-31 2011-01-05 Ｔｄｋ株式会社 無電解めっき液及びセラミック電子部品の製造方法

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Publication number Priority date Publication date Assignee Title
AT286058B (de) * 1968-01-09 1970-11-25 Photocircuits Corp Verfahren zur Vorbereitung von in geformtem oder ungeformtem Zustand vorliegenden Materialien, vorzugsweise von Isolierstoffen für die stromlose Metallisierung
DE2451217C2 (de) * 1974-10-29 1982-12-23 Basf Ag, 6700 Ludwigshafen Aktivierung von Substraten für die stromlose Metallisierung

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Chemistry of Coordination Compounds (1956), J.C. Bailar, Abschnitt 15, Seiten 487-508 *
Comprehensive Inorganic Chemistry (1975), Band 3, Seite 1323 *
The Organic Chemistry of Palladium (1971), Vol. I, Seite 137 *

Also Published As

Publication number Publication date
DE3025307A1 (de) 1982-01-28
JPS6354791B2 (enrdf_load_stackoverflow) 1988-10-31
EP0043485A1 (de) 1982-01-13
CA1169720A (en) 1984-06-26
ES503645A0 (es) 1982-06-01
ES8205269A1 (es) 1982-06-01
DE3170482D1 (en) 1985-06-20
ATE13319T1 (de) 1985-06-15
JPS5743977A (en) 1982-03-12

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