EP0082438B1 - Verfahren zur Aktivierung von Substratoberflächen für die stromlose Metallisierung - Google Patents

Verfahren zur Aktivierung von Substratoberflächen für die stromlose Metallisierung Download PDF

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Publication number
EP0082438B1
EP0082438B1 EP82111461A EP82111461A EP0082438B1 EP 0082438 B1 EP0082438 B1 EP 0082438B1 EP 82111461 A EP82111461 A EP 82111461A EP 82111461 A EP82111461 A EP 82111461A EP 0082438 B1 EP0082438 B1 EP 0082438B1
Authority
EP
European Patent Office
Prior art keywords
palladium
nickel
minutes
process according
solvent
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
EP82111461A
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German (de)
English (en)
French (fr)
Other versions
EP0082438A1 (de
Inventor
Kirkor Dr. Sirinyan
Henning Dr. Giesecke
Gerhard Dieter Dr. Wolf
Harold Dr. Ebneth
Rudolf Dr. Merten
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
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0082438A1 publication Critical patent/EP0082438A1/de
Application granted granted Critical
Publication of EP0082438B1 publication Critical patent/EP0082438B1/de
Expired 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

  • the invention relates to a method for activating substrate surfaces for the purpose of chemical metallization.
  • the polymer surface is changed so that caverns and vacuoles are formed.
  • certain polymers e.g. B. in 2-phase multicomponent graft or copolymers, such as AB-S polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
  • the ionogenic palladium is reduced either in an acidic tin (II) chloride bath or by introducing tin (11) chloride into a strongly hydrochloric acid palladium (II) chloride solution.
  • the excess protective colloid must be removed from the substrate surface so that a reduction in the metal ions, e.g. B. of copper, nickel, gold and cobalt in the metallization bath by catalytic action of active palladium centers on the substrate surface is possible.
  • the metal ions e.g. B. of copper, nickel, gold and cobalt in the metallization bath by catalytic action of active palladium centers on the substrate surface is possible.
  • the object of the present invention was to provide a new, gentle and procedurally simple method for activating substrate surfaces for the purpose of electroless metallization, with which even surfaces that are difficult to metallize can be provided with a well-adhering metal coating.
  • the task is solved in that one. used to activate organometallic compounds of palladium, the organic part of which are oligomeric, prepolymeric or polymeric compounds which contain double bonds.
  • the invention therefore relates to a method for activating substrate surfaces for the purpose of electroless metallization, the surface to be metallized, preferably without prior etching, with a palladium (II) organic compound of the above-mentioned homogeneously distributed in a solvent, in particular an organic solvent Type wetted, the solvent removed and the palladium (II) compound adhering to the surface to be metallized is reduced.
  • a palladium (II) organic compound of the above-mentioned homogeneously distributed in a solvent in particular an organic solvent Type wetted
  • oligomer, prepolymer and polymer are known to the person skilled in the art. Together, they comprise a molecular weight range of approximately 150 to 1,000,000, preferably 200 to 500,000.
  • the metal can be bound to the oligomer, prepolymer or polymer or to the corresponding monomer, which would be followed by the corresponding polymer reaction. It is also possible to carry out the polymer reaction and metal bonding in one operation.
  • the oligomeric, prepoly mer or polymeric compounds in addition to the groups that bind the metal to the polymer, further functional groups that are capable of binding the organometallic compound to the substrate to be activated or for further polymer reaction.
  • groups are carboxyl or ester groups.
  • organometallic compounds used in accordance with the invention known low-molecular organometallic compounds with ligand exchange with the oligomers, prepolymers or polymers are reacted, or known organometallic compounds with ligand exchange with low-molecular compounds which are suitable for polymer production are reacted and the polymer reaction is then carried out.
  • the organometallic compound can, for example, be dissolved or dispersed in the organic solvent, or it can also be a rubbing of the organometallic compounds with the solvent.
  • organometallic compound contains ligands that allow chemical fixation on the substrate surface, activation from the aqueous phase may also be possible.
  • An organic palladium compound is dissolved in an organic solvent. Mixtures of compounds can of course also be used. The concentration should be between 0.01 g and 10 g per liter, but can also be below or above in special cases.
  • Polar, protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol and tetrahydrofuran are particularly suitable as organic solvents.
  • Suitable substrates for the process according to the invention are, for. B. steels, titanium, glass, quartz, ceramics, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyester and textile fabrics, threads and fibers made of polyamide, polyester, polyolefins, polyacrylonitrile, polyvinyl halides, cotton and wool, and the like Mixtures or of copolymers of the monomers mentioned.
  • 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 pretreated 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 work steps: immersing the substrate in the solution of the organometallic compound, evaporating the solvent and immersing the surfaces activated in this way Metallization bath (reduction and metallization).
  • This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
  • the metallization baths which can be used in the process according to the invention are preferably baths. with nickel salts, cobalt salts, copper salt salts, gold and silver salts or their mixtures with one another or with iron salts.
  • Such metallization baths are known in the electroless metallization art.
  • oligomeric, prepolymeric and polymeric palladium-organic compounds can be used to produce directly activated moldings, using conventional technologies. These moldings can then be subjected to the reduction and metallization.
  • oligomeric, prepolymeric and polymeric organometallic compounds applied to substrates can of course be subjected to further reactions, for example crosslinking or grafting.
  • a polypropylene film (100 x 80 mm) is included.
  • Degreased methylene chloride and then 20 seconds in a solution of 18 g palladed polybutadiene with the average molecular weight M n 900 and 5.2% by weight of palladium (based on dry polybutadiene mass) immersed in 1 l of methylene chloride, after evaporation of the solvent at room temperature for 15 minutes in a slightly alkaline, aqueous nickel-plating bath, the 3.5 g of dimethylamine borane, 30 g Contains nickel chloride and 10 g citric acid in 1 I and adjusted to pH 8.2 with concentrated ammonia solution, is electroless nickel-plated.
  • the electrical resistance of the chemically deposited nickel layer is so low that the polypropylene foil washed after the chemical metallization is galvanically coated with copper of approximately 4.2 ⁇ m in thickness in a galvanic copper plating bath at 1.0 amps after 30 minutes.
  • a glass plate (100 x 80 mm) is degreased with methylene chloride and then immersed in 1 l methylene chloride in a solution of 7.2 g palladed polybutadiene with 7.1% by weight palladium (based on the dry polybutadiene mass) for 30 seconds, after which Evaporation of the solvent at room temperature according to Example 1 nickel-plated. After a minute, the plate is covered with a fine black nickel layer.
  • the nickel layer After about 15 minutes, the nickel layer has a thickness of 0.15 ⁇ m and can be switched and reinforced as a cathode in common galvanic metallization baths.
  • a metallized piece of fabric with a coating of 9 g / m 2 nickel is obtained.
  • a glass plate (100 x 100 mm) is sprayed with the above-mentioned prepolymer solution (blowing agent Frigen (R » after drying according to Example 1, nickel-plated for 9 minutes.
  • a glass fiber reinforced epoxy resin plate (100 x 100 mm) is sprayed according to Example 12 with palladium-coated prepolymer solution, after drying the layer according to Example 1, nickel-plated in an alkaline nickel plating bath. After 9 minutes, a nickel layer 0.1 ⁇ m thick is measured.
  • a 100 x 100 mm square of a fabric made of polyethylene terephthalate is sprayed according to Example 4 with palladed prepolymer solution (Frigen ( R ) as blowing agent) and after drying the layer according to Example 1 ver nods. After just one minute, the fabric is covered with a fine layer of nickel. After 10 minutes the chemically deposited amount of nickel is 10 g / m 2 .
  • Glass rods with a diameter of 8 mm and a length of 250 mm are coated with the above-mentioned palladed prepolymer solution by means of an immersion process, dried in a drying cabinet at 60 ° C. and then nickel-plated according to Example 1.
  • the nickel layer After about 5 minutes, the nickel layer has a thickness of about 0.2 p.m.
  • the rods are removed from the bath, rinsed with distilled water and reinforced as a cathode according to Example 1 in a galvanic copper plating bath at 1.0 amp. To 20 ⁇ m.
  • a 250 x 250 mm square of a wooden plate is sprayed with the prepolymer solution.
  • the lacquer layer is dried for 12 hours at room temperature and nickel-plated according to Example 1.
  • the electrical resistance of the chemical nickel layer is so low that the wood-metal composite material as the cathode. can be amplified in a galvanic nickel plating bath at 1.5 amp.
  • Glass rods with a diameter of 8 mm and a length of 250 mm are coated with the palladed prepolymer solution according to Example 15 by an immersion process, dried in a drying cabinet at 80 ° C. in 4.5 hours, then nickel-plated according to Example 1. After a chemical metallization time of approx. 6 minutes, the rods are covered with a nickel layer.
  • Example 16 The palladed prepolymer listed in Example 16 is printed on a glass fiber reinforced epoxy resin plate (150 x 50 mm) using the screen printing process, the prepolymer mask is cured in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to Example 1.
  • this printed circuit board is galvanically reinforced to 5 ⁇ m as the cathode in an acidic copper plating bath.
  • benzonitrile palladium dichloride 0.25 g of benzonitrile palladium dichloride are dissolved in 60 ml of ethanol. The solution is mixed with 26 ml of emulsifier-free polybutadiene latex at room temperature.
  • Films (40 x 80 mm) are made from the palladed latex by casting on glass plates. The foils are annealed in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to example 1.
  • the electrical resistance of this chemical nickel layer is so low that the metallized metal-polymer composite material is reinforced to 15 ⁇ m in an acidic copper plating bath as the cathode.
  • a 100 x 100 mm square of a 3 mm thick heat-resistant polycarbonate film is sprayed with a solution of 0.6 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride in 20 ml of n-butanol and 5 g of prepolymer solution according to Example 15 after evaporation the solvent is cured in a drying cabinet at 95 ° C. for 10 minutes and then nickel-plated according to example 1. After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 ⁇ m. The sample is removed from the bath, carefully rinsed with distilled water, reinforced according to Example 1 at 1.2 amps with a 7.5 ⁇ m copper layer.
  • a template for the production of printed circuits is placed on a 200 x 200 mm polyhydantoin film.
  • the test specimen is sprayed with the coating solution (Frigen (R) as blowing agent). After the solvent has evaporated, the stencil is removed from the film surface, the lacquer layer is cured in a drying cabinet at 50 ° C. in 5 hours and then nickel-plated according to Example 1.
  • test specimen is removed from the metallization bath and the partial nickel coating in a galvanic copper plating bath is increased to 5 ⁇ m at 0.9 amp./d M 2 .
  • a 25 x 80 mm, 1.5 mm thick glass fiber reinforced epoxy resin plate is coated with the above-mentioned lacquer by immersion, irradiated with a mercury lamp for 15 minutes after evaporation of the solvent and nickel-plated according to Example 1.
  • the nickel coating is so thick that it can be reinforced in a galvanic copper plating bath.
  • the polymerization is stopped and the solvent is removed in vacuo at 35 ° C.
  • the sticky polymer mass is mixed with 29 g of technical polystyrene.
  • the polymer mixture becomes a compact in a cylindrical chamber at 100 ° C and 1 bar molded with a thickness of approx. 2.0 mm and a diameter of 12.9 mm.
  • This molded part is nickel-plated according to Example 1. After approx. 6 minutes the nickel layer has a thickness of approx. 0.15 ⁇ m.
  • the underside of the carpet has a nickel layer.
  • Acetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride, mixed with oligomeric polybutadiene, stirred for 30 minutes at room temperature and freed from solvent and acetonitrile in vacuo.
  • Acetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride. Butadiene is introduced and the solvent and acetonitrile are distilled off in vacuo.

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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)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
EP82111461A 1981-12-23 1982-12-10 Verfahren zur Aktivierung von Substratoberflächen für die stromlose Metallisierung Expired EP0082438B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813150985 DE3150985A1 (de) 1981-12-23 1981-12-23 Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung
DE3150985 1981-12-23

Publications (2)

Publication Number Publication Date
EP0082438A1 EP0082438A1 (de) 1983-06-29
EP0082438B1 true EP0082438B1 (de) 1985-10-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP82111461A Expired EP0082438B1 (de) 1981-12-23 1982-12-10 Verfahren zur Aktivierung von Substratoberflächen für die stromlose Metallisierung

Country Status (4)

Country Link
US (2) US4493861A (enrdf_load_stackoverflow)
EP (1) EP0082438B1 (enrdf_load_stackoverflow)
JP (1) JPS58113366A (enrdf_load_stackoverflow)
DE (2) DE3150985A1 (enrdf_load_stackoverflow)

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DE19941043B4 (de) * 1999-08-28 2004-04-29 Robert Bosch Gmbh Bekeimungsbad und Verfahren zur Bekeimung von pulverförmigen Werkstoffen, Verfahren zur Metallisierung eines bekeimten pulverförmigen Werkstoffs und Verfahren zur Herstellung metallisch begrenzter Hohlkörper
US20040031404A1 (en) * 2002-08-19 2004-02-19 John Dixon Seamless embossing shim
US8465469B2 (en) * 2002-09-12 2013-06-18 Medtronic Vascular, Inc. Reinforced catheter and methods of making
CN1329554C (zh) * 2004-01-13 2007-08-01 长沙力元新材料股份有限公司 非金属基材表面化学镀覆金属的方法及其采用的前处理体系
EP2105451B1 (en) * 2006-10-23 2012-02-15 FUJIFILM Corporation Nitrile group-containing polymer and method of synthesizing the same, composition containing nitrile group-containing polymer, and laminate
KR101385086B1 (ko) * 2010-05-04 2014-04-14 유니-픽셀 디스플레이스, 인코포레이티드 전기 전도성 패턴을 가진 미세 구조 표면을 제조하는 방법
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EP0081129A1 (de) * 1981-12-05 1983-06-15 Bayer Ag Verfahren zur Aktivierung von Substratoberflächen für die stromlose Metallisierung

Also Published As

Publication number Publication date
EP0082438A1 (de) 1983-06-29
US4493861A (en) 1985-01-15
DE3266873D1 (en) 1985-11-14
US4622411A (en) 1986-11-11
JPH026834B2 (enrdf_load_stackoverflow) 1990-02-14
JPS58113366A (ja) 1983-07-06
DE3150985A1 (de) 1983-06-30

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