EP0082438A1 - Procédé d'activation des surfaces pour la métallisation sans courant - Google Patents

Procédé d'activation des surfaces pour la métallisation sans courant Download PDF

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Publication number
EP0082438A1
EP0082438A1 EP82111461A EP82111461A EP0082438A1 EP 0082438 A1 EP0082438 A1 EP 0082438A1 EP 82111461 A EP82111461 A EP 82111461A EP 82111461 A EP82111461 A EP 82111461A EP 0082438 A1 EP0082438 A1 EP 0082438A1
Authority
EP
European Patent Office
Prior art keywords
palladium
nickel
minutes
metallization
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.)
Granted
Application number
EP82111461A
Other languages
German (de)
English (en)
Other versions
EP0082438B1 (fr
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/fr
Application granted granted Critical
Publication of EP0082438B1 publication Critical patent/EP0082438B1/fr
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.
  • This is only possible with certain polymers, for example with 2-phase multicomponent grafts or copolymers, such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
  • 2-phase multicomponent grafts or copolymers such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
  • working with chromosulfuric acid or other oxidants is associated with a deterioration in the physical properties, for example the notched impact strength or the electrical surface resistance of the polymeric base material.
  • the ionogenic palladium is reduced either in an acidic tin (II) chloride bath or by introducing tin (II) 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. of copper, nickel, gold and cobalt in the metallization shading is possible through the catalytic action of active palladium centers on the substrate surface.
  • the object of the present invention was to provide a new, gentle and process-technically simple method for activating substrate surfaces for the purpose of electroless metallization, with which even hard-to-metallize surfaces can be provided with a well-adhering metal coating.
  • organometallic compounds of palladium are used, 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, being wetted with an organopalladium (II) compound homogeneously distributed in a solvent, in particular an organic solvent, the solvent removed and the organopalladium (II) compound adhering to the surface to be metallized is reduced, characterized in that the organic part of the organometallic compound is an oligomeric, prepolymeric or polymeric compound which contains double bonds.
  • 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.
  • Preferred organic compounds are homo- and copolymers of conjugated dienes, e.g. Styrene-butadiene copolymers, and unsaturated polyesters.
  • 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, prepolymeric or polymeric compounds have, in addition to the groups which bind the metal to the polymer, further functional groups which are capable of binding the organometallic compound to the substrate to be activated or of a further polymer reaction.
  • groups which bind the metal to the polymer 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, it can also be a rubbing of the organometallic compounds with the solvent.
  • organometallic compound contains ligands which allow chemical fixation on the substrate surface, activation from the aqueous phase may also be possible.
  • 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 suitable as organic solvents.
  • Suitable substrates for the process according to the invention are e.g. Steels, titanium, glass, quartz, ceramics, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters and textile fabrics, threads and fibers made of polyamide, polyester, polyolefins, polyacrylonitrile, polyvinyl halides, cotton and wool, and mixtures thereof or from copolymers of the monomers mentioned.
  • the organic solvent is removed.
  • Low boiling solvents are preferred by evaporation, e.g. removed in vacuum.
  • 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 there are others too Reducing agent 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 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.
  • metallising baths with nickel salts, C obaltsalzen, copper salts, gold salts 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 organic palladium 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.
  • 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 ent with methylene chloride greased and then immersed for 30 seconds in a solution of 7.2 g palladed polybutadiene with 7.1% by weight palladium (based on the dry polybutadiene mass) in 1 1 methylene chloride, after 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), 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 woven fabric made of polyethylene terephthalate is sprayed according to Example 4 with palladed prepolymer solution (frigen as blowing agent) and, after the layer has dried, is nickel-plated according to Example 1. 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 an immersion process, dried in a drying cabinet at 60 ° C. and then nickel-plated according to Example 1.
  • the nickel layer After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 ⁇ 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 made 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 can be reinforced as a cathode in a galvanic nickel plating bath at 1.5 amps.
  • Example 7 10 g of the alkyd resin used in Example 7 (60% in xylene) are mixed with 0.8 g of benzonitrile palladium dichloride in 20 ml of toluene at 30 ° C., then concentrated to 15 ml at room temperature and under a water jet vacuum.
  • a glass-fiber-reinforced epoxy resin plate is partially coated with the palladium-coated prepolymer solution mentioned in the screen printing process, after which it is nickel-plated at 60 ° C. in a drying cabinet according to Example 1.
  • Glass rods with a diameter of 3 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.
  • the latex contains 31.5% by weight of solid with a 100% gel content and has a pH of 6.6 and an average particle diameter of 0.285 ⁇ m. Its swelling index in toluene is 5.0.
  • 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 evaporating the Solvent in the 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 (freezing as a 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./dm 2 .
  • lacquer (15% strength in xylene) based on 1,4-polyisoprene with diazole crosslinker are mixed with 0.4 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride with stirring and nitrogen injection within one hour added in 5 ml of methylene chloride.
  • 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 underside of the carpet has a nickel layer.
  • Isobutyl vinyl ether palladium dichloride is obtained in an analogous manner from the acetonitrile palladium dichloride and isobutyl vinyl ether, melting point: 57-60 ° C.
  • a cetonitrile 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.
  • a cetonitrile 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 Procédé d'activation des surfaces pour la métallisation sans courant Expired EP0082438B1 (fr)

Applications Claiming Priority (2)

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

Publications (2)

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

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Family Applications (1)

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EP82111461A Expired EP0082438B1 (fr) 1981-12-23 1982-12-10 Procédé d'activation des surfaces pour la métallisation sans courant

Country Status (4)

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US (2) US4493861A (fr)
EP (1) EP0082438B1 (fr)
JP (1) JPS58113366A (fr)
DE (2) DE3150985A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3419755A1 (de) * 1984-05-26 1985-11-28 Bayer Ag, 5090 Leverkusen Chemisches versilberungsbad
EP0250867A1 (fr) * 1986-06-16 1988-01-07 International Business Machines Corporation Procédé d'activation en vue d'un dépôt de métal par voie chimique
DE3938710A1 (de) * 1989-11-17 1991-05-23 Schering Ag Komplexverbindungen mit oligomerem bis polymerem charakter
DE19941043A1 (de) * 1999-08-28 2001-03-01 Bosch Gmbh Robert Bekeimungsbad und Verfahren zur Bekeimung von pulverförmigen Werkstoffen, Verfahren zur Metallisierung eines bekeimten pulverförmigen Werkstoffs und Verfahren zur Herstellung metallisch begrenzter Hohlkörper

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DE3242162A1 (de) * 1982-11-13 1984-05-17 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von verbundwerkstoffen
DE3248778A1 (de) * 1982-12-31 1984-07-12 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung metallisierter poroeser festkoerper
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US4719145A (en) * 1983-09-28 1988-01-12 Rohm And Haas Company Catalytic process and systems
DE3339856A1 (de) * 1983-11-04 1985-05-15 Bayer Ag, 5090 Leverkusen Verfahren zur haftaktivierung von polyamidsubstraten fuer die stromlose metallisierung
DE3339857A1 (de) * 1983-11-04 1985-05-15 Bayer Ag, 5090 Leverkusen Verfahren zur vorbehandlung von polyamidsubstraten fuer die stromlose metallisierung
DE3407114A1 (de) * 1984-02-28 1985-09-05 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
JPS62149884A (ja) * 1985-12-24 1987-07-03 Nippon Mining Co Ltd 無電解銅めつきの前処理方法
JPH0694592B2 (ja) * 1986-04-22 1994-11-24 日産化学工業株式会社 無電解メッキ法
US5182135A (en) * 1986-08-12 1993-01-26 Bayer Aktiengesellschaft Process for improving the adherency of metallic coatings deposited without current on plastic surfaces
US4910072A (en) * 1986-11-07 1990-03-20 Monsanto Company Selective catalytic activation of polymeric films
US5075037A (en) * 1986-11-07 1991-12-24 Monsanto Company Selective catalytic activation of polymeric films
JP2760984B2 (ja) * 1987-02-26 1998-06-04 株式会社東芝 絶縁ゲート型サイリスタ
JPH01104782A (ja) * 1987-07-02 1989-04-21 Fuji Photo Film Co Ltd 無電解メッキ用触媒材料およびそれを用いた金属化材料
DE3743780A1 (de) * 1987-12-23 1989-07-06 Bayer Ag Verfahren zur verbesserung der haftfestigkeit von stromlos abgeschiedenen metallschichten auf polyimidoberflaechen
US5030742A (en) * 1988-12-16 1991-07-09 Ciba-Geigy Corporation Ultrathin layers of palladium(O) complexes
US5227223A (en) * 1989-12-21 1993-07-13 Monsanto Company Fabricating metal articles from printed images
US5279899A (en) * 1992-03-17 1994-01-18 Monsanto Company Sulfonated polyamides
US5517338A (en) * 1992-10-20 1996-05-14 Monsanto Company Composite mirrors
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
DE4319759A1 (de) * 1993-06-15 1994-12-22 Bayer Ag Pulvermischungen zum Metallisieren von Substratoberflächen
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
KR101459515B1 (ko) * 2006-10-23 2014-11-07 후지필름 가부시키가이샤 표면 금속막 재료와 그 제작방법, 금속패턴 재료와 그 제작방법, 폴리머층 형성용 조성물, 니트릴기 함유 폴리머와 그 합성방법, 니트릴기 함유 폴리머를 사용한 조성물, 및 적층체
JP5470503B2 (ja) * 2010-05-04 2014-04-16 ユニ−ピクセル・ディスプレイズ・インコーポレーテッド 導電性パターンを伴う微細構造表面の製作方法
US8591637B2 (en) * 2010-12-14 2013-11-26 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8591636B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method

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DE3148280A1 (de) * 1981-12-05 1983-06-09 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3419755A1 (de) * 1984-05-26 1985-11-28 Bayer Ag, 5090 Leverkusen Chemisches versilberungsbad
EP0250867A1 (fr) * 1986-06-16 1988-01-07 International Business Machines Corporation Procédé d'activation en vue d'un dépôt de métal par voie chimique
DE3938710A1 (de) * 1989-11-17 1991-05-23 Schering Ag Komplexverbindungen mit oligomerem bis polymerem charakter
DE19941043A1 (de) * 1999-08-28 2001-03-01 Bosch Gmbh Robert Bekeimungsbad und Verfahren zur Bekeimung von pulverförmigen Werkstoffen, Verfahren zur Metallisierung eines bekeimten pulverförmigen Werkstoffs und Verfahren zur Herstellung metallisch begrenzter Hohlkörper
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

Also Published As

Publication number Publication date
DE3266873D1 (en) 1985-11-14
JPH026834B2 (fr) 1990-02-14
US4622411A (en) 1986-11-11
DE3150985A1 (de) 1983-06-30
JPS58113366A (ja) 1983-07-06
US4493861A (en) 1985-01-15
EP0082438B1 (fr) 1985-10-09

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