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
• • 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
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/208—Multistep pretreatment with use of metal first
• • 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
  • C23C18/22—Roughening, e.g. by etching
  • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
• • 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 process of the invention is concerned with the pretreatment of plastic surfaces for the purpose of subsequent adhesive chemicogalvanic metallization.
• chemicogalvanic procedures comprise a series of process steps to which belong primarily the sensitization of the plastic, mostly with SnCl solution, the concurring activation with a noble metal solution, mostly with silver nitrate or palladium chloride solution and the chemicogalvanic deposition of a thin metal skin besides its electroplating and improvement.
• these disturbances can be completely eliminated if the decontamination of the etched plastic parts are taken up with a preferably aqueous, alkaline solution containing a material having primary, secondary, or tertiary amine groups or ammonia or quaternary ammonium bases, which on the one hand functions as a strong neutralizing agent, and on the other hand binds inhibiting metal ions which come from the etching, in the form of complexes which can be removed.
• sodium alkaline solutions of primary and secondary aliphatic amines having one or several amine groups which are able to build very stable complexes with metal ions.
• the detoxification solution can be used at room temperature, its activity increases, however, with mounting bath temperature, since with elevated temperatures, the diffusion speed also increases. Temperatures of 10 to 150 C., preferably 30 to C. are used.
• Examples of such compounds include propylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, N-methyl ethylene diamine, N,N- dimethyl ethylene diamine, N-ethyl hexamethylene diamine, bis (1,4-aminomethyl) cyclohexane, bis (1,4- aminoethyl) cyclohexane, bi's(l,4-aminopropyl)cyclohexane, bis(l,4-aminobutyl) cyclohexane, l,4-di(aminomethyl)-benzene, 1,4- diaminoethyD-benzene, 1,4 di (aminopropyl)-benzene, 1,4-di(aminobutyl-benzene, N- ethylI,4-di(aminobutyl)-benzene, ethylene diamine tetraacetic acid
• the amines are used preeminently in aqueous solution in an amout of 1 to 80% by weight of the bath liquid, preferably 2 to and most preferably 2 to 8%.
• ammonia or amines such as methyl amine, ethyl amine, butyl amine, dimethyl amine, dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine, tributyl amine, dimethyl propyl amine, or quaternary ammonium compounds, such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutyl ammonium hydroxide.
• alkalies e.g., sodium hydroxide and potassium hydroxide.
• alkali hydroxide e.g., sodium hydroxide and potassium hydroxide.
• the amine or ammonium compound containing bath can have 0.1 to by Weight of alkali, preferably 0.4 to 8% of sodium hydroxide.
• this intermediate bath is advantageously used after the etching of the plastic sample and after a short rinsing with water.
• the intermediate bath of the invention can be used with the intermediate bath of the invention either the conventional sensitization of the plastic samples with SnCl solution or also an activation process with a diluted noble metal salt solution, e.g., with 0.1 to 10% by weight, preferably 0.2 to 4% of silver or palladium compounds such as silver nitrate and palladium chloride or other noble metal compounds such as ammoniumchloroplatinate.
• baths containing nickel and/or cobalt and/or copper salts in amounts of 0.1 to 10% by weight, preferably 0.2 to 5% of the entire bath liquid.
• A's examples of such salts there can be used nickel chloride, cobaltous chloride, copper sulfate, nickel sulfate, cobaltous sulfate, zinc chloride, zinc sulfate.
• the etched plastic sample has been treated with an aqueous sodium alkali solution of ethylene diamine and nickel chloride of the following composition which has proven very advantageous:
• the process is primarily very advantageously usefulin the metallization of polypropylene modified with fillers which is additionally superior in heat stability to ABS plastics.
• EDA Wor ing conditions ethylene diamine.
• the aqueous EDA/NaOH decontami- 5 Bath: nation solution contained 60 grams ethylene diamine per liter and 40 grams NaOH per liter.
• the aqueous EDA/NaOH/NiCl decontamination solution contained 60 grams ethylene diamine/ liter, grams NaOH/liter and 30 grams NiCI /Iiter.
• the aqueous EDA/NaOH/CoCl decontamination solution contained grams ethylene diamine/liter, 40 grams NaOH/ liter and 30 grams CoCl /liter.
• the aqueous solution of decontaminant and activator contained 60 grams ethylene diamine/liter and 0.2 gram 15 AgNO liter.
• the aqueous sensitization solution contained 10 grams of SnCl liter and 25 grams of HCl/ liter.
• the activator solution contained 3 grams of NH /liter
• the reduction preliminary bath contained 7 grams/liter of NaOH in addition to the indicated amount of formalin or NaBH
• the time in the etching bath was 10 minutes for all 25 samples except those with 20% filler.
• the samples with 20% filler were kept in the etching bath 2 0 minutes.
• the polypropylene samples were composed of 55% polypropylene, 15% ethylene-vinylacetate copolymer and All temperatures are in degrees Centigrade.
• the polyethylene sample was composed of 30 polyethylene, 15 ethylene-vinylacetate copolymer and 20% CaSiO
• the polyvinyl chloride sample was composed of polyvinyl chloride and 20% SiO
• a process for the adhesive metallization of plastics including pretreating of the plastic surface with chromosulfuric acid to etch said surface and subsequent chemical metalliaztion from an aqueous metal salt bath and electroplating, the improvement comprising after the chromosulfuric acid etch, treating at 10 to 150 C. said plastic surface in an alkaline aqueous solution of ethylene diamine as an intermediate bath as a neutralizing agent and to bind metal ions coming from the etching, said solution containing 1 to 80% of the ethylene diamine, 0.1 to 30% of alkali and 0.1 to 10% of a member of the group consisting of nickel, cobalt, copper, silver, palladium and platinum salts.
• ethylene 1 diamine bath contains from 0.1 to 10% of a nickel, cobalt or copper salt based on the entire bath weight.
• plastic is selected from the group consisting of polypropylene, polyethylene, polyvinyl chloride and acrylonitrilebutadiene-styrene copolymer.

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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)

Applications Claiming Priority (1)

Publications (1)

Family

ID=5700271

Family Applications (1)

Country Status (4)

Cited By (11)

Families Citing this family (1)

• 1968
  • 1968-07-11 DE DE19681769778 patent/DE1769778A1/de active Pending
• 1969
  • 1969-07-07 FR FR6922990A patent/FR2016111A1/fr not_active Withdrawn
  • 1969-07-07 US US3702285D patent/US3702285A/en not_active Expired - Lifetime
  • 1969-07-10 AT AT663869A patent/AT290247B/de not_active IP Right Cessation

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