EP0650537B1 - Metallisation de matieres plastiques - Google Patents

Metallisation de matieres plastiques Download PDF

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Publication number
EP0650537B1
EP0650537B1 EP93914605A EP93914605A EP0650537B1 EP 0650537 B1 EP0650537 B1 EP 0650537B1 EP 93914605 A EP93914605 A EP 93914605A EP 93914605 A EP93914605 A EP 93914605A EP 0650537 B1 EP0650537 B1 EP 0650537B1
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EP
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Prior art keywords
nickel
layer
solution
metal
currentlessly
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 - Lifetime
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EP93914605A
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German (de)
English (en)
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EP0650537A1 (fr
Inventor
Mariola Brandes
Burkhard Bressel
Hermann-Josef Dr. Middeke
Hans-Jürgen Dr. SCHREIER
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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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
    • C23C18/22—Roughening, e.g. by etching
    • 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
    • C23C18/26—Roughening, e.g. by etching using organic liquids

Definitions

  • the invention relates to a method for metallization of plastics.
  • metallized plastic should look like solid metal if possible: a shiny one or have a satin surface and be corrosion resistant.
  • the metal application can be done by spraying, Steaming or other vacuum techniques (sputtering) or by painting or flame spraying.
  • the electroplating metallization of plastics is done by various methods. Usually is the substrate to be coated by a chemical pretreatment process roughened to a sufficient adhesive strength of the metal layer too to reach. In some cases, they are also sent to certain Treatment solutions adapted to the materials used, that do not contain chemicals that Roughen the polymer surface visibly. With thermal or corrosion is the liability of the pretreated substrate surfaces in this way generally not sufficient.
  • aqueous chromic acid, chromium / sulfuric acid solutions or mixtures thereof with phosphoric acid, sulfuric acid and permanganate solutions are typically used as etching solutions.
  • Chromium / sulfuric acid solutions in particular have been used for some time for the metallization of acrylonitrile / butadiene / styrene polymer (ABS) substrates (K. Stoeckert, in: Kunststoffe 55 (1965) 857).
  • glycol ethers such as diethylene glycol dimethyl ether (DE-39 22 477 A1, US Pat. No. 4,775,557), ethylene glycol non-ethyl ether (FR-A-22 22 459), N-methylpyrrolidone, dimethylformamide (DE-38 07 618 A1), dimethyl sulfoxide and propylene carbonate ( DE-AS 22 22 941).
  • Nickel and copper layers are deposited electrolessly as metal layers on polycarbonates, polysulphones, polyesters and ABS resins. The shielding of electromagnetic radiation is specified as the field of application.
  • DE-41 08 461 C1 describes swelling agents for PCB polymers before an alkaline-oxidative Etching step described, containing carbonic acid esters, for example propylene carbonate and ethylene carbonate.
  • carbonic acid esters are well suited for swelling of inner walls of boreholes in Epoxy resin material, but not satisfactory for surface treatment when used for Shielding against electromagnetic radiation, using plastics that are difficult to metallize are, for example polycarbonates, ABS copolymers with polycarbonates or polyphenylene oxide.
  • the most commonly used method uses the Generation of the roughening of a catalytic seeding the plastic surface, which consists, for example, Palladium particles from a palladium colloid to deposit on the polymer surface. Subsequently can be made of electroless copper or Nickel baths creates a firmly adhering metal layer become. Usually only small layer thicknesses are used formed, which then to generate the actual functional layer on electrolytic Walk with suitable metal baths to the desired one Layer thickness can be reinforced.
  • plastics metallized with this process are the already mentioned ABS material, Polypropylene, polyphenylene oxide, epoxy resins, polyimide, Polyamide and others.
  • polycarbonate resins or mixtures thereof other polymers used are the already mentioned ABS material, Polypropylene, polyphenylene oxide, epoxy resins, polyimide, Polyamide and others.
  • the Plastic parts have an inner and an outer surface on, with at least one of the surfaces pore-free, electrolessly deposited copper layer with a layer thickness of at least 0.125 ⁇ m and above an electrolessly deposited nickel layer with a Layer thickness of at least 0.125 microns is applied.
  • the plastics to be metallized becomes the toxic chromium / sulfuric acid process specified.
  • the adhesive strength of the metal coating is in the most cases after the so-called tape test judged. For this, a one-sided self-adhesive Adhesive tape on the metallized surface of the Plastic part pressed on and then with strong pull demolished again. With sufficient The metal layer must not adhere to any metal particles stick to the tape.
  • a major disadvantage of the methods described consists of solutions containing chromic acid Use etching medium as these solutions as aerosols are carcinogenic.
  • chromium (VI) ions very low limit values required in the wastewater. Therefore, a very high effort be operated during wastewater treatment. this makes possible much less effort for the Occupational safety and wastewater treatment.
  • chromic acid Another disadvantage of chromic acid is its property as a strong catalyst poison in the electroless To act metallization.
  • Chromium (VI) ions in the activation solution or the electroless baths lead to one significantly deteriorated occupancy of the plastic surface with metal.
  • Chromium (VI) residues from the polymer surfaces completely be rinsed off.
  • this leads to a very high flushing water requirement and secondly too long Procedural consequences as there are many rinsing steps in the process need to be integrated. For these reasons, there is the desire to add chromic acid through less toxic substances replace.
  • the invention is therefore based on the problem these known disadvantages of the prior art methods to avoid technology and that Optimize metallization processes.
  • the substrate is subjected to the etching process in a permanganate solution.
  • a particular advantage of the process is that instead of the usual etching solutions, the contain toxic chromic acid, less toxic and that Metallization process not disruptive etching media, such as for example, solutions containing permanganate become.
  • Another advantage of the method according to the invention consists in the more uniform roughening of the substrate than with the conventional methods.
  • the conventional methods such as the ABS copolymers, individual polymer areas through the Etching process detached from the polymer composite.
  • the method according to the invention finds one more uniform roughening of the polymer surface with less etching depth instead. This will make it smoother Appearance of the surface achieved.
  • the organic compounds ethylene glycol methyl ether acetate (CH 3 O-CH 2 CH 2 O-COCH 3 ), diethylene glycol ethyl ether acetate (C 2 H 5 O-CH 2 CH 2 O-CH 2 CH 2 O-COCH 3 ) and propylene glycol methyl ether acetate (CH 3 O-CH 2 CH 2 CH 2 O-COCH 3 ) proved to be particularly suitable.
  • the concentrations of these compounds can be set between about 5 vol.% And 95 vol.%, If necessary in water. In practice, a preferred range of 20% to 80% by volume has proven to be particularly suitable.
  • these compounds can also be used in mixtures with one another or with other compounds.
  • connections become the source solutions Solving other organic compounds, such as for example, lower alcohols or glycol ethers added.
  • Possible compounds are methanol, ethanol, n- and i-propanol, ethylene glycol, propylene glycol and Diethylene glycol monoethyl and butyl ether.
  • alkali hydroxide, ammonia or quaternary ammonium bases can be noted that this results in a faster Aging of the solution due to increased absorption of carbon dioxide from the air to form the appropriate Carbonate takes place, so that gradually Salting of the swelling solution results. This happens all the more faster the higher the working temperature.
  • the temperature of the treatment solution can be any Values between room temperature and the boiling point of the Accept solution. In any case, it is one on the special composition of the source solution, the process parameters the subsequent process stages and the temperature of the substrate to be coated adjust. Usually, however, one is above room temperature lying temperature selected, preferably 40 to 75 ° C.
  • the treatment time is the same depending on the parameters mentioned chosen so that sufficient liability of the Metal coating reached on the polymer surface becomes.
  • the swelling agent treatment is usually in the Dipping process carried out. However, it is also possible apply other methods by which the Plastic surfaces in contact with the swelling solution to be brought. These include spraying, gushing, Injecting the solution or other types of orders.
  • the solution Following the swelling agent treatment usually rinsed with water. Then follows the etching process with a permanganate-containing Solution, the solution usually also by Diving into contact with the plastic surface but there are other ways of contacting, such as spraying, Swell or splash, possible.
  • the most used solutions contain potassium and / or Sodium permanganate.
  • Sodium permanganate then used when concentrations of permanganate should be set that are higher than about 70 g / l are. In this case the concentration exceeds of the potassium salt, its solubility at room temperature.
  • other salts of permanganate can be used. Usually these are Salts used in alkaline solution.
  • the pH these solutions can, for example, with baking soda or Potassium hydroxide solution set to a value greater than 13 become.
  • the practical area for the above Permanganate concentrations range up to about 250 g / l.
  • these form Solutions when standing, but especially when Processing of plastic parts by implementation or Decomposition of the permanganate manganate compounds.
  • the manganate that has formed must be added again Permanganate can be reoxidized. This can be done by adding of strong oxidizing agents such as Sodium peroxodisulfate, sodium hypochlorite or others Salting takes place or, much more elegantly, through electrolytic regeneration in which the manganate ions oxidized to permanganate at an inert anode become.
  • the etching solutions are salts to stabilize the pH of the solution such as Phosphates and for improved wetting surface-active substances on the plastic surface admitted. In this case, mostly come because of their higher chemical resistance to oxidation Fluorosurfactants used.
  • the temperature of these solutions is preferably above 60 ° C selected, but depending on the remaining process parameters and the selected one Plastic also set lower temperatures become. Treatment times are usually between 1 and 20 minutes set. Also in this Case applies that the optimal treatment time of the Process parameters of the entire process and the Type of polymer depends. Most times are preferred between 2 and 6 minutes.
  • the substrate After creating the roughness on the polymer surface the substrate is generally coated with a reducing agent treated to residues of the oxidizing solution and adhering reaction products such as Remove manganese dioxide from the surface. Acidic solutions are used for this. Usually Hydrogen peroxide, hydrazine or hydrazine salt, hydroxylammonium salts, Glyoxal, oxalic acid or others Solutions containing compounds used.
  • Ethylenediaminetetraacetic acid ethylenediaminetetrakis (progan-2-ol) or tartrate complex solutions used.
  • Formaldehyde is used as the reducing agent.
  • the pH is generally above 1.
  • Nickel baths mostly contain hypophosphite Reducing agent. Therefore, they contain from these Deposited layers of baths depending on the process conditions up to 13% phosphorus.
  • the pH of these solutions can be set between 4 and 9.
  • Corresponding the temperature is chosen between Room temperature and 95 ° C can be.
  • complexing agents are in These baths mostly use hydroxycarboxylic acids. All of these baths also have stabilizers, shine-forming or ductility-increasing additives admitted. The treatment times depend on the desired layer thickness.
  • the invention consist of those applied to the substrate Metal layers of at least three layers, whereby - after pretreatment with the above-described swelling, etching and activation solutions - the first layer a metal layer of the metals nickel, Is cobalt, palladium, gold or their alloys and the metals from an electroless plating bath to be deposited, the second layer is de-energized deposited copper and the third layer a metal layer of the metals nickel, cobalt, Is palladium, gold or their alloys and the Metals from an electroless plating bath be deposited.
  • the advantage of the method according to the invention is in that a very high liability of the deposited Metal layers also immediately after Metallization is achieved.
  • the procedure is in Contrary to known methods according to the prior art Technology without problems for plastics such as polycarbonate or its mixtures with others Plastics, such as ABS, or others difficult to metallize polymers applicable.
  • the first metal layer can be in a special Embodiment as a thin, highly adhesive layer be trained on in an economic Process with higher deposition speed thicker metal layers are deposited.
  • Critical problems in the metallization of Polymer surfaces are the adhesive strength of the Metal layer on the surface that Environmental friendliness of the process (type of used Chemicals and chemical consumption) and the cost of the procedure. Between these parameters compromises can be found: an environmentally friendly and little aggressive pretreatment of the polymer surface often attracts a longer dwell time Treatment baths after themselves or worsens the Quality of the products, for example the Adhesion strength of the metal on the surface. So can the exchange of chromic acid or chromic sulfuric acid in the first pretreatment step Plastic surface against pretreatment with a source system and alkaline permanganate solution although the range of the procedure with regard to significantly expand metallizing plastics.
  • Nickel layers have been used for the purpose described with phosphorus or boron as an alloy component proven suitable. Below is one such Base metallization electroless applied in copper one to achieve sufficient Shielding effect necessary layer thickness. The shielding effect should be 20dB in the shielding Frequency range (10 kHz to 1 GHz) at least exceed. Then the copper layer with another electrolessly deposited metal layer (Nickel, cobalt, palladium, gold or alloys thereof) protected against corrosion.
  • the entire So the procedure is, first, the Plastic surface for the metallization to pre-treat, then to de-energize To activate metal deposition and then a layer made of nickel, cobalt, palladium, gold or one Electrolessly deposit alloy from these metals, then copper in one to achieve the Shielding necessary thickness and then preferably from the same electroless plating bath like in the first metallization step another Deposit metal layer as corrosion protection.
  • the Appropriate layer sequence of metals deposited on the plastic surface (copper, Nickel, chrome, tin, silver, palladium, gold or Alloys such as brass).
  • a molded part made of the plastic BAYBLEND, brand from Bayer AG, (polycarbonate / ABS blend) was metallized in accordance with the following procedure: 1. swell 10 min 4 0 ° C 2nd Etching in alkaline permanganate solution 10 min 7 0 ° C 3rd Hot rinse 1 min 5 0 ° C 4th To reduce 3 min 2 5 ° C 5. Pre-dive 1 min 2 5 ° C 6. Activate 3 min 3 5 ° C 7. To reduce 5 min 2 5 ° C 8th. Electroless copper plating 20 min 4 5 ° C
  • the swelling agent contained 70% by volume of diethylene glycol ethyl ether acetate in water.
  • the permanganate solution had the following composition: 100 g / l NaMnO 4 15 g / l Na 2 MnO 4 20 g / l NaOH.
  • the electroless copper bath contained formaldehyde as Reducing agent.
  • formaldehyde as Reducing agent.
  • Example 2 The same result as in Example 1 was obtained if instead of diethylene glycol ethyl ether acetate 50% by volume solution of ethylene glycol methyl ether acetate was used.
  • the Plastic PULSE brand of Dow Chemicals, Inc., (also a blend of polycarbonate and ABS) be metallized with adhesive.
  • Example 2 The same result as in Example 1 was obtained if as a swelling agent a 50 vol.% or 70 vol.% Solution of diethylene glycol ethyl ether acetate and 5 Vol.% N-propanol was used. In both cases became a permanent copper plating of the plastics BAYBLEND, PULSE and LEXAN, brand for one Polycarbonate from General Electric Plastics, reached.
  • the copper layer was tested in all of the tapes Cases detached from the plastic surface.
  • a pre-coppering step with a low deposition temperature which was specially adapted to the plastic surface, was inserted before the electroless copper plating in order to achieve better adhesion of the metal coating to the substrate surface.
  • the following procedure was used: 1. swell conditions see below 2nd Etching in alkaline permanganate solution 6 min 70 ° C 3rd Hot rinse 1 min 50 ° C 4th To reduce 2 min 25 ° C 5. Pre-dive 1 min 25 ° C 6. Activate 5 min 35 ° C 7. To reduce 5 min 25 ° C 8th. Electroless pre-copper plating 5 min 30 ° C 9. Electroless copper plating 20 min 45 ° C 10th Enable copper 1 min 25 ° C 11. Electroless nickel plating 10 min 40 ° C
  • the permanganate solution had the following composition: 140 g / l NaMnO 4 15 g / l Na 2 MnO 4 40 g / l NaOH.
  • a housing part made of plastic Acrylonitrile / butadiene / styrene (ABS) has been injected was in a 360g / l solution for ten minutes
  • Pretreated chromic acid and 360 g / l sulfuric acid rinsed with a solution of 80 g / l sodium sulfite 'detoxifies', then with a solution of 300 g / l Sodium chloride and 10 g / l hydrochloric acid treated and in a solution of 8.8 g / l tin (II) chloride, 11.25 g / l Hydrochloric acid and 0.15 g / l palladium chloride activated.
  • ABS plastic Acrylonitrile / butadiene / styrene
  • a plastic molded part made from Lexan BE2130 was added Room temperature for five minutes in a well that consisted of 15% of a diglycol ether in water, and after rinsing in a solution of 140 g / l Permanganate and 50 g / l sodium hydroxide at 65 ° C in 10 Minutes pretreated. That on the surface Manganese oxide was then deposited by a solution removed from hydrogen peroxide and sulfuric acid.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Claims (5)

  1. Procédé de revêtement de pièces en matière plastique avec des métaux, notamment pour le blindage contre le rayonnement électromagnétique par au moins l'une des couches métalliques déposées, comprenant les étapes de procédé suivantes :
    a/ trempage dans une solution de trempage contenant des composés organiques de la formule générale R1-(O-(CH2)n)m-OCO-R2 dans laquelle :
    R1, R2 = CKH2K+1
    n = 2 ou 3
    k, m = 1, 2, 3 ou 4 ;
    b/ attaque acide avec une solution contenant des ions permanganate ;
    c/ ensuite, revêtement des pièces en matière plastique avec des germes de métaux nobles afin d'activer les pièces en matière plastique pour la métallisation autocatalytique ultérieure ;
    d/ dépôt autocatalytique d'une première couche, en contact avec la matière plastique, faite de métaux choisis dans le groupe comprenant le nickel, le cobalt, le palladium, l'or et leurs alliages ;
    e/ dépôt autocatalytique sur celle-ci d'une deuxième couche métallique en cuivre ;
    f/ dépôt autocatalytique sur la deuxième couche d'au moins une troisième couche fait de métaux choisis dans le groupe comprenant le nickel, le cobalt. le palladium, l'or et leurs alliages.
  2. Procédé selon la revendication 1, caractérisé en ce que la première couche métallique appliquée par dépôt autocatalytique est déposée à une vitesse de dépôt inférieure à 5 µm par heure.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que la première couche métallique appliquée par dépôt autocatalytique se compose essentiellement de nickel.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que la première couche métallique appliquée par dépôt autocatalytique se compose d'un alliage de nickel et de phosphore ou d'un alliage de nickel et de bore.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que les pièces en matière plastique sont d'abord nettoyées avec une solution contenant un agent mouillant dans une étape de traitement séparée avant le traitement dans la solution de trempage.
EP93914605A 1992-07-02 1993-07-02 Metallisation de matieres plastiques Expired - Lifetime EP0650537B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4221948A DE4221948C1 (de) 1992-07-02 1992-07-02 Verfahren zur Metallisierung von Kunststoffen und Verwendung
DE4221948 1992-07-02
PCT/DE1993/000599 WO1994001599A1 (fr) 1992-07-02 1993-07-02 Metallisation de matieres plastiques

Publications (2)

Publication Number Publication Date
EP0650537A1 EP0650537A1 (fr) 1995-05-03
EP0650537B1 true EP0650537B1 (fr) 1999-12-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP93914605A Expired - Lifetime EP0650537B1 (fr) 1992-07-02 1993-07-02 Metallisation de matieres plastiques

Country Status (5)

Country Link
EP (1) EP0650537B1 (fr)
AT (1) ATE188261T1 (fr)
DE (2) DE4221948C1 (fr)
ES (1) ES2140461T3 (fr)
WO (1) WO1994001599A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008043125A1 (de) * 2008-10-23 2010-04-29 BSH Bosch und Siemens Hausgeräte GmbH Bedienelement für ein Haushaltsgerät
DE102015201562A1 (de) 2015-01-29 2016-08-04 Helmholtz-Zentrum Dresden - Rossendorf E.V. Verfahren zur Metallisierung von Kunststoffteilen sowie Lösung
EP3414364B1 (fr) 2016-02-12 2020-06-03 Biconex GmbH Procédé de prétraitement de pièces en plastique pour l'électroplacage

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3769061A (en) * 1971-06-14 1973-10-30 Shipley Co Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating
JPS5133833B2 (fr) * 1973-03-19 1976-09-22
US4515829A (en) * 1983-10-14 1985-05-07 Shipley Company Inc. Through-hole plating
ATE69352T1 (de) * 1984-05-29 1991-11-15 Enthone Zusammensetzung und verfahren zur konditionierung der oberflaeche von kunststoffsubstraten vor der metallplattierung.
US4601784A (en) * 1985-05-31 1986-07-22 Morton Thiokol, Inc. Sodium permanganate etch baths containing a co-ion for permanganate and their use in desmearing and/or etching printed circuit boards
EP0309243B1 (fr) * 1987-09-25 1993-08-18 Engelhard Technologies Limited Traitement de pré-décapage d'un substrat plastique
US4775557A (en) * 1987-11-09 1988-10-04 Enthone, Incorporated Composition and process for conditioning the surface of polycarbonate resins prior to metal plating
DE3807617A1 (de) * 1988-03-04 1989-09-14 Schering Ag Basismaterial aus epoxid-harz
JPH0719959B2 (ja) * 1988-04-25 1995-03-06 マクダーミツド インコーポレーテツド 金属被覆化用プリント回路通し孔の製法及び組成物
DE3922477A1 (de) * 1989-07-06 1991-01-17 Schering Ag Quellmittel zur vorbehandlung von kunstharzen vor einer stromlosen metallisierung
DE4108461C1 (fr) * 1991-03-13 1992-06-25 Schering Ag Berlin Und Bergkamen, 1000 Berlin, De

Also Published As

Publication number Publication date
ES2140461T3 (es) 2000-03-01
DE59309916D1 (de) 2000-02-03
WO1994001599A1 (fr) 1994-01-20
DE4221948C1 (de) 1993-10-21
EP0650537A1 (fr) 1995-05-03
ATE188261T1 (de) 2000-01-15

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