EP0096034B1 - Elektrofreie kupferniederschlagslösungen - Google Patents

Elektrofreie kupferniederschlagslösungen Download PDF

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Publication number
EP0096034B1
EP0096034B1 EP19820900581 EP82900581A EP0096034B1 EP 0096034 B1 EP0096034 B1 EP 0096034B1 EP 19820900581 EP19820900581 EP 19820900581 EP 82900581 A EP82900581 A EP 82900581A EP 0096034 B1 EP0096034 B1 EP 0096034B1
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EP
European Patent Office
Prior art keywords
solution
copper
cupric
substrate
ions
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Expired
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EP19820900581
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English (en)
French (fr)
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EP0096034A4 (de
EP0096034A1 (de
Inventor
Donald R. Ferrier
Harold L. Rhodenizer
Peter E. Kukanskis
John 1 Grunwald
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MacDermid Inc
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MacDermid Inc
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Publication of EP0096034A4 publication Critical patent/EP0096034A4/de
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    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • hypophosphite type reducing agents provide substantial advantage over some of the more conventional reducing agents, such as formaldehyde and the boro compounds, heretofore used almost exclusively in electroless copper plating.
  • the use of hypophosphite type reducing agents in electroless copper solutions heretofore has, however, been restricted in practical commercial plating operations to baths of pH values generally well in excess of pH 5.0.
  • This invention relates to improvements in electroless copper plating baths employing hypophosphite reducing agents, but having substantially lower pH operating ranges.
  • US-A-4209331 provides one of the first disclosures enabling commercially practical use of hypophosphite reducing agents in electrolessly plating copper onto non-conductors. That application deals extensively with what prior art there is relating to hypophosphite-type electroless copper plating solutions, and that disclosure is incorporated herein by reference. Essentially, it was shown that while hypophosphite has gained industry-wide acceptance for depositing nickel in electroless plating operations, there were no commercial processes being successfully used to the inventors' knowledge in which hypophosphite agents were employed to electrolessly plate copper. It is disclosed in that application that by maintaining a specified complexer/pH relationship in the copper bath at pH values of 5.0 to 13.0, plating of copper with hypophosphite reducing agents is practical, and that the system has advantages for commercial operations.
  • the invention here relates to the discovery that hypophosphite reducing agents can be usefully employed as reducing agents for divalent copper at a bath pH of about 2.0 to 3.5, to produce an electrically conductive copper film on a suitably catalyzed non-conductive substrate.
  • Such copper deposit has good conductivity, provides good adherence of the deposit to the substrate, and serves as an excellent base for further electrolytic deposition of additional copper or other metals.
  • an electroless copper deposition solution comprising, in addition to water, a soluble source of cupric ions, a complexing agent effective to maintain said cupric ions in solution at pH levels below 5.0, and a reducing agent effective to reduce cupric ions to copper as a deposited conductive metal film on a catalyzed non-conductive surface of a substrate when in contact with said solution, wherein said reducing agent is a soluble source of hypophosphite ions; said solution having a pH of from about 2.0 to 3.5 and said complexing agent being selected to be effective for coordination with said cupric ions within that range to prevent their precipitation from said solution, wherein said solution is free of significant concentrations of anions which would interfere if present with the reduction of the cupric ions by said hypophosphite reducing agent to produce said conductive copper film on a catalyzed surface of a substrate placed in contact with said solution.
  • a method of electrolessly depositing a copper plating on the surface of a substrate comprising the steps of: preparing a catalyzed, non-conductive surface of the substrate to render it more receptive to plating; immersing the substrate in a plating solution comprising, in addition to water, a soluble source of cupric ions, a complexing agent effective to maintain said cupric ions in solution, and a reducing agent effective to reduce said cupric ions to copper as a deposited metal conductive metal film on the prepared surface of the substrate when in contact with the solution, wherein said reducing agent is a soluble source of hypophosphite ions; selecting said complexing agent to be effective at pH levels of 2 to 3.5 for complexing the cupric ions; maintaining the pH of the solution in the range of 2 to 3.5; and maintaining said solution free of significant concentrations of anions which would interfere if present with the reduction of the cupric ions by said hypophosphite reducing agent to produce
  • Plating solutions embodying the invention concept include the usual major catergories of components; namely, a source of cupric ions and a solvent for these, usually water; complexing agent or mixtures thereof; and hypophosphite reducing agent.
  • the most effective complexing agents now known for the electroless copper baths of the invention are N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA), ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and alkali metal salts of these. These complexors will provide an electrically conductive copper film on a properly catalyzed non-conductive substrate in the pH range of 2 to 3.5, provided detrimental anions are not in solution.
  • cupric ion copper
  • cupric sulfate, nitrate or fluoborate can be used, and in contrast the cupric halides such as chloride, bromide, etc., also acetate, should be avoided as these will not allow deposition of an electrically conductive copper film when they are significantly present in solution.
  • Standard acid or alkaline adjustments can be used, such as by addition of sulfuric acid to lower pH and sodium or potassium hydroxide to raise pH.
  • an acid or base which would introduce one of the detrimental anions, for example hydrochloric acid must be avoided to keep the bath operative.
  • Concentrations of components can have a wide range and can be optimized within the range to produce the preferred conditions.
  • the concentra-- tion of the amine complexors such as EDTA and HEEDTA in solution is preferably at about one-to-one on a mole ratio basis with the cupric ion, while the NTA complexor is preferably on a two-to-one mole ratio with the cupric ion.
  • Lesser amounts of complexor will of course leave some copper uncomplexed. This can be tolerated within limits, provided precipitation of particles is insufficient to interfere with the desired degree of luster, smoothness, etc. in the finished plate.
  • On the higher ratio side there is no problem, as excess of complexor does not hinder the operation of the bath and in fact a slight excess can be helpful to accommodate for conditions of temporary, locally high copper concentration which may arise during bath replenishment operations.
  • hypophosphite is the most readily available hypophosphite material and is accordingly the preferred form of this reducing agent.
  • Hypophosphorous acid however is also available and could be used in conjunction with pH adjusters which might be required when using the acid.
  • concentration the optimum level is that which is sufficient to give an adequate copper film.
  • Working with large excess of reducer in solution does not normally impede bath operation, but neither does it offer any advantage.
  • the following examples illustrate preferred conditions for practicing the invention.
  • a typical workpiece comprising an automotive component molded of standard- commercial plating grade ABS is first cleaned to remove surface grime, oil, etc.
  • An alkaline cleaning solution is typically used here.
  • This is followed by chemical etch using mixed chromic-sulfuric or all chromic acid, also standard in the industry.
  • Typical operating conditions, concentrations and time of treatment are disclosed in U.S. Patent No. 3,515,649.
  • the workpiece is catalyzed. This can be accomplished in the "one-step" method using a mixed palladium- tin catalyst of commercial type. Such a catalyst is disclosed in U.S. Patent No. 3,352,518, along with its method of use.
  • accelerating solution a so-called "accelerating solution”.
  • accelerating baths can be employed, for example the one discfosed in the above mentioned patent No. 3,352,518, such accelerating baths generally consisting of an acid solution.
  • Alkaline accelerators such as sodium hydroxide solution have also been used successfully.
  • the workpiece is then ready after further rinsing for copper plating.
  • the novel copper bath used in this example has the following composition:
  • the bath is maintained at 155°F. (68°C) and when the work is immersed in it for 10 minutes, the thickness of copper plate obtained is 11 microinches (0.28 ⁇ m). In 30 minutes the thickness of deposit is 24 microinches (0.61 ⁇ m). The deposit is bright pink, a visual characteristic indicating good electrical conductivity. Coverage is complete on the catalyzed surface, and the deposit is well-adhered and is free of blisters and roughness.
  • This electroless plated substrate is rinsed, then placed in a standard electrolytic copper strike bath similar to any of those described in U.S. Patent Nos. 3,203,878, 3,257,294, 3,267,010 or 3,288,690, for example.
  • the electroplating is carried out at about 2 volts at a rate of about 20 amperes per square foot. Generally this is maintained for about 1 1/2 minutes, or until the thickness of deposit is sufficient to provide greater current-carrying capability. At such time the plating rate may then be increased, as for example to about 4 volts at 40 amperes per square foot (430.6 Amp - m- 2 ), and is continued until the total required thickness of copper is obtained.
  • the workpiece may be further electroplated with nickel, chromium, gold, etc., as may be required for any given application, using standard electroplating techniques. Much of the restriction on initial current density depends on the size and physical complexity of parts, along with the amount of rack contact area available per area of workpiece. If enough contacts are used, the need to monitor initial current densities is less critical; however in production experience, adequate rack contacts cannot always be found.
  • Peel strength tests on plated workpieces obtained from baths in accordance with this example show adherence values of about 8-10 pounds per inch (1.43-1.79 kg. cm- 1 ) for the copper deposit on ABS substrates. Similar levels of peel strength are obtained for other thermoplastic substrates including polyphenylene oxide, polypropylene, etc., as well as thermosetting substrates such as phenolic, epoxy, etc.
  • An electroless copper bath identical in all respects to that of the foregoing example is prepared except that a different complexor is used.
  • the complexor is "Hampene Na4" (Registered Trade Mark for tetrasodium EDTA) at the same concentration (0.05M) as before and the pH is again 3.
  • a bath temperature of 155°F (68.3°C) a bright pink electroless'copper deposit of 11 microinches (0.28 pm) is obtained in 10 minutes, which increases to 25 microinches (0.64 pm) in 30 minutes. Coverage of the workpiece is complete on the catalyzed surface, and the deposit is free of blisters and roughness and is well adhered to the substrate.
  • the deposit forms an excellent base for further metal plating to build up a desired total thickness.
  • adhesion tests made on the ABS substrate plated in accordance with this example show peel strengths which range from 8-10 pounds per inch (1.43-1.79 kg. cm- 1 ).
  • ABS workpiece is prepared for electroless plating in the manner described.
  • the electroless copper bath here is again identical to that of the first example except for complexor, which in this case is nitrilotriacetic acid (NTA) at 0.10M.
  • NTA nitrilotriacetic acid
  • a bright pink adherent copper deposit of 14 microinches (0.36 pm) is obtained in 10 minutes, and 27 microinches (0.69 um) in 30 minutes.
  • adhesion values 8-10 pounds per inch (1.43-1.79 kg - cm- 1 ) peel strength on ABS is recorded.
  • ABS workpiece is prepared for electroless plating as described in Example I.
  • the electroless copper bath here is again identical to that of Example I except for the copper salt, which in this case is copper fluoborate at 0.04M.
  • the copper salt which in this case is copper fluoborate at 0.04M.
  • a bright pink adherent copper deposit of 14 microinches (0.36 ⁇ m) is obtained in 10 minutes, and 29 (0.74 ⁇ m) microinches in 30 minutes.
  • adhesion values 8-10 pounds per inch (1.43-1.79 kg - cm- 1 ) peel strength on ABS is recorded.
  • ABS workpiece is prepared for electroless plating as described in Example I.
  • the electroless copper bath here is identical to that of Example II except for the copper salt which in this case is copper fluoborate at 0.04M.
  • the copper salt which in this case is copper fluoborate at 0.04M.
  • a bright pink adherent copper deposit of 12 microinches (0.30 ⁇ m) is obtained in 10 minutes, and 26 microinches (0.66 ⁇ m) in 30 minutes.
  • adhesion values 8-10 pounds per inch (1.43-1.79 kg - cm- 1 ) peel strength on ABS is recorded.
  • ABS workpiece is prepared for electroless plating as described in Example I.
  • the electroless copper bath here is again identical to that of Example I except for the coppr salt which in this case is copper nitrate at 0.04M.
  • the coppr salt which in this case is copper nitrate at 0.04M.
  • a good pink adherent copper deposit of 12 microinches (0.30 ⁇ m) is obtained in 10 minutes.
  • adhesion values of 8-10 pounds per inch (1.43-1.79 kg cm-') peel strength on ABS is recorded.
  • ABS workpiece is prepared for electroless plating as described in Example I.
  • the electroless copper bath here is again identical to that of Example I except for the copper salt which in this case is copper chloride at 0.04M.
  • the copper salt which in this case is copper chloride at 0.04M.
  • the copper salt which in this case is copper chloride at 0.04M.
  • no plating of a conductive copper film was obtained.
  • ABS workpiece is prepared for electroless plating as described in Example I.
  • the electroless copper bath here is again identical to that of Example I except for the copper salt which in this case is copper acetate at 0.04M.
  • the copper salt which in this case is copper acetate at 0.04M.
  • a dark brownish black film formed on the workpiece. The film was not appreciably conductive, and not useful for subsequent electroplating.
  • ABS workpiece is prepared for electroless plating as described in Example I.
  • the electroless copper bath here is again identical to that of Example I except that the copper salt in this case is copper bromide at 0.04M.
  • the copper salt in this case is copper bromide at 0.04M.
  • the solution pH of 3 no plating of a conductive copper film was obtained.
  • Table A gives a summary of results along these lines. The table shows that a wide variation of the copper concentration and reducer concentration can be utilized and still give good pink, conductive copper films. This is a positive benefit for commercial installations where varying parameters are experienced.
  • thermosetting substrates of the phenolformaldehyde as well as epoxy types can be plated in the invention baths, as can other types of thermoset plastics.
  • the invention is especially applicable to plating on plastics; that is, to applications where the plated part or workpiece is required to have a metal finish for decorative or protective purposes.
  • Automobile appliance and hardware parts are fields in which such applications more frequently arise. In such applications it is usually most practical to apply, initially, a thin deposit of copper by electroless deposition, after which additional thicknesses of copper, nickel, chromium, for example, or other metal can be added more rapidly and economically by standard electrodepositioh procedures.
  • the hypophosphite-reduced electroless copper baths of this invention are particularly suited for such applications. In this system the plating rate of copper on palladium/tin catalyzed plastic substrates is initially fast but slows as the copper thickness builds.
  • the preparation of the surface of the substrate generally includes the chromic-sulfuric or all- chromic etch procedure mentioned above of bare plastic surfaces.
  • the copper baths of the invention can be used, however, for printed circuitboard applications employing, for example, the "PLADD" process of MacDermid Incorporated, Waterbury, Connecticut, disclosed in U.S. Patent No. 3,620,933. In that system, a different substrate preparation is used, preliminary to electroless deposition of the copper. This is illustrated by the following example.
  • the workpiece here is to comprise a printed circuitboard which takes the form initially of a blank laminate consisting of aluminum foil bonded to a fiberglass reinforced epoxy resin substrate.
  • this blank laminate is placed in a hydrochloric acid bath to chemically strip off the aluminum foil, leaving the surface of the resin substrate especially suited for subsequent reception of electroless metal deposition.
  • This preliminary operation replaces the chromic-sulfuric etch step mentioned previously.
  • the stripped substrate after careful rinsing, is then catalyzed, following the same procedure of palladium-tin catalysis described in Example I.
  • the catalyzed board is then copper plated, using the same copper solution described in that earlier example. This produces a thin copper deposit across the entire surface of the substrate.
  • a mask or resist is then applied, as by screening, photo- polymeric development, etc., to define a desired printed circuit.
  • the masked (thin-plated) substrate is then further plated in an electrolytic bath, using the initial electroless deposit as a "bus" to build up additional metal thickness in the unmasked regions of the circuitboard.
  • the resist or mask is next chemically dissolved and the board is placed in a suitable copper etchant solution, such as that disclosed in U.S. Patent No. 3,466,208, for a time sufficient to remove the thin initial copper deposit previously covered by the resist, but insufficient to remove the substantially thicker circuit- defining regions of copper (or other metal) built up in the electrolytic plating bath.
  • This technique is sometimes referred to in the art as a semi- additive plating process.
  • the invention is applicable to the "subtractive" procedure for preparation of printed circuitboards having through-holes for interconnecting conductor areas on opposite surfaces of standard copper foil clad laminates.
  • the through-holes are punched in the blank board and the walls of the through-holes plated with copper electrolessly, using the copper solution of this invention after proper catalyzation of the . substrate. Additional thickness of the wall deposit can be provided by electrolytic deposition, if desired.
  • a resist is applied to produce a prescribed circuit pattern, and any exposed copper foil is then etched away, leaving the circuit pattern and through-hole interconnections.
  • the resist may or may not then be removed, depending on further plating requirements, such as gold plating of connector tab areas on the circuit, solder coating, etc.

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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)
  • Manufacturing Of Printed Wiring (AREA)

Claims (10)

1. Lösung zur stromlosen Niederschlagung von Kupfer, die zusätzlich zu Wasser eine lösliche Kupferionenquelle, ein komplexierendes Agens zur Aufrechterhaltung der Kupferionen in Lösung bei pH-Werten niedriger als 5,0 und ein Reduzieragens zur Reduzierung von Kupferionen zu Kupfer als niedergeschlagener leitender Metallfilm auf einer katalysierten, nichtleitenden Oberfläche eines Substrates bei Kontakt mit der genannten Lösung enthält, dadurch gekennzeichnet, daß das Reduzieragens eine lösliche Hypophosphitionenquelle ist, daß die genannte Lösung einen pH-Wert von etwa 2,0 bis 3,5 aufweist, daß das komplexierende Agens ausgewählt ist, um für die Koordination mit den Kupferionen innerhalb dieses Bereiches wirksam zu sein, um deren Ausfällung aus der genannten Lösung zu verhindern, daß die Lösung von bedeutenden Anionen-Konzentrationen frei ist, die bei ihrer Anwesenheit die Reduktion der Kupferionen durch das hypophosphite Reduzieragens stören würde, um den leitenden Kupferfilm auf einer katalysierten Oberfläche eines mit der Lösung in Kontakt gebrachten Substrates zu bilden.
2. Lösung zur stromlosen Niederschlagung von Kupfer nach Anspruch 1, dadurch gekennzeichnet, daß die genannte Lösung im wesentlichen frei ist von störenden Ionen aus der Gruppe, die aus Halogeniden und Acetaten besteht.
3. Lösung zur stromlosen Niederschlagung von Kupfer nach Anspruch 2, dadurch gekennzeichnet, daß das komplexierende Agens ausgewählt ist, aus N - hydroxyäthyl - äthylendiamintriacetatsäure (HEEDTA), Äthylendiamin-tetraacetatsäure (EDTA) und Nitrilotriacetatsäure (NTA).
4. Lösung zur stromlosen Niederschlagung von Kupfer nach Anspruch 2 oder 3, dadurch gekennzeichnet, daß die lösliche Kupferionenquelle aus der Gruppe ausgewählt ist, die aus Kupfersulfat, Kupferfluorborat und Kupfernitrat besteht.
5. Lösung zur stromlosen Niederschlagung von Kupfer nach Anspruch 3, dadurch gekennzeichnet, daß das Molverhältnis von HEEDTA und EDTA zum Kupferion etwa 1:1 und daß das Molverhältnis von NTA zum Kupferion etwa 2:1 beträgt.
6. Verfahren zur stromlosen Niederschlagung einer Kupferplattierung auf der Oberfläche eines Substrates, enthaltend die Schritte der Vorbereitung einer katalysierten, nichtleitenden Oberfläche des Substrates, um dieses für die plattierung aufnahmebereiter zu machen; Eintauchen des Substrates in eine Plattierungslösung, die zusätzlich zu Wasser eine lösliche Kupferionenquelle, ein komplexierendes Agens zum Beibehalten der Kupferionen in Lösung und eine Reduzieragens zum Reduzieren der Kupferionen zu Kupfer als niedergeschlagener, metalleitender Metallfilm auf der vorbereiteten Oberfläche des Substrates bei Kontakt mit der Lösung enthält, dadurch gekennzeichnet, daß das Reduzieragens eine lösliche Quelle aus Hypophosphitionen ist, daß ein komplexierendes Agens ausgewählt wird, das bei pH-Werten von 2,0 bis 3,5 zum Komplexieren der Kupferionen worksam ist, daß der pH-Wert der Lösung in dem Bereich von 2,0 bis 3,5 aufrechterhalten wird und daß die Lösung von bedeutenden Anionen-konzentrationen freigehalten wird, die bei ihrer Anwesenheit die Reduzierung der Kupferionen durch das hypophosphite Reduzieragens stören würde, um den leitenden Kupferfilm auf dem Substrat zu erzeugen.
7. Verfahren zur stromlosen Niederschlagung einer Kupferplattierung auf der Oberfläche eines Substrates nach Anspruch 6, dadurch gekennzeichnet, daß die Plattierungslösung im wesentlichen freigehalten wird von störenden Anionen der Gruppe, die aus Halogeniden und Acetaten beseht.
8. Verfahren zur stromlosen Niederschlagung einer Kupferplattierung auf der Oberfläche eines Substrates nach Anspruch 7, dadurch gekennzeichnet, daß das komplexierende Agens aus einer Gruppe ausgewählt wird, die aus HEEDTA, EDTA und NTA besteht.
9. Verfahren zur stromlosen Niederschlagung einer Kupferplattierung auf der Oberfläche eines Substrates nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die lösliche Kupferionenquelle aus einer Gruppe ausgewählt wird, die aus Kupfersulfat, Kupferfluorborat und Kupfernitrat besteht.
10. Verfahren zur stromlosen Niederschlagung einer Kupferplattierung auf der Oberfläche eines Substrates nach Anspruch 8, dadurch gekennzeichnet, daß das Molverhältnis von HEEDTA und EDTA zum Kupferion etwa 1:1 und das Moverhältnis von NTA zum Kupferion etwa 2:1 beträgt.
EP19820900581 1981-12-21 1981-12-21 Elektrofreie kupferniederschlagslösungen Expired EP0096034B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1981/001726 WO1983002287A1 (en) 1981-12-21 1981-12-21 Electroless copper deposition solutions

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EP0096034A1 EP0096034A1 (de) 1983-12-21
EP0096034A4 EP0096034A4 (de) 1984-05-03
EP0096034B1 true EP0096034B1 (de) 1986-09-10

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JP (1) JPS58502101A (de)
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US3515563A (en) * 1967-12-28 1970-06-02 Photocircuits Corp Autocatalytic metal plating solutions
US4279948A (en) * 1978-05-25 1981-07-21 Macdermid Incorporated Electroless copper deposition solution using a hypophosphite reducing agent
US4265943A (en) * 1978-11-27 1981-05-05 Macdermid Incorporated Method and composition for continuous electroless copper deposition using a hypophosphite reducing agent in the presence of cobalt or nickel ions

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JPS58502101A (ja) 1983-12-08
DE3175316D1 (en) 1986-10-16
EP0096034A4 (de) 1984-05-03
EP0096034A1 (de) 1983-12-21
WO1983002287A1 (en) 1983-07-07

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