EP0018592A1 - Process for the regeneration of ammoniacal etching solutions for etching metallic copper - Google Patents

Process for the regeneration of ammoniacal etching solutions for etching metallic copper Download PDF

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EP0018592A1
EP0018592A1 EP80102194A EP80102194A EP0018592A1 EP 0018592 A1 EP0018592 A1 EP 0018592A1 EP 80102194 A EP80102194 A EP 80102194A EP 80102194 A EP80102194 A EP 80102194A EP 0018592 A1 EP0018592 A1 EP 0018592A1
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Prior art keywords
etching
copper
ammoniacal
regeneration
poorly soluble
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German (de)
French (fr)
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Efthimios Dr. Konstantouros
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Siemens AG
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Siemens AG
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions

Definitions

  • the invention relates to a method for regenerating ammoniacal etching solutions for etching metallic copper, in particular for etching galvanized printed circuit boards.
  • Atmospheric oxygen is meant as 0 2 .
  • Air oxidation from Gu + to Cu ++ takes place spontaneously in the spray etching machine. A separate air supply is not necessary.
  • mixtures of NH 4 Cl and (NH 4 ) 2 CO 3 are preferably used as NH 4 salts.
  • the overall reaction for example with chloride, looks as follows:
  • the metallic copper is oxidized to [Cu (NH 3 ) 4 ] ++ ion using ammonia, ammonium salts and atmospheric oxygen.
  • the chemicals NH 3 and NH 4 salts are metered into the etching machine as aqueous solutions, so-called “supplementary solutions", during the etching process.
  • the resulting highly copper-containing etching concentrates are collected as an overflow and given to a relevant copper processing company, where, to our knowledge, the NH 3 is destroyed with chlorine and the copper is cemented with scrap iron (Fe). The transfer of the overflow to this company is associated with transport and processing costs.
  • the invention has for its object to provide a method for the regeneration of the ammoniacal etching solutions with which the NH 3 and NH 4 salts and the etched copper can be recovered in a relatively simple manner.
  • the recycling- developed to solve the task Veriahren consists in that with the help of a metal that is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium, the Cu ++ ion is reduced to metallic copper and the etching chemicals are re-formed, the metal itself becoming one poorly soluble hydroxide is oxidized.
  • Al is preferably used, since it does not form soluble amine complexes and does not release any toxic ions. The following reactions take place:
  • the decoupled solution is separated from the Cu and Al (OH) 3 sludge by filtration and reused as a supplementary solution for the etching process.
  • the cement copper is a heavy powder and is relatively easy to separate from the lighter hydroxide.
  • the ammonia property of dissolving some Al (OH) 3 as aluminate is completely prevented by the presence of the NH 4 salts.
  • the copper cementation is carried out in the form of an internal electrolysis, the deposited materials copper and aluminum hydroxide being obtained separately. This facilitates the regeneration process.
  • the anode compartment 3 is filled with supplementary solution and the cathode compartment 4 with a mixture of supplementary solution and etching solution.
  • An Al plate 5 is immersed in the anode compartment 3 as a base electrode as a soluble anode and a Cu plate 6 is immersed in the cathode compartment 4 as a nobler electrode.
  • electrolysis without an external power source internal electrolysis
  • the Al plate 5 emits electrons to the Cu plate 6 and decays itself into Al (OH) 3 after the following reaction:
  • the liquid in the cathode compartment 4 is completely decoupled, pure supplementary solution is formed. Part of it is removed and replaced with an etching solution.
  • the supplementary solution removed is metered into the etching machine for the etching process.
  • the overflow of the etching machine is decoupled in batches in the cathode space 4 and converted into supplementary solution.
  • the cathode liquid preferably consists of approx. 95% supplementary solution and 5% etching solution. This is necessary because of the difference in density (1.05 g / ml for the supplementary solution and 1.2 g / ml for the etching solution with approx.
  • the supplementary solution in the anode compartment 3 is separated from the Al (OH) 3 sludge by filtration and used again as the anode liquid.
  • the deposited Al (OH) 3 can be discarded.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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Abstract

Das erfindungsgemäße Recycling-Verfahren für ammoniakalische Ätzlösungen, welche außer den ätzfähigen Tetramminkupfer(II)-Ionen, Ammoniak und Ammoniumchlorid enthalten, besteht darin, daß mit Hilfe eines Metalls, das unedler ist als Kupfer und im pH-Bereich des Ätzmediums ein schwerlösliches Hydroxid bildet, das Cu<+><+>- Ion zu metallischem Kupfer reduziert wird und die Ätzchemikalien zurückgebildet werden, wobei das Metall selbst zu einem schwerlöslichen Hydroxid oxidiert wird. Der Regenerierprozeß wird vorzugsweise mit Hilfe eines Diaphragmas (2) als Elektrolyseprozeß ohne äußere Stromquelle durchgeführt, wobei das geätzte Kupfer im Kathodenraum (4) und das Al(OH)3 im Anodenraum (3) getrennt abgeschieden werden.The recycling process according to the invention for ammoniacal etching solutions which, in addition to the etchable tetrammin copper (II) ions, contain ammonia and ammonium chloride, consists in that with the aid of a metal which is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium , the Cu <+> <+> ion is reduced to metallic copper and the etching chemicals are regressed, the metal itself being oxidized to a poorly soluble hydroxide. The regeneration process is preferably carried out using a diaphragm (2) as an electrolysis process without an external power source, the etched copper in the cathode compartment (4) and the Al (OH) 3 in the anode compartment (3) being separated.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Regenerierung ammoniakalischer Ätzlösungen zum Ätzen von metallischem Kupfer, insbesondere zum Ätzen von galvanisierten Leiterplatten.The invention relates to a method for regenerating ammoniacal etching solutions for etching metallic copper, in particular for etching galvanized printed circuit boards.

Beispielsweise ist aus der DE-OS 26 25 869 bekannt, zum Ätzen von kupferkaschierten Leiterplatten wäßrige Lösungen zu verwenden, welche neben Tetramminkupfer(II)-Ionen noch Ammoniak und Ammoniumsalze enthalten. Beim Ätzen von metallischem Kupfer laufen hierbei folgende Reaktionen ab:

Figure imgb0001
Figure imgb0002
 For example, it is known from DE-OS 26 25 869 to use aqueous solutions for etching copper-clad printed circuit boards which, in addition to tetrammine copper (II) ions, also contain ammonia and ammonium salts. The following reactions occur when etching metallic copper:
Figure imgb0001
Figure imgb0002

Die Summe a) + b) ergibt die Gesamtreaktion c):

Figure imgb0003
The sum a) + b) gives the total reaction c):
Figure imgb0003

Als 02 ist Luftsauerstoff gemeint. Die Luftoxidation von Gu+ zu Cu++ findet in der Sprühätzmaschine spontan statt. Eine gesonderte Luftzufuhr ist nicht erforderlich.Atmospheric oxygen is meant as 0 2 . Air oxidation from Gu + to Cu ++ takes place spontaneously in the spray etching machine. A separate air supply is not necessary.

Als NH4-Salze werden nach DE-OS 26 25 869 vorzugsweise Gemische aus NH4Cl und (NH4)2CO3 verwendet. In Salzform sieht die Gesamtreaktion z.B. beim Chlorid wie folgt aus:

Figure imgb0004
According to DE-OS 26 25 869, mixtures of NH 4 Cl and (NH 4 ) 2 CO 3 are preferably used as NH 4 salts. In salt form, the overall reaction, for example with chloride, looks as follows:
Figure imgb0004

Daraus ist zu ersehen, daß das metallische Kupfer unter Verbrauch von Ammoniak, Ammoniumsalzen und Luftsauerstoff zu [Cu(NH3)4] ++-Ion oxidiert wird. Die Chemikalien NH3 und NH4-Salze werden in der Praxis als wäßrige Lösungen, sog. "Ergänzungslösungen", der Ätzmaschine während des Ätzprozesses zudosiert.It can be seen from this that the metallic copper is oxidized to [Cu (NH 3 ) 4 ] ++ ion using ammonia, ammonium salts and atmospheric oxygen. In practice, the chemicals NH 3 and NH 4 salts are metered into the etching machine as aqueous solutions, so-called "supplementary solutions", during the etching process.

Die hierbei entstehenden stark kupferhaltigen Ätzkonzentrate werden als Überlauf gesammelt und einem ein- schlägigen Kupferverarbeitungsbetrieb abgegeben, wo, unseres Wissens nach, das NH3 mit Chlor zerstört und das Kupfer mit Schrott (Fe) auszementiert wird. Die Abgabe des Überlaufs an diesen Betrieb ist mit Transport-und Verarbeitungskosten verbunden.The resulting highly copper-containing etching concentrates are collected as an overflow and given to a relevant copper processing company, where, to our knowledge, the NH 3 is destroyed with chlorine and the copper is cemented with scrap iron (Fe). The transfer of the overflow to this company is associated with transport and processing costs.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Regenerierung der ammoniakalischen Ätzlösungen zu schaffen, mit dem auf relativ einfache Weise die beim Kupferätzen verbrauchten Stoffe NH3 und NH4-Salze sowie das geätzte Kupfer zurückgewonnen werden können. Das zur Lösung der gestellten Aufgabe entwickelte Recycling-Veriahren besteht darin, daß mit Hilfe eines Metalls, das unedler ist als Kupfer und im pH-Bereich des Ätznediums ein schwerlösliches Hydroxid bildet, das Cu++-Ion zu metallischem Kupfer reduziert wird und die Ätzchemikalien zurückgebildet werden, wobei das Metall selbst zu einem schwerlöslichen Hydroxid oxidiert wird.The invention has for its object to provide a method for the regeneration of the ammoniacal etching solutions with which the NH 3 and NH 4 salts and the etched copper can be recovered in a relatively simple manner. The recycling- developed to solve the task Veriahren consists in that with the help of a metal that is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium, the Cu ++ ion is reduced to metallic copper and the etching chemicals are re-formed, the metal itself becoming one poorly soluble hydroxide is oxidized.

Von den für den Kupferzementationsprozeß geeigneten unedlen Metallen Al, Zn, Mg und Fe wird bevorzugt Al verwendet, da es keine löslichen Amminkomplexe bildet und keine toxischen Ionen abgibt. Es laufen hierbei folgende Reaktionen ab:

Figure imgb0005
Figure imgb0006
 Of the base metals Al, Zn, Mg and Fe, which are suitable for the copper cementation process, Al is preferably used, since it does not form soluble amine complexes and does not release any toxic ions. The following reactions take place:
Figure imgb0005
Figure imgb0006

Die Summe von e) und f) ergibt die Gesantreaktion g):

Figure imgb0007
The sum of e) and f) gives the total response g):
Figure imgb0007

Aus der Gleichung g) ist zu ersehen, daß mit Hilfe von Al praktisch die Umkehrung des Ätzprozesses nach Gleichung c) erreicht wird.From equation g) it can be seen that the inversion of the etching process according to equation c) is practically achieved with the aid of Al.

Die Rea.ktion g) sieht in der Chloridform wie folgt aus:

Figure imgb0008
The reaction g) looks like this in the chloride form:
Figure imgb0008

Ähnlich verläuft die Reaktion mit Fe:

Figure imgb0009
The reaction with Fe is similar:
Figure imgb0009

Durch Filtrieren wird die entkupferte Lösung vom Cu und Al(OH)3-Schlamm getrennt und als Ergänzungslösung für den Ätzprozeß wiederverwendet. Das Zementkupfer liegt als schweres Pulver vor und läßt sich von dem leichteren Hydroxid relativ leicht abtrennen. Ergänzend soll betont werden, daß die Eigenschaft des Ammoniaks, etwas Al(OH)3 als Aluminat aufzulösen, durch die Anwesenheit der NH4-Salze völlig unterbunden wird. Durch die vorzugsweise Verwendung eines Diaphragmas wird die Kupferzementation in Form einer inneren Elektrolyse durchgeführt, wobei die abgeschiedenen Stoffe Kupfer und Aluminiumhydroxid getrennt erhalten werden. Dies erleichtert den Regenerierprozeß.The decoupled solution is separated from the Cu and Al (OH) 3 sludge by filtration and reused as a supplementary solution for the etching process. The cement copper is a heavy powder and is relatively easy to separate from the lighter hydroxide. In addition, it should be emphasized that the ammonia property of dissolving some Al (OH) 3 as aluminate is completely prevented by the presence of the NH 4 salts. By preferably using a diaphragm, the copper cementation is carried out in the form of an internal electrolysis, the deposited materials copper and aluminum hydroxide being obtained separately. This facilitates the regeneration process.

Eine zur Durchführung des erfindungsgemäßen Verfahrens geeignete Apparatur ist in der Zeichnung dargestellt.An apparatus suitable for carrying out the method according to the invention is shown in the drawing.

Sie besteht aus einem Behälter 1, der mittels eines Diaphragmas 2 in einem Anodenraum 3 und einem Kathodenraum 4 unterteilt ist. Der Anodenraum 3 ist mit Ergänzungslösung und der Kathodenraum 4 mit einem Gemisch aus Ergänzungslösung und Ätzlösung gefüllt. In den Anodenraum 3 wird als unedle Elektrode eine Al-Platte 5 als lösliche Anode und in den Kathodenraum 4 als edlere Elektrode eine Cu-Platte 6 eingetaucht. Durch Verbinden beider Platten mit einem Metalldraht 7 beginnt sofort eine Elektrolyse ohne äußere Stromquelle (innere Elektrolyse). Hierbei gibt die Al-Platte 5 an die Cu-Platte 6 Elektronen ab und zerfällt selbst in Al(OH)3 nach folgender Reaktion:

Figure imgb0010
It consists of a container 1, which is divided into an anode space 3 and a cathode space 4 by means of a diaphragm 2. The anode compartment 3 is filled with supplementary solution and the cathode compartment 4 with a mixture of supplementary solution and etching solution. An Al plate 5 is immersed in the anode compartment 3 as a base electrode as a soluble anode and a Cu plate 6 is immersed in the cathode compartment 4 as a nobler electrode. By connecting both plates with a metal wire 7, electrolysis without an external power source (internal electrolysis) begins immediately. Here, the Al plate 5 emits electrons to the Cu plate 6 and decays itself into Al (OH) 3 after the following reaction:
Figure imgb0010

An der Cu-Elektrode wird gleichzeitig fest haftendes Kupfer abgeschieden:

Figure imgb0011
Firmly adhering copper is deposited on the Cu electrode at the same time:
Figure imgb0011

Als Gesamtreaktion ergibt sich die bereits erwähnte Gleichung g).The above-mentioned equation g) results as the overall reaction.

Auf diese Weise wird die Flüssigkeit im Kathodenraum 4 völlig entkupfert, es entsteht reine Ergänzungslösung. Ein Teil davon wird herausgenommen und durch Ätzlösung ersetzt. Die entnommene Ergänzungslösung wird der Ätzmaschine für den Ätzprozeß zudosiert. Der Überlauf der Ätzmaschine wird, wie oben beschrieben, im Kathodenraun 4 chargenweise entkupfert und in Ergänzungslösung umgewandelt. Die Kathodenflüssigkeit besteht vorzugsweise jeweils vor Beginn der Elektrolyse aus ca. 95% Ergänzungslösung und 5% Ätzlösung. Dies ist wegen des Dichte-Unterschieds (1,05 g/ml bei der Ergänzungslösung und 1,2 g/ml bei der Ätzlösung mit ca. 150 g Cu++/1) notwendig, um eine Wanderung von Ätzlösung in den Anodenraum 3 zu vermeiden, d.h. eine direkte Kupferzementation an der Al-Platte zu verhindern. Die Ergänzungslösung im Anodenraum 3 wird von Zeit zu Zeit durch Filtrieren vom Al(OH)3-Schlamm abgetrennt und wieder als Anodenflüssigkeit verwendet. Das abgeschiedene Al(OH)3 kann verworfen werden.In this way, the liquid in the cathode compartment 4 is completely decoupled, pure supplementary solution is formed. Part of it is removed and replaced with an etching solution. The supplementary solution removed is metered into the etching machine for the etching process. As described above, the overflow of the etching machine is decoupled in batches in the cathode space 4 and converted into supplementary solution. Before the start of electrolysis, the cathode liquid preferably consists of approx. 95% supplementary solution and 5% etching solution. This is necessary because of the difference in density (1.05 g / ml for the supplementary solution and 1.2 g / ml for the etching solution with approx. 150 g Cu ++ / 1) in order for migration of the etching solution into the anode compartment 3 avoid, ie to prevent direct copper cementation on the Al plate. From time to time, the supplementary solution in the anode compartment 3 is separated from the Al (OH) 3 sludge by filtration and used again as the anode liquid. The deposited Al (OH) 3 can be discarded.

Claims (5)

1. Verfahren zur Regenerierung ammoniakalischer Ätzlösungen zum Ätzen von metallischem Kupfer, insbesondere zum Ätzen von galvanisierten Leiterplatten, dadurch gekennzeichnet , daß mit Hilfe eines Metalls, das unedler ist als Kupfer und im pH-Bereich des Ätzmediums ein schwerlösliches Hydroxid bildet, das Cu++-Ion zu metallischem Kupfer reduziert wird und die Ätzchemikalien zurückgebildet werden, wobei das unedle Metall selbst zu einem schwerlöslichen Hydroxid oxidiert wird.1. A process for the regeneration of ammoniacal etching solutions for etching metallic copper, in particular for the etching of galvanized printed circuit boards, characterized in that with the aid of a metal that is less noble than copper and in the pH range of the etching medium forms a poorly soluble hydroxide, the Cu ++ Ion is reduced to metallic copper and the etching chemicals are regressed, the base metal itself being oxidized to a poorly soluble hydroxide. 2. Verfahren nach Anspruch 1, dadurch gekenneichnet, daß als Metall Aluminium bevorzugt wird.2. The method according to claim 1, characterized in that aluminum is preferred as the metal. 3. Verfahren nach Anspruch 1 und 2, wobei das anmoniakalische Ätzmittel Tetramminkupfer(II)-Ionen, Ammoniak und Ammoniumsalze, vorzugsweise Ammoniumchlorid und Ammoniumcarbonat, enthält, dadurch gekennzeichnet , daß das abgeätzte Kupfer und das bei der Ätzung verbrauchte Ammoniak und die Ammoniumsalze nach folgender Hauptreaktion zurückgewonnen werden:
Figure imgb0012
 3. The method according to claim 1 and 2, wherein the ammoniacal etchant contains tetrammine copper (II) ions, ammonia and ammonium salts, preferably ammonium chloride and ammonium carbonate, characterized in that the etched copper and the ammonia consumed in the etching and the ammonium salts according to the following Main reaction to be recovered:
Figure imgb0012
 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Ammoniak- und Ammoniumsalz-Lösung durch Filtrieren gereinigt wird.4. The method according to any one of claims 1 to 3, characterized in that the ammonia and ammonium salt solution is purified by filtration. 5.Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet , daß der Regenerierprozeß mit Hilfe eines Diaphragmas (2) als Elektrolyseprozeß ohne äußere Stromquelle durchgeführt wird, wobei das 5 geätzte Kupfer im Kathodenraum (4) und das Al(OH)3 im Anodenraum (3) getrennt abgeschieden werden.5.The method according to any one of claims 1 to 4, characterized in that the regeneration process is carried out with the aid of a diaphragm (2) as an electrolysis process without an external power source, the 5 etched copper in the cathode compartment (4) and the Al (OH) 3 in Anode compartment (3) can be separated.
EP80102194A 1979-04-30 1980-04-23 Process for the regeneration of ammoniacal etching solutions for etching metallic copper Withdrawn EP0018592A1 (en)

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DE2917597 1979-04-30
DE19792917597 DE2917597A1 (en) 1979-04-30 1979-04-30 METHOD FOR REGENERATING AMMONIACAL ETCH SOLUTIONS FOR ETCHING METALLIC COPPER

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EP0393270A1 (en) * 1989-04-21 1990-10-24 Ming-Hsing Lee Process for etching copper with ammoniacal etchant solution and reconditioning the used etchant solution

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Publication number Priority date Publication date Assignee Title
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US4280887A (en) 1981-07-28
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