EP0144742B1 - Process and apparatus for regenerating an ammoniacal etching solution - Google Patents

Process and apparatus for regenerating an ammoniacal etching solution Download PDF

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Publication number
EP0144742B1
EP0144742B1 EP84113228A EP84113228A EP0144742B1 EP 0144742 B1 EP0144742 B1 EP 0144742B1 EP 84113228 A EP84113228 A EP 84113228A EP 84113228 A EP84113228 A EP 84113228A EP 0144742 B1 EP0144742 B1 EP 0144742B1
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EP
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Prior art keywords
etching solution
etching
electrolysis cell
regenerated
chamber
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EP84113228A
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German (de)
French (fr)
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EP0144742A1 (en
Inventor
Leander Fürst
Walter Holzer
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Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
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Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich GmbH
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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 an ammoniacal etching solution, which is supplied for the reoxidation of the etching agent contained in the etching solution and which at least partially flows through an electrolysis cell to recover the etched metal.
  • the invention also relates to a plant for carrying out the method.
  • Alkaline etchants are used for etching metallic objects, in particular for the production of printed circuit boards, which are also known under the name “printed circuits”, especially when the printed circuit boards to be etched are metal parts which are not resistant to acidic etching media, for example made of lead, tin or nickel, exhibit.
  • a reoxidation of the alkaline etching solution after etching off the metal is carried out with the addition of ammonia gas and / or ammonium chloride in the presence of oxygen or air.
  • the amount of metal to be deposited in the electrolysis cell is regulated depending on the metal content of the etching solution to be regenerated.
  • the metal content in the etching solution should not fall below a minimum value.
  • the aim is to minimize the control delay. If the depleted etching solution is introduced into the etching chamber or the regenerated etching solution flowing to the etching chamber, the control delay also depends on the location and the local distance between the etching chamber and the regeneration system. The number of etching chambers connected to the regeneration system also influences the regulation.
  • the object of the invention is to provide a method for regenerating an etching solution which has a control which responds quickly to a change in the metal concentration in the etching solution and which works independently of local conditions in the installation of the regeneration system and etching chamber.
  • the etching solution depleted in metal ions and removed from the electrolytic cell is introduced directly into the etching solution to be regenerated, which flows away from the etching chamber, so that with the devices measuring the metal ion concentration in the etching solution, the actual value of the metal fraction in depleted in admixture can be achieved in a very short time of the etching solution. The dead time of the controlled system is thus significantly reduced.
  • a system for carrying out the method according to the invention is specified in claim 2.
  • the system has an inlet for the etching solution to be regenerated, which is removed from the etching chamber, and a return for regenerated etching solution to the etching chamber.
  • the etching solution is regenerated with the addition of oxygen.
  • an etchant line connected to the inlet for the etching solution to be regenerated part of the etching solution flows to an electrolysis cell for the deposition of etched metal.
  • an extraction line is connected to the electrolysis cell for the etching solution depleted in metal ions, which leads to the inflow of the etching solution to be regenerated.
  • a very compact arrangement and simple handling of the regeneration system results from the design of the system according to claim 5. Thereafter, the collecting container, electrolysis cell and delivery units for the etching solution and the oxygen supply are arranged within a common housing, which is attached to the etching chamber only via the inlet and the Connect the return.
  • a regeneration system connected to an etching chamber 1 with a rinsing chamber 2 is shown schematically.
  • the etching solution to be regenerated which contains ammonium sulfate in conjunction with copper tetrammine complex as the etchant, flows from the etching chamber 1 via an inlet 3 into a collecting container 4 which is connected to the etching chamber via a system of communicating tubes.
  • the etching solution in the inlet 3 flows in a connecting pipe in a natural gradient from the etching chamber 1 into the collecting container 4.
  • the etching solution to be regenerated is led from the collecting container 4 by means of a pump 5 via a pressure line 6 to a pipe connection 7, from which an etchant line 8 is led to an electrolysis cell 9.
  • a flow controller 10 used in the etchant line 8 determines the part of the etching solution flowing to the electrolytic cell 9.
  • a connecting line 11 to a liquid jet pump 12 is also connected to the pipe connection 7. Oxygen is introduced by means of the liquid jet pump 12 for the reoxidation of the etching solution flowing back to the etching chamber in the return 13.
  • a gas line 15 is connected to the suction nozzle 14 of the liquid jet pump, which leads into the electrolysis cell 9 in the gas space above the electrolyte and which is fed with oxygen which is formed on the anode 16 of the electrolysis cell 9 when metal is deposited on the cathode 17.
  • the liquid jet pump 12 uses the etching solution conveyed by the pump 5 via the pressure line 6 into the connecting line 11 as the working medium.
  • An ammonia line 18 leads to the supply of ammonia in the gas line 15 and is connected to a storage container 20 for ammonia which can be closed by means of a shut-off device 19.
  • Fresh ammonia can thus be introduced into the etching solution from the liquid jet pump 12 together with the gas containing oxygen drawn off from the electrolytic cell in order to regulate the pH of the etching solution.
  • the shut-off device 19 is operatively connected to a pH value measuring device 21 inserted in the etchant line 8 with a measuring electrode. If the pH falls below a predetermined permissible limit value, the shut-off device 19 is opened and ammonia is introduced into the etching solution.
  • the pH value measuring device switches the shut-off device 19 with the aid of electrical control units.
  • a pressure relief line 22 opens into the connecting line 11 and is led to the drainage of etching solution in the collecting container 4.
  • the device 23 is operatively connected to a magnetically controlled three-way valve 24 inserted at the end of the etchant line 8, to which on the one hand the end piece 8 'of the etchant line 8 leading to the electrolytic cell 9 is connected and on the other hand a bypass line 25 which opens into the collecting container 4.
  • the three-way valve 24 is open to the electrolytic cell 9. If the metal ion concentration of the etching solution falls below a predetermined value, the three-way valve 24 is switched over. The etching solution then flows off via the surrounding line 25. The electrolytic cell is switched off.
  • an electrolyte overflow 26 leads the etching solution depleted in metal ions to the collecting container 4 via a removal line 27.
  • the depleted etching solution is mixed with the etching solution to be regenerated in the collecting container and thus reduces its metal ion concentration.
  • the etching solution to be regenerated is sucked out of the collecting container 4 by the pump 5 and conveyed in the etching agent line 8 via flow controller 10 and pH value measuring device 21 to the device 23, which reacts to the reduced metal ion concentration in the etching solution.
  • a drain tank 28 which serves to empty the electrolysis cell and is connected to the bottom of the electrolysis cell 9 via an outlet 29 which can be shut off by means of a solenoid valve 30.
  • Etching solution can also flow from the electrolysis cell 9 into the drain container 28 via a second overflow 31.
  • a solvent pump 32 ensures circulation of the etching solution in the electrolytic cell 9.
  • the solvent pump dips with its suction line 33 into the drain container 28, into which the etching solution flows via the overflow 31, and conveys the etching solution back in its pressure line 35 via a filter 34 to the electrolytic cell.
  • the etching solution enters the electrolysis cell between anode 16 and cathode 17. After the electrolysis cell has been switched off, the etching solution is emptied into the drain container 28 by opening the solenoid valve 30. Before the electrolysis cell is operated again, the etching solution is conveyed back from the drain container into the electrolysis cell by means of the solvent pump 32.
  • an etching solution containing ammonium sulfate and copper tetrammine complex was used to etch copper.
  • 1501 etching solution were circulated between the etching chamber and the regeneration system.
  • the fresh etching solution contained 150 g ammonium sulfate and 50 g copper per liter.
  • the etching solution set to a pH of 9 was sprayed onto workpieces to be etched at a temperature of 50 ° C. by means of nozzles. Copper-clad printed circuit boards were etched.
  • the etching rate was 30 11m copper surface removal per minute.
  • the electrolysis cell installed in the regeneration plant had a separation rate of 600 g Cu / h.
  • the electrolysis cell operated with 860 A direct current, which corresponds with an electrode area of 860 cm 2 of a current density of 10 A / dm 2.
  • the etching solution was depleted by 20 g Cu / i as it passed through the electrolytic cell.
  • the etching solution was adjusted to its pH value of 9 as the setpoint by adding ammonia.
  • the flow controller worked at a setpoint of 30 I etching solution per hour with a control deviation of ⁇ 21 / h. If a metal concentration of 53 g Cu / I was measured by the device 23 in the etching solution when determining the metal content, the etching solution was directed to the electrolysis cell with the three-way valve in the appropriate position until the copper concentration had dropped to 50 g Cu / i. At this value, the three-way valve 24 was changed over and the electrolytic cell was switched off. The etching solution depleted of metal ions in the electrolysis cell was returned to the collecting container. There were short dead times for the controlled system.
  • the parts of the regeneration system shown schematically in the drawing are accommodated in the exemplary embodiment in a housing which has a collecting container 4, electrolysis cell 9 and the conveying units for the etching solution and the oxygen supply.
  • the conveying units include the pump 5 for conveying the etchant to be regenerated, the liquid jet pump 12 for introducing the gas containing oxygen and ammonia into the etching solution and the solvent pump 32 for circulating the etching solution in its composition as an electrolyte in the electrolytic cell 9.
  • the housing also contains flow controller 10, pH value measuring device 21 and device 23 for measuring the metal ion concentration.
  • the drain tank 28 for the electrolyte is located below the electrolysis cell - arranged in the housing next to the collecting tank 4.
  • the parts of the regeneration system are arranged in a space-saving manner in the housing.
  • the housing can only be connected to an etching chamber via inlet 3 and return 13. The local distance between the etching chamber and the regeneration system is irrelevant for the correct operation of the regeneration system.

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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)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Description

Die Erfindung bezieht sich auf ein Verfahren zum Regenerieren einer ammoniakalischen Ätzlösung, der zur Rückoxidazion des in der Ätzlösung enthaltenen Ätzmittels Sauerstoff zugeführt wird und die zumindest teilweise zur Rückgewinnung des abgeätzten Metalls eine Elektrolysezelle durchströmt. Gegenstand der Erfindung ist auch eine Anlage zur Durchführung des Verfahrens.The invention relates to a method for regenerating an ammoniacal etching solution, which is supplied for the reoxidation of the etching agent contained in the etching solution and which at least partially flows through an electrolysis cell to recover the etched metal. The invention also relates to a plant for carrying out the method.

Alkalische Ätzmittel werden zum Ätzen metallischer Gegenstände, insbesondere zur Herstellung von Leiterplatten, die auch unter der Bezeichnung «gedruckte Schaltungen» bekannt sind, vor allem dann verwendet, wenn die zu ätzenden Leiterplatten gegen saure Ätzmedien nichtbeständige Metallteile, beispielsweise aus Blei, Zinn oder Nickel, aufweisen. Eine Rückoxidation der alkalischen Ätzlösung nach Abätzen des Metalls wird unter Zugabe von Ammoniakgas und/oder Ammoniumchlorid in Gegenwart von Sauerstoff bzw. Luft durchgeführt.Alkaline etchants are used for etching metallic objects, in particular for the production of printed circuit boards, which are also known under the name “printed circuits”, especially when the printed circuit boards to be etched are metal parts which are not resistant to acidic etching media, for example made of lead, tin or nickel, exhibit. A reoxidation of the alkaline etching solution after etching off the metal is carried out with the addition of ammonia gas and / or ammonium chloride in the presence of oxygen or air.

Aus DE-OS 3 031 567 ist (entsprechend zu EP-A-0 046 522) es bekannt, in der Ätzlösung Katalysatorteilchen zu suspendieren, die das Ätzen selbst, aber auch die Rückoxidation der Ätzlösung beschleunigen und so den Zusatz chemischer Oxidationsmittel ersparen, die zu toxischen Restlösungen führen. Bei dem bekannten Verfahren werden die abgeätzten Metalle in einer Elektrolysezelle abgeschieden. Hierzu durchströmt ein Teil der Ätzlösung, die Ammoniumsulfat enthält, die Elektrolysezelle. Die abgeschiedenen Metalle werden an der Kathode der Elektrolysezelle abgeschieden, an der Anode entsteht Sauerstoff. Die an Metallionen abgereicherte Ätzlösung fliesst zur Ätzkammer zurück.From DE-OS 3 031 567 (corresponding to EP-A-0 046 522) it is known to suspend catalyst particles in the etching solution which accelerate the etching itself but also the reoxidation of the etching solution and thus save the addition of chemical oxidizing agents lead to toxic residual solutions. In the known method, the etched metals are deposited in an electrolytic cell. For this purpose, part of the etching solution containing ammonium sulfate flows through the electrolytic cell. The deposited metals are deposited on the cathode of the electrolytic cell, oxygen is generated on the anode. The etching solution depleted in metal ions flows back to the etching chamber.

Die Metallmenge, die in der Elektrolysezelle abzuscheiden ist, wird in Abhängigkeit vom Metallgehalt der zu regenerierenden Ätzlösung geregelt. Der Metallgehalt in der Ätzlösung soll einen Mindestwert nicht unterschreiten. Dabei wird eine möglichst geringe Regelverzögerung angestrebt. Wird die abgereicherte Ätzlösung in die Ätzkammer oder die zur Ätzkammer strömende regenerierte Ätzlösung eingeführt, so ist die Regelverzögerung auch vom Standort und von örtlicher Entfernung zwischen Ätzkammer und Regenerieranlage abhängig. Auch die Anzahl von an der Regenerieranlage angeschlossenen Ätzkammern beeinflusst das Regeln.The amount of metal to be deposited in the electrolysis cell is regulated depending on the metal content of the etching solution to be regenerated. The metal content in the etching solution should not fall below a minimum value. The aim is to minimize the control delay. If the depleted etching solution is introduced into the etching chamber or the regenerated etching solution flowing to the etching chamber, the control delay also depends on the location and the local distance between the etching chamber and the regeneration system. The number of etching chambers connected to the regeneration system also influences the regulation.

Aufgabe der Erfindung ist es, ein Verfahren zum Regenerieren einer Ätzlösung zu schaffen, das eine auf eine Änderung der Metallkonzentration in der Ätzlösung rasch ansprechende Regelung aufweist, die unabhängig von örtlichen Gegebenheiten bei der Aufstellung von Regenerieranlage und Ätzkammer arbeitet.The object of the invention is to provide a method for regenerating an etching solution which has a control which responds quickly to a change in the metal concentration in the etching solution and which works independently of local conditions in the installation of the regeneration system and etching chamber.

Diese Aufgabe wird bei einem Verfahren der eingangs angegebenen Art gemäss der Erfindung durch die in Patentanspruch 1 angegebenen Massnahmen gelöst. Die aus der Elektrolysezelle entnommene, an Metallionen abgereicherte Ätzlösung wird unmittelbar in die von der Ätzkammer abfliessende, zu regenrierende Ätzlösung eingeführt, so dass sich mit den die Metallionenkonzentration in der Ätzlösung messenden Einrichtungen in sehr kurzer Zeit der durch Zumischen abgereicherter Ätzlösung erreichte Istwert des Metallanteils in der Ätzlösung ermitteln lässt. Die Totzeit der Regelstrecke wird somit erheblich verkürzt.This object is achieved in a method of the type specified at the outset according to the invention by the measures specified in claim 1. The etching solution depleted in metal ions and removed from the electrolytic cell is introduced directly into the etching solution to be regenerated, which flows away from the etching chamber, so that with the devices measuring the metal ion concentration in the etching solution, the actual value of the metal fraction in depleted in admixture can be achieved in a very short time of the etching solution. The dead time of the controlled system is thus significantly reduced.

Eine Anlage zum Durchführen des erfindungsgemässen Verfahrens ist in Patentanspruch 2 angegeben. Die Anlage weist einen Zulauf für aus der Ätzkammer entnommene, zu regenerierende Ätzlösung und einen Rücklauf für regenerierte Ätzlösung zur Ätzkammer auf. Die Ätzlösung wird unter Zufuhr von Sauerstoff regeneriert. In einer am Zulauf für die zu regenerierende Ätzlösung angeschlossenen Ätzmittelleitung strömt ein Teil der Ätzlösung zu einer Elektrolysezelle zum Abscheiden abgeätzten Metalls. Um eine vom Standort von Regenerieranlage und Ätzkammer unabhängige Regelung mit kurzer Regelverzögerung zu erreichen, ist an der Elektrolysezelle für die an Metallionen abgereicherte Ätzlösung eine Entnahmeleitung angeschlossen, die zum Zulauf der zu regenrierenden Ätzlösung geführt ist.A system for carrying out the method according to the invention is specified in claim 2. The system has an inlet for the etching solution to be regenerated, which is removed from the etching chamber, and a return for regenerated etching solution to the etching chamber. The etching solution is regenerated with the addition of oxygen. In an etchant line connected to the inlet for the etching solution to be regenerated, part of the etching solution flows to an electrolysis cell for the deposition of etched metal. In order to achieve a control with a short control delay that is independent of the location of the regeneration system and etching chamber, an extraction line is connected to the electrolysis cell for the etching solution depleted in metal ions, which leads to the inflow of the etching solution to be regenerated.

In weiterer Ausgestaltung der Erfindung nach Patentansprüchen 2 und 3 ist vorgesehen, die Entnahmeleitung an der Elektrolysezelle an einem Überlauf für Elektrolyt anzuschliessen. An Metallionen abgereicherte Ätzlösung wird so unmittelbar nach Einströmen zu regenerierender Ätzlösung in die Elektrolysezelle aus dieser abgeführt und mit zu regenerierender Ätzlösung vermischt. Dies führt zu einer weiteren Verkürzung der Totzeit der Regelstrecke. Die Entnahmeleitung mündet in einem Auffangbehälter, in den aus der Ätzkammer abgeführtes, zu regenerierendes Ätzmittel über ein kommunizierendes Röhrensystem einläuft. Ätzkammer und Auffangbehälter weisen daher stets den gleichen Ätzlösungsspiegel auf, zusätzliche Förderaggregate zum Überlaufen von Ätzlösung aus der Ätzkammer zur Regenerieranlage entfallen.In a further embodiment of the invention according to claims 2 and 3, it is provided to connect the extraction line to the electrolysis cell to an overflow for electrolyte. Etching solution depleted in metal ions is thus removed from the electrolytic cell immediately after flowing into the electrolytic cell to be regenerated and mixed with the etching solution to be regenerated. This leads to a further reduction in the dead time of the controlled system. The extraction line opens into a collecting container into which the etchant to be regenerated, which is discharged from the etching chamber, flows in via a communicating tube system. The etching chamber and the collecting container therefore always have the same etching solution level, and additional conveying units for overflowing etching solution from the etching chamber to the regeneration system are dispensed with.

Eine sehr kompakte Anordnung und eine einfache Handhabung der Regenerieranlage ergibt sich durch die Ausbildung der Anlage nach Patentanspruch 5. Danach sind Auffangbehälter, Elektrolysezelle und Förderaggregate für die Ätzlösung sowie die Sauerstoffzufuhr innerhalb eines gemeinsamen Gehäuses angeordnet, das an der Ätzkammer lediglich über den Zulauf und den Rücklauf anzuschliessen ist.A very compact arrangement and simple handling of the regeneration system results from the design of the system according to claim 5. Thereafter, the collecting container, electrolysis cell and delivery units for the etching solution and the oxygen supply are arranged within a common housing, which is attached to the etching chamber only via the inlet and the Connect the return.

Die Erfindung wird nachfolgend anhand eines in der Zeichnung schematisch wiedergegebenen Ausführungsbeispieles näher erläutert.The invention is explained in more detail below on the basis of an exemplary embodiment shown schematically in the drawing.

In der Zeichnung ist eine an eine Ätzkammer 1 mit Spülkammer 2 angeschlossene Regenerieranlage schematisch dargestellt. Die zu regeneriende Ätzlösung, die Ammoniumsulfat in Verbindung mit Kupfertetramminkomplex als Ätzmittel enthält, fliesst aus der Ätzkammer 1 über einen Zulauf 3 in einen Auffangbehälter 4, der an der Ätzkammer über ein System kommunizierender Röhren angeschlossen ist. Im Ausführungsbeispiel fliesst die Ätzlösung im Zulauf 3 in einem Verbindungsrohr in natürlichem Gefälle aus der Ätzkammer 1 in den Auffangbehälter 4 ein. Vom Auffangbehälter 4 wird die zu regenerierende Ätzlösung mittels einer Pumpe 5 über eine Druckleitung 6 zu einem Rohranschluss 7 geführt, von dem ausgehend eine Ätzmittelleitung 8 zu einer Elektrolysezelle 9 geführt ist. Ein in der Ätzmittelleitung 8 eingesetzter Durchflussregler 10 bestimmt den zur Elektrolysezelle 9 strömenden Teil der Ätzlösung.In the drawing, a regeneration system connected to an etching chamber 1 with a rinsing chamber 2 is shown schematically. The etching solution to be regenerated, which contains ammonium sulfate in conjunction with copper tetrammine complex as the etchant, flows from the etching chamber 1 via an inlet 3 into a collecting container 4 which is connected to the etching chamber via a system of communicating tubes. In the exemplary embodiment, the etching solution in the inlet 3 flows in a connecting pipe in a natural gradient from the etching chamber 1 into the collecting container 4. The etching solution to be regenerated is led from the collecting container 4 by means of a pump 5 via a pressure line 6 to a pipe connection 7, from which an etchant line 8 is led to an electrolysis cell 9. A flow controller 10 used in the etchant line 8 determines the part of the etching solution flowing to the electrolytic cell 9.

Am Rohranschluss 7 ist noch eine Verbindungsleitung 11 zu einer Flüssigkeitsstrahlpumpe 12 angeschlossen. Mittels der Flüssigkeitsstrahlpumpe 12 wird zur Rückoxidation der zur Ätzkammer im Rücklauf 13 zurückströmenden Ätzlösung Sauerstoff eingeführt. Am Saugstutzen 14 der Flüssigkeitsstrahlpumpe ist eine Gasleitung 15 angeschlossen, die in der Elektrolysezelle 9 im Gasraum oberhalb des Elektrolyten mündet und die mit Sauerstoff gespeist wird, der an der Anode 16 der Elektrolysezelle 9 beim Abscheiden von Metall an der Kathode 17 gebildet wird. Als Arbeitsmittel dient der Flüssigkeitsstrahlpumpe 12 die von der Pumpe 5 über die Druckleitung 6 in die Verbindungsleitung 11 geförderte Ätzlösung.A connecting line 11 to a liquid jet pump 12 is also connected to the pipe connection 7. Oxygen is introduced by means of the liquid jet pump 12 for the reoxidation of the etching solution flowing back to the etching chamber in the return 13. A gas line 15 is connected to the suction nozzle 14 of the liquid jet pump, which leads into the electrolysis cell 9 in the gas space above the electrolyte and which is fed with oxygen which is formed on the anode 16 of the electrolysis cell 9 when metal is deposited on the cathode 17. The liquid jet pump 12 uses the etching solution conveyed by the pump 5 via the pressure line 6 into the connecting line 11 as the working medium.

In die Gasleitung 15 führt zur Zufuhr von Ammoniak eine Ammoniakleitung 18, die an einem mittels einer Absperrvorrichtung 19 verschliessbaren Vorratsbehälter 20 für Ammoniak angeschlossen ist. Von der Flüssigkeitsstrahlpumpe 12 ist somit mit dem aus der Elektrolysezelle abgesaugten, Sauerstoff enthaltenden Gas zugleich frisches Ammoniak in die Ätzlösung einleitbar, um den pH-Wert der Ätzlösung zu regulieren. Die Absperrvorrichtung 19 steht zu diesem Zweck mit einem in der Ätzmittelleitung 8 eingesetzten pH-Wert-Messgerät 21 mit einer Messelektrode in Wirkverbindung. Fällt der pH-Wert unter einen vorgegebenen zulässigen Grenzwert ab, so wird die Absperrvorrichtung 19 geöffnet und in die Ätzlösung Ammoniak eingeleitet. Das pH-Wert-Messgerät schaltet die Absperrvorrichtung 19 mit Hilfe elektrischer Steuereinheiten.An ammonia line 18 leads to the supply of ammonia in the gas line 15 and is connected to a storage container 20 for ammonia which can be closed by means of a shut-off device 19. Fresh ammonia can thus be introduced into the etching solution from the liquid jet pump 12 together with the gas containing oxygen drawn off from the electrolytic cell in order to regulate the pH of the etching solution. For this purpose, the shut-off device 19 is operatively connected to a pH value measuring device 21 inserted in the etchant line 8 with a measuring electrode. If the pH falls below a predetermined permissible limit value, the shut-off device 19 is opened and ammonia is introduced into the etching solution. The pH value measuring device switches the shut-off device 19 with the aid of electrical control units.

Vor der Flüssigkeitsstrahlpumpe 12 mündet in die Verbindungsleitung 11 eine Druckentlastungsleitung 22, die zum Ablauf von Ätzlösung in den Auffangbehälter 4 geführt ist.In front of the liquid jet pump 12, a pressure relief line 22 opens into the connecting line 11 and is led to the drainage of etching solution in the collecting container 4.

In der Ätzmittelleitung 8 befindet sich neben dem Durchflussregler 10 und dem pH-Wert-Messgerät 21 noch ein Gerät 23 zur Messung der Metallionenkonzentration. Die Metallionenkonzentration in der Ätzlösung bestimmt die Arbeitsweise der Elektrolysezelle. Das Gerät 23 steht hierzu in Wirkverbindung mit einem am Ende der Ätzmittelleitung 8 eingesetzten, magnetisch gesteuerten Dreiwegeventil 24, an das einerseits das zur Elektrolysezelle 9 geführte Endstück 8' der Ätzmittelleitung 8 angeschlossen ist und andererseits eine Umgehungsleitung 25, die im Auffangbehälter 4 mündet. Das Dreiwegeventil 24 ist zur Elektrolysezelle 9 hin geöffnet. Fällt die Metallionenkonzentration der Ätzlösung unter einen vorbestimmten Wert, so wird das Dreiwegeventil 24 umgeschaltet. Die Ätzlösung fliesst dann über die Umgebungsleitung 25 ab. Die Elektrolysezelle wird abgeschaltet.In addition to the flow controller 10 and the pH value measuring device 21, there is also a device 23 for measuring the metal ion concentration in the etchant line 8. The metal ion concentration in the etching solution determines the functioning of the electrolytic cell. For this purpose, the device 23 is operatively connected to a magnetically controlled three-way valve 24 inserted at the end of the etchant line 8, to which on the one hand the end piece 8 'of the etchant line 8 leading to the electrolytic cell 9 is connected and on the other hand a bypass line 25 which opens into the collecting container 4. The three-way valve 24 is open to the electrolytic cell 9. If the metal ion concentration of the etching solution falls below a predetermined value, the three-way valve 24 is switched over. The etching solution then flows off via the surrounding line 25. The electrolytic cell is switched off.

Vom Ausgang der Elektrolysezelle führt ein Elektrolytüberlauf 26 die an Metallionen abgereicherte Ätzlösung über eine Entnahmeleitung 27 zum Auffangbehälter 4. Die hier abgereicherte Ätzlösung wird im Auffangbehälter mit der zu regenerierenden Ätzlösung vermischt und verringert so deren Metallionenkonzentration.From the outlet of the electrolytic cell, an electrolyte overflow 26 leads the etching solution depleted in metal ions to the collecting container 4 via a removal line 27. The depleted etching solution is mixed with the etching solution to be regenerated in the collecting container and thus reduces its metal ion concentration.

Die zu regenerierende Ätzlösung wird aus dem Auffangbehälter 4 von der Pumpe 5 abgesaugt und in der Ätzmittelleitung 8 über Durchflussregler 10 und pH-Wert-Messgerät 21 zum Gerät 23 gefördert, das auf die verminderte Metallionenkonzentration in der Ätzlösung reagiert.The etching solution to be regenerated is sucked out of the collecting container 4 by the pump 5 and conveyed in the etching agent line 8 via flow controller 10 and pH value measuring device 21 to the device 23, which reacts to the reduced metal ion concentration in the etching solution.

Unterhalb der Elektrolysezelle 9 befindet sich noch ein Ablaufbehälter 28. Er dient der Entleerung der Elektrolysezelle und ist über einen Auslauf 29, der mittels eines Magnetventils 30 absperrbar ist, am Boden der Elektrolysezelle 9 angeschlossen. Ätzlösung kann aus der Elektrolysezelle 9 in den Ablaufbehälter 28 auch über einen zweiten Überlauf 31 einfliessen.Below the electrolysis cell 9 there is also a drain tank 28. It serves to empty the electrolysis cell and is connected to the bottom of the electrolysis cell 9 via an outlet 29 which can be shut off by means of a solenoid valve 30. Etching solution can also flow from the electrolysis cell 9 into the drain container 28 via a second overflow 31.

Für einen Umlauf von Ätzlösung in der Elektrolysezelle 9 sorgt eine Lösungsmittelpumpe 32. Die Lösungsmittelpumpe taucht mit ihrer Saugleitung 33 in den Ablaufbehälter 28 ein, in den die Ätzlösung über den Überlauf 31 einfliesst, und fördert die Ätzlösung über einen Filter 34 in ihrer Druckleitung 35 zurück zur Elektrolysezelle. Die Ätzlösung tritt im Ausführungsbeispiel zwischen Anode 16 und Kathode 17 in die Elektrolysezelle ein. Nach Abschalten der Elektrolysezelle wird die Ätzlösung durch Öffnen des Magnetventils 30 in den Ablaufbehälter 28 entleert. Vor erneutem Betrieb der Elektrolysezelle wird die Ätzlösung aus dem Ablaufbehälter mittels der Lösungsmittelpumpe 32 in die Elektrolysezelle zurückbefördert.A solvent pump 32 ensures circulation of the etching solution in the electrolytic cell 9. The solvent pump dips with its suction line 33 into the drain container 28, into which the etching solution flows via the overflow 31, and conveys the etching solution back in its pressure line 35 via a filter 34 to the electrolytic cell. In the exemplary embodiment, the etching solution enters the electrolysis cell between anode 16 and cathode 17. After the electrolysis cell has been switched off, the etching solution is emptied into the drain container 28 by opening the solenoid valve 30. Before the electrolysis cell is operated again, the etching solution is conveyed back from the drain container into the electrolysis cell by means of the solvent pump 32.

Im Ausführungsbeispiel wurde zum Ätzen von Kupfer eine Ammoniumsulfat und Kupfertetramminkomplex enthaltende Ätzlösung verwendet. Zwischen Ätzkammer und Regenerieranlage wurden 1501 Ätzlösung im Kreislauf geführt. Die frische Ätzlösung enthielt 150 g Ammoniumsulfat und 50 g Kupfer pro Liter. In der Ätzkammer wurde die auf einen pH-Wert von 9 eingestellte Ätzlösung mit einer Temperatur von 50°C mittels Düsen auf zu ätzende Werkstücke versprüht. Es wurden kupferkaschierte Leiterplatten geätzt. Die Ätzgeschwindigkeit betrug dabei 30 11m Kupferoberflächenabtrag pro Minute.In the exemplary embodiment, an etching solution containing ammonium sulfate and copper tetrammine complex was used to etch copper. 1501 etching solution were circulated between the etching chamber and the regeneration system. The fresh etching solution contained 150 g ammonium sulfate and 50 g copper per liter. In the etching chamber, the etching solution set to a pH of 9 was sprayed onto workpieces to be etched at a temperature of 50 ° C. by means of nozzles. Copper-clad printed circuit boards were etched. The etching rate was 30 11m copper surface removal per minute.

Die in der Regenerieranlage installierte Elektrolysezelle wies eine Abscheideleistung von 600 g Cu/h auf. Die Elektrolysezelle arbeitete mit 860 A Gleichstrom, dies entspricht bei einer Elektrodenfläche von 860 cm2 einer Stromdichte von 10 A/dm2. Durch Abscheiden von Metall an der Kathode wurde die Ätzlösung bei ihrem Durchlauf durch die Elektrolysezelle um 20 g Cu/i abgereichert.The electrolysis cell installed in the regeneration plant had a separation rate of 600 g Cu / h. The electrolysis cell operated with 860 A direct current, which corresponds with an electrode area of 860 cm 2 of a current density of 10 A / dm 2. By depositing metal on the cathode, the etching solution was depleted by 20 g Cu / i as it passed through the electrolytic cell.

In der Regenerieranlage wurde die Ätzlösung durch Zugabe von Ammoniak auf ihren pH-Wert von 9 als Sollwert eingestellt. Der Durchflussregler arbeitete bei einem Sollwert von 30 I Ätzlösung pro Stunde mit einer Regelabweichung von ± 21/h. Wurde bei Bestimmung des Metallgehaltes vom Gerät 23 in der Ätzlösung eine Kupferkonzentration von 53 g Cu/I gemessen, so wurde bei entsprechender Stellung des Dreiwegeventils Ätzlösung zur Elektrolysezelle geleitet, bis die Kupferkonzentration auf 50 g Cu/i abgesunken war. Bei diesem Wert wurde das Dreiwegeventil 24 umgestellt und die Elektrolysezelle abgeschaltet. Die in der Elektrolysezelle an Metallionen abgereicherte Ätzlösung wurde in den Auffangbehälter zurückgeführt. Es ergaben sich kurze Totzeiten für die Regelstrecke.In the regeneration plant, the etching solution was adjusted to its pH value of 9 as the setpoint by adding ammonia. The flow controller worked at a setpoint of 30 I etching solution per hour with a control deviation of ± 21 / h. If a metal concentration of 53 g Cu / I was measured by the device 23 in the etching solution when determining the metal content, the etching solution was directed to the electrolysis cell with the three-way valve in the appropriate position until the copper concentration had dropped to 50 g Cu / i. At this value, the three-way valve 24 was changed over and the electrolytic cell was switched off. The etching solution depleted of metal ions in the electrolysis cell was returned to the collecting container. There were short dead times for the controlled system.

Im Verlaufe von acht Betriebsstunden wurden 5,5 kg Kupfer an der Kathode abgeschieden. Diese Menge abgeschiedenen Kupfers entspricht 67% dertheoretisch abscheidbaren Kupfermenge, bezogen auf den durch die Elektrolysezelle geflossenen Strom.In the course of eight operating hours, 5.5 kg of copper were deposited on the cathode. This amount of deposited copper corresponds to 67% of the theoretically depositable amount of copper, based on the current flowing through the electrolytic cell.

Die in der Zeichnung schematisch wiedergegebenen Teile der Regenerieranlage sind im Ausführungsbeispiel in einem Gehäuse untergebracht, das Auffangbehälter 4, Elektrolysezelle 9 und die Förderaggregate für die Ätzlösung und die Sauerstoffzufuhr aufweist. Zu den Förderaggregaten gehören die Pumpe 5 zur Förderung des zu regenerierenden Ätzmittels, die Flüssigkeitsstrahlpumpe 12 zum Einbringen des Sauerstoff und Ammoniak enthaltenden Gases in die Ätzlösung sowie die Lösungsmittelpumpe 32 für den Umlauf der Ätzlösung in ihrer Zusammensetzung als Elektrolyt in der Elektrolysezelle 9.The parts of the regeneration system shown schematically in the drawing are accommodated in the exemplary embodiment in a housing which has a collecting container 4, electrolysis cell 9 and the conveying units for the etching solution and the oxygen supply. The conveying units include the pump 5 for conveying the etchant to be regenerated, the liquid jet pump 12 for introducing the gas containing oxygen and ammonia into the etching solution and the solvent pump 32 for circulating the etching solution in its composition as an electrolyte in the electrolytic cell 9.

Das Gehäuse enthält darüberhinaus auch Durchflussregler 10, pH-Wert-Messgerät 21 sowie Gerät 23 zur Messung der Metallionenkonzentration. Unterhalb der Elektrolysezelle befindet sich - im Gehäuse neben dem Auffangbehälter 4 angeordnet - der Ablaufbehälter 28 für den Elektrolyt. Die Teile der Regenerieranlage sind im Gehäuse raumsparend angeordnet. Das Gehäuse ist an einer Ätzkammer nur noch über Zulauf 3 und Rücklauf 13 anzuschliessen. Die örtliche Entfernung zwischen Ätzkammer und Regenerieranlage spielt für den ordnungsgemässen Betrieb der Regenerieranlage keine Rolle.The housing also contains flow controller 10, pH value measuring device 21 and device 23 for measuring the metal ion concentration. The drain tank 28 for the electrolyte is located below the electrolysis cell - arranged in the housing next to the collecting tank 4. The parts of the regeneration system are arranged in a space-saving manner in the housing. The housing can only be connected to an etching chamber via inlet 3 and return 13. The local distance between the etching chamber and the regeneration system is irrelevant for the correct operation of the regeneration system.

Claims (5)

1. Process for regenerating an ammoniacal etching solution, into which oxygen is fed for reoxidation of the etching agent contained in the etching solution, and which at least in part flows through an electrolysis cell for recovery of the etched-off metal, characterised in that the etching solution depleted of metal ions in the electrolysis cell is introduced into the etching solution which is to be regenerated and which is taken from the etching chamber.
2. Apparatus for regenerating an ammoniacal etching solution, with a supply conduit for etching solution which is taken from the etching chamber and which is to be regenerated, and with a return conduit to the etching chamber for etching solution regenerated with infeed of oxygen, also with an electrolysis cell into which opens an etching agent conduit, connected to the supply, for a portion of the etching solution, characterised in that there is connected to the electrolysis cell (9) a discharge conduit (27) for etching solution which has been depleted of metal ions and which is conducted to the supply conduit (3) supplying the etching solution which is to be regenerated.
3. Apparatus according to claim 2, characterised in that the discharge conduit (27) is connected to an electrolyte overflow (26) of the electrolysis cell (9).
4. Apparatus according to claim 2 or 3, characterised in that the discharge conduit (27) opens into a collecting container (4) into which runs, through a communicating pipe system, etching solution which is to be regenerated and which has been taken from the etching chamber (1).
5. Apparatus according to one of the preceding claims 2 to 4, characterised in that collecting container (4), electrolysis cell (9), and circulation and delivery devices (5, 12, 32) for the etching solution and infeed of oxygen are arranged within a common housing which is connectable to the etching chamber (1) by means of the supply conduit (3) and the return conduit (13).
EP84113228A 1983-11-08 1984-11-02 Process and apparatus for regenerating an ammoniacal etching solution Expired EP0144742B1 (en)

Applications Claiming Priority (2)

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DE3340342 1983-11-08
DE19833340342 DE3340342A1 (en) 1983-11-08 1983-11-08 METHOD AND PLANT FOR REGENERATING AN AMMONIA ACID SOLUTION

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EP0144742B1 true EP0144742B1 (en) 1987-07-15

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DE4014429A1 (en) * 1990-05-05 1991-11-07 Hoechst Ag METHOD FOR REGULATING THE FLOW RATE IN THE ELECTROCHEMICAL REGENERATION OF CHROME SULFURIC ACID
US5248398A (en) * 1990-11-16 1993-09-28 Macdermid, Incorporated Process for direct electrolytic regeneration of chloride-based ammoniacal copper etchant bath
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DE3464768D1 (en) 1987-08-20
EP0144742A1 (en) 1985-06-19
JPH0536509B2 (en) 1993-05-31
DE3340342A1 (en) 1985-05-15
JPS60116789A (en) 1985-06-24
US4557811A (en) 1985-12-10

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