EP0048381B1 - Process for the regeneration of hydrochloric copper chloride etching solutions - Google Patents

Process for the regeneration of hydrochloric copper chloride etching solutions Download PDF

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Publication number
EP0048381B1
EP0048381B1 EP81107037A EP81107037A EP0048381B1 EP 0048381 B1 EP0048381 B1 EP 0048381B1 EP 81107037 A EP81107037 A EP 81107037A EP 81107037 A EP81107037 A EP 81107037A EP 0048381 B1 EP0048381 B1 EP 0048381B1
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Prior art keywords
etching
bell
regeneration
oxygen
gas
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German (de)
French (fr)
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EP0048381A1 (en
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Efthimios Dr. Rer. Nat. Dipl.-Chem. Konstantouros
Karl Höck
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/7287—Liquid level responsive or maintaining systems

Definitions

  • the invention relates to a method for the regeneration of hydrochloric acid chloride etching solutions, which are preferably used in the manufacture of printed circuit boards for the etching of non-galvanized printed circuit boards, the etching and regeneration taking place in separate devices, between which the etching solution is cycled or continuously carried out in the circuit and the regeneration is preferably carried out is carried out with oxygen gas, with a bell, into which the used up etched from an etching machine is sprayed for regeneration above.
  • the literature mostly does not consider the formation of the easily soluble CuCI 2 complex from the poorly soluble CuCI salt.
  • the inactive copper (I) ion formed during the etching is oxidized to etchable copper (II) ion.
  • DE-AS 1 621 437 deals with a device for supplying chlorine gas to an etching agent regeneration plant.
  • the chlorine gas is introduced directly into the etching machine of the etching machine using an injector (water jet pump principle), the monovalent copper (I) ion being oxidized to copper (II) ion according to the following equation:
  • DE-PS 1 225465 is based on a method for etching copper with a copper (II) chloride solution. In this known method, regeneration takes place according to the equation
  • the copper (II) chloride solution is in a tank. Diluted hydrochloric acid and sodium chlorate are kept ready in two storage containers and added to the etching bath in the required amount by an automatic control device.
  • the inflow of hydrochloric acid is controlled by a pH measuring probe, an amplifier and a control valve and the inflow of sodium chlorate by a photocell, an amplifier and a control valve.
  • aqueous solutions of hydrogen peroxide and hydrochloric acid are metered into the etching machine by measuring the redox potential or the pH.
  • the present invention has for its object to provide an exhaust air-free process for the continuous regeneration of hydrochloric acid etching solutions using oxygen gas.
  • This object is achieved in that a bell set up in a flat standing container containing caustic agent is provided with a supply line in the upper part for oxygen, that the regenerated etching collects at the bottom of the standing container, from where it flows back into the etching machine as an overflow and that due to the negative pressure generated during the reaction, the etching increases and this level change serves to control two level switches in the inner surface of the bell, which open or close the supply line of the regeneration gas, and thereby only as much oxygen into the bell is replenished as was consumed.
  • a bell-like container as an oxidation vessel. It is important that the presence of an oxidizing atmosphere enclosed and regulated in the reaction vessel is ensured.
  • the present invention does not use frits which experience has shown to damage or clog them easily and, as a result, they have to be replaced.
  • the method according to the invention also requires less maintenance and does not give off exhaust air from the regeneration vessel.
  • Another advantage is that there is no loss in the gas used for regeneration, since all the gas enclosed in the bell is used to 100%.
  • the device is also characterized by a higher regeneration speed, since it works with pure oxidizing gas and not with air (20% oxygen content).
  • Another advantage is the automated introduction of the gas used for regeneration by means of a level switch, so that the introduction can be regulated as required.
  • the concentration of the etching solution is preferably set so that no solubility product is exceeded at the respective operating temperatures. At room temperature, for example, the following concentrations have proven to be favorable:
  • the salt KCI is not used up during the etching. It serves as a chloride ion supplier to form the easily soluble copper (I) complex CuCl 2 - and thus to increase the reaction rate.
  • the copper (I) complex is oxidized, the chloride ion is released again (see equation of the regeneration process).
  • the etching time for 35 ym Cu layer is 45 "at 25 ° C and 1 to 1.5 bar spray pressure.
  • hydrochloric acid and KCI solution are added.
  • the overflow here is collected.
  • the metering of the chemicals can be automated, via the density measurement for the KCI solution and the pH measurement for the hydrochloric acid.
  • the regeneration takes place at the phase interface between the oxidizing gas and the sprayed-on etching solution, it is necessary to make the phase interface mentioned as large as possible in the reaction space.
  • mist nozzles are used on the one hand to spray the etching solution and, on the other hand, absorbent and corrosion-resistant fabrics or felt materials are hung vertically, which are available in a large selection on the market.
  • the regeneration of the absorbed etching solution also takes place when the spray pump is switched off.
  • the absorbency of felts of 2 mm thickness can be up to approx. 2 I per m 2 .
  • the etching solution in the bell is sprayed on through mist nozzles in order to enlarge the phase interface between the etching solution and the oxidizing gas and thus to increase the regeneration rate.
  • the phase interface can be increased on the one hand and the regeneration of the absorbed caustic solution can be continued even when the spray pump is switched off.
  • the invention is explained on the basis of a schematic representation of the method according to the invention for the regeneration of a copper chloride etching by means of oxygen gas.
  • a regeneration bell 1 is shown in a standing container 2.
  • the used etching 4 is introduced with a pump 5 via a line 6 into the top of the regeneration bell and sprayed over the hanging tissue or felt cloth 7.
  • the gas 10 used for regeneration is fed via a line 11 to the regeneration bell.
  • a connection 12 for a connecting line to the vacuum pump is indicated.
  • the regenerated etching 13 collects in the lower part of the regeneration bell.
  • S1, S2 denote two level switches which, depending on the respective height N1, N2 of the regenerated etching 13, switch the supply of the oxidizing gas on or off via a control device 14.
  • the gas volume varies between the values V1 and V2.
  • the circular operating sequence is shown with the arrows.
  • the used etchant 4 is continuously sucked out of the etching chamber of the etching machine 3 and sprayed into the regeneration bell 1, the copper (I) ion, as already mentioned, according to the equation is oxidized.
  • By consuming z. B. Oxygen constantly decreases the gas pressure in the bell. As a result, the etching solution 13 slowly rises in the bell.
  • the oxygen supply is controlled by level switches S1 and S2 (float or photocells). This ensures that the etchant level in the bell oscillates between a lower N1 and an upper limit N2, so that there is always enough gas in the bell for the regeneration process.
  • the gas volume consequently varies between the values V1 and V2.
  • the bell shape of the reaction vessel 1 is by no means absolutely necessary. You can also conditionally z. B. take any other shape due to spatial conditions or by the number and size of the felt cloths 7.

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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 betrifft ein Verfahren zur Regenerierung salzsaurer Kupferchlorid-Ätzlösungen, die vorzugsweise in der Leiterplattenfertigung zum Ätzen von nicht galvanisierten Leiterplatten dienen, wobei das Ätzen und Regenerieren in gesonderten Vorrichtungen erfolgt, zwischen denen die Ätzlösung im Kreislauf taktweise oder kontinuierlich geführt wird und die Regenerierung vorzugsweise mit Sauerstoffgas vorgenommen wird, mit einer Glocke, in die zur Regenerierung die aus einer Ätzmaschine abgesaugte, verbrauchte Ätze oben eingesprüht wird.The invention relates to a method for the regeneration of hydrochloric acid chloride etching solutions, which are preferably used in the manufacture of printed circuit boards for the etching of non-galvanized printed circuit boards, the etching and regeneration taking place in separate devices, between which the etching solution is cycled or continuously carried out in the circuit and the regeneration is preferably carried out is carried out with oxygen gas, with a bell, into which the used up etched from an etching machine is sprayed for regeneration above.

In der deutschen Patentschrift 1 207 183 ist ein kontinuierliches Regenerierverfahren für insbesondere bei der Herstellung gedruckter Schaltungen verwendete kupferhaltige Ätzlösungen beschrieben und dargestellt. Die Regeneriereinrichtung besteht aus einem hohen Standbehälter, der am Boden Fritten für die Feinverteilung zugeführter Preßluft enthält. Das Ätzmittel zirkuliert kontinuierlich zwischen Standbehälter und Ätzmaschine. Dabei finden folgende Reaktionen statt:

  • Ätzprozeß:
    Figure imgb0001
    Figure imgb0002
  • Regenerierprozeß:
    Figure imgb0003
German patent 1 207 183 describes and depicts a continuous regeneration process for copper-containing etching solutions used in particular in the production of printed circuits. The regeneration device consists of a tall standing container that contains frits on the bottom for the fine distribution of compressed air supplied. The etchant circulates continuously between the standing container and the etching machine. The following reactions take place:
  • Etching process:
    Figure imgb0001
    Figure imgb0002
  • Regeneration process:
    Figure imgb0003

In der Literatur wird meistens - einfachheitshalber - die Bildung des leichtlöslichen CuCI2 -Komplexes aus dem schwerlöslichen CuCI-Salz nicht in Betracht gezogen. Beim Regenerieren wird das beim Ätzen gebildete inaktive Kupfer (I)-Ion zu ätzfähigem Kupfer (ll)-lon oxidiert.For the sake of simplicity, the literature mostly does not consider the formation of the easily soluble CuCI 2 complex from the poorly soluble CuCI salt. During regeneration, the inactive copper (I) ion formed during the etching is oxidized to etchable copper (II) ion.

In der DE-AS 1 621 437 wird eine Vorrichtung zum Zuführen von Chlorgas in eine Ätzmittelregenerierungsanlage behandelt. Das Chlorgas wird nach diesem Verfahren über einen Injektor (Wasserstrahlpumpen-Prinzip) direkt in die Ätze der Ätzmaschine eingeleitet, wobei das einwertige Kupfer(I)-lon nach der folgenden Gleichung zu Kupfer(II)-lon oxidiert wird:

Figure imgb0004
DE-AS 1 621 437 deals with a device for supplying chlorine gas to an etching agent regeneration plant. The chlorine gas is introduced directly into the etching machine of the etching machine using an injector (water jet pump principle), the monovalent copper (I) ion being oxidized to copper (II) ion according to the following equation:
Figure imgb0004

Der DE-PS 1 225465 liegt ein Verfahren zum Ätzen von Kupfer mit einer Kupfer(II)-Clorid-Lösung zugrunde. Bei diesem bekannten Verfahren erfolgt die Regenerierung nach der Gleichung

Figure imgb0005
DE-PS 1 225465 is based on a method for etching copper with a copper (II) chloride solution. In this known method, regeneration takes place according to the equation
Figure imgb0005

In einem Tank befindet sich die Kupfer(II)-Chlorid-Lösung. In zwei Vorratsbehältern werden verdünnte Salzsäure und Natriumchlorat bereitgehalten und durch eine automatische Regeleinrichtung dem Ätzbad in der erforderlichen Menge zugesetzt. Durch eine pH-Meßsonde, einen Verstärker und ein Steuerventil wird hierbei der Zufluß an Salzsäure und durch eine Fotozelle, einen Verstärker und ein Steuerventil der Zufluß an Natriumchlorat gesteuert.The copper (II) chloride solution is in a tank. Diluted hydrochloric acid and sodium chlorate are kept ready in two storage containers and added to the etching bath in the required amount by an automatic control device. The inflow of hydrochloric acid is controlled by a pH measuring probe, an amplifier and a control valve and the inflow of sodium chlorate by a photocell, an amplifier and a control valve.

In der Zeitschrift Elektronik, 1969, Heft 11, ist auf den Seiten 335 und 336 der Aufsatz »Moderne Ätzverfahren für Druckschaltungen« abgedruckt. Das Regenerieren geht mit Wasserstoffperoxid und Salzsäure nach der folgenden Gleichung vor sich:

Figure imgb0006
Pages 335 and 336 of the article "Modern Etching Processes for Pressure Circuits" are printed in the magazine Elektronik, 1969, issue 11. The regeneration is carried out with hydrogen peroxide and hydrochloric acid according to the following equation:
Figure imgb0006

Die wäßrigen Lösungen von Wasserstoffperoxid und Salzsäure werden über die Messung des Redoxpotentials bzw. des pH-Wertes in die Ätzmaschine zudosiert.The aqueous solutions of hydrogen peroxide and hydrochloric acid are metered into the etching machine by measuring the redox potential or the pH.

Bei dem in der DE-AS 2 008 766 beschriebenen Verfahren erfolgt ein Regenerieren mit sauerstoffhaltigem Gas unter Rückgewinnung des geätzten Kupfers durch Elektrolyse.In the process described in DE-AS 2 008 766, regeneration with oxygen-containing gas takes place with recovery of the etched copper by electrolysis.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein abluftfreies Verfahren zur kontinuierlichen Regenerierung von salzsauren Kupferchlorid-Ätzlösungen mittels Sauerstoffgas zu schaffen. Diese Aufgabe wird dadurch gelöst, daß eine in einem ätzmittelhaltigen flachen Standbehälter aufgestellte Glocke mit einer Zuführleitung im oberen Teil für Sauerstoff versehen ist, daß sich die regenerierte Ätze am Boden des Standbehälters sammelt, von wo aus sie als Überlauf in die Ätzmaschine zurückfließt und daß der durch den bei der Reaktion verbrauchten Sauerstoff entstehende Unterdruck ein Ansteigen der Ätze bewirkt und diese Niveauveränderung zur Steuerung von zwei Niveauschaltern in der inneren Mantelfläche der Glocke dient, die die Zuleitung des Regeneriergases öffnen bzw. schließen, und dadurch jeweils nur so viel Sauerstoff in die Glocke nachdosiert wird, wie verbraucht wurde. An dieser Stelle soll gesagt werden, daß es nicht unbedingt notwendig ist, einen glockenähnlichen Behälter als Oxidationsgefäß zu benützen. Wichtig ist, daß das Vorhandensein einer im Reaktionsgefäß eingeschlossenen und regulieruaren Oxidationsatmosphäre gewährleistet ist.The present invention has for its object to provide an exhaust air-free process for the continuous regeneration of hydrochloric acid etching solutions using oxygen gas. This object is achieved in that a bell set up in a flat standing container containing caustic agent is provided with a supply line in the upper part for oxygen, that the regenerated etching collects at the bottom of the standing container, from where it flows back into the etching machine as an overflow and that due to the negative pressure generated during the reaction, the etching increases and this level change serves to control two level switches in the inner surface of the bell, which open or close the supply line of the regeneration gas, and thereby only as much oxygen into the bell is replenished as was consumed. At this point it should be said that it is not absolutely necessary to use a bell-like container as an oxidation vessel. It is important that the presence of an oxidizing atmosphere enclosed and regulated in the reaction vessel is ensured.

In der vorliegenden Erfindung werden im Gegensatz zum Patent 1 207 183 keine Fritten verwendet, die erfahrungsgemäß leicht beschädigt oder verstopft werden und infolgedessen ausgewechselt werden müssen- Das Verfahren nach der Erfindung erfordert außerdem eine geringere Wartung und ergibt keine Abluft aus dem Regeneriergefäß.In contrast to patent 1 207 183, the present invention does not use frits which experience has shown to damage or clog them easily and, as a result, they have to be replaced. The method according to the invention also requires less maintenance and does not give off exhaust air from the regeneration vessel.

Ein weiterer Vorteil besteht darin, daß bei dem zur Regenerierung dienenden Gas kein Verlust eintritt, da alles in der Glocke eingeschlossene Gas zu 100% ausgenützt wird. Darüber hinaus zeichnet sich die Vorrichtung auch durch eine höhere Regeneriergeschwindigkeit aus, da mit reinem Oxidationsgas und nicht mit Luft (20% Sauerstoffgehalt) gearbeitet wird. Vorteilhaft ist ferner die automatisierte Einleitung des zur Regenerierung dienenden Gases mittels Niveauschalter, so daß die Einleitung nach Bedarf geregelt werden kann.Another advantage is that there is no loss in the gas used for regeneration, since all the gas enclosed in the bell is used to 100%. In addition, the device is also characterized by a higher regeneration speed, since it works with pure oxidizing gas and not with air (20% oxygen content). Another advantage is the automated introduction of the gas used for regeneration by means of a level switch, so that the introduction can be regulated as required.

Die Konzentration der Ätzlösung wird vorzugsweise so eingestellt, daß bei den jeweiligen Betriebs temperaturen kein Löslichkeitsprodukt überschritten wird. Bei Zimmertemperatur haben sich beispielsweise folgende Konzentrationen als günstig erwiesen:

Figure imgb0007
Figure imgb0008
Figure imgb0009
 The concentration of the etching solution is preferably set so that no solubility product is exceeded at the respective operating temperatures. At room temperature, for example, the following concentrations have proven to be favorable:
Figure imgb0007
Figure imgb0008
Figure imgb0009

Das Salz KCI wird beim Ätzen nicht verbraucht. Es dient als Chloridion-Lieferant zur Bildung des leichtlöslichen Kupfer(I)-Komplexes CuCl2- und somit zur Erhöhung der Reaktionsgeschwindigkeit. Beim Oxidieren des Kupfer(I)-Komplexes wird das Chloridion wieder frei (siehe Gleichung des Regenerierprozesses).The salt KCI is not used up during the etching. It serves as a chloride ion supplier to form the easily soluble copper (I) complex CuCl 2 - and thus to increase the reaction rate. When the copper (I) complex is oxidized, the chloride ion is released again (see equation of the regeneration process).

Die Ätzdauer für 35 ym Cu-Auflage beträgt 45" bei 25° C und 1 bis 1,5 bar Sprühdruck.The etching time for 35 ym Cu layer is 45 "at 25 ° C and 1 to 1.5 bar spray pressure.

Nach dem Verbrauch der Salzsäure durch den Ätzprozeß werden Salzsäure und KCI-Lösung zugesetzt. Der Überlauf hierbei wird gesammelt.After the hydrochloric acid has been consumed by the etching process, hydrochloric acid and KCI solution are added. The overflow here is collected.

Die Zudosierung der Chemikalien kann automatisiert werden, und zwar über die Dichtemessung für die KCI-Lösung und über die pH-Messung für die Salzsäure.The metering of the chemicals can be automated, via the density measurement for the KCI solution and the pH measurement for the hydrochloric acid.

Da sich die Regenerierung an der Phasengrenzfläche zwischen Oxidationsgas und aufgesprühter Ätzlösung abspielt, ist es notwendig, im Reaktionsraum die genannte Phasengrenzfläche möglichst groß zu gestalten. Zu diesem Zweck werden einerseits Nebeldüsen zum Aufsprühen der Ätzlösung verwendet und andererseits saugfähige und korrosionsbeständige Gewebe oder Filzmaterialien senkrecht aufgehängt, die auf dem Markt in großer Auswahl angeboten werden. In diesem Zusammenhang soll betont werden, daß die Regenerierung der aufgesaugten Ätzlösung auch bei ausgeschalteter Sprühpumpe stattfindet. Die Saugfähigkeit von Filzen von 2 mm Dicke kann bis zu ca. 2 I pro m2 betragen.Since the regeneration takes place at the phase interface between the oxidizing gas and the sprayed-on etching solution, it is necessary to make the phase interface mentioned as large as possible in the reaction space. For this purpose, mist nozzles are used on the one hand to spray the etching solution and, on the other hand, absorbent and corrosion-resistant fabrics or felt materials are hung vertically, which are available in a large selection on the market. In this context, it should be emphasized that the regeneration of the absorbed etching solution also takes place when the spray pump is switched off. The absorbency of felts of 2 mm thickness can be up to approx. 2 I per m 2 .

Das Aufsprühen der Ätzlösung in der Glocke durch Nebeldüsen geschieht, um die Phasengrenzfläche zwischen Ätzlösung und Oxidationsgas zu vergrößern und somit die Regeneriergeschwindigkeit zu steigern. Durch die Verwendung von korrosionsbeständigen und saugfähigen Geweben oder Filzen kann einerseits die Phasengrenzfläche zusätzlich erhöht werden und andererseits die Regenerierung der aufgesaugten Ätzlösung auch bei ausgeschalteter Sprühpumpe fortgeführt werden.The etching solution in the bell is sprayed on through mist nozzles in order to enlarge the phase interface between the etching solution and the oxidizing gas and thus to increase the regeneration rate. By using corrosion-resistant and absorbent fabrics or felts, the phase interface can be increased on the one hand and the regeneration of the absorbed caustic solution can be continued even when the spray pump is switched off.

Die Erfindung wird anhand einer schematischen Darstellung des erfindungsgemäßen Verfahrens zur Regenerierung einer Kupferchlorid-Ätze mittels Sauerstoffgas erläutert.The invention is explained on the basis of a schematic representation of the method according to the invention for the regeneration of a copper chloride etching by means of oxygen gas.

In der Mitte der Fig. 1 ist eine Regenerierglocke 1 in einem Standbehälter 2 dargestellt. Aus einer Ätzmaschine 3 wird die verbrauchte Ätze 4 mit einer Pumpe 5 über eine Leitung 6 oben in die Regenerierglocke eingeleitet und über die hängenden Gewebe bzw. Filztücher 7 versprüht. Aus einer Flasche 8 mit einem Magnetventil 9 wird das zum Regenerieren verwendete Gas 10 über eine Leitung 11 der Regenerierglocke zugeführt. An der Leitung 11 ist ein Anschluß 12 für eine Verbindungsleitung zur Vakuumpumpe angedeutet. Im unteren Teil der Regenerierglocke sammelt sich die regenerierte Ätze 13. Mit S1, S2 sind zwei Niveauschalter bezeichnet, die in Abhängigkeit der jeweiligen Höhe N1, N2 der regenerierten Ätze 13 über ein Steuergerät 14 die Zufuhr des Oxidationsgases ein- bzw. ausschalten. Das Gasvolumen variiert zwischen den Werten V1 und V2.In the middle of FIG. 1, a regeneration bell 1 is shown in a standing container 2. From an etching machine 3, the used etching 4 is introduced with a pump 5 via a line 6 into the top of the regeneration bell and sprayed over the hanging tissue or felt cloth 7. From a bottle 8 with a solenoid valve 9, the gas 10 used for regeneration is fed via a line 11 to the regeneration bell. On line 11, a connection 12 for a connecting line to the vacuum pump is indicated. The regenerated etching 13 collects in the lower part of the regeneration bell. S1, S2 denote two level switches which, depending on the respective height N1, N2 of the regenerated etching 13, switch the supply of the oxidizing gas on or off via a control device 14. The gas volume varies between the values V1 and V2.

Mit den Pfeilen ist der kreislaufförmige Betriebsablauf dargestellt. Das verbrauchte Ätzmittel 4 wird aus der Ätzkammer der Ätzmaschine 3 fortlaufend abgesaugt und in die Regenerierglocke 1 eingesprüht, wobei das Kupfer(I)-lon, wie bereits erwähnt wurde, nach der Gleichung

Figure imgb0010
aufoxidiert wird. Durch den Verbrauch von z. B. Sauerstoff nimmt ständig der Gasdruck in der Glocke ab. Das hat zur Folge, daß die Ätzlösung 13 in der Glocke langsam hochsteigt. Die Sauerstoffzufuhr wird durch die Niveauschalter S1 und S2 (Schwimmer oder Fotozellen) gesteuert. Damit wird erreicht, daß das Ätzmittelniveau in der Glocke zwischen einer unteren N1 und einer oberen Grenze N2 pendelt, so daß in der Glocke immer genügend Gas für den Regenerierprozeß vorhanden ist. Das Gasvolumen variiert infolgedessen zwischen den Werten V1 und V2. Die Glockenform des Reaktionsgefäßes 1 ist, wie bereits betont, keineswegs unbedingt notwendig. Sie kann auch, bedingt z. B. durch räumliche Gegebenheiten oder durch die Anzahl und Größe der Filztücher 7 jede andere beliebige Form einnehmen.The circular operating sequence is shown with the arrows. The used etchant 4 is continuously sucked out of the etching chamber of the etching machine 3 and sprayed into the regeneration bell 1, the copper (I) ion, as already mentioned, according to the equation
Figure imgb0010
 is oxidized. By consuming z. B. Oxygen constantly decreases the gas pressure in the bell. As a result, the etching solution 13 slowly rises in the bell. The oxygen supply is controlled by level switches S1 and S2 (float or photocells). This ensures that the etchant level in the bell oscillates between a lower N1 and an upper limit N2, so that there is always enough gas in the bell for the regeneration process. The gas volume consequently varies between the values V1 and V2. As already emphasized, the bell shape of the reaction vessel 1 is by no means absolutely necessary. You can also conditionally z. B. take any other shape due to spatial conditions or by the number and size of the felt cloths 7.

Claims (4)

1. A process for the regeneration of hydrochloric acid copper chloride etching solutions which in the production of printed circuit boards, are preferably used for etching non-electroplated printed circuit boards, wherein etching and regenerating are effected in separate devices between which the etching solution is circulated in pulsed or continuous manner, and the regeneration is carried out using oxygen gas, with a bell into which for regeneration, the spent etching liquid, which is sucked from the etching machine, is sprayed from above, characterised in that the bell (1) is arranged in a etchant-containing flat stationary vessel (2) and is provided in its upper part with a supply line (11) for oxygen; that the regenerated etching liquid (13) is collected at the base of the stationary vessel (2), from whence it flows back as overflow into the etching machine; and that the reduced pressure which is produced by the oxygen consumed during the reaction, causes the etching liquid to rise, and this change in level serves to control two level switches (S1, S2) in the inner casing surface of the bell, which level switches open the supply line for the regenerating gas (10), or close it (9), as the case may be. whereby only as much oxygen as has been consumed is fed into the bell in a measured manner.
2. A process as claimed in Claim 1, characterised in that atomising nozzles are used for spraying the etching liequid into the bell.
3. A process as claimed in Claim 1 and 2, characterised in that corrosion-resistant and absorbent fabrics or felts (7) are suspended in the gas chamber of the bell.
4. A process as claimed in Claim 1 to 3, characterised in that the bell consists of a transparent, corrosion-resistant material.
EP81107037A 1980-09-23 1981-09-07 Process for the regeneration of hydrochloric copper chloride etching solutions Expired EP0048381B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3035864 1980-09-23
DE19803035864 DE3035864A1 (en) 1980-09-23 1980-09-23 DEVICE FOR REGENERATING SALT ACID COPPER CHLORIDE ACET SOLUTIONS

Publications (2)

Publication Number Publication Date
EP0048381A1 EP0048381A1 (en) 1982-03-31
EP0048381B1 true EP0048381B1 (en) 1985-04-17

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EP81107037A Expired EP0048381B1 (en) 1980-09-23 1981-09-07 Process for the regeneration of hydrochloric copper chloride etching solutions

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US (1) US4388276A (en)
EP (1) EP0048381B1 (en)
DE (1) DE3035864A1 (en)

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EP2927347A1 (en) 2014-04-01 2015-10-07 Sigma Engineering Ab Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent

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US5227010A (en) * 1991-04-03 1993-07-13 International Business Machines Corporation Regeneration of ferric chloride etchants
JP2500402B2 (en) * 1991-09-05 1996-05-29 上村工業株式会社 Etching rate measuring method and etching rate measuring device
JP3142195B2 (en) * 1993-07-20 2001-03-07 大日本スクリーン製造株式会社 Chemical supply device
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CN102807294A (en) * 2011-05-31 2012-12-05 无锡尚德太阳能电力有限公司 Recirculation system for treating used etching liquid
CN103422154A (en) * 2012-05-24 2013-12-04 叶福祥 Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution
CN105060567A (en) * 2015-08-23 2015-11-18 长春黄金研究院 Treating method for acid waste water containing chlorine
CN110342566A (en) * 2019-06-24 2019-10-18 重庆瀚渝再生资源有限公司 A kind of process preparing alkaline etching liquid using acidic etching liquid
CN114351147A (en) * 2021-12-30 2022-04-15 广东臻鼎环境科技有限公司 Full-automatic safe and efficient acid etching solution regeneration system for chlorine
CN114855171B (en) * 2022-04-01 2024-03-26 安徽中科冉图环保科技有限公司 acidic etching liquid waste liquid treatment system and method
CN115287659B (en) * 2022-08-04 2024-03-29 深圳天华机器设备股份有限公司 Etching liquid regeneration device and regeneration process

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP2927347A1 (en) 2014-04-01 2015-10-07 Sigma Engineering Ab Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent
US9920434B2 (en) 2014-04-01 2018-03-20 Sigma Engineering Ab Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent

Also Published As

Publication number Publication date
DE3035864A1 (en) 1982-05-06
EP0048381A1 (en) 1982-03-31
US4388276A (en) 1983-06-14

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