EP0053719B1 - Process for etching metal surfaces - Google Patents

Process for etching metal surfaces Download PDF

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Publication number
EP0053719B1
EP0053719B1 EP81109230A EP81109230A EP0053719B1 EP 0053719 B1 EP0053719 B1 EP 0053719B1 EP 81109230 A EP81109230 A EP 81109230A EP 81109230 A EP81109230 A EP 81109230A EP 0053719 B1 EP0053719 B1 EP 0053719B1
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Prior art keywords
solution
etching
copper
etching solution
hydrogen peroxide
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German (de)
French (fr)
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EP0053719A1 (en
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Dieter C. Ing. Grad. Schmid
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Gebrueder Schmid GmbH and Co
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Gebrueder Schmid GmbH and Co
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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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • 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 etching metal surfaces, in particular printed circuits, as specified in the preamble of claim 1.
  • etching with copper chloride and regeneration with hydrochloric acid / hydrogen peroxide or chlorine gas are known.
  • etching is generally carried out using ammoniacal-alkaline etching agents; iron-III chloride or ammonium persulfate is also used in special cases.
  • the copper sulfate formed in this reaction is more suitable than copper chloride for further use. There is also the possibility of creating a closed cycle without waste water problems within the etching process and of recovering the etched copper.
  • the hydrogen peroxide is added to the etching solution only shortly before it is applied to the circuit to be etched or even only during the application, in an amount which is sufficient for the respective etching process, but which is so it is small that after the etching process, the solution dripping from the circuit contains essentially no more peroxide.
  • the amount of peroxide added is relatively easy to adjust and regulate.
  • This method has the advantage that catalytic decomposition of the peroxide in the etching solution collected after the etching process can no longer take place since there is practically no peroxide in this etching solution.
  • the etching solution can therefore be pumped back into a storage tank in a manner known per se and used again for a new etching process. Nevertheless, the etching process proceeds in the desired manner, because in the reaction area, i. H. on the circuit, the required amount of peroxide is added to the etching solution, so that the desired decomposition of the peroxide, oxidation of the metal and etching of the copper take place here.
  • the etched copper is at least partially removed from the etching solution after each etching process.
  • the copper is preferably removed electrolytically from the etching solution.
  • the copper is removed from the etching solution by cooling the etching solution and thereby precipitating copper sulfate.
  • etching solution and the hydrogen peroxide are sprayed separately onto the circuit to be etched.
  • any contact between the peroxide and the etched-off copper in the etching solution is reliably avoided before the substances meet in the reaction area.
  • the etching process of the printed circuit boards, which are coated with copper, a lacquer, photoresist material or metal resist, such as lead tin, between guide rollers 1 in the horizontal direction takes place in the interior of a housing 2, which has a collecting container 3 for the etching solution dripping from the printed circuit boards below the feed path of the printed circuit boards.
  • the printed circuit boards are inserted along the feed path formed by the guide rollers 1 into the housing 2 and leave it again on the opposite side.
  • stations for pre-treatment and stations for post-treatment of the printed circuit boards are connected upstream or downstream of the etching housing.
  • the etching solution collected in the collecting container 3 is fed by means of a suitable pump 6 via a line 7 either to an electrolysis vessel 8 or to a cooling station 9. After passing through the electrolysis vessel or the cooling station, a pump 10 conveys the etching solution into a collecting container 11.
  • the etching solution is fed to the spray nozzles 4 by means of a pump 12 or via a line 13.
  • this is fed from a storage container for oxidizing agent separated from the collecting container 11 by means of a pump 15 to the line 13, so that a mixture of the etching solution and the oxidizing agent is sprayed onto the printed circuit boards through the spray nozzles. It is also possible to spray the oxidizing agent evenly through separate nozzles.
  • an acid for example sulfuric acid or phosphoric acid
  • the oxidizing agent in the storage container 14 is hydrogen peroxide.
  • phosphoric acid can also be used, in which case corresponding phosphates are formed.
  • This etchant can be fed directly to the collecting container 11 and applied again to the printed circuit boards by means of the pump 12 with the addition of the appropriate amount of the peroxide.
  • This procedure also has the advantage that the etching solution supplied to the collecting container 11 contains little copper, so that when this low-copper etching solution is mixed with peroxide from the storage container, the catalytic decomposition of the peroxide is reduced. It is entirely possible to produce the mixture of etching solution and peroxide shortly before it is applied to the printed circuit boards and to spray it through common nozzles.
  • separate spray nozzles are provided for the etching solution and peroxide, so that the reactive mixture is only formed on the circuit boards themselves. In this case, any catalytic decomposition of the peroxide before the actual reaction is avoided with certainty.

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

Description

Die Erfindung betrifft ein Verfahren zum Ätzen von Metalloberflächen, insbesondere gedruckten Schaltungen, wie es im Oberbegriff des Anspruches 1 angegeben ist.The invention relates to a method for etching metal surfaces, in particular printed circuits, as specified in the preamble of claim 1.

Bei gedruckten Schaltungen, die mit Siebdrucklack oder einem Fotoresistmaterial beschichtet sind, ist das Ätzen mit Kupferchlorid und das Regenerieren mit Salzsäure/Wasserstoffperoxid bzw. Chlorgas bekannt. Bei Schaltungen, die Metalle als Ätzresistmaterial verwenden, wird allgemein mit ammoniakalkalischen Ätzmitteln geätzt, für Sonderfälle findet auch noch Eisen-IIIchlorid bzw. Ammoniumpersulfat Verwendung.In printed circuits which are coated with screen printing lacquer or a photoresist material, etching with copper chloride and regeneration with hydrochloric acid / hydrogen peroxide or chlorine gas are known. In the case of circuits which use metals as the etching resist material, etching is generally carried out using ammoniacal-alkaline etching agents; iron-III chloride or ammonium persulfate is also used in special cases.

Alle diese Ätzprozesse arbeiten zufriedenstellend, jedoch weisen sie den Nachteil auf, daß bei diesen Verfahren sehr große Mengen an verbrauchter, mit Kupfer angereicherter Ätzflüssigkeit anfallen, die zur Aufarbeitung in Tankwagen abtransportiert werden müssen. Dieses Verfahren ist sehr aufwendig und gefährlich.All of these etching processes work satisfactorily, but they have the disadvantage that very large amounts of used, copper-enriched etching liquid are produced in these processes, which have to be transported away in tankers for processing. This process is very complex and dangerous.

Diese Schwierigkeiten lassen sich grundsätzlich vermeiden, wenn man die Ätzung nach folgender Formel durchführt.

Figure imgb0001
These difficulties can generally be avoided if the etching is carried out according to the following formula.
Figure imgb0001

Das bei dieser Reaktion entstehende Kupfersulfat ist für weitere Verwendung geeigneter als Kupferchlorid. Außerdem besteht die Möglichkeit, innerhalb des Ätzprozesses einen geschlossenen Kreislauf ohne Abwasserprobleme zu schaffen und das abgeätzte Kupfer zurückzugewinnen.The copper sulfate formed in this reaction is more suitable than copper chloride for further use. There is also the possibility of creating a closed cycle without waste water problems within the etching process and of recovering the etched copper.

Dieser Ätzprozess ist an sich bekannt, eine praktische Anwendung scheiterte aber bisher an dem Problem, daß Kupfer in der sauren Lösung katalytisch auf das Wasserstoffperoxid wirkt und dieses zersetzt, so daß einmal der Verbrauch des Peroxids unrentabel hoch wird und zum anderen durch die Gasbildung bei der Zersetzung des Peroxids die die Ätzlösung im Kreislauf führenden Pumpen nicht gleichmäßig oder zum Teil gar nicht fördern, außerdem tritt eine unkontrollierbare Wärmebildung auf.This etching process is known per se, but a practical application has hitherto failed because of the problem that copper in the acidic solution has a catalytic effect on and decomposes the hydrogen peroxide, so that the consumption of the peroxide becomes unprofitably high and the gas formation in the process Decomposition of the peroxide does not evenly or partially do not promote the pumps carrying the etching solution in the circuit, and there is also an uncontrollable heat generation.

Um hier Abhilfe zu schaffen, sind eine Vielzahl von Versuchen bekannt, bei denen der Säure und Wasserstoffperoxid enthaltenden Ätzlösung Zusatzstoffe zugegeben werden, die die Zersetzung des Peroxids verhindern sollen. Keines dieser Verfahren hat sich jedoch praktisch durchsetzen können, da der Zusatz von Fremdstoffen immer zusätzliche Probleme und höhere Kosten verursacht.In order to remedy this, a large number of tests are known in which additives are added to the etching solution containing acid and hydrogen peroxide, which additives are intended to prevent the decomposition of the peroxide. However, none of these methods has been successful in practice since the addition of foreign substances always causes additional problems and higher costs.

Es ist Aufgabe der Erfindung, ein gattungsgemäßes Verfahren derart zu verbessern, daß die Probleme der katalytischen Zersetzung des Wasserstoffperoxids auch ohne Fremdzusätze gelöst werden.It is an object of the invention to improve a generic method in such a way that the problems of the catalytic decomposition of the hydrogen peroxide are solved even without external additives.

Diese Aufgabe wird bei einem Verfahren der eingangs beschriebenen Art erfindungsgemäß durch die im kennzeichnenden Teil von Anspruch 1 angegebenen Merkmale gelöst.This object is achieved according to the invention in a method of the type described in the introduction by the features specified in the characterizing part of claim 1.

Es ist im Rahmen des erfindungsgemäßen Verfahrens also wesentlich, daß der Ätzlösung das Wasserstoffperoxid erst kurz vor dem Aufbringen auf die zu ätzende Schaltung oder sogar erst während des Aufbringens zugegeben wird, und zwar in einer Menge, die für den jeweiligen Ätzvorgang ausreicht, die aber so gering ist, daß nach dem Ätzvorgang in der von der Schaltung abtropfenden Lösung im wesentlichen kein Peroxid mehr enthalten ist. Die Zugabemenge des Peroxids läßt sich relativ leicht einstellen und regeln.It is therefore essential in the context of the method according to the invention that the hydrogen peroxide is added to the etching solution only shortly before it is applied to the circuit to be etched or even only during the application, in an amount which is sufficient for the respective etching process, but which is so it is small that after the etching process, the solution dripping from the circuit contains essentially no more peroxide. The amount of peroxide added is relatively easy to adjust and regulate.

Dieses Verfahren hat den Vorteil, daß eine katalytische Zersetzung des Peroxides in der nach dem Ätzvorgang gesammelten Ätzlösung nicht mehr stattfinden kann, da praktisch kein Peroxid in dieser Ätzlösung vorliegt. Die Ätzlösung kann daher in an sich bekannter Weise in einen Vorratstank zurückgepumpt und von diesem wieder für einen erneuten Ätzvorgang verwendet werden. Trotzdem verläuft der Ätzvorgang in der erwünschten Weise, denn im Reaktionsbereich, d. h. auf der Schaltung, wird der Ätzlösung die erforderliche Menge des Peroxides zugesetzt, so daß hier die gewünschte Zersetzung des Peroxides, Oxydation des Metalls und das Abätzen des Kupfers stattfinden.This method has the advantage that catalytic decomposition of the peroxide in the etching solution collected after the etching process can no longer take place since there is practically no peroxide in this etching solution. The etching solution can therefore be pumped back into a storage tank in a manner known per se and used again for a new etching process. Nevertheless, the etching process proceeds in the desired manner, because in the reaction area, i. H. on the circuit, the required amount of peroxide is added to the etching solution, so that the desired decomposition of the peroxide, oxidation of the metal and etching of the copper take place here.

Bei einer vorteilhaften Weiterbildung des erfindungsgemäßen Verfahrens ist vorgesehen, daß man der Ätzlösung nach jedem Ätzvorgang das abgeätzte Kupfer zumindest teilweise entzieht. Vorzugsweise entfernt man das Kupfer dabei elektrolytisch aus der Ätzlösung.In an advantageous development of the method according to the invention, the etched copper is at least partially removed from the etching solution after each etching process. The copper is preferably removed electrolytically from the etching solution.

Bei Verwendung von Schwefelsäure ist es auch günstig, wenn das Kupfer durch Abkühlen der Ätzlösung und dadurch bedingtes Ausfällen von Kupfersulfat aus der Ätzlösung entfernt wird.When using sulfuric acid, it is also expedient if the copper is removed from the etching solution by cooling the etching solution and thereby precipitating copper sulfate.

Besonders vorteilhaft ist es, wenn man die Ätzlösung und das Wasserstoffperoxid getrennt auf die zu ätzende Schaltung aufsprüht. Dadurch wird jeder Kontakt des Peroxides und des abge- ätzten Kupfers in der Ätzlösung mit Sicherheit vermieden, bevor sich die Substanzen im Reaktionsbereich treffen.It is particularly advantageous if the etching solution and the hydrogen peroxide are sprayed separately onto the circuit to be etched. As a result, any contact between the peroxide and the etched-off copper in the etching solution is reliably avoided before the substances meet in the reaction area.

Die nachfolgende Beschreibung bevorzugter Ausführungsformen der Erfindung dient im Zusammenhang mit der Zeichnung der näheren Erläuterung. Die Zeichnung zeigt eine schematische Darstellung des erfindungsgemäßen Abätzverfahrens.The following description of preferred embodiments of the invention serves in conjunction with the drawing for a more detailed explanation. The drawing shows a schematic representation of the etching process according to the invention.

Der Ätzvorgang der mit Kupfer, einem Lack, Fotoresistmaterial oder Metallresist wie Bleizinn überzogenen, zwischen Führungswalzen 1 in horizontaler Richtung vorgeschobenen Leiterplatten erfolgt im Inneren eines Gehäuses 2, welches unterhalb der Vorschubbahn der Leiterplatten einen Auffangbehälter 3 für die von den Leiterplatten abtropfende Ätzlösung aufweist. Die Leiterplatten werden dabei längs der durch die Führungswalzen 1 gebildeten Vorschubbahn in das Gehäuse 2 eingeführt und verlassen dieses auf der gegenüberliegenden Seite wieder. In aus der Zeichnung nicht ersichtlicher Weise sind dem Ätzgehäuse Stationen zum Vorbehandeln sowie Stationen zum Nachbehandeln der Leiterplatten vor- bzw. nachgeschaltet.The etching process of the printed circuit boards, which are coated with copper, a lacquer, photoresist material or metal resist, such as lead tin, between guide rollers 1 in the horizontal direction takes place in the interior of a housing 2, which has a collecting container 3 for the etching solution dripping from the printed circuit boards below the feed path of the printed circuit boards. The printed circuit boards are inserted along the feed path formed by the guide rollers 1 into the housing 2 and leave it again on the opposite side. In out In the drawing, which cannot be seen, stations for pre-treatment and stations for post-treatment of the printed circuit boards are connected upstream or downstream of the etching housing.

Zum Aufbringen der Ätzlösung auf die Leiterplatten befinden sich oberhalb und unterhalb der Vorschubbahn Sprühdüsen 4 bzw. 5, aus denen die Ätzlösung gegen die Leiterplatte gesprüht werden kann.To apply the etching solution to the printed circuit boards, there are spray nozzles 4 and 5 above and below the feed path, from which the etching solution can be sprayed against the printed circuit board.

Die im Auffangbehälter 3 gesammelte Ätzlösung wird mittels einer geeigneten Pumpe 6 über eine Leitung 7 entweder einem Elektrolysegefäß 8 oder einer Kühlstation 9 zugeführt. Nach dem Durchlaufen des Elektrolysegefäßes bzw. der Kühlstation fördert eine Pumpe 10 die Ätzlösung in einen Sammelbehälter 11.The etching solution collected in the collecting container 3 is fed by means of a suitable pump 6 via a line 7 either to an electrolysis vessel 8 or to a cooling station 9. After passing through the electrolysis vessel or the cooling station, a pump 10 conveys the etching solution into a collecting container 11.

Aus diesem Sammelbehälter 11 wird die Ätzlösung mittels einer Pumpe 12 den Sprühdüsen 4 bzw. über eine Leitung 13 zugeführt. Außerdem wird aus einem vom Sammelbehälter 11 getrennten Vorratsbehälter für Oxidationsmittel dieses mittels einer Pumpe 15 der Leitung 13 zugeführt, so daß durch die Sprühdüsen ein Gemisch der Ätzlösung und des Oxidationsmittels auf die Leiterplatten aufgesprüht wird. Außerdem ist es möglich, das Oxidationsmittel gleichmäßig durch gesonderte Düsen zu versprühen.From this collecting container 11, the etching solution is fed to the spray nozzles 4 by means of a pump 12 or via a line 13. In addition, this is fed from a storage container for oxidizing agent separated from the collecting container 11 by means of a pump 15 to the line 13, so that a mixture of the etching solution and the oxidizing agent is sprayed onto the printed circuit boards through the spray nozzles. It is also possible to spray the oxidizing agent evenly through separate nozzles.

Gemäß der Erfindung befindet sich in dem Sammelbehälter 11 im wesentlichen eine Säure, beispielsweise Schwefelsäure oder Phosphorsäure. Das Oxidationsmittel im Vorratsbehälter 14 ist Wasserstoffperoxid.According to the invention, there is essentially an acid, for example sulfuric acid or phosphoric acid, in the collecting container 11. The oxidizing agent in the storage container 14 is hydrogen peroxide.

Im Betrieb gelangt die Säure zusammen mit dem Wasserstoffperoxid auf die Leiterplatten. Dort läuft der Ätzprozess nach folgenden Formeln ab :

Figure imgb0002
Figure imgb0003
 In operation, the acid gets onto the circuit boards together with the hydrogen peroxide. The etching process there follows the following formulas:
Figure imgb0002
Figure imgb0003

Anstelle der Schwefelsäure kann auch Phosphorsäure verwendet werden, wobei sich dann entsprechende Phosphate bilden.Instead of sulfuric acid, phosphoric acid can also be used, in which case corresponding phosphates are formed.

Wesentlich ist dabei, daß die Zugabemenge des Peroxides derart dosiert wird, daß zwar der Ätzvorgang möglichst vollständig abläuft, daß aber andererseits in der von der Leiterplatte abtropfenden Ätzlösung praktisch kein Peroxid mehr enthalten ist. Dadurch sammelt sich im Auffangbehälter 3 im wesentlichen ein Gemisch aus Schwefelsäure (Phosphorsäure), Wasser und Kupfersulfat (Kupferphosphat).It is essential that the amount of peroxide added is metered in such a way that the etching process takes place as completely as possible, but that on the other hand practically no more peroxide is contained in the etching solution dripping from the circuit board. As a result, a mixture of sulfuric acid (phosphoric acid), water and copper sulfate (copper phosphate) essentially collects in the collecting container 3.

Dieses Ätzmittel kann unmittelbar dem Sammelbehälter 11 zugeführt und mittels der Pumpe 12 erneut unter Zusatz der geeigneten Menge des Peroxids auf die Leiterplatten aufgebracht werden.This etchant can be fed directly to the collecting container 11 and applied again to the printed circuit boards by means of the pump 12 with the addition of the appropriate amount of the peroxide.

. Weiterhin ist es bei diesem Verfahren ohne weiteres möglich, das Kupfer aus der Ätzlösung zurückzugewinnen.. Furthermore, with this method it is easily possible to recover the copper from the etching solution.

Dies kann entweder im Elektrolysegefäß 8 durch elektrolytische Abscheidung des metallischen Kupfers nach folgender Gleichung

Figure imgb0004
erfolgen oder in der Kühlstation 9 durch Abkühlung der Ätzlösung und Ausfällung des Kupfersulfats. In diesem Falle ist es notwendig, der Ätzlösung Schwefelsäure im Überschuß zuzugeben bzw. die Sulfatverluste durch die Ausfällung des Kupfersulfats durch Zugabe zusätzlicher Schwefelsäure auszugleichen.This can be done either in the electrolysis vessel 8 by electrolytic deposition of the metallic copper according to the following equation
Figure imgb0004
 take place or in the cooling station 9 by cooling the etching solution and precipitating the copper sulfate. In this case, it is necessary to add an excess of sulfuric acid to the etching solution or to compensate for the sulfate losses due to the precipitation of the copper sulfate by adding additional sulfuric acid.

Dieses Vorgehen hat weiterhin den Vorteil, daß die dem Sammelbehälter 11 zugeführte Ätzlösung wenig Kupfer enthält, so daß bei einer Vermischung dieser kupferarmen Ätzlösung mit Peroxid aus dem Vorratsbehälter die katalytische Zersetzung des Peroxids herabgesetzt wird. Es ist durchaus möglich, die Mischung aus Ätzlösung und Peroxid bereits kurz vor dem Aufbringen auf die Leiterplatten herzustellen und durch gemeinsame Düsen zu versprühen.This procedure also has the advantage that the etching solution supplied to the collecting container 11 contains little copper, so that when this low-copper etching solution is mixed with peroxide from the storage container, the catalytic decomposition of the peroxide is reduced. It is entirely possible to produce the mixture of etching solution and peroxide shortly before it is applied to the printed circuit boards and to spray it through common nozzles.

In einem abgewandelten Ausführungsbeispiel sind für Ätzlösung und Peroxid getrennte Sprühdüsen vorgesehen, so daß das reaktionsfähige Gemisch erst auf den Leiterplatten selbst gebildet wird. In diesem Falle wird jede katalytische Zersetzung des Peroxids vor der eigentlichen Reaktion mit Sicherheit vermieden.In a modified embodiment, separate spray nozzles are provided for the etching solution and peroxide, so that the reactive mixture is only formed on the circuit boards themselves. In this case, any catalytic decomposition of the peroxide before the actual reaction is avoided with certainty.

Claims (5)

1. Process for etching metal surfaces, in particular printed circuits, wherein the metal (such as copper) is corroded off the circuit by means of a solution containing sulfuric acid or phosphoric acid and hydrogen peroxide and this solution is passed through a cycle and used repeatedly for etching, characterized in that hydrogen peroxide is added to the solution immediately prior to each application or during application to the circuit to be etched in such an amount that it is just sufficient for each etching procedure and substantially no hydrogen peroxide remains in the solution after the etching procedure.
2. Process as defined in claim 1, characterized in that after each etching procedure the copper corroded off is at least partially removed from the solution.
3. Process as defined in claim 2, characterized in that the copper is removed from the solution electrolytically.
4. Process as defined in claim 2, characterized in that when sulfuric acid is used the copper is removed from the solution by cooling said solution and thereby causing precipitation of copper sulfate.
5. Process as defined in any of the preceding claims, characterized in that the solution and the hydrogen peroxide are sprayed separately onto the circuit to be etched.
EP81109230A 1980-12-10 1981-10-29 Process for etching metal surfaces Expired EP0053719B1 (en)

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Application Number Priority Date Filing Date Title
DE19803046477 DE3046477A1 (en) 1980-12-10 1980-12-10 "METHOD FOR ETCHING METAL SURFACES"
DE3046477 1980-12-10

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EP0053719A1 EP0053719A1 (en) 1982-06-16
EP0053719B1 true EP0053719B1 (en) 1987-09-09

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DE2358683A1 (en) * 1973-11-24 1975-06-05 Kalman Von Dipl Phys Soos Pickling, etching or cleaning of metals, esp. steel - using ozone accelerator in addn. to the other chemicals
IT1083401B (en) * 1977-05-27 1985-05-21 Alfachimici Spa ACID SOLUTION FOR SELECTIVE COPPER ATTACK

Cited By (1)

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Publication number Priority date Publication date Assignee Title
DE4206626A1 (en) * 1992-03-03 1993-09-09 Heidelberger Druckmasch Ag METHOD FOR REDUCING DUBLIERS WHEN STARTING A SHEET PRINTING MACHINE

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EP0053719A1 (en) 1982-06-16
DE3176426D1 (en) 1987-10-22

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