EP0137123A2 - Etching solution containing ammonium sulfate, and process for regenerating it - Google Patents

Etching solution containing ammonium sulfate, and process for regenerating it Download PDF

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Publication number
EP0137123A2
EP0137123A2 EP84107605A EP84107605A EP0137123A2 EP 0137123 A2 EP0137123 A2 EP 0137123A2 EP 84107605 A EP84107605 A EP 84107605A EP 84107605 A EP84107605 A EP 84107605A EP 0137123 A2 EP0137123 A2 EP 0137123A2
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EP
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Prior art keywords
etching solution
etching
ammonium sulfate
solution
weight
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP84107605A
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German (de)
French (fr)
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EP0137123B1 (en
EP0137123A3 (en
Inventor
Leander Fürst
Walter Holzer
Bertel Prof. Dr. Kastening
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Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Original Assignee
Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich GmbH
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Publication of EP0137123A2 publication Critical patent/EP0137123A2/en
Publication of EP0137123A3 publication Critical patent/EP0137123A3/en
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Publication of EP0137123B1 publication Critical patent/EP0137123B1/en
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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
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline compositions for etching copper or alloys thereof
    • 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 an ammoniacal etching solution specified in the preamble of claim 1 and to a regeneration process of the; Art.
  • Alkaline etchants such as ammoniacal copper tetrammine salt solutions, 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 that are not resistant to acidic etching media, for example made of lead, tin or nickel.
  • a re-oxidation of the alkaline etching solution after etching off the metal is carried out with the addition of ammonia gas and / or ammonium salt in the presence of oxygen or air.
  • the object of the invention is to provide an ammoniacal etching solution in which, without the addition of suspended catalyst particles, the regeneration of the etching solution is accelerated as well as the deposition - etched copper in an electrolysis cell is made possible with extensive oxygen development at the anode, whereby the electrolyte is degraded and one C hlorinal to be substantially avoided.
  • An etching solution having the chlorine ion concentration specified in claim 2 is preferably used.
  • a solution of 150 g of ammonium sulfate and 50 g of copper per liter was adjusted to a pH of 9.5 by adding gaseous ammonia.
  • the solution was gassed with air for oxidation.
  • the potential the solution was measured at room temperature using a platinum pen against a mercury / mercury oxide reference electrode.
  • etching solutions containing ammonium sulfate the invention is also applicable to etching solutions which, like the aforementioned etching solution, contain oxygen-containing anions, such as, for example, etching solutions containing ammonium nitrate or ammonium carbonate.
  • Another embodiment shows that the addition of chlorine ions also increases the etching rate that can be achieved with the etching solution.
  • copper-coated circuit boards were etched at a temperature of 40 ° C. using an etching solution of 150 g per liter of ammonium sulfate and 80 g per liter of copper in the form of copper tetramine sulfate, which was adjusted to a pH of 9.2 by gassing with ammonia.
  • the mean etching rate achieved with this starting solution was 7.8 ⁇ m per minute.
  • ammonium chloride an additional 0.2% by weight of chlorine ions were dissolved in the etching solution. With this etching solution, the etching speed could be increased to 11.7 ⁇ m per minute.
  • a further increase in the chlorine ion concentration by adding ammonium chloride to a total of 0.4% by weight increases the etching rate only slightly. The etching rate at this concentration was 12.3 ⁇ m per minute.

Abstract

Eine ammoniumsulfathaltige Ätzlösung wird durch Rückoxidation des in der Ätzlösung enthaltenden Ätzmittels unter Zufuhr von Sauerstoff regeneriert, Das mit der Ätzlösung abgeätzte Metall wird in einer Elektrolysezelle aus der Ätzlösung abgeschieden. Die Elektrolysezelle wird zumindest von einem Teil der Atzlösung durchströmt. Um sowohl die Regeneration der Ätzlösung zu beschleunigen als auch die Abscheidung abgeätzten Kupfers in der Elektrolysezelle sicherzustellen, enthält die Ätzlösung 0,5 bis 0,4 Gew.%, bevorzugt 0,1 bis 0,3 Gew.% Chlorionen.An etching solution containing ammonium sulfate is regenerated by re-oxidation of the etchant contained in the etching solution while supplying oxygen. The metal etched off with the etching solution is separated from the etching solution in an electrolysis cell. At least part of the etching solution flows through the electrolytic cell. In order to both accelerate the regeneration of the etching solution and to ensure the deposition of etched copper in the electrolysis cell, the etching solution contains 0.5 to 0.4% by weight, preferably 0.1 to 0.3% by weight, of chlorine ions.

Description

Die Erfindung bezieht sich auf eine im Oberbegriff des Patentanspruches 1 angegebene ammoniakalische Ätzlösung sowie auf ein Regenerationsverfahren der ; in Patentanspruch 2 angegebenen Art.The invention relates to an ammoniacal etching solution specified in the preamble of claim 1 and to a regeneration process of the; Art.

Alkalische Ätzmittel, aie Ammoniakalische Kupfertetramminsalz-Lösungen 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 nicht beständige Metallteile, beispielsweise aus Blei, Zinn oder Nickel aufweisen. Eine Rückoxidation der alkalischen Ätzlösung nach Abätzen des Metalls wird unter Zugabe von Ammoniakgas und/oder Ammoniumsalz in Gegenwart von Sauerstoff bzw. Luft durchgeführt.Alkaline etchants, such as ammoniacal copper tetrammine salt solutions, 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 that are not resistant to acidic etching media, for example made of lead, tin or nickel. A re-oxidation of the alkaline etching solution after etching off the metal is carried out with the addition of ammonia gas and / or ammonium salt in the presence of oxygen or air.

Aus DE-OS 30 31 567 ist es bekannt, in der Ätzlösung Katalysatorteilchen zu suspensieren, 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 nur ein Teil der Ätzlösung die Elektrolysezelle. Dieser Teil wird nach Abscheiden des Metalls als frische Ätzlösung zur Ätzkammer zurückgeführt und kann als Spüllösung für die nach dem Ätzen von Katalysatorteilchen zu reinigenden Leiterplatten verwendet werden. Dem Vorzug einer guten Kupferabscheidung in der Elektrolysezelle steht der Nachteil gegenüber, daß vor Eintritt in die Elektrolysezelle die in der Ätzlösung suspendierten Katalysatorteilchen abzutrennen sind.From DE-OS 30 31 567 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 which lead to toxic residual solutions. In the known method, the etched metals are deposited in an electrolytic cell. For this purpose, only a part of the etching solution flows through the electrolytic cell. After the metal has been deposited, this part is returned to the etching chamber as a fresh etching solution and can be used as a rinsing solution for the circuit boards to be cleaned after the etching of catalyst particles. The advantage of good copper deposition in the electrolysis cell is offset by the disadvantage that the catalyst particles suspended in the etching solution have to be separated off before entering the electrolysis cell.

Bekannt ist auch das Ätzen von Leiterplatten unter Verwendung ammoniumchloridhaltiger Ätzlösungen mit einem ammoniakalischen Kupferkomplex als Ätzmittel. Würde eine solche Lösung zur Abscheidung von Kupfer in eine Elektrolysezelle geleitet, so ist mit einer Zersetzung des Elektrolyten und mit nicht erwünschter Chlorentwicklung an der Anode zu rechnen.It is also known to etch printed circuit boards using etching solutions containing ammonium chloride with an ammoniacal copper complex as the etchant. If such a solution for the deposition of copper were passed into an electrolytic cell, decomposition of the electrolyte and undesired chlorine development at the anode can be expected.

Aufgabe der Erfindung ist es, eine ammoniakalische Ätzlösung anzugeben, bei der ohne Zugabe suspendierter Katalysatorteilchen sowohl die Regeneration der Ätzlösung beschleunigt ist als auch die Abscheidung - abgeätzten Kupfers in einer Elektrolysezelle ermöglicht wird unter weitgehender Sauerstoffentwicklung an der Anode, wobei ein Abbau des Elektrolyten und eine Chlorentwicklung im wesentlichen vermieden werden soll.The object of the invention is to provide an ammoniacal etching solution in which, without the addition of suspended catalyst particles, the regeneration of the etching solution is accelerated as well as the deposition - etched copper in an electrolysis cell is made possible with extensive oxygen development at the anode, whereby the electrolyte is degraded and one C hlorentwicklung to be substantially avoided.

Diese Aufgabe wird bei einer Ätzlösung der eingangs bezeichneten Art gemäß der Erfindung durch die im Patentanspruch 1 genannte Zugabe einer geringen Chlorionenmenge gelöst.This object is achieved in an etching solution of the type mentioned at the outset according to the invention by the addition of a small amount mentioned in claim 1 C hlorionenmenge dissolved.

Es hat sich herausgestellt, daß der Zusatz von Chlorid zur Ätzlösung die Regeneration.dann beschleunigt, wenn die Chlorionen-Konzentration nicht höher als O,4 Gew.% eingestellt ist. Eine darüberhinausgehende Zugabe von Chlorid verschlechtert die Regenerationsgeschwindigkeit unter die einer reinen Ammoniumsulfat-Lösung mit Kupfertetraminsulfat als Ätzmittel. Bei sehr viel höherem Chlorionen-Gehalt wird zwar das Regenerieren wieder beschleunigt, jedoch treten dann die oben angegebenen Nachteile bei Verwendung von Ammoniumchlorid-Ätzlösungen wieder verstärkt auf.It has been found that the addition of chloride to the etching solution accelerates the regeneration when the chlorine ion concentration is not higher than 0.4% by weight. An additional addition of chloride deteriorates the regeneration rate below that of a pure ammonium sulfate solution with copper tetramine sulfate as an etchant. If the chlorine ion content is much higher, the regeneration is accelerated again, but then the above-mentioned disadvantages occur again when using ammonium chloride etching solutions.

Bevorzugt wird eine Ätzlösung mit in Anspruch 2 angegebener Chlorionen-Konzentration eingesetzt.An etching solution having the chlorine ion concentration specified in claim 2 is preferably used.

Ein Verfahren zum Regenerieren der Ätzlösung unter Verwendung einer Ammoniumsulfat-Ätzlösung mit geringer Chlorionen-Konzentration ist in Patentansprüchen 3 und 4 angegeben.A method for regenerating the etching solution using an ammonium sulfate etching solution with a low chlorine ion concentration is specified in patent claims 3 and 4.

Nachfolgend sind anhand eines in der Zeichnung wiedergegebenen Diagrammes Ausführungsbeispiele für die Erfindung beschriebenExemplary embodiments of the invention are described below using a diagram shown in the drawing

Eine Lösung von 150 g Ammoniumsulfat und 50 g Kupfer pro Liter wurde durch Zugabe gasförmigen Ammoniaks auf einen pH-Wert von 9,5 eingestellt. Die Lösung wurde zur Oxidation mit Luft begast. Das Potential der Lösung wurde bei Raumtemperatur über einen Platinstift gegen eine Quecksilber/Quecksilberoxid-Referenzelektrode gemessen.A solution of 150 g of ammonium sulfate and 50 g of copper per liter was adjusted to a pH of 9.5 by adding gaseous ammonia. The solution was gassed with air for oxidation. The potential the solution was measured at room temperature using a platinum pen against a mercury / mercury oxide reference electrode.

In der Lösung wurden anschließend 20 g Kupferpulver gelöst, was eine Absenkung des Potentials in der Lösung um 330 Millivolt (mV) zur Folge hatte. Der zeitliche Verlauf des Potentials in der sich wieder regenerierenden Ätzlösung ist in der Zeichnung mit Kurve I wiedergegeben. Das Endpotential in der Lösung von 260 mV wurde nach 60 Minuten erreicht.Then 20 g of copper powder were dissolved in the solution, which resulted in a reduction of the potential in the solution by 330 millivolts (mV). The time course of the potential in the regenerating etching solution is shown in the drawing with curve I. The final potential in the solution of 260 mV was reached after 60 minutes.

Durch Zugabe von Ammoniumchlorid wurden verschiedene Chlorionen-Konzentrationen eingestellt. Die Kurven II bis V zeigen die Regeneration von Ätzlösungen mit Chlorionen-Konzentrationen von 0,1 bis 0,6 Gew.% Chlorionen in der Lösung. Mit 0,1 Gew.% wurde das Endpotential von 280 mV gegenüber der Lösung nach Kurve I bereits nach 43 Minuten erreicht, eine geringe Verbesserung ergab sich noch bei 0,4 Gew.% Chlorionen in der Lösung. Mit 0,6 Gew.% Chlorionen-Konzentration stellte sich das Endpotential erst nach 84 Minuten ein.Various chlorine ion concentrations were set by adding ammonium chloride. Curves II to V show the regeneration of etching solutions with chlorine ion concentrations of 0.1 to 0.6% by weight of chlorine ions in the solution. With 0.1 wt.%, The E was achieved ndpotential of 280 mV compared to the solution according to curve I already after 43 minutes a small improvement was still at 0.4 wt.% Of chlorine ions in the solution. With a concentration of 0.6% by weight of chlorine ions, the final potential was only reached after 84 minutes.

Die Erfindung ist über ammoniumsulfathaltige Ätzlösungen hinaus auch bei Ätzlösungen anwendbar, die ebenso wie die vorgenannte Ätzlösung sauerstoffhaltige Anionen enthalten, wie beispielsweise bei Ammoniumnitrat- oder Ammoniumcarbonat enthaltenden Ätzlösungen.In addition to etching solutions containing ammonium sulfate, the invention is also applicable to etching solutions which, like the aforementioned etching solution, contain oxygen-containing anions, such as, for example, etching solutions containing ammonium nitrate or ammonium carbonate.

Ein weiteres Ausführungsbeispiel zeigt, daß durch die Zugabe von Chlorionen auch die mit der Ätzlösung erzielbare Ätzgeschwindigkeit angehoben wird. So wurden mit einer Ätzlösung von 150 g pro Liter Ammoniumsulfat und 80 g pro Liter Kupfer in Form von Kupfertetraminsulfat, die auf einen pH-Wert von 9,2 durch Begasen mit Ammoniak eingestellt war, bei einer Temperatur von 40 °C kupferbeschichtete Leiterplatten geätzt. Die mit dieser Ausgangslösung erreichte mittlere Ätzgeschwindigkeit betrug 7,8 µm pro Minute. Durch Zugabe von Ammoniumchlorid wurden in der Ätzlösung zusätzlich 0,2 Gew.% Chlorionen gelöst. Mit dieser Ätzlösung konnte die Ätzgeschwindigkeit auf 11,7 µm pro Minute gesteigert werden. Ein weiteres Anheben der Chlorionen-Konzentration durch die Zugabe von Ammmoniumchlorid auf insgesamt 0,4 Gew.% vergrößert die Ätzgeschwindigkeit nur noch gering. Die Ätzgeschwindigkeit betrug bei dieser Konzentration 12,3 µm pro Minute.Another embodiment shows that the addition of chlorine ions also increases the etching rate that can be achieved with the etching solution. Thus, copper-coated circuit boards were etched at a temperature of 40 ° C. using an etching solution of 150 g per liter of ammonium sulfate and 80 g per liter of copper in the form of copper tetramine sulfate, which was adjusted to a pH of 9.2 by gassing with ammonia. The mean etching rate achieved with this starting solution was 7.8 μm per minute. By adding ammonium chloride, an additional 0.2% by weight of chlorine ions were dissolved in the etching solution. With this etching solution, the etching speed could be increased to 11.7 µm per minute. A further increase in the chlorine ion concentration by adding ammonium chloride to a total of 0.4% by weight increases the etching rate only slightly. The etching rate at this concentration was 12.3 µm per minute.

Claims (4)

1. Ammoniumsulfathaltige Ätzlösung, die zum Regenerieren durch Rückoxidation des in der Ätzlösung enthaltenen Ätzmittels unter Zufuhr von Sauerstoff und zum Abscheiden abgeätzten Metalls aus der Ätzlösung in einer Elektrolysezelle geeignet ist, die zumindest von einem Teil der Ätzlösung durchströmt wird, dadurch gekennzeichnet, daß die Ätzlösung 0,05 bis O 4 Gew.% Chlorionen enthält.1. Ammonium sulfate-containing etching solution, which is suitable for regeneration by re-oxidation of the etchant contained in the etching solution while supplying oxygen and for separating etched-off metal from the etching solution in an electrolytic cell, through which at least part of the etching solution flows, characterized in that the etching solution Contains 0.05 to O 4% by weight of chlorine ions. 2. Ätzlösung nach Anspruch 1, dadurch gekennzeichnet, daß die Ätzlösung O,1 bis 0,3 Gew.% Chlorionen enthält.2. Etching solution according to claim 1, characterized in that the etching solution contains 0.1 to 0.3% by weight of chlorine ions. 3. Verfahren zum Regenerieren einer ammoniumsulfathaltigen Ätzlösung durch Rückoxidation des in der Ätzlösung enthaltenen Ätzmittels unter Zufuhr von Sauerstoff und durch Abscheiden abgeätzten Metalls aus der Ätzlösung in einer Elektrolysezelle, die zumindest von einem Teil der Ätzlösung durchströmt wird, dadurch gekennzeichnet, daß der Ätzlösung 0,05 bis 0,4 Gew.% Chlorionen zugegeben werden.3. A method for regenerating an etching solution containing ammonium sulfate by re-oxidation of the etching agent contained in the etching solution while supplying oxygen and by separating etched metal from the etching solution in an electrolysis cell through which at least part of the etching solution flows, characterized in that the etching solution 0 , 05 to 0.4% by weight of chlorine ions are added. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der Ätzlösung 0.1 bis 0,3 Gew.% Chlorionen zugegeben werden.4. The method according to claim 3, characterized in that 0.1 to 0.3 wt.% Chlorine ions are added to the etching solution.
EP84107605A 1983-07-07 1984-06-30 Etching solution containing ammonium sulfate, and process for regenerating it Expired EP0137123B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3324450 1983-07-07
DE3324450A DE3324450A1 (en) 1983-07-07 1983-07-07 AMMONIUM SULFATE-CONTAINING ETCH SOLUTION AND METHOD FOR REGENERATING THE ETCH SOLUTION

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EP0137123A2 true EP0137123A2 (en) 1985-04-17
EP0137123A3 EP0137123A3 (en) 1986-05-07
EP0137123B1 EP0137123B1 (en) 1988-06-01

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EP84107605A Expired EP0137123B1 (en) 1983-07-07 1984-06-30 Etching solution containing ammonium sulfate, and process for regenerating it

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US (1) US4564428A (en)
EP (1) EP0137123B1 (en)
JP (1) JPH07100875B2 (en)
DE (2) DE3324450A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3429902A1 (en) * 1984-08-14 1986-02-27 Hans Höllmüller Maschinenbau GmbH & Co, 7033 Herrenberg METHOD FOR ETCHING COPPER FILMS ON BOARDS UNDER ELECTROLYTIC RECOVERY OF COPPER FROM THE ACET SOLUTION
US4784785A (en) * 1987-12-29 1988-11-15 Macdermid, Incorporated Copper etchant compositions
US5248398A (en) * 1990-11-16 1993-09-28 Macdermid, Incorporated Process for direct electrolytic regeneration of chloride-based ammoniacal copper etchant bath
US5085730A (en) * 1990-11-16 1992-02-04 Macdermid, Incorporated Process for regenerating ammoniacal chloride etchants
CN102019430B (en) * 2009-09-18 2012-09-05 福建师范大学福清分校 Method for recovering copper from alkaline etching waste liquid and recycling alkaline etching liquid
US11037792B2 (en) * 2018-10-25 2021-06-15 Taiwan Semiconductor Manufacturing Company Ltd. Semiconductor structure etching solution and method for fabricating a semiconductor structure using the same etching solution

Citations (3)

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Publication number Priority date Publication date Assignee Title
FR2156249A1 (en) * 1971-10-12 1973-05-25 Shipley Co
FR2179267A1 (en) * 1972-04-05 1973-11-16 Hoellmueller Maschbau H Etching copper - with alkaline soln contg ammonium salt for dissolving copper, and complex former
EP0046522A1 (en) * 1980-08-21 1982-03-03 Forschungszentrum Jülich Gmbh Method for the regeneration of an ammoniacal etchant

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CH568225A5 (en) * 1973-06-22 1975-10-31 Sulzer Ag
US3999564A (en) * 1976-01-09 1976-12-28 Pesek Engineering & Mfg. Co. Continuous etching and etched material recovery system
DE2850564C2 (en) * 1978-11-22 1982-12-23 Kernforschungsanlage Jülich GmbH, 5170 Jülich Method and device for regenerating an etching solution containing copper (II) chloride and / or iron (III) chloride in an electrolytic cell
DE2917597A1 (en) * 1979-04-30 1980-11-13 Siemens Ag METHOD FOR REGENERATING AMMONIACAL ETCH SOLUTIONS FOR ETCHING METALLIC COPPER
JPS5610677A (en) * 1979-07-06 1981-02-03 Tokyo Shibaura Electric Co Refrigerating plant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2156249A1 (en) * 1971-10-12 1973-05-25 Shipley Co
FR2179267A1 (en) * 1972-04-05 1973-11-16 Hoellmueller Maschbau H Etching copper - with alkaline soln contg ammonium salt for dissolving copper, and complex former
EP0046522A1 (en) * 1980-08-21 1982-03-03 Forschungszentrum Jülich Gmbh Method for the regeneration of an ammoniacal etchant

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EP0137123B1 (en) 1988-06-01
EP0137123A3 (en) 1986-05-07
JPS6052600A (en) 1985-03-25
DE3471693D1 (en) 1988-07-07
US4564428A (en) 1986-01-14
JPH07100875B2 (en) 1995-11-01
DE3324450A1 (en) 1985-01-17

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