EP0144742B1 - Verfahren und Anlage zum Regenerieren einer ammoniakalischen Ätzlösung - Google Patents

Verfahren und Anlage zum Regenerieren einer ammoniakalischen Ätzlösung 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
European Patent Office
Prior art keywords
etching solution
etching
electrolysis cell
regenerated
chamber
Prior art date
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.)
Expired
Application number
EP84113228A
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German (de)
English (en)
French (fr)
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EP0144742A1 (de
Inventor
Leander Fürst
Walter Holzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Original Assignee
Elo Chem Atztechnik GmbH
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich GmbH
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Publication date
Application filed by Elo Chem Atztechnik GmbH, Forschungszentrum Juelich GmbH, Kernforschungsanlage Juelich GmbH filed Critical Elo Chem Atztechnik GmbH
Publication of EP0144742A1 publication Critical patent/EP0144742A1/de
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Publication of EP0144742B1 publication Critical patent/EP0144742B1/de
Expired legal-status Critical Current

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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)
EP84113228A 1983-11-08 1984-11-02 Verfahren und Anlage zum Regenerieren einer ammoniakalischen Ätzlösung Expired EP0144742B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833340342 DE3340342A1 (de) 1983-11-08 1983-11-08 Verfahren und anlage zum regenerieren einer ammoniakalischen aetzloesung
DE3340342 1983-11-08

Publications (2)

Publication Number Publication Date
EP0144742A1 EP0144742A1 (de) 1985-06-19
EP0144742B1 true EP0144742B1 (de) 1987-07-15

Family

ID=6213744

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84113228A Expired EP0144742B1 (de) 1983-11-08 1984-11-02 Verfahren und Anlage zum Regenerieren einer ammoniakalischen Ätzlösung

Country Status (4)

Country Link
US (1) US4557811A (enrdf_load_stackoverflow)
EP (1) EP0144742B1 (enrdf_load_stackoverflow)
JP (1) JPS60116789A (enrdf_load_stackoverflow)
DE (2) DE3340342A1 (enrdf_load_stackoverflow)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3429902A1 (de) * 1984-08-14 1986-02-27 Hans Höllmüller Maschinenbau GmbH & Co, 7033 Herrenberg Verfahren zum aetzen von kupferfilmen auf leiterplatten unter elektrolytischer rueckgewinnung von kupfer aus der aetzloesung
US4784785A (en) * 1987-12-29 1988-11-15 Macdermid, Incorporated Copper etchant compositions
DE3839651A1 (de) * 1988-11-24 1990-05-31 Hoellmueller Hans Anlage zum aetzen von gegenstaenden
CA2029444A1 (en) * 1990-03-21 1991-09-22 Raymond A. Letize System and process for etching with and regenerating, alkaline ammoniacal etchant solution
DE4014429A1 (de) * 1990-05-05 1991-11-07 Hoechst Ag Verfahren zur regelung des durchsatzes bei der elektrochemischen regeneration von chromschwefelsaeure
US5085730A (en) * 1990-11-16 1992-02-04 Macdermid, Incorporated Process for regenerating ammoniacal chloride etchants
US5248398A (en) * 1990-11-16 1993-09-28 Macdermid, Incorporated Process for direct electrolytic regeneration of chloride-based ammoniacal copper etchant bath
US5417818A (en) * 1993-11-24 1995-05-23 Elo-Chem Atztechnik Gmbh Process for the accelerated etching and refining of metals in ammoniacal etching systems
US6322675B1 (en) * 2000-02-14 2001-11-27 Carrier Corporation Copper removal system for absorption cooling unit
US7404904B2 (en) * 2001-10-02 2008-07-29 Melvin Stanley Method and apparatus to clean particulate matter from a toxic fluid
KR100964543B1 (ko) * 2008-10-31 2010-06-21 주식회사 하이소닉 소형 카메라모듈용 커버 및 그 제조방법 및 이를 장착한 소형 카메라모듈
CN120569515A (zh) * 2023-01-13 2025-08-29 叶涛 一种电解辅助碱性氯化铜氨蚀刻工作液氧化再生的方法及其设备

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964453A (en) * 1957-10-28 1960-12-13 Bell Telephone Labor Inc Etching bath for copper and regeneration thereof
US3772105A (en) * 1970-07-24 1973-11-13 Shipley Co Continuous etching process
US3705061A (en) * 1971-03-19 1972-12-05 Southern California Chem Co In Continuous redox process for dissolving copper
BE789944A (fr) * 1971-10-12 1973-02-01 Shipley Co Regeneration d'une solution usagee d'attaque du cuivre
DE2216269A1 (de) * 1972-04-05 1973-10-18 Hoellmueller Maschbau H Verfahren zum aetzen von kupfer und kupferlegierungen
DE2521282C2 (de) * 1975-05-13 1977-03-03 Siemens Ag Prozessteueranlage zum selbsttaetigen analysieren und auffrischen von galvanischen baedern
JPS5617429A (en) * 1979-07-23 1981-02-19 Noriyuki Yoshida Inputting method for character and symbol to computer system with video interface
DE3031567A1 (de) * 1980-08-21 1982-04-29 Elochem Ätztechnik GmbH, 7758 Meersburg Verfahren zum regenerieren einer ammoniakalischen aetzloesung
CS218296B1 (en) * 1980-10-30 1983-02-25 Antonin Stehlik Method of continuous regeneration of the iron trichloride solution

Also Published As

Publication number Publication date
JPS60116789A (ja) 1985-06-24
US4557811A (en) 1985-12-10
DE3464768D1 (en) 1987-08-20
EP0144742A1 (de) 1985-06-19
JPH0536509B2 (enrdf_load_stackoverflow) 1993-05-31
DE3340342A1 (de) 1985-05-15

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