EP0141905B1 - Procédé pour compenser par voie électrochimique l'oxydation par l'air dans la régénération électrochimique de solution de décapage de cuivre contenant du chlorure - Google Patents

Procédé pour compenser par voie électrochimique l'oxydation par l'air dans la régénération électrochimique de solution de décapage de cuivre contenant du chlorure Download PDF

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Publication number
EP0141905B1
EP0141905B1 EP84108467A EP84108467A EP0141905B1 EP 0141905 B1 EP0141905 B1 EP 0141905B1 EP 84108467 A EP84108467 A EP 84108467A EP 84108467 A EP84108467 A EP 84108467A EP 0141905 B1 EP0141905 B1 EP 0141905B1
Authority
EP
European Patent Office
Prior art keywords
anode
electrochemical
chloride
process according
copper
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
EP84108467A
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German (de)
English (en)
Other versions
EP0141905A1 (fr
Inventor
Rudi Dr. Dipl.-Chem. Ott
Heribert Reith
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.)
OFFERTA DI LICENZA AL PUBBLICO
Original Assignee
Robert Bosch GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP0141905A1 publication Critical patent/EP0141905A1/fr
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Publication of EP0141905B1 publication Critical patent/EP0141905B1/fr
Expired legal-status Critical Current

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Classifications

    • 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 is based on a method according to the preamble of the main claim.
  • etching solutions for metals that contain copper (II) chloride or iron (III) chloride the copper (I) chloride or iron (II) chloride formed during the etching becomes partly due to the oxygen in the air Cull or Fell oxidizes according to the reaction equation
  • the intermediate copper (II) oxide reacts according to (2) with the consumption of additional hydrochloric acid
  • This side reaction is noticeable by a pH increase in copper etching solutions containing chloride.
  • the air oxidation of CuCI is particularly noticeable when the etching solution is used for spray etching, since the surface of the solution exposed to the air is particularly large.
  • Such etching solutions such as CuCl 2 hydrochloric acid or CuCl 2 alkali chloride, can be regenerated electrochemically according to the chemical equations (3), (4), (5) by means of appropriate electrolysis devices:
  • the method according to the invention with the characterizing features of the main claim has the advantage, in addition to the normally preferred chloride oxidation, that an electrochemical decomposition of water into gaseous oxygen and hydrogen ions according to the reaction equation is also carried out on the anode can be realized.
  • the oxygen formed in this reaction escapes essentially in gaseous form from the etching solution, since the solubility for oxygen, in contrast to that for chlorine, is only very low.
  • the hydrogen ions remain in the solution, which in the desired manner ensure that the pH remains essentially constant and thus compensate for the air oxidation of CuCI, which occurs particularly during spray etching.
  • etching solution was sprayed onto the printed circuit boards at a pressure of 2.5 bar.
  • the etching solution had a volume of 660 I, contained 150 g / I KCl and 50 g / I Cu and had a temperature of 50 ° C.
  • This solution was pumped by the etching system into a regeneration system, as described in DE-OS 3303594 is described.
  • Two cells were connected in series and the anodes consisted of titanium rods 8 mm in diameter with an iridium oxide coating. The anode surface area was 14.3 dm 2 per cell.
  • the anode material was wrapped with a filter cloth made of polypropylene in the form of 8 mm wide strips in such a way that the strips abut each other in order to obtain gaps in the casing so that the gases released at the anode can escape oxygen and chlorine.
  • a current of 550 A and a voltage of 19.5 V flowed in the rain cells connected in series.
  • the electrochemical process was controlled by detecting the copper (I) ions with the help of the redox potential and switching off the current at a value of 375 mV. If the regeneration system was operated without the PCBs being etched, the pH fell from the initial 2.5 to approximately 1.9 after approximately 1 1/2 hours.
  • the current yield for the reaction according to equation (6) depends on the current density with which the regeneration system is operated and for example at 30 A / dm 2 at 20%, at 50 A / dm 2 at 45% and at 90 A / dm 2 is finally 60%.
  • the choice of the anodic current density is therefore one possibility, the amount of hydrogen ions formed to adapt to the amount of Cu (t) ions oxidized by the air, for example by controlling the anodic current density in such a way that the pH is kept constant at, for example, 2.0.
  • Another possibility of matching the amount of H 'formed to the amount of Cu (I) ions oxidized by the air lies in the type of anode coating by changing the porosity or by varying the number and type of gas gaps.

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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)

Claims (6)

1. Procédé pour compenser électrochimique- ment l'oxydation par l'air dans le cas de la régénération électrochimique de solutions d'attaques chimiques contenant des chlorures de cuivre, cette solution d'attaque chimique étant alors canalisée à travers une installation de régénération qui comporte une cathode et une anode non solubles, auxquelles est appliquée une tension continue, de façon que du cuivre métallique soit déposé sur la cathode, tandis qu'il se forme sur l'anode du chlore, qui oxyde le chlorure de cuivre monovalent en chlorure de cuivre bivalent, procédé caractérisé en ce que l'anode, en vue de décomposer l'eau en oxygène gazeux et en ions hydrogène, est entourée d'un matériau poreux agissant comme diaphragme qui empêche l'accès des ions chlore à l'anode.
2. Procédé selon la revendication 1, caractérisé en ce que ce matériau poreux est appliqué de façon adhérente sur le matériau d'anode.
3. Procédé selon la revendication 2, caractérisé en ce que le matériau d'anode est constitué de titane, de niobium ou de tantale revêtus d'un métal du groupe du platine, ou de titane, de niobium ou de tantale revêtus d'oxydes métalliques, ces oxydes étant de préférence des oxydes de métaux du groupe du platine, ou bien que le matériau d'anode est constitué de graphite.
4. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériaux poreux est constitué d'un matériau filtrant.
5. Procédé selon la revendication 4, caractérisé en ce que le matériau poreux est constitué d'un matériau filtrant polypropylène.
6. Procédé selon la revendication 5, caractérisé en ce que le matériau filtrant polypropylène est enroulé sous la forme de bandes contiguës autour de l'anode.
EP84108467A 1983-08-23 1984-07-18 Procédé pour compenser par voie électrochimique l'oxydation par l'air dans la régénération électrochimique de solution de décapage de cuivre contenant du chlorure Expired EP0141905B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3330349A DE3330349A1 (de) 1983-08-23 1983-08-23 Verfahren zur elektrochemischen kompensation der luftoxidation bei der elektrochemischen regenerierung von chloridhaltigen kupferaetzloesungen
DE3330349 1983-08-23

Publications (2)

Publication Number Publication Date
EP0141905A1 EP0141905A1 (fr) 1985-05-22
EP0141905B1 true EP0141905B1 (fr) 1986-10-08

Family

ID=6207205

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84108467A Expired EP0141905B1 (fr) 1983-08-23 1984-07-18 Procédé pour compenser par voie électrochimique l'oxydation par l'air dans la régénération électrochimique de solution de décapage de cuivre contenant du chlorure

Country Status (2)

Country Link
EP (1) EP0141905B1 (fr)
DE (2) DE3330349A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4010035A1 (de) * 1990-03-29 1991-10-02 Hoellmueller Maschbau H Vorrichtung zur elektrolytischen regeneration eines chlorid- und metallionen enthaltenden aetzmittels
DE69219063T2 (de) * 1991-10-28 1997-11-20 Nittetsu Mining Co Ltd Verfahren zum Regenerieren von Ätzmitteln

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2008766B2 (de) * 1970-02-23 1971-07-29 Licentia Patent Verwaltungs GmbH, 6000 Frankfurt Verfahren zum regenerieren einer kupferhaltigen aetzloesung insbesondere fuer die herstellung von gedruckten schaltungen
DE2241462A1 (de) * 1972-08-23 1974-03-07 Bach & Co Verfahren zum rueckgewinnen einer kupfer(ii)-chlorid enthaltenden aetzloesung
DE2641905C2 (de) * 1976-09-17 1986-03-20 Geb. Bakulina Galina Aleksandrovna Batova Verfahren zur Regenerierung verbrauchter Ätzlösungen
DE2650912A1 (de) * 1976-11-06 1978-05-18 Hoellmueller Maschbau H Elektrolytische regeneration eines aetzmittels
DE2850564C2 (de) * 1978-11-22 1982-12-23 Kernforschungsanlage Jülich GmbH, 5170 Jülich Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle

Also Published As

Publication number Publication date
DE3330349A1 (de) 1985-03-14
DE3460905D1 (en) 1986-11-13
EP0141905A1 (fr) 1985-05-22

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