EP0141905A1 - 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 PDFInfo
- Publication number
- EP0141905A1 EP0141905A1 EP84108467A EP84108467A EP0141905A1 EP 0141905 A1 EP0141905 A1 EP 0141905A1 EP 84108467 A EP84108467 A EP 84108467A EP 84108467 A EP84108467 A EP 84108467A EP 0141905 A1 EP0141905 A1 EP 0141905A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anode
- copper
- electrochemical
- chloride
- regeneration
- 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.)
- Granted
Links
- 238000005530 etching Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000008929 regeneration Effects 0.000 title claims abstract description 13
- 238000011069 regeneration method Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 title claims abstract description 11
- 230000003647 oxidation Effects 0.000 title claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract description 6
- -1 hydrogen ions Chemical class 0.000 claims abstract description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 229910052715 tantalum Inorganic materials 0.000 claims 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002476 CuII Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002553 FeIII Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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 CuII or FeIII. 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 CuCl 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 CuC1 2 hydrochloric acid or CuCl 2 alkali chloride can be regenerated electrochemically according to the chemical equations (3), (4), (5) using appropriate electrolysis devices:
- circuit boards were prepared by the spray - etching process etched by the etching solution was sprayed with a pressure of 2.5 bar to the printed circuit boards.
- the etching solution had a volume of 660 1, contained 150 g / 1 KC1 and 50 g / 1 Cu and had a temperature of 50 ° C.
- This solution was pumped from the etching system into a regeneration system as described in DE-OS 33 03 594.
- 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 were oxygen and Chlorine can escape.
- a current of 550 A at a voltage of 19.5 V flowed in the regeneration 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 etching printed circuit boards, the pH value fell from 2.5 initially to approximately 1.9 after approximately 1 1/2 hours.
- the current yield for the reaction according to equation (6) is dependent 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 a possibility, the amount of hydrogen ions formed to the amount of Cu (I) ions oxidized by the air. to adapt, for example, by controlling the anodic current density so that the pH is kept constant at, for example, 2.0.
- Other ways 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 varying the number and type of gas gaps.
Landscapes
- 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)
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 true EP0141905A1 (fr) | 1985-05-22 |
| EP0141905B1 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014800A1 (fr) * | 1990-03-29 | 1991-10-03 | Hans Höllmüller Maschinenbau GmbH & Co. | Dispositif de regeneration electrolytique d'un reactif d'attaque contenant des ions chlorure et metal |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69219063T2 (de) * | 1991-10-28 | 1997-11-20 | Nittetsu Mining Co Ltd | Verfahren zum Regenerieren von Ätzmitteln |
Citations (5)
| 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 |
| DE2641905A1 (de) * | 1976-09-17 | 1978-03-23 | Kutscherenko | Verfahren zur regenerierung verbrauchter aetzloesungen |
| DE2650912A1 (de) * | 1976-11-06 | 1978-05-18 | Hoellmueller Maschbau H | Elektrolytische regeneration eines aetzmittels |
| EP0011799A1 (fr) * | 1978-11-22 | 1980-06-11 | Forschungszentrum Jülich Gmbh | Procédé et appareil pour la régénération d'une solution de décapage contenant du chlorure cuivrique et/ou du chlorure ferrique dans une cellule d'électrolyse |
-
1983
- 1983-08-23 DE DE3330349A patent/DE3330349A1/de not_active Withdrawn
-
1984
- 1984-07-18 EP EP84108467A patent/EP0141905B1/fr not_active Expired
- 1984-07-18 DE DE8484108467T patent/DE3460905D1/de not_active Expired
Patent Citations (5)
| 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 |
| DE2641905A1 (de) * | 1976-09-17 | 1978-03-23 | Kutscherenko | Verfahren zur regenerierung verbrauchter aetzloesungen |
| DE2650912A1 (de) * | 1976-11-06 | 1978-05-18 | Hoellmueller Maschbau H | Elektrolytische regeneration eines aetzmittels |
| EP0011799A1 (fr) * | 1978-11-22 | 1980-06-11 | Forschungszentrum Jülich Gmbh | Procédé et appareil pour la régénération d'une solution de décapage contenant du chlorure cuivrique et/ou du chlorure ferrique dans une cellule d'électrolyse |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014800A1 (fr) * | 1990-03-29 | 1991-10-03 | Hans Höllmüller Maschinenbau GmbH & Co. | Dispositif de regeneration electrolytique d'un reactif d'attaque contenant des ions chlorure et metal |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0141905B1 (fr) | 1986-10-08 |
| DE3460905D1 (en) | 1986-11-13 |
| DE3330349A1 (de) | 1985-03-14 |
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