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EP0048381B1 - Procédé pour la régénération de solutions de chlorure de cuivre chlorhydrique destinées à la gravure - Google Patents

Procédé pour la régénération de solutions de chlorure de cuivre chlorhydrique destinées à la gravure Download PDF

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Publication number
EP0048381B1
EP0048381B1 EP81107037A EP81107037A EP0048381B1 EP 0048381 B1 EP0048381 B1 EP 0048381B1 EP 81107037 A EP81107037 A EP 81107037A EP 81107037 A EP81107037 A EP 81107037A EP 0048381 B1 EP0048381 B1 EP 0048381B1
Authority
EP
European Patent Office
Prior art keywords
etching
bell
regeneration
oxygen
gas
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
EP81107037A
Other languages
German (de)
English (en)
Other versions
EP0048381A1 (fr
Inventor
Efthimios Dr. Rer. Nat. Dipl.-Chem. Konstantouros
Karl Höck
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP0048381A1 publication Critical patent/EP0048381A1/fr
Application granted granted Critical
Publication of EP0048381B1 publication Critical patent/EP0048381B1/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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/7287—Liquid level responsive or maintaining systems

Definitions

  • the invention relates to a method for the regeneration of hydrochloric acid chloride etching solutions, which are preferably used in the manufacture of printed circuit boards for the etching of non-galvanized printed circuit boards, the etching and regeneration taking place in separate devices, between which the etching solution is cycled or continuously carried out in the circuit and the regeneration is preferably carried out is carried out with oxygen gas, with a bell, into which the used up etched from an etching machine is sprayed for regeneration above.
  • the literature mostly does not consider the formation of the easily soluble CuCI 2 complex from the poorly soluble CuCI salt.
  • the inactive copper (I) ion formed during the etching is oxidized to etchable copper (II) ion.
  • DE-AS 1 621 437 deals with a device for supplying chlorine gas to an etching agent regeneration plant.
  • the chlorine gas is introduced directly into the etching machine of the etching machine using an injector (water jet pump principle), the monovalent copper (I) ion being oxidized to copper (II) ion according to the following equation:
  • DE-PS 1 225465 is based on a method for etching copper with a copper (II) chloride solution. In this known method, regeneration takes place according to the equation
  • the copper (II) chloride solution is in a tank. Diluted hydrochloric acid and sodium chlorate are kept ready in two storage containers and added to the etching bath in the required amount by an automatic control device.
  • the inflow of hydrochloric acid is controlled by a pH measuring probe, an amplifier and a control valve and the inflow of sodium chlorate by a photocell, an amplifier and a control valve.
  • aqueous solutions of hydrogen peroxide and hydrochloric acid are metered into the etching machine by measuring the redox potential or the pH.
  • the present invention has for its object to provide an exhaust air-free process for the continuous regeneration of hydrochloric acid etching solutions using oxygen gas.
  • This object is achieved in that a bell set up in a flat standing container containing caustic agent is provided with a supply line in the upper part for oxygen, that the regenerated etching collects at the bottom of the standing container, from where it flows back into the etching machine as an overflow and that due to the negative pressure generated during the reaction, the etching increases and this level change serves to control two level switches in the inner surface of the bell, which open or close the supply line of the regeneration gas, and thereby only as much oxygen into the bell is replenished as was consumed.
  • a bell-like container as an oxidation vessel. It is important that the presence of an oxidizing atmosphere enclosed and regulated in the reaction vessel is ensured.
  • the present invention does not use frits which experience has shown to damage or clog them easily and, as a result, they have to be replaced.
  • the method according to the invention also requires less maintenance and does not give off exhaust air from the regeneration vessel.
  • Another advantage is that there is no loss in the gas used for regeneration, since all the gas enclosed in the bell is used to 100%.
  • the device is also characterized by a higher regeneration speed, since it works with pure oxidizing gas and not with air (20% oxygen content).
  • Another advantage is the automated introduction of the gas used for regeneration by means of a level switch, so that the introduction can be regulated as required.
  • the concentration of the etching solution is preferably set so that no solubility product is exceeded at the respective operating temperatures. At room temperature, for example, the following concentrations have proven to be favorable:
  • the salt KCI is not used up during the etching. It serves as a chloride ion supplier to form the easily soluble copper (I) complex CuCl 2 - and thus to increase the reaction rate.
  • the copper (I) complex is oxidized, the chloride ion is released again (see equation of the regeneration process).
  • the etching time for 35 ym Cu layer is 45 "at 25 ° C and 1 to 1.5 bar spray pressure.
  • hydrochloric acid and KCI solution are added.
  • the overflow here is collected.
  • the metering of the chemicals can be automated, via the density measurement for the KCI solution and the pH measurement for the hydrochloric acid.
  • the regeneration takes place at the phase interface between the oxidizing gas and the sprayed-on etching solution, it is necessary to make the phase interface mentioned as large as possible in the reaction space.
  • mist nozzles are used on the one hand to spray the etching solution and, on the other hand, absorbent and corrosion-resistant fabrics or felt materials are hung vertically, which are available in a large selection on the market.
  • the regeneration of the absorbed etching solution also takes place when the spray pump is switched off.
  • the absorbency of felts of 2 mm thickness can be up to approx. 2 I per m 2 .
  • the etching solution in the bell is sprayed on through mist nozzles in order to enlarge the phase interface between the etching solution and the oxidizing gas and thus to increase the regeneration rate.
  • the phase interface can be increased on the one hand and the regeneration of the absorbed caustic solution can be continued even when the spray pump is switched off.
  • the invention is explained on the basis of a schematic representation of the method according to the invention for the regeneration of a copper chloride etching by means of oxygen gas.
  • a regeneration bell 1 is shown in a standing container 2.
  • the used etching 4 is introduced with a pump 5 via a line 6 into the top of the regeneration bell and sprayed over the hanging tissue or felt cloth 7.
  • the gas 10 used for regeneration is fed via a line 11 to the regeneration bell.
  • a connection 12 for a connecting line to the vacuum pump is indicated.
  • the regenerated etching 13 collects in the lower part of the regeneration bell.
  • S1, S2 denote two level switches which, depending on the respective height N1, N2 of the regenerated etching 13, switch the supply of the oxidizing gas on or off via a control device 14.
  • the gas volume varies between the values V1 and V2.
  • the circular operating sequence is shown with the arrows.
  • the used etchant 4 is continuously sucked out of the etching chamber of the etching machine 3 and sprayed into the regeneration bell 1, the copper (I) ion, as already mentioned, according to the equation is oxidized.
  • By consuming z. B. Oxygen constantly decreases the gas pressure in the bell. As a result, the etching solution 13 slowly rises in the bell.
  • the oxygen supply is controlled by level switches S1 and S2 (float or photocells). This ensures that the etchant level in the bell oscillates between a lower N1 and an upper limit N2, so that there is always enough gas in the bell for the regeneration process.
  • the gas volume consequently varies between the values V1 and V2.
  • the bell shape of the reaction vessel 1 is by no means absolutely necessary. You can also conditionally z. B. take any other shape due to spatial conditions or by the number and size of the felt cloths 7.

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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 (4)

1. Procédé de régénération de solutions chlorhydriques de chlorure de cuivre destinées à la gravure, qui servent de préférence dans la fabrication de plaquettes de circuits imprimés en vue de graver des plaquettes de circuits imprimés qui ne sont pas galvanisées, la gravure et la régénération s'effectuant dans des installations distinctes entre lesquelles la solution destinée à la gravure est envoyée en continu ou en discontinu en circuit fermé et la régénération étant effectuée par de l'oxygène gazeux, avec une cloche dans le haut de laquelle la solution de gravure, qui est usée et aspirée de la machine de gravure, est pulvérisée en vue d'être régénérée, caractérisé en ce que la cloche (1) qui est placée dans un récipient (2) posé debout, plat et contenant de l'agent de gravure, est munie d'un conduit d'entrée (11) d'oxygène à la partie supérieure, en ce que la solution de gravure (13) régénérée se rassemble au fond du récipient (2) d'où elle s'écoule à nouveau par trop-plein dans la machine de gravure et en ce que la dépression créée par l'oxygène consommé dans la réaction provoque une ascension de la solution destinée à la gravure et cette variation de niveau sert à commander deux interrupteurs sensibles au niveau (S1, S2) qui sont montés dans la surface latérale intérieure de la cloche, et qui ouvrent et ferment (9) le conduit d'arrivée (10) du gaz régénérant, en sorte qu'il n'est introduit de manière dosée dans la cloche chaque fois qu'autant d'oxygène qu'il en a été consommé.
2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à utiliser des atomiseurs pour la pulvérisation de la solution destinée à la gravure dans la cloche.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'ilconsiste à suspendre des tissus ou du feutre (7) résistant à la corrosion et absorbant dans l'espace de la cloche qui est réservé au gaz.
4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que la cloche est en un matériau transparent résistant à la corrosion.
EP81107037A 1980-09-23 1981-09-07 Procédé pour la régénération de solutions de chlorure de cuivre chlorhydrique destinées à la gravure Expired EP0048381B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3035864 1980-09-23
DE19803035864 DE3035864A1 (de) 1980-09-23 1980-09-23 Vorrichtung zur regenerierung salzsaurer kupferchlorid-aetzloesungen

Publications (2)

Publication Number Publication Date
EP0048381A1 EP0048381A1 (fr) 1982-03-31
EP0048381B1 true EP0048381B1 (fr) 1985-04-17

Family

ID=6112661

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81107037A Expired EP0048381B1 (fr) 1980-09-23 1981-09-07 Procédé pour la régénération de solutions de chlorure de cuivre chlorhydrique destinées à la gravure

Country Status (3)

Country Link
US (1) US4388276A (fr)
EP (1) EP0048381B1 (fr)
DE (1) DE3035864A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2927347A1 (fr) 2014-04-01 2015-10-07 Sigma Engineering Ab Oxydation de cuivre dans une solution d'attaque de cuivre par l'utilisation d'oxygène et/ou de l'air comme agent oxydant

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0178347B1 (fr) * 1984-10-19 1988-09-07 Ibm Deutschland Gmbh Procédé de régénération automatique de solutions de découpage à base de chlorure cuivrique
US5013395A (en) * 1987-08-28 1991-05-07 International Business Machines Corporation Continuous regeneration of acid solution
US5227010A (en) * 1991-04-03 1993-07-13 International Business Machines Corporation Regeneration of ferric chloride etchants
JP2500402B2 (ja) * 1991-09-05 1996-05-29 上村工業株式会社 エッチング速度の測定方法及びエッチング速度測定装置
JP3142195B2 (ja) * 1993-07-20 2001-03-07 大日本スクリーン製造株式会社 薬液供給装置
JPH0990643A (ja) * 1995-09-27 1997-04-04 Dainippon Screen Mfg Co Ltd 基板処理装置
AU3307697A (en) * 1996-06-21 1998-01-07 Jordan Holding Company Return circuit for vapor recovery system
DE19700470A1 (de) * 1997-01-09 1998-07-16 Depeltronik S A Verfahren zum Regenerieren von Ätzflüssigkeiten, insbesondere Leiterplattenätzflüssigkeiten, und Vorrichtung hierfür
SE531697C2 (sv) * 2007-07-11 2009-07-07 Sigma Engineering Ab Etsnings- och återvinningsförfarande
CN102807294A (zh) * 2011-05-31 2012-12-05 无锡尚德太阳能电力有限公司 处理已使用蚀刻液的再循环系统
CN103422154A (zh) * 2012-05-24 2013-12-04 叶福祥 电路板酸性废蚀刻液氯化亚铜(Cu+,CuCL)离子隔膜电积再生
CN105060567A (zh) * 2015-08-23 2015-11-18 长春黄金研究院 一种酸性含氯废水的处理方法
CN110342566A (zh) * 2019-06-24 2019-10-18 重庆瀚渝再生资源有限公司 一种利用酸性蚀刻液制备碱性蚀刻液的工艺方法
CN114351147B (zh) * 2021-12-30 2025-03-04 广东臻鼎环境科技有限公司 一种氯气全自动安全高效再生酸性蚀刻液系统
CN114855171B (zh) * 2022-04-01 2024-03-26 安徽中科冉图环保科技有限公司 一种酸性蚀刻液废液处理系统和方法
CN115287659B (zh) * 2022-08-04 2024-03-29 深圳天华机器设备股份有限公司 一种蚀刻药水再生装置及再生工艺

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1514939A (en) * 1922-02-09 1924-11-11 Wallace & Tiernan Co Inc Chlorinator
US2771460A (en) * 1952-11-18 1956-11-20 Babcock & Wilcox Co Residual pulp liquor oxidizing means
US3083129A (en) * 1958-10-01 1963-03-26 Gen Dynamics Corp Method of etching copper with rejuvenation and recycling
DE1207183B (de) * 1962-04-12 1965-12-16 Siemens Ag Kontinuierliches Regenerierverfahren fuer insbesondere bei der Herstellung gedruckter Schaltungen verwendete kupferhaltige AEtzloesungen
US3306792A (en) * 1963-08-05 1967-02-28 Siemens Ag Continuously regenerating coppercontaining etching solutions
GB1142024A (en) * 1965-04-26 1969-02-05 Chemcut Corp Improvements in and relating to apparatus and methods of regenerating etchant solutions
CH505213A (de) * 1968-11-07 1971-03-31 Saba Gmbh Verfahren zum Ätzen von Kupfer und Kupferlegierungen, insbesondere von kupferkaschierten Schichtpressstoffen
US3600244A (en) * 1969-02-20 1971-08-17 Ibm Process of etching metal with recovery or regeneration and recycling
GB1398639A (en) * 1972-08-05 1975-06-25 Kanebo Ltd Generation of gaseous formaldehyde from formaldehyde polymer
US4101608A (en) * 1975-09-10 1978-07-18 Martin L. Towler Oxygen impregnation method
US4042444A (en) * 1976-04-26 1977-08-16 General Dynamics Etchant rejuvenation control system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2927347A1 (fr) 2014-04-01 2015-10-07 Sigma Engineering Ab Oxydation de cuivre dans une solution d'attaque de cuivre par l'utilisation d'oxygène et/ou de l'air comme agent oxydant
US9920434B2 (en) 2014-04-01 2018-03-20 Sigma Engineering Ab Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent

Also Published As

Publication number Publication date
US4388276A (en) 1983-06-14
EP0048381A1 (fr) 1982-03-31
DE3035864A1 (de) 1982-05-06

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