WO2009023988A1 - Procédé et système d'attaque de cuivre - Google Patents

Procédé et système d'attaque de cuivre Download PDF

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Publication number
WO2009023988A1
WO2009023988A1 PCT/CN2007/002524 CN2007002524W WO2009023988A1 WO 2009023988 A1 WO2009023988 A1 WO 2009023988A1 CN 2007002524 W CN2007002524 W CN 2007002524W WO 2009023988 A1 WO2009023988 A1 WO 2009023988A1
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WO
WIPO (PCT)
Prior art keywords
copper
etching
source
solution
cucl
Prior art date
Application number
PCT/CN2007/002524
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English (en)
Chinese (zh)
Inventor
King Tim Tse
Original Assignee
King Tim Tse
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 King Tim Tse filed Critical King Tim Tse
Priority to PCT/CN2007/002524 priority Critical patent/WO2009023988A1/fr
Publication of WO2009023988A1 publication Critical patent/WO2009023988A1/fr

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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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic 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 present invention relates to a method and system for etching copper. More specifically, the present invention relates to a method and system for etching copper using a copper bath comprising a copper source, a chlorine source, a bromine source, and an iodine source.
  • BACKGROUND OF THE INVENTION Etching liquids currently mainly used include CuC.l 2 /HCl, FeCl 3 /HCl, Cu(NH 3 ) 4 Cl 2 /NH 3 and the like.
  • the etching is performed as follows to produce an etching waste liquid containing CuCl.
  • etching waste liquid containing CuCl by electrolysis.
  • a method of etching a waste liquid by electrolytic treatment which converts CuCl into CuCl 2 by chlorine gas generated on the anode side (in which waste liquid is introduced), is also disclosed in Japanese Laid-Open Patent Publication No. SHO 56-17429, Copper is extracted from the cathode side (wherein the liquid is also passed into the waste liquid) by electrodeposition of copper ions into metallic copper by electrolysis.
  • a method of treating an etching solution containing CuCl is also provided in Chinese Patent Application No. 92112389.2, which comprises electrolyzing an etching waste liquid containing CuCl by an electrolytic process, generating copper at a cathode, and supplying chlorine gas generated at the anode to another The etching waste liquid used in the etching process is batched, thereby regenerating the etching waste liquid.
  • this method also deals with toxic chlorine gas, causing problems in terms of cost and reliability.
  • the etching is performed as follows to produce FeCl 2 and
  • etching is performed as follows.
  • an extraction method is usually employed.
  • a method for reusing etching waste liquid is proposed in W096/35827, which comprises mixing an etching waste liquid and an extracting agent under stirring for extraction, separating and reusing a regenerated etching liquid having a reduced copper concentration, and extracting copper.
  • the agent is subjected to back extraction to transfer the copper contained therein to an aqueous acid-copper sulfate aqueous solution, and the stripped extractant is washed with a cleaning liquid, wherein the stripped copper sulfate is subjected to electrolysis to produce copper.
  • a method for treating an etching waste liquid is also proposed in Chinese Patent Application No. 01107503.1, which comprises the following steps of centrifugally extracting and extracting the etching waste liquid to obtain a raffinate, and the raffinate liquid is turned into a regenerated etching liquid after degreasing, and etching the waste liquid.
  • the copper in the stripping solution after the centrifugal stripping combined process can be electrolyzed to produce copper.
  • etching copper which comprises etching copper with a copper etching solution, electrolyzing the copper-etched copper solution, and regenerating the copper-etched liquid to regenerate the copper-etched copper.
  • the liquid return is again used to etch copper.
  • This method does not generate toxic gases such as chlorine, and the copper waste liquid is almost zero-emission, so that it does not affect the environment.
  • the method can also utilize the oxidant generated during electrolysis without causing waste of energy, thereby reducing costs.
  • the method can be carried out simply, reliably and easily.
  • the present invention also provides a system for etching copper by performing the method. The inventors have found through extensive research and experiments that the object of the present invention can be achieved by using a copper plating solution containing a copper source, a chlorine source, a bromine source, and an iodine source.
  • an aspect of the present invention provides a method of etching copper, comprising the steps of: (1) providing a copper etching solution containing a copper source, a chlorine source, a bromine source, and an iodine source; ( 2 ) etching the copper with the copper etching solution (3) electrolyzing the copper solution after etching copper to regenerate the copper solution; (4) returning the regenerated copper solution to the step
  • the copper source comprises CuCl 2 .
  • the chlorine source includes NaCl and HCl.
  • the pH in steps (2) and (3) is about 0.1-1.5, preferably the pH in step (2) is 1 and the pH in step (3) is 1.5. Further, in the step (3), the electrolysis termination potential is 1050 mV or less, and preferably the electrolysis termination potential is 600 to 800 mV.
  • the method of the present invention also includes the step of replenishing the lost copper bath.
  • Another aspect of the invention relates to the use of the process of the invention in the metal recycling industry, the hydrometallurgy industry, electronic circuit boards and metal surface treatments.
  • a further aspect of the present invention provides a system for etching copper, comprising: a copper etching machine; an electrolytic copper machine; and a copper etching solution, wherein the copper etching liquid contains a copper source, a chlorine source, a bromine source, and a source of exchange.
  • the copper source comprises CuCl 2 .
  • the chlorine source includes NaCl and HCl.
  • the copper bath contains 250 g/l NaCl, 40 g/l HCK 50 g/l CuCl 2 , lOg/1 1 (3 ⁇ 4 and 30 g/l BrCl m ) .
  • the system of the present invention also includes an apparatus that supplements the copper bath.
  • the invention additionally provides a method of etching copper, comprising the steps of:
  • the copper is sprayed and etched in the copper etching machine at a speed of 10-15 kg/h.
  • the copper solution is sent to the electrolytic copper. machine;
  • Figure 1 is a block diagram illustrating one embodiment of the method of the present invention
  • FIG. 2 is a block diagram illustrating one embodiment of the system of the present invention. detailed description
  • the method for etching copper of the present invention comprises the following steps: (1) providing a copper etching solution containing a copper source, a chlorine source, a bromine source, and an iodine source; (2) etching the copper with the copper etching solution; (3) etching the copper The subsequent copper plating liquid is electrolyzed to regenerate the copper etching solution; ( 4 ) returning the regenerated copper etching liquid to the step (1).
  • the etched copper solution contains a source of bromine and an iodine source, excess energy can be stored during electrolysis, and even at a lower pH (for example, a pH of 0.1-1.5), chlorine gas is not generated, thereby causing no Waste of energy, there is no need to deal with toxic chlorine.
  • the bromine source and the iodine source may be in any suitable form.
  • a copper etching liquid to the invention preferably comprises BrCl m 5-30g / l of ICl n and 10-80g / l of.
  • etching and electrolysis are carried out as follows:
  • the copper source may be in any suitable form including, for example, CuCl 2 .
  • the source of chlorine can be in any suitable form, such as NaCl and HCl, wherein the ratio of NaCl to HCl can be adjusted depending on the desired pH.
  • NaCl, The content of HC1 and CuCl 2 may be an amount generally used in the art, for example, the amount of NaCl is 150-250 g/l, the amount of HC1 is 40-60 g/l, and the amount of CuCl 2 is 50-150 g/l.
  • the copper content of the copper etching liquid in the step (1) may be any suitable amount.
  • the copper content of the copper etching solution in the step (1) is about 50 g/l
  • the copper content of the copper etching solution after etching the copper in the step (3) is about 80 g/l, and the etching is regenerated in the step (4).
  • the copper content of the copper solution is about 50 g/l.
  • the temperature in the etching and electrolysis steps may be any suitable temperature, for example, 50 to 60 °C.
  • the temperature in the step of etching and electrolysis is 50-60 ° C
  • the copper plating liquid has a certain amount of evaporation, so that the copper is replenished once every some time, for example every 4 hours. The liquid is simultaneously taken out of the copper produced on the cathode in the electrolysis step.
  • the pH in the steps of etching and electrolysis may be any suitable value. Preferably, the pH is from 0.1 to 1.5.
  • the electrolysis termination potential in the electrolysis step it can be any suitable value.
  • the electrolysis termination potential is preferably 1050 mV or less, for example 600-800 mV, to convert Br-, ⁇ and C1- to BrCl m and ICl n .
  • FIG. 1 is a block diagram illustrating one embodiment of the method of the present invention.
  • a copper-containing liquid containing a copper source, a chlorine source, a bromine source, and an iodine source is supplied from the copper-copper tank 1 to the copper etching machine 2.
  • copper is placed in the material, and the copper is etched with the copper solution.
  • the copper etching solution after etching the copper is filtered by the filter 4, and sent to the electrolytic copper machine 5 for electrolysis.
  • the electrolytic copper machine 5 when the electrolysis potential is raised to the electrolysis termination potential, the copper recrystallization is completed, and the regenerated copper solution is returned to the copper etching machine 2. Accordingly, the intake ⁇ ! Continuous loop right foot copper etching method of the present invention. In addition, at intervals, the copper-copper solution 3 can be performed, and the electrolytic copper can be taken out 6.
  • the present invention also provides a system for etching copper, the system comprising a copper etching machine; an electrolytic copper machine; and a copper plating solution, wherein the copper etching solution contains a copper source, a chlorine source, a bromine source, and an iodine source.
  • Figure 2 illustrates one embodiment of the system of the present invention.
  • copper is etched with a copper etch liquid, and then the etched copper etched copper liquid is sent through a filter 23 into the electrolytic cell 26 of the electrolytic copper machine 24.
  • the electrolytic copper machine 24 includes a "rectifier 25" and an electrolytic cell 26.
  • the copper-etched copper solution is electrolyzed and then returned to the copper etching machine 22.
  • the system further includes a circulation pump. 27.
  • Example 1 The method of etching copper of the present invention is carried out using a system comprising:
  • Copper etching machine PVC (polyvinyl chloride) body with liquid capacity of 10001, circulating pump of 5hp (horsepower), flow rate 4001/min, feeding speed 400mm/min, temperature 50°C, pHl, copper in feed The amount of 50g / l, the copper content of the liquid is 80g / l;
  • Electrolytic copper machine Dimensions 1100 X 1100 X 1000mm PP (polypropylene) body, capacity
  • Anode 800 X 800 X lmm coated titanium electrode 6 pieces, cathode: 900 ⁇ 900 ⁇ lmm titanium sheet 3 pieces, diaphragm: glass fiber membrane
  • Copper etching solution NaC1250g/l, HC140g/l, ICl n lOg/1, BrCl m 30g/l, CuCl 2 50g/l.
  • the method is as follows: First, the copper etching solution is placed in a copper etching machine and heated to 50 ° C; then the material copper is sprayed and etched with copper etching liquid at a speed of 10-15 kg / h; When the copper content reaches 80g/l, it is sent to the electrolytic copper machine for electrolysis; when the electrolysis potential reaches 800mV, the copper solution is regenerated and returned to the copper etching machine.
  • Electrolytic energy consumption is about 2000 kWh/t, and the overall energy consumption is about 3000 kWh/t.
  • the above is a unit, and if the output is to be increased, the number of units can be increased proportionally.
  • the method and system of the invention adopts a copper solution containing a copper source, a chlorine source, a bromine source and an iodine source, so that the copper etching and the electrolytic copper can work together, so that the copper etching industry recovers the copper and copper recycling industry.
  • the cost is greatly reduced and the production process is simple, reliable and environmentally friendly.

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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)

Abstract

L'invention concerne un traitement d'attaque de cuivre, qui comprend les étapes suivantes consistant à : (1) se procurer une solution d'attaque de cuivre contenant une source de cuivre, une source de chlore, une source de brome et une source d'iode ; (2) attaquer le cuivre avec la solution d'attaque de cuivre ; (3) soumettre la solution d'attaque de cuivre à une électrolyse après l'attaque de cuivre, régénérant ainsi la solution d'attaque de cuivre ; (4) renvoyer la solution d'attaque de cuivre ainsi régénérée à l'étape (1). L'invention concerne également un système pour exécuter le traitement d'attaque de cuivre.
PCT/CN2007/002524 2007-08-21 2007-08-21 Procédé et système d'attaque de cuivre WO2009023988A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2007/002524 WO2009023988A1 (fr) 2007-08-21 2007-08-21 Procédé et système d'attaque de cuivre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2007/002524 WO2009023988A1 (fr) 2007-08-21 2007-08-21 Procédé et système d'attaque de cuivre

Publications (1)

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WO2009023988A1 true WO2009023988A1 (fr) 2009-02-26

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85106153A (zh) * 1985-08-15 1987-03-04 汉斯·荷尔米勒机器制造有限公司 在印刷电路板上蚀刻铜膜的方法
RU1807089C (ru) * 1990-07-23 1993-04-07 Харьковский государственный университет им.А.М.Горького Раствор дл химического травлени меди
JPH08232084A (ja) * 1995-02-23 1996-09-10 Hitachi Chem Co Ltd 銅箔の表面処理液並びにその処理液を用いた多層プリント配線板の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85106153A (zh) * 1985-08-15 1987-03-04 汉斯·荷尔米勒机器制造有限公司 在印刷电路板上蚀刻铜膜的方法
RU1807089C (ru) * 1990-07-23 1993-04-07 Харьковский государственный университет им.А.М.Горького Раствор дл химического травлени меди
JPH08232084A (ja) * 1995-02-23 1996-09-10 Hitachi Chem Co Ltd 銅箔の表面処理液並びにその処理液を用いた多層プリント配線板の製造方法

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