CN101443480A - Recyclable etching solution - Google Patents

Recyclable etching solution Download PDF

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Publication number
CN101443480A
CN101443480A CNA2006800418069A CN200680041806A CN101443480A CN 101443480 A CN101443480 A CN 101443480A CN A2006800418069 A CNA2006800418069 A CN A2006800418069A CN 200680041806 A CN200680041806 A CN 200680041806A CN 101443480 A CN101443480 A CN 101443480A
Authority
CN
China
Prior art keywords
etching solution
copper
etching
biphenyl
acetyl bromide
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.)
Pending
Application number
CNA2006800418069A
Other languages
Chinese (zh)
Inventor
K·纳赫迪德里迪
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.)
EVE RECYCLING SARL
Original Assignee
EVE RECYCLING SARL
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 EVE RECYCLING SARL filed Critical EVE RECYCLING SARL
Publication of CN101443480A publication Critical patent/CN101443480A/en
Pending 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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline 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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • ing And Chemical Polishing (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to an aqueous etching solution which is recyclable by reducing a copper concentration during operation, is used for copper etching, in particular for printed circuits and for producing copper articles and which generally comprises water, ammonium, copper carbonate and ammonium carbonate. The inventive etching solution also comprises bromoacetylbiphenyland the derivatives thereof in the form of an additional catalyst.

Description

But the etching solution of recycling
Technical field
The present invention relates to a kind of passing through and reduce copper content and callable moisture etching (gravure) solution.This solution is used in the etching of carrying out copper in printed circuit board industry and the copper fitting industry especially.Solution is made up of ammonia, copper carbonate, volatile salt and water usually.
Background technology
Traditional etching solution presents various ways.It is used in particular for the etching of printed circuit board (PCB).In printed circuit board (PCB) was made, it was very important quickening etching process.This need accelerate the recovery of copper, to realize the balance between the amount that reclaim and etched copper.The stability of process also is to guarantee that the etching quality persistence is to obtain the important factor of similar elements.
In making the process of printed circuit board (PCB), can utilize silk screen printing or schematic circuit is sheltered to form " resist pattern (une image de r é siste) " by photosensitive method.Make not etched by this copper surface of sheltering covering with suitable etching solution.
Under the another kind of situation of making double-sided printed-circuit board, plated through-hole and track are protected by metal resist (r é sis te).Peel off organic resist, utilize suitable solution that exposed copper is etched away.By this method, the plated through-hole of conduction and track are protected by the metal resist in utilizing the etching treatment procedure that carries out operation based on the solution of mantoquita and ammonia.
Shortcoming is that etching speed is limited, and the regeneration process of etching solution slowly and directly influences the chemical parameters of producing and has unstable.
Summary of the invention
Task of the present invention has chemical parameters stability when being to accelerate etching speed, accelerating the regeneration of used solution and making this solution be used for etching treatment procedure once more.
For reaching this purpose, make etching solution contain acetyl bromide biphenyl and derivative thereof as other catalyzer.
The present invention has been proved to be able to accelerate treating processes, because as the same regeneration process that promotes used etching solution of the acetyl bromide biphenyl of catalyzer.It also brings into play the effect that hinders the factor of quickening of eliminating, and accelerates the recycling of copper.
Use acetyl bromide biphenyl as additional catalyst and accelerator thus, its consumption is the 5-200mg/l etching solution, and preferable amount is 70mg/l.
Acetyl bromide biphenyl preferably impels title complex [Cu (NH as 4-acetyl bromide biphenyl C14H11BrO 3) 2] +In regeneration process, be oxidized to title complex [Cu (NH 3) 4] ++Like this, the regenerative process of etching solution will be accelerated.[Cu (NH 3) 2] +Ion can slow down etching treatment procedure and increase the recycling of copper, based on this, and [Cu (NH in etching process 3) 2] +Should be oxidized, that is be oxidized to [Cu (NH 3) 4] ++, in the recycling process, should utilize stablizer to make [Cu (NH 3) 2] +Stable.Etching process is undertaken by following reaction:
Cu+[Cu(NH 3) 4] ++→2[Cu(NH 3) 2] +
Regeneration section is to utilize NH4+, NH3 and oxygen to cooperate to be undertaken by following reaction:
4[Cu(NH 3) 4] +++4NH 3+4NH ++O 2→4[Cu(NH 3) 4] +++2HO
Recycling is partly undertaken by following reaction by electric current:
[Cu(NH 3) 2] +→1/2Cu+1/2[Cu(NH 3) 4] ++
[Cu(NH 3) 2] ++e-→Cu+2NH 3
[Cu(NH 3) 4] +++2e-→Cu+4NH 3
In treating processes, the raising of the oxidation rate of copper has improved etching speed constantly.Vanadium Pentoxide or other alum compound are used for improving etching speed as catalyzer.
In addition; confirm; use the additional catalyst contain the catalyzer of the alum that can improve etching speed and to contain acetyl biphenyl can improve the oxidation rate of used etching solution in the present invention, and can be used for improving recycling speed as stablizer.
Like this, the reproduction speed of etching speed and used etching solution will be enhanced simultaneously, simultaneously this process recycling speed of possessing stability and having raising.
Just printed circuit board (PCB) is by the treating processes particularly important of etching machine for making printed circuit board (PCB) for These characteristics, and the effect of etching machine is sprayed the copper surface with continuous or mode intermittently just.
Embodiment
Confirm that following solution has best effect:
Solution 1:
Every liter of 60-140 copper is corresponding to the CuCO of 117-272g/l 3
Every liter of 62-156g carbonate is corresponding to (the NH of 100-250g/l 4) 2CO 3
0.4-0.8 rise/liter ammonia solution.
0.4-0.6 premium on currency.
The 200-1500mg/l Vanadium Pentoxide.
5-200mg/l 4-acetyl bromide biphenyl.
Solution 2:
Every liter of 100g copper is corresponding to the CuCO of 194g/l 3
Every liter of 109g carbonate is corresponding to (the NH of 175g/l 4) 2CO 3
0.5 rise/rise ammonia solution.
0.5 premium on currency.
The 1100mg/l Vanadium Pentoxide.
70mg/l 4-acetyl bromide biphenyl.

Claims (15)

  1. But 1, by electrolysis at the etching solution of recycling chemically; it is used in particular for the etching to the copper of printed circuit board (PCB) and copper fitting industry; it is made up of portion water, ammonia, copper carbonate and volatile salt usually; it is characterized in that described etching solution comprises acetyl bromide biphenyl and derivative thereof as additional catalyst.
  2. 2, etching solution according to claim 1 is characterized in that, adds acetyl bromide biphenyl and the derivative thereof of about 10-100mg/l in etching solution.
  3. 3, etching solution according to claim 1 and 2 is characterized in that, described etching solution contains the acetyl bromide biphenyl of the 40mg/l that has an appointment.
  4. According to claim 1-3 etching solution one of at least, it is characterized in that 4, that adopt as the catalyzer of etching solution is 4-acetyl bromide biphenyl C14H11BrO.
  5. 5, according to claim 1-4 etching solution one of at least, it is characterized in that the pH value of etching solution is adjusted to about 7.8-9, in particular for 8.2.
  6. 6, according to claim 1-5 etching solution one of at least, it is characterized in that described etching solution contains the cupric ion of 60-140g/1.
  7. 7, according to claim 1-6 etching solution one of at least, it is characterized in that described etching solution contains the CuCO of 117-272g/l 3, particularly contain the CuCO of 194g/l 3
  8. 8, according to claim 1-7 etching solution one of at least, it is characterized in that described etching solution contains 62-156g/l carbonate, corresponding to (the NH of 100-250g/l 4) 2CO 3, particularly contain 109g/l carbonate.
  9. According to claim 1-8 etching solution one of at least, it is characterized in that 9, it contains 25% the ammonia of 0.3-0.61/1.
  10. 10, according to claim 1-9 etching solution one of at least, it is characterized in that it contains the water of 0.3-0.61/1.
  11. 11, according to claim 1-10 etching solution one of at least, it is characterized in that it contains alum or other the corresponding alum compound of 200-1500mg/l.
  12. 12, etching solution according to claim 11 is characterized in that, described etching solution contains the Vanadium Pentoxide (V of the 1100mg/l that has an appointment 2O 5).
  13. 13, according to claim 1-12 etching solution one of at least, it is characterized in that described etching solution contains the particularly nitrate of 35g/l of 0.5-100g/l of having an appointment.
  14. 14, according to claim 1-13 etching solution one of at least, it is characterized in that, according to selecting to utilize O 2Or air is continuously or off and on its gasification.
  15. 15, according to claim 1-14 etching solution one of at least, it is characterized in that the temperature of etching solution is adjusted to 40-60 ℃, particularly 54 ℃.
CNA2006800418069A 2005-11-10 2006-11-09 Recyclable etching solution Pending CN101443480A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TNSN.05.283 2005-11-10
TN05283 2005-11-10

Publications (1)

Publication Number Publication Date
CN101443480A true CN101443480A (en) 2009-05-27

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ID=37982804

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006800418069A Pending CN101443480A (en) 2005-11-10 2006-11-09 Recyclable etching solution

Country Status (6)

Country Link
EP (1) EP2010695A2 (en)
JP (1) JP2009516071A (en)
KR (1) KR20080075148A (en)
CN (1) CN101443480A (en)
DE (1) DE102006036888A1 (en)
WO (1) WO2007055669A2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154646A (en) * 2011-03-04 2011-08-17 侯延辉 Acidic etching solution not generating chlorine and catalyst of acidic etching solution
CN102019430B (en) * 2009-09-18 2012-09-05 福建师范大学福清分校 Method for recovering copper from alkaline etching waste liquid and recycling alkaline etching liquid
CN106702387A (en) * 2015-11-18 2017-05-24 陶克（苏州）机械设备有限公司 On-line alkaline ammonium sulfate etching waste liquid cyclic regeneration system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105603434B (en) * 2016-03-20 2018-04-13 华南理工大学 A kind of method of photocatalysis PCB acidic etching liquid recyclings

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4311551A (en) * 1979-04-12 1982-01-19 Philip A. Hunt Chemical Corp. Composition and method for etching copper substrates
DE3429902A1 (en) * 1984-08-14 1986-02-27 Hans Höllmüller Maschinenbau GmbH & Co, 7033 Herrenberg METHOD FOR ETCHING COPPER FILMS ON BOARDS UNDER ELECTROLYTIC RECOVERY OF COPPER FROM THE ACET SOLUTION
AT395177B (en) * 1990-07-05 1992-10-12 Provera Gmbh RESOLUTION
DE19800605A1 (en) * 1998-01-12 1999-07-15 Helmar Haug Ammoniacal sulfate solution for etching copper clad circuit boards and other copper or copper alloy articles
DE102004030924A1 (en) * 2004-06-25 2006-01-19 Elo-Chem-Csm Gmbh Electrolytically regenerable etching solution

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102019430B (en) * 2009-09-18 2012-09-05 福建师范大学福清分校 Method for recovering copper from alkaline etching waste liquid and recycling alkaline etching liquid
CN102154646A (en) * 2011-03-04 2011-08-17 侯延辉 Acidic etching solution not generating chlorine and catalyst of acidic etching solution
CN103602986A (en) * 2011-03-04 2014-02-26 侯延辉 Acidic etching liquid
CN103614726A (en) * 2011-03-04 2014-03-05 侯延辉 Etching method
CN103602986B (en) * 2011-03-04 2015-07-29 侯延辉 A kind of acidic etching liquid
CN103614726B (en) * 2011-03-04 2015-07-29 侯延辉 A kind of engraving method
CN106702387A (en) * 2015-11-18 2017-05-24 陶克（苏州）机械设备有限公司 On-line alkaline ammonium sulfate etching waste liquid cyclic regeneration system

Also Published As

Publication number Publication date
WO2007055669A2 (en) 2007-05-18
DE102006036888A1 (en) 2007-05-16
KR20080075148A (en) 2008-08-14
JP2009516071A (en) 2009-04-16
WO2007055669A3 (en) 2007-11-01
EP2010695A2 (en) 2009-01-07

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Open date: 20090527