CN105887092A - PCB acid etching liquid suitable for ozone recycling method - Google Patents

PCB acid etching liquid suitable for ozone recycling method Download PDF

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Publication number
CN105887092A
CN105887092A CN201610275202.6A CN201610275202A CN105887092A CN 105887092 A CN105887092 A CN 105887092A CN 201610275202 A CN201610275202 A CN 201610275202A CN 105887092 A CN105887092 A CN 105887092A
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China
Prior art keywords
etching liquid
pcb
acidic etching
content
applicable
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CN201610275202.6A
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CN105887092B (en
Inventor
黄洪
邢征
司徒粤
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN201610275202.6A priority Critical patent/CN105887092B/en
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    • 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
    • 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

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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)

Abstract

The invention discloses PCB acid etching liquid suitable for an ozone recycling method. The PCB acid etching liquid is prepared from bivalence copper with the content being 130 g/L-170 g/L, high-solubility chlorate with the content being 120 g/L-200 g/L, hydrochloric acid with the content being 1.5 mol/L-2.5 mol/L, a stabilizing agent with the content being 1 g/L-10 g/L, a wetting agent with the content being 0.1 g/L-0.3 g/L and a banking agent with the content being 0.1 g/L-0.5 g/L. According to the PCB acid etching liquid, sodium chloride in the original process is removed, chlorate higher in solubility is adopted so that crystallization can be convenient, the formula totally adapts to a new technological process, subsequent crystallization treatment is facilitated, and an original acid etching liquid formula is simplified.

Description

A kind of ozone absorption method of being applicable to PCB Acidic etching liquid
Technical field
The present invention relates to PCB (printed circuit board (PCB)) Manufacturing Techniques field, be specifically related to a kind of PCB acidic etching liquid being applicable to ozone absorption method.
Background technology
In printed circuit board manufactures, rerouting except, outside addition process etc., traditional printed circuit board is all to be removed by the part copper that need not on PCB plate in chemical reaction mode so that it is the circuitous pattern needed for formation more.And the mode of the figure transfer used as circuitous pattern part or painting wire mark makes the photic antibody erosion agent of organic compound objects system or uses metal resist layer to cover circuitous pattern surface, prevent metallic copper etched.Therefore, indispensable important step during etch process is currently manufactured printed circuit board plate.At present PCB industry internal layer the most frequently used for H2O2/HCl System and NaClO3Both acidic etching liquids of/HCl system, the kind of this type of etching solution is many, and the difference of formula can cause the etching quality effect obtained variant.But either hydrogen peroxide or sodium chlorate, the most unavoidably come up against a series of problems.Hydrogen peroxide storage difficulty, easily decomposes, easily causes potential safety hazard.Although sodium chlorate is the most stable, but along with the carrying out of reaction, the amount of sodium chloride constantly rises so that sodium chloride eventually exceeds its dissolubility and separates out, and etching causes inevitably impact.Currently designed go out a set of system utilizing ozone to carry out oxidation regeneration, but be not adapted to new reaction system by the formula of former process conditions.
Summary of the invention
Because above reason, it is an object of the invention to propose a kind of PCB acidic etching liquid being applicable to ozone absorption method, solve to use the acidic etching liquid formulation challenges under new technique.
The purpose of the present invention is achieved through the following technical solutions.
A kind of PCB acidic etching liquid being applicable to ozone absorption method, the component of this PCB acidic etching liquid includes: mother solution copper, hydrochloric acid, tranquilizer, shore protection agent, wetting agent, the chlorate of highly dissoluble and water.
Preferably, described mother solution copper is copper chloride (CuCl2)；Described tranquilizer is carbamide；Described shore protection agent is mercapto benzothiazole (MBT)；Described wetting agent is 2-ethylhexanol sulphuric acid vinegar sodium；The chlorate of described highly dissoluble is the chlorate that dissolubility is higher than copper chloride.
Preferably, the chlorate of described highly dissoluble is calcium chloride or zinc chloride.
Preferably, described mother solution copper content in PCB acidic etching liquid is 130 ~ 170g/L.
Preferably, described hydrochloric acid content in PCB acidic etching liquid is 1.5 ~ 2.5mol/L.
Preferably, the chlorate of described highly dissoluble content in PCB acidic etching liquid is 120 ~ 200g/L.
Preferably, described tranquilizer content in PCB acidic etching liquid is 1 ~ 10g/L.
Preferably, described wetting agent content in PCB acidic etching liquid is 0.1 ~ 0.3g/L.
Preferably, described shore protection agent content in PCB acidic etching liquid is 0.1 ~ 0.5g/L.
Preferably, the described PCB acidic etching liquid temperature when spray is 45 ~ 55 DEG C.
Compared with prior art, the invention have the advantages that and technique effect:
The present invention removes the sodium chloride in script technique, then uses the chlorate that dissolubility is bigger to facilitate crystallization, and this formula adapts to new technological flow, beneficially later crystallization completely and processes, and simplifies acid etching formula of liquid originally.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
A kind of PCB acidic etching liquid being applicable to ozone absorption method, mixed by following each component, and the content of each component is in etching solution: etching mother solution copper (copper chloride) 150g/L, hydrochloric acid 2mol/L, calcium chloride 160g/L, tranquilizer (carbamide) 5g/L, wetting agent (2-ethylhexanol sulphuric acid vinegar sodium) 0.2g/L, shore protection agent (MBT) 0.3g/L, remaining is water.
The acidic etching processes of this system there occurs following reaction:
1, erosion copper reaction: metallic copper is lost by the cupric in solution and bites off, reaction equation:
3Cu+3CuCl2 → 6CuCl
2, regenerative response: metallic copper is etched the Cu in tank liquor2+Aoxidize and dissolve, the 2Cu generated+The ozone oxidation being passed into again in system is oxidized to Cu through serial reaction2+, and these Cu2+Continue again, with the metallic copper on plate face reacts, therefore to make etching solution more metallic copper can be stung eating away.Here it is the circular regeneration reaction of etching solution, see below reaction equation: 2CuCl+O3 + 2HCl → 2CuCl2 + H2O +O2
3, reaction only: Cu+O3 +2HCl → CuCl2 + H2O + O2
PCB acidic etching liquid under the process conditions carrying out oxid-reclamatiom utilization under the conditions of ozone that the present embodiment uses eliminates oxidant originally；Under conditions of spray temperature is 50 DEG C, etch uniformity can reach 98%；Etching factor 3.5.The stability of effective guarantee etching solution and the precision of circuit etching figure, it is effectively improved the speed of circuit etching figure, and get rid of the sodium chloride that dissolubility is less than copper chloride completely, then use the chlorate of high-dissolvability to instead of sodium chloride, while ensureing chlorine ion concentration, can obtain, during ensure that later crystallization, the copper chloride that purity is higher, and the highly dissoluble chloride after crystallizing further is reusable.
Embodiment 2
A kind of PCB acidic etching liquid being applicable to ozone absorption method, the content of etching solution component and each component is: etching mother solution copper (copper chloride) 130g/L, hydrochloric acid 1.5mol/L, calcium chloride 120g/L, tranquilizer (carbamide) 1g/L, wetting agent (2-ethylhexanol sulphuric acid vinegar sodium) 0.1g/L, shore protection agent (MBT) 0.1g/L, remaining is water.
The acidic etching processes of this system there occurs following reaction:
1, erosion copper reaction: metallic copper is lost by the cupric in solution and bites off, reaction equation:
3Cu+3CuCl2 → 6CuCl
2, regenerative response: metallic copper is etched the Cu in tank liquor2+Aoxidize and dissolve, the 2Cu generated+The ozone oxidation being passed into again in system is oxidized to Cu through serial reaction2+, and these Cu2+Continue again, with the metallic copper on plate face reacts, therefore to make etching solution more metallic copper can be stung eating away.Here it is the circular regeneration reaction of etching solution, see below reaction equation: 2CuCl+O3 + 2HCl → 2CuCl2 + H2O +O2
3, reaction only: Cu+O3 +2HCl → CuCl2 + H2O + O2
PCB acidic etching liquid under the process conditions carrying out oxid-reclamatiom utilization under the conditions of ozone that the present embodiment uses eliminates oxidant originally；Under conditions of spray temperature is 50 DEG C, etch uniformity can reach 90%；Etching factor 3.2.The stability of effective guarantee etching solution and the precision of circuit etching figure, it is effectively improved the speed of circuit etching figure, and get rid of the sodium chloride that dissolubility is less than copper chloride completely, then use the chlorate of high-dissolvability to instead of sodium chloride, while ensureing chlorine ion concentration, can obtain, during ensure that later crystallization, the copper chloride that purity is higher, and the highly dissoluble chloride after crystallizing further is reusable.
Embodiment 3
A kind of PCB acidic etching liquid being applicable to ozone absorption method, the content of etching solution component and each component is: etching mother solution copper (copper chloride) 170g/L, hydrochloric acid 2.5mol/L, calcium chloride 200g/L, tranquilizer (carbamide) 10g/L, wetting agent (2-ethylhexanol sulphuric acid vinegar sodium) 0.3g/L, shore protection agent (MBT) 0.5g/L, remaining is water.
The acidic etching processes of this system there occurs following reaction:
1, erosion copper reaction: metallic copper is lost by the cupric in solution and bites off, reaction equation:
3Cu+3CuCl2 → 6CuCl
2, regenerative response: metallic copper is etched the Cu in tank liquor2+Aoxidize and dissolve, the 2Cu generated+The ozone oxidation being passed into again in system is oxidized to Cu through serial reaction2+, and these Cu2+Continue again, with the metallic copper on plate face reacts, therefore to make etching solution more metallic copper can be stung eating away.Here it is the circular regeneration reaction of etching solution, see below reaction equation: 2CuCl+O3 + 2HCl → 2CuCl2 + H2O +O2
3, reaction only: Cu+O3 +2HCl → CuCl2 + H2O + O2
PCB acidic etching liquid under the process conditions carrying out oxid-reclamatiom utilization under the conditions of ozone that the present embodiment uses eliminates oxidant originally；Under conditions of spray temperature is 50 DEG C, etch uniformity can reach 90%；Etching factor 3.2.The stability of effective guarantee etching solution and the precision of circuit etching figure, it is effectively improved the speed of circuit etching figure, and get rid of the sodium chloride that dissolubility is less than copper chloride completely, then use the chlorate of high-dissolvability to instead of sodium chloride, while ensureing chlorine ion concentration, can obtain, during ensure that later crystallization, the copper chloride that purity is higher, and the highly dissoluble chloride after crystallizing further is reusable.
Those of ordinary skill in the field are it is understood that the foregoing is only the specific embodiment of the present invention; it is not limited to the present invention; all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included within the scope of the present invention.

Claims (10)

1. the PCB acidic etching liquid being applicable to ozone absorption method, it is characterised in that the component of this PCB acidic etching liquid comprises: mother solution copper, hydrochloric acid, tranquilizer, shore protection agent, wetting agent, the chlorate of highly dissoluble and water.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described mother solution copper is copper chloride；Described tranquilizer is carbamide；Described shore protection agent is mercapto benzothiazole；Described wetting agent is 2-ethylhexanol sulphuric acid vinegar sodium；The chlorate of described highly dissoluble is the chlorate that dissolubility is higher than copper chloride.
A kind of PCB being applicable to ozone absorption method the most according to claim 2 Acidic etching liquid, it is characterised in that the chlorate of described highly dissoluble is calcium chloride or zinc chloride.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described mother solution copper content in PCB acidic etching liquid is 130 ~ 170g/L.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described hydrochloric acid content in PCB acidic etching liquid is 1.5 ~ 2.5mol/L.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that the chlorate of described highly dissoluble content in PCB acidic etching liquid is 120 ~ 200g/L.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described tranquilizer content in PCB acidic etching liquid is 1 ~ 10g/L.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described wetting agent content in PCB acidic etching liquid is 0.1 ~ 0.3g/L.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described shore protection agent content in PCB acidic etching liquid is 0.1 ~ 0.5g/L.
A kind of PCB being applicable to ozone absorption method the most according to claim 1 Acidic etching liquid, it is characterised in that described PCB The acidic etching liquid temperature when spray is 45 ~ 55 DEG C.
CN201610275202.6A 2016-04-28 2016-04-28 A kind of PCB acidic etching liquid suitable for ozone absorption method Expired - Fee Related CN105887092B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108174520A (en) * 2017-12-20 2018-06-15 深圳市板明科技有限公司 Liquid medicine is lost in a kind of sudden strain of a muscle suitable for MSAP techniques

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636282A (en) * 1985-06-20 1987-01-13 Great Lakes Chemical Corporation Method for etching copper and composition useful therein
CN1629357A (en) * 2003-12-16 2005-06-22 清英实业有限公司 Surface coarsening agent for copper or copper alloys
CN102995021A (en) * 2011-09-08 2013-03-27 关东化学株式会社 Etching solution composition and etching method for copper and copper alloy
CN103890233A (en) * 2012-09-28 2014-06-25 Mec股份有限公司 Microetching agent for copper, supplementary liquid for same, and manufacturing method for circuit board
CN103952702A (en) * 2014-05-04 2014-07-30 深圳市实锐泰科技有限公司 Etching liquid and method for etching fine lines of flexible circuit board by using same
CN104073804A (en) * 2014-06-17 2014-10-01 长沙牧泰莱电路技术有限公司 PCB (Polychlorinated Biphenyl) acidic etching solution

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636282A (en) * 1985-06-20 1987-01-13 Great Lakes Chemical Corporation Method for etching copper and composition useful therein
CN1629357A (en) * 2003-12-16 2005-06-22 清英实业有限公司 Surface coarsening agent for copper or copper alloys
CN102995021A (en) * 2011-09-08 2013-03-27 关东化学株式会社 Etching solution composition and etching method for copper and copper alloy
CN103890233A (en) * 2012-09-28 2014-06-25 Mec股份有限公司 Microetching agent for copper, supplementary liquid for same, and manufacturing method for circuit board
CN103952702A (en) * 2014-05-04 2014-07-30 深圳市实锐泰科技有限公司 Etching liquid and method for etching fine lines of flexible circuit board by using same
CN104073804A (en) * 2014-06-17 2014-10-01 长沙牧泰莱电路技术有限公司 PCB (Polychlorinated Biphenyl) acidic etching solution

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张招贤等: "《涂层钛电极》", 31 May 2014, 北京：冶金工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108174520A (en) * 2017-12-20 2018-06-15 深圳市板明科技有限公司 Liquid medicine is lost in a kind of sudden strain of a muscle suitable for MSAP techniques
CN108174520B (en) * 2017-12-20 2020-08-28 深圳市板明科技股份有限公司 Flash etching liquid medicine suitable for MSAP (multiple-addition-fragmentation chain) process

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