CN105887092B - A kind of PCB acidic etching liquid suitable for ozone absorption method - Google Patents
A kind of PCB acidic etching liquid suitable for ozone absorption method Download PDFInfo
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- CN105887092B CN105887092B CN201610275202.6A CN201610275202A CN105887092B CN 105887092 B CN105887092 B CN 105887092B CN 201610275202 A CN201610275202 A CN 201610275202A CN 105887092 B CN105887092 B CN 105887092B
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- acidic etching
- etching liquid
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- pcb acidic
- pcb
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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 a kind of PCB acidic etching liquids suitable for ozone absorption method, the component of the PCB acidic etching liquid and the content of each component are as follows: etching solution divalent copper content is 130-170g/L, the chlorination salt content of highly dissoluble is 120 ~ 200g/L, the content of hydrochloric acid is 1.5 ~ 2.5mol/L, stabilization agent is 1-10g/L, wetting agent is 0.1g/L ~ 0.3g/L, and shore protection agent is 0.1g/L ~ 0.5g/L.The present invention removes the sodium chloride in script technique, then the chlorate for using solubility bigger, to facilitate crystallization, this formula adapts to new technological flow completely, is conducive to later crystallization processing, simplifies script acid etching formula of liquid.
Description
Technical field
The present invention relates to PCB (printed circuit board) technical field of manufacturing process, and in particular to one kind is suitable for ozone and recycles
The PCB acidic etching liquid of method.
Background technique
In printed circuit board manufacture, in addition to multiple wiring, addition process etc. is outer, and traditional printed circuit board is all with chemistry
Reactive mode is removed the part copper not needed on PCB plate, forms it into required circuitous pattern.And as circuit
Visuals using pattern transfer or applying makes the photic antibody of organic compound objects system lose agent or using metal by the way of wire mark
Resist layer covers circuitous pattern surface, and metallic copper is prevented to be etched.Therefore, etch process is currently manufactured printed circuit board
Indispensable important step in plate.It is H that PCB industry internal layer is most common at present2O2/ HCl system and NaClO3/HCl
Both acidic etching liquids of system, the type of such etching solution is more, the etching quality effect that the difference of formula will lead to
It is variant.However either hydrogen peroxide or sodium chlorate, it all unavoidably comes up against a series of problems in production.Hydrogen peroxide
Storage is difficult, easily decomposes, easily initiation security risk.Although sodium chlorate is very stable, with the progress of reaction, the amount of sodium chloride is continuous
Rise, so that sodium chloride eventually exceeds the precipitation of its solubility, etching is caused inevitably to influence.A currently designed arbitrage out
The system of oxidation regeneration is carried out with ozone, but has not been adapted to new reaction system by the formula of original process condition.
Summary of the invention
In view of above reason, it is an object of the invention to propose a kind of PCB acidity erosion suitable for ozone absorption method
Liquid is carved, is solved using the acidic etching liquid formulation challenges under new technology.
The purpose of the present invention is achieved through the following technical solutions.
A kind of PCB acidic etching liquid suitable for ozone absorption method, the component of the PCB acidic etching liquid includes: mother liquor
Copper, hydrochloric acid, stabilization agent, shore protection agent, wetting agent, the chlorate and water of highly dissoluble.
Preferably, the mother liquor copper is copper chloride (CuCl2)；The stabilization agent is urea；The shore protection agent is
Mercapto benzothiazole (MBT)；The wetting agent is 2-ethylhexanol sulfuric acid vinegar sodium；The chlorate of the highly dissoluble is molten
Chlorate Xie Du higher than copper chloride.
Preferably, the chlorate of the highly dissoluble is calcium chloride or zinc chloride.
Preferably, content of the mother liquor copper in PCB acidic etching liquid is 130 ~ 170g/L.
Preferably, content of the hydrochloric acid in PCB acidic etching liquid is 1.5 ~ 2.5mol/L.
Preferably, content of the chlorate of the highly dissoluble in PCB acidic etching liquid is 120 ~ 200g/L.
Preferably, content of the stabilization agent in PCB acidic etching liquid is 1 ~ 10g/L.
Preferably, content of the wetting agent in PCB acidic etching liquid is 0.1 ~ 0.3g/L.
Preferably, content of the shore protection agent in PCB acidic etching liquid is 0.1 ~ 0.5g/L.
Preferably, temperature of the PCB acidic etching liquid in spray is 45 ~ 55 DEG C.
Compared with prior art, the invention has the advantages that and technical effect:
The present invention removes the sodium chloride in script technique, then the chlorate for using solubility bigger is crystallized with facilitating, this
Formula adapts to new technological flow completely, is conducive to later crystallization processing, simplifies script acid etching formula of liquid.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
A kind of PCB acidic etching liquid suitable for ozone absorption method, is mixed by following each component, and in etching solution
The content of each component are as follows: etching mother liquor copper (copper chloride) 150g/L, hydrochloric acid 2mol/L, calcium chloride 160g/L, stabilization agent (urea)
5g/L, wetting agent (2-ethylhexanol sulfuric acid vinegar sodium) 0.2g/L, shore protection agent (2-mercaptobenzothiazole) 0.3g/L, remaining is water.
Following reaction has occurred in the acidic etching processes of this system:
1, erosion copper reaction: metallic copper is bitten off by the cupric erosion in solution, reaction equation:
3Cu+3CuCl2 → 6CuCl
2, regenerative response: metallic copper is etched the Cu in tank liquor2+It aoxidizes and dissolves, 2Cu generated+It is passed into body again
Ozone oxidation in system is oxidized to Cu by serial reaction2+, and these Cu2+Continue again with the metallic copper reaction in plate face, therefore
Enable etching solution that more metallic coppers are stung eating away.Here it is the reactions of the circular regeneration of etching solution, see below reaction equation: 2CuCl
+ O3 + 2HCl → 2CuCl2 + H2O +O2
3, net reaction: Cu+O3 +2HCl → CuCl2 + H2O + O2
The PCB acidic etching liquid carried out under the conditions of ozone under the process conditions that oxid-reclamatiom utilizes that the present embodiment uses
Eliminate the oxidant of script；Etch uniformity can achieve 98% under conditions of spraying temperature and being 50 DEG C；Etching factor
3.5.The effective guarantee stability of etching solution and the precision of circuit etching figure, effectively improve the speed of circuit etching figure
Degree, and completely removes the solubility sodium chloride smaller than copper chloride, then uses the chlorate of high-dissolvability instead of sodium chloride,
While guaranteeing chlorine ion concentration, the available higher copper chloride of purity during later crystallization ensure that, and it is further
Highly dissoluble chloride after crystallization is reusable.
Embodiment 2
A kind of PCB acidic etching liquid suitable for ozone absorption method, the content of etching solution component and each component are as follows: etching
Mother liquor copper (copper chloride) 130g/L, hydrochloric acid 1.5mol/L, calcium chloride 120g/L, stabilization agent (urea) 1g/L, wetting agent (2- ethyl
Alcohol sulfuric acid vinegar sodium) 0.1g/L, shore protection agent (2-mercaptobenzothiazole) 0.1g/L, remaining is water.
Following reaction has occurred in the acidic etching processes of this system:
1, erosion copper reaction: metallic copper is bitten off by the cupric erosion in solution, reaction equation:
3Cu+3CuCl2 → 6CuCl
2, regenerative response: metallic copper is etched the Cu in tank liquor2+It aoxidizes and dissolves, 2Cu generated+It is passed into body again
Ozone oxidation in system is oxidized to Cu by serial reaction2+, and these Cu2+Continue again with the metallic copper reaction in plate face, therefore
Enable etching solution that more metallic coppers are stung eating away.Here it is the reactions of the circular regeneration of etching solution, see below reaction equation: 2CuCl
+ O3 + 2HCl → 2CuCl2 + H2O +O2
3, net reaction: Cu+O3 +2HCl → CuCl2 + H2O + O2
The PCB acidic etching liquid carried out under the conditions of ozone under the process conditions that oxid-reclamatiom utilizes that the present embodiment uses
Eliminate the oxidant of script；Etch uniformity can achieve 90% under conditions of spraying temperature and being 50 DEG C；Etching factor
3.2.The effective guarantee stability of etching solution and the precision of circuit etching figure, effectively improve the speed of circuit etching figure
Degree, and completely removes the solubility sodium chloride smaller than copper chloride, then uses the chlorate of high-dissolvability instead of sodium chloride,
While guaranteeing chlorine ion concentration, the available higher copper chloride of purity during later crystallization ensure that, and it is further
Highly dissoluble chloride after crystallization is reusable.
Embodiment 3
A kind of PCB acidic etching liquid suitable for ozone absorption method, the content of etching solution component and each component are as follows: etching
Mother liquor copper (copper chloride) 170g/L, hydrochloric acid 2.5mol/L, calcium chloride 200g/L, stabilization agent (urea) 10g/L, wetting agent (2- second
Base alcohol sulfuric acid vinegar sodium) 0.3g/L, shore protection agent (2-mercaptobenzothiazole) 0.5g/L, remaining is water.
Following reaction has occurred in the acidic etching processes of this system:
1, erosion copper reaction: metallic copper is bitten off by the cupric erosion in solution, reaction equation:
3Cu+3CuCl2 → 6CuCl
2, regenerative response: metallic copper is etched the Cu in tank liquor2+It aoxidizes and dissolves, 2Cu generated+It is passed into body again
Ozone oxidation in system is oxidized to Cu by serial reaction2+, and these Cu2+Continue again with the metallic copper reaction in plate face, therefore
Enable etching solution that more metallic coppers are stung eating away.Here it is the reactions of the circular regeneration of etching solution, see below reaction equation: 2CuCl
+ O3 + 2HCl → 2CuCl2 + H2O +O2
3, net reaction: Cu+O3 +2HCl → CuCl2 + H2O + O2
The PCB acidic etching liquid carried out under the conditions of ozone under the process conditions that oxid-reclamatiom utilizes that the present embodiment uses
Eliminate the oxidant of script；Etch uniformity can achieve 90% under conditions of spraying temperature and being 50 DEG C；Etching factor
3.2.The effective guarantee stability of etching solution and the precision of circuit etching figure, effectively improve the speed of circuit etching figure
Degree, and completely removes the solubility sodium chloride smaller than copper chloride, then uses the chlorate of high-dissolvability instead of sodium chloride,
While guaranteeing chlorine ion concentration, the available higher copper chloride of purity during later crystallization ensure that, and it is further
Highly dissoluble chloride after crystallization is reusable.
It should be understood by those ordinary skilled in the art that: the above is only a specific embodiment of the present invention, and
It is not used in the limitation present invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done,
It should be included within protection scope of the present invention.
Claims (1)
1. a kind of PCB acidic etching liquid suitable for ozone absorption method, which is characterized in that the group subpackage of the PCB acidic etching liquid
Contain: mother liquor copper, hydrochloric acid, stabilization agent, shore protection agent, wetting agent, the chlorate and water of highly dissoluble；
The mother liquor copper is copper chloride；The stabilization agent is urea；The shore protection agent is mercapto benzothiazole；Described
Wetting agent is 2-ethylhexanol sulfuric acid vinegar sodium；The chlorate of the highly dissoluble is the solubility chlorate higher than copper chloride；
The chlorate of the highly dissoluble is calcium chloride or zinc chloride；
Content of the mother liquor copper in PCB acidic etching liquid is 130 ~ 170g/L；
Content of the hydrochloric acid in PCB acidic etching liquid is 1.5 ~ 2.5mol/L；
Content of the chlorate of the highly dissoluble in PCB acidic etching liquid is 120 ~ 200g/L；
Content of the stabilization agent in PCB acidic etching liquid is 1 ~ 10g/L；
Content of the wetting agent in PCB acidic etching liquid is 0.1 ~ 0.3g/L；
Content of the shore protection agent in PCB acidic etching liquid is 0.1 ~ 0.5g/L；
Temperature of the PCB acidic etching liquid in spray is 45 ~ 55 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610275202.6A CN105887092B (en) | 2016-04-28 | 2016-04-28 | A kind of PCB acidic etching liquid suitable for ozone absorption method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610275202.6A CN105887092B (en) | 2016-04-28 | 2016-04-28 | A kind of PCB acidic etching liquid suitable for ozone absorption method |
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| Publication Number | Publication Date |
|---|---|
| CN105887092A CN105887092A (en) | 2016-08-24 |
| CN105887092B true CN105887092B (en) | 2019-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610275202.6A Expired - Fee Related CN105887092B (en) | 2016-04-28 | 2016-04-28 | A kind of PCB acidic etching liquid suitable for ozone absorption method |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Family Cites Families (6)
| 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 |
| JP5885971B2 (en) * | 2011-09-08 | 2016-03-16 | 関東化學株式会社 | Etching solution for copper and copper alloy |
| CN103890233B (en) * | 2012-09-28 | 2016-01-20 | Mec股份有限公司 | The manufacture method of copper micro-etching agent and replenisher and circuit card |
| 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 |
| CN104073804B (en) * | 2014-06-17 | 2016-06-22 | 长沙牧泰莱电路技术有限公司 | A kind of PCB acidic etching liquid |
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Granted publication date: 20190115 |