CN113862675A - Single-liquid type acidic etching solution and recovery method thereof - Google Patents

Single-liquid type acidic etching solution and recovery method thereof Download PDF

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CN113862675A
CN113862675A CN202111029462.2A CN202111029462A CN113862675A CN 113862675 A CN113862675 A CN 113862675A CN 202111029462 A CN202111029462 A CN 202111029462A CN 113862675 A CN113862675 A CN 113862675A
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liquid
solution
chloride
etching
etching solution
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黄文涛
张伟奇
李再强
汪前程
梁民
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Shenzhen Qixin Environmental Protection Technology Co ltd
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Shenzhen Qixin Environmental Protection Technology Co ltd
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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
    • C23F1/10—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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses a single-liquid acidic etching solution and a recovery method of the single-liquid acidic etching solution, wherein the single-liquid acidic etching solution comprises a sub-solution, and the sub-solution comprises hydrochloric acid, ammonium chloride, potassium chloride and ferric chloride. By adding potassium chloride and ferric trichloride, the dissolution of metal copper and oxides thereof in the acidic etching solution is improved, and the copper dissolution amount in the etching solution is also improved, so that the quality of the etching solution is improved; in addition, a large amount of chloride ions exist in the etching solution, and the amount of dissolved copper is increased by adding potassium chloride and ferric trichloride, so that the introduction of other impurity ions is reduced.

Description

Single-liquid type acidic etching solution and recovery method thereof
Technical Field
The invention relates to the technical field of etching solutions, in particular to a single-liquid acidic etching solution and a recovery method of the single-liquid acidic etching solution.
Background
In the manufacturing process of Printed Circuit Boards (PCBs), a desired circuit pattern is formed by removing unnecessary portions of the circuit board by a chemical reaction. The acid etching solution is used for corroding a copper-clad plate in the manufacturing industry of the printed circuit board, and removing copper which is not protected by printing ink or a dry film to obtain a circuit pattern.
The acid etching solution comprises a single-liquid acid etching solution and a double-liquid acid etching solution, wherein the single-liquid acid etching solution is widely applied to the manufacturing process of the circuit board due to high etching speed and low cost, but the copper dissolving amount of the single-liquid acid etching solution is generally low, the copper ion content is about 95g/L, and the quality of the etching solution is influenced.
Disclosure of Invention
The invention mainly aims to provide a single-liquid type acidic etching solution and a recovery method thereof, and aims to solve the problem of low copper dissolving amount of the conventional single-liquid type acidic etching solution.
In order to achieve the purpose, the invention provides a single-liquid type acidic etching solution which comprises a sub-solution, wherein the sub-solution comprises hydrochloric acid, ammonium chloride, potassium chloride and ferric chloride.
Optionally, in the sub-solution, the acid equivalent is 3.0-5.0N, the ammonia nitrogen value is 25000-40000 ppm, and the chloride ion concentration is 190-250 g/L.
Optionally, the concentration of the potassium chloride in the seed solution is 10-80 g/L.
Optionally, in the sub-liquid, the concentration of ferric trichloride is 1-40 g/L.
Optionally, the single-liquid type acidic etching solution further comprises a mother liquid, wherein the mother liquid comprises hydrochloric acid, ammonium chloride, potassium chloride, ferric chloride and copper chloride.
In addition, the invention also provides a recovery method of the single-liquid type acidic etching solution, which comprises the following steps:
recovering waste etching liquid discharged from the etching line;
performing electrolytic treatment on the etching waste liquid to reduce the copper content in the etching waste liquid;
and adding an additive into the waste etching solution after the electrolytic treatment to obtain a regenerated sub-solution of the single-solution type acidic etching solution.
Optionally, the additive comprises ammonium chloride.
According to the technical scheme provided by the invention, the single-liquid type acidic etching solution comprises a sub-solution, the sub-solution comprises hydrochloric acid, ammonium chloride, potassium chloride and ferric trichloride, and the dissolution of metal copper and oxides thereof in the acidic etching solution is improved by adding the potassium chloride and the ferric trichloride, so that the copper dissolving amount in the etching solution is improved, and the quality of the etching solution is improved; in addition, a large amount of chloride ions exist in the etching solution, and the amount of dissolved copper is increased by adding potassium chloride and ferric trichloride, so that the introduction of other impurity ions is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The single-liquid type acidic etching solution has been widely applied to the manufacturing process of circuit boards due to high etching speed and low cost, but the single-liquid type acidic etching solution generally has low copper dissolving amount, and the copper ion content is about 95g/L, so that the quality of the etching solution is influenced.
In view of this, the present invention provides a single-liquid type acidic etching solution, and aims to provide an acidic etching solution with high copper dissolution rate while ensuring etching rate. In this embodiment, the single-liquid type acidic etching solution includes a sub-liquid, and the sub-liquid includes hydrochloric acid, ammonium chloride, potassium chloride, and ferric chloride. For convenience of description, the single-liquid type acidic etching solution is hereinafter referred to as an acidic etching solution.
It is understood that the acidic etching solution includes a sub-solution and a mother solution. The base solution of the reaction is colloquially referred to in the printed circuit board industry as a mother solution, and the make-up solution used for make-up, which is copper-free as compared to the base solution, is colloquially referred to in the industry as a daughter solution. The components of the seed liquid purchased from the market at present are generally ammonium chloride and hydrochloric acid, and different manufacturers can adjust the concentrations of the ammonium chloride and the hydrochloric acid.
Compared with the existing seed solution, on the basis, the potassium chloride is added to replace part of ammonium chloride to supplement chloride ions, so that the dissolution of the acid etching solution to metal copper and metal copper oxide is improved on the premise of ensuring the etching rate, and the copper dissolution amount is also improved; and the copper dissolving amount of the etching solution is further improved by adding ferric trichloride.
In the technical scheme provided by the invention, the sub-liquid of the single-liquid type acidic etching liquid comprises hydrochloric acid, ammonium chloride, potassium chloride and ferric chloride, and the dissolution of metal copper and oxides thereof in the acidic etching liquid is improved by adding the potassium chloride and the ferric chloride, so that the copper dissolution amount in the etching liquid is improved, and the quality of the etching liquid is improved; meanwhile, by adding ferric trichloride and potassium chloride, the problems that a pipeline and an etching line nozzle are blocked by copper chloride crystals due to overhigh copper ions in the etching solution are solved; in addition, a large amount of chloride ions exist in the etching solution, and the amount of dissolved copper is increased by adding potassium chloride and ferric trichloride, so that the introduction of other impurity ions is reduced.
In one embodiment, the acid equivalent in the seed solution is 3.0-5.0N, the ammonia nitrogen value is 25000-40000 ppm, and the chloride ion concentration is 190-250 g/L. It is understood that the chloride ions are derived from hydrochloric acid, ammonium chloride, potassium chloride and ferric chloride, i.e., chloride ions contained in hydrochloric acid, chloride ions contained in ammonium chloride, chloride ions contained in potassium chloride, and chloride ions contained in ferric chloride, and that the sum of these chloride ions is the final measured chloride ion concentration.
The specific concentration of the potassium chloride is not limited, and in one embodiment, the concentration of the potassium chloride in the sub-solution is 10-80 g/L, that is, 10-80 g of potassium chloride is added to 1L of single-solution type acidic etching solution, for example, the concentration of the potassium chloride may be 10g/L, 25g/L, 35g/L, 46g/L, 57g/L, 72g/L, or 80 g/L.
Further, in another embodiment, the concentration of ferric trichloride in the sub-solution is 1-40 g/L, that is, 1-20 g of ferric trichloride is added to 1L of the single-solution type acidic etching solution, for example, the concentration of ferric trichloride may be 1g/L, 5g/L, 7g/L, 15g/L, 20g/L, 25g/L, 40 g/L. In the embodiment, when the single-liquid acidic etching solution is used for processing a circuit board, the temperature of the etching solution is controlled to be 45-50 ℃, and the pressure of the etching nozzle is controlled to be 1.5-3.0 kg/cm2。
In this embodiment, the single-liquid acidic etching solution further includes a mother liquid, and the mother liquid includes hydrochloric acid, ammonium chloride, potassium chloride, ferric chloride, and copper chloride. Further, the mother liquor is less acidic than the daughter liquor.
In a preferred embodiment, in the sub-solution, the acid equivalent is 3.0-5.0N, the ammonia nitrogen value is 25000-40000 ppm, the concentration of chloride ions is 190-250 g/L, the concentration of ferric trichloride is 1-40 g/L, and the concentration of potassium chloride is 10-80 g/L, and by designing the components of the sub-solution and the concentrations of the components, the etching solution can ensure that the copper dissolving amount is higher on the premise of higher etching rate, and the copper dissolving amount can reach 120-140 g/L; meanwhile, by adding ferric trichloride and potassium chloride, the problem that the pipeline and the etching nozzle are blocked by copper chloride crystals due to overhigh copper ions in the etching waste liquid at a lower temperature is solved.
Further, the invention also provides a recovery method of the single-liquid type acidic etching solution, which comprises the following steps:
step S10, recovering waste etching solution discharged from the etching line;
specifically, in the process of etching the copper foil by the mother solution (also called etching tank solution, etching working solution and etching basic solution) of the acidic etching solution, the metal copper on the circuit board reacts with the divalent copper ions in the etching mother solution to generate cuprous ions, the cuprous ions and the ammonium ions are complexed to generate cuprous ammonia complex ions, and the cuprous ammonia complex ions react with oxygen in the air to generate divalent cupric ammonia complex ions to continuously participate in the etching reaction. The concentration of copper ions in the etching mother solution is continuously increased along with the continuous reaction of copper on a circuit board and bivalent copper in the etching solution, the acidity is continuously reduced, and the specific gravity is continuously increased, so in order to maintain the stability of the acidic etching solution, a sub-solution is required to be added to dilute the mother solution, so that the copper ions and the acidity in the acidic etching solution in the etching tank are maintained in a stable range, the sub-solution is added from the bottom of the etching tank through a specific gravity controller of the mother solution, the volume of the solution in the etching tank is expanded along with the addition of the sub-solution, the top of the acidic etching solution overflows through an overflow port, and the overflowing part of the acidic etching solution flows into a waste liquid barrel through the overflow port to become etching waste liquid.
Step S20, carrying out electrolytic treatment on the etching waste liquid to reduce the copper content in the etching waste liquid;
the etching waste liquid in the waste liquid barrel is conveyed to an electrolytic cell for electrolysis, copper ions in the waste liquid can be separated out into copper simple substances in a cathode area, and then the regenerated liquid (the waste liquid with low copper content) in an anode area is conveyed to the regenerated liquid barrel.
And step S30, adding an additive into the waste etching solution after the electrolytic treatment to obtain a regenerated sub-solution of the single-solution type acidic etching solution.
Specifically, the regenerated liquid in the regenerated liquid barrel is conveyed to the blending barrel, and the additive is added into the blending barrel to adjust various parameters of the regenerated liquid in the blending barrel.
In this embodiment, the additive includes ammonium chloride, and the concentration of chloride ions in the regenerated solution can be increased by adding ammonium chloride, thereby obtaining a regenerated sub-solution of the single-solution type acidic etching solution. It should be noted that when the regenerated sub-solution is prepared after the waste solution is electrolyzed for a plurality of times, ammonium chloride is supplemented because the loss of potassium chloride and ferric trichloride is little, but the potassium chloride and the ferric trichloride are lost after repeated use, and at this time, the potassium chloride and the ferric trichloride can be supplemented according to 1-5% of the initial concentration.
It is understood that the regenerated sub-solution is to be reused as a sub-solution, and therefore, the parameters of the regenerated sub-solution are prepared according to the parameters of the sub-solution. At present, a technical scheme that mother liquor is copper chloride, ammonium chloride and hydrochloric acid exists, that is, the sub-liquor is only ammonium chloride and hydrochloric acid, but therefore, when chloride ions need to be supplemented to the regenerated liquor to prepare the parameters of the sub-liquor, if the ammonium chloride is supplemented, because the solubility of the ammonium chloride is low, heat absorption is serious during dissolution, and thus, the concentration of the chloride ions in the regenerated sub-liquor is not high due to the fact that the ammonium chloride cannot be dissolved during preparation of the regenerated sub-liquor, so that the etching rate of the regenerated sub-liquor returning to a production line is influenced; the effect of increasing the chloride ion concentration by supplementing sodium chloride is far less than that of ammonium chloride.
In the technical scheme of the invention, through the addition of ferric trichloride and potassium chloride and the design of the concentration of the ferric trichloride and the potassium chloride, when ammonium chloride is added to supplement chloride ions, the content of the chloride ions in the regenerated sub-solution can be higher, so that the etching rate is not reduced when the recovered regenerated sub-solution is used as the sub-solution. Specifically, the etching waste liquid contains potassium chloride, the potassium chloride has high solubility, the heat absorption is general in the dissolving process, the concentration of chloride ions can be adjusted to a high position, and the effect difference between the potassium ions and ammonium ions in the etching process is small due to the large radius of the potassium ions.
Therefore, the invention ensures that the impurity ions in the waste liquid are less through the design of the components of the sub-liquid and the concentration of the components; meanwhile, the waste etching solution is convenient to recycle, and the etching rate of the recycled regenerated sub-solution as the sub-solution is not reduced; in addition, the problem that the pipeline is blocked by crystallization due to overhigh concentration of copper ions in the etching waste liquid can be avoided.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
(1) Sub-liquid parameters of the single-liquid type acidic etching liquid: acidity of 4.0N, ammonia nitrogen of 35000ppm, and chloride ion concentration of 220g/L, wherein the concentration of potassium chloride is 40g/L, and the concentration of ferric trichloride is 5 g/L.
(2) The etch line parameters were: the temperature is 50 ℃, and the nozzle pressure is 2.0kg/cm2The etching rate was found to be 32.4 um/min.
(3) The parameters of the waste etching solution collected from the etching line are tested as follows: the acidity is 0.5N, the copper ion content is 120g/L, the chloride ion content is 208g/L, the ammonia nitrogen content is 32000ppm, and the waste liquid does not crystallize below 10 ℃.
(4) Carrying out electrolytic copper extraction treatment on the etching waste liquid to obtain a regenerated liquid, wherein the measured parameters of the regenerated liquid are as follows: the acidity is 3.8N, the concentration of copper ions is 6g/L, and the ammonia nitrogen is 18000 ppm; according to the difference between the parameters of the regeneration liquid and the seed liquid, adding ammonium chloride into the regeneration liquid to obtain the regeneration seed liquid, wherein the parameters of the regeneration seed liquid are as follows: the acidity is 3.8N, the copper ion concentration is 4g/L, the ammonia nitrogen concentration is 30000ppm, and the chloride ion concentration is 210g/L (the ammonium chloride can not be dissolved when being supplemented).
(5) The regenerated seed solution is used as seed solution, and the etching rate is measured to be 32.8um/min after the seed solution is returned to a production line for use.
Example 2
(1) Sub-liquid parameters of the single-liquid type acidic etching liquid: acidity of 3.0N, ammonia nitrogen of 25000ppm, chloride ion concentration of 190g/L, wherein the concentration of potassium chloride is 80g/L, and the concentration of ferric trichloride is 1 g/L.
(2) The etch line parameters were: the temperature is 50 ℃, and the nozzle pressure is 2.0kg/cm2The etching rate was measured to be 28.6 um/min.
(3) The parameters of the waste etching solution collected from the etching line are tested as follows: acidity of 0.5N, copper ion of 140g/L, chloride ion of 195g/L, ammonia nitrogen of 28000ppm, and no crystallization of waste liquid at 10 ℃ below.
(4) Carrying out electrolytic copper extraction treatment on the etching waste liquid to obtain a regenerated liquid, wherein the measured parameters of the regenerated liquid are as follows: the acidity is 3.8N, the concentration of copper ions is 6g/L, and the ammonia nitrogen is 18000 ppm; according to the difference between the parameters of the regenerated liquid and the sub-liquid, adding ammonium bicarbonate and ammonium chloride into the regenerated liquid to obtain regenerated sub-liquid, wherein the parameters of the regenerated sub-liquid are as follows: the acidity is 3.0N, the copper ion concentration is 4g/L, the ammonia nitrogen concentration is 290000ppm, and the chloride ion concentration is 190g/L (the ammonium chloride can not be dissolved when being supplemented).
(5) The regenerated seed solution is used as seed solution, and the etching rate is measured to be 29.8um/min after the seed solution is returned to a production line for use.
Example 3
(1) Sub-liquid parameters of the single-liquid type acidic etching liquid: the acidity is 5.0N, the ammonia nitrogen is 40000ppm, the chloride ion concentration is 250g/L, wherein the potassium chloride concentration is 10g/L, and the ferric chloride concentration is 40 g/L.
(2) The etch line parameters were: the temperature is 50 ℃, and the nozzle pressure is 2.0kg/cm2The etching rate was measured to be 48.5 um/min.
(3) The parameters of the waste etching solution collected from the etching line are tested as follows: the acidity is 0.8N, the copper ion content is 120g/L, the chloride ion content is 228g/L, the ammonia nitrogen content is 35000ppm, and the waste liquid does not crystallize below 10 ℃.
(4) Carrying out electrolytic copper extraction treatment on the etching waste liquid to obtain a regenerated liquid, wherein the measured parameters of the regenerated liquid are as follows: the acidity is 3.8N, the concentration of copper ions is 6g/L, and the ammonia nitrogen is 18000 ppm; according to the difference between the parameters of the regenerated liquid and the seed liquid, adding hydrochloric acid and ammonium chloride into the regenerated liquid to obtain regenerated seed liquid, wherein the parameters of the regenerated seed liquid are as follows: the acidity is 4.8N, the copper ion concentration is 4g/L, the ammonia nitrogen concentration is 37000ppm, and the chloride ion concentration is 240g/L (which cannot be dissolved when the ammonium chloride is supplemented).
(5) The regenerated seed solution is used as seed solution, and the etching rate is measured to be 47.0um/min after the seed solution is returned to a production line for use.
Comparative example 1
(1) Sub-liquid parameters of the single-liquid type acidic etching liquid: acidity of 4.0N, ammonia nitrogen of 35000ppm, and chloride ion of 225 g/L.
(2) The etch line parameters were: the temperature was 50 ℃ and the nozzle pressure was 2.0kg/cm2, and the etch rate was measured to be 28.5 um/min.
(3) The parameters of the waste etching solution collected from the etching line are tested as follows: acidity of 0.5N, copper ion of 95g/L, chloride ion of 202g/L, ammonia nitrogen of 32000ppm, and green crystallization of waste liquid below 10 ℃.
(4) Carrying out electrolytic copper extraction treatment on the etching waste liquid to obtain a regenerated liquid, wherein the measured parameters of the regenerated liquid are as follows: the acidity is 3.8N, the concentration of copper ions is 6g/L, and the ammonia nitrogen is 16000 ppm; according to the difference between the parameters of the regeneration liquid and the seed liquid, adding ammonium chloride into the regeneration liquid to obtain the regeneration seed liquid, wherein the parameters of the regeneration seed liquid are as follows: the acidity is 3.8N, the concentration of copper ions is 4g/L, the ammonia nitrogen is 30000ppm, and the concentration of chloride ions is 195g/L (the chloride can not be dissolved when being supplemented with ammonium chloride).
(5) The regenerated seed solution is used as seed solution, and the etching rate is measured to be 22.6um/min after the seed solution is returned to a production line for use.
Comparative example 2
(1) Sub-liquid parameters of the single-liquid type acidic etching liquid: acidity of 4.0N, ammonia nitrogen of 35000ppm, potassium chloride of 40g/L, and chloride ion of 220 g/L.
(2) The etch line parameters were: the temperature was 50 ℃ and the nozzle pressure was 2.0kg/cm2, and the etch rate was measured to be 30.0 um/min.
(3) The parameters of the waste etching solution collected from the etching line are tested as follows: acidity of 0.5N, copper ion of 100g/L, chloride ion of 202g/L, ammonia nitrogen of 32000ppm, and green crystallization of waste liquid below 10 ℃.
(4) Carrying out electrolytic copper extraction treatment on the etching waste liquid to obtain a regenerated liquid, wherein the measured parameters of the regenerated liquid are as follows: the acidity is 3.6N, the concentration of copper ions is 8g/L, and the ammonia nitrogen is 16000 ppm; according to the difference between the parameters of the regeneration liquid and the seed liquid, adding ammonium chloride into the regeneration liquid to obtain the regeneration seed liquid, wherein the parameters of the regeneration seed liquid are as follows: the acidity is 3.8N, the concentration of copper ions is 5g/L, the ammonia nitrogen is 30000ppm, and the concentration of chloride ions is 205g/L (the chloride ions can not be dissolved when being supplemented with ammonium chloride).
(5) The regenerated seed solution is used as seed solution, and the etching rate is measured to be 27.6um/min after the seed solution is returned to a production line for use.
As can be seen from the examples and the comparative examples (it should be noted that the parameters of the etching waste liquid and the mother liquid in the examples and the comparative examples are almost the same, and the parameters of the etching waste liquid, the regeneration liquid and the regeneration sub-liquid are all parameters which are changed compared with the sub-liquid, while the parameters of the potassium chloride and the ferric chloride are not shown because the parameters are basically unchanged), the acid etching liquid provided by the invention has a high copper dissolving amount of 120-140 g/L through the design of the components and the mixture ratio of the components; meanwhile, green crystals can not appear at a lower temperature, namely below 10 ℃, so that the pipeline is not easy to block; in addition, the etching rate can not be reduced after the etching waste liquid is recycled and returns to the production line again.
Specifically, while no crystallization occurred in the etching waste liquid of example, while the copper ion concentration of the etching waste liquid of comparative example 1 and comparative example 2 was lower than that of example, green crystallization occurred mainly because the solubility of ammonium chloride was low, and when the temperature was lowered, ammonium chloride was precipitated from the etching waste liquid, and the surface adsorbed copper chloride to form coprecipitation when ammonium chloride was precipitated, which is also the reason why the copper ion concentration was low in comparative example 1; in comparative example 2, ammonium chloride concentration was reduced by replacing ammonium chloride with a portion of potassium chloride, which has higher solubility than ammonium chloride, so that ammonium chloride was not precipitated when the temperature was lowered and thus coprecipitation was not formed, whereas in the example of the present invention, ammonium chloride precipitation was prevented by further adding ferric chloride on the basis of comparative example 2, possibly because of the hydrolysis of ferric chloride.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims (7)

1. The single-liquid type acidic etching solution is characterized by comprising a sub-liquid, wherein the sub-liquid comprises hydrochloric acid, ammonium chloride, potassium chloride and ferric chloride.
2. The single-liquid acidic etching solution of claim 1, wherein the acid equivalent in the sub-solution is 3.0-5.0N, the ammonia nitrogen value is 25000-40000 ppm, and the chloride ion concentration is 190-250 g/L.
3. The single-liquid acidic etching solution according to claim 2, wherein the concentration of the potassium chloride in the sub-solution is 10 to 80 g/L.
4. The single-liquid acidic etching solution of claim 2, wherein the concentration of ferric trichloride in the sub-solution is 1-40 g/L.
5. The single-liquid acidic etching solution of claim 1, further comprising a mother liquor comprising hydrochloric acid, ammonium chloride, potassium chloride, ferric chloride, and cupric chloride.
6. A method for recovering a one-pack type acidic etching solution as set forth in any one of claims 1 to 5, comprising the steps of:
recovering waste etching liquid discharged from the etching line;
performing electrolytic treatment on the etching waste liquid to reduce the copper content in the etching waste liquid;
and adding an additive into the waste etching solution after the electrolytic treatment to obtain a regenerated sub-solution of the single-solution type acidic etching solution.
7. The method of claim 6, wherein the additive comprises ammonium chloride.
CN202111029462.2A 2021-09-01 2021-09-01 Single-liquid type acidic etching solution and recovery method thereof Pending CN113862675A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106119852A (en) * 2015-08-31 2016-11-16 叶旖婷 The electrolytic recovery of a kind of acid copper chloride etching liquid and regeneration technology
CN110172701A (en) * 2019-05-08 2019-08-27 深圳市祺鑫天正环保科技有限公司 Acidic etching liquid system for regenerating and recycling

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106119852A (en) * 2015-08-31 2016-11-16 叶旖婷 The electrolytic recovery of a kind of acid copper chloride etching liquid and regeneration technology
CN110172701A (en) * 2019-05-08 2019-08-27 深圳市祺鑫天正环保科技有限公司 Acidic etching liquid system for regenerating and recycling

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