CN112030164A - Ammonia nitrogen-free acidic etching solution - Google Patents
Ammonia nitrogen-free acidic etching solution Download PDFInfo
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- CN112030164A CN112030164A CN201910477206.6A CN201910477206A CN112030164A CN 112030164 A CN112030164 A CN 112030164A CN 201910477206 A CN201910477206 A CN 201910477206A CN 112030164 A CN112030164 A CN 112030164A
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- 238000005530 etching Methods 0.000 title claims abstract description 176
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 83
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 74
- 239000000654 additive Substances 0.000 claims abstract description 72
- 230000000996 additive effect Effects 0.000 claims abstract description 68
- 239000007800 oxidant agent Substances 0.000 claims abstract description 66
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 58
- 230000001590 oxidative effect Effects 0.000 claims abstract description 54
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011780 sodium chloride Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004202 carbamide Substances 0.000 claims abstract description 26
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 24
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 19
- 230000033116 oxidation-reduction process Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 7
- 235000013877 carbamide Nutrition 0.000 description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 18
- 229910001431 copper ion Inorganic materials 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 6
- 230000028161 membrane depolarization Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- KCOYHFNCTWXETP-UHFFFAOYSA-N (carbamothioylamino)thiourea Chemical compound NC(=S)NNC(N)=S KCOYHFNCTWXETP-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
Landscapes
- 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 provides an ammonia nitrogen-free acidic etching solution, which comprises an oxidant and an acidic etching solution additive, wherein the oxidant and the acidic etching solution additive do not contain ammonia nitrogen; the weight ratio of the oxidant to the acidic etching solution additive is (0.8-1.0): (2-2.5); the oxidant comprises the following components in percentage by weight: 12 to 20 percent of sodium chlorate, 12 to 18 percent of sodium chloride, 0.5 to 1.5 percent of urea and 60.5 to 75.5 percent of water; the acid etching solution additive comprises the following components in percentage by weight: 16 to 25 percent of hydrogen chloride, 2 to 5 percent of sodium chloride, 0.5 to 1.5 percent of thiourea and 68.5 to 81.5 percent of water. The acid etching solution without ammonia nitrogen avoids the use of ammonia nitrogen from the source, so that PCB production enterprises do not need to treat production wastewater with ammonia nitrogen water and the like, and the acid etching solution adds an etching rate improving component in an additive, so that the production speed of etching is ensured, and the etching effect is better than that of the acid etching solution adopting the ammonia nitrogen component.
Description
Technical Field
The invention relates to the technical field of Printed Circuit Board (PCB) etching, in particular to an ammonia nitrogen-free acidic etching solution.
Background
In the manufacturing process of Printed Circuit Boards (PCBs), unwanted portions of a circuit board are typically removed by chemical reaction to form a desired circuit pattern. 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 traditional acid etching solution needs to be added with ammonia nitrogen components, such as ammonium chloride, to achieve the etching effect, when the etching waste liquid is treated, the ammonia nitrogen is easy to exceed the standard, the emission standard of the ammonia nitrogen in the waste water of PCB production enterprises in the prior art is increasingly strict, the requirement on the direct discharge of the ammonia nitrogen is 1ppm, and the acid etching solution using the ammonia nitrogen components is easy to cause the waste water emission to be not up to the standard or increase the waste water treatment cost.
Therefore, how to develop the acid etching solution without ammonia nitrogen is a technical problem to be solved in the field of PCB industry; moreover, the acid etching solution product without ammonia nitrogen not only meets the requirement of environmental protection, but also meets the requirements of PCB production enterprises on production speed, quality and other aspects.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the acid etching solution without ammonia nitrogen, so that the use of ammonia nitrogen is avoided from the source, and PCB production enterprises do not need to carry out ammonia nitrogen washing and other treatment on production wastewater.
In order to achieve the purpose, the invention provides the following technical scheme:
an ammonia nitrogen-free acidic etching solution comprises an oxidant and an additive, wherein the oxidant and the additive do not contain ammonia nitrogen; the weight ratio of the oxidant to the acidic etching solution additive is (0.8-1.0): (2-2.5);
the oxidant comprises the following components in percentage by weight:
12 to 20 percent of sodium chlorate, 12 to 18 percent of sodium chloride, 0.5 to 1.5 percent of urea and 60.5 to 75.5 percent of water;
the acid etching solution additive comprises the following components in percentage by weight:
16 to 25 percent of hydrogen chloride, 2 to 5 percent of sodium chloride, 0.5 to 1.5 percent of thiourea and 68.5 to 81.5 percent of water.
In the acid etching solution system, the chloride without ammonia nitrogen is used for replacing the chloride containing ammonia nitrogen components to achieve the purposes of removing the ammonia nitrogen and maintaining the balance of the system; the acid etching liquid additive uses the etching rate improving component hydrogen chloride, and can ensure the production speed of etching completely.
Among oxidizing agents, sodium chlorate is oxidizing and can oxidize metallic copper to generate copper ions. And sodium chloride combines copper ions generated by oxidation with chloride ions to form a complex, so that precipitates are prevented from being generated. Urea is a component for preventing lateral etching, and can ensure the precision of etching.
In the additive, thiourea is a complexing agent of cuprous ions, so that the stability of the cuprous ions in the bath solution is ensured, and the stable etching rate is maintained; the depolarization effect in thiourea can reduce the influence of monovalent copper ions on the etching speed.
According to the invention, by optimizing the use ratio of the oxidant and the acidic etching solution additive, the use amount of the oxidant and the acidic etching solution is reduced while the optimal etching effect is ensured, and the method is economical, environment-friendly, stable in etching rate and uniform in etching.
As a preferred embodiment of the technical solution of the present invention, the weight ratio of the oxidizing agent to the acidic etching solution additive is 1: 2.5;
the oxidant comprises the following components in percentage by weight:
12% of sodium chlorate, 12% of sodium chloride, 0.5% of urea and 75.5% of water;
the acid etching solution additive comprises the following components in percentage by weight:
16% of hydrogen chloride, 2% of sodium chloride, 0.5% of thiourea and 81.5% of water.
As a preferred embodiment of the technical solution of the present invention, the weight ratio of the oxidizing agent to the acidic etching solution additive is 0.8: 2;
the oxidant comprises the following components in percentage by weight:
20% of sodium chlorate, 18% of sodium chloride, 1.5% of urea and 60.5% of water;
the acid etching solution additive comprises the following components in percentage by weight:
25% of hydrogen chloride, 5% of sodium chloride, 1.5% of thiourea and 68.5% of water.
As a preferred embodiment of the technical solution of the present invention, the weight ratio of the oxidizing agent to the acidic etching solution additive is 0.9: 2.2;
the oxidant comprises the following components in percentage by weight:
15% of sodium chlorate, 15% of sodium chloride, 0.5% of urea and 69.5% of water;
the acid etching solution additive comprises the following components in percentage by weight:
20% of hydrogen chloride, 4% of sodium chloride, 0.5% of thiourea and 75.5% of water.
As a preferred embodiment of the technical scheme of the invention, the concentration of the urea in the oxidant is 1-1.3 g/L.
As a preferred embodiment of the technical scheme of the invention, the concentration of thiourea in the acid etching solution additive is 0.6-0.7 g/L.
By optimizing the concentration of urea in the oxidant and the concentration of thiourea in the acid etching solution additive, the lateral erosion can be effectively prevented, the stability of divalent copper ions can be ensured, and the etching solution has stable and good etching performance.
As a preferred embodiment of the technical scheme of the invention, the pH range of the acidic etching solution is 2.0-2.5, and the oxidation-reduction potential is controlled between 500-550 mv.
Based on the technical scheme, the invention has the following technical effects:
(1) the acid etching solution without ammonia nitrogen provided by the invention does not contain ammonia nitrogen components in the whole etching system, so that the problems that the waste water discharge does not reach the standard and the waste water needs to be washed are solved; in the subsequent copper-containing waste liquid recovery process, ammonia distillation and other links aiming at ammonia nitrogen treatment are not needed, the method is economical and environment-friendly, and the production cost and the waste liquid treatment cost are effectively reduced.
(2) According to the ammonia nitrogen-free acidic etching solution, the addition of the oxidant and the acidic etching solution additive is controlled through the automatic addition system, and under the mutual cooperation of the hydrogen chloride serving as the etching rate improving component, the urea serving as the side etching prevention component, the thiourea serving as the complexing agent and the chloride in the oxidant and the acidic etching solution additive, an etching system is stable, the etching production speed is high, and the overall etching effect is better than that of the acidic etching solution adopting the ammonia nitrogen component.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. The invention provides a preferred embodiment. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
An ammonia nitrogen-free acidic etching solution comprises an oxidant and an additive, wherein the oxidant and the additive do not contain ammonia nitrogen; wherein, the oxidant comprises the following components in parts by weight: 12g of sodium chlorate, 12g of sodium chloride, 0.5g of urea and 75.5g of water; the acid etching solution additive comprises the following components in parts by weight: 16mL of hydrogen chloride (concentrated hydrochloric acid), 2g of sodium chloride, 0.5g of thiourea and 81.5g of water. Namely, 100g of each of the oxidizing agent and the acidic etching solution additive was prepared.
In the using process, the weight ratio of the oxidant to the acid etching solution additive is 1: 2.5, i.e. 2.5 equivalents of the acidic etching solution additive per equivalent of the oxidizing agent.
In the acid etching solution system, the chloride without ammonia nitrogen is used for replacing the chloride containing ammonia nitrogen components to achieve the purposes of removing the ammonia nitrogen and maintaining the balance of the system at the same time.
In the oxidant, sodium chlorate has oxidability and can oxidize metallic copper to generate copper ions; the sodium chloride combines copper ions generated by oxidation with chloride ions to form a complex, so that precipitates are prevented from being generated; urea is a component for preventing lateral etching, and can ensure the precision of etching.
In the acid etching solution additive, hydrogen chloride (concentrated hydrochloric acid) is used as an etching rate improving component, so that the production speed of etching can be fully ensured; thiourea is a complexing agent of cuprous ions, so that the stability of the cuprous ions in the bath solution is ensured, and the stable etching rate is maintained; the depolarization effect in thiourea can reduce the influence of monovalent copper ions on the etching speed.
Example 2
An ammonia nitrogen-free acidic etching solution comprises an oxidant and an additive, wherein the oxidant and the additive do not contain ammonia nitrogen; wherein, the oxidant comprises the following components in parts by weight: 20g of sodium chlorate, 18g of sodium chloride, 1.5g of urea and 60.5g of water; the acid etching solution additive comprises the following components in parts by weight: 25g of hydrogen chloride, 5g of sodium chloride, 1.5g of thiourea and 68.5g of water. Namely, 100g of each of the oxidizing agent and the acidic etching solution additive was prepared.
In the using process, the weight ratio of the oxidant to the acid etching solution additive is 0.8: 2, i.e. 8g of oxidizing agent, 20g of acidic etching solution additive is used.
In the acid etching solution system, the chloride without ammonia nitrogen is used for replacing the chloride containing ammonia nitrogen components to achieve the purposes of removing the ammonia nitrogen and maintaining the balance of the system at the same time.
In the oxidant, sodium chlorate has oxidability and can oxidize metallic copper to generate copper ions; the sodium chloride combines copper ions generated by oxidation with chloride ions to form a complex, so that precipitates are prevented from being generated; urea is a component for preventing lateral etching, and can ensure the precision of etching.
In the acid etching solution additive, hydrogen chloride (concentrated hydrochloric acid) is used as an etching rate improving component, so that the production speed of etching can be fully ensured; thiourea is a complexing agent of cuprous ions, so that the stability of the cuprous ions in the bath solution is ensured, and the stable etching rate is maintained; the depolarization effect in thiourea can reduce the influence of monovalent copper ions on the etching speed.
Example 3
An ammonia nitrogen-free acidic etching solution comprises an oxidant and an additive, wherein the oxidant and the additive do not contain ammonia nitrogen; wherein, the oxidant comprises the following components in parts by weight: 15g of sodium chlorate, 15g of sodium chloride, 0.5g of urea and 69.5g of water; the acid etching solution additive comprises the following components in parts by weight: 20g of hydrogen chloride, 4g of sodium chloride, 0.5g of thiourea and 75.5g of water. Namely, 100g of each of the oxidizing agent and the acidic etching solution additive was prepared.
In the using process, the weight ratio of the oxidant to the acid etching solution additive is 0.9: 2.2, when 9g of the oxidizing agent was used, 22g of the acidic etching solution additive was used.
In the acid etching solution system, the chloride without ammonia nitrogen is used for replacing the chloride containing ammonia nitrogen components to achieve the purposes of removing the ammonia nitrogen and maintaining the balance of the system at the same time.
In the oxidant, sodium chlorate has oxidability and can oxidize metallic copper to generate copper ions; the sodium chloride combines copper ions generated by oxidation with chloride ions to form a complex, so that precipitates are prevented from being generated; urea is a component for preventing lateral etching, and can ensure the precision of etching.
In the acid etching solution additive, hydrogen chloride (concentrated hydrochloric acid) is used as an etching rate improving component, so that the production speed of etching can be fully ensured; thiourea is a complexing agent of cuprous ions, so that the stability of the cuprous ions in the bath solution is ensured, and the stable etching rate is maintained; the depolarization effect in thiourea can reduce the influence of monovalent copper ions on the etching speed.
Example 4
An ammonia nitrogen-free acidic etching solution comprises an oxidant and an additive, wherein the oxidant and the additive do not contain ammonia nitrogen; wherein, the oxidant comprises the following components in parts by weight: 13g of sodium chlorate, 17g of sodium chloride, 1g of urea and 70g of water; the acid etching solution additive comprises the following components in parts by weight: 17g of hydrogen chloride, 3g of sodium chloride, 1g of thiourea and 79g of water. Namely, 100g of each of the oxidizing agent and the acidic etching solution additive was prepared.
In the using process, the weight ratio of the oxidant to the acid etching solution additive is 1: 2.2, when 10g of the oxidizing agent was used, 22g of the acidic etching solution additive was used.
In the acid etching solution system, the chloride without ammonia nitrogen is used for replacing the chloride containing ammonia nitrogen components to achieve the purposes of removing the ammonia nitrogen and maintaining the balance of the system at the same time.
In the oxidant, sodium chlorate has oxidability and can oxidize metallic copper to generate copper ions; the sodium chloride combines copper ions generated by oxidation with chloride ions to form a complex, so that precipitates are prevented from being generated; urea is a component for preventing lateral etching, and can ensure the precision of etching.
In the acid etching solution additive, hydrogen chloride (concentrated hydrochloric acid) is used as an etching rate improving component, so that the production speed of etching can be fully ensured; thiourea is a complexing agent of cuprous ions, so that the stability of the cuprous ions in the bath solution is ensured, and the stable etching rate is maintained; the depolarization effect in thiourea can reduce the influence of monovalent copper ions on the etching speed.
Comparative example 1
Monomer system 100mL acid etching solution and preparation method thereof:
sodium chlorate: 20g, sodium chloride: 17g, ammonium chloride: 4g, additive: 1.5g, concentrated hydrochloric acid: 1mL, and the balance being water.
Adding sodium chlorate, sodium chloride, ammonium chloride and additives (ureas including urea, thiourea, dithiourea and the like) into a beaker, and adding water for dissolving; and adding concentrated hydrochloric acid, adding water to 100mL, and uniformly stirring to obtain the acidic etching solution.
Comparative example 2
Monomer system 100mL acid etching solution and preparation method thereof:
sodium chlorate: 25g, sodium chloride: 9.5g, ammonium chloride: 3g, additive: 1.2g, concentrated hydrochloric acid: 1mL, and the balance being water.
Adding sodium chlorate, sodium chloride, ammonium chloride and additives (ureas including urea, thiourea, dithiourea and the like) into a beaker, and adding water for dissolving; and adding concentrated hydrochloric acid, adding water to 100mL, and uniformly stirring to obtain the acidic etching solution.
Comparative example 3
Monomer system 100mL acid etching solution and preparation method thereof:
sodium chlorate: 26g, sodium chloride: 10g, ammonium chloride: 4g, additive: 1g, concentrated hydrochloric acid: 1mL, and the balance being water.
Adding sodium chlorate, sodium chloride, ammonium chloride and additives (ureas including urea, thiourea, dithiourea and the like) into a beaker, and adding water for dissolving; and adding concentrated hydrochloric acid, adding water to 100mL, and uniformly stirring to obtain the acidic etching solution.
The copper-clad plate is etched by the acid etching solution without ammonia nitrogen of the embodiment 1-4 and the acid etching solution with ammonia nitrogen of the comparative example 1-2, and the etching results are shown in the table 1.
TABLE 1 comparison of etching results of copper-clad plate with the acid etching solution containing ammonia nitrogen and the acid etching solution containing ammonia nitrogen
| Example 1 | The etching depth is moderate, the etching speed is rapid and controllable, and the preset requirements are met. |
| Example 2 | The etching depth is micro-deep, the etching speed is rapid and controllable, and the preset requirements are met. |
| Example 3 | The etching depth is moderate, the etching speed is rapid and controllable, and the preset requirements are met. |
| Example 4 | The etching depth is shallow, the etching speed is rapid and controllable, and the preset requirements are met. |
| Comparative example 1 | The etching depth is small, the etching speed is slow, the etching time is long, and the requirements are basically met. |
| Comparative example 2 | The etching depth is too deep, the etching speed is slow, the etching time is long, and the requirements are not met. |
| Comparative example 3 | The etching depth is too shallow, the etching speed is slow, the etching time is long, and the requirements are not met. |
As can be seen from Table 1, the use of the ammonia nitrogen-free acidic etching solution of examples 1-4 has moderate etching depth on the copper-clad plate, high and controllable etching speed, and the etched product meets the predetermined requirements; and the acid etching solution of ammonia nitrogen is used in the comparative examples 1-3, and the etching depth or the etching depth is too shallow, so that the etching requirement of the product is difficult to meet.
Moreover, compared with the etching solution containing ammonia nitrogen in comparative examples 1-3, the acid etching solution containing no ammonia nitrogen in examples 1-4 does not need ammonia nitrogen post-treatment of water washing for the product wastewater after etching; in the subsequent copper-containing waste liquid recovery process, ammonia distillation and other links aiming at ammonia nitrogen treatment are not needed, the method is economical and environment-friendly, and the production cost and the waste liquid treatment cost are effectively reduced.
Example 5
The acid etching solution without ammonia nitrogen of the embodiment 1-4 has the following specific using process:
when the production line uses the ammonia nitrogen-free acid etching solution, the addition of the oxidant and the acid etching additive is controlled by an automatic addition system. The automatic addition system controls two parameters, one being the oxidation-reduction potential and the other being the acid equivalent in the bath.
The oxidation-reduction potential is controlled between 500mv and 550mv, when the oxidation-reduction potential is lower than 500mv, the probe of the automatic adding system transmits a signal back to the host of the automatic adding system, the host starts the power supply of the dosing pump, the dosing pump adds the oxidant into the production tank mother liquor, and the oxidant oxidizes the monovalent copper ions in the production tank mother liquor into divalent copper ions, thereby improving the oxidation-reduction potential.
When the oxidation-reduction potential reaches 550mv, the probe of the automatic adding system transmits a signal back to the main machine of the automatic adding system, the main machine cuts off the power supply of the dosing pump, and the dosing pump stops dosing.
Similarly, the acidity (pH) of the production tank is set to be between 2.0 and 2.5 acid equivalent, when the acid equivalent of the mother liquor of the production tank is less than 2.0, a probe for detecting the acidity transmits a signal back to the automatic addition system de host, and the host turns on the power supply of the addition pump to add the acid etching additive into the tank liquor. When the acidity rises to 2.5 equivalent, the probe also transmits a signal back to the host computer, the host computer cuts off the power supply of the addition pump, and the addition pump stops working. The above steps are repeated in a circulating way, and as long as the automatic adding system works normally, the parameters of each liquid in the production tank are always controlled within the set range.
Through statistics of the use conditions of a plurality of production lines, the optimal weight ratio of the oxidant to the acidic etching solution additive is 1: 2.5. that is, for every equivalent of the oxidizing agent, 2.5 equivalents of the acidic etchant additive are used.
In addition, when the concentration of urea in the oxidant is 1-1.3g/L, the etching factor is larger, which indicates that the lateral erosion degree is smaller; among the additives, in the case of both cost, the etching rate is optimum when the concentration of thiourea is 0.6 to 0.7 g/L.
The foregoing is merely exemplary and illustrative of the structures of the present invention, which are described in some detail and detail, and are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications are possible without departing from the inventive concept, and such obvious alternatives fall within the scope of the invention.
Claims (7)
1. The ammonia nitrogen-free acidic etching solution is characterized by comprising an oxidant and an additive, wherein the oxidant and the additive do not contain ammonia nitrogen; the weight ratio of the oxidant to the acidic etching solution additive is (0.8-1.0): (2-2.5);
the oxidant comprises the following components in percentage by weight:
12 to 20 percent of sodium chlorate, 12 to 18 percent of sodium chloride, 0.5 to 1.5 percent of urea and 60.5 to 75.5 percent of water;
the acid etching solution additive comprises the following components in percentage by weight:
16 to 25 percent of hydrogen chloride, 2 to 5 percent of sodium chloride, 0.5 to 1.5 percent of thiourea and 68.5 to 81.5 percent of water.
2. The ammonia nitrogen-free acidic etching solution of claim 1, wherein the weight ratio of the oxidant to the acidic etching solution additive is 1: 2.5;
the oxidant comprises the following components in percentage by weight:
12% of sodium chlorate, 12% of sodium chloride, 0.5% of urea and 75.5% of water;
the acid etching solution additive comprises the following components in percentage by weight:
16% of hydrogen chloride, 2% of sodium chloride, 0.5% of thiourea and 81.5% of water.
3. The ammonia nitrogen-free acidic etching solution of claim 1, wherein the weight ratio of the oxidant to the acidic etching solution additive is 0.8: 2;
the oxidant comprises the following components in percentage by weight:
20% of sodium chlorate, 18% of sodium chloride, 1.5% of urea and 60.5% of water;
the acid etching solution additive comprises the following components in percentage by weight:
25% of hydrogen chloride, 5% of sodium chloride, 1.5% of thiourea and 68.5% of water.
4. The ammonia nitrogen-free acidic etching solution of claim 1, wherein the weight ratio of the oxidant to the acidic etching solution additive is 0.9: 2.2;
the oxidant comprises the following components in percentage by weight:
15% of sodium chlorate, 15% of sodium chloride, 0.5% of urea and 69.5% of water;
the acid etching solution additive comprises the following components in percentage by weight:
20% of hydrogen chloride, 4% of sodium chloride, 0.5% of thiourea and 75.5% of water.
5. The acid etching solution without ammonia nitrogen of any claim 1 to 4, wherein the concentration of urea in the oxidant is 1 to 1.3 g/L.
6. The acid etching solution without ammonia nitrogen of any claim 1 to 4, wherein the concentration of thiourea in the acid etching solution additive is 0.6 to 0.7 g/L.
7. The ammonia nitrogen-free acidic etching solution as claimed in any one of claims 1 to 4, wherein the pH of the acidic etching solution is in the range of 2.0 to 2.5, and the oxidation-reduction potential is controlled between 500-550 mv.
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| CN107604361A (en) * | 2017-11-09 | 2018-01-19 | 佛山市华希盛化工有限公司 | A kind of acidic etching liquid and preparation method thereof |
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| CN107604361A (en) * | 2017-11-09 | 2018-01-19 | 佛山市华希盛化工有限公司 | A kind of acidic etching liquid and preparation method thereof |
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| 顾江 主编, 西安电子科技大学出版社 * |
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