CN114045494A - Low-acidity etching production method for PCB and two-liquid type acidic etching liquid system - Google Patents
Low-acidity etching production method for PCB and two-liquid type acidic etching liquid system Download PDFInfo
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- CN114045494A CN114045494A CN202111241051.XA CN202111241051A CN114045494A CN 114045494 A CN114045494 A CN 114045494A CN 202111241051 A CN202111241051 A CN 202111241051A CN 114045494 A CN114045494 A CN 114045494A
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- 238000005530 etching Methods 0.000 title claims abstract description 225
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 79
- 239000000654 additive Substances 0.000 claims abstract description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- QYTOONVFPBUIJG-UHFFFAOYSA-N azane;cyanic acid Chemical compound [NH4+].[O-]C#N QYTOONVFPBUIJG-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 10
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011780 sodium chloride Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000028571 Occupational disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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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)
Abstract
The invention belongs to the technical field of acid etching, and particularly relates to a low-acidity etching production method for a PCB (printed Circuit Board) and a two-liquid type acid etching liquid system, wherein an acid reducing auxiliary agent of the acid etching liquid adopted in the etching production comprises one or two of cyanate and oxalic dihydrazide; the cyanate comprises sodium cyanate, potassium cyanate or ammonium cyanate. The cyanate and the dihydrazide ethanedioic acid are used as the deacidification auxiliary agent of the etching solution and the additive formed by the deacidification auxiliary agent, and are applied to the acidic etching solution of the PCB, so that the etching rate can be accelerated, and the etching factor can be improved; and after the acid etching solution produced by the PCB is mixed with the etching solution additive, the concentration of the adopted oxidant is reduced, and the acid equivalent of the whole system is reduced. The used etching solution additive can replace 31% of industrial concentrated hydrochloric acid which is adopted traditionally, the etching rate reaches 40-50 mu m/min, the etching factor reaches 4.0-5.0, and the etching solution is greatly superior to the traditional two-solution type acidic etching solution.
Description
Technical Field
The invention belongs to the technical field of acid etching, and particularly relates to a low-acidity etching production method for a PCB and a two-liquid type acid etching liquid system.
Background
With the updating iteration and increasingly powerful functions of electronic products, the requirements for various accessories of the combined electronic products are also high, and especially the requirements for the precision and the conductivity of the PCB called as the 'electronic product' are continuously improved. Therefore, PCB manufacturers are also continuously improving their comprehensive process capability, and currently, more than 50% of the world's PCB manufacturing capacity is in china, and the chinese PCB manufacturers are faced with not only the improvement of technology and manufacturing capability but also the increase of labor cost and the increasing of environmental protection pressure.
The core benefits of a PCB enterprise are the speed (etch rate) at which the circuit board is manufactured, and the maximum degree of precision (etch factor) at which the circuit board can be manufactured, which determine the competitive power of the enterprise and the upper limit on the economic gain.
In addition, the problem of environmental pollution in the manufacturing process is also one of the core concerns of PCB manufacturing enterprises. For example, in acid etching production, the etching rate is faster when the acid equivalent is higher, and when the acid equivalent in the acid etching production tank exceeds 2.5, the following negative effects are brought about: firstly, when the acidity in the acid etching production tank exceeds 2.5 equivalent, the ink or dry film is easily attacked, so that the circuit is notched or dogtooth-shaped, and the conductivity is influenced; secondly, when the acidity exceeds 2.5 equivalents, the following side reactions are liable to occur in the production tank: 6H++5Cl-+ClO3 -→2Cl2↑+3H2O, chlorine generated by the reaction is a highly toxic gas, which can cause serious safety accidents; thirdly, when the acid equivalent of the acid etching production tank exceeds 2.5, a large amount of hydrogen chloride in the production tank liquid is volatilized into the air because the production tank liquid is kept above 50 ℃ for a long time. Wherein, the vast majority is absorbed by the tail gas absorption system to cause the increase of the flake caustic soda consumption of the tail gas absorption system and simultaneously improve the requirement on the absorption capacity of the tail gas absorption system in unit time, and the operation cost and the equipment investment are increased. A small part of hydrogen chloride overflows into the air of a workshop to influence the body health of production staff, and seriously causes occupational diseases of respiratory tracts; fourth, acid etchingWhen the acid equivalent of the production tank is more than 2.5, the acidity of the washing water is increased, and more caustic soda flakes are required to be added to a wastewater station for neutralization, so that the wastewater treatment cost is increased.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a low acidity etching method for PCB and a two-liquid type acidic etching solution system, and further provide an etching solution deacidification assistant added into an acidic etching solution, which can increase an etching rate, increase an etching factor and reduce an acid equivalent of the etching system in etching production.
The technical content of the invention is as follows:
the invention provides an etching solution deacidification auxiliary agent for improving the production quality of acid etching, which comprises one or two of cyanate and oxalic dihydrazide;
the cyanate comprises sodium cyanate, potassium cyanate or ammonium cyanate;
in the acid etching production, the concentration of cyanate is 400-1000 mg/L, and the concentration of oxalic acid dihydrazide is 70-100 mg/L;
when cyanate and oxalic dihydrazide are mixed for use, the volume ratio of cyanate to oxalic dihydrazide is (1-4): (1-4).
The invention also provides an etching solution additive for improving the production quality of acid etching, and the etching solution additive comprises the deacidification auxiliary agent, ammonium chloride and sodium chloride;
the acid equivalent of the etching solution additive is 4.0-7.0;
in the acid etching production, the working concentration of ammonium chloride is 3000-30000mg/L, and the working concentration of sodium chloride is 5000-50000 mg/L.
The invention also provides a low-acidity two-liquid type acidic etching liquid system applying the etching liquid additive to PCB production.
The invention also provides a low-acidity two-liquid type acidic etching solution system applied to the low-tail gas production of the PCB, and the acidic etching solution comprises an oxidant and the etching solution additive;
the acid etching solution is applied to PCB production, the acid equivalent of the formed working tank solution is 0.4-1.5, the concentration of an oxidant is 180-400 g/L, and the concentration of chloride ions in the tank solution is 240-270 g/L;
the oxidant comprises one of sodium chlorate and sodium hypochlorite.
The invention also provides a low-acidity etching production method for the PCB, which comprises the following steps of carrying out etching production on the PCB by adopting the acid etching solution system, wherein the acid equivalent of the working tank solution in the production is 0.4-1.5, the etching rate is increased to 40-50 mu m/min, and the etching factor is 4.0-5.0.
The invention has the following beneficial effects:
in the low-acidity production etching method, cyanate and oxalic dihydrazide are used as deacidification auxiliary agents to form etching solution additives with sodium chloride, sodium chloride and the like, and the etching solution additives are applied to the PCB acidic etching solution, so that the etching rate can be accelerated, and the etching factor can be improved; and the concentration of the adopted oxidant in the acidic etching solution for producing the low tail gas of the PCB is 180-400 g/L. Compared with the traditional acid etching, the acidity of the production tank liquid of the acid etching is lower, the used etching liquid additive can replace the traditionally adopted 31 percent industrial concentrated hydrochloric acid, the highly dangerous and volatile 31 percent industrial concentrated hydrochloric acid is not used any more, the pollution is reduced, the environment is improved, and the development direction of the acid etching is generally met; in addition, in the production of acid etching, the etching rate reaches 40-50 mu m/min, and the etching factor reaches 4.0-5.0, which is greatly superior to that of the traditional acid etching solution (the etching rate is 25-35 mu m/min, and the etching factor is 3.0-4.0);
the cyanate and the oxalic dihydrazide are applied to the acid etching solution for producing the PCB to form a low-acidity system, so that the etching rate and the etching factor are improved, the acid equivalent is reduced, the generation of chlorine is reduced, the production requirement of PCB manufacturing enterprises is met, the PCB manufacturing environment is greatly improved, the market development is adapted, the environment-friendly route is reached, and the application and the expansion of the etching technology can be greatly contributed.
Detailed Description
The present invention is described in further detail in the following detailed description with reference to specific embodiments, which are intended to be illustrative only and not to be limiting of the scope of the invention, as various equivalent modifications of the invention will become apparent to those skilled in the art after reading the present invention and are intended to be included within the scope of the appended claims.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
In the existing acid etching production of PCB, hydrochloric acid is needed to be added to etch simple substance copper, so that a large amount of chloride ions exist in the acid etching bath solution:
in the etching production, bivalent copper ions in the bath solution oxidize elemental copper to generate monovalent copper: cu2++Cu→2Cu+The reaction directly occurs on the PCB, and redundant simple substance copper is etched from the PCB;
then the etching solution in the bath solution oxidizes the monovalent copper ions into divalent copper ions: 6H++6Cu++ClO3 -→6Cu2++Cl-+3H2O, the reaction occurs in the bath solution, and can be regarded as a regeneration process of divalent copper ions;
therefore, the chlorine ions in the bath solution mainly play a role in stabilizing free bivalent copper ions as a main complexing agent of the bivalent copper ions; therefore, the chloride ion concentration affects the rate of acidic etching. In order to determine the optimum chloride ion concentration, the other production conditions were fixed, the etching temperature was 50 ℃, the upper pressure was 2.2KG, the lower pressure was 2.0KG, the redox potential was 550mV, the acid equivalent was 1.2, and the specific gravity was 1.290, and the chloride ion concentration in the bath solution was varied independently.
The average etch rate and etch factor were tested as follows:
TABLE 1 etching Effect test
As can be seen from Table 1, the average etching rate was high at a low concentration of chloride ion but the etching factor was not satisfactory at all for production, and both the average etching rate and the average etching factor were decreased at a concentration of chloride ion exceeding 300g/L, which is caused by a large increase in the etching beach level due to a sharp decrease in the etching rate.
Therefore, the optimum concentration range of the chloride ions in the acid etching production tank can be determined to be 250-300 g/L.
In addition, the acidity of the etching environment is also critical, and within a certain range, the higher the acid equivalent, the faster the etching rate; but a series of negative effects occur, and decreasing acidity affects the etching rate. Therefore, by adding the acid reducing additive of the embodiment of the invention, the following reaction can be promoted to proceed:
Cu2++Cu→2Cu+；
6Cu++ClO3 -→6Cu2++Cl-+3H2O；
4H++O2+4Cu+→6Cu2+3H2O；
can simultaneously realize the improvement of the etching rate and the etching factor and reduce the acid equivalent of the system.
When other reaction conditions were fixed, the etching temperature was 50 ℃, the upper pressure was 2.2KG, the lower pressure was 2.0KG, the redox potential was 550mV, the acid equivalent was 1.2, and the specific gravity was 1.290, and the concentration of cyanate in the acidic etching bath was changed, the results of the obtained etching rate and etching factor were as shown in tables 2, 3, and 4.
Example 1
An etching production method applied to PCB board low tail gas and low acidity, the etching production adopts acidic etching solution system comprising oxidant and etching solution additive;
the oxidant comprises one of sodium chlorate and sodium hypochlorite;
the etching solution additive comprises cyanate, ammonium chloride and sodium chloride, the acid equivalent is 5.0-5.5, the additive is used, the acid equivalent is 0.8-1.2 through detection, the concentration of an oxidant is 320-370 g/L, and the concentration of chloride ions in the tank liquid is 240-250 g/L, so that the acid etching solution is lower in acidity, efficient and safe compared with the traditional acid etching solution using 31% industrial concentrated hydrochloric acid;
the working concentration of the ammonium chloride is 15000-20000 mg/L, and the working concentration of the sodium chloride is 35000-40000 mg/L;
the cyanate comprises sodium cyanate, potassium cyanate or ammonium cyanate, the use effects of the cyanate at different concentrations are respectively shown in the following table, the acid etching environment is 50 ℃, the upper pressure is 2.2kg, the lower pressure is 2.0kg, the oxidation reduction potential is 550mv, the etching time is 1h under the condition that the acid equivalent is 1.2N, the etching effect data is recorded every 10min, and the obtained etching rate range and the value of the average etching factor are shown in the following table.
TABLE 2 etching Effect test
| Concentration of sodium cyanate (mg/L) | 100 | 200 | 300 | 400 | 500 |
| Etching Rate (. mu.m/min) | 28～32 | 30～34 | 33～37 | 38～42 | 40～43 |
| Etching factor | 3.1 | 3.2 | 3.8 | 4.2 | 4.3 |
| Concentration of sodium cyanate (mg/L) | 600 | 700 | 800 | 900 | 1000 |
| Etching Rate (. mu.m/min) | 44～48 | 42～46 | 41～45 | 38～41 | 33～38 |
| Etching factor | 4.4 | 4.7 | 4.6 | 4.5 | 4.0 |
As shown in Table 2, the addition of sodium cyanate accelerates the etching rate and increases the etching factor; the optimal range of the concentration is 400-800 mg/L.
TABLE 3 etching Effect test
As can be seen from Table 3, the addition of potassium cyanate accelerates the etching rate and increases the etching factor; the optimal range of the concentration is 600-1000 mg/L.
TABLE 4 etching Effect test
| Concentration of ammonium cyanate (mg/L) | 100 | 200 | 300 | 400 | 500 |
| Etching Rate (. mu.m/min) | 30～33 | 32～36 | 35～39 | 36～40 | 38～43 |
| Etching factor | 3.2 | 3.3 | 3.3 | 3.7 | 4.1 |
| Concentration of ammonium cyanate (mg/L) | 600 | 700 | 800 | 900 | 1000 |
| Etching Rate (. mu.m/min) | 42～46 | 44～49 | 43～46 | 43～47 | 42～45 |
| Etching factor | 4.3 | 4.3 | 4.5 | 4.7 | 4.6 |
As can be seen from Table 4, the addition of ammonium cyanate accelerates the etching rate and increases the etching factor; the optimal range of the concentration is 500-900 mg/L.
Example 2
An etching production method applied to PCB board low tail gas and low acidity, the etching production adopts acidic etching solution system comprising oxidant and etching solution additive;
the oxidant comprises one of sodium chlorate and sodium hypochlorite;
the etching solution additive comprises oxalic dihydrazide, ammonium chloride and sodium chloride, the acid equivalent is 4.0-5.0, the use of the additive enables the detected acid equivalent in the formed acidic etching working tank solution to be 0.4-0.8, the concentration of sodium chlorate serving as an oxidant is 300-400 g/L, and the concentration of chloride ions is 260-270 g/L;
the working concentration of the ammonium chloride is 20000-30000 mg/L, and the working concentration of the sodium chloride is 5000-10000 mg/L.
The concentration of the oxalic acid dihydrazide in the solution was varied under the conditions of an acid etching environment of 50 ℃, an upper pressure of 2.2kg, a lower pressure of 2.0kg, a redox potential of 550mv and an acid equivalent of 1.2N, and the results are shown in the following table.
TABLE 5 etch Effect test
| Concentration of oxalic acid dihydrazide (mg/L) | 0 | 10 | 20 | 30 | 40 | 50 |
| Etching Rate (. mu.m/min) | 30～46 | 31～45 | 33～45 | 35～46 | 35～44 | 36～47 |
| Etching factor | 3.4 | 3.6 | 3.7 | 3.7 | 3.6 | 4.1 |
| Concentration of oxalic acid dihydrazide (mg/L) | 60 | 70 | 80 | 90 | 100 | 110 |
| Etching Rate (. mu.m/min) | 35～46 | 37～48 | 38～47 | 39～49 | 38～47 | 36～45 |
| Etching factor | 4.3 | 4.3 | 4.4 | 4.8 | 4.5 | 3.9 |
As shown in Table 5, the addition of the oxalic dihydrazide can increase the etching rate and improve the etching factor, and when the concentration of the oxalic dihydrazide in the solution is between 70 and 100mg/L, the stability of the etching rate is high, and the etching factor is more ideal.
Example 3
An etching production method applied to PCB board low tail gas and low acidity, the etching production adopts acidic etching solution system comprising oxidant and etching solution additive;
the etching solution additive comprises a deacidification auxiliary agent, ammonium chloride and sodium chloride, wherein the deacidification auxiliary agent is formed by mixing 700mg/L sodium cyanate and 90mg/L oxalic acid dihydrazide, the acid equivalent is 5.0-6.0, the acid equivalent is 1.0-1.2 through detection in acid etching working tank liquid formed after mixing, the concentration of an oxidant is 200-300 g/L, and the concentration of chloride ions in the tank liquid is 250-260 g/L;
the working concentration of the ammonium chloride is 10000-15000mg/L, and the working concentration of the sodium chloride is 25000-30000 mg/L;
the volume ratio of cyanate to oxalic dihydrazide in the solution was changed under the conditions of an acid etching environment of 50 ℃, an upper pressure of 2.2kg, a lower pressure of 2.0kg, a redox potential of 550mv, and an acid equivalent of 1.2N.
TABLE 6 test of etching effect
| Volume ratio of mixture | 1:1 | 1:2 | 1:3 | 1:4 | 1:5 | 1:6 |
| Etching Rate (. mu.m/min) | 44～47 | 43～46 | 44～47 | 45～48 | 40～43 | 40～42 |
| Etching factor | 4.6 | 4.7 | 4.5 | 4.6 | 3.8 | 3.9 |
| Volume ratio of mixture | 7:1 | 6:1 | 5:1 | 4:1 | 3:1 | 2:1 |
| Etching Rate (. mu.m/min) | 39～42 | 39～41 | 40～42 | 40～42 | 44～47 | 45～48 |
| Etching factor | 4.0 | 3.9 | 4.1 | 4.0 | 4.5 | 4.6 |
As can be seen from table 6, when the mixing volume ratio of sodium cyanate to oxalic dihydrazide is 1: (1-3) and (2-4): 1, the etching rate and the etching factor are higher, which shows that the volume ratio of the sodium cyanate to the oxalic dihydrazide is (1-4): (1-3).
Example 4
An etching production method applied to PCB board low tail gas and low acidity, the etching production adopts acidic etching solution system comprising oxidant and etching solution additive;
the acidic etching solution comprises an oxidant and an etching solution additive;
the etching solution additive comprises a deacidification auxiliary agent, ammonium chloride and sodium chloride, wherein the deacidification auxiliary agent is formed by mixing 1000mg/L potassium cyanate and 70mg/L oxalic acid dihydrazide, the acid equivalent is 5.5-6.0, the acid equivalent is 1.3-1.5 in acid etching working tank liquid formed after mixing, the concentration of an oxidant is 180-230 g/L, and the concentration of chloride ions in the tank liquid is 250-260 g/L through detection;
the working concentration of the ammonium chloride is 5000-10000mg/L, and the working concentration of the sodium chloride is 45000-50000 mg/L.
The etching environment conditions were the same as above.
TABLE 7 test of etching effect
| Volume ratio of mixture | 1:1 | 1:2 | 1:3 | 1:4 | 1:5 | 1:6 |
| Etching Rate (. mu.m/min) | 43～46 | 44～48 | 45～50 | 43～48 | 39～42 | 39～40 |
| Etching factor | 4.6 | 4.5 | 4.5 | 4.7 | 4.3 | 4.3 |
| Volume ratio of mixture | 7:1 | 6:1 | 5:1 | 4:1 | 3:1 | 2:1 |
| Etching Rate (. mu.m/min) | 38～40 | 38～40 | 40～42 | 44～46 | 45～49 | 44～47 |
| Etching factor | 4.0 | 4.1 | 4.2 | 4.4 | 4.7 | 4.5 |
As can be seen from table 7, when the mixing volume ratio of potassium cyanate to oxalic dihydrazide is 1: (1-4) and (1-4): 1, the etching rate and the etching factor are both high, and the etching rate and the etching factor are both high, which shows that the mixing volume ratio of the potassium cyanate and the oxalic dihydrazide is (1-4): (1-4).
Example 5
An etching production method applied to PCB board low tail gas and low acidity, the etching production adopts acidic etching solution system comprising oxidant and etching solution additive;
the etching solution additive comprises an acid reducing additive, ammonium chloride and sodium chloride, wherein the acid reducing additive is formed by mixing 900mg/L of ammonium cyanate and 80mg/L of oxalic acid dihydrazide, the acid equivalent is 6.5-7.0, the acid equivalent is 1.1-1.4 through detection in acid etching working tank liquid formed after mixing, the concentration of an oxidant is 230-250 g/L, and the concentration of chloride ions in the tank liquid is 260-270 g/L;
the working concentration of the ammonium chloride is 3000-8000mg/L, and the working concentration of the sodium chloride is 5000-10000 mg/L.
The etching environment conditions were the same as above.
TABLE 8 test of etching effect
| Volume ratio of mixture | 1:1 | 1:2 | 1:3 | 1:4 | 1:5 | 1:6 |
| Etching Rate (. mu.m/min) | 44～47 | 43～47 | 43～46 | 43～46 | 40～42 | 40～41 |
| Etching factor | 4.7 | 4.5 | 4.6 | 4.5 | 4.1 | 4.0 |
| Volume ratio of mixture | 7:1 | 6:1 | 5:1 | 4:1 | 3:1 | 2:1 |
| Etching Rate (. mu.m/min) | 38～41 | 40～42 | 39～41 | 42～46 | 44～48 | 43～47 |
| Etching factor | 4.1 | 4.2 | 4.0 | 4.5 | 4.7 | 4.8 |
As can be seen from table 8, when the mixing volume ratio of ammonium cyanate to oxalic dihydrazide is 1: (1-4) and (1-4): 1, the etching rate and the etching factor are both high, and the etching rate and the etching factor are both high, which shows that the mixing volume ratio of the ammonium cyanate and the oxalic dihydrazide is (1-4): (1-4).
Therefore, in the etching production of low tail gas and low acidity of the PCB, when the cyanate is mixed with the oxalic dihydrazide to be used as the deacidification auxiliary agent of the etching solution, the etching rate can be increased, and the etching factor can be improved; after the acid reducing auxiliary agent is mixed with the acid etching solution produced by the PCB, compared with the traditional acid etching, the acidity of the production tank solution of the acid etching is lower, and the used etching solution additive can replace the traditional 31 percent industrial concentrated hydrochloric acid, so that the production environment is more excellent; in addition, in the production of acid etching, the etching rate reaches 40-50 μm/min, and the etching factor reaches 4.0-5.0, which is greatly superior to the traditional acid etching solution (the etching rate is 25-35 μm/min, and the etching factor is 3.0-4.0).
Claims (9)
1. An etching solution deacidification auxiliary agent for improving the production quality of acid etching is characterized in that the etching solution deacidification auxiliary agent comprises one or two of cyanate and oxalic dihydrazide;
the cyanate comprises sodium cyanate, potassium cyanate or ammonium cyanate.
2. The etching solution deacidification auxiliary agent according to claim 1, wherein in the acid etching production, the working concentration of cyanate is 400-1000 mg/L, and the working concentration of oxalic acid dihydrazide is 70-100 mg/L.
3. The etching solution deacidification auxiliary agent according to claim 1, wherein when cyanate and oxalic dihydrazide are mixed for use, the volume ratio of cyanate to oxalic dihydrazide is (1-4): (1-4).
4. An etching solution additive for improving the production quality of acid etching, which is characterized in that the etching solution additive comprises the acid reducing additive, ammonium chloride and sodium chloride according to any one of claims 1 to 3;
the acid equivalent of the etching solution additive is 4.0-7.0.
5. A low acidity two-liquid type acidic etching liquid system using the etching liquid additive of claim 4 in PCB production.
6. A low acidity two-liquid type acidic etching solution system for low tail gas production of PCB board, wherein the composition of the acidic etching solution comprises oxidant and the etching solution additive of claim 4.
7. The acidic etching solution system of claim 6, wherein the acidic etching solution is used in PCB production, and the acid equivalent of the working bath solution is 0.4-1.5, the concentration of the oxidant is 180-400 g/L, and the concentration of the chloride ion in the bath solution is 240-270 g/L.
8. The acidic etchant system of claim 6 wherein the oxidizing agent comprises one of sodium chlorate and sodium hypochlorite.
9. A low acidity etching production method for PCB is characterized in that the method comprises the following steps, the acid etching liquid system of any one of claims 6 to 8 is adopted to carry out etching production on the PCB, and the acid equivalent of the working bath liquid in the production is 0.4 to 1.5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130408A (en) * | 1993-09-08 | 1996-09-04 | 菲布罗技术公司 | Copper etchant solution additives |
| US6212769B1 (en) * | 1999-06-29 | 2001-04-10 | International Business Machines Corporation | Process for manufacturing a printed wiring board |
| JP2005068524A (en) * | 2003-08-27 | 2005-03-17 | C Uyemura & Co Ltd | Etching solution |
| CN101379219A (en) * | 2005-10-25 | 2009-03-04 | 德国艾托科技公司 | Composition and method for improved adhesion of polymeric materials to copper or copper alloy surfaces |
| US20180090500A1 (en) * | 2013-12-31 | 2018-03-29 | Taiwan Semiconductor Manufacturing Company Limited | Semiconductor arrangement with capacitor and method of fabricating the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130408A (en) * | 1993-09-08 | 1996-09-04 | 菲布罗技术公司 | Copper etchant solution additives |
| US6212769B1 (en) * | 1999-06-29 | 2001-04-10 | International Business Machines Corporation | Process for manufacturing a printed wiring board |
| JP2005068524A (en) * | 2003-08-27 | 2005-03-17 | C Uyemura & Co Ltd | Etching solution |
| CN101379219A (en) * | 2005-10-25 | 2009-03-04 | 德国艾托科技公司 | Composition and method for improved adhesion of polymeric materials to copper or copper alloy surfaces |
| US20180090500A1 (en) * | 2013-12-31 | 2018-03-29 | Taiwan Semiconductor Manufacturing Company Limited | Semiconductor arrangement with capacitor and method of fabricating the same |
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