CN100540745C - alkaline etching liquid and production method thereof - Google Patents
alkaline etching liquid and production method thereof Download PDFInfo
- Publication number
- CN100540745C CN100540745C CNB2007100762965A CN200710076296A CN100540745C CN 100540745 C CN100540745 C CN 100540745C CN B2007100762965 A CNB2007100762965 A CN B2007100762965A CN 200710076296 A CN200710076296 A CN 200710076296A CN 100540745 C CN100540745 C CN 100540745C
- Authority
- CN
- China
- Prior art keywords
- liquid
- etching
- sub
- alkali etching
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005530 etching Methods 0.000 title claims abstract description 53
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 230000002950 deficient Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000007858 starting material Substances 0.000 claims abstract description 4
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052802 copper Inorganic materials 0.000 abstract description 20
- 239000012452 mother liquor Substances 0.000 abstract description 13
- 230000003628 erosive effect Effects 0.000 abstract description 10
- 239000011734 sodium Substances 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 238000001311 chemical methods and process Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
Abstract
The present invention relates to utilize chemical process to make PCB go up the etching solution that forms circuit, the method that relates in particular to the sub-liquid of alkali etching, alkali etching mother liquor and produce the sub-liquid of alkali etching.The sub-liquid of alkali etching comprises 10%～12% liquefied ammonia, 1.25%～1.27% food carbon, 0.3% additive, 24%～25% agricultural ammonium and 62%～64% water, and the composition of described additive comprises that sulfo-flows sour sodium, phosphoric acid composite salt and KuALIMATE S * S 40.The alkali etching mother liquor is except that the composition that comprises the sub-liquid of above-mentioned alkali etching, and other adds the copper of 130+10g/L.The method of the above-mentioned alkaline etching liquid of described production comprises: (1) adds an amount of water in producing groove; (2) proportionally add starting material liquefied ammonia, food carbon and agricultural ammonium and additive; (3) treat to test after raw material dissolves fully; (4) the qualified warehouse-in of a.; Or the defective adjustment warehousing after passing of b..Alkaline etching liquid provided by the invention is fit to automatic addition manner to be used, and easy to use, stability is good, does not precipitate to be easy to management erosion copper constant rate, washing property excellence.
Description
Technical field
The present invention relates to utilize chemical process to make PCB go up the etching solution that forms circuit, the method that relates in particular to the sub-liquid of alkali etching, alkali etching mother liquor and produce the sub-liquid of alkali etching.
Background technology
Etching is an operation necessary in PCB (the printed circuit board) production process, etching work procedure normally cooperates etching solution to finish by etching machine, etching solution comprises etching mother liquor and the sub-liquid of etching, and the sub-liquid of etching mother liquor and etching is to be combined by multipleization and thing.
Introduce a kind of principle of work of engraving method commonly used below: the etching mother liquor is in operating process, in etching machine, directly be sprayed on the PCB, unwanted unnecessary copper is stung eating away, because of copper etched, make that the proportion of mother liquor is more and more heavy, rise and drive specific gravity control device ball float, when reaching a certain degree, proportion starts added automatically system, sub-liquid adds among the mother liquor, unnecessary mother liquor is discharged, because the interpolation of sub-liquid, proportion reduces gradually, and when ball float was reduced to a certain degree, added automatically system promptly stopped automatically.Above-mentioned circulation will be in etching process repeats again and again, and cupric not in the sub-liquid, and mother liquor then from beginning to join after groove builds bath, can forever not use and need change groove.
Etching work procedure is very crucial in the production process of PCB, etching work procedure is well-done and poor, can directly influence the quality and the performance of whole printed circuit board (PCB), so, in order to promote quality product, meeting the market requirement, product innovation is being continually developed in PCB manufacturer and supply commercial city thereof.
Summary of the invention
The object of the present invention is to provide the sub-liquid of a kind of novel alkaline etching, can cooperate automatic interpolation, easy to use, this purpose is realized by following technical scheme:
The sub-liquid of a kind of alkali etching, comprise 10%～12% liquefied ammonia, 1.25%～1.27% food carbon, 0.3% additive, 24%～25% agricultural ammonium and 62%～64% water, the composition of described additive comprises that sulfo-flows sour sodium, phosphoric acid composite salt and KuALIMATE S * S 40.
Another purpose of the present invention is to provide a kind of method of producing the sub-liquid of above-mentioned alkali etching, and this another purpose is realized by following technical scheme:
A kind of method of producing above-mentioned alkaline etching liquid may further comprise the steps:
(1) in producing groove, adds an amount of water;
(2) proportionally add starting material liquefied ammonia, food carbon and agricultural ammonium and additive;
(3) treat to test after raw material dissolves fully;
(4) the qualified warehouse-in of a.; Or the defective adjustment warehousing after passing of b..
Alkaline etching liquid provided by the invention is fit to automatic addition manner to be used, and easy to use, stability is good, does not precipitate to be easy to management erosion copper constant rate, washing property excellence.
Embodiment
One, the composition of the sub-liquid of alkali etching:
The sub-liquid of the alkali etching that present embodiment provides comprises: 10%～12% liquefied ammonia, 1.25%～1.27% food carbon, 0.3% additive, 24%～25% agricultural ammonium and 62%～64% water, the composition of described additive comprises Sulfothiorine, phosphoric acid composite salt and KuALIMATE SXS 40 (ヒ sodium xylene sulfonate).
Two, the composition of alkali etching mother liquor:
The alkali etching mother liquor is except that the composition that comprises the sub-liquid of alkali etching, and other adds the copper of 130 ± 10g/L.
Three, the sub-liquid specification of alkali etching:
Proportion (25 ℃): 1.025 ± 0.05
Chloride ion content: 160 ± 10g/L
Alkali equivalent: 6.0 ± 0.5N
Four, the operating restraint of alkali etching mother liquor:
PH value (25 ℃): 8.0～8.6
Proportion (49 ℃): 1.17～1.19 (best 1.18)
Copper content: 130 ± 10g/L
Five, etching primitive reaction formula:
Cu(NH
3)
4Cl
2+?Cu→?2Cu(NH
3)
2Cl
(etching solution) (metallic copper) (monovalence copper)
2Cu(NH
3)
2Cl+2NH
4Cl+2NH
4OH+1/2?O
2→2Cu(NH
3)
4Cl
2+3H
2O
(monovalence copper) (etching solution)
In brief:
Cu
++ + Cu
0 → 2Cu
+
(etching solution) (metallic copper) (monovalence copper)
2Cu
+ + 1/2?O
2 →2Cu
++ + O
--
(monovalence copper) (etching solution)
The existence of univalent copper ion will make erosion copper speed reduce.
Six, the control of etching solution pH value and influence:
NH
4OH←——Cu(NH
3)
4Cl
2——→NH
4Cl
| |
PH＞9.2 pH values control PH＜7.8
Cu(OH)
2 Cu(OH)xClx
Light blue, the precipitation of mud shape.Mazarine, the precipitation of sand shape.
Seven, erosion copper amount:
Because of adding automatically, so erosion copper amount is far below theoretical value.On the practical experience, different according to control custom and equipment are about 120～140g/L.
Eight, the relation of erosion copper speed and pH value:
When about PH=7.0, erosion copper speed begins to descend.Correct pH value will be different because of the content of ammonium chloride.Because of higher ammonium chloride content will be because of the effect of common-ion effect, and make that under identical ammoniacal liquor content pH value will present situation on the low side.
The invention provides alkaline etching liquid under normal operating condition, erosion copper speed is at 35～45 μ m/min.Nine, sedimentary generation:
Sedimentary generation is often started because of in too high or too low pH value.When pH value is less than about 7.8, promptly produce the precipitation of sand shape mazarine.When pH value is approximately higher than 9.2, promptly produce the precipitation of light blue mud shape.
Generally speaking, to maintain more than 8.8 always and can not fall be unlikely thing to pH value.Unless copper too high levels, or chlorion deficiency make that the ratio of Cu/Cl is higher and can form the precipitation (Cu (OH) of above-mentioned light blue mud shape
2).Can add excessive a little ammonium chloride and make pH value be reduced to 8.0～8.6 operating restraint this moment.
Ten, lateral erosion:
Alkaline etching liquid of the present invention is under normal operating condition, and the lateral erosion factor can reach more than 3 easily.
11, the analytical procedure of alkaline etching liquid of the present invention:
(1) Cu
++Mensuration:
Required reagent: 0.1M EDTA (2 Na)
The damping fluid of PH=10
M.X. indicator
Analytical procedure:
1. correctly drawing the 1ml sample adds in the 250ml beaker.
2. the D.I. water that adds about 100ml.
3. the damping fluid that adds about 15ml pH=10.
4. add the about 0.2g of M.X. indicator.
5. with 0.1 M EDTA titration, change green till the purple gradually by mazarine to terminal.
Calculate: consumption ml number * 6.35=Cu++ (g/l) of EDTA
(2) Cl
-Mensuration:
Required reagent: 0.1N AgNO3 solution
10% acetum
10% potassium bichromate indicator
Analytical procedure:
1. correctly drawing the 1ml sample adds in the 250ml beaker.
2. 10% acetic acid that adds about 20ml.
3. add about 3～6 indicator.
With the 0.1N silver nitrate titration it, to there being tawny to be settled out current its terminal point that is.
Calculate: the consumption ml number * 0.1=Cl of Silver Nitrate
-Concentration (mol/l)
(3) OH
-Mensuration:
Required reagent: 0.5N HCl solution
The M.O indicator
Analytical procedure:
1. correctly get the 2ml sample and place Erlenmeyer flask, add the about 100ml of water.
2. adding M.O indicator 3-5 drips.
3. with the 0.5NHCl titration, terminal point is extremely red by dried tangerine peel.
Calculate:
Alkali valency (N)=0.5N HCl consumes ml number * 0.25
12, produce the method for the sub-liquid of alkali etching, may further comprise the steps:
(1) in producing groove, adds an amount of water;
(2) proportionally add starting material liquefied ammonia, food carbon and agricultural ammonium and additive;
(3) treat to test after raw material dissolves fully;
(4) the qualified warehouse-in of a.; Or the defective adjustment warehousing after passing of b..
Claims (2)
1. sub-liquid of alkali etching, comprise 10%～12% liquefied ammonia, 1.25%～1.27% food carbon, 0.3% additive, 24%～25% agricultural ammonium and 62%～64% water, the composition of described additive comprises Sulfothiorine, phosphoric acid composite salt and KuALIMATE SXS 40.
2. a method of producing the sub-liquid of the described alkali etching of claim 1 comprises the steps:
(1) in producing groove, adds an amount of water;
(2) proportionally add starting material liquefied ammonia, food carbon and agricultural ammonium and additive;
(3) treat to test after raw material dissolves fully;
(4) the qualified warehouse-in of a.; Or the defective adjustment warehousing after passing of b..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100762965A CN100540745C (en) | 2007-07-04 | 2007-07-04 | alkaline etching liquid and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100762965A CN100540745C (en) | 2007-07-04 | 2007-07-04 | alkaline etching liquid and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101078121A CN101078121A (en) | 2007-11-28 |
| CN100540745C true CN100540745C (en) | 2009-09-16 |
Family
ID=38905775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100762965A Expired - Fee Related CN100540745C (en) | 2007-07-04 | 2007-07-04 | alkaline etching liquid and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100540745C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819026A (en) * | 2014-03-10 | 2014-05-28 | 惠州Tcl环境科技有限公司 | Resource utilization method of high-concentration ammonia nitrogen waste liquid |
| CN107740105A (en) * | 2017-11-09 | 2018-02-27 | 佛山市华希盛化工有限公司 | A kind of alkaline etching liquid and preparation method thereof |
| CN113088974B (en) * | 2021-04-08 | 2022-05-10 | 广东连发助剂厂有限公司 | Alkaline copper etching solution and production process thereof |
-
2007
- 2007-07-04 CN CNB2007100762965A patent/CN100540745C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 碱性蚀刻盐的研制. 叶瑾亮，李伟浩.广东化工，第4期. 2002 |
| 碱性蚀刻盐的研制. 叶瑾亮，李伟浩.广东化工，第4期. 2002 * |
| 铜表面化学蚀刻的研究. 朱绒霞.应用化工，第34卷第5期. 2005 |
| 铜表面化学蚀刻的研究. 朱绒霞.应用化工，第34卷第5期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101078121A (en) | 2007-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634801B (en) | Low-acidity acidic etching regenerant and acidic etching mother liquor thereof | |
| CN101517131B (en) | Method of preparing electrolytic copper solution acidified with sulfuric acid, sulfuric-acid-acidified electrolytic copper solution prepared by the preparation method, and electrodeposited copper film | |
| CN100540745C (en) | alkaline etching liquid and production method thereof | |
| CN104073804A (en) | PCB (Polychlorinated Biphenyl) acidic etching solution | |
| CN104109848A (en) | Environmentally-friendly chemical gilding liquid | |
| CN102787316A (en) | Micro-etching solution for PCB (printed circuit board) electroplating and preparation method of micro-etching solution | |
| CN105177584A (en) | Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function | |
| CN101833341B (en) | Automatic control system of PH value in alkaline etching and control method thereof | |
| JP5604307B2 (en) | Etching solution for copper or copper alloy, etching method, and regeneration management method of etching solution | |
| CN100567574C (en) | A kind of copper etching liquid composition and production method thereof | |
| CN103695881A (en) | Normal-temperature sludgeless fast phosphating liquid and preparation method thereof | |
| CN101760200A (en) | Alkaline etching solution | |
| CN105386058B (en) | One kind automating polishing fluid based on Phosphoric Acid aluminium alloy | |
| JP2010046653A (en) | Method for treating waste liquid | |
| CN1989274B (en) | Electrolytically recoverable etching solution | |
| CN109790629B (en) | Efficient and environment-friendly alkaline copper chloride etching solution for printed circuit board | |
| US3837945A (en) | Process of etching copper circuits with alkaline persulfate and compositions therefor | |
| CN102605364B (en) | Intermediate-temperature low-sediment and low-emission thick membrane phosphorizing liquid and phosphorizing method thereof | |
| CN110093606A (en) | A kind of etching solution and preparation method thereof for pcb board | |
| CN110078250A (en) | The processing method of chemical nickle-plating wastewater | |
| CN107012465B (en) | A kind of copper etchant solution and its application | |
| CN105776312B (en) | A kind of alkaline recovery method containing copper etchant solution of failure | |
| CN102730744B (en) | Process of removing calcium and magnesium from high-purity plating-stage copper sulfate | |
| CN112850778A (en) | Preparation method of basic copper chloride | |
| CN106906460A (en) | A kind of fast bonderizing liquor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Yang Huanjun Document name: Notification to Pay the Fees |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 519085 Zhuhai Jinding Science and Technology Industrial Park, Jin Feng Road, No. 26, No. Patentee after: Zhuhai Shun Ze Polytron Technologies Inc Address before: 519085 Zhuhai Jinding Science and Technology Industrial Park, Jin Feng Road, No. 26, No. Patentee before: Zhuhai Shunze Electronic Industry Co., Ltd. |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Yang Huanjun Document name: Notification of Passing Examination on Formalities |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090916 Termination date: 20210704 |