CN114574863A - Low-loss black hole micro-etching solution and preparation method and application thereof - Google Patents
Low-loss black hole micro-etching solution and preparation method and application thereof Download PDFInfo
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- CN114574863A CN114574863A CN202210235760.5A CN202210235760A CN114574863A CN 114574863 A CN114574863 A CN 114574863A CN 202210235760 A CN202210235760 A CN 202210235760A CN 114574863 A CN114574863 A CN 114574863A
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- 238000005530 etching Methods 0.000 title abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052802 copper Inorganic materials 0.000 claims abstract description 87
- 239000010949 copper Substances 0.000 claims abstract description 87
- 239000004020 conductor Substances 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 238000005260 corrosion Methods 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- JCAYXDKNUSEQRT-UHFFFAOYSA-N 2-aminoethoxyboronic acid Chemical compound NCCOB(O)O JCAYXDKNUSEQRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 76
- 230000000694 effects Effects 0.000 description 20
- 238000005259 measurement Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 9
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 8
- 238000013329 compounding Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241001424392 Lucia limbaria Species 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical group [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical group CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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)
Abstract
The application relates to the technical field of printed circuit board processing, in particular to a low-black hole micro-etching solution and a preparation method and application thereof. The low-loss black hole microetching liquid consists of the following components in parts by weight: sulfuric acid 30-50 ‰, H2O2 8-10 per mill, 0.8-1.2 per mill of copper protection component, 1.0-2.0 per mill of dispersant, 0.8-1.5 per mill of corrosion inhibitor, 0.3-1.0 per mill of hydrogen peroxide stabilizer and the balance of water; the copper protection component is one or more of dodecadilute succinic acid, monoethanolamine borate and triethanolamine borate. This application is through the low black hole of reducing of above-mentioned ratio loses liquid a little, when effectively having stripped the black hole conducting material of copper face, has reduced the loss of copper face, and the black hole conducting material that peels off is difficult for the anti-sticking on the copper face to the surface property and the yields of PCB board have been ensured.
Description
Technical Field
The application relates to the technical field of printed circuit board processing, in particular to a low-black hole micro-etching solution and a preparation method and application thereof.
Background
The black hole technology is a technology for depositing a layer of black high-quality conductive nano carbon on a hole wall and performing subsequent electroplating operation by utilizing the excellent conductivity of the layer of medium, and is also a key process of a circuit board manufacturing process.
The black hole micro-etching treatment technology in the related technology mainly comprises a Sodium Persulfate (SPS) system, a composite potassium salt (PPS) system or a sulfuric acid-hydrogen peroxide system, wherein the Sodium Persulfate (SPS) system and the composite potassium salt (PPS) system can carry out micro-etching stripping on the black hole conductive material, and the Sodium Persulfate (SPS) system and the composite potassium salt (PPS) system have the advantage that the black hole conductive material can be cleanly stripped in the etching amount of 1min and 1um at the temperature of 32 ℃, so that the black hole micro-etching treatment technology is widely applied.
Although the sulfuric acid-hydrogen peroxide system can also complete black hole microetching treatment, the application is often limited, the main reason is that the black hole conductive material can be stripped only by the etching amount of more than 2um, the loss of the copper surface after stripping is generally large, and the stripped black hole conductive material is easily adsorbed on the copper surface again, so that the process requirements are difficult to meet, and the commercial value is low.
Disclosure of Invention
In order to ensure the stripping effect of a sulfuric acid-hydrogen peroxide system, reduce the loss of a copper surface and ensure that the stripped black hole conductive material is not easy to adhere to the copper surface reversely, the application provides the low-black hole micro-etching solution and the preparation method and the application thereof.
In a first aspect, the present application provides a low-loss black hole microetching solution, which adopts the following technical scheme:
the low-loss black hole microetching liquid is characterized by comprising the following components in parts by weight: sulfuric acid 30-50 ‰, H2O28-10%, 0.8-1.2% of copper protecting component, 1.0-2.0% of dispersant, 0.8-1.5% of corrosion inhibitor, 0.3-1.0% of hydrogen peroxide stabilizer and the balance of water;
the copper protection component is one or more of dodecadilute succinic acid, monoethanolamine borate and triethanolamine borate.
By adopting the technical scheme, the catalyst is prepared from the sulfuric acid and H2O2The copper-protecting component, the dispersant and the hydrogen peroxide stabilizer are blended to form a mixed aqueous solution, the loss of the copper surface can be effectively reduced while the black hole conductive material can be fully stripped by biting and eroding the copper surface within 1min, and the stripped black holeThe conductive material is not easy to settle and gather and is reversely adhered to the copper surface;
the reason for this analysis may be due to: the copper protecting component and the dispersing agent used in the method can promote the stripping of the black hole conductive material, and simultaneously can reduce the polarity of the stripped black hole conductive material so as to reduce the phenomenon of settlement and aggregation among molecules due to Van der Waals force, so that the black hole conductive material is not easy to adhere to a copper surface in a reverse mode, and under the action of the copper protecting component and the corrosion inhibitor, the loss of the copper surface is low, the biting amount is only 0.7-1.0um, so that the surface performance and the yield of the PCB are guaranteed.
Preferably, the copper protection component consists of dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1 (0.1-0.2) to (0.1-0.2).
By adopting the technical scheme, the copper protection component formed by mixing the proportioning components has stronger polarity and copper surface affinity, and can replace the water film of the copper surface after being combined with the copper surface, so that the loss rate of the copper surface is reduced, and the influence on the stripping of the black hole conductive material is not easily caused.
Preferably, the dispersant is one or more of BYK-346, BYK-163, 1, 4-butanediol and Dow 2A 1.
Preferably, the dispersant consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1 (1-2) to (6-8).
By adopting the technical scheme, the dispersant formed by mixing the components according to the proportion can effectively promote the stripping of the black hole conductive material, and can be compounded with the copper protection component to reduce the polarity of the black hole conductive material and increase the dispersion effect of the black hole conductive material, so that the phenomenon that the black hole conductive material is settled and gathered on the copper surface again is reduced;
in addition, the components of the dispersing agent also have a compounding effect, when the multi-component dispersing agent is compounded and used, the loss of a copper surface is small, the black hole conductive material is thoroughly stripped, and the obtained PCB has excellent surface performance and yield.
Preferably, the corrosion inhibitor is one or more of citric acid, ethylene diamine tetraacetic acid and ethylene diamine tetraacetic acid sodium salt.
By adopting the technical scheme, the corrosion inhibitor of the components can slow down the biting corrosion of hydrogen peroxide on the copper surface so as to reduce the loss of the copper surface, and is not easy to influence the stripping effect of the black hole conductive material after being compounded with the copper protection component.
Preferably, the hydrogen peroxide stabilizer is one or more of diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether and triethylene glycol dimethyl ether.
By adopting the technical scheme, the hydrogen peroxide stabilizer with the components can slow down the decomposition of hydrogen peroxide so as to ensure the stripping effect of the black hole conductive material, and can be compounded with the dispersant to reduce the phenomenon that the black hole conductive material is settled and gathered on the copper surface again.
Preferably, the water is deionized water, and the conductivity of the deionized water is less than 5 us/cm.
By adopting the technical scheme, compared with raw water such as tap water and the like, the deionized water with low conductivity has lower contents of metal ions and chloride ions, and can effectively reduce the toxic action of conductive ions such as chloride ions on the micro-etching effect, thereby ensuring the stripping effect of the black hole micro-etching liquid.
In a second aspect, the present application provides a method for preparing a low-loss black hole microetching solution, which adopts the following technical scheme: a preparation method of a low-loss black hole micro-etching solution comprises the following steps: weighing sulfuric acid and H according to the proportion2O2The copper-protecting component, the wetting agent, the dispersing agent, the corrosion inhibitor, the hydrogen peroxide stabilizer and the water are uniformly mixed to obtain the copper-protecting copper-plating solution.
By adopting the technical scheme, the operation is simple, various conditions are easy to control, and meanwhile, the obtained low-loss black hole micro-etching solution is relatively stable in performance, has a good stripping effect and small copper surface loss, so that the low-loss black hole micro-etching solution has a wide market prospect and is suitable for industrialized production.
In a third aspect, the present application provides an application of a low-loss black hole microetching solution, which adopts the following technical scheme:
the low-loss black hole micro-etching solution can effectively strip the black hole conductive material on the copper surface with low copper surface loss, and meanwhile, the stripped black hole conductive material is not easy to adhere to the copper surface reversely.
Through adopting above-mentioned technical scheme, compare need frequently trade the groove, and the lower SPS of life and PPS system, the hydrogen peroxide solution of sulfuric acid that this application was changed can realize automatic the interpolation, when the extension traded the groove frequency, can also reduce the waste liquid and discharge, practices thrift man-hour, reduces the energy consumption, therefore has higher commercial value.
In summary, the present application has the following beneficial effects:
1. the application is carried out by the above sulfuric acid, H2O2The copper-protecting component, the wetting agent, the dispersing agent and the hydrogen peroxide stabilizer are compounded, so that the stripped black hole conductive material is not easy to adhere to the copper surface while the black hole conductive material is effectively stripped with low copper loss, and the surface performance and the yield of the PCB are guaranteed;
2. the copper protection component formed by mixing the components according to the proportion can not only fully strip the black hole conductive material on the basis of reducing the loss of the copper surface, but also reduce the phenomenon that the black hole conductive material is settled and gathered on the copper surface again;
3. the low-loss black hole micro-etching solution obtained by the process has excellent stripping effect, small copper surface loss and simple and easy preparation method, thereby having wide market prospect and being suitable for large-scale industrialized production and processing;
4. the low-loss black hole micro-etching solution obtained in the application can be automatically added, the groove changing frequency is prolonged, meanwhile, the black hole conducting material on the copper surface can be effectively stripped on the basis of reducing the loss of the copper surface, and the stripped black hole conducting material is not easy to adhere to the copper surface in a reverse adhesion mode, so that the low-loss black hole micro-etching solution has higher commercial value compared with SPS and PPS systems.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the examples of the present application are commercially available, except for the following specific descriptions:
BYK-346, BYK-163, available from Bick chemical Co., Ltd, Germany;
dow 2a1, purchased from dow chemical company, usa;
the Chuanqian AOI online detection device, model JX-600X, was purchased from Shenzhen Chuanfeng electronic device factory.
Examples
Example 1
The low-loss black hole microetching solution comprises the following components in 1kg, the corresponding weight of the components is shown in the table 1, and the low-loss black hole microetching solution is prepared by the following preparation method:
weighing sulfuric acid and H according to the proportion2O2The copper protection component, the wetting agent, the dispersing agent, the corrosion inhibitor, the hydrogen peroxide stabilizer and the water are mixed at 2000r/min for 30min to be uniform, and the low-loss black hole micro-etching solution is obtained;
wherein the copper-protecting component is dodecyl succinic acid, the dispersant is BYK-346, the corrosion inhibitor is citric acid, the hydrogen peroxide stabilizer is diethylene glycol methyl ethyl ether, and the water is deionized water with the conductivity of 1 us/cm.
Examples 2 to 6
A low loss black hole microetching solution which differs from example 1 in that the components and their respective weights are shown in table 1.
TABLE 1 EXAMPLES 1-6 Low loss Black hole microetching solutions compositions and weights (g) thereof
Example 7
The low-black hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid and monoethanolamine borate according to the weight ratio of 1: 0.2.
Example 8
The low-black-hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid and triethanolamine borate according to the weight ratio of 1: 0.2.
Example 9
The low-black hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.05: 0.05.
Example 10
The low-black hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.1: 0.1.
Example 11
The low-black hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.15: 0.15.
Example 12
The low-black hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.2: 0.2.
Example 13
The low-black hole micro-etching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.3: 0.3.
Example 14
A low-loss black hole microetching solution which is different from the solution of example 1 in that the dispersant is BYK-163.
Example 15
A low-loss black hole microetching solution which is different from the microetching solution of the embodiment 1 in that the dispersing agent is dow 2a 1.
Example 16
A low-loss black hole microetching solution is different from the microetching solution in example 1 in that a dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1:0.5: 3.
Example 17
A low-loss black hole microetching solution is different from the microetching solution in example 1 in that a dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1:1: 6.
Example 18
A low-loss black hole microetching solution is different from the microetching solution in example 1 in that a dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1:1.5: 7.
Example 19
A low-loss black hole microetching solution is different from the microetching solution in example 1 in that a dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1:2: 8.
Example 20
A low-loss black hole micro-etching solution is different from the embodiment 1 in that a dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 according to the weight ratio of 1:3: 10.
Example 21
A low-loss black hole micro-etching solution, which is different from the solution in the embodiment 1 in that the corrosion inhibitor is ethylene diamine tetraacetic acid.
Example 22
The low-loss black hole micro-etching solution is different from the embodiment 1 in that the corrosion inhibitor is ethylene diamine tetraacetic acid sodium salt, and in the application, the corrosion inhibitor is ethylene diamine tetraacetic acid disodium.
Example 23
A low-loss black hole micro-etching solution, which is different from the solution in the embodiment 1 in that the corrosion inhibitor is prepared from citric acid and ethylene diamine tetraacetic acid in a weight ratio of 1: 0.5.
Example 24
The low-loss black hole micro-etching solution is different from the embodiment 2 in that the hydrogen peroxide stabilizer is ethylene glycol monomethyl ether.
Example 25
The low-black-hole micro-etching solution is different from the embodiment 2 in that a hydrogen peroxide stabilizer consists of diethylene glycol methyl ethyl ether and triethylene glycol dimethyl ether according to the weight ratio of 1: 0.3.
Example 26
The low-black hole micro-etching solution is different from the micro-etching solution in the embodiment 2 in that hydrogen peroxide stabilizers, namely diethylene glycol methyl ethyl ether and ethylene glycol monomethyl ether, are composed according to the weight ratio of 1: 0.2.
Performance test
Firstly, selecting a plurality of low-loss black hole micro-etching solutions prepared in the embodiment and taking the low-loss black hole micro-etching solutions as detection objects for standby application, then, after stripping the black hole conductive materials on the PCB according to the using method in the application example, testing the copper surface undercut amount um and the carbon residue rate (the number of carbon residue plates/the total number of plates) and adopting an AOI (automated optical inspection) online detection device to detect, and identifying and recording the carbon residue plates;
the detection steps of the bite quantity um are as follows:
1) taking a double-sided copper-clad plate (with the roughness of Ra being 0.2um), deoiling and washing, placing the double-sided copper-clad plate in an oven to dry for 15 minutes at 105 +/-5 ℃, and cooling the double-sided copper-clad plate in a drier to room temperature;
2) balance weighing G1 (unit: gram, please be accurate to 2 bits after decimal point);
3) passing the copper-clad plate through a microetching cylinder according to set time or transmission speed;
4) after secondary washing and blow-drying, placing the mixture in an oven to dry the mixture for 15 minutes at 105 +/-5 ℃, and cooling the mixture to room temperature in a drier;
5) balance weighing G2 (unit: gram, please be accurate to 2 bits after decimal point);
6) the area S of the test panel (sum of the areas on both sides, unit: cm2)
And (3) calculating: microetching amount (um) [ (G1-G2)/8.96 XS ]. times.10000
Application example
Application example 1
A black hole micro-etching treatment process uses the low-loss black hole micro-etching solution prepared in the embodiment 1, when the black hole micro-etching treatment is required to be carried out on a PCB, the low-loss black hole micro-etching solution is added into a tank of a production line, then equipment is started to carry out circulating spraying for 15min, the temperature is controlled to be 32 ℃, and then the copper surface micro-etching treatment can be started through the assembly line operation.
Application examples 2 to 6
The difference between the low-loss black hole micro-etching solution and the application example 1 is that the low-loss black hole micro-etching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: application examples 2-6 comparison table of use conditions of low-loss black hole microetching liquid
| Group of | Low-loss black hole micro-etching liquid |
| Application example 2 | From example 2 |
| Application example 3 | From example 3 |
| Application example 4 | From example 4 |
| Application example 5 | From example 5 |
| Application example 6 | From example 6 |
Comparative example 1
A low-black hole micro-etching solution is different from the application example 1 in that a copper protection component is not included.
The obtained low-loss black hole microetching liquids were used according to the treatment processes in application examples 1 to 6 and comparative example 1, and the biting amount um and the char yield thereof were measured according to the measurement procedures and the measurement standards, and the average values of the measurement results are shown in the following table.
From the above table, it can be seen that the low-loss black hole microetching solution prepared in application examples 1-6 can effectively strip the black hole conductive material, and simultaneously reduce the risk of the black hole conductive material reversely sticking to the copper surface, the corrosion amount is only 0.7-1.0um, the carbon residue rate is only 0.37-0.48%, and is respectively reduced by 55-68% and 17-36% compared with comparative example 1 which does not contain a copper protection component;
it can be seen that the above-mentioned sulfuric acid, H2O2The copper-protecting component, the dispersing agent and the hydrogen peroxide stabilizer are blended to form a mixed aqueous solution, the black hole conductive material can be fully stripped within 1min by biting and eroding the copper surface, the loss of the copper surface can be effectively reduced, and the stripped black hole conductive material is not easy to settle, gather and inversely adhere to the copper surface;
particularly, the low-loss black hole micro-etching solution prepared in the application examples 3-5 has better stripping effect and less copper surface loss, and the biting amount is only 0.8-0.9 um; the carbon residue rate is only 0.37-0.42%;
it can be seen that application examples 3-5 are preferred examples, the component proportion is the optimal proportion, the copper surface loss can be effectively reduced, and meanwhile, the low-black hole micro-etching solution is endowed with an excellent stripping effect, so that the surface performance and the yield of the PCB are guaranteed, and in addition, when the components such as the copper protection component exceed a certain threshold value, the copper surface loss can be further reduced, but the stripping effect is affected, referring to application example 6.
The reason for analyzing the above experimental results is probably that the copper protecting component and the dispersing agent can reduce the polarity of the stripped black hole conductive material, reduce the phenomenon that molecules are deposited and gathered due to van der Waals force and reversely adhered to the copper surface, and remarkably reduce the loss of the copper surface under the compounding action of the affinity replacement water film of the copper protecting component and the corrosion inhibitor, thereby ensuring the surface performance and the yield of the PCB.
Application examples 7 to 13
The difference between the low-loss black hole micro-etching solution and the application example 1 is that the low-loss black hole micro-etching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: application examples 7-13 use condition comparison table of low-loss black hole microetching liquid
The obtained low-loss black hole microetching solution was used according to the treatment process in application examples 7 to 13, and the biting amount um and the char yield thereof were measured according to the measurement procedures and the measurement standards, and the average values of the measurement results were recorded in the following table.
From the above table, it can be seen that the low-loss black hole micro-etching solutions prepared in application examples 7-13 can effectively strip the black hole conductive material and reduce the risk of the black hole conductive material reversely sticking to the copper surface, and the loss of the copper surface is low, and the biting amount is only 0.7-1.0 um; the carbon residue rate is 0.36-0.48%;
therefore, the copper film has strong polarity and copper surface affinity, and after the copper film is combined with the copper surface, the water film on the copper surface can be replaced, so that the loss rate of the copper surface is reduced, and the influence on the stripping of the black hole conductive material is not easily caused.
Particularly, the low-loss black hole micro-etching solution prepared in the application examples 10-12 has excellent copper surface loss and stripping effect, the biting amount is only 0.7-0.8um, the carbon residue rate is 0.36-0.38%, and the copper surface loss and the stripping effect are respectively reduced by 11-30% and 16-25% compared with the groups of the application examples 1 and 7-8 which do not use three components simultaneously;
it can be seen that application examples 9-11 are preferred examples, the copper protecting component has a compounding effect among the components, and when the copper protecting component is compounded by dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1 (0.1-0.2) to (0.1-0.2), the performances are optimal, and compared with other compounding ratios, for example: in application examples 9 and 13, the biting amount and the carbon residue rate were reduced by 13 to 22% and 10 to 16%, respectively.
Application examples 14 to 20
The difference between the low-loss black hole micro-etching solution and the application example 1 is that the low-loss black hole micro-etching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: application examples 14-20 comparison table of use conditions of low-loss black hole microetching liquid
| Group of | Low-loss black hole micro-etching liquid |
| Application example 14 | From example 14 |
| Application example 15 | From example 15 |
| Application example 16 | From example 16 |
| Application example 17 | From example 17 |
| Application example 18 | From example 18 |
| Application example 19 | From example 19 |
| Application example 20 | Prepared from example 20 |
The resulting low-loss black hole microetching solution was used according to the treatment process described in application examples 14 to 20, and the seizing amount um and the char yield thereof were measured according to the measurement procedures and the measurement standards described above, and the average values of the measurement results were recorded in the following table.
From the above table, it can be seen that the low-loss black hole micro-etching solution prepared in application examples 14 to 20 can effectively strip the black hole conductive material and reduce the risk of the black hole conductive material reversely sticking to the copper surface, and the biting amount of the low-loss black hole micro-etching solution is 0.9 to 1.0 um; the carbon residue rate is 0.36-0.48%;
therefore, the dispersant prepared by mixing the components according to the proportion can play a better role in surface activation and dispersion, and can be compounded with the copper protection component to reduce the polarity of the black hole conductive material, so that the phenomenon that the black hole conductive material is settled and gathered on a copper surface again is reduced.
Particularly, the low-loss black hole micro-etching solution prepared in the application examples 17 to 19 has a good stripping effect, the biting amount is 0.9um, the carbon residue rate is 0.36 to 0.38 percent, and the content is respectively reduced by 10 percent and 10 to 25 percent compared with that of any one of the dispersing agents used in the application examples 1 and 14 to 15;
it can be seen that the application examples 17-19 are preferred examples, the components of the PCB have a compound effect, and when the dispersant consists of BYK-346, BYK-163 and Dow 2A1 according to the weight ratio of 1 (1-2) to (6-8), the copper surface undercut amount is small, the black hole conductive material is thoroughly stripped, and the obtained PCB has excellent surface performance and yield.
Application examples 21 to 23
The difference between the low-loss black hole micro-etching solution and the application example 1 is that the low-loss black hole micro-etching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table (b): application examples 21-23 use condition comparison table of low-loss black hole microetching liquid
| Group of | Low-loss black hole micro-etching liquid |
| Application example 21 | From example 21 |
| Application example 22 | Prepared from example 22 |
| Application example 23 | From example 23 |
The obtained low-loss black hole microetching liquid was used according to the treatment process in application examples 21 to 23, and the biting amount um and the char yield thereof were measured according to the measurement procedures and the measurement standards, and the average values of the measurement results were recorded in the following table.
From the above table, it can be seen that the low-loss black hole micro-etching solutions prepared in the application examples 21 to 23 can effectively strip the black hole conductive material and reduce the risk of the black hole conductive material reversely sticking to the copper surface, and the biting amount is only 0.8 to 1.0 um; the carbon residue rate is only 0.46-0.52%;
therefore, the corrosion inhibitor of the components can slow down the biting corrosion of hydrogen peroxide on the copper surface so as to reduce the loss of the copper surface, and after the corrosion inhibitor is compounded with the copper protecting component, the stripping effect of the black hole conductive material is not easily influenced.
Application examples 24 to 26
The difference between the low-loss black hole micro-etching solution and the application example 1 is that the low-loss black hole micro-etching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: application examples 24-26 comparison table of use conditions of low-loss black hole microetching liquid
| Group of | Low-loss black hole micro-etching liquid |
| Application example 24 | Prepared from example 24 |
| Application example 25 | Prepared from example 25 |
| Application example 26 | From example 26 |
The obtained low-loss black hole micro-etching solution was used according to the treatment process in application examples 24 to 26, and the biting amount um and the carbon residue rate thereof were measured according to the above measurement procedures and measurement standards, and the average values of the measurement results are recorded in the following table.
As can be seen from the above table, the low-loss black hole micro-etching solutions prepared in the application examples 24-26 can effectively strip the black hole conductive material and reduce the risk of the black hole conductive material reversely sticking to the copper surface, and the etching amount is only 1.0 um; the carbon residue rate is only 0.46-0.50%; therefore, the hydrogen peroxide stabilizer with the components can slow down the decomposition of hydrogen peroxide so as to ensure the stripping effect of the black hole conductive material, and can be compounded with the dispersant to reduce the phenomenon that the black hole conductive material is settled and gathered on the copper surface again; in addition, a certain compounding effect is achieved among multiple components of the hydrogen peroxide stabilizer, particularly the compounding effect of diethylene glycol methyl ethyl ether and triethylene glycol dimethyl ether is excellent, see application example 25.
The specific application example is only for explaining the application, and is not limiting to the application, and a person skilled in the art can make modifications without inventive contribution to the application example as required after reading the present specification, but all of them are protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. The low-loss black hole microetching liquid is characterized by comprising the following components in parts by weight: sulfuric acid 30-50 ‰, H2O2 8-10 per mill, 0.8-1.2 per mill of copper protection component, 1.0-2.0 per mill of dispersant, 0.8-1.5 per mill of corrosion inhibitor, 0.3-1.0 per mill of hydrogen peroxide stabilizer and the balance of water;
the copper protection component is one or more of dodecadilute succinic acid, monoethanolamine borate and triethanolamine borate.
2. The low-loss black hole microetching solution as claimed in claim 2, wherein the copper protecting component comprises dodecavinyl succinic acid, monoethanolamine borate and triethanolamine borate in a weight ratio of 1 (0.1-0.2) to (0.1-0.2).
3. The low loss black hole microetching solution according to claim 1, wherein the dispersant is one or more of BYK-346, BYK-163, 1, 4-butanediol, and dow 2a 1.
4. The low loss black hole microetching solution according to claim 3, wherein the dispersant consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1 (1-2) to (6-8).
5. The low loss black hole microetching solution according to claim 1, wherein the corrosion inhibitor is one or more of citric acid, ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid sodium salt.
6. The low-loss black hole microetching solution according to claim 1, wherein the hydrogen peroxide stabilizer is one or more of diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether and triethylene glycol dimethyl ether.
7. The low loss black hole microetching solution according to claim 1, wherein the water is deionized water having an electrical conductivity of less than 5 us/cm.
8. The method for preparing the low-loss black hole microetching solution according to any one of claims 1 to 7, wherein the sulfuric acid and the H are weighed according to the mixture ratio2O2The copper-protecting component, the wetting agent, the dispersing agent, the corrosion inhibitor, the hydrogen peroxide stabilizer and the water are uniformly mixed to obtain the copper-protecting copper-plating solution.
9. The use of the low-loss black hole microetching solution according to any one of claims 1 to 7 in black hole microetching treatment, which can effectively strip the black hole conductive material on the copper surface with low copper surface loss, and the stripped black hole conductive material is not easy to adhere to the copper surface.
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