CN114574863B - Low-loss black hole microetching solution and preparation method and application thereof - Google Patents
Low-loss black hole microetching solution and preparation method and application thereof Download PDFInfo
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- CN114574863B CN114574863B CN202210235760.5A CN202210235760A CN114574863B CN 114574863 B CN114574863 B CN 114574863B CN 202210235760 A CN202210235760 A CN 202210235760A CN 114574863 B CN114574863 B CN 114574863B
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 claims abstract description 70
- 239000010949 copper Substances 0.000 claims abstract description 70
- 239000004020 conductor Substances 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 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-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 7
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 74
- 230000000694 effects Effects 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 238000005259 measurement Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 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 6
- 238000005530 etching Methods 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000002508 compound effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001424392 Lucia limbaria Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 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
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007921 spray Substances 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
Abstract
The application relates to the technical field of printed circuit board processing, in particular to a low-loss black hole microetching solution, a preparation method and application thereof. The low-loss black hole microetching solution consists of the following components in percentage by weight: sulfuric acid 30-50% 2 O 2 8 to 10 per mill, 0.8 to 1.2 per mill of copper-protecting component, 1.0 to 2.0 per mill of dispersant, 0.8 to 1.5 per mill of corrosion inhibitor, 0.3 to 1.0 per mill of hydrogen peroxide stabilizer and the balance of water; the copper-protecting component is one or more of dodecyl succinic acid, monoethanolamine borate and triethanolamine borate. According to the low-loss black hole microetching solution, the copper surface black hole conductive material is effectively stripped, the loss of the copper surface is reduced, and the stripped black hole conductive material is not easy to reversely adhere to the copper surface, so that the surface performance and the yield of the PCB are ensured.
Description
Technical Field
The application relates to the technical field of printed circuit board processing, in particular to a low-loss black hole microetching solution, a preparation method and application thereof.
Background
The black hole technology is to deposit a layer of black high-quality conductive nano carbon on the hole wall, and the subsequent electroplating operation is carried out by utilizing the excellent conductivity of the medium layer, which is also a key process for manufacturing the circuit board, but black hole liquid is not only adsorbed on fibers in the holes, but also adsorbed on the metal copper surface, and the bonding force of electroplating is influenced by the existence of black hole liquid on the surface, so that the black hole microetching technology is generated.
The related technology for treating the black hole microetching 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 microetch the black hole conductive material completely under the condition of 32 ℃ in the etching amount of 1min and 1um, and the system is widely applied.
Although the sulfuric acid-hydrogen peroxide system can also finish the microetching treatment of the black holes, the application is often limited, and the main reason is that the etching amount is more than 2um to peel off the black hole conductive material cleanly, the copper surface loss is generally large after the peeling, the peeled black hole conductive material is easy to be adsorbed on the copper surface again, so that the processing requirement is difficult to meet, and the commercial value is low.
Disclosure of Invention
The application provides a low-loss black hole microetching solution and a preparation method and application thereof, and aims to ensure the stripping effect of a sulfuric acid-hydrogen peroxide system, reduce copper surface loss and ensure that stripped black hole conductive materials are not easy to reversely adhere to the copper surface.
In a first aspect, the application provides a low-loss black hole microetching solution, which adopts the following technical scheme:
the low-loss black hole microetching solution is characterized by comprising the following components in percentage by weight: sulfuric acid 30-50% 2 O 2 8-10%, copper-protecting component 0.8-1.2%, dispersant 1.0-2.0%, corrosion inhibitor 0.8-1.5%, hydrogen peroxide stabilizer 0.3-1.0%, and water for the rest;
the copper-protecting component is one or more of dodecyl succinic acid, monoethanolamine borate and triethanolamine borate.
By adopting the technical scheme, the sulfuric acid and H are used for preparing the catalyst 2 O 2 The mixed aqueous solution formed by blending the copper-protecting component, the dispersing agent and the hydrogen peroxide stabilizer can realize the full stripping of the black hole conductive material by biting the copper surface within 1min, and simultaneously can effectively reduce the loss of the copper surface, and the stripped black hole conductive material is not easy to subside and aggregate and is reversely adhered on the copper surface;
the reason for this analysis may be due to: the copper-protecting component and the dispersing agent used in the application can not only promote stripping of the black hole conductive material, but also reduce the polarity of the stripped black hole conductive material so as to reduce the phenomenon of sedimentation and aggregation among molecules due to Van der Waals force, so that the copper-protecting component and the dispersing agent are not easy to reversely adhere to a copper surface, and the copper surface has lower loss and the biting amount is only 0.7-1.0um under the action of the copper-protecting component and the corrosion inhibitor, thereby ensuring the surface performance and the yield of the PCB.
Preferably, the copper-protecting component consists of (0.1-0.2) of (by weight ratio of (dodecyl succinic acid), monoethanolamine borate and triethanolamine borate.
Through adopting above-mentioned technical scheme, the copper protection component that is mixed by above-mentioned ratio component, it itself has stronger polarity and copper surface affinity, and it is after combining with the copper surface, can replace the water film of copper surface to reduce the loss rate of copper surface, in addition be difficult for causing the influence to the stripping of black hole conductive material.
Preferably, the dispersant is one or more of BYK-346, BYK-163, 1, 4-butanediol and Dow 2A1.
Preferably, the dispersant consists of BYK-346, BYK-163 and Dow 2A1 in the weight ratio of 1 (1-2) to 6-8.
By adopting the technical scheme, the dispersing agent formed by mixing the components according to the proportion can effectively promote the peeling of the black hole conductive material, can be compounded with the copper-protecting component to reduce the polarity of the black hole conductive material and increase the dispersing effect of the black hole conductive material, thereby reducing the phenomenon that the black hole conductive material is redeposited and accumulated on a copper surface;
in addition, the components of the dispersing agent also have a compound effect, when the multi-component compound type PCB is used, copper surface loss is small, and meanwhile, the black hole conductive material is thoroughly stripped, so that the PCB has excellent surface performance and yield.
Preferably, the corrosion inhibitor is one or more of citric acid, ethylenediamine tetraacetic acid and ethylenediamine tetraacetic acid sodium salt.
By adopting the technical scheme, the corrosion inhibitor of the components can slow down the biting of hydrogen peroxide on the copper surface so as to reduce the loss of the copper surface, and the stripping effect of the black hole conductive material is not easily affected after the corrosion inhibitor is 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 of the components can not only slow down the decomposition of hydrogen peroxide so as to ensure the stripping effect of the black hole conductive material, but also reduce the phenomenon that the black hole conductive material is redeposited and accumulated on the copper surface by being compounded with the dispersing agent.
Preferably, the water is deionized water, and the conductivity of the deionized water is less than 5us/cm.
By adopting the technical scheme, compared with raw water such as tap water, the deionized water with low conductivity has lower content of metal ions and chloride ions, and can effectively reduce the toxic effect of the conductive ions such as chloride ions on microetching effect, thereby guaranteeing the stripping effect of the black hole microetching solution.
In a second aspect, the application provides a preparation method of a low-loss black hole microetching solution, which adopts the following technical scheme: the preparation method of the low-loss black hole microetching solution comprises the following steps: weighing sulfuric acid and H according to the proportion 2 O 2 And uniformly mixing the copper-protecting component, the wetting agent, the dispersing agent, the corrosion inhibitor, the hydrogen peroxide stabilizer and the water.
By adopting the technical scheme, the method is simple to operate, various conditions are easy to control, the performance of the obtained low-loss black hole microetching solution is relatively stable, the stripping effect is excellent, and the copper surface loss is small, so that the method has a wide market prospect and is suitable for industrialized production.
In a third aspect, the application provides an application of a low-loss black hole microetching solution, which adopts the following technical scheme:
the application of the low-loss black hole microetching solution in the black hole microetching treatment can effectively strip the black hole conductive material on the copper surface with lower copper surface loss, and meanwhile, the stripped black hole conductive material is not easy to reversely adhere to the copper surface.
By adopting the technical scheme, compared with SPS and PPS systems which need frequent groove replacement and have lower service life, the sulfuric acid hydrogen peroxide used by the application can realize automatic addition, can reduce waste liquid discharge, save working hours and reduce energy consumption while prolonging the groove replacement frequency, thereby having higher commercial value.
In summary, the application has the following beneficial effects:
1. the application uses the sulfuric acid and H 2 O 2 The copper-protecting component, the wetting agent, the dispersing agent and the hydrogen peroxide stabilizer are compounded, so that the black hole conductive material is effectively stripped by low-loss copper loss, and meanwhile, the stripped black hole conductive material is not easy to reversely adhere to a copper surface, and the surface performance and the yield of the PCB are ensured;
2. according to the copper-protecting component mixed by the above proportioning components, the black hole conductive material can be fully stripped on the basis of reducing copper surface loss, and the phenomenon that the black hole conductive material is redeposited and accumulated on a copper surface can be reduced;
3. the low-loss black hole microetching solution obtained by the process has the advantages of small copper surface loss and simple preparation method besides good stripping effect, so that the low-loss black hole microetching solution has wide market prospect and is suitable for mass industrialized production and processing;
4. the low-loss black hole microetching solution obtained in the application can realize automatic addition, prolong the groove changing frequency, simultaneously can effectively strip the black hole conductive material on the copper surface on the basis of reducing the loss of the copper surface, and the stripped black hole conductive material is not easy to be reversely stuck on the copper surface, thereby having 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, purchased from Pick chemical Co., germany;
ceramic 2A1, purchased from the american ceramic chemical company;
the model JX-600X of the Chuangjinfeng AOI on-line detection device is purchased from Chuangjinfeng electronic equipment factory in Shenzhen city.
Examples
Example 1
The low-loss black hole microetching solution is prepared by the following preparation method, wherein each component and the corresponding weight of each component are shown in table 1 according to each 1 kg:
weighing sulfuric acid and H according to the proportion 2 O 2 Mixing the copper-protecting component, the wetting agent, the dispersing agent, the corrosion inhibitor, the hydrogen peroxide stabilizer and water for 30min at 2000r/min to obtain low-loss black hole microetching solution;
wherein the copper-protecting component is dodecyl succinic acid, the dispersing agent 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 conductivity of 1 us/cm.
Examples 2 to 6
A low-loss black hole microetching solution was different from example 1 in that the respective components and their respective weights are shown in Table 1.
TABLE 1 Low loss black hole microetching solutions of examples 1-6 each component and weight (g)
Example 7
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl succinic acid and monoethanolamine borate in the weight ratio of 1:0.2.
Example 8
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl succinic acid and triethanolamine borate according to the weight ratio of 1:0.2.
Example 9
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.05:0.05.
Example 10
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.1:0.1.
Example 11
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.15:0.15.
Example 12
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl succinic acid, monoethanolamine borate and triethanolamine borate according to the weight ratio of 1:0.2:0.2.
Example 13
The low-loss black hole microetching solution is different from the embodiment 1 in that the copper-protecting component consists of dodecyl 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 is different from the embodiment 1 in that the dispersing agent is BYK-163.
Example 15
A low-loss black hole microetching solution is different from the embodiment 1 in that the dispersing agent is Dow 2A1.
Example 16
A low-loss black hole microetching solution is different from the embodiment 1 in that the dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 according to the weight ratio of 1:0.5:3.
Example 17
A low-loss black hole microetching solution is different from the embodiment 1 in that the dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 according to the weight ratio of 1:1:6.
Example 18
A low-loss black hole microetching solution is different from the embodiment 1 in that the dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 according to the weight ratio of 1:1.5:7.
Example 19
A low-loss black hole microetching solution is different from the embodiment 1 in that the dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 according to the weight ratio of 1:2:8.
Example 20
A low-loss black hole microetching solution is different from the embodiment 1 in that the 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 microetching solution is different from the embodiment 1 in that the corrosion inhibitor is ethylenediamine tetraacetic acid.
Example 22
The difference between the low-loss black hole microetching solution and the embodiment 1 is that the corrosion inhibitor is ethylenediamine tetraacetic acid sodium salt, and the application is ethylenediamine tetraacetic acid disodium salt.
Example 23
The low-loss black hole microetching solution is different from the embodiment 1 in that the corrosion inhibitor comprises citric acid and ethylenediamine tetraacetic acid according to the weight ratio of 1: 0.5.
Example 24
The difference between the low-loss black hole microetching solution and the embodiment 2 is that the hydrogen peroxide stabilizer is ethylene glycol monomethyl ether.
Example 25
The difference between the low-loss black hole microetching solution and the embodiment 2 is that the 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 difference between the low-loss black hole microetching solution and the embodiment 2 is that the hydrogen peroxide stabilizer 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 microetching solutions prepared in the embodiment, taking the microetching solutions as detection objects for standby, then, after the black hole conductive materials on the PCB are stripped according to the using method in the application example, testing the copper surface biting amount um and the carbon residue rate (the number of carbon residue plates/the total number of plates) of the microetching solutions, and detecting the microetching solutions by using a invasive front AOI (automatic inspection) on-line detection device, so as to identify and record the carbon residue plates;
the detection steps of the biting amount um are as follows:
1) Taking a double-sided copper-clad plate (roughness is Ra=0.2 um), placing the copper-clad plate in an oven to dry for 15 minutes at 105+/-5 ℃ after the oil removal and water washing procedures, and cooling to room temperature in a dryer;
2) Balance weight G1 (unit: gram, please get 2 bits after decimal point);
3) The copper-clad plate is passed through a microetching cylinder according to a set time or a set transmission speed;
4) Washing with secondary water, drying in an oven at 105+ -5deg.C for 15min, and cooling to room temperature in a dryer;
5) Balance weight G2 (unit: gram, please get 2 bits after decimal point);
6) The test panel area S (sum of two areas, unit: cm 2 )
And (3) calculating: microetching amount (um) = [ (G1-G2)/8.96×s ] ×10000
Application example
Application example 1
A black hole microetching treatment process comprises the steps of adding a low-loss black hole microetching solution prepared in the embodiment 1 into a tank cylinder of a production line when the black hole microetching solution is required to be subjected to black hole microetching treatment on a PCB, starting equipment to circularly spray for 15min, and controlling the temperature to 32 ℃, so that copper surface microetching treatment can be started through pipelining.
Application examples 2 to 6
The difference between the low-loss black hole microetching solution and the application example 1 is that the low-loss black hole microetching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: use condition comparison table of low-loss black hole microetching solution in application examples 2-6
| Group of | Low-loss black hole microetching 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-loss black hole microetching solution is different from application example 1 in that it does not contain a copper-protecting component.
The low loss black hole microetching solutions obtained in the treatment processes of the above application examples 1 to 6 and comparative example 1 were used, and the biting amount um and the carbon residue ratio thereof were measured according to the above measurement steps and measurement standards, and the average value of the measurement results was recorded in the following table.
As can be seen from the above table, the low-loss black hole microetching solutions prepared in application examples 1-6 can effectively strip the black hole conductive material, reduce the risk of reversely sticking the black hole conductive material on the copper surface, and have the biting amount of only 0.7-1.0um, the carbon residue rate of only 0.37-0.48%, and respectively reduce 55-68% and 17-36% compared with comparative example 1 which does not contain copper protection components;
it can be seen that the above-mentioned sulfuric acid, H 2 O 2 The mixed aqueous solution formed by blending the copper-protecting component, the dispersing agent and the hydrogen peroxide stabilizer can be used for 1minThe copper surface is etched to realize the full stripping of the black hole conductive material, the loss of the copper surface can be effectively reduced, and the stripped black hole conductive material is not easy to subside and gather and is reversely adhered to the copper surface;
in particular, the low-loss black hole microetching solution prepared in application examples 3-5 has better stripping effect, less copper surface loss and only 0.8-0.9um of etching amount; the carbon residue rate is only 0.37-0.42%;
it can be seen that application examples 3-5 are preferred examples, and the composition ratio is an optimal ratio, so that copper surface loss can be effectively reduced, and meanwhile, a good stripping effect is given to the low-loss black hole microetching solution, so that the surface performance and the yield of the PCB are guaranteed, and in addition, when the copper protection component and other components exceed a certain threshold value, the copper surface loss can be further reduced, but the stripping effect is affected, and reference is made to application example 6.
The experimental result is analyzed that the reason is probably because the used copper-protecting component and the dispersant can reduce the polarity of the stripped black hole conductive material, reduce the phenomenon that molecules are reversely stuck on the copper surface due to the sedimentation and aggregation of Van der Waals force, and obviously reduce the loss of the copper surface under the combined action of the hydrophilic 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 microetching solution and the application example 1 is that the low-loss black hole microetching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: use condition comparison table of low-loss black hole microetching solution in application examples 7-13
The low loss black hole microetching solutions obtained by the treatment processes in application examples 7 to 13 were used and tested for the biting amount um and carbon residue ratio according to the above-mentioned measurement steps and measurement standards, and the average value of the test results was recorded in the following table.
As can be seen from the above table, the low-loss black hole microetching solutions prepared in application examples 7 to 13 can effectively strip the black hole conductive material and reduce the risk of reversely sticking the black hole conductive material on the copper surface, and the copper surface has lower loss, and the etching amount is only 0.7 to 1.0um; the carbon residue rate is 0.36-0.48%;
the copper-based conductive material has stronger polarity and copper surface affinity, and can replace a 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 stripping of the black hole conductive material is not easy to influence.
In particular, the low-loss black hole microetching solution prepared in application examples 10-12 has better 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 compared with the application examples 1 and 7-8, the groups of three components which are not used simultaneously are respectively reduced by 11-30% and 16-25%;
it can be seen that application examples 9-11 are preferred examples, the copper-protecting components have a compound effect, and when the copper-protecting components are compounded by 1 (0.1-0.2) of (by weight ratio) of dodecenyl succinic acid, monoethanolamine borate and triethanolamine borate, the copper-protecting components have optimal performances, and compared with other compound ratios, for example: the biting and carbon residue rates of application examples 9 and 13 were reduced by 13-22% and 10-16%, respectively.
Application examples 14 to 20
The difference between the low-loss black hole microetching solution and the application example 1 is that the low-loss black hole microetching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: use condition comparison table of low-loss black hole microetching solution in application examples 14-20
| Group of | Low-loss black hole microetching 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 | From example 20 |
The low loss black hole microetching solutions obtained by the treatment processes in application examples 14 to 20 were used and tested for the biting amount um and carbon residue ratio according to the above-mentioned measurement steps and measurement standards, and the average value of the test results was recorded in the following table.
As can be seen from the above table, the low-loss black hole microetching solutions prepared in application examples 14-20 can effectively strip the black hole conductive material and reduce the risk of reversely sticking the black hole conductive material on the copper surface, and the biting amount is 0.9-1.0um; the carbon residue rate is 0.36-0.48%;
the dispersing agent prepared by mixing the components in the proportion can play a better role in surface activation and dispersion, and can be compounded with the copper-protecting component to reduce the polarity of the black hole conductive material, so that the phenomenon that the black hole conductive material is redeposited and accumulated on a copper surface is reduced.
In particular, the low-loss black hole microetching solution prepared in application examples 17-19 has better stripping effect, the biting amount is 0.9um, the carbon residue rate is 0.36-0.38%, and compared with application examples 1 and 14-15, the single use of any one of the dispersing agents is respectively reduced by 10% and 10-25%;
it can be seen that 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 in a weight ratio of 1 (1-2) to 6-8, the copper surface biting amount is small, and meanwhile, the black hole conductive material is thoroughly stripped, so that the PCB has excellent surface performance and good yield.
Application examples 21 to 23
The difference between the low-loss black hole microetching solution and the application example 1 is that the low-loss black hole microetching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: use condition comparison table of low-loss black hole microetching solution in application examples 21-23
| Group of | Low-loss black hole microetching liquid |
| Application example 21 | From example 21 |
| Application example 22 | From example 22 |
| Application example 23 | From example 23 |
The low loss black hole microetching solutions obtained by the treatment processes in application examples 21 to 23 were used and tested for the biting amount um and carbon residue ratio according to the above-mentioned measurement steps and measurement standards, and the average value of the test results was recorded in the following table.
As can be seen from the above table, the low-loss black hole microetching solutions prepared in application examples 21-23 can effectively strip the black hole conductive material and reduce the risk of reversely sticking the black hole conductive material on the copper surface, and the etching amount is only 0.8-1.0um; the carbon residue rate is only 0.46-0.52%;
therefore, the corrosion inhibitor of the components not only can slow down the biting of hydrogen peroxide on the copper surface so as to reduce the loss of the copper surface, but also is not easy to influence the stripping effect of the black hole conductive material after being compounded with the copper protection component, in addition, the protection effect of ethylenediamine tetraacetic acid on the copper surface is better, the biting amount of the copper surface can be further reduced, but the final stripping effect, especially the ethylenediamine tetraacetic acid sodium salt, is influenced to a certain extent, and the side effect is stronger, so that the corrosion inhibitor is generally compounded with citric acid for use.
Application examples 24 to 26
The difference between the low-loss black hole microetching solution and the application example 1 is that the low-loss black hole microetching solution is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: use condition comparison table of low-loss black hole microetching solution in application examples 24-26
| Group of | Low-loss black hole microetching liquid |
| Application example 24 | From example 24 |
| Application example 25 | From example 25 |
| Application example 26 | From example 26 |
The low loss black hole microetching solutions obtained by the treatment processes in the above application examples 24 to 26 were used, and the biting amount um and the carbon residue ratio thereof were measured according to the above measurement steps and measurement standards, and the average value of the measurement results was recorded in the following table.
As can be seen from the above table, the low-loss black hole microetching solutions prepared in application examples 24 to 26 can effectively strip the black hole conductive material and reduce the risk of reversely sticking the black hole conductive material on the copper surface, and the etching amount is only 1.0um; the carbon residue rate is only 0.46-0.50%; therefore, the hydrogen peroxide stabilizer of the components can not only slow down the decomposition of hydrogen peroxide to ensure the stripping effect of the black hole conductive material, but also reduce the phenomenon that the black hole conductive material is redeposited and accumulated on the copper surface by being compounded with the dispersing agent; in addition, the hydrogen peroxide stabilizer has a certain compounding effect among multiple components, particularly diethylene glycol methyl ethyl ether and triethylene glycol dimethyl ether, and the compounding effect is better, see application example 25.
The present embodiment is merely illustrative of the present application and is not intended to limit the present application, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but are protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. The low-loss black hole microetching solution is characterized by comprising the following components in percentage by weight: sulfuric acid 30-50% 2 O 2 8 to 10 per mill, 0.8 to 1.2 per mill of copper-protecting component, 1.0 to 2.0 per mill of dispersant, 0.8 to 1.5 per mill of corrosion inhibitor, 0.3 to 1.0 per mill of hydrogen peroxide stabilizer and the balance of water;
the copper-protecting component is one or more of dodecenyl succinic acid, monoethanolamine borate and triethanolamine borate.
2. The low-loss black hole microetching solution according to claim 1, wherein the copper-protecting component consists of dodecenyl succinic acid, monoethanolamine borate and triethanolamine borate in a weight ratio of 1 (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 2A1.
4. The low-loss black hole microetching solution according to claim 3, wherein the dispersing agent consists of BYK-346, BYK-163 and Dow 2A1 in a weight ratio of 1 (1-2): 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, ethylenediamine tetraacetic acid and ethylenediamine tetraacetic 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 a conductivity of less than 5us/cm.
8. A method for preparing the low-loss black hole microetching solution according to any one of claims 1 to 7, which is characterized by weighing sulfuric acid and H according to the proportion 2 O 2 And uniformly mixing the copper-protecting component, the dispersing agent, the corrosion inhibitor, the hydrogen peroxide stabilizer and the water.
9. Use of the low-loss black hole microetching solution according to any one of claims 1 to 7 in black hole microetching treatment, wherein the peeled black hole conductive material is not easily reversely stuck on the copper surface while the black hole conductive material on the copper surface can be effectively peeled off with low copper surface loss.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378270A (en) * | 1981-10-29 | 1983-03-29 | Learonal, Inc. | Method of etching circuit boards and recovering copper from the spent etch solutions |
| JP2005206859A (en) * | 2004-01-21 | 2005-08-04 | Ebara Udylite Kk | Method of producing member for electronic component |
| JP2006052425A (en) * | 2004-08-10 | 2006-02-23 | C Uyemura & Co Ltd | Soft-etching solution and plating method |
| CN109735845A (en) * | 2019-02-23 | 2019-05-10 | 上海富柏化工有限公司 | It is a kind of that hole is prevented to enclose the micro-corrosion liquid to whiten |
| CN110079804A (en) * | 2019-06-17 | 2019-08-02 | 广州三孚新材料科技股份有限公司 | Copper surface micro-etching agent and preparation method thereof |
| CN111206249A (en) * | 2020-03-28 | 2020-05-29 | 黄钟扬 | Chloride ion-resistant copper surface microetching agent and preparation method thereof |
| CN111349937A (en) * | 2020-03-20 | 2020-06-30 | 盐城维信电子有限公司 | Micro-etching solution for copper or copper alloy surface and treatment method thereof |
| CN112064026A (en) * | 2020-08-03 | 2020-12-11 | 罗山县金硕电子材料有限公司 | Novel copper surface roughness corrosion stabilizer and preparation method thereof |
| CN112877694A (en) * | 2020-12-31 | 2021-06-01 | 南通赛可特电子有限公司 | Micro-etching solution for treating copper surface |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6464578B2 (en) * | 2013-08-01 | 2019-02-06 | 三菱瓦斯化学株式会社 | Method for manufacturing printed wiring board |
-
2022
- 2022-03-10 CN CN202210235760.5A patent/CN114574863B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378270A (en) * | 1981-10-29 | 1983-03-29 | Learonal, Inc. | Method of etching circuit boards and recovering copper from the spent etch solutions |
| JP2005206859A (en) * | 2004-01-21 | 2005-08-04 | Ebara Udylite Kk | Method of producing member for electronic component |
| JP2006052425A (en) * | 2004-08-10 | 2006-02-23 | C Uyemura & Co Ltd | Soft-etching solution and plating method |
| CN109735845A (en) * | 2019-02-23 | 2019-05-10 | 上海富柏化工有限公司 | It is a kind of that hole is prevented to enclose the micro-corrosion liquid to whiten |
| CN110079804A (en) * | 2019-06-17 | 2019-08-02 | 广州三孚新材料科技股份有限公司 | Copper surface micro-etching agent and preparation method thereof |
| CN111349937A (en) * | 2020-03-20 | 2020-06-30 | 盐城维信电子有限公司 | Micro-etching solution for copper or copper alloy surface and treatment method thereof |
| CN111206249A (en) * | 2020-03-28 | 2020-05-29 | 黄钟扬 | Chloride ion-resistant copper surface microetching agent and preparation method thereof |
| CN112064026A (en) * | 2020-08-03 | 2020-12-11 | 罗山县金硕电子材料有限公司 | Novel copper surface roughness corrosion stabilizer and preparation method thereof |
| CN112877694A (en) * | 2020-12-31 | 2021-06-01 | 南通赛可特电子有限公司 | Micro-etching solution for treating copper surface |
Non-Patent Citations (1)
| Title |
|---|
| 印制线路板内层黑氧化前处理微蚀液的研制;麦裕良;张小春;栾安博;;电镀与涂饰(第01期) * |
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