CN114214677A - Acidic copper plating deep hole agent, preparation method thereof and electroplating method - Google Patents
Acidic copper plating deep hole agent, preparation method thereof and electroplating method Download PDFInfo
- Publication number
- CN114214677A CN114214677A CN202111683286.4A CN202111683286A CN114214677A CN 114214677 A CN114214677 A CN 114214677A CN 202111683286 A CN202111683286 A CN 202111683286A CN 114214677 A CN114214677 A CN 114214677A
- Authority
- CN
- China
- Prior art keywords
- copper plating
- copper
- deep hole
- electroplating
- acidic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000010949 copper Substances 0.000 title claims abstract description 167
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 167
- 238000007747 plating Methods 0.000 title claims abstract description 165
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 72
- 238000009713 electroplating Methods 0.000 title claims abstract description 62
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229920006295 polythiol Polymers 0.000 claims abstract description 10
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 44
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 23
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QUOQRPBNPNXNQE-UHFFFAOYSA-N naphthalen-2-yl propane-1-sulfonate Chemical compound CCCS(=O)(=O)Oc1ccc2ccccc2c1 QUOQRPBNPNXNQE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001431 copper ion Inorganic materials 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 description 28
- 239000010959 steel Substances 0.000 description 28
- 239000002253 acid Substances 0.000 description 15
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000005536 corrosion prevention Methods 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- -1 β -naphthol propane sulfonic acid sodium salt Chemical compound 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses an acidic copper plating deep hole agent, a preparation method thereof and an electroplating method, wherein the preparation method comprises the following steps: and mixing the aqueous solution of sodium naphthol sulfonate with the aqueous solution of polythiol, and reacting to obtain the acidic copper plating deep hole agent. The acidic copper plating deep hole agent prepared by the preparation method provided by the invention can improve the adsorption capacity to copper ions, improve the current efficiency of a copper plating low-electricity area and the deep plating capacity of the low-electricity area, and improve the consistency of a copper plating layer, so that the anti-corrosion capacity of the low-electricity area is improved, and the problems of poor consistency and poor anti-corrosion capacity of the copper plating layer in the inner cavity of a deep hole product, which are obtained by the conventional electroplating process and electroplating liquid, are effectively solved. The electroplating method provided by the invention has simple process, does not need complex additives, and realizes electroplating of deep-hole products to be plated with copper on the basis of ensuring fine crystallization and corrosion resistance of the plating layer.
Description
Technical Field
The invention relates to the field of electroplating, in particular to an acidic copper plating deep hole agent, a preparation method thereof and an electroplating method.
Background
In the current society, the autonomous production of large-scale equipment and reliable products is continuously promoted, and the requirements of partial products on the surface treatment of deep-hole parts are higher and higher. For example, in the circuit board industry, electroplating of blind holes or through holes is a common method. However, the existing deep-hole part copper plating process has various additives and complex operation process, and the deep-hole product obtained by adopting the existing electroplating process and electroplating solution has poor consistency of the copper plating layer in the inner cavity and poor corrosion resistance.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an acidic copper plating deep hole agent, a preparation method thereof and an electroplating method, and aims to solve the problems of poor consistency and poor corrosion resistance of a copper plating layer in a cavity of a deep hole product obtained by adopting the existing electroplating process and electroplating solution.
The technical scheme of the invention is as follows:
the invention provides a preparation method of an acidic copper plating deep hole agent, which comprises the following steps:
and mixing the aqueous solution of sodium naphthol sulfonate with the aqueous solution of polythiol, and reacting to obtain the acidic copper plating deep hole agent.
Optionally, the mass ratio of the sodium naphthol sulfonate to the polythiol is (95-100): (1-5).
Alternatively, the sodium naphthol sulfonate is selected from sodium β -naphthol propane sulfonate and the polythiol is selected from 2, 2' -dithiodiethanol.
Optionally, the mass ratio of the sodium beta-naphthol propane sulfonate to the 2, 2' -dithiodiethanol is 98: 2.
Optionally, the reaction temperature is 100 ℃ and the reaction time is 30-50 min.
In a second aspect of the invention, an acidic copper plating deep hole agent is provided, wherein the acid copper plating deep hole agent is prepared by the preparation method.
In a third aspect of the present invention, there is provided an electroplating method, comprising the steps of:
placing a product to be plated with copper in an aqueduct containing copper plating solution;
the acid copper plating deep hole agent is added into the copper plating solution, and the current is switched on for electroplating.
Optionally, the copper plating solution comprises the following components in concentration:
200-220g/L of copper sulfate, 65-70g/L of sulfuric acid, 80-120ppm of chloride ions and the balance of water.
Optionally, the acidic copper plating deep hole agent is added into the copper plating solution according to the proportion that each liter of copper plating solution contains 5-10g of acidic copper plating deep hole agent.
Optionally, the electroplating temperature is 25-30 ℃, the pH value is 1-1.5, and the current density is 2-4A/dm2。
Has the advantages that: the acid copper plating deep hole agent prepared by the preparation method provided by the invention can improve the adsorption capacity to copper ions, improve the current efficiency of a copper plating low-electricity area and the deep plating capacity of the low-electricity area, and has good consistency of a copper plating layer and fine crystallization of the copper plating layer, thereby improving the corrosion resistance of the low-electricity area and effectively solving the problems of poor consistency and poor corrosion resistance of the copper plating layer in the inner cavity of a deep hole product obtained by the existing electroplating process and electroplating liquid.
Drawings
FIG. 1 is a flow chart of a plating method in an embodiment of the present invention.
Detailed Description
The invention provides an acid copper plating deep hole agent, a preparation method thereof and an electroplating method, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The existing deep-hole part copper plating process has various additives and complex operation process, and the deep-hole product obtained by adopting the existing electroplating process and electroplating solution has poor consistency of the copper plating layer in the inner cavity and poor corrosion resistance. Based on this, the embodiment of the invention provides a preparation method of an acidic copper plating deep hole agent, which comprises the following steps:
and mixing the aqueous solution of sodium naphthol sulfonate with the aqueous solution of polythiol, and reacting to obtain the acidic copper plating deep hole agent.
The acidic copper-plating deep hole agent prepared by the preparation method provided by the embodiment can improve the adsorption capacity to copper ions, the current efficiency of a copper-plating low-electricity area and the deep plating capacity of the low-electricity area, the copper plating layer has good consistency, the copper plating layer has fine crystallization, so that the corrosion resistance of the low-electricity area is improved, and the problems of poor consistency and poor corrosion resistance of the copper plating layer in the inner cavity of a deep hole product obtained by the existing electroplating process and electroplating liquid can be effectively solved through a salt spray test.
In one embodiment, the mass ratio of the sodium naphthol sulfonate to the polythiol is (95 to 100): (1-5).
In one embodiment, the sodium naphthol sulfonate is selected from sodium β -naphthol propane sulfonate and the polythiol is selected from 2, 2' -dithiodiethanol, but is not limited thereto. In the present embodiment, the acidic copper plating drilling agent is obtained by mixing an aqueous solution of β -naphthol propane sulfonic acid sodium salt with an aqueous solution of 2, 2' -dithiodiethanol and then reacting the mixture.
In one embodiment, the mass ratio of the sodium β -naphthol propane sulfonate to the 2, 2' -dithiodiethanol is 98: 2.
In one embodiment, the reaction is carried out at 100 ℃ for 30-50 min. In the specific implementation, the aqueous solution of the beta-naphthol sodium propane sulfonate and the aqueous solution of the 2, 2' -dithiodiethanol are mixed and then react for 30min at the temperature of 100 ℃, and the acidic copper plating deep hole agent is obtained after the reaction.
In one embodiment, the sodium beta-naphthol propane sulfonate may be selected from one or more of sodium beta-naphthol-4-propane sulfonate, sodium beta-naphthol-5-propane sulfonate, sodium beta-naphthol-6-propane sulfonate, sodium beta-naphthol-7-propane sulfonate.
The embodiment of the invention also provides an acidic copper plating deep hole agent, wherein the acid copper plating deep hole agent is prepared by the preparation method of the embodiment of the invention. In the embodiment, the acidic copper plating deep hole agent can be used as a polysulfide surfactant to improve the adsorption capacity of copper ions, so that copper layer lattices can grow normally during copper plating, the quality of a plating layer is improved, the current efficiency of a copper plating low-voltage area and the deep plating capacity of the low-voltage area are improved, the consistency of the copper plating layer is good, the corrosion resistance of the low-voltage area is improved, and the problems of poor consistency and poor corrosion resistance of the copper plating layer in the inner cavity of a deep hole product obtained by adopting the conventional electroplating process and electroplating liquid are effectively solved.
The embodiment of the invention also provides an electroplating method, which comprises the following steps:
s1, placing the product to be plated with copper in an aqueduct containing copper plating solution;
and S2, adding the acidic copper plating deep hole agent into the copper plating solution, and switching on the current to carry out electroplating.
The electroplating method provided by the embodiment has a simple process, does not need complex additives, and realizes electroplating of deep-hole products to be plated with copper on the basis of ensuring fine crystallization and corrosion resistance of the plating layer.
Before step S1, the method further includes the steps of pretreating the copper product to be plated by spraying, rinsing, acid degreasing, washing and the like. Specifically, a suitable pretreatment process is selected according to actual needs.
In step S1, the product to be plated with copper may be, but is not limited to, a hole-filling circuit board to be plated with copper, a package substrate, a metal member, a metal tube, etc.
In one embodiment, the copper plating solution comprises the following concentrations of components:
200-220g/L of copper sulfate, 65-70g/L of sulfuric acid, 80-120ppm of chloride ions and the balance of water.
That is, the concentration of copper sulfate is 200-220g/L, the concentration of sulfuric acid is 65-70g/L, and the concentration of chloride ion is 80-120ppm based on the copper plating solution.
In the copper plating solution, copper sulfate provides copper ions, and the phenomenon of scorching is easily caused in a high current density area due to the low content of the copper ions; when the copper ion is too high, the copper sulfate is easy to crystallize out, therefore, the preferred concentration of the copper sulfate is 200-220 g/L.
The sulfuric acid plays a conductive role in the copper plating solution, and the bath voltage can be increased and is easy to be burnt due to the low sulfuric acid content; the sulfuric acid content is too high, and the anode is easy to passivate, so that the preferable concentration of the sulfuric acid is 65-70 g/L.
The chlorine ions are used for catalysis, the content of the chlorine ions is too low, the coating is easy to have stripes in a high and medium current area, and has mist deposition in a low current area; too high a level of chloride ions, reduced brightness and fill level, copper chloride formation on the anode, causing anode passivation and increased cell voltage, thus, a preferred concentration of chloride ions is 80-120 ppm.
In one embodiment, the copper plating solution comprises the following concentrations of components:
220g/L of copper sulfate 205-. In this embodiment, a jar opener may also be added as needed. The specific components of the jar opener are not limited, and the jar opener in the prior art can be selected according to actual needs.
In one embodiment, the product to be plated with copper is placed in an aqueduct containing copper plating solution as a cathode, and phosphorus copper is used as an anode.
In step S2, the acidic copper-plating deep hole agent is the acidic copper-plating deep hole agent according to the above embodiment of the present invention.
In one embodiment, the acidic copper plating longhole agent is added to the copper plating bath in a proportion of 5 to 10 grams of acidic copper plating longhole agent per liter of copper plating bath. That is, 5-10g of acidic copper plating deep hole agent is added into one liter of copper plating solution containing 200-220g/L of copper sulfate, 65-70g/L of sulfuric acid, 80-120ppm of chloride ions and the balance of water.
In one embodiment, the electroplating is carried out at a temperature of 25-30 deg.C, a pH of 1-1.5, and a current density of 2-4A/dm2。
The invention is further illustrated by the following specific examples.
Example 1
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-4-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-4-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 200g/L, the concentration of sulfuric acid is 65g/L, the concentration of chloride ions is 80ppm, and the concentration of the cylinder opening agent is 5 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the blind hole depth of 50mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 5g of acidic copper plating deep hole agent into each liter of copper plating solution, connecting current, and electroplating (electroplating temperature is 25 deg.C, pH value is 1, and current density is 2A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
Example 2
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-5-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-5-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 220g/L, the concentration of sulfuric acid is 70g/L, the concentration of chloride ions is 120ppm, and the concentration of the cylinder opening agent is 10 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the blind hole depth of 55mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 10g of acidic copper plating deep hole agent into each liter of copper plating solution, connecting current, and electroplating (the electroplating temperature is 25 ℃, the pH value is 1.2, and the current density is 2A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
Example 3
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-6-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-6-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 210g/L, the concentration of sulfuric acid is 70g/L, the concentration of chloride ions is 100ppm, and the concentration of the cylinder opening agent is 8 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the depth of a blind hole of 65mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 8g of acidic copper plating deep hole agent into each liter of copper plating solutionAdding the acid copper plating deep hole agent into the copper plating solution, switching on current, and electroplating (the electroplating temperature is 25 ℃, the pH value is 1.5, and the current density is 2A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
Example 4
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-7-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-7-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 200g/L, the concentration of sulfuric acid is 65g/L, the concentration of chloride ions is 80ppm, and the concentration of the cylinder opening agent is 9 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the blind hole depth of 50mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 5g of acidic copper plating deep hole agent into each liter of copper plating solution, connecting current, and electroplating (electroplating temperature is 25 deg.C, pH is 1.2, and current density is 2A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
Example 5
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-7-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-7-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 210g/L, the concentration of sulfuric acid is 70g/L, the concentration of chloride ions is 90ppm, and the concentration of the cylinder opening agent is 10 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the blind hole depth of 60mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 5g of acidic copper plating deep hole agent into each liter of copper plating solution, connecting current, and electroplating (the electroplating temperature is 25 ℃, the pH value is 1, and the current density is 3A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
Example 6
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-4-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-4-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 210g/L, the concentration of sulfuric acid is 73g/L, the concentration of chloride ions is 90ppm, and the concentration of the cylinder opening agent is 6 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the blind hole depth of 60mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 7g of acidic copper plating deep hole agent into each liter of copper plating solution, connecting current, and electroplating (the electroplating temperature is 25 ℃, the pH value is 1.2, and the current density is 3A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
Example 7
Preparing an acidic copper plating deep hole agent:
according to the proportion of sodium beta-naphthol-5-propane sulfonate: and 2,2 '-dithiodiethanol (98: 2) by mass, mixing an aqueous solution of beta-naphthol-5-propanesulfonic acid sodium salt with the mass concentration of 10% with 2, 2' -dithiodiethanol with the mass concentration of 10%, and reacting at the temperature of 100 ℃ for 30min to obtain the acidic copper plating deep hole agent.
Preparing a copper plating solution:
copper sulfate, sulfuric acid, chloride ions, a cylinder opening agent and pure water are fully mixed, so that the concentration of copper sulfate in the copper plating solution is 215g/L, the concentration of sulfuric acid is 73g/L, the concentration of chloride ions is 110ppm, and the concentration of the cylinder opening agent is 10 g/L.
The electroplating method comprises the following steps:
sequentially carrying out spraying, rinsing, acid oil removal and water washing treatment processes on a steel pipe (with the blind hole depth of 60mm) to be plated with copper to obtain a steel pipe with a clean surface to be plated with copper;
placing the steel pipe with clean surface to be plated with copper in the aqueduct containing the copper plating solution as a cathode;
adding 8g of acidic copper plating deep hole agent into each liter of copper plating solution, connecting current, and electroplating (the electroplating temperature is 25 ℃, the pH value is 1.2, and the current density is 2.5A/dm)2And the anode is phosphor copper).
The embodiment can ensure that deep plating is realized on a steel pipe with a deep hole, the consistency of the copper plating layer is good, the plating rate on the inner hole is 100%, and no rust spot exists after 48 hours when a salt spray test is carried out, so that the corrosion prevention requirement of a product is met.
In conclusion, the acid copper plating deep hole agent prepared by the preparation method provided by the invention can improve the adsorption capacity to copper ions, improve the current efficiency of a copper plating low-voltage area and the deep plating capacity of the low-voltage area, and has good consistency of a copper plating layer, so that the corrosion resistance of the low-voltage area is improved, and the problems of poor consistency and poor corrosion resistance of the copper plating layer in the inner cavity of a deep hole product obtained by the conventional electroplating process and electroplating liquid are effectively solved. The electroplating method provided by the invention has simple process, does not need complex additives, and realizes electroplating of deep-hole products to be plated with copper on the basis of ensuring fine crystallization and corrosion resistance of the plating layer.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the acidic copper plating deep hole agent is characterized by comprising the following steps:
and mixing the aqueous solution of sodium naphthol sulfonate with the aqueous solution of polythiol, and reacting to obtain the acidic copper plating deep hole agent.
2. The method of claim 1, wherein the mass ratio of sodium naphthol sulfonate to polythiol is (95-100): (1-5).
3. The method of claim 1 wherein said sodium naphthol sulfonate is selected from the group consisting of sodium β -naphthol propane sulfonate and said polythiol is selected from the group consisting of 2, 2' -dithiodiethanol.
4. The method of claim 3, wherein the mass ratio of the sodium beta-naphthol propane sulfonate to the 2, 2' -dithiodiethanol is 98: 2.
5. The method for preparing the acidic copper-plating deep hole agent according to claim 4, wherein the reaction temperature is 100 ℃ and the reaction time is 30-50 min.
6. An acidic copper plating deep hole agent, characterized by being prepared by the preparation method according to any one of claims 1 to 5.
7. An electroplating method, comprising the steps of:
placing a product to be plated with copper in an aqueduct containing copper plating solution;
adding the acidic copper plating deep hole agent of claim 6 into the copper plating solution, and switching on the current to carry out electroplating.
8. The plating method according to claim 7, wherein the copper plating solution comprises the following components in concentrations:
200-220g/L of copper sulfate, 65-70g/L of sulfuric acid, 80-120ppm of chloride ions and the balance of water.
9. An electroplating method according to claim 8, wherein the acidic copper plating bath is added with an acidic copper plating bath in a proportion of 5 to 10g of the acidic copper plating bath per liter of the copper plating bath.
10. The electroplating method according to claim 9, wherein the electroplating is carried out at a temperature of 25 to 30 ℃, a pH of 1 to 1.5, and a current density of 2 to 4A/dm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111683286.4A CN114214677A (en) | 2021-12-30 | 2021-12-30 | Acidic copper plating deep hole agent, preparation method thereof and electroplating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111683286.4A CN114214677A (en) | 2021-12-30 | 2021-12-30 | Acidic copper plating deep hole agent, preparation method thereof and electroplating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114214677A true CN114214677A (en) | 2022-03-22 |
Family
ID=80707687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111683286.4A Pending CN114214677A (en) | 2021-12-30 | 2021-12-30 | Acidic copper plating deep hole agent, preparation method thereof and electroplating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114214677A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220709A (en) * | 1996-05-30 | 1999-06-23 | 恩索恩Omi公司 | Alkoxylated dimercaptans as copper additives |
| US20110030785A1 (en) * | 2009-08-04 | 2011-02-10 | Precursor Energetics, Inc. | Methods and materials for caigas aluminum-containing photovoltaics |
| WO2013157639A1 (en) * | 2012-04-19 | 2013-10-24 | ディップソール株式会社 | Copper-nickel alloy electroplating bath and plating method |
| CN105040047A (en) * | 2015-07-21 | 2015-11-11 | 安徽江威精密制造有限公司 | Sliver-plating electroplate liquid and preparation method thereof |
| CN109851774A (en) * | 2018-12-26 | 2019-06-07 | 温州大学 | One kind amphiphilic polymer of polyethylene glycol groups containing cystine linkage and preparation method thereof and purposes |
| CN111373077A (en) * | 2017-09-15 | 2020-07-03 | 上村工业株式会社 | Sn or Sn alloy plating solution and method for producing Sn or Sn alloy plating |
-
2021
- 2021-12-30 CN CN202111683286.4A patent/CN114214677A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220709A (en) * | 1996-05-30 | 1999-06-23 | 恩索恩Omi公司 | Alkoxylated dimercaptans as copper additives |
| US20110030785A1 (en) * | 2009-08-04 | 2011-02-10 | Precursor Energetics, Inc. | Methods and materials for caigas aluminum-containing photovoltaics |
| WO2013157639A1 (en) * | 2012-04-19 | 2013-10-24 | ディップソール株式会社 | Copper-nickel alloy electroplating bath and plating method |
| CN105040047A (en) * | 2015-07-21 | 2015-11-11 | 安徽江威精密制造有限公司 | Sliver-plating electroplate liquid and preparation method thereof |
| CN111373077A (en) * | 2017-09-15 | 2020-07-03 | 上村工业株式会社 | Sn or Sn alloy plating solution and method for producing Sn or Sn alloy plating |
| CN109851774A (en) * | 2018-12-26 | 2019-06-07 | 温州大学 | One kind amphiphilic polymer of polyethylene glycol groups containing cystine linkage and preparation method thereof and purposes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111945192B (en) | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board | |
| CN105200467B (en) | A kind of Gravure hard copper additive and plating solution | |
| CN104498946A (en) | Steel plate surface phosphatization method | |
| CN102080241A (en) | Low-concentration weakly alkaline cyanide-free copper plating and bath solution preparing method | |
| CN104195487A (en) | On-batch steel hot galvanizing environment-friendly type multi-effect galvanization helping liquid and use method thereof | |
| CN102758228A (en) | Sulfonic acid type semi-bright pure tin electroplating solution | |
| CN112593219B (en) | Solution for direct electroless copper plating of aluminum substrates and application method thereof | |
| CN103695881B (en) | Room temperature is without slag fast bonderizing liquor and preparation method thereof | |
| CN104562107A (en) | Highly-corrosion-resistant environment-friendly black tin-cobalt alloy electroplating liquid and electroplating method thereof. | |
| CN107190288B (en) | Preparation method of HEDP copper-plated pore-free thin layer | |
| CN114214677A (en) | Acidic copper plating deep hole agent, preparation method thereof and electroplating method | |
| CN105369305A (en) | A copper-nickel alloy electroplating solution and an electroplating method thereof | |
| CN115522238B (en) | Cyanide-free gold electroplating solution of sodium gold sulfite and electroplating process thereof | |
| CN107227472A (en) | A kind of engineering super-hydrophobic coat of metal and preparation method thereof | |
| CN100362141C (en) | Propanetriol non-cyanide bright copper plating liquid | |
| CN106011824A (en) | Environment-friendly passivating solution used for mechanical plating | |
| CN104911655A (en) | Electroplating solution with excellent performance | |
| CN215103561U (en) | High corrosion resistance coating structure of iron casting galvanized iron alloy | |
| CN110079842B (en) | Potassium chloride cadmium cobalt alloy plating solution, preparation method and electroplating process thereof | |
| CN110904473B (en) | 5G antenna environment-friendly copper plating process | |
| TWI645078B (en) | Functional chromium layer with improved corrosion resistance | |
| CN102206840B (en) | Alkaline chloride copper-plating treatment agent and preparation method thereof | |
| EP1580304B1 (en) | Tin plating electrolyte composition and method for electroplating surfaces with tin | |
| KR100321374B1 (en) | METHOD FOR MANUFACTURING Zn/Fe ALLOY ELECTROPLATED STEEL SHEET EXCELLENT IN PLATING ADHESION, SURFACE ROUGHNESS AND APPEARANCE | |
| CN104962960A (en) | Copper electroplating liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220322 |
|
| RJ01 | Rejection of invention patent application after publication |