CN111088509A - Acidic copper plating additive and preparation method thereof - Google Patents
Acidic copper plating additive and preparation method thereof Download PDFInfo
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- CN111088509A CN111088509A CN202010051253.7A CN202010051253A CN111088509A CN 111088509 A CN111088509 A CN 111088509A CN 202010051253 A CN202010051253 A CN 202010051253A CN 111088509 A CN111088509 A CN 111088509A
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- copper plating
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- 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
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Abstract
The invention discloses an acidic copper plating additive which is prepared from the following raw materials in parts by weight: primary complexes, secondary complexes, surfactants, and other additives; the main complex is sodium polydithio-dipropyl sulfosulfonate; the auxiliary complex is 2-mercapto benzimidazole copper salt; the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.35 to 0.45; the other additive is 5-methylbenzotriazole. The acidic copper plating additive can greatly improve the plating adhesion of a copper plated product, remarkably improve the corrosion resistance, improve the glossiness and enable the surface to be smooth and bright.
Description
Technical Field
The invention relates to the technical field of additives for electroplating, in particular to an acidic copper plating additive and a preparation method thereof.
Background
Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by using the principle of electrolysis, and is a process of attaching a layer of metal film on the surface of a metal or other material product by using the action of electrolysis, thereby having the effects of preventing metal oxidation (such as corrosion), improving wear resistance, conductivity, light reflection, corrosion resistance (such as copper sulfate and the like), enhancing the appearance and the like.
Copper electroplating is the most prominent method for achieving electrical interconnections in electronic products, and organic additives are commonly used to achieve uniform conductive patterns and to obtain coatings with good properties. The present copper electroplating additive for manufacturing printed circuit boards mainly comprises: three of the most important components, accelerator, inhibitor and leveler. The accelerator can accelerate the deposition of copper, the inhibitor and the leveling agent mainly have the functions of improving the overpotential of the deposition of copper, refining grains and improving the uniform plating capacity of plating solution, and a uniform and bright plating layer can be obtained through the synergistic effect of the three additives.
Chinese patent CN104630837A discloses an electroplating solution and an electroplating method for acidic copper plating of an anthrone dye system, wherein the electroplating additive comprises chloride ions, anthrone dye, dimethyl phthalein amidosulfonate, polyethylene glycol, polyethylene imine alkyl compound and polyethylene imine alkyl salt, the allowable electroplating solution temperature is 15-40 ℃, and the average electrolytic current density is 15-40 mA/cm 2. In addition, in order to consider the aspects of the appearance, the mechanical property and the like of the copper foil, the components of the additive applied in industry are complex, Chinese patent CN101302635A discloses a pre-plating additive for a copper plating process, the pre-plating additive comprises two parts of a main light-emitting agent and a light-assisting agent, the pre-plating additive is difficult to regulate and control in the production process, and once the proportion of the additive is out of order, purification and re-feeding are possibly needed.
However, the copper plating additives currently used have the following problems:
1. the performance of the plated layer is not improved well, such as the corrosion resistance is not good enough and the glossiness is low;
2. the performance of the electroplating solution is not improved well.
Based on the situation, the invention provides an acidic copper plating additive and a preparation method thereof, which can effectively solve the problems.
Disclosure of Invention
The invention aims to provide an acidic copper plating additive and a preparation method thereof. The acidic copper plating additive can greatly improve the plating adhesion of a copper plated product, remarkably improve the corrosion resistance, improve the glossiness and enable the surface to be smooth and bright.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an acidic copper plating additive is prepared from the following raw materials in parts by weight:
primary complexes, secondary complexes, surfactants, and other additives;
the main complex is sodium polydithio-dipropyl sulfosulfonate;
the auxiliary complex is 2-mercapto benzimidazole copper salt;
the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.35 to 0.45;
the other additive is 5-methylbenzotriazole.
The acidic copper plating additive can greatly improve the plating adhesion of a copper plated product, remarkably improve the corrosion resistance, improve the glossiness and enable the surface to be smooth and bright.
Preferably, the dosage of the acidic copper plating additive is that the content of each raw material in each liter of electrogalvanizing plating solution is respectively as follows: 10-20 mg/L of main complex, 4-8 mg/L of auxiliary complex, 45-75 mg/L of surfactant and 8-13 mg/L of other additives.
Preferably, the dosage of the acidic copper plating additive is that the content of each raw material in each liter of electrogalvanizing plating solution is respectively as follows: 12-18 mg/L of main complex, 5-7.2 mg/L of auxiliary complex, 50-68 mg/L of surfactant and 9-12 mg/L of other additives.
Preferably, the dosage of the acidic copper plating additive is that the content of each raw material in each liter of electrogalvanizing plating solution is respectively as follows: 14mg/L of main complex, 6.1mg/L of auxiliary complex, 60mg/L of surfactant and 10.7mg/L of other additives.
Preferably, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 3.5-5.
Preferably, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 4-4.5.
The invention also provides a preparation method of the acidic copper plating additive, which comprises the following steps:
A. respectively calculating the addition amount of each raw material of the acidic copper plating additive according to the total volume of the electrolytic copper plating solution;
B. and weighing each raw material of the acidic copper plating additive according to the calculation result for later use, wherein the sum of the raw materials of the acidic copper plating additive is the acidic copper plating additive.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the acidic copper plating additive can greatly improve the plating adhesion of a copper plated product, remarkably improve the corrosion resistance, improve the glossiness and enable the surface to be smooth and bright.
The acidic copper plating additive disclosed by the invention is prepared by selecting raw materials and optimizing the content of each raw material, and the optimal formula is as follows: the dosage of the acidic copper plating additive is that each liter of electrogalvanizing plating solution contains the following raw materials: 14mg/L of main complex, 6.1mg/L of auxiliary complex, 60mg/L of surfactant and 10.7mg/L of other additives; the main complex is sodium polydithio-dipropyl sulfosulfonate; the auxiliary complex is 2-mercapto benzimidazole copper salt; the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.35 to 0.45; the other additive is 5-methylbenzotriazole. After the copper is added, copper is plated, the adhesion (ISO) grade of the obtained product coating (the thickness is 10 mu m) can reach 2, and the product coating has no corrosion after a salt spray test for more than 800 hours; the glossiness of the plating layer can reach 362 Gs; and the performances of the galvanizing plating solution such as current efficiency, dispersibility and the like are all improved well.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
Example 1:
an acidic copper plating additive is prepared from the following raw materials in parts by weight:
primary complexes, secondary complexes, surfactants, and other additives;
the main complex is sodium polydithio-dipropyl sulfosulfonate;
the auxiliary complex is 2-mercapto benzimidazole copper salt;
the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.35 to 0.45;
the other additive is 5-methylbenzotriazole.
Preferably, the dosage of the acidic copper plating additive is that the content of each raw material in each liter of electrogalvanizing plating solution is respectively as follows: 10-20 mg/L of main complex, 4-8 mg/L of auxiliary complex, 45-75 mg/L of surfactant and 8-13 mg/L of other additives.
Preferably, the dosage of the acidic copper plating additive is that the content of each raw material in each liter of electrogalvanizing plating solution is respectively as follows: 12-18 mg/L of main complex, 5-7.2 mg/L of auxiliary complex, 50-68 mg/L of surfactant and 9-12 mg/L of other additives.
Preferably, the dosage of the acidic copper plating additive is that the content of each raw material in each liter of electrogalvanizing plating solution is respectively as follows: 14mg/L of main complex, 6.1mg/L of auxiliary complex, 60mg/L of surfactant and 10.7mg/L of other additives.
Preferably, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 3.5-5.
Preferably, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 4-4.5.
The invention also provides a preparation method of the acidic copper plating additive, which comprises the following steps:
A. respectively calculating the addition amount of each raw material of the acidic copper plating additive according to the total volume of the electrolytic copper plating solution;
B. and weighing each raw material of the acidic copper plating additive according to the calculation result for later use, wherein the sum of the raw materials of the acidic copper plating additive is the acidic copper plating additive.
Example 2:
an acidic copper plating additive is prepared from the following raw materials in parts by weight:
primary complexes, secondary complexes, surfactants, and other additives;
the main complex is sodium polydithio-dipropyl sulfosulfonate;
the auxiliary complex is 2-mercapto benzimidazole copper salt;
the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.35;
the other additive is 5-methylbenzotriazole.
In this embodiment, the amount of the acidic copper plating additive is, per liter of the electrogalvanizing plating solution, the content of each raw material is: 12mg/L of main complex, 5mg/L of auxiliary complex, 50mg/L of surfactant and 9mg/L of other additives.
In this embodiment, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to be 4.
In this embodiment, the method for preparing the acidic copper plating additive comprises the following steps:
A. respectively calculating the addition amount of each raw material of the acidic copper plating additive according to the total volume of the electrolytic copper plating solution;
B. and weighing each raw material of the acidic copper plating additive according to the calculation result for later use, wherein the sum of the raw materials of the acidic copper plating additive is the acidic copper plating additive.
Example 3:
an acidic copper plating additive is prepared from the following raw materials in parts by weight:
primary complexes, secondary complexes, surfactants, and other additives;
the main complex is sodium polydithio-dipropyl sulfosulfonate;
the auxiliary complex is 2-mercapto benzimidazole copper salt;
the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.45 of;
the other additive is 5-methylbenzotriazole.
In this embodiment, the amount of the acidic copper plating additive is, per liter of the electrogalvanizing plating solution, the content of each raw material is: 18mg/L of main complex, 7.2mg/L of auxiliary complex, 68mg/L of surfactant and 12mg/L of other additives.
In this embodiment, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 4.5.
In this embodiment, the method for preparing the acidic copper plating additive comprises the following steps:
A. respectively calculating the addition amount of each raw material of the acidic copper plating additive according to the total volume of the electrolytic copper plating solution;
B. and weighing each raw material of the acidic copper plating additive according to the calculation result for later use, wherein the sum of the raw materials of the acidic copper plating additive is the acidic copper plating additive.
Example 4:
an acidic copper plating additive is prepared from the following raw materials in parts by weight:
primary complexes, secondary complexes, surfactants, and other additives;
the main complex is sodium polydithio-dipropyl sulfosulfonate;
the auxiliary complex is 2-mercapto benzimidazole copper salt;
the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.42;
the other additive is 5-methylbenzotriazole.
In this embodiment, the amount of the acidic copper plating additive is, per liter of the electrogalvanizing plating solution, the content of each raw material is: 14mg/L of main complex, 6.1mg/L of auxiliary complex, 60mg/L of surfactant and 10.7mg/L of other additives.
In this embodiment, hydrochloric acid is also included; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to be 4.2.
In this embodiment, the method for preparing the acidic copper plating additive comprises the following steps:
A. respectively calculating the addition amount of each raw material of the acidic copper plating additive according to the total volume of the electrolytic copper plating solution;
B. and weighing each raw material of the acidic copper plating additive according to the calculation result for later use, wherein the sum of the raw materials of the acidic copper plating additive is the acidic copper plating additive.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (7)
1. The acidic copper plating additive is characterized by being prepared from the following raw materials in parts by weight:
primary complexes, secondary complexes, surfactants, and other additives;
the main complex is sodium polydithio-dipropyl sulfosulfonate;
the auxiliary complex is 2-mercapto benzimidazole copper salt;
the surfactant is a mixture of phenethyl phenol polyoxyethylene ether and 2-mercaptobenzimidazole, wherein the molar ratio of the phenethyl phenol polyoxyethylene ether to the 2-mercaptobenzimidazole is 1: 0.35 to 0.45;
the other additive is 5-methylbenzotriazole.
2. The acidic copper plating additive according to claim 1, wherein the amount of the acidic copper plating additive is, per liter of the electrogalvanizing plating solution, the content of each raw material is: 10-20 mg/L of main complex, 4-8 mg/L of auxiliary complex, 45-75 mg/L of surfactant and 8-13 mg/L of other additives.
3. The acidic copper plating additive according to claim 1, wherein the amount of the acidic copper plating additive is, per liter of the electrogalvanizing plating solution, the content of each raw material is: 12-18 mg/L of main complex, 5-7.2 mg/L of auxiliary complex, 50-68 mg/L of surfactant and 9-12 mg/L of other additives.
4. The acidic copper plating additive according to claim 1, wherein the amount of the acidic copper plating additive is, per liter of the electrogalvanizing plating solution, the content of each raw material is: 14mg/L of main complex, 6.1mg/L of auxiliary complex, 60mg/L of surfactant and 10.7mg/L of other additives.
5. The acidic copper plating additive of claim 1 further comprising hydrochloric acid; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 3.5-5.
6. The acidic copper plating additive of claim 1 further comprising hydrochloric acid; and the hydrochloric acid is used for adjusting the pH value of the electrogalvanizing plating solution to 4-4.5.
7. A process for the preparation of an acidic copper plating additive according to any of claims 1 to 6, comprising the steps of:
A. respectively calculating the addition amount of each raw material of the acidic copper plating additive according to the total volume of the electrolytic copper plating solution;
B. and weighing each raw material of the acidic copper plating additive according to the calculation result for later use, wherein the sum of the raw materials of the acidic copper plating additive is the acidic copper plating additive.
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| CN202010051253.7A CN111088509A (en) | 2020-01-17 | 2020-01-17 | Acidic copper plating additive and preparation method thereof |
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| CN202010051253.7A CN111088509A (en) | 2020-01-17 | 2020-01-17 | Acidic copper plating additive and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892706A (en) * | 2020-07-23 | 2020-11-06 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | PEG (polyethylene glycol) coupled heterocyclic compound and application thereof in acid bright copper plating |
| US11932959B2 (en) | 2021-10-26 | 2024-03-19 | Contemporary Amperex Technology Co., Limited | Copper plating solution and negative electrode composite current collector prepared using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302635A (en) * | 2008-01-18 | 2008-11-12 | 梁国柱 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
| CN103320820A (en) * | 2013-06-18 | 2013-09-25 | 河南江河机械有限责任公司 | Acid bright copper-plating electroplating process |
-
2020
- 2020-01-17 CN CN202010051253.7A patent/CN111088509A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302635A (en) * | 2008-01-18 | 2008-11-12 | 梁国柱 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
| CN103320820A (en) * | 2013-06-18 | 2013-09-25 | 河南江河机械有限责任公司 | Acid bright copper-plating electroplating process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892706A (en) * | 2020-07-23 | 2020-11-06 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | PEG (polyethylene glycol) coupled heterocyclic compound and application thereof in acid bright copper plating |
| US11932959B2 (en) | 2021-10-26 | 2024-03-19 | Contemporary Amperex Technology Co., Limited | Copper plating solution and negative electrode composite current collector prepared using same |
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