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CN-119663384-B - Imidazolyl surface treatment additive and preparation method and application thereof

CN119663384BCN 119663384 BCN119663384 BCN 119663384BCN-119663384-B

Abstract

The invention relates to an imidazole-based surface treatment additive, and a preparation method and application thereof, and belongs to the technical field of surface treatment. In order to solve the problems of narrow current density range and quick consumption of brightening agent in the acid copper plating brightening area, the invention provides a preparation method of an imidazole-based surface treatment additive, dissolving sodium hydroxide, imidazole or imidazole derivatives and pyridine or pyridine derivatives in deionized water, adding epoxy chloropropane into the obtained mixed system, and reacting until the epoxy chloropropane suspension is not observed, thus obtaining the imidazolyl surface treatment additive. The imidazole-based electroplating additive prepared by the invention is applied to acid sulfate copper plating, can obviously improve the brightness of a copper plating layer in a low current density area, realizes that a plating layer is mirror bright within a wide current density range of 0.1-10A/dm 2 , keeps the glossiness above 480GU, can obviously reduce the consumption rate of a main brightening agent of a sulfur-containing compound, and has excellent application potential.

Inventors

  • LI DEYU
  • LIU YUHANG
  • WU BO
  • LI NING
  • WU JINHUI
  • DING JIAO
  • WANG YANAN

Assignees

  • 哈尔滨工业大学

Dates

Publication Date
20260508
Application Date
20241216

Claims (7)

  1. 1. The application of the imidazole-based surface treatment additive in acid copper plating is characterized in that sodium hydroxide, imidazole or imidazole derivatives, pyridine or pyridine derivatives are dissolved in deionized water, epichlorohydrin is added into the obtained mixed system, and the imidazole-based surface treatment additive is obtained after the epichlorohydrin suspension is not observed, wherein the number ratio of imidazole rings in the imidazole or imidazole derivatives to the epoxide rings of the epichlorohydrin is 0.1-10:0.1-10, and the number ratio of imidazole rings in the imidazole or imidazole derivatives to pyridine rings in the pyridine or pyridine derivatives is 0.1-10:0.1-10.
  2. 2. The use of an imidazole-based surface treatment additive in acid copper plating according to claim 1, wherein the imidazole derivative is a product in which 1 to 4 hydrogen atoms on an imidazole ring are substituted by substituents, the substituents are hydrocarbon groups, halogens 、-NH 2 、-NHR、-NR 2 、-PH 2 、-PHR、-PR 2 、-OH、-SH、-OR、-SR、-SO 2 H、-SO 3 H、-CHO、-COR、-CORNH 2 、-COOH、-COOR、-C≡N、-N=O、-NO 2 、-NH-NH 2 、-CO(NH 2 )、-SiR 3 、-B(OH) 2 or N-containing S heterocyclic substituents, and R represents a hydrocarbon group.
  3. 3. The use of an imidazole-based surface treatment additive according to claim 1 or 2 in acid copper plating, wherein the pyridine derivative is a product obtained by connecting 1-5 substituents in all C, N atoms on a pyridine ring, wherein the substituents are hydrocarbon groups, halogen 、-NH 2 、-NHR、-NR 2 、-PH 2 、-PHR、-PR 2 、-OH、-SH、-OR、-SR、-SO 2 H、-SO 3 H、-CHO、-COR、-CORNH 2 、-COOH、-COOR、-C≡N、-N=O、-NO 2 、-NH-NH 2 、-CO(NH 2 )、-SiR 3 、-B(OH) 2 or N-containing and S-containing heterocyclic substituents, and R represents hydrocarbon groups.
  4. 4. The use of an imidazole-based surface treatment additive in acid copper plating according to claim 3, wherein the concentration of sodium hydroxide in the mixed system is 1-100 mol/L.
  5. 5. The application of the imidazole-based surface treatment additive in acid copper plating, as claimed in claim 4, wherein the acid bright copper plating solution used for acid copper plating comprises 10-1000 mg/L polyether surfactant, 5-50 mg/L sulfur compound main brightening agent, 5-100 mg/L dye leveling agent, 1-100 mu L imidazole-based surface treatment additive, 100-300 g/L copper sulfate pentahydrate, 50-200 g/L98 mass% concentrated sulfuric acid and 10-300 mg/L37-mass% concentrated hydrochloric acid.
  6. 6. The use of an imidazole-based surface treatment additive in acid copper plating according to claim 5 wherein the polyether surfactant is polyethylene oxide polypropylene oxide monobutyl ether and the sulfur-containing compound main brightening agent is sodium polydithio-dipropyl sulfonate.
  7. 7. The use of an imidazole-based surface treatment additive in acid copper plating according to claim 6, wherein the bright area current density range is 0.1-10A/dm 2 when the acid bright copper plating solution is used for acid copper plating.

Description

Imidazolyl surface treatment additive and preparation method and application thereof Technical Field The invention belongs to the technical field of surface treatment, and particularly relates to an imidazole-based surface treatment additive, and a preparation method and application thereof. Background The acid sulfate copper plating is an electroplating process widely applied to the fields of daily hardware electroplating, printed circuit boards, electroforming and the like, and improves the conductivity of a base material by forming a plating layer on the surface of the base material, thereby improving the appearance, corrosion resistance and saving cost. In the acidic sulfate copper plating process, the current density range of the bright area directly influences the performance indexes such as brightness, uniformity, compactness, adhesion and the like of the plating layer. The acidic sulfate copper plating can obtain a bright, smooth and uniform plating layer in a proper current density range. However, the surface treatment technology such as acidic sulfate copper plating has a problem that the current density range in the bright area is not wide enough, and if the current density exceeds the range, the brightness of the plating layer is significantly reduced, and other quality problems such as roughness, scorching and the like of the plating layer may occur. At the same time, the quality of the coating, the electroplating efficiency and the energy consumption are all significantly affected by various additives. The acidic sulfate copper plating additive is divided into brightening agent, inhibitor and leveling agent. The brightening agent can form stable complex with copper ions, and the reduction rate and the deposition mode of the copper ions are controlled, so that a higher brightness and a more uniform deposition layer can be obtained in the forming process of the coating. The most common brightening agent is sodium polydithio-dipropyl sulfonate (SPS), and can refine crystal grains to obtain a coating with mirror surface brightness. However, SPS is embedded in the plating layer during the electroplating process, and the chemical properties of SPS are not stable enough and are easy to be oxidized and decomposed, so that the problem of faster consumption of brightening agent during the electroplating process is also existed. Disclosure of Invention The invention provides an imidazole-based surface treatment additive, a preparation method and application thereof, and aims to solve the problems of narrow current density range and quick consumption of brightening agent in an acid copper plating bright area. The technical scheme of the invention is as follows: The preparation method of the imidazole-based surface treatment additive comprises the steps of dissolving sodium hydroxide, imidazole or imidazole derivatives, pyridine or pyridine derivatives in deionized water, adding epichlorohydrin into the obtained mixed system, and reacting until an epichlorohydrin suspension is not observed to obtain the imidazole-based surface treatment additive, wherein the number ratio of imidazole rings in the imidazole or imidazole derivatives to epoxide rings in the epichlorohydrin is 0.1-10:0.1-10, and the number ratio of imidazole rings in the imidazole or imidazole derivatives to pyridine rings in the pyridine or pyridine derivatives is 0.1-10:0.1-10. Further, the imidazole derivative is a product of substituting 1-4 hydrogen atoms on an imidazole ring by substituent groups, wherein the substituent groups are hydrocarbon groups, halogen 、-NH2、-NHR、-NR2、-PH2、-PHR、-PR2、-OH、-SH、-OR、-SR、-SO2H、-SO3H、-CHO、-COR、-CORNH2、-COOH、-COOR、-C≡N、-N＝O、-NO2、-NH-NH2、-CO(NH2)、-SiR3、-B(OH)2 or N-containing and S-containing heterocyclic substituent groups, or substituent groups obtained by substituting hydrogen atoms or substituent groups in one group by one or more groups, and R represents hydrocarbon groups. Further, the pyridine derivative is a product obtained by connecting 1-5 substituents in all C, N atoms on a pyridine ring, wherein the substituents are hydrocarbon groups, halogen 、-NH2、-NHR、-NR2、-PH2、-PHR、-PR2、-OH、-SH、-OR、-SR、-SO2H、-SO3H、-CHO、-COR、-CORNH2、-COOH、-COOR、-C≡N、-N＝O、-NO2、-NH-NH2、-CO(NH2)、-SiR3、-B(OH)2 or N-containing and S-containing heterocyclic substituents, or substituents obtained by substituting hydrogen atoms or substituents in one group by one or more groups, and R represents hydrocarbon groups. Further, the concentration of sodium hydroxide in the mixed system is 1-100 mol/L. The invention provides an imidazole-based surface treatment additive prepared by a preparation method of the imidazole-based surface treatment additive. The invention provides an application of an imidazole-based surface treatment additive in electroplating or electroless plating. Further, the electroplating is acid copper electroplating. Further, the acidic bright copper plating solution used for acidic copper plating comprises the follow