Composite electroplating solution and preparation method thereof

Abstract

The invention provides a composite electroplating solution and a preparation method thereof. Comprising the following components in parts by weight: 20-40 parts of copper sulfate, 15-25 parts of nickel chloride, 10-20 parts of trimethylamine borane, 10-20 parts of polyethylene glycol, 30-50 parts of sodium allylsulfonate, 10-20 parts of sodium potassium tartrate tetrahydrate, 12-18 parts of potassium citrate, 4-8 parts of alkylphenol polyoxyethylene ether, 3-7 parts of sodium dithiodipropane sulfonate, 2-6 parts of bisphenol-A polyoxypropylene ether, 1-5 parts of vinyl ether and 6-10 parts of alkyl glycoside. By compounding the ion source, the complexing agent, the brightener and the like, under the interaction of all the components, the performance of the electroplating liquid in the aspects of deep plating, diffusion, binding force, structural strength and the like is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of electroplating solution preparation, and specifically relates to a composite electroplating solution and a preparation method thereof. Background Art

[0002] Electroplating solution refers to the liquid medium used in the electroplating process, which contains metal ions that can be deposited on the substrate and other auxiliary components. Electroplating is a process of depositing one metal onto the surface of another material by electrolysis, usually used to improve the appearance of the material, increase wear resistance, corrosion resistance or other functional purposes.

[0003] Electroplating copper is a very important type of electroplating, and is often used for the base of molds, nickel plating, chrome plating, silver plating, gold plating, etc. It is mainly divided into acid copper plating and alkaline copper plating. Acid copper plating is widely used, but some metal parts cannot be directly plated with acid copper and need pretreatment or pre-plating. Early alkaline copper plating mostly used cyanide as a complexing agent, which had good electroplating performance and strong environmental adaptability, but it was highly toxic and caused great environmental pollution, and its use has been restricted.

[0004] Patent CN103938232A discloses a cyanide-free electroplating solution and its application. The patent uses sodium gold sulfite as the gold salt. However, the salt has poor stability. Gold is easily decomposed and reduced at high temperature to precipitate. At the same time, because the formula components are too simple, the resulting coating has poor brightness. In addition, patent CN101906649A discloses a cyanide-free electroplating gold plating solution and an electroplating method using the cyanide-free electroplating gold plating solution. The solution uses gold chloride as the gold salt. Under the action of current, chloride ions promote the corrosion of trivalent gold ions to the substrate. Summary of the invention

[0005] The purpose of the present invention is to provide a composite electroplating solution, which improves the performance of the electroplating solution in terms of deep plating, diffusion, bonding force, structural strength, etc. through the combination of ion sources, complexing agents, brighteners, etc. under the interaction of various components.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: A composite electroplating solution comprises the following components in parts by weight: 20-40 parts of copper sulfate, 15-25 parts of nickel chloride, 10-20 parts of trimethylamine borane, 10-20 parts of polyethylene glycol, 30-50 parts of sodium propylene sulfonate, 10-20 parts of potassium sodium tartrate, 12-18 parts of potassium citrate, 4-8 parts of alkylphenol polyoxyethylene ether, 3-7 parts of sodium polydisulfide dipropylene sulfonate, 2-6 parts of bisphenol-A polyoxypropylene ether, 1-5 parts of vinyl ether, and 6-10 parts of alkyl polyglycoside.

[0007] Preferably, the following components are included in parts by weight: 30 parts of copper sulfate, 20 parts of nickel chloride, 15 parts of trimethylamine borane, 16 parts of polyethylene glycol, 45 parts of sodium propylene sulfonate, 16 parts of potassium sodium tartrate, 15 parts of potassium citrate, 6 parts of alkylphenol polyoxyethylene ether, 5 parts of sodium polydisulfide propane sulfonate, 5 parts of bisphenol-A polyoxypropylene ether, 4 parts of vinyl ether, and 8 parts of alkyl glycoside.

[0008] The preparation method of the composite electroplating solution comprises the following steps: S1: by weight, 20-40 parts of copper sulfate, 15-25 parts of nickel chloride, 10-20 parts of trimethylamine borane and 10-20 parts of polyethylene glycol are mixed, and ultrasonically vibrated at a temperature of 35-45° C. for 10-20 minutes to obtain a first mixture; S2: by weight, 30-50 parts of sodium propylene sulfonate, 10-20 parts of sodium potassium tartrate and 12-18 parts of potassium citrate are mixed, and the mixture is stirred at a temperature of 60-70° C. for 20-30 minutes; then the first mixture obtained in step S1 is added, and stirring is continued for 30-50 minutes to obtain a second mixture; S3: Mix 4-8 parts of alkylphenol polyoxyethylene ether and 3-7 parts of sodium polydisulfide propane sulfonate by weight, and stir at a temperature of 40-60° C. for 15-25 minutes; then add the second mixture obtained in step S2, and continue stirring for 35-45 minutes to obtain a third mixture; S4: by weight, 2-6 parts of bisphenol-A polyoxypropylene ether and 1-5 parts of vinyl ether are mixed, and stirred at a temperature of 30-40° C. for 10-20 minutes; then the third mixture obtained in step S3 is added, and stirring is continued for 15-25 minutes to obtain a fourth mixture; S5: Add 6-10 parts of alkyl polyglycoside by weight to the fourth mixture obtained in step S4, and stir the mixture at 70-90° C. for 1-3 hours to obtain a composite electroplating solution.

[0009] Preferably, according to the method for preparing a composite electroplating solution according to claim 3, it is characterized in that step S1 is optimized as follows: 30 parts of copper sulfate, 20 parts of nickel chloride, 15 parts of trimethylamine borane and 16 parts of polyethylene glycol are mixed by weight, and ultrasonically vibrated at a temperature of 38°C for 16 minutes to obtain a first mixture.

[0010] Preferably, the power of ultrasonic vibration is 2500-3500W.

[0011] Preferably, step S2 is optimized as follows: by weight, 45 parts of sodium propylene sulfonate, 16 parts of sodium potassium tartrate and 15 parts of potassium citrate are mixed, and stirred at a temperature of 65° C. and a speed of 450 r / min for 26 min; then the first mixture obtained in step S1 is added, and stirring is continued at a speed of 600 r / min for 46 min to obtain a second mixture.

[0012] Preferably, step S3 is optimized as follows: by weight, 6 parts of alkylphenol polyoxyethylene ether and 5 parts of sodium polydisulfide propane sulfonate are mixed, and stirred at a temperature of 55° C. at a rate of 450 r / min for 18 min; then the second mixture obtained in step S2 is added, and stirring is continued at a rate of 500 r / min for 40 min to obtain a third mixture.

[0013] Preferably, step S4 is optimized as follows: by weight, 5 parts of bisphenol-A polyoxypropylene ether and 4 parts of vinyl ether are mixed, and stirred at a temperature of 35° C. and a speed of 350 r / min for 15 min; then the third mixture obtained in step S3 is added, and stirring is continued at a speed of 600 r / min for 22 min to obtain a fourth mixture.

[0014] Preferably, step S5 is optimized as follows: 8 parts by weight of alkyl glycoside are added to the fourth mixture obtained in step S4, and the mixture is stirred at a temperature of 80° C. and a speed of 550 r / min for 2.5 hours to obtain a composite electroplating solution.

[0015] Preferably, in step S5, 6-10 parts of alkyl glycoside are added to the fourth mixture obtained in step S4 at a rate of 3-6 drops / min.

[0016] Compared with the prior art, the advantages and beneficial effects of the present invention are: 1. The present invention uses copper sulfate, nickel chloride and trimethylamine borane as copper ion source, nickel ion source and boron source respectively, and can form a copper-nickel-boron coating on the base plated part during electroplating, so that the coating has excellent hardness and modulus.

[0017] 2. The present invention uses sodium propylene sulfonate, potassium sodium tartrate and potassium citrate as complexing agents to form complexes with metal ions, thereby improving the stability of metal ions and better controlling the deposition rate; alkylphenol polyoxyethylene ether and sodium polydisulfide dipropylene sulfonate are used as brightening and leveling agents to form a smoother coating, and the coating is tightly combined with the surface of the substrate; under the action of bisphenol-A polyoxypropylene ether, vinyl ether and alkyl polyglycoside, the dispersibility and deep plating ability of the electroplating solution are stronger. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] The sources of raw materials of the present invention are as follows: Polyethylene glycol came from Shanghai Yuanye Biotechnology Co., Ltd. with item number S30184, alkylphenol polyoxyethylene ether came from Shanghai Yuanye Biotechnology Co., Ltd. with item number B65867, sodium polydisulfide dipropane sulfonate came from Shanghai Yuanye Biotechnology Co., Ltd. with item number S30613, bisphenol-A polyoxypropylene ether came from Hubei Jusheng Technology Co., Ltd. with item number JS0093, and alkyl glycoside came from Wuhan Jiyesheng Chemical Co., Ltd. with item number 4690.

[0020] Example 1 This embodiment provides a method for preparing a composite electroplating solution, comprising the following steps: S1: 20 g of copper sulfate, 15 g of nickel chloride, 10 g of trimethylamine borane and 10 g of polyethylene glycol were mixed, and ultrasonically vibrated at 2500 W for 10 min at 35° C. to obtain a first mixture; S2: 30 g of sodium propylene sulfonate, 10 g of sodium potassium tartrate and 12 g of potassium citrate were mixed, and the mixture was stirred at 60° C. and 450 r / min for 20 min; then the first mixture obtained in step S1 was added, and the mixture was stirred at 600 r / min for 30 min to obtain a second mixture; S3: 4 g of alkylphenol polyoxyethylene ether and 3 g of sodium polydisulfide dipropane sulfonate were mixed, and stirred at a temperature of 40° C. and a speed of 450 r / min for 15 min; then the second mixture obtained in step S2 was added, and the stirring was continued at a speed of 500 r / min for 35 min to obtain a third mixture; S4: 2 g of bisphenol-A polyoxypropylene ether and 1 g of vinyl ether were mixed and stirred at 30° C. for 10 min; then the third mixture obtained in step S3 was added and stirred at a rate of 600 r / min for 15 min to obtain a fourth mixture; S5: Add 6 g of alkyl polyglycoside to the fourth mixture obtained in step S4 at a rate of 3 drops / min, and stir the mixture at a rate of 550 r / min at a temperature of 70° C. for 1 h to obtain a composite electroplating solution.

[0021] Example 2 This embodiment provides a method for preparing a composite electroplating solution, comprising the following steps: S1: 40 g of copper sulfate, 25 g of nickel chloride, 20 g of trimethylamine borane and 20 g of polyethylene glycol were mixed, and ultrasonically vibrated at a temperature of 45° C. and a power of 3500 W for 20 min to obtain a first mixture; S2: 50 g of sodium propylene sulfonate, 20 g of sodium potassium tartrate and 18 g of potassium citrate were mixed, and the mixture was stirred at 70° C. and 450 r / min for 30 min; then the first mixture obtained in step S1 was added, and the mixture was stirred at 600 r / min for 50 min to obtain a second mixture; S3: 8 g of alkylphenol polyoxyethylene ether and 7 g of sodium polydisulfide propane sulfonate were mixed, and stirred at a temperature of 60° C. and a speed of 450 r / min for 25 min; then the second mixture obtained in step S2 was added, and the stirring was continued at a speed of 500 r / min for 45 min to obtain a third mixture; S4: 6 g of bisphenol-A polyoxypropylene ether and 5 g of vinyl ether were mixed and stirred at 40° C. for 20 min; then the third mixture obtained in step S3 was added and stirred at a rate of 600 r / min for 25 min to obtain a fourth mixture; S5: adding 10 g of alkyl polyglycoside to the fourth mixture obtained in step S4 at a rate of 6 drops / min, stirring and reacting at a rate of 550 r / min at a temperature of 90° C. for 3 h to obtain a composite electroplating solution.

[0022] Example 3 This embodiment provides a method for preparing a composite electroplating solution, comprising the following steps: S1: 30 g of copper sulfate, 20 g of nickel chloride, 15 g of trimethylamine borane and 16 g of polyethylene glycol were mixed, and ultrasonically vibrated at 3000 W for 16 min at 38° C. to obtain a first mixture; S2: 45 g of sodium propylene sulfonate, 16 g of sodium potassium tartrate and 15 g of potassium citrate were mixed, and the mixture was stirred at a temperature of 65° C. and a speed of 450 r / min for 26 min; then the first mixture obtained in step S1 was added, and the mixture was stirred at a speed of 600 r / min for 46 min to obtain a second mixture; S3: 6 g of alkylphenol polyoxyethylene ether and 5 g of sodium polydisulfide dipropane sulfonate were mixed, and stirred at a temperature of 55° C. and a speed of 450 r / min for 18 min; then the second mixture obtained in step S2 was added, and the stirring was continued at a speed of 500 r / min for 40 min to obtain a third mixture; S4: 5 g of bisphenol-A polyoxypropylene ether and 4 g of vinyl ether were mixed and stirred at 35° C. for 15 min; then the third mixture obtained in step S3 was added and stirred at a rate of 600 r / min for 22 min to obtain a fourth mixture; S5: adding 8 g of alkyl polyglycoside to the fourth mixture obtained in step S4 at a rate of 5 drops / min, stirring and reacting at a temperature of 80° C. at a rate of 550 r / min for 2.5 h to obtain a composite electroplating solution.

[0023] Comparative Example 1 The difference between this comparative example and Example 1 is that trimethylamine borane is not added in step S1, and the other steps are the same.

[0024] Comparative Example 2 The difference between this comparative example and Example 1 is that nickel chloride is not added in step S1, and the other steps are the same.

[0025] Comparative Example 3 The difference between this comparative example and Example 1 is that sodium propylene sulfonate is not added in step S2, and the other steps are the same.

[0026] Comparative Example 4 The difference between this comparative example and Example 1 is that potassium citrate is not added in step S2, and the other steps are the same.

[0027] Comparative Example 5 The difference between this comparative example and Example 1 is that alkylphenol polyoxyethylene ether is not added in step S3, and the other steps are the same.

[0028] Comparative Example 6 The difference between this comparative example and Example 1 is that no alkyl glycoside is added in step S5, and the other steps are the same.

[0029] Performance Test: Stability test. After preparing the plating solution, place it at room temperature for 24 hours. If the plating solution is clear and no metal film is formed on the surface of the plating solution, it is judged to be stable; if the plating solution is turbid, or a metal film is formed on the surface of the liquid, it is judged to be unstable. Hardness test. Use a hardness tester (Mitutoyo, HM-200) to test the hardness of the coating. Deep plating ability test. Make the test board into a metallographic microscope slice, observe and record the thickness of the inner and outer plating layers of the through-hole under a 200x microscope, and test the deep plating ability. The calculation formula is: plating thickness ratio = plating thickness inside the through-hole / plating thickness outside the through-hole × 100%. When the plating thickness ratio is 90% 120%, the deep plating ability is better, and the closer the plating thickness ratio is to 100%, the better the deep plating ability.

[0030] The test results are shown in the following table.

[0031] Table 1 Performance test results

[0032] From the above performance test results, it can be seen that the stability, tensile strength PSI and coating thickness ratio of Examples 1-3 are relatively good; in particular, the comprehensive performance of Example 3 is the most outstanding. However, because Comparative Examples 1-6 do not adopt the necessary technical solutions, their corresponding performance tests are significantly worse than those of the Examples. The above experimental results further prove the importance of the technical solutions defined in the present invention for its technical effects.

[0033] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A composite electroplating solution, characterized in that: The invention comprises the following components in parts by weight: 20-40 parts of copper sulfate, 15-25 parts of nickel chloride, 10-20 parts of trimethylamine borane, 10-20 parts of polyethylene glycol, 30-50 parts of sodium propylene sulfonate, 10-20 parts of potassium sodium tartrate, 12-18 parts of potassium citrate, 4-8 parts of alkylphenol polyoxyethylene ether, 3-7 parts of sodium polydisulfide dipropylene sulfonate, 2-6 parts of bisphenol-A polyoxypropylene ether, 1-5 parts of vinyl ether and 6-10 parts of alkyl polyglycoside.

2. A composite electroplating solution according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 30 parts of copper sulfate, 20 parts of nickel chloride, 15 parts of trimethylamine borane, 16 parts of polyethylene glycol, 45 parts of sodium propylene sulfonate, 16 parts of potassium sodium tartrate, 15 parts of potassium citrate, 6 parts of alkylphenol polyoxyethylene ether, 5 parts of sodium polydisulfide propane sulfonate, 5 parts of bisphenol-A polyoxypropylene ether, 4 parts of vinyl ether and 8 parts of alkyl glycoside.

3. A method for preparing a composite electroplating solution, characterized in that: The steps include: S1: by weight, 20-40 parts of copper sulfate, 15-25 parts of nickel chloride, 10-20 parts of trimethylamine borane and 10-20 parts of polyethylene glycol are mixed, and ultrasonically vibrated at a temperature of 35-45° C. for 10-20 minutes to obtain a first mixture; S2: by weight, 30-50 parts of sodium propylene sulfonate, 10-20 parts of sodium potassium tartrate and 12-18 parts of potassium citrate are mixed, and the mixture is stirred at a temperature of 60-70° C. for 20-30 minutes; then the first mixture obtained in step S1 is added, and stirring is continued for 30-50 minutes to obtain a second mixture; S3: Mix 4-8 parts of alkylphenol polyoxyethylene ether and 3-7 parts of sodium polydisulfide propane sulfonate by weight, and stir at a temperature of 40-60° C. for 15-25 minutes; then add the second mixture obtained in step S2, and continue stirring for 35-45 minutes to obtain a third mixture; S4: by weight, 2-6 parts of bisphenol-A polyoxypropylene ether and 1-5 parts of vinyl ether are mixed, and stirred at a temperature of 30-40° C. for 10-20 minutes; then the third mixture obtained in step S3 is added, and stirring is continued for 15-25 minutes to obtain a fourth mixture; S5: Add 6-10 parts of alkyl polyglycoside by weight to the fourth mixture obtained in step S4, and stir the mixture at 70-90° C. for 1-3 hours to obtain a composite electroplating solution.

4. The method for preparing a composite electroplating solution according to claim 3, characterized in that: Step S1 is optimized as follows: by weight, 30 parts of copper sulfate, 20 parts of nickel chloride, 15 parts of trimethylamine borane and 16 parts of polyethylene glycol are mixed, and ultrasonically vibrated at a temperature of 38° C. for 16 minutes to obtain a first mixture.

5. The method for preparing a composite electroplating solution according to claim 3 or 4, characterized in that: The power of ultrasonic vibration is 2500-3500W.

6. The method for preparing a composite electroplating solution according to claim 3, characterized in that: Step S2 is optimized as follows: by weight, 45 parts of sodium propylene sulfonate, 16 parts of sodium potassium tartrate and 15 parts of potassium citrate are mixed, and stirred at a temperature of 65° C. and a speed of 450 r / min for 26 min; then the first mixture obtained in step S1 is added, and stirring is continued at a speed of 600 r / min for 46 min to obtain a second mixture.

7. The method for preparing a composite electroplating solution according to claim 3, characterized in that: Step S3 is optimized as follows: by weight, 6 parts of alkylphenol polyoxyethylene ether and 5 parts of sodium polydisulfide propane sulfonate are mixed, and stirred at a temperature of 55° C. and a speed of 450 r / min for 18 min; Then, the second mixture obtained in step S2 was added, and stirring was continued at a rate of 500 r / min for 40 min to obtain a third mixture.

8. The method for preparing a composite electroplating solution according to claim 3, characterized in that: Step S4 is optimized as follows: by weight, 5 parts of bisphenol-A polyoxypropylene ether and 4 parts of vinyl ether are mixed, and stirred at a temperature of 35° C. and a speed of 350 r / min for 15 min; Then, the third mixture obtained in step S3 was added, and stirring was continued at a speed of 600 for 22 minutes to obtain a fourth mixture.

9. The method for preparing a composite electroplating solution according to claim 3, characterized in that: Step S5 is optimized as follows: 8 parts by weight of alkyl glycoside are added to the fourth mixture obtained in step S4, and the mixture is stirred at a temperature of 80° C. and a speed of 550 r / min for 2.5 hours to obtain a composite electroplating solution.

10. The method for preparing a composite electroplating solution according to claim 3 or 9, characterized in that: In step S5, 6-10 parts of alkyl glycoside are added to the fourth mixture obtained in step S4 at a rate of 3-6 drops / min.

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