High-speed pure tin electroplating matte tin additive and preparation method thereof

Abstract

The invention discloses a high-speed pure tin electroplating matte tin additive and a preparation method thereof, and aims to solve the problem that a high-speed electroplating additive in the prior art is difficult to meet the actual requirements of microelectronic packaging. According to the method, the wetting agent, the grain refiner, the solvent and the antioxidant are carefully selected and proportioned, so that the speed of an electroplating production line is increased, the thickness and uniformity of a plating layer are kept, the cost is reduced, and the corrosion resistance of a product is improved. The preparation method of the additive comprises the following steps: firstly adding water in a certain proportion, then adding the solvent, the wetting agent, the grain refiner, the antioxidant, the stabilizer, the solubilizer and the antistatic agent which are metered, and finally adding water to a required scale and uniformly stirring. The embodiment shows specific raw material components and contents and electroplating process conditions, and proves the effectiveness of the additive disclosed by the invention. By using the additive disclosed by the invention, the electroplating effects that the high-area scorching area is less than 1mm and the usable current density is greater than 25A / dm < 2 > can be realized, and the electroplating quality and the production efficiency are remarkably improved.

Description

Technical Field

[0001] The invention relates to the field of electrochemical material surface treatment, in particular to a high-speed pure tin electroplating matte tin additive and a preparation method thereof. Background Art

[0002] Today, as the electronic components industry adopts fully automatic large-scale production technology and market competition becomes increasingly fierce, people have also put forward higher requirements for the electronic electroplating industry it serves, such as the thickness and uniformity of the coating of each batch of products must be consistent, the electroplating area must be strictly controlled, and the cost must be reduced. However, ordinary electroplating equipment cannot meet the needs of actual production, and it is also difficult to meet product performance requirements. High-speed electroplating is more in line with the actual needs of microelectronic packaging, and therefore has gradually become the first choice for electroplating of electronic components.

[0003] In order to meet the development of high-speed electroplating, the research on related electroplating additives also needs to be vigorously developed. At present, a large number of electroplating additive research works are mainly based on ordinary electroplating, which is difficult to cope with high-speed electroplating with extremely high current density. Although there are foreign electroplating additive manufacturers who have conducted in-depth research on additives specifically for high-speed electroplating, and have actual product applications, there are still certain defects in some performance aspects. For China, there are many studies on high-speed electroplating process equipment, but the research on matching electroplating additives is very limited. The high-speed electroplating matte tin additives on the market can only meet low-speed production. If the speed of the electroplating production line is increased, the current needs to be increased for sufficient coating thickness, resulting in rough crystallization and poor corrosion resistance. Summary of the invention

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] A high-speed pure tin electroplating matte tin additive, the raw material components are calculated per liter, and the composition and content are as follows:

[0006] Wetting agent: 5-200g;

[0007] Grain refiner: 5-200g;

[0008] Solvent: 100-200g;

[0009] Antioxidants: 5-100g;

[0010] Stabilizer: 5-30g;

[0011] Solubilizer: 5-30g;

[0012] Antistatic agent: 5-30g;

[0013] The balance is water.

[0014] Preferably, the wetting agent is one of isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1302, isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305 and isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310, or a mixture of two or more thereof; preferably, tridecanol polyoxyethylene polyoxypropylene ether E-1302, isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305 and isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310, and the mass ratio of tridecanol polyoxyethylene polyoxypropylene ether E-1302: isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305: isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310 is 0.5-3:0.5-2:5.

[0015] Preferably, the grain refiner is one of sodium 2,6-naphthalene disulfonate, sodium 2,7-naphthalene disulfonate and sodium 1,6-naphthalene disulfonate, or a mixture of two or more thereof; preferably sodium 2,6-naphthalene disulfonate, sodium 2,7-naphthalene disulfonate and sodium 1,6-naphthalene disulfonate, and the mass ratio of sodium 2,6-naphthalene disulfonate: sodium 2,7-naphthalene disulfonate: sodium 1,6-naphthalene disulfonate is 2:0.5-3:0.5-5.

[0016] Preferably, the solvent is one of 1,2-propylene glycol, 1,3-propylene glycol and ethylene glycol, or a mixture of two or more thereof; preferably, 1,2-propylene glycol, 1,3-propylene glycol and ethylene glycol, and the mass ratio of 1,2-propylene glycol: 1,3-propylene glycol: ethylene glycol is 0.5-3:0.5-3:5.

[0017] Preferably, the antioxidant is one of 4-tert-octylphenol, tert-butyl-p-diphenol and tert-butyl-hydroquinone, or a mixture of two or more thereof; preferably, 4-tert-octylphenol, tert-butyl-p-diphenol and tert-butyl-hydroquinone, and the mass ratio of 4-tert-octylphenol: tert-butyl-p-diphenol: tert-butyl-hydroquinone is 0.5-3:2:0.5-5.

[0018] Preferably, the stabilizer is any one of polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), polypropylene glycol (PPG), and polyethylene oxide (PEO); the solubilizer is any one of a quaternary ammonium salt (such as hexadecyltrimethylammonium chloride), Tween-80 (polysorbate-80), PEG-400, and sorbitan monooleate (Span80); the antistatic agent is any one of polyacrylamide (PAM), zinc stearate, ethoxylated amine, and sulfosuccinate.

[0019] Preferably, the mass ratio of the stabilizer, the solubilizer and the antistatic agent is 1:1:1. Among them, the stabilizer is preferably polyethylene glycol; the solubilizer is preferably a quaternary ammonium salt (such as hexadecyltrimethylammonium chloride); and the antistatic agent is preferably polyacrylamide.

[0020] The present invention also provides a method for preparing the above-mentioned high-speed pure tin electroplating matte tin additive, comprising the following steps:

[0021] First add 30% water;

[0022] Add measured solvent;

[0023] Add measured wetting agent, grain refiner and antioxidant, as well as selected stabilizer, solubilizer and antistatic agent, add water to the required scale and stir evenly.

[0024] The technical solution of the present invention has the following beneficial effects:

[0025] The high-speed pure tin electroplating matt tin additive of the present invention is carefully selected from wetting agents, grain refiners, antioxidants, stabilizers, solubilizers and antistatic agents. Under the condition of achieving the same coating thickness during the electroplating process, the speed of the electroplating production line can be increased, the electroplating time can be saved, and the production efficiency can be improved. The high-zone burnt area of ​​the electroplating layer obtained by this method is less than 1mm, and the usable current density is greater than 25A / dm 2 .

[0026] Among them, after adding stabilizer, solubilizer and antistatic agent, the high-speed pure tin electroplating matte tin additive of the present invention further optimizes the stability and uniformity of the electroplating process, and significantly improves the corrosion resistance of the coating. The use of stabilizer effectively reduces the defects of the coating under high-speed electroplating conditions, while the solubilizer improves the solubility of the additive components in the electroplating solution, ensuring a uniform chemical reaction. The introduction of antistatic agent reduces the surface defects caused by static electricity during the electroplating process and improves the surface finish of the coating. These improvements not only improve the speed and efficiency of the electroplating production line, but also further enhance the quality and durability of the coating. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. 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.

[0028] Embodiment 1:

[0029] A high-speed pure tin electroplating matte tin additive, the raw material components are calculated per liter, and the composition and content are as follows:

[0030] Wetting agent: 150g;

[0031] Grain refiner: 100g;

[0032] Solvent: 100g;

[0033] Antioxidants: 20g;

[0034] Stabilizer: 20g (polyethylene glycol);

[0035] Solubilizer: 20g (quaternary ammonium salt);

[0036] Antistatic agent: 20g (polyacrylamide);

[0037] The balance is water.

[0038] The wetting agents are tridecanol polyoxyethylene polyoxypropylene ether E-1302, isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305 and isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310, and the mass ratio of tridecanol polyoxyethylene polyoxypropylene ether E-1302: isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305: isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310 is 1:1:5.

[0039] The grain refiners are sodium 2,6-naphthalene disulfonate, sodium 2,7-naphthalene disulfonate and sodium 1,6-naphthalene disulfonate; the mass ratio of sodium 2,6-naphthalene disulfonate: sodium 2,7-naphthalene disulfonate: sodium 1,6-naphthalene disulfonate is 2:2:1.

[0040] The solvents are 1,2-propylene glycol, 1,3-propylene glycol and ethylene glycol; the mass ratio of 1,2-propylene glycol: 1,3-propylene glycol: ethylene glycol is 1:1:5.

[0041] The antioxidants are 4-tert-octylphenol, tert-butyl-p-diphenol and tert-butyl-hydroquinone, and the mass ratio of 4-tert-octylphenol: tert-butyl-p-diphenol: tert-butyl-hydroquinone is 1:2:1.

[0042] The water is pure water.

[0043] The above-mentioned method for preparing a matte tin additive for high-speed pure tin electroplating comprises the following steps:

[0044] First add 30% water;

[0045] Add measured solvent;

[0046] Add measured wetting agent, grain refiner and antioxidant, as well as selected stabilizer, solubilizer and antistatic agent, add water to the required scale and stir evenly.

[0047] Take Example 1 to prepare a high-speed pure tin electroplating matte tin additive to prepare the electroplating solution for Hoffmann cell film making, and the process conditions are as follows:

[0048] Tin methanesulfonate 223mL / L, current 5A;

[0049] Methanesulfonic acid 100mL / L, temperature 45℃;

[0050] Matt tin additive 50mL / L, time 1min;

[0051] Through Hoch trough punching, the high-zone charring area is less than 1mm, and the usable current density is >25A / dm 2 .

[0052] Embodiment 2:

[0053] A high-speed pure tin electroplating matte tin additive, the raw material components are calculated per liter, and the composition and content are as follows:

[0054] Wetting agent: 160g;

[0055] Grain refiner: 80g;

[0056] Solvent: 140g;

[0057] Antioxidants: 40g;

[0058] Stabilizer: 25g (polyethylene glycol);

[0059] Solubilizer: 25g (quaternary ammonium salt);

[0060] Antistatic agent: 25g (polyacrylamide);

[0061] The balance is water.

[0062] The wetting agents are tridecanol polyoxyethylene polyoxypropylene ether E-1302, isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305 and isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310, and the mass ratio of tridecanol polyoxyethylene polyoxypropylene ether E-1302: isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305: isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310 is 2:1:5.

[0063] The grain refiners are sodium 2,6-naphthalene disulfonate, sodium 2,7-naphthalene disulfonate and sodium 1,6-naphthalene disulfonate; the mass ratio of sodium 2,6-naphthalene disulfonate: sodium 2,7-naphthalene disulfonate: sodium 1,6-naphthalene disulfonate is 2:3:2.

[0064] The solvents are 1,2-propylene glycol, 1,3-propylene glycol and ethylene glycol; the mass ratio of 1,2-propylene glycol: 1,3-propylene glycol: ethylene glycol is 2:1:5.

[0065] The antioxidants are 4-tert-octylphenol, tert-butyl-p-diphenol and tert-butyl-hydroquinone, and the mass ratio of 4-tert-octylphenol: tert-butyl-p-diphenol: tert-butyl-hydroquinone is 0.5:2:1.

[0066] The remaining water is pure water.

[0067] The above-mentioned method for preparing the high-speed pure tin electroplating matte tin additive is referred to Example 1.

[0068] Take the preparation of high-speed pure tin electroplating matt tin additive in Example 2 to prepare the electroplating solution for Hodgson trough film making. The process conditions refer to Example 1. Through the Hodgson trough film making, the high-zone charred area is less than 1mm, and the usable current density is >25A / dm 2 .

[0069] Embodiment three:

[0070] A high-speed pure tin electroplating matte tin additive, the raw material components are calculated per liter, and the composition and content are as follows:

[0071] Wetting agent: 200g (E-1302:E-1305:E-1310=3:2:5);

[0072] Grain refiner: 50g (sodium 2,6-naphthalene disulfonate: sodium 2,7-naphthalene disulfonate: sodium 1,6-naphthalene disulfonate = 2:3:5);

[0073] Solvent: 200g (1,2-propylene glycol:1,3-propylene glycol:ethylene glycol=3:3:5);

[0074] Antioxidant: 100g (4-tert-octylphenol: tert-butyl-p-diphenol: tert-butyl-hydroquinone = 3:2:5);

[0075] Stabilizer: 30g (polyvinyl pyrrolidone);

[0076] Solubilizer: 30 g (Tween-80);

[0077] Antistatic agent: 30g (zinc stearate);

[0078] The balance is water.

[0079] The above-mentioned method for preparing the high-speed pure tin electroplating matte tin additive is referred to Example 1.

[0080] Take the preparation of high-speed pure tin electroplating matt tin additive in Example 2 to prepare the electroplating solution for Hodgson trough film making. The process conditions refer to Example 1. Through the Hodgson trough film making, the high-zone charred area is less than 1mm, and the usable current density is >25A / dm 2 .

[0081] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-speed pure tin electroplating matte tin additive, characterized in that: Calculated per liter, its composition and content are: wetting agent: 5-200g; Grain refiner: 5-200g; Solvent: 100-200g; Antioxidants: 5-100g; Stabilizer: 5-30g; Solubilizer: 5-30g; Antistatic agent: 5-30g; The balance is water.

2. The high-speed pure tin electroplating matte tin additive according to claim 1, characterized in that: The wetting agent is one of isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1302, isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1305 and isomeric tridecanol polyoxyethylene polyoxypropylene ether E-1310, or a mixture of two or more thereof.

3. The high-speed pure tin electroplating matte tin additive according to claim 2, characterized in that: The grain refiner is one of sodium 2,6-naphthalene disulfonate, sodium 2,7-naphthalene disulfonate and sodium 1,6-naphthalene disulfonate or a mixture of two or more thereof.

4. The high-speed pure tin electroplating matte tin additive according to claim 3, characterized in that: The solvent is one or a mixture of two or more of 1,2-propylene glycol, 1,3-propylene glycol and ethylene glycol.

5. The high-speed pure tin electroplating matte tin additive according to claim 4, characterized in that: The antioxidant is one or a mixture of two or more of 4-tert-octylphenol, tert-butylhydroquinone and tert-butylhydroquinone.

6. The high-speed pure tin electroplating matte tin additive according to claim 5, characterized in that: The stabilizer is one of polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), polypropylene glycol (PPG), and polyethylene oxide (PEO); the solubilizer is one of quaternary ammonium salt (such as hexadecyltrimethylammonium chloride), Tween-80 (polysorbate-80), PEG-400, and sorbitan monooleate (Span 80); and the antistatic agent is one of polyacrylamide (PAM), zinc stearate, ethoxylated amine, and sulfosuccinate.

7. The high-speed pure tin electroplating matte tin additive according to claim 6, characterized in that: The specific mass ratio of the wetting agent, grain refiner, solvent, antioxidant, stabilizer, solubilizer and antistatic agent is: Wetting agent: the mass ratio of isotridecyl alcohol polyoxyethylene polyoxypropylene ether E-1302, isotridecyl alcohol polyoxyethylene polyoxypropylene ether E-1305 and isotridecyl alcohol polyoxyethylene polyoxypropylene ether E-1310 is 0.5-3:0.5-2:5; Grain refiner: the mass ratio of sodium 2,6-naphthalene disulfonate, sodium 2,7-naphthalene disulfonate and sodium 1,6-naphthalene disulfonate is 2:0.5-3:0.5-5; Solvent: The mass ratio of 1,2-propylene glycol, 1,3-propylene glycol and ethylene glycol is 0.5-3:0.5-3:5; Antioxidant: the mass ratio of 4-tert-octylphenol, tert-butyl-p-diphenol and tert-butyl-hydroquinone is 0.5-3:2:0.5-5; The mass ratio of stabilizer, solubilizer and antistatic agent is 1:1:

1.

8. The high-speed pure tin electroplating matte tin additive according to claim 7, characterized in that: The stabilizer is polyethylene glycol; the solubilizer is a quaternary ammonium salt; and the antistatic agent is polyacrylamide.

9. The method for preparing a matte tin additive for high-speed pure tin electroplating according to any one of claims 1 to 8, characterized in that: The following steps are involved: (a) first add 30% water; (b) adding a measured amount of solvent; (c) adding measured amounts of wetting agent, grain refiner, antioxidant, and selected stabilizer, solubilizer and antistatic agent; (d) Add water to the required mark and stir well.

10. A high-speed pure tin electroplating method using the additive according to any one of claims 1 to 8, characterized in that: The process conditions of the method are: Tin methanesulfonate: 223mL / L; Current: 5A; Methanesulfonic acid: 100mL / L; Temperature: 45℃; Matt tin additive: 50mL / L; Time: 1min.