Copper electroplating brightener and preparation and application methods thereof

Abstract

The invention discloses an electrocoppering brightener and a preparation method and an application method thereof, and belongs to the technical field of electrocoppering processes, the electrocoppering brightener comprises a brightener A and a brightener B; wherein the brightener A is prepared from the following components: M, N, SP, P and organic dye RLZ; and the brightener B comprises the following components: P and SP. In addition, the invention provides a method for preparing the brightener A agent by respectively adding M, N, SP, P and organic dye RLZ into a reaction kettle filled with deionized water and stirring at controlled temperature. The invention relates to a method for preparing a brightener B by respectively adding P and SP into a reaction kettle filled with deionized water and stirring at a controlled temperature. Furthermore, the invention also discloses an application method of applying the brightening agent A and the brightening agent B to electrocoppering cylinder opening. The copper electroplating brightener solves the technical problems that an existing copper electroplating brightener is poor in dispersing capacity, rough in plating layer crystallization, lack of brightness and the like.

Description

Technical Field

[0001] The invention relates to the technical field of chemical copper plating technology, in particular to an electroplating copper brightener and a preparation and application method thereof. Background Art

[0002] Copper plating is a technology that deposits a layer of copper on the metal surface through an electrochemical process. Currently, this technology is widely used in circuit board manufacturing and is often referred to as copper plating or pore plating in the industry. This is a self-catalytic redox reaction. Specifically, copper plating mainly uses electrochemical principles to attach a layer of copper to the metal surface by electrolysis. In the copper plating process, an electrolyte containing copper ions, such as a copper sulfate solution, is usually used. When current passes through, copper ions are attracted to the cathode, that is, the metal to be plated, and are reduced to metallic copper on it, thereby depositing on the metal surface to form a copper film.

[0003] Electroplating copper brightener is a chemical used for cleaning and polishing the surface of electroplated copper; specifically, it is mainly used in the electroplating copper process to enhance the gloss and brightness of the copper coating; in addition, it is also widely used in electronics, construction, handicrafts and other fields to enhance the beauty and durability of copper products by restoring and improving the gloss of the copper surface.

[0004] Based on this, Chinese patent CN106609385A discloses a high-filled copper brightener for copper electroplating, which contains at least 7-8 parts of dye compounds, 3.4-3.6 parts of sodium polydisulfide propane sulfonate, 4.2-4.4 parts of tetrathioterephthalate, 1.8-2 parts of 1,4-butynediol, 5.6-5.8 parts of thiomorpholine, 12-15 parts of tetrahydrofuran, and 85-88 parts of water, by weight.

[0005] However, the electroplating copper brightener disclosed in the prior art still has technical problems such as poor dispersibility, rough crystallization of the coating, and lack of brightness. Specifically, sulfate copper plating is widely used in the current electroplating industry due to its advantages such as simple composition, low cost, and convenient maintenance. But at the same time, sulfate electrolyte also has disadvantages such as poor dispersibility, rough crystallization of the coating, and lack of brightness during the electroplating process. Therefore, to obtain a copper plating layer with good brightness, leveling and toughness, the key is to select an electroplating copper brightener with excellent performance; and a brightener with excellent performance has the characteristics of strong leveling ability, wide range of bright current density, small coating stress, good ductility and toughness. Summary of the invention

[0006] Based on this, it is necessary to provide a copper electroplating brightener and its preparation and application method in order to solve the technical problems of poor dispersion ability, rough coating crystallization, lack of brightness and the like existing in the existing copper electroplating brightener.

[0007] A copper electroplating brightener comprises the following steps: brightener A and brightener B; wherein the components of brightener A include: M, N, SP, P and organic dye RLZ; and the components of brightener B include: P and SP.

[0008] Specifically, M is 2-mercaptobenzoimidazole, N is ethylenethiourea, SP is sodium poly(disulfide-bis(propylene sulfonate)) and P is polyethylene glycol, and M=10000.

[0009] Specifically, in parts by mass, the components of brightener A include: 0.872 parts of M, 0.594 parts of N, 15 parts of P, 10 parts of SP and 0.06 parts of organic dye RLZ.

[0010] Specifically, based on parts by mass, the components of brightener B include: 290 parts of P and 89 parts of SP.

[0011] Further, a method for preparing the aforementioned electroplating copper brightener comprises the following steps: S11: weigh 0.872 g of M into a 500 mL beaker, add 200 mL of deionized water at 90°C to 100°C into the beaker, and stir until M is completely dissolved; S12: When the temperature of the system in the beaker drops to 80°C to 85°C, 0.594 g of N is added thereto and stirred evenly until N is completely dissolved; S13: When the temperature of the system in the beaker drops to 70°C to 75°C, add 15 g of P therein and stir evenly until P is completely dissolved; S14: When the temperature of the system in the beaker drops to 40°C to 45°C, add 10 g of SP and stir evenly until the SP is completely dissolved; S15: When the temperature of the system in the beaker drops to room temperature, add 0.06 g of organic dye RLZ therein, stir until the organic dye RLZ is completely dissolved, and then transfer all the solution in the beaker into a 1 L volumetric flask to make up the volume to prepare brightener A.

[0012] Further, a method for preparing the aforementioned electroplating copper brightener comprises the following steps: S21: weigh 290 g of P into a 500 mL beaker, add 200 mL of deionized water at 70° C. to the beaker, and stir until P is completely dissolved; S22: When the temperature of the system in the beaker drops to 40°C-45°C, add 89 g of SP and stir evenly until SP is completely dissolved. Then, transfer all the solution in the beaker into a 1 L volumetric flask to make up the volume to prepare brightener B.

[0013] Further, a method for applying the aforementioned electroplating copper brightener is characterized in that it comprises the following steps: S1: Prepare the following materials: copper sulfate 60g / L, sulfuric acid 240g / L, Cl- 60mg / L, brightener A 1mL / L, brightener B 0.2mL / L.

[0014] S2: Clean the working cylinder first; then add 2 / 3 volume of DI water into the working cylinder; S3: Start pumping in the working cylinder and add 60g / L Cu2SO4·5H2O; S4: Carefully and slowly add 240 g / L AR grade 98% H2SO4; S5: Analyze and adjust the contents of Cu2SO4·5H2O, H2SO4 and Cl- to make each component within the control range; S6: When the temperature in the working cylinder drops to 22°C to 30°C, add 1 mL / L of brightener A into it; S7: Continue to add 0.2mL / L of brightener B into the working cylinder; S8: Dummy electrolysis condition control parameters are: 5ASF * 6 hours, 20ASF * 2 hours S9: Complete the copper electroplating tank opening process.

[0015] In summary, the present invention proposes a copper electroplating brightener, which includes: brightener A and brightener B; wherein brightener A includes the following components: M, N, SP, P and organic dye RLZ; brightener B includes the following components: P and SP. In addition, the present invention proposes a method for preparing brightener A by respectively putting M, N, SP, P and organic dye RLZ into a reactor filled with deionized water to control the temperature and stir; and a method for preparing brightener B by respectively putting P and SP into a reactor filled with deionized water to control the temperature and stir. Furthermore, the present invention also discloses an application method of using the aforementioned brightener A and brightener B to open a copper electroplating tank.

[0016] Specifically, the compounding of sulfate copper plating brightener and organic dye can effectively improve the problems of insufficient brightness, poor leveling, large coating stress, poor plating solution stability, etc. of sulfate copper plating brightener series at medium and low potentials. The electroplating copper brightener disclosed in the prior art has the defects of small working temperature range and easy decomposition at high temperature; therefore, when using the existing electroplating copper brightener, it is easy to cause the copper-plated products to have appearance defects such as pinholes or pitting. Moreover, in the preparation process of electroplating copper brightener, the relative combination and relative content of each additive need to be strictly controlled to avoid the electroplating copper brightener having technical problems such as poor dispersibility, rough coating crystallization, and lack of brightness.

[0017] The present invention optimizes the brightener formula and compounding it with organic dyes, which can significantly improve the quality and stability of the coating and meet the needs of copper-plated products in different fields. Therefore, the present invention solves the technical problems of poor dispersibility, rough crystallization of the coating, lack of brightness, etc. of the existing electroplating copper brightener. DETAILED DESCRIPTION

[0018] In order to make the above-mentioned purpose, features and advantages of the present invention more obvious and easy to understand, the specific implementation mode of the present invention is described in detail below in conjunction with specific embodiments. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0019] Specifically, the present invention provides a copper electroplating brightener, which includes: brightener A and brightener B; wherein brightener A includes the following components: M, N, SP, P and an organic dye RLZ; brightener B includes the following components: P and SP.

[0020] Specifically, M may be 2-mercaptobenzoimidazole, N may be ethylenethiourea, SP may be sodium poly(disulfide-bis(propylene sulfonate)), and P may be polyethylene glycol, and M=10000.

[0021] Furthermore, the preparation method of the aforementioned brightener A is as follows: S11: Accurately weigh 0.872 g of M into a 500 mL beaker, add 200 mL of 90°C to 100°C deionized water into the beaker, and stir until completely dissolved; S12: When the temperature of the system in the beaker drops to 80°C to 85°C, add 0.594 g of N accurately weighed therein and stir evenly until it is completely dissolved; S13: When the temperature in the beaker drops to 70°C to 75°C, add 15 g of P and stir evenly until it is completely dissolved; S14: When the temperature in the beaker drops to 40°C to 45°C, add 10 g of SP and stir evenly until it is completely dissolved; S15: When the temperature in the beaker drops to room temperature, add 0.06 g of organic dye RLZ accurately weighed therein, stir until completely dissolved, and then transfer all the solution in the beaker into a 1 L volumetric flask to set the volume for later use.

[0022] Furthermore, the preparation method of the aforementioned brightener B is: S21: Accurately weigh 290 g of P into a 500 mL beaker, add 200 mL of deionized water at 70°C to 75°C into the beaker, and stir until completely dissolved; S22: When the temperature in the beaker drops to 40°C-45°C, add 89 g of SP and stir evenly until it is completely dissolved. Then transfer all the solution in the beaker into a 1 L volumetric flask and make up the volume for later use.

[0023] Further, a method for applying the aforementioned electroplating copper brightener comprises the following steps: S1: Prepare the following materials: copper sulfate 60g / L, sulfuric acid 240g / L, Cl- 60mg / L, brightener A 1mL / L, brightener B 0.2mL / L.

[0024] S2: Clean the working cylinder first; then add 2 / 3 volume of DI water into the working cylinder; S3: Start pumping in the working cylinder and add 60g / L Cu2SO4·5H2O; S4: Carefully and slowly add 240 g / L AR grade 98% H2SO4; S5: Analyze and adjust the contents of Cu2SO4·5H2O, H2SO4 and Cl- to make each component within the control range; S6: When the temperature in the working cylinder drops to 22°C to 30°C, add 1 mL / L of brightener A into it; S7: Add 0.2mL / L of brightener B into the working cylinder; S8: Dummy electrolysis condition control parameters are: 5ASF * 6 hours, 20ASF * 2 hours.

[0025] Thus, the copper electroplating tank opening process is completed.

[0026] In summary, the present invention proposes a copper electroplating brightener, which includes: brightener A and brightener B; wherein brightener A includes the following components: M, N, SP, P and organic dye RLZ; brightener B includes the following components: P and SP. In addition, the present invention proposes a method for preparing brightener A by respectively putting M, N, SP, P and organic dye RLZ into a reactor filled with deionized water to control the temperature and stir; and a method for preparing brightener B by respectively putting P and SP into a reactor filled with deionized water to control the temperature and stir. Furthermore, the present invention also discloses an application method of using the aforementioned brightener A and brightener B to open a copper electroplating tank.

[0027] Specifically, the compounding of sulfate copper plating brightener and organic dye can effectively improve the problems of insufficient brightness, poor leveling, large coating stress, poor plating solution stability, etc. of sulfate copper plating brightener series at medium and low potentials. The electroplating copper brightener disclosed in the prior art has the defects of small working temperature range and easy decomposition at high temperature; therefore, when using the existing electroplating copper brightener, it is easy to cause the copper-plated products to have appearance defects such as pinholes or pitting. Moreover, in the preparation process of electroplating copper brightener, the relative combination and relative content of each additive need to be strictly controlled to avoid the electroplating copper brightener having technical problems such as poor dispersibility, rough coating crystallization, and lack of brightness.

[0028] The present invention optimizes the brightener formula and compounding it with organic dyes, which can significantly improve the quality and stability of the coating and meet the needs of copper-plated products in different fields. Therefore, the present invention solves the technical problems of poor dispersibility, rough crystallization of the coating, lack of brightness, etc. of the existing electroplating copper brightener.

[0029] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0030] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A copper electroplating brightener, characterized in that: It includes: Brightener A and brightener B; wherein, the components of brightener A include: M, N, SP, P and organic dye RLZ; the components of brightener B include: P and SP.

2. The copper electroplating brightener according to claim 1, characterized in that: M is: 2-mercaptobenzoimidazole, N is ethylenethiourea, SP is sodium polydisulfide dipropane sulfonate and P is polyethylene glycol, M=10000.

3. The copper electroplating brightener according to claim 2, characterized in that: In parts by mass, the components of brightener A include: 0.872 parts of M, 0.594 parts of N, 15 parts of P, 10 parts of SP and 0.06 parts of organic dye RLZ.

4. The copper electroplating brightener according to claim 3, characterized in that: By mass, the components of brightener B include: 290 parts of P and 89 parts of SP.

5. A method for preparing a copper electroplating brightener as claimed in claim 4, characterized in that: It includes the following steps: S11: weigh 0.872 g of M into a 500 mL beaker, add 200 mL of deionized water at 90°C to 100°C into the beaker, and stir until M is completely dissolved; S12: When the temperature of the system in the beaker drops to 80°C to 85°C, 0.594 g of N is added thereto and stirred evenly until N is completely dissolved; S13: When the temperature of the system in the beaker drops to 70°C to 75°C, add 15 g of P therein and stir evenly until P is completely dissolved; S14: When the temperature of the system in the beaker drops to 40°C to 45°C, add 10 g of SP and stir evenly until the SP is completely dissolved; S15: When the temperature of the system in the beaker drops to room temperature, add 0.06 g of organic dye RLZ therein, stir until the organic dye RLZ is completely dissolved, and then transfer all the solution in the beaker into a 1 L volumetric flask to make up the volume to prepare brightener A.

6. The method for preparing a copper electroplating brightener according to claim 5, characterized in that: It includes the following steps: S21: weigh 290 g of P into a 500 mL beaker, add 200 mL of deionized water at 70° C. to the beaker, and stir until P is completely dissolved; S22: When the temperature of the system in the beaker drops to 40°C-45°C, add 89 g of SP and stir evenly until SP is completely dissolved. Then, transfer all the solution in the beaker into a 1 L volumetric flask to make up the volume to prepare brightener B.

7. A method for applying the copper electroplating brightener according to claim 6, characterized in that: It includes the following steps: S1: Prepare the following materials: copper sulfate 60g / L, sulfuric acid 240g / L, Cl- 60mg / L, brightener A 1mL / L, brightener B 0.2mL / L.

8. S2: Clean the working cylinder first; then add 2 / 3 volume of DI water into the working cylinder; S3: Start pumping in the working cylinder and add 60g / L Cu2SO4·5H2O; S4: Carefully and slowly add 240 g / L AR grade 98% H2SO4; S5: Analyze and adjust the contents of Cu2SO4·5H2O, H2SO4 and Cl- to make each component within the control range; S6: When the temperature in the working cylinder drops to 22°C to 30°C, add 1 mL / L of brightener A into it; S7: Continue to add 0.2mL / L of brightener B into the working cylinder; S8: Dummy electrolysis condition control parameters are: 5ASF * 6 hours, 20ASF * 2 hours S9: Complete the copper electroplating tank opening process.