Metal surface electrochemical oil removal liquid and application thereof

Abstract

The invention relates to the technical field of metal surface treatment, and discloses a metal surface electrochemical oil removal liquid and application thereof.The metal surface electrochemical oil removal liquid comprises 23-66 g / L of basic salt and 4-7 g / L of hexamethylenetetramine, and the oil removal liquid is applied to copper base material surface oil removal. The oil removal liquid does not increase the corrosion risk of a metal substrate, is high in oil removal capacity and oil removal efficiency, and has a better oil removal effect at normal temperature.

Description

Technical Field

[0001] The invention relates to the technical field of metal surface treatment, and in particular to a metal surface electrochemical degreasing liquid and application thereof. Background Art

[0002] In industrial manufacturing, oily substances such as lubricating oil, cutting fluid and anti-rust oil are easily attached to the surface of metal substrates. The presence of these oily substances will not only affect the subsequent surface treatment processes such as electroplating, welding and coating, but also reduce the adhesion and corrosion resistance of the equipment. Electrochemical degreasing technology is one of the methods for removing oil stains from the surface of metal substrates. It applies an electric field in the electrolyte to cause an electrochemical reaction on the surface of the substrate, generate bubbles and local heating, and then the grease attached to the surface of the substrate is emulsified, decomposed or detached, thereby achieving the purpose of cleaning. For example, Chinese patent CN106591933A discloses an electrolyte for degreasing and rust removal on metal surfaces. Each liter of electrolyte contains 30-50g of trisodium phosphate, 40-60g of sodium nitrate, 10-20g of hexamethylenetetramine and 100-120g of potassium chloride. The preparation method is to dissolve various solid raw materials in the electrolyte in water and adjust the pH to 1-2 with 30% hydrochloric acid. However, during the electrolysis process, the combined effect of electric current and acidic electrolyte will increase the corrosion risk of the metal substrate. At the same time, the electrolyte contains strong acid components, which will cause environmental pollution. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides a metal surface electrochemical degreasing liquid and its application. The degreasing liquid is alkaline, does not increase the corrosion risk of the metal substrate, and has high degreasing efficiency.

[0004] The specific technical scheme of the present invention is: A metal surface electrochemical degreasing liquid comprises 23-66 g / L alkaline salt and 4-7 g / L hexamethylenetetramine.

[0005] The present invention selects hexamethylenetetramine as a surfactant, which can accelerate the emulsification and decomposition process of grease. At the same time, after adding hexamethylenetetramine, the Tafel slope of the copper substrate is significantly reduced, which shows that the presence of hexamethylenetetramine reduces the polarization resistance in the electrochemical degreasing process, enhances the kinetic characteristics of the reaction, and realizes rapid degreasing. Alkaline salts can produce saponification, react with grease to generate water-soluble glycerol and salts of higher fatty acids, and remove grease. In addition, alkaline salts can neutralize acidic substances in grease and convert them into water-soluble salts, making it easier for grease to be separated from the metal surface and dissolved in water, thereby improving degreasing efficiency. The components used in the present invention are free of strong acids and alkalis, and the corrosion risk of the metal substrate will not be increased.

[0006] Preferably, the alkaline salt includes at least one of sodium carbonate, sodium silicate, sodium phosphate, sodium citrate and ammonium benzoate.

[0007] Preferably, the alkaline salt includes sodium silicate, sodium phosphate and sodium carbonate.

[0008] Preferably, the concentration of sodium silicate is 20-30 g / L, the concentration of sodium phosphate is 2-6 g / L, and the concentration of sodium carbonate is 20-30 g / L.

[0009] Preferably, 2-4 g / L sodium dodecylbenzene sulfonate is also included.

[0010] In the above technical scheme, hexamethylenetetramine and sodium dodecylbenzene sulfonate are selected as surfactants, and there is a synergistic effect between hexamethylenetetramine and sodium dodecylbenzene sulfonate. Specifically, since sodium dodecylbenzene sulfonate can enter the micelle of hexamethylenetetramine, the repulsive force between the ion heads is weakened, and a high-strength mixed interface film is formed. In addition, due to the strong interaction between the hydrophobic chains of the two, mixed micelles are more easily formed, and the critical micelle concentration of the composite solution is reduced, thereby increasing the surface activity of the surfactant, reducing the surface tension of the solution, and further improving the oil removal efficiency.

[0011] Preferably, the alkaline salt includes sodium carbonate, sodium citrate and ammonium benzoate.

[0012] Preferably, the concentration of sodium carbonate is 14-16 g / L, the concentration of sodium citrate is 3-5 g / L, and the concentration of ammonium benzoate is 6-8 g / L.

[0013] The present invention also provides an application of a metal surface electrochemical degreasing liquid in degreasing a copper substrate surface. The metal surface electrochemical degreasing liquid is the above-mentioned degreasing liquid, comprising the following steps: placing a copper substrate and an anode material in the degreasing liquid at 20-60° C., and performing an electrochemical degreasing treatment.

[0014] In the above technical scheme, if the temperature of the degreasing liquid is too low, the degreasing effect will be reduced and even corrosion will occur on the copper surface; if the temperature of the degreasing liquid is too high, hexamethylenetetramine or sodium dodecylbenzene sulfonate will be inactivated as a surfactant, reducing the degreasing ability. At the same time, if the temperature is too high, the evaporation of the solution will be accelerated, increasing the production cost.

[0015] Preferably, the electrochemical degreasing treatment time is 10-30s.

[0016] As a preferred method, the current density used in the electrochemical degreasing treatment is 4-12A / dm 2 .

[0017] In the above technical solution, too low current density will cause incomplete electrochemical reaction and reduce the oil removal speed and effect; too high current density will increase energy consumption and aggravate the hydrogen permeation effect, causing excessive corrosion of the copper substrate.

[0018] Preferably, the copper substrate and the anode material are placed in a degreasing solution at 55-60°C, and the electrochemical degreasing treatment time is 25-30s, and the current density is 10-12A / dm 2 .

[0019] Preferably, the copper substrate and the anode material are placed in a degreasing liquid at 25-40°C, and the electrochemical degreasing treatment time is 25-30s, and the current density is 10-12A / dm 2 .

[0020] In the above technical solution, the degreasing liquid can be used for degreasing at room temperature without the need for special heating equipment to heat the degreasing liquid, which not only reduces the risk of thermal damage to the substrate, but also reduces the energy consumption of the process.

[0021] Preferably, the anode material is platinum mesh.

[0022] Compared with the prior art, the present invention has the following advantages: (1) High oil removal efficiency: The present invention uses hexamethylenetetramine as a surfactant, which can accelerate the emulsification and decomposition process of grease. At the same time, after adding hexamethylenetetramine, the Tafel slope of the copper substrate is significantly reduced, which indicates that the presence of hexamethylenetetramine reduces the polarization resistance in the electrochemical oil removal process, enhances the kinetic characteristics of the reaction, and achieves rapid oil removal; the alkaline salt can produce saponification, react with the grease to generate water-soluble glycerol and salts of higher fatty acids to remove the grease. In addition, the alkaline salt can neutralize the acidic substances in the grease and convert them into water-soluble salts, so that the grease is more easily separated from the metal surface and dissolved in water, thereby improving the oil removal efficiency; (2) Good degreasing effect: The water contact angle of the treated copper substrate surface is measured, and the morphology of the silver-plated layer and the corrosion resistance are measured after silver plating. The test results show that the copper substrate surface after degreasing by the degreasing liquid of the present invention has high cleanliness, and all indicators are better than those of commercially available products. The coating is uniform without blistering, peeling, etc. The adhesion test reaches the 5B grade of the international standard ASTM D3359, which proves that the degreasing liquid of the present invention has a good degreasing effect, which is significantly improved compared with the existing products. (3) Achieving oil removal at room temperature: Examples 23 and 24 show that the oil removal liquid of the present invention can be used for electrochemical oil removal at room temperature (25-40°C), with an oil removal rate of more than 91% and no corrosion. No additional heating equipment is required to heat the oil removal liquid, which not only reduces the risk of thermal damage to the substrate, but also reduces the energy consumption of the process. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a diagram of the oil removal rate of Examples 23-29 of the present invention; Figure 2 is a diagram of the oil removal rate of Examples 30-34 of the present invention; Figure 3 is a diagram of the oil removal rate of Examples 35-41 of the present invention; Figure 4 Graphs of water contact angles measured in Example 26 of the present invention, Comparative Example 1 and Blank Example 1; Figure 5 It is the SEM picture of the zinc coating layer obtained in Example 26 of the present invention, Comparative Example 1 and Blank Example 1; Figure 6 It is the Tafel curve of Example 26 of the present invention, Comparative Example 1 and Blank Example 1 in 3.5% NaCl solution. DETAILED DESCRIPTION

[0024] The present invention is described below by specific examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. Without departing from the spirit and scope of the inventive concept, changes and advantages that can be thought of by those skilled in the art are included in the present invention, and the attached claims and any equivalents thereof are the protection scope of the present invention.

[0025] Unless otherwise defined, all technical terms and scientific terms used in the present invention have the same meanings as those commonly understood by ordinary technicians in the field to which the present disclosure belongs. Unless otherwise specified, the raw materials and equipment used in the present invention are conventional raw materials and equipment in the field and can be obtained from conventional commercial channels; unless otherwise specified, the methods used in the present invention are conventional methods in the field.

[0026] It should be noted that the materials used in the following examples are as follows: Copper sheet: from high-purity metal material research, the copper sheet is cut into specifications of 2cm×2cm×0.2mm; Platinum mesh: from high-purity metal material research; Artificial oil pollution: obtained by mixing 15W-40 engine oil and KR-0058 cutting fluid in a ratio of 1:1; 15W-40 engine oil comes from Qianli Jiangshan Auto Parts Store, and KR-0058 cutting fluid comes from Jiangsu Kuorun Chemical Co., Ltd.; Commercially available degreasing liquid: LQN-1048 electroplating cleaning agent, from Guangzhou Liannuo Chemical Technology Co., Ltd.; the pH of the product is 11.5-13.5; Silver plating solution: Q / YS.801 Yishun brand, from Guangzhou Yishun Chemical Co., Ltd.

[0027] Embodiment 1: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 14 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 6 g / L ammonium benzoate.

[0028] The preparation method is as follows: dissolving the above raw materials in water, mixing them in sequence, stirring them evenly, and obtaining the degreasing liquid.

[0029] Embodiment 2: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 14 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 7 g / L ammonium benzoate.

[0030] The preparation method is the same as that in Example 1.

[0031] Embodiment 3: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 14 g / L anhydrous sodium carbonate, 5 g / L sodium citrate and 8 g / L ammonium benzoate.

[0032] The preparation method is the same as that in Example 1.

[0033] Embodiment 4: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 15 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 7 g / L ammonium benzoate.

[0034] The preparation method is the same as that in Example 1.

[0035] Embodiment 5: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 15 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0036] The preparation method is the same as that in Example 1.

[0037] Embodiment 6: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 15 g / L anhydrous sodium carbonate, 5 g / L sodium citrate and 6 g / L ammonium benzoate.

[0038] The preparation method is the same as that in Example 1.

[0039] Embodiment 7: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate.

[0040] The preparation method is the same as that in Example 1.

[0041] Embodiment 8: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 6 g / L ammonium benzoate.

[0042] The preparation method is the same as that in Example 1.

[0043] Embodiment 9: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 5 g / L sodium citrate and 7 g / L ammonium benzoate.

[0044] The preparation method is the same as that in Example 1.

[0045] Embodiment 10: A metal surface electrochemical degreasing liquid comprises the following components: 4 g / L hexamethylenetetramine, 2 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0046] The preparation method is the same as that in Example 1.

[0047] Embodiment 11: A metal surface electrochemical degreasing liquid comprises the following components: 4 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0048] The preparation method is the same as that in Example 1.

[0049] Embodiment 12: A metal surface electrochemical degreasing liquid comprises the following components: 4 g / L hexamethylenetetramine, 4 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0050] The preparation method is the same as that in Example 1.

[0051] Embodiment 13: A metal surface electrochemical degreasing liquid comprises the following components: 5 g / L hexamethylenetetramine, 2 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0052] The preparation method is the same as that in Example 1.

[0053] Embodiment 14: A metal surface electrochemical degreasing liquid comprises the following components: 5 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0054] The preparation method is the same as that in Example 1.

[0055] Embodiment 15: A metal surface electrochemical degreasing liquid comprises the following components: 5 g / L hexamethylenetetramine, 4 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0056] The preparation method is the same as that in Example 1.

[0057] Embodiment 16: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 2 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0058] The preparation method is the same as that in Example 1.

[0059] Embodiment 17: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0060] The preparation method is the same as that in Example 1.

[0061] Embodiment 18: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 4 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0062] The preparation method is the same as that in Example 1.

[0063] Embodiment 19: A metal surface electrochemical degreasing liquid comprises the following components: 7 g / L hexamethylenetetramine, 2 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0064] The preparation method is the same as that in Example 1.

[0065] Embodiment 20: A metal surface electrochemical degreasing liquid comprises the following components: 20 g / L sodium silicate, 2 g / L sodium phosphate, 20 g / L anhydrous sodium carbonate and 4 g / L hexamethylenetetramine.

[0066] The preparation method is as follows: dissolving the above raw materials in water, mixing them in sequence, stirring them evenly, and obtaining the degreasing liquid.

[0067] Embodiment 21: A metal surface electrochemical degreasing liquid comprises the following components: 25 g / L sodium silicate, 4 g / L sodium phosphate, 25 g / L anhydrous sodium carbonate and 5 g / L hexamethylenetetramine.

[0068] The preparation method is the same as that of Example 20.

[0069] Embodiment 22: A metal surface electrochemical degreasing liquid comprises the following components: 30 g / L sodium silicate, 6 g / L sodium phosphate, 30 g / L anhydrous sodium carbonate and 6 g / L hexamethylenetetramine.

[0070] The preparation method is the same as that of Example 20.

[0071] Embodiment 23: The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: at room temperature of 25°C, the degreasing liquid is added to an electrolytic cell, the copper substrate is fixed in the degreasing liquid as a cathode, the platinum mesh is fixed in the degreasing liquid as an anode, the electrolytic cell is connected to a DC power supply, and an electrochemical degreasing treatment is performed, and the current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0072] Embodiment 24: The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: at room temperature of 40°C, the degreasing liquid is added to an electrolytic cell and heated to 40°C, a copper substrate is fixed in the degreasing liquid as a cathode, a platinum mesh is fixed in the degreasing liquid as an anode, the electrolytic cell is connected to a DC power supply, and an electrochemical degreasing treatment is performed, and the current density is controlled to be 10A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0073] Embodiment 25: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 50°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0074] Embodiment 26: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0075] Embodiment 27: The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 70°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0076] Embodiment 28: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 80°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a direct current power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0077] Embodiment 29: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid to an electrolytic cell and heating the degreasing liquid to 90°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0078] Embodiment 30: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 10s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0079] Embodiment 31: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 15s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0080] Embodiment 32: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 20s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0081] Embodiment 33: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 25s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0082] Embodiment 34: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The processing time is 35s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0083] Embodiment 35: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid to an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 4 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0084] Embodiment 36: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 6A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0085] Embodiment 37: The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 8A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0086] Embodiment 38: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a direct current power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 12 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0087] Embodiment 39: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 14 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0088] Embodiment 40: The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 16 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0089] Embodiment 41: The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 6 g / L hexamethylenetetramine, 3 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 60°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 18 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0090] Comparative Example 1: The commercially available LQN-1048 electroplating cleaning agent was used as the degreasing liquid. The degreasing liquid was added to the electrolytic cell and heated to 60°C. The copper substrate was fixed in the degreasing liquid as the cathode, and the platinum mesh was fixed in the degreasing liquid as the anode. The electrolytic cell was connected to a DC power supply for electrochemical degreasing treatment. The current density was controlled to be 10A / dm 2The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried.

[0091] Comparative Example 2: A metal surface electrochemical degreasing liquid comprises the following components: 2 g / L hexamethylenetetramine, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0092] The preparation method is the same as that in Example 1.

[0093] Comparative Example 3: A metal surface electrochemical degreasing liquid comprises the following components: 4 g / L hexamethylenetetramine, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0094] The preparation method is the same as that in Example 1.

[0095] Comparative Example 4: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L hexamethylenetetramine, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0096] The preparation method is the same as that in Example 1.

[0097] Comparative Example 5: A metal surface electrochemical degreasing liquid comprises the following components: 8 g / L hexamethylenetetramine, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0098] The preparation method is the same as that in Example 1.

[0099] Comparative Example 6: A metal surface electrochemical degreasing liquid comprises the following components: 10 g / L hexamethylenetetramine, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0100] The preparation method is the same as that in Example 1.

[0101] Comparative Example 7: A metal surface electrochemical degreasing liquid comprises the following components: 2 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0102] The preparation method is the same as that in Example 1.

[0103] Comparative Example 8: A metal surface electrochemical degreasing liquid comprises the following components: 4 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0104] The preparation method is the same as that in Example 1.

[0105] Comparative Example 9: A metal surface electrochemical degreasing liquid comprises the following components: 6 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0106] The preparation method is the same as that in Example 1.

[0107] Comparative Example 10: A metal surface electrochemical degreasing liquid comprises the following components: 8 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0108] The preparation method is the same as that in Example 1.

[0109] Comparative Example 11: A metal surface electrochemical degreasing liquid comprises the following components: 10 g / L sodium dodecylbenzene sulfonate, 16 g / L anhydrous sodium carbonate, 4 g / L sodium citrate and 8 g / L ammonium benzoate.

[0110] The preparation method is the same as that in Example 1.

[0111] Comparative Example 12: The invention discloses an application of an electrochemical degreasing liquid on a metal surface in degreasing a copper substrate surface. The degreasing liquid comprises 9 g / L sorbitan monooleate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: at room temperature of 40°C, adding the degreasing liquid into an electrolytic cell and heating the degreasing liquid to 40°C, fixing the copper substrate as a cathode in the degreasing liquid, fixing a platinum mesh as an anode in the degreasing liquid, connecting the electrolytic cell to a DC power supply, and performing electrochemical degreasing treatment. The current density is controlled to be 10 A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0112] Comparative Example 13 The invention discloses an application of an electrochemical degreasing liquid for metal surface in degreasing the surface of a copper substrate. The degreasing liquid comprises 9 g / L sodium lignin sulfonate, 16 g / L anhydrous sodium carbonate, 3 g / L sodium citrate and 8 g / L ammonium benzoate. The specific steps are as follows: at room temperature of 40°C, the degreasing liquid is added to an electrolytic cell and heated to 40°C, the copper substrate is fixed in the degreasing liquid as a cathode, the platinum mesh is fixed in the degreasing liquid as an anode, the electrolytic cell is connected to a DC power supply, and an electrochemical degreasing treatment is performed, and the current density is controlled to be 10A / dm 2 The treatment time is 30s. After the electrochemical degreasing treatment is completed, the copper substrate is taken out from the above degreasing liquid, rinsed and dried, and subsequent processing can be carried out after drying.

[0113] Blank example 1: A copper substrate that has not been subjected to electrochemical degreasing treatment was used as a blank control for Example 18 and Comparative Example 1.

[0114] Test Example 1: According to JB / T 4323-2019 "Water-based Metal Cleaner", the oil removal rate of Examples 1-9 was determined as follows: the surface of the copper sheet was first cleaned with ethanol and distilled water, dried and weighed as m1; the artificial oil stain was evenly applied to the surface of the copper sheet, left to stand for 20 minutes, and the oil stain accumulated at the lower end was scraped off and weighed as m2; the copper sheet was used as the cathode and the platinum mesh was used as the anode, and electrolytic degreasing was performed at 50°C for 20 seconds, with a current density of 7A / dm 2 After degreasing, take out the copper sheet, heat and dry it at 60°C for 20 minutes, weigh it and record it as m3, and calculate the degreasing rate η according to the following formula: η% = ((m2-m3)) / ((m2-m1))×100%, and measure the pH value of the degreasing liquid prepared in Examples 1-9. The results are shown in Table 1.

[0115] Table 1 pH value and oil removal rate of Examples 1-9 Example pH Oil removal rate (%) 1 12.2 92.52 2 12.3 93.95 3 12.4 92.93 4 12.2 92.92 5 12.3 93.77 6 12.4 94.65 7 12.2 96.42 8 12.3 95.38 9 12.2 94.61 It can be seen from the above table that the pH values ​​of the degreasing liquids prepared in all the examples are greater than 12, and the degreasing rates are greater than 92.5%, indicating that the degreasing liquids can remove oil quickly and have good degreasing effects.

[0116] Test Example 2: According to JB / T 4323-2019 "Water-based Metal Cleaners", the oil removal rates of Examples 23-41 were measured respectively, and the results are as follows: Figure 1-3 As shown. Figure 1 As shown, the oil removal rates of Examples 23-29 are all greater than 91.0%, indicating that the oil removal effect of the oil removal liquid is good within the temperature range of 25-90°C. Figure 1It can be seen that within the temperature range of 55-90℃, the oil removal rate of the oil removal liquid can reach more than 97.0%, proving that the oil removal effect of the oil removal liquid in this temperature range is the best. Figure 2 As shown, the oil removal rates of Examples 30-34 are all greater than 92.0%, indicating that when the electrochemical oil removal treatment time is 10-35s, the oil removal effect of the oil removal liquid is good. Figure 2 It can be seen that when the electrochemical degreasing treatment time is 25-35s, the degreasing rate of the degreasing liquid can reach more than 98.0%, proving that the degreasing effect of this electrochemical degreasing treatment time is optimal. Figure 3 As shown, the oil removal rates of Examples 35-41 are all greater than 92.0%, indicating that the current density is 4-18 A / dm 2 When the oil removal liquid has good oil removal effect, Figure 3 It can be seen that when the current density is 10-18A / dm 2 , the oil removal rate of the oil removal liquid can reach more than 99.0%, proving that the oil removal effect is optimal in this current density range.

[0117] Test Example 3: The water contact angle of the copper substrate after degreasing treatment in Example 26 and Comparative Example 1 and the copper substrate of Blank Example 1 was measured by a contact angle measuring instrument produced by Audlino Co., Ltd. of Germany and corresponding analysis and testing software. The measurement results are as follows: Figure 4 shown. Figure 4 In the figure, a is blank example 1, b is comparative example 1, and c is the measured result of Example 26. Figure 4 It can be seen that the water contact angle on the surface of the copper sheet after degreasing is significantly smaller than that before degreasing, and the water contact angle on the surface of the copper substrate in Example 26 is smaller than that in Comparative Example 1, which means that the emulsification effect of the degreasing liquid of the present invention is better than that of commercially available products, so that water molecules can fully contact with the surface of the copper sheet, reducing the solid-liquid interfacial tension between the surface of the copper sheet and the water molecules, and improving the degreasing effect.

[0118] The copper substrates after degreasing treatment in Example 26 and Comparative Example 1 and the copper substrate of Blank Example 1 were silver plated. The commercially available Q / YS.801 Yishun brand silver plating solution was selected. The VEGA3SBU and related software produced by Czech Tescan Company were used to measure the morphology of the silver plated layer. The SEM images at magnifications of 1000, 3000 and 6000x were measured respectively. The measurement results are shown in FIG. Figure 5 shown. Figure 5 In the figure, ac is the silver-plated layer on the surface of the copper substrate in Comparative Example 1, df is the silver-plated layer on the surface of the copper substrate in Example 26, and gi is the silver-plated layer on the surface of the copper substrate in Blank Example 1. Figure 5It can be seen that the silver-plated layer on the surface of the copper substrate in Example 26 has a uniform surface, a dense coating, less missed plating, and a high coating quality; the silver-plated layer on the surface of the copper substrate in Comparative Example 1 has a more obvious missed plating phenomenon, and the surface is relatively rough, and the coating quality is poor; the silver-plated layer on the surface of the copper substrate in Blank Example 1 has a more obvious missed plating phenomenon, a large surface roughness, and a worse coating quality. This proves that: after degreasing with the degreasing liquid of the present invention, the amount of oil stains on the surface of the copper substrate is less, the residual oil stains are easy to rinse, the silver-plated layer can fully contact the surface of the copper sheet during silver plating, the surface activity of the test piece is good, and the speed of grain formation is fast. When electroplating for a short time, the higher the surface activity of the test piece, the more uniform and dense the plating layer is formed, the less leakage plating phenomenon of the obtained silver-plated layer is, and the surface uniformity is good; while after degreasing with the commercially available product, the amount of oil stains on the surface of the copper substrate is large, and there are still residues after rinsing, the surface activity of the test piece is poor, the speed of grain formation is slow, and the quality of the silver-plated copper sheet obtained during silver plating is poor, which affects the quality and service life of the copper sheet. This proves that the degreasing liquid of the present invention has a better degreasing effect.

[0119] In addition, according to the international standard ASTM D3359-17, the adhesion of the silver-plated layer on the surface of the copper substrate of Example 26 was tested. The test results showed that the edge of the coating cut was smooth and there was no coating shedding, reaching the 5B grade of the standard, which proves that the degreasing liquid of the present invention has a good degreasing effect and the obtained coating has good adhesion.

[0120] A three-electrode system was used on the Chenhua electrochemical workstation to test the linear voltammetric curve (LSV) and Tafel polarization curve (Tafel) of the above-mentioned silver-plated copper substrate in a 3.5% NaCl solution. The Ag / AgCl electrode was used as the reference electrode, the platinum electrode was used as the auxiliary electrode, and the copper substrate was used as the working electrode. During the linear voltammetric test, the scan rate was 50 mV / s. The measured results are shown in Table 2. The Tafel curve results obtained from the LSV curve are shown in Table 2. Figure 6 shown.

[0121] Table 2 Self-corrosion current and corrosion potential data Sample Corrosion potential / mV Self-corrosion current / μA Blank example 1 -310.3 67.2 Comparative Example 1 -279.2 29.8 Embodiment 26 -260.4 27.9 Depend on Figure 6 As can be seen from Table 2, compared with Blank Example 1 and Comparative Example 1, the corrosion potential of Example 26 is more positive, and the corrosion current is only 27.9 μA, which is much smaller than 67.2 μA of Blank Example 1, which means that the corrosion rate of the silver-plated copper substrate after degreasing with the degreasing liquid of the present invention is 1 / 2 of the silver-plated copper substrate without degreasing, indicating that the residual amount of oil on the surface of the copper substrate after degreasing is small, the zinc plating layer is of high quality, the plating layer is more uniform and has good bonding strength, so its corrosion resistance is stronger; according to the experimental data, the Tafel slope of the degreasing liquid of the present invention is reduced by about 40% compared with the commercially available degreasing liquid, which directly indicates that the degreasing liquid of the present invention has higher current efficiency and faster degreasing speed.

[0122] Test Example 4: The surface tension and oil removal rate of the degreasing liquid prepared in Examples 10-18 and Comparative Examples 2-11 were tested. The specific method for testing the surface tension was as follows: using the hanging ring method, at an ambient temperature of 20±5°C, the surface tension of the degreasing liquid with a mass concentration of 10 g / L was measured by a JYW-200A automatic interfacial tension meter; the method for testing the oil removal rate was the same as that of Test Example 1, and the results are shown in the following table.

[0123] Table 3 Surface tension and oil removal rate of Examples 10-18 and Comparative Examples 2-11 It can be seen from Table 3 that the oil removal rates of the oil removal liquids prepared in all embodiments are greater than 90.4%, with the highest reaching 96.58, and the oil removal effects are better than those of Comparative Examples 2-11. It can be seen that hexamethylenetetramine and sodium dodecylbenzene sulfonate have a synergistic effect, and there is no correlation between the surface tension of the oil removal liquid containing the composite surfactant of hexamethylenetetramine and sodium dodecylbenzene sulfonate and its oil removal rate, which is inconsistent with the relationship between the surface tension of the oil removal liquid containing a single hexamethylenetetramine surfactant and a single sodium dodecylbenzene sulfonate surfactant and the oil removal rate.

[0124] Test Example 5 Comparing the oil removal rates of Example 24 and Comparative Examples 12 and 13 at room temperature of 40°C, the test standards and test methods are the same as those of Test Example 1, and the test results are shown in the following table.

[0125] Table 4 Oil removal rate of Example 24 and Comparative Examples 12 and 13 Sample Oil removal rate Embodiment 24 94.37 Comparative Example 12 88.81 Comparative Example 13 88.54 It can be seen from Table 4 that at 40°C, the oil removal rate of the oil removal liquid prepared by the present invention is much higher than that of the comparative example, which proves that the oil removal liquid of the present invention can be electrochemically degreased at room temperature and has better oil removal ability than conventional ones.

[0126] The raw materials and equipment used in the present invention, unless otherwise specified, are all commonly used raw materials and equipment in the art; the methods used in the present invention, unless otherwise specified, are all conventional methods in the art.

[0127] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A metal surface electrochemical degreasing liquid, characterized in that: It includes 23-66 g / L alkaline salt and 4-7 g / L hexamethylenetetramine.

2. The electrochemical degreasing liquid for metal surface according to claim 1, characterized in that: The alkaline salt includes one or more of sodium carbonate, sodium silicate, sodium phosphate, sodium citrate and ammonium benzoate.

3. The electrochemical degreasing liquid for metal surface according to claim 2, characterized in that: The alkaline salts include sodium silicate, sodium phosphate and sodium carbonate.

4. The electrochemical degreasing liquid for metal surface according to claim 3, characterized in that: The concentration of sodium silicate is 20-30g / L, the concentration of sodium phosphate is 2-6g / L, and the concentration of sodium carbonate is 20-30g / L.

5. The electrochemical degreasing liquid for metal surface according to claim 2, characterized in that: Also includes 2-4 g / L sodium dodecylbenzene sulfonate.

6. The electrochemical degreasing liquid for metal surface according to claim 5, characterized in that: Such basic salts include sodium carbonate, sodium citrate and ammonium benzoate.

7. The electrochemical degreasing liquid for metal surface according to claim 6, characterized in that: The concentration of sodium carbonate is 14-16 g / L, the concentration of sodium citrate is 3-5 g / L, and the concentration of ammonium benzoate is 6-8 g / L.

8. Use of a metal surface electrochemical degreasing liquid in degreasing a copper substrate surface, the metal surface electrochemical degreasing liquid being the degreasing liquid according to any one of claims 1 to 7, characterized in that: The following steps are involved: The copper substrate and anode material are placed in a degreasing liquid at 20-60°C for electrochemical degreasing treatment.

9. The use of a metal surface electrochemical degreasing liquid according to claim 8 in degreasing the surface of a copper substrate, characterized in that: The electrochemical degreasing treatment time is 10-30s.

10. Use of a metal surface electrochemical degreasing liquid according to claim 9 in degreasing a copper substrate surface, characterized in that: The current density used in electrochemical degreasing treatment is 4-12A / dm 2 .

11. The use of a metal surface electrochemical degreasing liquid according to claim 10 in degreasing a copper substrate surface, characterized in that: Place the copper substrate and anode material in a degreasing solution at 55-60°C. The electrochemical degreasing treatment time is 25-30s and the current density is 10-12A / dm 2 .

12. The use of a metal surface electrochemical degreasing liquid according to claim 10 in degreasing a copper substrate surface, characterized in that: Place the copper substrate and anode material in a degreasing solution at 25-40°C. The electrochemical degreasing treatment time is 25-30s and the current density is 10-12A / dm 2 .

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