Environment-friendly copper material surface cleaning agent and preparation method thereof

Abstract

The invention discloses an environment-friendly copper material surface cleaning agent and a preparation method thereof, and relates to the field of cleaning agents. The rust remover comprises the following components in percentage by weight: 3-8% of a rust remover, 0.1-1% of a chelating agent, 0.2-1% of a nonionic surfactant, 0.01-0.05% of a corrosion inhibitor, 0.3-1% of a stabilizer, 0.5-2% of a pH regulator and the balance of water. The preparation method comprises the following steps: adding the nonionic surfactant and the stabilizer into water, stirring for 5-10 minutes to completely dissolve the nonionic surfactant and the stabilizer, then adding the rust remover, the chelating agent and the corrosion inhibitor, stirring for 10-15 minutes, finally adding the pH regulator, stirring for 3-6 minutes, and regulating the pH to 3.5-5.5, thereby obtaining the rust remover. The cleaning agent has an excellent cleaning effect and can effectively remove impurities such as an oxide layer, particulate pollutants and organic residues on the surface of a copper material, the surface of the cleaned copper material is bright and free of oxidation, the components are mainly plant extracted acid, and the cleaning agent has high safety and environmental friendliness and is suitable for an ultrasonic cleaning process.

Description

Technical Field

[0001] The invention belongs to the technical field of cleaning agents, and in particular relates to an environmentally friendly copper surface cleaning agent and a preparation method thereof. Background Art

[0002] With the continuous progress of modern industry, copper and its alloys have been widely used in many fields such as electronics, electrical, construction and automobiles due to their excellent electrical conductivity, thermal conductivity and good mechanical properties. However, during the thermal pretreatment, storage and use, the surface of copper is susceptible to oxidation, corrosion or contamination by various pollutants, which not only affects the appearance quality of the material, but also may have an adverse effect on its performance and service life. Therefore, effective cleaning technology is essential to maintain the best condition of copper.

[0003] Patent CN 115466965 A discloses a metal cleaning agent and its preparation method. The invention includes 1-30% fluoride, 1-10% organic amine complexing agent, 1-15% surfactant, 1-5% penetrant, 5-30% alkali metal hydroxide, 30-70% inorganic salt, and 0.01-0.1% corrosion inhibitor by weight percentage. The synergistic effect principle between fluoride and organic amine complexing agent is applied to copper cleaning agent, so that the copper cleaning agent can remove oil and rust in one step, with a short process flow and water and energy saving. However, this method contains a large amount of fluoride and strong alkali components, which are harmful to the human body and the environment. Patent CN 114990559 A discloses a cleaning agent for brass. The cleaning agent is composed of sulfuric acid, ferrous sulfate, hydrogen peroxide, ethanol or acetic acid, benzotriazole and water. The brass after cleaning has high finish, will not change color after being placed for more than 24 hours, and there is basically no odor during the cleaning process. However, this method has a relatively high sulfuric acid content, which will significantly increase the corrosion to the copper surface, and has great harm to human health and the ecological environment. Patent CN 113136581 A discloses a copper surface cleaning agent and its preparation method. First, the introduced substance is simultaneously generated into a polymer precursor and N- (6-aminohexyl) -1,6-hexanediamine pentamethylenephosphonic acid, and the two reaction products are combined with each other to form a composite copolymer with strong cleaning ability. Subsequently, through multi-step modification, the prepared copper surface cleaning agent product has good dispersibility, a stable system, and strong cleaning ability. However, this method has complex preparation steps and high costs, and cannot well realize industrial environmentally friendly large-scale production.

[0004] Therefore, the copper surface cleaning field urgently needs an environmentally friendly, efficient, safe, low-corrosive cleaning agent with a simple preparation method. Summary of the invention

[0005] In order to solve the above problems, the present invention provides an environmentally friendly copper surface cleaning agent and a preparation method thereof, which can effectively remove impurities such as oxide layer, particulate pollutants and organic residues on the surface of copper materials, while ensuring that the treated copper surface meets the requirements of low corrosion, no oxidation, bright surface and no residue.

[0006] To achieve the above object, the present invention adopts the following technical solution: An environmentally friendly copper surface cleaning agent and a preparation method thereof, which relate to the field of cleaning agents. The invention is characterized in that the cleaning agent comprises the following components by weight percentage: 3-8% rust remover, 0.1-1% chelating agent, 0.2-1% nonionic surfactant, 0.01-0.05% corrosion inhibitor, 0.3-1% stabilizer, 0.5-2% pH adjuster, and the balance is water.

[0007] Furthermore, the rust remover is a natural acid, and the natural acid is one or more of citric acid, glycolic acid, gluconic acid, and malic acid.

[0008] Furthermore, the chelating agent is one or more of nitrilotriacetic acid, gluconic acid, sodium gluconate, ethylenediaminetetraacetic acid, and disodium ethylenediaminetetraacetate.

[0009] Furthermore, the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and fatty acid methyl ester polyoxyethylene ether.

[0010] Furthermore, the corrosion inhibitor is one or more of benzotriazole, methylbenzotriazole, and benzimidazole.

[0011] Furthermore, the stabilizer is one or both of triethanolamine and ethylenediamine.

[0012] Furthermore, the pH adjuster is one or more of acetic acid, phosphoric acid and hydrochloric acid.

[0013] Furthermore, the acetic acid concentration is 50 wt %, the phosphoric acid concentration is 60 wt %, and the hydrochloric acid concentration is 10 wt %.

[0014] Furthermore, the pH value of the cleaning agent is 3.5-5.5.

[0015] A method for preparing an environmentally friendly copper surface cleaning agent comprises the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing a nonionic surfactant, a stabilizer and water, and stirring at a speed of 300 to 800 r / min for 5 to 10 min to obtain a mixed solution A; S3, adding the rust remover, chelating agent and corrosion inhibitor to the mixed solution A, stirring at a speed of 300 to 800 r / min for 5 to 8 min to obtain a mixed solution B; S4. Adjust the pH of the mixed solution B to 3.5-5.5 to obtain a copper surface cleaning agent.

[0016] The present invention utilizes the property that surfactant can significantly reduce the surface tension of solution. Firstly, surfactant, stabilizer and deionized water are used to prepare mixed solution A to increase the stability of cleaning agent and the dissolution rate of subsequent components. Then rust remover, chelating agent and corrosion inhibitor are added, and finally pH regulator is added.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses natural acids such as citric acid as rust removers, based on the dissolution and complexation of the surface oxide layer of the copper material by the acidic substance, soluble salts are formed to restore the surface performance and brightness of the copper material, the copper material loss is low, and it is environmentally friendly; the added nonionic surfactant can significantly reduce the surface tension of the cleaning agent, improve the wetting ability of the cleaning agent to the copper material, remove impurities such as particulate pollutants and organic residues through emulsification and dispersion, increase the contact area between the rust remover and the oxide layer, and improve the cleaning efficiency; the added chelating agent has different degrees of chelating ability for most metal ions, and can form a stable chelate with the dissolved soluble salt to prevent re-adsorption; the reactive groups on the added corrosion inhibitor molecules react with the oxide matrix on the surface of the copper material to form a continuous precipitation film or an insoluble coordination film, thereby inhibiting the oxidation process of the copper material. The four work synergistically, can efficiently remove impurities such as the oxide layer, particulate pollutants and organic residues on the surface of the material, and ensure that the treated copper surface meets the requirements of low corrosion, no oxidation, bright surface and no residue.

[0018] The cleaning agent used in the present invention has a main component of non-toxic natural acid, is easily degradable, is friendly to human health and the ecological environment, and has the advantages of being environmentally friendly, highly efficient, having a simple production process, and having low copper material loss. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a comparison diagram before and after the cleaning agent provided by the present invention is used to clean heat-treated red copper.

[0020] Figure 2 This is a comparison diagram before and after the cleaning agent provided by the present invention cleans the heat-treated brass.

[0021] Figure 3 This is a comparison diagram before and after the cleaning agent provided by the present invention is used to clean heat-treated bronze. DETAILED DESCRIPTION

[0022] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, the purpose of which is to help those skilled in the art understand the content of the present invention in more detail, thereby making a clearer and more definite definition of the protection scope of the present invention, rather than limiting the present invention. All other embodiments obtained by ordinary technicians in this field without making creative work belong to the protection scope of the present invention.

[0023] Example 1 An environmentally friendly copper surface cleaning agent, the components and their corresponding weight percentages are shown in Table 1: Table 1 The composition of the copper surface cleaning agent in Example 1 The copper surface cleaning agent of Example 1 of the present application is prepared by the following steps: S1. Weigh each raw material component according to the weight percentage in Table 1; S2, mixing fatty alcohol polyoxyethylene ether, triethanolamine and water, and stirring at a speed of 300 r / min for 6 min to obtain a mixed solution A; S3, adding citric acid, nitrilotriacetic acid and benzotriazole to the mixed solution A, stirring at a speed of 500 r / min for 8 min to obtain a mixed solution B; S4. Add acetic acid to adjust the pH of the mixed solution B to 4.2 to obtain a copper surface cleaning agent.

[0024] Example 2 An environmentally friendly copper surface cleaning agent, the components and their corresponding weight percentages are shown in Table 2: Table 2 Copper surface cleaning agent formulation composition in Example 2 The copper surface cleaning agent of Example 2 of the present application is prepared by the following steps: S1. Weigh each raw material component according to the weight percentage in Table 2; S2, mixing fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, triethanolamine and water, and stirring at a speed of 400 r / min for 6 min to obtain a mixed solution A; S3, adding citric acid, glycolic acid, disodium ethylenediaminetetraacetate and benzotriazole into the mixed solution A, stirring at a speed of 400 r / min for 5 min to obtain a mixed solution B; S4. Add hydrochloric acid to adjust the pH of the mixed solution B to 3.9 to obtain a copper surface cleaning agent.

[0025] Example 3 An environmentally friendly copper surface cleaning agent, the components and their corresponding weight percentages are shown in Table 3: Table 3 Copper surface cleaning agent formulation composition in Example 3 The copper surface cleaning agent of Example 3 of the present application is prepared by the following steps: S1. Weigh each raw material component according to the weight percentage in Table 3; S2, mixing fatty alcohol polyoxyethylene ether, triethanolamine and water, and stirring at a speed of 600 r / min for 7 min to obtain a mixed solution A; S3, adding malic acid, glycolic acid, gluconic acid, ethylenediaminetetraacetic acid and benzotriazole into the mixed solution A, stirring at a speed of 800 r / min for 8 min to obtain a mixed solution B; S4. Phosphoric acid is added to adjust the pH of the mixed solution B to 4.5 to obtain a copper surface cleaning agent.

[0026] Example 4 An environmentally friendly copper surface cleaning agent, the components and their corresponding weight percentages are shown in Table 4: Table 4 Copper surface cleaning agent formulation composition in Example 4 The copper surface cleaning agent of Example 4 of the present application is prepared by the following steps: S1. Weigh each raw material component according to the weight percentage in Table 4; S2, mixing fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, triethanolamine, ethylenediamine and water, and stirring at a speed of 800 r / min for 9 min to obtain a mixed solution A; S3, adding citric acid, gluconic acid, malic acid, nitrilotriacetic acid, sodium gluconate, benzotriazole and methylbenzotriazole to the mixed solution A, stirring at a speed of 800 r / min for 6 min to obtain a mixed solution B; S4. Add acetic acid to adjust the pH of the mixed solution B to 4.6 to obtain a copper surface cleaning agent.

[0027] Example 5 An environmentally friendly copper surface cleaning agent, the components and their corresponding weight percentages are shown in Table 5: Table 5 Copper surface cleaning agent formulation composition in Example 5 The copper surface cleaning agent of Example 5 of the present application is prepared by the following steps: S1. Weigh each raw material component according to the weight percentage in Table 5; S2, mixing fatty alcohol polyoxyethylene ether, triethanolamine and water, and stirring at a speed of 500 r / min for 8 min to obtain a mixed solution A; S3, adding citric acid, malic acid, glycolic acid, gluconic acid, benzotriazole and benzimidazole into the mixed solution A, stirring at a speed of 600 r / min for 7 min to obtain a mixed solution B; S4. Phosphoric acid is added to adjust the pH of the mixed solution B to 4.0 to obtain a copper surface cleaning agent.

[0028] Example 6 An environmentally friendly copper surface cleaning agent, the components and their corresponding weight percentages are shown in Table 6: Table 6 The composition of the copper surface cleaning agent in Example 6 The copper surface cleaning agent of Example 6 of the present application is prepared by the following steps: S1. Weigh each raw material component according to the weight percentage in Table 6; S2, mixing fatty alcohol polyoxyethylene ether, triethanolamine and water, and stirring at a speed of 400 r / min for 6 min to obtain a mixed solution A; S3, adding citric acid, glycolic acid, disodium ethylenediaminetetraacetate and benzimidazole into the mixed solution A, stirring at a speed of 800 r / min for 8 min to obtain a mixed solution B; S4. Add acetic acid and phosphoric acid to adjust the pH of the mixed solution B to 3.7 to obtain a copper surface cleaning agent.

[0029] Performance testing The performance of the copper surface cleaning agent prepared in Examples 1 to 6 of the present invention was tested. Three types of heat-treated copper materials were placed in a container, and a cleaning solution was poured into the container to cover the copper materials. Ultrasonic treatment was performed at 20 to 70°C for a certain period of time. The copper materials were taken out and rinsed with water. The cleaning effect was observed, and the quality of the copper materials and the changes in surface brightness before and after cleaning were measured. The results are shown in Table 7.

[0030] Table 7 Changes in quality and surface brightness of three different types of copper before and after cleaning Figure 1 This is a comparison diagram of the cleaning agent prepared in Example 1 before and after cleaning the heat-treated copper. Figure 2 This is a comparison diagram of the cleaning agent prepared in Example 3 before and after cleaning the heat-treated brass. Figure 3 This is a comparison of the cleaning agent prepared in Example 5 before and after cleaning the heat-treated bronze. Figures 1 to 3It can be seen that the cleaning agent prepared by the present invention has a good cleaning effect on copper materials of different types and can effectively remove pollutants such as oxide layers on the surface of copper materials.

[0031] In summary, the copper surface cleaning agent of the present application can effectively remove the oxide layer, particulate pollutants, organic residues and other impurities on the surface of the material, ensuring that the surface of the treated copper material meets the requirements of surface cleanliness and brightness. In addition, the cleaning agent used in the present invention is mainly composed of natural products, which are easily degradable, friendly to human health and the ecological environment, and has the advantages of environmental protection, high efficiency, simple production process, and low copper material loss.

[0032] The above description is only a preferred embodiment of the present invention. It should be pointed out that after reading this specification, those skilled in the art may make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. An environmentally friendly copper surface cleaning agent and a preparation method thereof, characterized in that: The invention comprises the following components by weight percentage: 3-8% of rust remover, 0.1-1% of chelating agent, 0.2-1% of nonionic surfactant, 0.01-0.05% of corrosion inhibitor, 0.3-1% of stabilizer, 0.5-2% of pH regulator, and the balance is water.

2. The copper surface cleaning agent according to claim 1, characterized in that: The rust remover is a natural acid, and the natural acid is one or more of citric acid, glycolic acid, gluconic acid and malic acid.

3. The copper surface cleaning agent according to claim 1, characterized in that: The chelating agent is one or more of nitrilotriacetic acid, gluconic acid, sodium gluconate, ethylenediaminetetraacetic acid, and disodium ethylenediaminetetraacetate.

4. The copper surface cleaning agent according to claim 1, characterized in that: The nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and fatty acid methyl ester polyoxyethylene ether.

5. The copper surface cleaning agent according to claim 1, characterized in that: The corrosion inhibitor is one or more of benzotriazole, methylbenzotriazole and benzimidazole.

6. The copper surface cleaning agent according to claim 1, characterized in that: The stabilizer is one or both of triethanolamine and ethylenediamine.

7. The copper surface cleaning agent according to claim 1, characterized in that: The pH adjuster is one or more of acetic acid, phosphoric acid and hydrochloric acid.

8. The copper surface cleaning agent according to claim 1, characterized in that: The pH value of the cleaning agent is 3.5-5.

5.

9. The method for preparing an environmentally friendly copper surface cleaning agent according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Weigh each raw material component according to weight percentage; S2, mixing a nonionic surfactant, a stabilizer and water, and stirring at a speed of 300 to 800 r / min for 5 to 10 min to obtain a mixed solution A; S3, adding the rust remover, chelating agent and corrosion inhibitor to the mixed solution A, stirring at a speed of 300 to 800 r / min for 10 to 15 min to obtain a mixed solution B; S4. Add the pH adjuster into the mixed solution B, stir for 3 to 6 minutes at a rotation speed of 300 to 500 r / min, and adjust the pH to 3.5 to 5.5 to obtain the copper surface cleaning agent.

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