Production process and production equipment of high-performance cleaning agent for copper material

Abstract

The invention relates to the technical field of cleaning agent production, in particular to a production process and production equipment of a high-performance cleaning agent for copper materials. The cleaning agent is prepared from the following components in percentage by weight: 5.7 to 10.99 percent of sulfamic acid, 15 to 25 percent of organic carboxylic acid compounded by citric acid and tartaric acid, 1.03 to 14.05 percent of ethanol, 0.58 to 1.28 percent of lauryl sodium sulfate, 1.19 percent of benzotriazole, 10.15 to 14.89 percent of sodium pyrophosphate, 3 to 5 percent of fatty alcohol-polyoxyethylene ether, 2 to 4 percent of EDTA (Ethylene Diamine Tetraacetic Acid) disodium and the balance of deionized water. The cleaning agent has the decontamination ability of an amino acid system and the environmental protection property of an organic acid system, is not easy to over-corrode, and solves the problem of high component decomposition rate in a key reaction stage through precise temperature control.

Description

Technical Field

[0001] This invention relates to the field of cleaning agent production technology, specifically to a production process and equipment for a high-performance cleaning agent for copper. Background Technology

[0002] During processing and storage, copper materials can develop oxide layers, oil stains, fingerprints, and other contaminants on their surface, affecting the quality of subsequent electroplating, welding, and other processes. Cleaning can remove these impurities, improving the surface activity and appearance of the copper. Copper cleaning agents typically consist of acidic or alkaline solutions combined with corrosion inhibitors and surfactants, effectively dissolving oxides and protecting the substrate.

[0003] Traditional cleaning agents have the following shortcomings in production: 1. Traditional processes mostly use a single aminosulfonic acid or organic acid system. Although the aminosulfonic acid system has strong detergency, the pH fluctuates greatly, which can easily lead to over-corrosion of copper. The organic acid system is environmentally friendly, but it has low efficiency in removing oxide scale and lacks corrosion inhibitors and brightening synergistic components. The copper material after surface treatment will become misty in a short time. 2. Temperature control depends on manual adjustment, which leads to a high decomposition rate of components in the key reaction stages. Summary of the Invention

[0004] To address the problems in the existing technology, this invention provides a production process and equipment for a high-performance cleaning agent for copper materials, which combines the cleaning power of an amino acid system with the environmental friendliness of an organic acid system and is less prone to over-corrosion.

[0005] The technical solution adopted by this invention to solve its technical problem is:

[0006] In a first aspect, the present invention provides a production process for a high-performance cleaning agent for copper materials, comprising the following components: 5.7-10.99 wt% aminosulfonic acid, 15-25 wt% organic carboxylic acid compounded from citric acid and tartaric acid, 1.03-14.05 wt% ethanol, 0.58-1.28 wt% sodium dodecyl sulfate, 1.19 wt% benzotriazole, 10.15-14.89 wt% sodium pyrophosphate, 3-5 wt% fatty alcohol polyoxyethylene ether, 2-4 wt% disodium EDTA, and the balance being deionized water.

[0007] By adopting the above technical solution, aminosulfonic acid, as a solid strong acid, provides a stable acidic environment and forms a synergistic deoxidizing layer with organic carboxylic acids. The composite system of ethanol and surfactant can enhance the penetration of oil stains, benzotriazole can inhibit intergranular corrosion of copper, and sodium pyrophosphate can effectively prevent the redeposition of metal ions. Through the combination of aminosulfonic acid and organic carboxylic acids, this process combines the decontamination ability of amino acid system with the environmental friendliness of organic acid system and is not prone to over-corrosion.

[0008] Specifically, it includes the following steps:

[0009] Dissolve organic carboxylic acids, aminosulfonic acid, and sodium pyrophosphate in 30% deionized water and heat to 50-60℃ while stirring.

[0010] Add surfactant and ethanol, and heat to 60-70℃ for 30 minutes;

[0011] After cooling to 40℃, add benzotriazole and 0.5-2wt% defoamer, and stir until transparent.

[0012] By adopting the above technical solution, the 50-60℃ pre-dissolution stage prioritizes the treatment of poorly soluble components such as sodium pyrophosphate and aminosulfonic acid to avoid precipitation in subsequent reactions. The gradient temperature rise to 60-70℃ can control the surfactant self-assembly process and ensure the stability of the micelle structure.

[0013] Specifically, 0.5 to 1 part of calixpyrrole is added as a gloss enhancer, the pH value is adjusted to 8.5-11.5, and 4.35-6.76 wt% of bentonite is added as a suspension stabilizer.

[0014] Specifically, benzotriazole and methylbenzotriazole in a 1:1-3 ratio are used as corrosion inhibitors, and disodium EDTA and sodium citrate in a 1:2 ratio are used as complexing agents.

[0015] By adopting the above technical solutions, methylbenzotriazole expands its applicable corrosion inhibition temperature range to 40-80℃, forming a broad-spectrum anti-corrosion combination with benzotriazole. When disodium EDTA and sodium citrate are mixed in a 1:2 ratio, it provides protection for Cu... 2 The complexation efficiency has been greatly improved.

[0016] Specifically, the reaction process is protected by nitrogen, with an oxygen content of ≤200ppm and a temperature control accuracy of ±1℃.

[0017] By adopting the above technical solution, the nitrogen protection system reduces the decomposition rate of aminosulfonic acid and avoids the generation of by-products such as ammonium sulfate. The ±1℃ temperature control accuracy can ensure the stability of the sodium pyrophosphate hydrolysis rate and maintain the effective phosphorus content.

[0018] Specifically, a two-stage filtration system is used, with a 200-mesh stainless steel filter screen in the front stage and a 5μm polypropylene filter element in the back stage.

[0019] Specifically, the final product must pass conductivity and corrosion tests. The conductivity standard is ≤50μS / cm, and the corrosion test standard is ≤0.1mg / cm³ weight loss of the copper sheet. 2 .

[0020] Secondly, the present invention provides a production apparatus that employs the above-mentioned production process for production, including:

[0021] A reaction vessel with a polytetrafluoroethylene lining is equipped with an anchor-type agitator, a nitrogen inlet, and a PID temperature control module.

[0022] The spray system is connected to the cover at the top of the reactor, and the flow rate can be adjusted from 10 to 50 L / min.

[0023] By adopting the above technical solutions, the PTFE lining can withstand pH 1-12 environments, avoiding metal ion contamination during cleaning. The anchor-type stirring paddle generates axial and radial composite flow patterns, effectively improving mixing efficiency compared to ordinary paddles. The PID temperature control module can work in conjunction with the heat exchange structure of this equipment to precisely control the temperature inside the reactor, thereby avoiding the problem of high component decomposition rates in key reaction stages caused by the reliance on manual temperature control in the past.

[0024] Specifically, it is equipped with a plate heat exchanger and a series filtration system, which includes a 10μm stainless steel pre-filter and a 5μm polypropylene fine filter.

[0025] Specifically, the entire equipment is resistant to acid and alkali corrosion, has a temperature control range of 20-80℃, and a pressure tolerance of ≥0.6MPa.

[0026] The beneficial effects of this invention are:

[0027] (1) The present invention describes a high-performance cleaning agent production process and equipment for copper materials. Sulfamic acid, as a solid strong acid, provides a stable acidic environment and forms a synergistic deoxidation layer with organic carboxylic acids. The composite system of ethanol and surfactant can enhance the penetration of oil stains. Benzotriazole can inhibit intergranular corrosion of copper materials. Sodium pyrophosphate can effectively prevent the redeposition of metal ions. By combining sulfamic acid with organic carboxylic acids, this process combines the cleaning ability of amino acid system with the environmental friendliness of organic acid system and is not prone to over-corrosion.

[0028] (2) The copper high-performance cleaning agent production process and its production equipment described in this invention can be used in conjunction with the plate heat exchanger of this equipment through the PID temperature control module to accurately control the temperature inside the reactor, thereby avoiding the problem of high component decomposition rate in key reaction stages caused by the previous reliance on manual temperature control. Attached Figure Description

[0029] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0030] Figure 1 This is a schematic diagram of the overall structure of the production equipment of the present invention;

[0031] Figure 2 This is a schematic diagram of the front view of the production equipment of the present invention after sectional cutting;

[0032] Figure 3 This is a schematic diagram of the spray system structure of the present invention.

[0033] In the diagram: 1. Reactor; 2. Anchor-type agitator; 3. Nitrogen inlet; 4. PID temperature control module; 5. Spray system; 6. Plate heat exchanger; 7. Series filtration system; 701. Stainless steel pre-filter; 702. Polypropylene fine filter. Detailed Implementation

[0034] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0035] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0036] Secondly, the term "an embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single embodiment or an embodiment selectively excluded from other embodiments.

[0037] Example 1 is the first embodiment of the present invention. This embodiment provides a production process for a high-performance cleaning agent for copper materials, comprising the following components: 5.7-10.99 wt% aminosulfonic acid, 15-25 wt% organic carboxylic acid compounded from citric acid and tartaric acid, 1.03-14.05 wt% ethanol, 0.58-1.28 wt% sodium dodecyl sulfate, 1.19 wt% benzotriazole, 10.15-14.89 wt% sodium pyrophosphate, 3-5 wt% fatty alcohol polyoxyethylene ether AEO-93, 2-4 wt% disodium EDTA, and the balance being deionized water.

[0038] When in use, aminosulfonic acid, as a solid strong acid, provides a stable acidic environment and, when combined with organic carboxylic acids, forms a synergistic deoxidizing layer. The ethanol and surfactant composite system can enhance the penetration of oil stains, benzotriazole can inhibit intergranular corrosion of copper, and sodium pyrophosphate can effectively prevent the redeposition of metal ions. By combining aminosulfonic acid with organic carboxylic acids, this process combines the detergency of amino acid systems with the environmental friendliness of organic acid systems, and is less prone to over-corrosion.

[0039] For example, the present invention also includes the following steps:

[0040] Dissolve organic carboxylic acids, aminosulfonic acid, and sodium pyrophosphate in 30% deionized water and heat to 50-60℃ while stirring.

[0041] Add surfactant and ethanol, and heat to 60-70℃ for 30 minutes;

[0042] After cooling to 40℃, add benzotriazole and 0.5-2wt% defoamer, and stir until transparent.

[0043] When using it, the poorly soluble components such as sodium pyrophosphate and aminosulfonic acid should be treated first during the 50-60℃ pre-dissolution stage to avoid precipitation in the subsequent reaction. The gradient temperature rise to 60-70℃ can control the self-assembly process of the surfactant and ensure the stability of the micelle structure.

[0044] For example, the present invention further includes adding 0.5 to 1 part of calixpyrrole as a gloss enhancer, adjusting the pH value to 8.5-11.5, and containing 4.35-6.76 wt% bentonite as a suspension stabilizer.

[0045] During use, calix pyrrole molecules are directionally adsorbed onto the copper surface to form a protective film, enhancing the metallic luster after polishing.

[0046] For example, the present invention also includes using benzotriazole and methylbenzotriazole in a 1:1-3 ratio as a corrosion inhibitor, and EDTA disodium and sodium citrate in a 1:2 ratio as a complexing agent.

[0047] When used, methylbenzotriazole extends the applicable corrosion inhibition temperature range to 40-80℃, forming a broad-spectrum anti-corrosion combination with benzotriazole. When disodium EDTA and sodium citrate are mixed in a 1:2 ratio, it has a good effect on Cu... 2 The complexation efficiency is greatly improved.

[0048] For example, the present invention also includes a reaction process protected by nitrogen, an oxygen content of ≤200ppm, and a temperature control accuracy of ±1℃.

[0049] During use, the nitrogen protection system reduces the decomposition rate of aminosulfonic acid to <0.3%, avoiding the generation of byproducts such as ammonium sulfate. The ±1℃ temperature control accuracy ensures a stable sodium pyrophosphate hydrolysis rate and maintains the effective phosphorus content.

[0050] For example, the present invention also includes a two-stage filtration system, with a 200-mesh stainless steel filter screen in the front stage and a 5μm polypropylene filter element in the rear stage.

[0051] When in use, the combination of a 200-mesh stainless steel screen and a 5μm polypropylene filter element greatly reduces the content of solid impurities in the cleaning agent and effectively reduces the failure rate of spray nozzle clogging.

[0052] For example, the present invention also includes the requirement that the final product passes conductivity and corrosion tests, with a conductivity standard of ≤50 μS / cm and a corrosion test standard of ≤0.1 mg / cm for copper sheet weight loss. 2 .

[0053] In use, the conductivity should be ≤50μS / cm and the weight loss of the copper sheet should be ≤0.1mg / cm. 2 Dual-indicator control can effectively improve the pass rate.

[0054] like Figure 1-3 As shown, this embodiment provides a production equipment that uses the above-described process for production, including:

[0055] The reactor 1, lined with polytetrafluoroethylene, is equipped with an anchor-type stirring paddle 2, a nitrogen inlet 3, and a PID temperature control module 4.

[0056] The spray system 5 is connected to the cover at the top of the reactor 1, and the flow rate can be adjusted from 10 to 50 L / min.

[0057] During use, the PTFE lining is resistant to pH 1-12 environments, preventing metal ion contamination during cleaning. The anchor-type stirring paddle 2 generates axial and radial composite flow patterns, effectively improving mixing efficiency compared to ordinary paddles. The PID temperature control module 4 can work in conjunction with the heat exchange structure of this equipment to precisely control the temperature inside the reactor 1, thereby avoiding the problem of high component decomposition rates in key reaction stages caused by the reliance on manual temperature control in the past.

[0058] For example, such as Figure 1-3 As shown, the present invention also includes a plate heat exchanger 6 and a series filtration system 7, the series filtration system 7 comprising a 10μm stainless steel pre-filter 701 and a 5μm polypropylene fine filter 702.

[0059] When in use, the plate heat exchanger 6 achieves precise temperature control of ±0.5℃, which is more energy-efficient than the shell-and-tube heat exchanger.

[0060] For example, such as Figure 1-3 As shown, the entire equipment is resistant to acid and alkali corrosion, has a temperature control range of 20-80℃, and a pressure tolerance of ≥0.6MPa.

[0061] When in use, the 0.6MPa pressure resistance standard meets the requirements of the vacuum degassing process and can effectively improve the safety factor.

[0062] When using this invention, deionized water accounting for 38.2% to 58.4% of the total mass is weighed according to the formula and placed in a polytetrafluoroethylene reactor. Then, 10.15% to 14.89% of sodium pyrophosphate, 5.7% to 10.99% of aminosulfonic acid, and 15% to 25% of an organic carboxylic acid compounded with citric acid and tartaric acid are added sequentially. The anchor-type stirring paddle is started at 120 rpm and the temperature is raised to 55±1℃. The reactor is purged with nitrogen until the oxygen content is ≤200ppm to prevent the oxidative decomposition of aminosulfonic acid.

[0063] Slowly add 3%–5% AEO-9 and 0.58%–1.28% sodium dodecyl sulfate, heat to 65°C and maintain for 30 minutes to form a uniform micelle system. Precisely control the temperature ±0.5°C using a plate heat exchanger, and add 1.03%–14.05% ethanol to promote surfactant penetration.

[0064] After cooling to 40℃, add 1.19% benzotriazole and 1:1-3 methylbenzotriazole as a corrosion inhibitor, and simultaneously add 0.5-1 part calixpyrrole to improve gloss. After passing through a two-stage filtration of 200 mesh + 5μm, and testing the conductivity to be ≤50μS / cm, fill the product.

[0065] Aminosulfonic acid, as a solid strong acid, provides a stable acidic environment and, when combined with organic carboxylic acids, forms a synergistic deoxidizing layer. The ethanol-surfactant composite system can enhance the penetration of oil stains, benzotriazole can inhibit intergranular corrosion of copper, and sodium pyrophosphate can effectively prevent the redeposition of metal ions. By combining aminosulfonic acid with organic carboxylic acids, this process combines the detergency of amino acid systems with the environmental friendliness of organic acid systems, and is less prone to over-corrosion.

[0066] The PID temperature control module 4 can work in conjunction with the plate heat exchanger 6 of this equipment to precisely control the temperature inside the reactor 1, thereby avoiding the problem of high component decomposition rate in key reaction stages caused by the reliance on manual temperature control in the past.

[0067] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of protection claimed by the present invention. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A production process for a high-performance cleaning agent for copper materials, characterized in that, It contains the following components: 5.7-10.99 wt% aminosulfonic acid, 15-25 wt% organic carboxylic acid compounded from citric acid and tartaric acid, 1.03-14.05 wt% ethanol, 0.58-1.28 wt% sodium dodecyl sulfate, 1.19 wt% benzotriazole, 10.15-14.89 wt% sodium pyrophosphate, 3-5 wt% fatty alcohol polyoxyethylene ether (AEO-9), 2-4 wt% disodium EDTA, and the balance being deionized water.

2. The production process of a high-performance cleaning agent for copper materials according to claim 1, characterized in that, Includes the following steps: Dissolve organic carboxylic acids, aminosulfonic acid, and sodium pyrophosphate in 30% deionized water and heat to 50-60℃ while stirring. Add surfactant and ethanol, and heat to 60-70℃ for 30 minutes; After cooling to 40℃, add benzotriazole and 0.5-2wt% defoamer, and stir until transparent.

3. The production process of a high-performance cleaning agent for copper materials according to claim 1, characterized in that, Add 0.5-1 part of calixpyrrole as a gloss enhancer, adjust the pH value to 8.5-11.5, and add 4.35-6.76 wt% bentonite as a suspension stabilizer.

4. The production process of a high-performance cleaning agent for copper materials according to claim 1, characterized in that, A 1:1-3 mixture of benzotriazole and methylbenzotriazole was used as a corrosion inhibitor, and a 1:2 mixture of disodium EDTA and sodium citrate was used as a complexing agent.

5. The production process of a high-performance cleaning agent for copper materials according to claim 1, characterized in that, The reaction process is protected by nitrogen, with an oxygen content of ≤200ppm and a temperature control accuracy of ±1℃.

6. The production process of a high-performance cleaning agent for copper materials according to claim 1, characterized in that, It adopts a two-stage filtration system, with a 200-mesh stainless steel filter screen in the front stage and a 5μm polypropylene filter element in the rear stage.

7. The production process of a high-performance cleaning agent for copper materials according to claim 1, characterized in that, The final product must pass conductivity and corrosion tests. The conductivity standard is ≤50μS / cm, and the corrosion test standard is ≤0.1mg / cm³ weight loss of the copper sheet. 2 .

8. The production equipment for a high-performance copper cleaning agent production process according to any one of claims 1-7, characterized in that, include: A reaction vessel (1) with a polytetrafluoroethylene lining is equipped with an anchor-type stirring paddle (2), a nitrogen inlet (3) and a PID temperature control module (4); The spray system (5) is connected to the cover at the top of the reactor (1), and the flow rate is adjustable from 10 to 50 L / min.

9. The production equipment for the production process of a high-performance cleaning agent for copper materials according to claim 8, characterized in that: It is equipped with a plate heat exchanger (6) and a series filtration system (7), which includes a 10 μm stainless steel pre-filter (701) and a 5 μm polypropylene fine filter (702).

10. The production equipment for a high-performance copper cleaning agent production process according to claim 8, characterized in that: The entire equipment is resistant to acid and alkali corrosion, with a temperature control range of 20-80℃ and a pressure tolerance of ≥0.6MPa.

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