Silver-based micro-nano structure protective quick-dry cleaning agent and preparation and use methods thereof

Abstract

The invention provides a silver-based micro-nano structure protective quick-dry cleaning agent and a preparation and use method thereof, and belongs to the technical field of preparation and use of molded board cleaning agents. The cleaning agent is composed of isopropanol, ethyl acetate, a nonionic surfactant and a chelating agent. Wherein the mass ratio of the isopropanol to the ethyl acetate is 70: (10-30), the mass of the nonionic surfactant accounts for 5%-15% of the mass of the cleaning agent, and the mass of the chelating agent accounts for 5%-10% of the mass of the cleaning agent. According to the cleaning agent, a basic organic solvent system is reasonably constructed, and a proper amount of nonionic surfactant and complexing agent are introduced, so that organic dirt, adhesive residues and oxide layers are efficiently removed, and meanwhile, the surface appearance stability and reflection integrity of patterns of a silver-based micro-nano structure are maintained.

Description

Technical Field

[0001] This invention belongs to the technical field of detergent preparation and use, and particularly relates to the technical field of cleaning agent preparation and use for molded plates. Specifically, it relates to a silver-based micro-nano structure protective quick-drying cleaning agent and its preparation and use method. Background Technology

[0002] With the development of micro-nano manufacturing and high-precision pattern transfer technology, silver plates used in embossing processes are widely used in flexographic printing, optical anti-counterfeiting, and electronic device manufacturing due to their excellent conductivity, optical properties, and pattern fidelity. Compared to nickel plates, silver plates typically have complex textured structures at the micron to nanometer scale, placing higher demands on the physical and chemical stability of the cleaning process. In practical applications, silver plates are susceptible to contaminants such as processing residues, airborne organic dust particles, and ink droplets. Incomplete cleaning can lead to distortion of the embossed pattern, reduced adhesion, and even affect the final appearance of the embossed product.

[0003] Most commonly used silver plate cleaners are based on single organic solvents, such as isopropanol, ethanol, and acetone. Their cleaning ability is relatively limited, and they are easily volatile, making it difficult to achieve sufficient wetting and removal of contaminants on complex surfaces. Existing technology CN109504550A discloses a laser holographic embossing plate cleaner, comprising the following components in parts by weight: 2 parts nonionic surfactant. 5 parts, Gemini surfactant 8 10 parts, solubilizer 2 5 parts, 3 additives 4 parts, defoamer 0.4g 0.6 parts, sodium ethylenediaminetetraacetate 0.4 parts 0.6 parts, deionized water 75 85 samples were collected. The nonionic surfactants included octylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether in a 3:2 mass ratio; the solubilizers included ethylene glycol monobutyl ether and propylene glycol in a 1:4 mass ratio. This cleaning agent is effective for cleaning nickel plates, but it is not applicable to cleaning laser holographic molding silver plates. While introducing highly polar solvents or acid / base additives to enhance the cleaning ability of silver plates often carries the risk of corrosion to the silver surface structure, traditional cleaning methods frequently rely on repeated mechanical wiping, which can easily cause scratches, collapse, or edge lifting of the silver layer's microstructure, severely affecting the plate's lifespan and the integrity and consistency of the pattern.

[0004] Therefore, it is necessary to develop a protective cleaning agent for silver-based micro / nano structures with mild cleaning properties, good material compatibility, and a moderate evaporation rate, capable of efficiently removing silver surface contaminants while protecting the integrity of the micro / nano structures. Furthermore, a scrubbing device compatible with this cleaning agent should be developed to avoid damage to the micro / nano structures or silver layer migration and detachment caused by repeated mechanical wiping. Summary of the Invention

[0005] To overcome the problems of low cleaning efficiency, easy damage to micro / nano structures, and excessively high or low volatility of cleaning agents in the cleaning process of silver-based micro / nano structures (or silver-based molded plates) in existing technologies, this invention provides a protective quick-drying cleaning agent for silver-based micro / nano structures, its preparation method, and its application method. This cleaning agent achieves efficient removal of organic dirt, residual adhesive, and oxide layers by rationally constructing a basic organic solvent system and introducing appropriate amounts of nonionic surfactants and complexing agents, while maintaining the surface morphology stability and reflective integrity of the silver-based micro / nano structure pattern.

[0006] Specifically, in order to achieve the above objectives, the present invention adopts the following technical solution: A silver-based micro / nano structure protective quick-drying cleaning agent is composed of isopropanol, ethyl acetate, nonionic surfactant and chelating agent; wherein the mass ratio of isopropanol to ethyl acetate is 70:(10~30), the mass of the nonionic surfactant accounts for 5%~15% of the mass of the cleaning agent, and the mass of the chelating agent accounts for 5%~10% of the mass of the cleaning agent.

[0007] In a preferred embodiment, the nonionic surfactant includes at least one of Tween surfactants, Span surfactants, fatty alcohol polyoxyethylene ether surfactants, and alkylphenol polyoxyethylene ether surfactants.

[0008] In a further preferred embodiment, the Tween surfactant is Tween 80.

[0009] In a further preferred embodiment, the Span surfactant is Span 80.

[0010] In a further preferred embodiment, the fatty alcohol polyoxyethylene ether surfactant is at least one of AEO-2, AEO-3, AEO-7, and AEO-9.

[0011] In a further preferred embodiment, the alkylphenol polyoxyethylene ether surfactant is nonylphenol polyoxyethylene ether.

[0012] In a preferred embodiment, the chelating agent is at least one of the following: disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, disodium pentacarboxymethyldiaminepentaacetate, disodium tricarboxymethyldiaminetriacetate, sodium citrate, and sodium gluconate.

[0013] The preparation method of the silver-based micro / nano structure protective quick-drying cleaning agent includes the following steps: S1. Mix the isopropanol and the ethyl acetate evenly to obtain a basic organic solvent system; S2. Add a nonionic surfactant to the basic organic solvent system and mix thoroughly. S3. Add the chelating agent to the obtained mixture and dissolve it completely. The resulting solution is the cleaning agent.

[0014] In a preferred embodiment, the solution obtained in step S3 is filtered through a 0.22 μm polytetrafluoroethylene microporous membrane, and the resulting filtrate is the cleaning agent.

[0015] In a preferred embodiment, the mixing in step S2 is achieved by stirring with a magnetic stirrer at a speed of 200-400 rpm for 10-30 minutes.

[0016] The method for cleaning silver-based micro-nano structures using the aforementioned silver-based micro-nano structure protective quick-drying cleaning agent includes the following steps: wiping the surface of the silver-based micro-nano structure at a uniform speed in one direction with a dust-free wiping material moistened by the cleaning agent.

[0017] In a preferred embodiment, the dust-free wiping material is any one of microfiber dust-free cloth, polyester fiber clean cloth, or polyurethane foam-coated fiber composite material, or any of the aforementioned materials after heat sealing.

[0018] In a preferred embodiment, a scrubbing device is used in conjunction with the cleaning agent to clean the silver-based micro / nano structure. The scrubbing device includes a drive unit, a cleaning agent reservoir, a pressure regulating device, and a wiping assembly. The cleaning agent reservoir is mounted on the drive unit. The wiping assembly includes a support structure, and the dust-free wiping material is wrapped around the surface of the support structure. The wiping assembly is connected to the drive unit via the drive assembly. The cleaning agent is stored in the cleaning agent reservoir, which has a control valve channel communicating with the wiping assembly. The pressure regulating device is mounted on the wiping assembly.

[0019] In a further preferred embodiment, the driving device is any one of a stepper motor, a servo motor, a linear driver, or a pneumatic drive.

[0020] In a further preferred embodiment, the drive component is any one of a lead screw drive mechanism, a synchronous belt drive mechanism, a linear guide drive mechanism, or a cam mechanism.

[0021] In a further preferred embodiment, the pressure regulating device is any one of a spring loading mechanism, a pneumatic pressure regulating unit, a hydraulic micro-pressure control unit, or an electronic force feedback regulating unit.

[0022] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: (1) The cleaning agent provided by the present invention has excellent surface wettability and penetration stripping ability, and can effectively remove grease, dust and particulate contamination adhering to the surface of silver substrate.

[0023] (2) The present invention introduces nonionic surfactants and chelating agents into the cleaning agent, and the synergistic effect of the two avoids structural damage caused by strong polar solvents or mechanical wiping.

[0024] (3) The present invention uses a mixed system of isopropanol and ethyl acetate with moderate evaporation rate, which takes into account both cleaning efficiency and quick-drying characteristics, and facilitates cleaning of silver-based micro-nano structures and subsequent molding processes.

[0025] (4) The cleaning agent preparation and scrubbing method provided by the present invention is simple, fast, safe and environmentally friendly. The scrubbing method is particularly suitable for silver-based micro-nano structures with high requirements for pattern accuracy and surface micro-nano structure integrity.

[0026] (5) The cleaning agent formula provided by the present invention can be finely adjusted according to different pollution characteristics, and has good scalability and industrial adaptability. Attached Figure Description

[0027] Figure 1 Patterns of uncleaned silver-based micro / nano structures; Figure 2 The image shows a pattern of a silver-based micro / nano structure after cleaning with the cleaning agent described in Example 1 of this invention. Figure 3 The image shows a pattern of a silver-based micro / nano structure after cleaning with the cleaning agent in Comparative Example 3 of this invention. Figure 4 The image shows a pattern of a silver-based micro / nano structure after cleaning with the cleaning agent in Comparative Example 3 of this invention. Figure 5 This is a front view of the scrubbing device in Embodiment 5 of the present invention and a front view of the silver-based micro / nano structure wrapped around the surface of the molding roller; Figure 6 for Figure 5 Side view of the wiping assembly and silver-based micro / nano structure.

[0028] In the figure: 1. Drive unit; 2. Cleaning agent reservoir; 3. Pressure regulating device; 4. Wiping assembly; 5. Silver-based micro-nano structure; 6. Molding roller. Detailed Implementation

[0029] The following description, in conjunction with embodiments, clearly and completely describes the technical solutions of this application, so that those skilled in the art can fully understand this application. Obviously, the described embodiments are merely some preferred embodiments of this application, and not all embodiments. Any equivalent modifications or substitutions made by those skilled in the art to the following embodiments without creative effort are within the protection scope of this application.

[0030] The isopropanol, ethyl acetate, and disodium ethylenediaminetetraacetate used in the following examples were all analytical grade reagents. The nonionic surfactants used included at least one of Tween surfactants, Span surfactants, fatty alcohol polyoxyethylene ether (AEO) surfactants, and alkylphenol polyoxyethylene ether surfactants. At least one of disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, disodium pentacarboxymethyldiaminepentaacetate, disodium tricarboxymethyldiaminetriacetate, sodium citrate, or sodium gluconate was also used.

[0031] As an example, the nonionic surfactant is any one of Tween 80, Span 80, AEO-2, AEO-3, AEO-7, AEO-9, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether.

[0032] Example 1 A silver-based micro / nano structure protective quick-drying cleaner is composed of the following components in parts by weight: 70 parts isopropanol, 20 parts ethyl acetate, 10 parts Span 80, and 5.5 parts disodium ethylenediaminetetraacetate.

[0033] The preparation method of this cleaning agent includes the following steps: S1. Preparation of basic organic solvent system: Take 70g isopropanol and 20g ethyl acetate, place them in a 250mL sealed glass beaker, and stir for 15min at room temperature (25℃) to form a transparent homogeneous basic organic solvent system.

[0034] S2. Adding surfactant: Slowly add 10g of Span 80 to the basic organic solvent system in step S1, and stir with a magnetic stirrer at 300rpm for 20min until completely dissolved and mixed evenly.

[0035] S3. Addition of complexing agent: Weigh 5.5g of disodium ethylenediaminetetraacetate and add it to the mixture obtained in step S2. Continue stirring for 15 minutes until fully dissolved.

[0036] S4. Filtration and storage: Filter the solution obtained in step S3 through a 0.22 μm polytetrafluoroethylene microporous membrane to remove any possible particulate impurities. Immediately transfer the filtrate to a brown, light-proof, sealed glass bottle and store it at room temperature away from light.

[0037] Example 2 A silver-based micro / nano structure protective quick-drying cleaner is composed of the following components in parts by weight: 70 parts isopropanol, 30 parts ethyl acetate, 15 parts Tween 80, and 9 parts dipotassium ethylenediaminetetraacetate.

[0038] The preparation method of this cleaning agent includes the following steps: S1. Preparation of basic organic solvent system: Take 70g isopropanol and 30g ethyl acetate, place them in a 250mL sealed glass beaker, and stir for 20min at room temperature (25℃) to form a clear homogeneous basic organic solvent system.

[0039] S2. Adding surfactant: Slowly add 15g of Tween 80 to the basic organic solvent system in step S1, and stir with a magnetic stirrer at 350rpm for 25min until completely dissolved and mixed evenly.

[0040] S3. Addition of complexing agent: Weigh 9g of dipotassium ethylenediaminetetraacetate and add it to the mixture obtained in step S2. Continue stirring for 20 minutes to dissolve it completely.

[0041] S4. Filtration and storage: Filter the solution obtained in step S3 through a 0.22 μm polytetrafluoroethylene microporous membrane to remove any possible particulate impurities. Immediately transfer the filtrate to a brown, light-proof, sealed glass bottle and store it at room temperature away from light.

[0042] Example 3 A silver-based micro / nano structure protective quick-drying cleaner is composed of the following components in parts by weight: 70 parts isopropanol, 10 parts ethyl acetate, 5 parts fatty alcohol polyoxyethylene ether AEO-2, and 9.5 parts disodium pentacarboxymethyldiaminepentaacetate.

[0043] The preparation method of this cleaning agent includes the following steps: S1. Preparation of basic organic solvent system: Take 70g isopropanol and 10g ethyl acetate, place them in a 250mL sealed glass beaker, and stir for 10min at room temperature (25℃) to form a clear homogeneous basic organic solvent system.

[0044] S2. Adding surfactant: Slowly add 5g of fatty alcohol polyoxyethylene ether AEO-2 to the basic organic solvent system in step S1, and stir with a magnetic stirrer at 200rpm for 30min until completely dissolved and mixed evenly.

[0045] S3. Addition of complexing agent: Weigh 9.5g of disodium pentacarboxymethyldiaminepentaacetate and add it to the mixture obtained in step S2. Continue stirring for 30 minutes to dissolve it completely.

[0046] S4. Filtration and storage: Filter the solution obtained in step S3 through a 0.22 μm polytetrafluoroethylene microporous membrane to remove any possible particulate impurities. Immediately transfer the filtrate to a brown, light-proof, sealed glass bottle and store it at room temperature away from light.

[0047] Example 4 A silver-based micro / nano structure protective quick-drying cleaner is composed of the following components in parts by weight: 70 parts isopropanol, 25 parts ethyl acetate, 18 parts nonylphenol polyoxyethylene ether, 3 parts sodium citrate, and 3 parts sodium gluconate.

[0048] The preparation method of this cleaning agent includes the following steps: S1. Preparation of basic organic solvent system: Take 70g isopropanol and 25g ethyl acetate, place them in a 250mL sealed glass beaker, and stir for 30min at room temperature (25℃) to form a clear homogeneous basic organic solvent system.

[0049] S2. Adding surfactant: Slowly add 18g of nonylphenol polyoxyethylene ether to the basic organic solvent system in step S1, and stir with a magnetic stirrer at 400rpm for 10min until completely dissolved and mixed evenly.

[0050] S3. Addition of complexing agent: Weigh 3g of sodium citrate and 3g of sodium gluconate, add them to the mixture obtained in step S2, and continue stirring for 10 minutes to dissolve them completely.

[0051] S4. Filtration and storage: Filter the solution obtained in step S3 through a 0.22 μm polytetrafluoroethylene microporous membrane to remove any possible particulate impurities. Immediately transfer the filtrate to a brown, light-proof, sealed glass bottle and store it at room temperature away from light.

[0052] Example 5 like Figure 5 and Figure 6 As shown, a wiping device for use with a silver-based micro / nano structure protective quick-drying cleaner includes four functional subsystems: (A) a mechanical drive subsystem, including a drive device 1 and a drive assembly, for achieving uniform unidirectional movement of the wiping assembly 4. (B) a contact / pressure regulation subsystem, including a pressure regulation device 3, for controlling the constant contact force between the wiping head of the wiping assembly 4 and the surface of the silver-based micro / nano structure. (C) a liquid supply subsystem, including a cleaner reservoir 2, a control valve channel, and a metering pump, for quantitatively transporting the cleaner to the wiping assembly 4 and wetting the wiping assembly 4. (D) a control and detection subsystem, including a programmable logic controller (PLC) or microcontroller unit (MCU), sensors, and a human-machine interface (HMI), for achieving closed-loop coordination and safety protection of the movement, liquid supply, and pressure control of each component.

[0053] (A) Mechanical drive subsystem The drive unit 1 is a servo motor. The wiping assembly 4 is a dust-free wiping material. The servo motor is fixedly connected to one end of a ball screw via a flange, and the other end of the ball screw is connected to the base of the wiping assembly 4 via a nut. A guide rail is mounted on the frame, and the wiping assembly 4 moves at a uniform speed in a linear motion along a predetermined direction by cooperating with the guide rail via a slider. The rotation of the servo motor is converted into linear displacement by the ball screw, realizing the uniform unidirectional movement of the wiping assembly 4 on the surface of the silver-based micro / nano structure 5 (e.g., ...). Figure 6 (As indicated by the arrow). The servo motor has built-in encoder feedback, which is used to monitor the position and speed signals of the wiping assembly 4 in real time. After the encoder signal is processed by the control and detection subsystem, it is synchronized with the liquid supply subsystem to ensure that the wiping path of the wiping assembly 4 is consistent and the speed is stable.

[0054] (B) Contact / Pressure Regulation Subsystem The pressure regulating device 3 is mounted on the wiping assembly 4 to apply a constant and appropriate contact pressure to the surface of the silver-based micro / nano structure 5 during wiping, preventing damage to the silver layer or cleaning dead zones caused by pressure fluctuations. The pressure regulating device 3 employs a pneumatic pressure regulating unit, including: (a) an actuator: a miniature cylinder or pneumatic diaphragm actuator (with a force-balancing diaphragm) for outputting constant pressure; (b) regulating elements: a proportional valve (e.g., a proportional solenoid valve, a pneumatic proportional valve), an air source regulator, a precision pressure reducing valve, and a flow regulating valve for controlling the air pressure and flow rate entering the cylinder; and (c) a detection element: a pressure sensor (which can be a load sensor or a piezoelectric sensor) for real-time monitoring of the contact force between the wiping head of the wiping assembly 4 and the silver-based micro / nano structure 5. The pressure sensor is installed at the support point of the wiping head of the wiping assembly 4, and its signal is converted into a 4~20mA signal by an amplifier / transmitter and input to the PLC or MCU of the control and detection subsystem. The PLC or MCU uses a PID (proportional, integral, derivative) algorithm to perform closed-loop control of the proportional valve's opening and closing degree, adjusting the output force to maintain the pressure of the wiping assembly 4 within the set range (0.2~1.0 N / cm). 2 )Inside.

[0055] (C) Liquid supply subsystem The cleaning agent reservoir 2 is mounted on the drive unit 1 and is used to store silver-based micro-nano structure protective quick-drying cleaning agent. The cleaning agent reservoir 2 is connected to the wiping assembly 4 through a control valve channel with a valve. The control valve channel is an integrated fluid delivery manifold, which includes a liquid delivery pipeline, a metering device (metering pump or proportional valve), a check valve or throttling device, a filter assembly, an online flow / pressure sensor, and a quick-shut-off valve. The control valve channel is connected to the wiping head of the wiping assembly 4 through a solvent-resistant flexible hose (such as PTFE, PVC, or chemically resistant polyurethane); the flexible hose is constrained by a cable chain to prevent twisting during movement. The connection between the drive unit 1 and the control valve channel consists of two parts: electrical signal connection and mechanical flexible delivery. The displacement and speed signals of the servo motor are fed back to the PLC or MCU in real time. The PLC or MCU calculates and issues a liquid supply control command to the metering pump based on the wiping position of the wiping assembly 4, thereby realizing synchronous and quantitative control of wiping movement and cleaning agent release, keeping the wiping assembly 4 in a uniformly wetted state.

[0056] (D) Control and Detection Subsystem The PLC or embedded MCU serves as the core control unit, connecting to the servo motor, proportional valve, pressure sensor, and HMI via signal interfaces. The control and detection subsystem achieves automated control of wiping, liquid addition, and contact pressure through three closed-loop coordination (displacement closed loop, pressure closed loop, and liquid supply closed loop). Simultaneously, the PLC can be programmed with abnormal alarms and safety protection procedures; when abnormal pressure or flow is detected, it automatically stops the drive and liquid supply actions to ensure the silver-based micro / nano structure 5 remains undamaged.

[0057] In the above-described cleaning device, the silver-based micro / nano structure 5 is fixed to the surface of the molding roller 6 by adhesive bonding or direct coating. The wiping path and speed of the wiping component 4, as well as the target pressure parameters for contact between the wiping component 4 and the silver-based micro / nano structure 5, are set. After all systems of the device are started, the mechanical drive subsystem moves the wiping component 4 along the surface of the silver-based micro / nano structure 5 at a set speed. The contact / pressure regulation subsystem maintains a stable contact force between the wiping component 4 and the silver-based micro / nano structure 5 in real time. The liquid supply subsystem releases cleaning agent synchronously in proportion to wet the wiping material of the wiping component 4. Through these coordinated actions, uniform, gentle, and efficient cleaning of the surface of the silver-based micro / nano structure 5 is achieved, avoiding fiber shedding or pattern damage, and improving cleaning quality and the service life of the silver-based micro / nano structure.

[0058] It should be noted that, in addition to servo motors, the drive unit can also use stepper motors, linear drivers, or pneumatic drive units. Besides lead screw mechanisms (such as ball screws), the drive components can also use synchronous belt drives, linear guide drives, or cam mechanisms. In addition to pneumatic pressure regulating units, the pressure regulating device can also use spring-loaded hydraulic micro-pressure control units or electronically controlled force feedback regulating units.

[0059] Comparative Example 1 A silver-based micro / nano structure protective quick-drying cleaning agent is composed of the following components in parts by weight: 70 parts isopropanol, 20 parts ethyl acetate, and 5 parts disodium ethylenediaminetetraacetate. The difference between this comparative example and Example 1 is that no nonionic surfactant is added. The preparation method of this cleaning agent differs from Example 1 in that step S2 is omitted.

[0060] Comparative Example 2 A silver-based micro / nano structure protective quick-drying cleaning agent is composed of the following components in parts by weight: 70 parts isopropanol, 20 parts ethyl acetate, 20 parts Span 80, and 5 parts disodium ethylenediaminetetraacetate. The difference between this comparative example and Example 1 is that the amount of nonionic surfactant used is twice that of Example 1. The preparation methods of this cleaning agent are the same as those of Example 1, except for the amount of nonionic surfactant.

[0061] Comparative Example 3 A silver-based micro / nano structure protective quick-drying cleaning agent is composed of the following components in parts by weight: 70 parts isopropanol, 20 parts ethyl acetate, and 10 parts Span 80. The difference between this comparative example and Example 1 is that no complexing agent is added. The preparation method of this cleaning agent differs from Example 1 in that step S3 is omitted.

[0062] Comparative Example 4 A silver-based micro / nano structure protective quick-drying cleaning agent is composed of the following components in parts by weight: 70 parts isopropanol, 20 parts ethyl acetate, 10 parts Span 80, and 15 parts disodium ethylenediaminetetraacetate. The difference between this comparative example and Example 1 is that the amount of complexing agent used is three times that of Example 1. The preparation methods of this cleaning agent and Example 1 are identical except for the amount of complexing agent.

[0063] Comparative Example 5 A silver-based micro / nano structure protective quick-drying cleaning agent is composed of the following components in parts by weight: 70 parts isopropanol, 20 parts ethylene glycol monobutyl ether, 10 parts Span 80, and 5 parts disodium ethylenediaminetetraacetate. That is, the cleaning agent provided in this comparative example replaces the ethyl acetate in Example 1 with an equal mass of ethylene glycol monobutyl ether. The difference between the preparation method of this cleaning agent and Example 1 is that the ethyl acetate in step S1 is replaced with ethylene glycol monobutyl ether.

[0064] Comparative Example 6 A silver-based micro / nano structure protective quick-drying cleaning agent is composed of the following components in parts by weight: 70 parts propylene glycol, 20 parts ethyl acetate, 10 parts Span 80, and 5 parts disodium ethylenediaminetetraacetate. That is, the cleaning agent provided in this comparative example replaces the isopropanol in Example 1 with an equal mass of propylene glycol. The difference in the preparation method of this cleaning agent from Example 1 is that the isopropanol in step S1 is replaced with propylene glycol.

[0065] Cleaning agent performance evaluation To verify the cleaning effects of the different cleaning agents prepared in the above examples and comparative examples, the cleaning agents prepared in Examples 1-4 and Comparative Examples 1-6 were evaluated using the following methods.

[0066] 1. Sample preparation A silver substrate with a silver-based micro / nano structure was used as the sample to be cleaned. The sample was prepared using conventional micro / nano lithography and electroforming processes, and its surface contained regularly distributed micro / nano patterns. A 0.002 g / cm² mixture of grease / dust contaminant (liquid paraffin to toner mass ratio of 10:1) was uniformly coated onto the sample surface and allowed to stand naturally for 30 minutes to obtain the contaminated sample. Each cleaning agent was prepared according to its formulation, and equal volumes (1 mL) of each were used for testing.

[0067] 2. Wiping conditions Using microfiber cleanroom cloth (10cm x 10cm), under fixed pressure conditions (0.6N / cm) 2 The surface of the contaminated sample was wiped back and forth 5 cm in length at a speed of approximately 2 cm / s, with 5 back-and-forth wiping cycles. Each test was repeated 3 times, and the average value was taken as the test result.

[0068] 3. Determination of quick-drying time Cleaning agent was applied simultaneously during the wiping process, and a stopwatch was used to record the time it took for the sample surface to completely recover from a wet state to the point where there were no obvious liquid marks. The experimental environment was room temperature 25±3℃, relative humidity 50±5%, and normal pressure.

[0069] 4. Determination of the retention rate of the micro / nano structure of the silver plate Before and after wiping, the sample surface was imaged at the same location using an optical microscope (500× magnification) and a scanning electron microscope (5kV accelerating voltage). The area of ​​the silver plate micro / nano pattern retained after wiping was statistically analyzed using ImageJ software to calculate the retention rate. The retention rate was defined as: Retention rate (%) = (Area of ​​intact pattern after wiping / Area of ​​pattern before wiping) × 100%.

[0070] 5. Wetting performance test The wetting properties of different cleaning agents were evaluated using a contact angle meter. The specific method was as follows: 50 μL of cleaning agent was dropped onto the surface to be tested, and the initial contact angle was recorded; simultaneously, the time required for the droplet to spread from its initial state to complete spread was recorded as the wetting rate. The wetting performance test method can refer to GB / T 30693-2014 "Measurement of the contact angle between plastic films and water".

[0071] The above methods can be used to systematically evaluate the quick-drying properties, wettability, and effects on the integrity of silver-based micro / nano structure patterns of cleaning agents with different compositions. The experimental results are shown in Tables 1 and 2.

[0072] Table 1. Results of cleaning silver-based micro / nano structures using cleaning agents with different compositions.

[0073] As shown in Table 1, the cleaning agents prepared in Examples 1 and 2 exhibited excellent cleaning performance and pattern protection, with the pattern structure retention rate of the silver-based micro / nano structures after wiping exceeding 99%, and drying was rapid (1-2 seconds). Examples 3 and 4 showed slightly less effectiveness. Figure 1 and Figure 2 As shown, the silver-based micro / nano structure surface exhibits no obvious scratches, stains, or uneven coloring, indicating that the synergistic mechanism of the surfactant and complexing agent in the formulation effectively enhances the wettability, detergency, and structural protection properties of the detergent. The isopropanol and ethyl acetate solvent combination system used in this application, due to its rapid evaporation and low residue, enables rapid drying and uniform cleaning, minimizing damage to the micro / nano structure and thus improving structural integrity and durability while maintaining cleaning effectiveness.

[0074] In contrast, Comparative Examples 1 and 3 (without surfactants or complexing agents, respectively) showed significant deficiencies in the tests. The absence of surfactants in Comparative Example 1 resulted in ineffective dispersion and emulsification of organic pollutants on the surface of the silver-based micro / nano structure, leading to poor solution wettability, reduced cleaning efficiency, and a drying time of 5–10 seconds. Figure 3As shown, numerous significant scratches appeared after wiping, with localized yellowing, indicating physical damage to the silver-based micro / nanostructure during the cleaning process. Comparative Examples 5 and 6 both used alcohol / ether solvents with higher boiling points and lower vapor pressures to replace the low-boiling-point solvents in this application. Experimental results show that this substitution significantly slowed the overall evaporation rate of the solvent system, significantly prolonged the residence time of the wet film formed after wiping, and expanded the curing / drying window. This delayed effect causes the residual solvent to induce localized swelling or wetting stress at the edges of the silver-based micro / nanostructure, easily leading to damage and collapse of the surface coating. This results in a significant decrease in the pattern retention rate of the silver-based micro / nanostructure after cleaning.

[0075] In Comparative Examples 2 and 4, excessive amounts of surfactants or complexing agents led to a decrease in system stability and pattern protection performance. On the one hand, surfactants (such as Span 80 and Tween 80), as hydrophobic-hydrophilic interface modifiers, can effectively reduce the surface tension of detergents and promote the dispersion and removal of contaminants under appropriate conditions, thereby improving cleaning efficiency. However, when the amount added is too high, the intermolecular interactions of surfactants in the system are enhanced, which may form more stable micelle or microemulsion structures, increasing the viscosity of the system and delaying solvent evaporation, thus leading to a decrease in quick-drying performance. The micelle structure interferes with the wetting and desorption process of the silver-based micro / nanostructure surface, easily causing interface residues or solvent retention, affecting the clarity and integrity of pattern boundaries. On the other hand, complexing agents (such as disodium EDTA) can form stable complexes with metal ions or particulate contaminants under appropriate conditions, preventing their deposition on the surface of silver-based micro / nanostructures. However, when the complexing agent is excessive, the pH value and electrolyte strength of the system may change, thereby causing chemical disturbances between the solution and the surface of the silver-based micro / nanostructure, increasing the risk of slight corrosion. Furthermore, the presence of excessive complexing agents may compete with surfactants for adsorption, weakening their interfacial regulation function and reducing their ability to protect silver-based micro / nano structures during the cleaning process. Figure 4 As shown, numerous fine scratches were observed on the surface of the silver-based micro / nanostructure after wiping, with slight yellowing in some areas, resulting in a significant visual difference compared to the pattern of the untreated silver-based micro / nanostructure. This indicates that the cleaning agent caused mechanical disturbance and surface morphology damage to the surface micro / nanostructure during use, leading to a decrease in pattern integrity retention and consequently affecting subsequent functional stability and pattern recognition performance.

[0076] Table 2 Surface wetting properties of cleaning agents with different compositions

[0077] Using the proportions of nonionic surfactant and complexing agent as in Examples 1 and 2, highly efficient wetting and diffusion were achieved, with a significantly reduced contact angle (<23°) and a fast wetting speed (1-2 s). Therefore, uniform and rapid coverage of the silver-based micro / nano structure surface was achieved, with a retention rate approaching 100%. In Examples 3 and 4, the composition was adjusted, resulting in a slight decrease in wetting ability compared to Examples 1 and 2, but still maintaining high cleaning efficiency. In Comparative Example 1, the cleaning agent prepared without surfactant showed significantly poorer wetting properties, a significantly increased contact angle, and a significantly prolonged wetting time, leading to greater damage to the silver-based micro / nano structure during cleaning. Comparative Example 2 used a larger amount of surfactant, which, although reducing the contact angle compared to Comparative Example 1, caused some compatibility loss due to excessive accumulation, slowing down the wetting speed. In Comparative Example 3, the cleaning agent prepared without chelating agent had a large contact angle with the silver-based micro / nano structure surface, resulting in poor wetting properties and incomplete cleaning. In Comparative Example 4, the excessive amount of chelating agent led to decreased cleaning agent stability and uneven wetting. The altered polarity and volatility of the solvent used in Comparative Example 5 resulted in a decrease in the wettability of the cleaning agent. Comparative Example 6, using a different solvent, also significantly reduced the wettability of the cleaning agent and resulted in poor drying speed, leading to incomplete surface cleaning. Therefore, the cleaning agent provided by this invention, in its composition, utilizes a reasonable ratio of nonionic surfactant and chelating agent to significantly reduce the contact angle and increase the wetting speed, thereby achieving rapid and uniform wetting and cleaning of silver-based micro / nano structures while maintaining structural integrity.

[0078] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Various modifications and variations can be made to the present invention by any person skilled in the art. Any simple equivalent changes and modifications made based on the scope of protection of this invention and the content of the specification should be included within the scope of protection of the present invention.

Claims

1. A silver-based micro / nano structure protective quick-drying cleaning agent, characterized in that, It is composed of isopropanol, ethyl acetate, nonionic surfactant and chelating agent; wherein the mass ratio of isopropanol to ethyl acetate is 70:(10~30), the mass of nonionic surfactant accounts for 5%~15% of the mass of the detergent, and the mass of chelating agent accounts for 5%~10% of the mass of the detergent.

2. The cleaning agent according to claim 1, characterized in that, The nonionic surfactant includes at least one of Tween surfactants, Span surfactants, fatty alcohol polyoxyethylene ether surfactants, and alkylphenol polyoxyethylene ether surfactants.

3. The cleaning agent according to claim 1, characterized in that, The chelating agent is at least one of the following: disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, disodium pentacarboxymethyldiaminepentaacetate, disodium tricarboxymethyldiaminetriacetate, sodium citrate, and sodium gluconate.

4. A method for preparing the cleaning agent according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Mix the isopropanol and the ethyl acetate evenly to obtain a basic organic solvent system; S2. Add a nonionic surfactant to the basic organic solvent system and mix thoroughly. S3. Add the chelating agent to the obtained mixture and dissolve it completely. The resulting solution is the cleaning agent.

5. The preparation method according to claim 4, characterized in that, The solution obtained in step S3 is filtered through a 0.22 μm polytetrafluoroethylene microporous membrane, and the resulting filtrate is the cleaning agent.

6. The preparation method according to claim 4, characterized in that, In step S2, the mixture is stirred evenly using a magnetic stirrer at a speed of 200-400 rpm for 10-30 minutes.

7. A method for cleaning silver-based micro / nano structures using the cleaning agent according to any one of claims 1 to 3, characterized in that, Includes the following steps: The surface of the silver-based micro / nano structure is wiped uniformly in one direction using a dust-free wiping material moistened with the cleaning agent.

8. The method according to claim 7, characterized in that, The dust-free wiping material is any one of microfiber dust-free cloth, polyester fiber clean cloth, polyurethane foam-coated fiber composite material, or any of the aforementioned materials after heat sealing treatment.

9. The method according to claim 7, characterized in that, The silver-based micro / nano structure is cleaned using a scrubbing device in conjunction with the cleaning agent; the scrubbing device includes a drive unit, a cleaning agent reservoir, a pressure regulating device, and a wiping assembly; the cleaning agent reservoir is located on the drive unit; The wiping assembly includes a support structure, and the dust-free wiping material is wrapped around the surface of the support structure; the wiping assembly is connected to the driving device through the driving assembly; the cleaning agent is stored in the cleaning agent reservoir, and the cleaning agent reservoir is provided with a control valve channel communicating with the wiping assembly; the pressure regulating device is provided on the wiping assembly.

10. The method according to claim 9, characterized in that, The driving device is any one of a stepper motor, servo motor, linear driver, or pneumatic drive device; or / and the driving assembly is any one of a screw drive mechanism, synchronous belt drive mechanism, linear guide drive mechanism, or cam mechanism; or / and the pressure regulating device is any one of a spring loading mechanism, pneumatic pressure regulating unit, hydraulic micro-pressure control unit, or electronic force feedback regulating unit.

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