Nanosilver microcapsule, underwater self-cleaning window, and preparation method and application thereof

Abstract

The application provides a kind of nano silver microcapsule, underwater self-cleaning window and its preparation method and application, relating to antifouling technical field.The nano silver microcapsule disclosed by the application includes a core layer and a shell layer located on the surface of the core layer, the material of the core layer contains nano silver powder, and the material of the shell layer contains polyacrylamide;The thickness ratio of the core layer and the shell layer is (0.4-1):1;The D50 particle size of the nano silver microcapsule is 180-220nm.Through the design of the structure of the nano silver microcapsule, it can achieve slow release underwater, remove the organisms attached to the underwater window, and has certain transparency, which can be applied to the camera.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of antifouling technology, in particular to a kind of nano-silver microcapsule, underwater self-cleaning window and its preparation method and application. BACKGROUND

[0002] When underwater camera is used underwater for a long time, underwater organisms will adhere to the surface of the window, resulting in unclear imaging on the surface of the window, thereby affecting the performance of the product.

[0003] The commonly used underwater antifouling measures currently include mechanical cleaning method, high-pressure water gun spraying method, ultrasonic or ultraviolet antifouling method, coating antifouling method, and electrochemical antifouling method. Among them, the mechanical cleaning method is mainly processed by manual method, which generally needs to take the camera out of the water surface for processing, which is time-consuming and laborious. If the processing is carried out underwater, a wiper is generally used, which has high cost and complex structure and high failure rate. The high-pressure water gun spraying method needs to be processed out of the water surface, and the equipment structure is complex and the cost is high, which is difficult to be applied on a large scale. The ultrasonic or ultraviolet antifouling method interferes with the normal growth of pollutants by long-time ultrasonic and ultraviolet treatment, so as to achieve the effect of removing pollutants. However, this method also interferes with the normal growth of underwater fish and other organisms, so it is not suitable. The coating antifouling method coats a low-surface-energy antifouling coating on the surface to prevent organisms from adhering to the surface. However, the performance of the existing coating will quickly decay after long-time underwater use. The electrochemical antifouling method kills the adhering objects by electrolysis, but it has a great impact on the survival of other organisms in water, so it is also not suitable.

[0004] Therefore, it is urgent to provide an antifouling product or method which can be used underwater without using complex structure equipment and has little impact on the growth of aquatic organisms. SUMMARY

[0005] The present application provides a kind of nano-silver microcapsule, underwater self-cleaning window and its preparation method and application, to solve the problem of underwater antifouling difficulty.

[0006] In order to solve the above technical problems, according to the first aspect of the present application, a kind of nano-silver microcapsule is provided, including core layer and the shell layer located on the surface of core layer, the material of core layer includes nano-silver powder, the material of shell layer includes polyacrylamide;The thickness ratio of core layer and shell layer is (0.4-1):1;The D50 particle size of nano-silver microcapsule is 180-220nm.

[0007] Further, the material of the core layer further comprises a binder, and the mass ratio of the nano-silver powder and the binder in the material of the core layer is (1.5-5):1.

[0008] Further, the binder is at least one of polyvinyl alcohol, polyvinylpyrrolidone and cetyltrimethylammonium bromide.

[0009] According to a second aspect of the present application, a method for preparing nano-silver microcapsules is provided, comprising the following steps:

[0010] S1, mixing nano-silver powder and a solution containing a binder to obtain a nano-silver powder dispersion liquid, and then drying to obtain composite particles;

[0011] S2, dispersing the composite particles in an organic solvent to obtain an organic phase; dissolving acrylamide in water to obtain an aqueous solution, adding a crosslinking agent to the aqueous solution to obtain an aqueous phase;

[0012] S3, adding the aqueous phase to the organic phase to obtain a mixed solution; stirring the mixed solution, and adding an initiator to the mixed solution to cause a polymerization reaction to obtain nano-silver microcapsules.

[0013] Further, the mass ratio of the nano-silver powder to the binder is (1.5-5):1.

[0014] Further, the mass fraction of the binder in the nano-silver powder dispersion liquid is 10%-20%.

[0015] Further, the organic phase further contains a dispersant, and the mass ratio of the composite particles to the dispersant is (10-15):1.

[0016] Further, the mass fraction of the composite particles in the organic phase is 20%-30%.

[0017] Further, the mass fraction of acrylamide in the aqueous phase is 30%-50%.

[0018] Further, the mass ratio of the composite particles to acrylamide in the mixed solution is (1-2):1.

[0019] Further, the mass fraction of the crosslinking agent in the mixed solution is 0.5%-2%.

[0020] Further, the mass fraction of the initiator is 0.3%-0.6% based on the mass fraction of acrylamide being 100%.

[0021] Further, the dispersant is at least one of tetrachloroethylene, sorbitan oleate, 2-methyl-2-pentanol, and sodium dodecyl sulfate; and / or the crosslinking agent is at least one of N,N-cystamine diacrylamide, divinylbenzene, and diisocyanate; and / or the initiator is at least one of potassium persulfate, sodium sulfite, and ammonium persulfate; and / or the organic solvent is at least one of ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

[0022] Further, the dispersant is a compound reagent with a mass ratio of tetrachloroethylene to sorbitan peroleate of (12-20):1; and / or, the polymerization reaction condition is: temperature 40-50℃, time 2-5h; and / or, after the polymerization reaction, the nano-silver microcapsule is obtained by one-time drying, cleaning, and two-time drying.

[0023] According to a third aspect of the present application, there is provided an underwater self-cleaning window, comprising a heating layer, a transparent layer, an antibacterial layer, and an ion exchange membrane layer arranged in sequence; the material of the antibacterial layer comprises the nano-silver microcapsule or the nano-silver microcapsule prepared by the preparation method, and the antibacterial layer further comprises an acrylic resin; the material of the ion exchange membrane layer is a cation exchange membrane.

[0024] Further, the material of the heating layer comprises at least one of a silver nanowire film, a gold nanowire film, a copper nanowire film, and an ITO film.

[0025] Further, the material of the transparent layer comprises at least one of polycarbonate and glass.

[0026] Further, the mass ratio of the nano-silver microcapsule to the acrylic resin in the material of the antibacterial layer is 1:(6-10).

[0027] Further, the thickness of the antibacterial layer is 1-5μm.

[0028] Further, the cation exchange membrane comprises at least one of a perfluorocarbon cation exchange membrane, a sulfonic acid type cation exchange membrane, and a low-permeability ion exchange membrane.

[0029] According to a fourth aspect of the present application, there is provided a preparation method of an underwater self-cleaning window, comprising the following steps:

[0030] (1) performing surface cleaning and activation on the transparent layer;

[0031] (2) dispersing the nano-microcapsule into the acrylic resin to obtain an antibacterial material, coating the antibacterial material on one side of the activated transparent layer to form an antibacterial layer, and then adhering an ion exchange membrane to the surface of the antibacterial layer and drying until the antibacterial material is in a semi-cured state;

[0032] (3) adhering the heating layer to the other side of the activated transparent layer to obtain the underwater self-cleaning window.

[0033] According to a fifth aspect of the present application, there is provided an application of the above-mentioned underwater self-cleaning window in a camera.

[0034] The present application designs the structure of the nano-silver microcapsule, so that the nano-silver microcapsule has a slow-release performance, does not have a great influence on the growth of aquatic organisms, and can also make the window containing the material have a self-cleaning effect, the antibacterial material can be precipitated to the surface of the window, antibacterial and antifouling are achieved, a device with a complex structure does not need to be used, and the cost is low. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 It is a scanning electron microscope image of the nano-silver microcapsule in the embodiment 1 of the present application.

[0036] Figure 2 It is a structure schematic diagram of the underwater self-cleaning window in the embodiment of the present application.

[0037] Among them, the above drawings include the following reference signs: 1, heating layer; 2, transparent layer; 3, antibacterial layer; 4, ion exchange membrane layer. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0039] As described in the background art of the present application, the surface of the underwater window is easy to attach underwater organisms, and the existing underwater decontamination technology will affect the growth of other organisms while removing the contaminants on the surface of the window, and needs to use a device with a complex structure additionally. In order to solve the above technical problems, in a typical embodiment of the present application, a nano-silver microcapsule is provided, which includes a core layer and a shell layer located on the surface of the core layer, the material of the core layer contains nano-silver powder, and the material of the shell layer contains polyacrylamide; the thickness ratio of the core layer and the shell layer is (0.4-1):1; the D50 particle size of the nano-silver microcapsule is 180-220 nm.

[0040] The D50 particle size of the nano-silver powder is 180-220 nm, which has good antibacterial property, and the coating of the nano-silver powder with polyacrylamide can achieve the slow release of silver ions under heating conditions. The above-mentioned limitation of the thickness ratio of the core layer and the shell layer of the nano-silver microcapsule and the size of the nano-silver powder and the nano-microcapsule can make the nano-silver microcapsule have a suitable slow-release rate, which can kill the underwater organisms attached to the window when applied to the underwater window, and does not affect the growth of other organisms in the water.

[0041] In a preferred embodiment of the present application, the material of the core layer further comprises a binder, and the mass ratio of the nano-silver powder to the binder in the material of the core layer is (1.5-5):1. Preferably, the binder is at least one of polyvinyl alcohol, polyvinylpyrrolidone and cetyltrimethylammonium bromide.

[0042] By adding the binder and limiting the mass ratio of the binder to the nano-silver powder, good bonding force between the core and the shell can be achieved, and the problem of collapse of the core-shell structure after long-term use can be avoided. In addition, by optimizing the type of the binder, the dispersibility of the nano-silver powder can be improved, and the slow-release effect can be improved.

[0043] In another typical embodiment of the present application, a preparation method of the nano-silver microcapsule is provided, comprising the following steps:

[0044] S1, mixing the nano-silver powder and a solution containing a binder to obtain a nano-silver powder dispersion liquid, and then drying to obtain composite particles;

[0045] S2, dispersing the composite particles in an organic solvent to obtain an organic phase; dissolving acrylamide in water to obtain an aqueous solution, adding a crosslinking agent to the aqueous solution to obtain an aqueous phase;

[0046] S3, adding the aqueous phase to the organic phase to obtain a mixed solution; stirring the mixed solution, and adding an initiator to the mixed solution to cause a polymerization reaction to obtain the nano-silver microcapsule.

[0047] The nano-silver microcapsule with a core-shell structure is formed by in-situ polymerization on the surface of the composite particles by using a reverse suspension polymerization method, and the material has high strength and is more stable, and can act underwater for a long time.

[0048] In a preferred embodiment of the present application, the mass ratio of the nano-silver powder to the binder is (1.5-5):1.

[0049] By optimizing the mass ratio of the nano-silver powder to the binder as described above, the bonding strength of the core layer and the shell layer can be improved, and the nano-silver powder can be well dispersed, and the nano-microcapsule has certain transparency.

[0050] In a preferred embodiment of the present application, the mass fraction of the binder in the nano-silver powder dispersion liquid is 10%-20%. By the above limitation, the composition of the nano-silver powder and the binder in the prepared composite particles can be more uniform.

[0051] In a preferred embodiment of the present application, the organic phase further contains a dispersant, and the mass ratio of the composite particles to the dispersant is (10-15):1. In the organic phase, the mass fraction of the composite particles is 20%-30%.

[0052] The addition of the dispersant helps to improve the dispersibility of the composite particles in the organic phase, to prepare the nano-silver capsules of suitable size, and to facilitate the slow release.

[0053] In a preferred embodiment of the present application, the mass fraction of acrylamide in the aqueous phase is 30%-50%.

[0054] The mass fraction of acrylamide is controlled to ensure that the polymerization reaction proceeds sufficiently and that the shell of the nano-silver microcapsule is more uniform.

[0055] In a preferred embodiment of the present application, the mass ratio of the composite particles to acrylamide in the mixed solution is (1-2):1.

[0056] The mass ratio of the composite particles to acrylamide is limited to control the thickness ratio of the core layer to the shell, which is beneficial to improving the slow release effect.

[0057] In a preferred embodiment of the present application, the mass fraction of the crosslinking agent in the mixed solution is 0.5%-2%.

[0058] The above limitation on the amount of the crosslinking agent is also to further improve the polymerization reaction efficiency and to obtain the polyacrylamide that can slowly release silver ions after being heated.

[0059] In a preferred embodiment of the present application, the mass fraction of the initiator is 0.3%-0.6% based on the mass fraction of 100% acrylamide. The initiator can activate the reaction center on the monomer molecule, and the addition of the initiator in the above amount can improve the reaction efficiency.

[0060] Typically but not limitedly, the dispersant is at least one of tetrachloroethylene, sorbitan oleate, 2-methyl-2-pentanol, and sodium dodecyl sulfate; and / or, the crosslinking agent is at least one of N,N-cystamine diacrylamide, divinylbenzene, and diisocyanate; and / or, the initiator is at least one of potassium persulfate, sodium sulfite, and ammonium persulfate; and / or, the organic solvent is at least one of ethyl acetate, butyl acetate (BAC), and propylene glycol methyl ether acetate.

[0061] In a preferred embodiment of the present application, the dispersant is a compounded reagent of tetrachloroethylene and sorbitan oleate in a mass ratio of (12-20):1. The selection of these two materials for compounding can effectively reduce the interfacial tension, which is beneficial to the formation of droplets, and can also participate in the control and improvement of the polymerization reaction of polyacrylamide to obtain nano-silver microcapsules with concentrated particle size distribution and uniform encapsulation.

[0062] In a preferred embodiment of the present application, the polymerization reaction conditions are: temperature 40-50℃, time 2-5h.

[0063] Typically but not limitedly, after the polymerization reaction, the nanosilver microcapsules are obtained by drying, ultrasonic cleaning with reagents such as anhydrous ethanol, and drying again.

[0064] Typically but not limitedly, stirring is needed during preparation of the organic phase to improve the dispersibility of the composite particles. In S1, the solution containing the binder is an aqueous solution containing the binder, and the aqueous solution is prepared by heating to 50-60°C, and stirring can be assisted.

[0065] In another typical embodiment of the present application, a self-cleaning underwater view window is provided, a schematic diagram of the structure of which is shown in Figure 1 The antibacterial layer comprises the nanosilver microcapsules or the nanosilver microcapsules prepared by the method described above, and further comprises an acrylic resin. The ion exchange membrane layer is made of a cation exchange membrane, which allows the nanosilver and silver ions to pass through but not water.

[0066] By selecting the materials of the antibacterial layer and the ion exchange membrane layer, in the above self-cleaning underwater view window, the nanosilver microcapsules near the transparent layer in the antibacterial layer can be broken after the heating of the heating layer, and the nanosilver migrates from the side near the transparent layer to the ion exchange membrane layer, and the nanosilver microcapsules move to the side of the transparent layer, and finally reach a concentration balance. The nanosilver enters the cells of the underwater organisms adsorbed on the surface of the view window through the ion exchange membrane layer, and the microorganisms are removed.

[0067] Typically but not limitedly, the material of the heating layer comprises at least one of a silver nanowire film, a gold nanowire film, a copper nanowire film, and an ITO film.

[0068] Typically but not limitedly, the material of the transparent layer comprises at least one of polycarbonate and glass, and can be a composite of polycarbonate and acrylonitrile-butadiene-styrene. The above materials still have good stability and high light transmittance after heating.

[0069] In a preferred embodiment of the present application, the mass ratio of the nanosilver microcapsules to the acrylic resin in the material of the antibacterial layer is 1: (6-10).

[0070] The acrylic resin has good transparency, and the composite particles can be uniformly dispersed in the acrylic resin, which is easy to process into the antibacterial layer. The composite particles are easy to migrate in the acrylic resin after heating.

[0071] In a preferred embodiment of the present application, the thickness of the antibacterial layer is 1-5 μm.

[0072] The above preferred thickness of the antibacterial layer is to balance the good transparency and antibacterial property, so that the view window can present good photographic effect after being applied to the camera.

[0073] Typically but not limitedly, the cation exchange membrane comprises at least one of perfluorocarbon cation exchange membrane, sulfonic acid type cation exchange membrane, low permeability ion exchange membrane, such as Fumasep FS-9100-PK, CMI-7000S, IONSEPTM, Fumaep E-620.

[0074] In another typical embodiment of the present application, a preparation method of the underwater self-cleaning view window is provided, comprising the following steps:

[0075] (1) surface cleaning and activation of the transparent layer;

[0076] (2) dispersing the nano-microcapsule into the acrylic resin to obtain the antibacterial material, coating the antibacterial material on one side of the activated transparent layer to form the antibacterial layer, and then adhering the ion exchange membrane to the surface of the antibacterial layer and drying to a semi-cured state of the antibacterial material;

[0077] (3) adhering the heating layer to the other side of the activated transparent layer to obtain the underwater self-cleaning view window.

[0078] Typically but not limitedly, in step (1), the surface cleaning method is to clean the transparent layer material under ultrasonic condition with acetone and anhydrous ethanol, and then naturally dry after cleaning; the activation method includes any one or more of plasma method, ultraviolet ozone method, chemical oxidation method, coupling agent method, etc.

[0079] Typically but not limitedly, in step (2), the coating method includes any one of roll coating, suspension coating, spraying and silk printing, etc.

[0080] Typically but not limitedly, in step (2), the drying condition is: temperature 65-75℃, time 10-15min.

[0081] In a typical embodiment of the present application, the above underwater self-cleaning view window is also provided for application in a camera.

[0082] The present application will be further described in detail below in combination with specific examples, which cannot be understood as limiting the scope of the present application.

[0083] The information of some components in the examples and comparative examples is as follows:

[0084] Nano-silver powder: D50 particle size is 180nm-220nm;

[0085] Material of the heating layer: silver nanowire film, thickness is 2.5μm;

[0086] Material of transparent layer: glass, thickness of 2mm;

[0087] Material of ion exchange film layer: cation exchange film, Fumaep E-620, thickness of 25μm.

[0088]

Nano-silver microcapsule

[0089] Example 1

[0090] In one embodiment of the nano-silver microcapsule, the preparation method of the nano-silver microcapsule is as follows:

[0091] S1, prepare a polyvinyl alcohol aqueous solution with a mass fraction of 15% of the binder polyvinyl alcohol at 55℃, and stir during the preparation process at a stirring rate of 700rpm, then add nano-silver powder into the polyvinyl alcohol aqueous solution, mix thoroughly to make the polyvinyl alcohol and the nano-silver powder stick together, and obtain composite particles after drying; the mass ratio of the nano-silver powder and the polyvinyl alcohol is 3:1;

[0092] S2, take dispersant tetrachloroethylene and sorbitan peroleate according to a mass ratio of 15:1, dissolve them in an organic solvent, and add the composite particles under the stirring condition of 850rpm to obtain an organic phase; prepare an aqueous solution with a mass fraction of 40% of acrylamide, and add a crosslinking agent N,N-cystamine dipropylene amide to obtain an aqueous phase; in the organic phase, the mass ratio of the dispersant and the composite particles is 1:15, and the mass fraction of the composite particles in the organic phase is 20%;

[0093] S3, add the above-mentioned aqueous phase into the organic phase to obtain a uniformly dispersed suspension, and under the stirring condition of 800rpm, acrylamide monomer droplets collide with crosslinking agent particles and are adsorbed on the surface of the crosslinking agent particles; gradually add initiators potassium persulfate and sodium sulfite into the suspension, and after 3h of reaction at 45℃, the monomer droplets are initiated to polymerize by the initiators; then dry and evaporate the water in the system, and then wash twice with anhydrous ethanol by ultrasonic, and dry to obtain nano-silver microcapsules with a core-shell structure, Figure 1 which is a scanning electron microscope image of the nano-silver microcapsule, and it can be seen from the image that it has a core-shell structure; the mass ratio of the composite particles and acrylamide in the suspension is 1:1, and the mass fraction of the crosslinking agent in the suspension is 0.5%; the mass fraction of acrylamide is 100%, the mass fraction of the initiator is 0.4%, and the mass ratio of potassium persulfate and sodium sulfite in the initiator is 1.08:1.

[0094] Examples 2-5

[0095] The embodiments of the nano-silver microcapsule of the present application, embodiments 2-5, differ from embodiment 1 in that the mass ratio of nano-silver powder and binder is different (the mass of nano-silver powder is the same) when preparing the composite particles, and the type of binder is different. Among them, the binder in embodiment 2 is polyvinylpyrrolidone, the mass ratio of nano-silver powder and binder is 1.5:1, the binder in embodiment 3 is hexadecyl trimethyl ammonium bromide, the mass ratio of nano-silver powder and binder is 5:1, the mass ratio of nano-silver powder and polyvinyl alcohol in embodiment 4 is 1.2:1, and the mass ratio of nano-silver powder and polyvinyl alcohol in embodiment 5 is 6:1.

[0096] Embodiments 6-9

[0097] The embodiments of the nano-silver microcapsule of the present application, embodiments 6-9, differ from embodiment 1 only in that the mass ratio of composite particles and acrylamide in the suspension (the mass of the composite particles is the same) in S3 is different. Among them, the mass ratio of composite particles and acrylamide in embodiment 6 is 1.5:1, the mass ratio of composite particles and acrylamide in embodiment 7 is 2:1, the mass ratio of composite particles and acrylamide in embodiment 8 is 1:1.2, and the mass ratio of composite particles and acrylamide in embodiment 9 is 2.5:1.

[0098] Embodiment 10

[0099] An embodiment of the nano-silver microcapsule of the present application, this embodiment differs from embodiment 1 only in that the type of dispersant is different (the total amount of dispersant is the same), and only tetrachloroethylene is used.

[0100] Table 1 is a data table of the thickness ratio of the core layer and the shell layer in the nano-silver microcapsule in embodiments 1-10.

[0101] Table 1

[0102]

[0103]

Underwater self-cleaning window

[0104] Embodiments 11-20

[0105] The embodiments of the underwater self-cleaning window of the present application, the structural diagram of the underwater self-cleaning window described in embodiments 11-20 is as shown in Figure 2 1, heating layer; 2, transparent layer; 3, antibacterial layer; 4, ion exchange membrane layer, the preparation method is as follows:

[0106] (1) acetone and anhydrous ethanol were used to clean the glass under ultrasonic conditions, and the glass was naturally dried after cleaning; then the glass was activated by plasma method to obtain the activated transparent layer;

[0107] (2) dispersing the nano-silver microcapsules into the acrylic resin to obtain an antibacterial material, rolling the antibacterial material onto one side of the activated transparent layer to form an antibacterial layer, and then attaching the cation exchange film to the surface of the antibacterial layer and drying at 30°C for 3h to a semi-cured state, wherein the thickness of the antibacterial layer is 3.5μm, and the mass ratio of the nano-silver microcapsules to the acrylic resin is 1:8;

[0108] (3) attaching the material of the heating layer to the other side of the activated transparent layer to obtain the underwater self-cleaning view window.

[0109] The nano-silver microcapsules used in Examples 11-20 are the nano-silver microcapsules described in Examples 1-10, respectively.

[0110] Examples 21-24

[0111] The underwater self-cleaning view windows of the embodiments of the present application, the underwater self-cleaning view windows described in Examples 21-22 differ from Example 11 only in that the thickness of the antibacterial layer in step (2) is different. In Example 21, the thickness of the antibacterial layer is 1μm, in Example 22, the thickness of the antibacterial layer is 5μm, in Example 23, the thickness of the antibacterial layer is 0.5μm, and in Example 24, the thickness of the antibacterial layer is 6μm.

[0112]

Performance Test

[0113] Antibacterial property and antibacterial durability: referring to GB / T 21866-2008, test against Staphylococcus aureus, and record the antibacterial rate test results in Table 2;

[0114] Transmittance: place the prepared sample in a clamp, use a remote HAM-300 (visible-infrared band spectral haze meter) to test the transmittance, and record the test results in Table 2.

[0115] Table 2

[0116]

[0117] From the above test results, it can be seen that the underwater self-cleaning view window prepared by the nano-silver microcapsules in the present application has good antibacterial property and high transmittance, and is suitable for application in underwater cameras.

[0118] In addition, it can be found from the test results of Comparative Examples 11-15 that when the mass ratio of the nano-silver powder and the binder is (1.5-5):1, the underwater self-cleaning window has high transmittance, antibacterial property and antibacterial durability. It can be found from the test results of Comparative Example 11 and Examples 16-19 that when the mass ratio of the composite particles and the acrylamide is (1-2):1, the underwater self-cleaning window has better comprehensive performance. It can be found from the test results of Comparative Example 11 and Example 20 that when the dispersing agent is a compound reagent with a mass ratio of tetrachloroethylene and sorbitan peroleate being (12-20):1, the underwater self-cleaning window has obviously higher transmittance and antibacterial durability. It can be found from the test results of Comparative Example 11 and Examples 21-24 that the thickness of the antibacterial layer has a great influence on the transmittance and antibacterial durability, and when the thickness of the antibacterial layer is 1-5 μm, the underwater self-cleaning window has good transmittance, antibacterial property and antibacterial durability.

[0119] The preferred embodiments of the present application have been described above with the preferred embodiments, but the present application is not limited to the above examples. It will be appreciated by those skilled in the art that the present application can be variously changed and modified. Any modification, equivalent replacement, improvement, etc. within the principles of the present application should be included in the scope of the present application.

Claims

1. An underwater self-cleaning window, characterized in that: The invention comprises a heating layer, a transparent layer, an antibacterial layer and an ion exchange membrane layer stacked in sequence; the antibacterial layer is made of nanosilver microcapsules and acrylic resin, and the nanosilver microcapsules are dispersed in the acrylic resin to obtain the antibacterial layer material; the ion exchange membrane layer is made of a cation exchange membrane; The thickness of the antibacterial layer is 1-5 μm; The nanosilver microcapsules consist of a core layer and a shell layer located on the surface of the core layer. The core layer is made of nanosilver powder and a binder, and the shell layer is made of polyacrylamide. The thickness ratio of the core layer to the shell layer is (0.4-1):

1. The D50 particle size of the nanosilver microcapsules is 180-220 nm. In the core layer, the mass ratio of the nanosilver powder to the binder is (1.5-5):

1.

2. The underwater self-cleaning window according to claim 1, characterized in that: The binder is at least one of polyvinyl alcohol, polyvinyl pyrrolidone, and cetyltrimethylammonium bromide.

3. The underwater self-cleaning window according to claim 1, characterized in that: The preparation method of the nano silver microcapsules comprises the following steps: S1, mixing nano silver powder and a solution containing a binder to obtain a nano silver powder dispersion, and then drying to obtain composite particles; S2, dispersing the composite particles in an organic solvent to obtain an organic phase; dissolving acrylamide in water to obtain an aqueous solution, and adding a crosslinking agent to the aqueous solution to obtain an aqueous phase; S3, adding the aqueous phase to the organic phase to obtain a mixed solution; stirring the mixed solution, and adding an initiator to the mixed solution to cause a polymerization reaction to obtain the nanosilver microcapsules; The mass ratio of the nano silver powder to the binder is (1.5-5):

1.

4. The underwater self-cleaning window according to claim 3, characterized in that: In the nano silver powder dispersion, the mass fraction of the binder is 10%-20%; and / or The organic phase further contains a dispersant, and the mass ratio of the composite particles to the dispersant is (10-15):1; and / or In the organic phase, the mass fraction of the composite particles is 20%-30%; and / or In the aqueous phase, the mass fraction of acrylamide is 30%-50%; and / or In the mixed solution, the mass ratio of the composite particles to the acrylamide is (1-2):1; and / or In the mixed solution, the mass fraction of the cross-linking agent is 0.5%-2%; and / or Based on the mass fraction of acrylamide being 100%, the mass fraction of the initiator is 0.3%-0.6%.

5. The underwater self-cleaning window according to claim 4, characterized in that: The dispersant is at least one of tetrachloroethylene, sorbitan oleate, 2-methyl-2-pentanol, and sodium lauryl sulfate; and / or the cross-linking agent is at least one of N,N-cystamine diacrylamide, divinylbenzene, and diisocyanate; and / or the initiator is at least one of potassium persulfate, sodium sulfite, and ammonium persulfate; and / or the organic solvent is at least one of ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

6. The underwater self-cleaning window according to claim 5, characterized in that: The dispersant is a compound reagent with a mass ratio of tetrachloroethylene to sorbitan oleate of (12-20):1; and / or The polymerization reaction conditions are: temperature 40-50°C, time 2-5h; and / or After the polymerization reaction is completed, the nanosilver microcapsules are obtained by primary drying, washing, and secondary drying.

7. The underwater self-cleaning window according to claim 1, characterized in that: The material of the heating layer comprises at least one of a silver nanowire film, a gold nanowire film, a copper nanowire film, and an ITO film; and / or The material of the transparent layer comprises at least one of polycarbonate and glass; and / or The mass ratio of the nanosilver microcapsules to the acrylic resin in the antibacterial layer is 1:(6-10); and / or The cation exchange membrane comprises at least one of a perfluorinated cation exchange membrane, a sulfonic acid cation exchange membrane, and a low permeability ion exchange membrane.

8. A method for preparing an underwater self-cleaning window according to any one of claims 1 to 7, characterized in that: The steps include: (1) Clean and activate the surface of the transparent layer; (2) dispersing nanosilver microcapsules in acrylic resin to obtain an antibacterial material, coating the antibacterial material on one side of the activated transparent layer to form an antibacterial layer, laminating an ion exchange membrane to the surface of the antibacterial layer, and drying until the antibacterial material is in a semi-cured state; (3) Laminating the heating layer to the other side of the activated transparent layer to obtain the underwater self-cleaning window.

9. Use of the underwater self-cleaning window according to any one of claims 1 to 7 in a camera.

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