A super-wettability antiviral protective mask and its preparation method

Abstract

The present invention relates to a super-wetting antiviral protective mask and a preparation method thereof. A nano-adsorption disinfection super-hydrophilic protective coating is coated on the inner side of the skin-friendly layer, and a nano-super anti-droplet antiviral super-hydrophobic protective coating is coated on the outer side of the antibacterial layer. The nano-super anti-droplet antiviral super-hydrophobic protective coating comprises the following components: polar group fluoropolymer, water-based fluorocarbon resin, inorganic nanowire, tetraethyl orthosilicate, absolute ethanol and ammonia water; the inner side nano-adsorption disinfection super-hydrophilic protective coating comprises the following components: chitosan quaternary ammonium salt, water-based polyurethane resin. Since the nano-super anti-droplet antiviral super-hydrophobic protective coating is coated on the outer side of the mask, the adhesion of virus-containing droplets can be strongly repelled for a long time; since the nano-adsorption disinfection super-hydrophilic protective coating is coated on the inner side of the mask, it has extremely high surface energy and extremely strong electrostatic adsorption effect, enabling the adsorbed virus and droplets to present a fully spread contact, greatly improving the inactivation rate of antibacterial active substances against viruses.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial masks, and particularly to a superwetting antiviral protective mask and a preparation method thereof. Background Art

[0002] Using protective masks such as disposable medical masks and medical surgical masks is an effective means to prevent the interpersonal transmission of infectious respiratory diseases. However, due to their design and manufacturing processes, currently commercially available medical masks have many defects: on the one hand, although the non-woven fabric layer of medical masks has a certain degree of water resistance, it cannot isolate large-area water droplets, and virus droplets, virus aerosols, etc. can adhere to the surface of the non-woven fabric; on the other hand, the middle layer of medical masks is a ultra-thin polypropylene meltblown material, usually treated with electret (positive charge). Although it can filter most microorganisms, it is easily neutralized by other negatively charged particles in the environment and becomes ineffective; these shortcomings result in the inability of medical masks to effectively resist the adhesion of bacteria, viruses, etc. for a long time during use.

[0003] In response to this, the Chinese invention patent with the application number 202010190843.8 discloses an antibacterial and antiviral mask and a preparation method thereof. An antibacterial outer layer is made using inorganic antibacterial agents such as nano-zinc oxide, nano-titanium dioxide, bismuth tungstate, nano-silver sol or Ag@C core-shell structured nanoparticles, an egg white lysozyme is used to make a lysozyme middle layer, and an aminopeptidase is used as an antiviral agent to make an antiviral outer layer. The prepared mask has a relatively thorough antibacterial and antiviral effect. However, this antibacterial and antiviral mask has the following problems: Although lysozyme and aminopeptidase can kill bacteria and viruses on the mask, due to the activity limitations of lysozyme and aminopeptidase, and the need to activate the biological activity of the enzyme under suitable humidity, temperature, and carbon dioxide concentration conditions, therefore, this antibacterial and antiviral mask does not have a lasting antibacterial and antiviral effect.

[0004] The Chinese invention patent with the application number 202010171182.4 discloses a long-lasting antiviral fabric, a preparation method thereof, and a mask composed thereof. First, the fabric is impregnated in a sodium chloride solution and dried to prepare a sodium chloride coating attached to the lower surface of the fabric. Then, a dye layer is made using rose bengal dye or a derivative of rose gallate dye and attached to the upper surface of the fabric. The prepared mask has good bactericidal and antiviral effects and a long service life. However, this mask has the following problems: Rose bengal dye forms singlet oxygen molecules when exposed to light and air. Although this singlet oxygen molecule is a powerful antibacterial agent that can kill a variety of bacteria, fungi, and viruses, at room temperature in a gas environment, the lifespan of singlet oxygen molecules can be up to more than 1 hour. Therefore, to a certain extent, it will cause harm to the human body. Summary of the Invention

[0005] In view of this, it is necessary to provide a super-wetting antiviral protective mask and its preparation method for the problems. The super-wetting antiviral protective mask provided by the present invention has a long-lasting antibacterial and antiviral effect and good biological safety.

[0006] In the first aspect, the present invention provides a super-wetting antiviral protective mask, which successively has a skin-friendly layer, an isolation and filtration layer, and an antibacterial layer from the inside to the outside. A nano-adsorption disinfection super-hydrophilic protective coating is coated on the inner side of the skin-friendly layer, and a nano-super anti-droplet antiviral super-hydrophobic protective coating is coated on the outer side of the antibacterial layer.

[0007] The nano-super anti-droplet antiviral super-hydrophobic protective coating comprises the following components:

[0008] Polar group fluoropolymer, water-based fluorocarbon resin, inorganic nanowire, tetraethyl orthosilicate, absolute ethanol and ammonia water;

[0009] The inner side nano-adsorption disinfection super-hydrophilic protective coating comprises the following components: chitosan quaternary ammonium salt, water-based polyurethane resin.

[0010] Further, the polar group fluoropolymer is one of 3,3,3-trifluoropropyltriethoxysilane, (pentafluoroethyl)trimethylsilane or 1H,1H,2H,2H-perfluorohexyltrichlorosilane.

[0011] Further, the inorganic nanowire is one of silicon dioxide nanowire, titanium dioxide nanowire or aluminum oxide nanowire.

[0012] Further, the water-based fluorocarbon resin is one of DF-M05, DF-01L, FEM-101, HT-610FY or 121A.

[0013] Further, the water-based polyurethane resin is one of PU-2944, 1500F, 1402F or DB-716.

[0014] In the second aspect, the present invention provides a preparation method of a super-wetting antiviral protective mask, comprising the following steps:

[0015] (1) Prepare an inorganic nanowire mixture: After mixing absolute ethanol and ammonia water, mix the absolute ethanol / ammonia water solution with the inorganic nanowire, stir and ultrasonically disperse to prepare an inorganic nanowire mixture;

[0016] (2) Prepare low surface energy inorganic nanowires: Add the polar group fluoropolymer and tetraethyl orthosilicate to the inorganic nanowire mixture prepared in step (1), prepare a precursor solution, stir evenly, centrifuge to collect a white precipitate, wash the white precipitate, and finally dry to prepare low surface energy inorganic nanowires;

[0017] (3) Weigh the low surface energy inorganic nanowires prepared in step (2) and the waterborne fluorocarbon resin according to a mass ratio of 1:4 to 20, then add anhydrous ethanol / aqueous solution, stir and ultrasonically disperse to obtain the nano super anti-droplet antiviral superhydrophobic protective coating slurry;

[0018] (4) Dissolve chitosan quaternary ammonium salt in water and stir at high speed to obtain an aqueous solution of chitosan quaternary ammonium salt, then add it to the waterborne polyurethane resin solution and stir evenly to prepare the nano adsorption disinfection superhydrophilic protective coating slurry;

[0019] (5) Uniformly coat the nano super anti-droplet antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, and uniformly coat the nano adsorption disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, and leave it to dry at room temperature;

[0020] (6) Stack the skin-friendly layer coated with the nano adsorption disinfection superhydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano super anti-droplet antiviral superhydrophobic protective coating in sequence from the inside to the outside, and perform hot rolling treatment to obtain the super-infiltration antiviral protective mask.

[0021] Preferably, in step (1), the anhydrous ethanol / ammonia aqueous solution and the inorganic nanowires are mixed according to a mass ratio of 5431 - 7706:162 - 2700; the volume ratio of anhydrous ethanol to ammonia in the anhydrous ethanol / ammonia aqueous solution is 8:0.1 to 10.

[0022] Preferably, in step (2), the polar group fluoropolymer, tetraethyl orthosilicate, and inorganic nanowire mixture are mixed according to a mass ratio of 10 - 325:1 - 21:15 - 350.

[0023] Preferably, in step (3), the low surface energy inorganic nanowires, waterborne fluorocarbon resin, and anhydrous ethanol / aqueous solution are mixed according to a mass ratio of 1:4 - 20:6 - 80.

[0024] Preferably, in step (4), the aqueous solution of chitosan quaternary ammonium salt and the waterborne polyurethane resin solution are mixed according to a mass ratio of 8 - 256:5 - 35.

[0025] Compared with the prior art, the advantages of the present invention are as follows:

[0026] The preparation method of a super-wetting antiviral protective mask of the present invention is to first prepare low-surface-energy nanowires and a chitosan quaternary ammonium salt aqueous solution. The low-surface-energy nanowires are stirred and mixed with a water-soluble fluoropolymer to prepare a nano super anti-droplet antiviral super-hydrophobic protective coating. The chitosan quaternary ammonium salt aqueous solution is stirred and mixed with a water-soluble polymer to prepare a nano adsorption disinfection super-hydrophilic protective coating. Then, the nano super anti-droplet antiviral super-hydrophobic protective coating slurry is uniformly coated on the outer side of the antibacterial layer of the mask, and the nano adsorption disinfection super-hydrophilic protective coating slurry is uniformly coated on the inner side of the skin-friendly layer of the mask. Since the nano super anti-droplet antiviral super-hydrophobic protective coating is coated on the outer side of the mask, it has an ultra-low surface energy and ultra-high stability, and can strongly repel the adhesion of virus-containing droplets for a long time; since the nano adsorption disinfection super-hydrophilic protective coating is coated on the inner side of the mask, it has a very high surface energy and a strong electrostatic adsorption effect, making the adsorbed virus and droplets show a fully spread contact, greatly improving the inactivation rate of antibacterial active substances against the virus. Description of the Drawings

[0027] Figure 1 It is the SEM image of the nano super anti-droplet antiviral super-hydrophobic protective coating slurry;

[0028] Figure 2 It is the hydrophobic effect diagram of the nano super anti-droplet antiviral super-hydrophobic protective coating;

[0029] Figure 3 It is the hydrophilic effect diagram of the nano adsorption disinfection super-hydrophilic protective coating. Detailed Embodiments

[0030] Since the protective mask is extremely likely to adhere to droplets containing bacteria or viruses, as well as nasal mucus, blood, sweat and tears during use, resulting in weak and short-term clinical or daily protection effects. For this reason, the present invention provides a super-wetting antiviral protective mask, which successively has a skin-friendly layer, an isolation and filtration layer, and an antibacterial layer from the inside to the outside. The skin-friendly layer is made of ordinary sanitary gauze or non-woven fabric, the isolation and filtration layer is made of an ultra-fine polypropylene fiber melt-blown material layer, the antibacterial layer is made of non-woven fabric or an ultra-thin polypropylene melt-blown material layer, and the inner side of the skin-friendly layer is coated with a nano adsorption disinfection super-hydrophilic protective coating, and the outer side of the antibacterial layer is coated with a nano super anti-droplet antiviral super-hydrophobic protective coating.

[0031] Among them, the nano super anti-droplet antiviral super-hydrophobic protective coating includes the following components:

[0032] Polar group fluoropolymer, water-based fluorocarbon resin, inorganic nanowires, tetraethyl orthosilicate, absolute ethanol and ammonia water;

[0033] Among them, the inner side nano adsorption disinfection super-hydrophilic protective coating includes the following components: chitosan quaternary ammonium salt, water-based polyurethane resin.

[0034] The polar group fluoropolymer is one of 3,3,3-trifluoropropyltriethoxysilane, (pentafluoroethyl)trimethylsilane, or 1H,1H,2H,2H-perfluorohexyltrichlorosilane.

[0035] The inorganic nanowire is one of silicon dioxide nanowires, titanium dioxide nanowires, or aluminum oxide nanowires.

[0036] The aqueous fluorocarbon resin is one of DF-M05, DF-01L, FEM-101, HT-610FY, or 121A.

[0037] The aqueous polyurethane resin is one of PU-2944, 1500F, 1402F, or DB-716.

[0038] The present invention provides a method for preparing a super-wettable antiviral protective mask, comprising the following steps:

[0039] (1) Prepare an inorganic nanowire mixture: Mix the inorganic nanowire with absolute ethanol and ammonia water with a mass concentration of 25%, stir at room temperature with a magnetic stirrer, and disperse by ultrasonic wave with an ultrasonic instrument at room temperature for 15 - 20 min with an ultrasonic power of 80% to obtain an inorganic nanowire mixture; ultrasonic dispersion in this step can make the inorganic nanowires disperse evenly in the absolute ethanol / ammonia water mixed solution without agglomeration. Since ammonia water is a weakly alkaline solution, it is beneficial to the reaction of the subsequently added polar group fluoropolymer.

[0040] (2) Prepare low surface energy inorganic nanowires: Add the polar group fluoropolymer and tetraethyl orthosilicate to the inorganic nanowire mixture prepared in step (1) to prepare a precursor solution, stir evenly at room temperature with a magnetic stirrer, and centrifuge at room temperature to collect a white precipitate with a centrifugal speed greater than 5000 rpm. Then wash the white precipitate with absolute ethanol to remove small molecule impurities adhering to the surface of the low surface energy inorganic nanowire solid, and finally dry it in a constant temperature electrothermal blast drying oven under the drying conditions: 60 °C for 24 h to obtain low surface energy inorganic nanowires. In this step, ultra-low surface energy inorganic nanowires are prepared by hydrolysis deposition, with a simple process, easy operation, and low preparation cost. Stirring is required during the reaction process to enable the hydrolysis reaction of the polar group fluoropolymer and tetraethyl orthosilicate under the condition of ammonia water and deposit and modify on the surface of the inorganic nanowires.

[0041] (3) Weigh the low-surface-energy inorganic nanowires prepared in step (2) and the waterborne fluorocarbon resin according to a mass ratio of 1:4 to 20, and then add absolute ethanol / aqueous solution, where the volume ratio of absolute ethanol to water is 10:1 to 40. Stir and ultrasonically disperse to make the low-surface-energy inorganic nanowires evenly dispersed in the waterborne fluorocarbon resin solution without agglomeration, thereby obtaining a nano super anti-droplet and antiviral superhydrophobic protective coating slurry with good liquid repellent effect and mechanical properties. In this step, due to the use of waterborne fluorocarbon resin, the prepared nano super anti-droplet and antiviral superhydrophobic protective coating has a lower surface energy, which is more conducive to repelling the spreading of liquids. The low-surface-energy inorganic nanowires and the waterborne fluorocarbon resin are combined in a mass ratio of 1:4 to 20, which can achieve excellent liquid repellent effect, and the prepared nano super anti-droplet and antiviral superhydrophobic protective coating has good mechanical properties. Figure 1 The SEM image of the nano super anti-droplet and antiviral superhydrophobic protective coating slurry is shown as follows.

[0042] (4) Dissolve chitosan quaternary ammonium salt with a molecular weight of 10,000 to 50,000 in water and stir at high speed to obtain a chitosan quaternary ammonium salt aqueous solution, and then add it to the waterborne polyurethane resin solution and stir evenly to prepare a nano adsorptive disinfection superhydrophilic protective coating slurry.

[0043] (5) Uniformly coat the nano super anti-droplet and antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, and the coating thickness is 10 μm. This coating does not crack and has excellent liquid repellent effect. Uniformly coat the nano adsorptive disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, and the coating thickness is 10 μm. This coating does not crack and has excellent liquid repellent effect. Leave it to dry at room temperature for 2 to 5 days.

[0044] (6) As Figure 2 、 3 shown, stack the skin-friendly layer coated with the nano super anti-droplet and antiviral superhydrophobic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano adsorptive disinfection superhydrophilic protective coating in sequence from the inside to the outside, and then carry out hot rolling treatment under the conditions of 50 °C and 0.3 MPa to obtain a superwetting antiviral protective mask.

[0045] Among them, in step (1), the absolute ethanol / ammonia aqueous solution and the inorganic nanowires are mixed according to a mass ratio of 5431 - 7706:162 - 2700; the volume ratio of absolute ethanol to ammonia in the absolute ethanol / ammonia aqueous solution is 8:0.1 to 10; the solid content of the inorganic nanowires in the inorganic nanowire mixture is 2 to 35%.

[0046] Among them, in the step (2), the polar group fluoropolymer, tetraethyl orthosilicate, and inorganic nanowire mixture are mixed in a mass ratio of 10 - 325:1 - 21:15 - 350. The solid content of the polar group fluoropolymer in the precursor solution is 1 - 20%, and the solid content of tetraethyl orthosilicate in the precursor solution is 0.1 - 2%.

[0047] Among them, in the step (3), the low surface energy inorganic nanowires, waterborne fluorocarbon resin, and anhydrous ethanol / aqueous solution are mixed in a mass ratio of 1:4 - 20:6 - 80. The volume ratio of anhydrous ethanol to water in the anhydrous ethanol / aqueous solution is 10:1 - 40.

[0048] Among them, in the step (4), the chitosan quaternary ammonium salt aqueous solution and the waterborne polyurethane resin solution are mixed in a mass ratio of 8 - 256:5 - 35. The solid content of chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt solution is 5 - 40%, and the solid content of the waterborne polyurethane resin is 1% - 10%.

[0049] Among them, in the step (5), the coating method is one of spraying, spin coating, brushing, and roll coating.

[0050] A super - wettability antiviral protective mask prepared by the method of the present invention, due to the ultra - low surface energy and ultra - high stability on the outer side, can strongly and long - term repel the adhesion of virus - containing droplets; the inner side has extremely high surface energy and strong electrostatic adsorption, making the adsorbed viruses and droplets show full - spread contact, greatly improving the inactivation rate of antibacterial active substances against viruses.

[0051] The outer - side nano - super anti - droplet antiviral super - hydrophobic protective coating and the inner - side nano - adsorption disinfection super - hydrophilic protective coating constructed by the present invention have a dual antibacterial mechanism of physical antibacterial and chemical antibacterial, with long - lasting and high - efficient antibacterial and antiviral effects. The raw materials used in the present invention are safe, non - toxic, the preparation process is simple, easy to operate, and low - cost. The prepared super - wettability antiviral protective mask has excellent timeliness, mechanical stability, chemical stability, and good biological safety and stability.

[0052] In order to further illustrate the present invention, the following takes examples to describe in detail the super - wettability antiviral protective mask and its preparation method provided by the present invention.

[0053] The present invention does not limit the sources of the raw materials used. Unless otherwise specified, the raw materials used in the present invention are all ordinary commercially available products in the technical field, among which:

[0054] The waterborne fluorocarbon resin DF - 01L is purchased from Shanghai 3F New Materials Co., Ltd., model: DF - 01L.

[0055] The waterborne fluorocarbon resin FEM-101 was purchased from Shandong Moore Chemical Co., Ltd., model: FEM-101.

[0056] The waterborne fluorocarbon resin HT-610FY was purchased from Shandong Moore Chemical Co., Ltd., model: HT-610FY.

[0057] The waterborne fluorocarbon resin 121A was purchased from DuPont Company of the United States, model: 121A.

[0058] The waterborne polyurethane resin PU-2944 was purchased from Guangzhou Guanzhi New Materials Technology Co., Ltd., model: PU-2944.

[0059] The waterborne polyurethane resin 1500F was purchased from Guangzhou Slok New Polymer Co., Ltd., model: 1500F.

[0060] The waterborne polyurethane resin 1402F was purchased from Guangzhou Slok New Polymer Co., Ltd., model: 1402F.

[0061] The waterborne polyurethane resin DB-716 was purchased from Jining Huakai Resin Co., Ltd., model: DB-716.

[0062] Example 1:

[0063] The preparation method of a super-wettable antiviral protective mask in this example includes the following steps:

[0064] (1) Prepare an inorganic nanowire mixture: After mixing anhydrous ethanol and ammonia water with a mass concentration of 25% according to a volume ratio of 8:0.1, mix the anhydrous ethanol / ammonia water solution with silicon dioxide nanowires according to a mass ratio of 6403:162, stir, and then ultrasonically disperse for 5 minutes to obtain a silicon dioxide nanowire mixture; the solid content of silicon dioxide nanowires in the silicon dioxide nanowire mixture is 2%. The size of the silicon dioxide nanowires is 10 nm.

[0065] (2) Prepare low surface energy inorganic nanowires: Mix 3,3,3-trifluoropropyltriethoxysilane, tetraethyl orthosilicate and the silicon dioxide nanowire mixture according to a mass ratio of 75:3:50 to prepare a precursor solution. The solid content of 3,3,3-trifluoropropyltriethoxysilane in the precursor solution is 3%, and the solid content of tetraethyl orthosilicate is 0.12%. After stirring evenly, centrifuge to collect the white precipitate, wash the white precipitate with anhydrous ethanol, and dry it to prepare low surface energy silicon dioxide nanowires;

[0066] (3) Mix low surface energy silica nanowires, aqueous fluorocarbon resin DF-M05, and anhydrous ethanol / water solution in a mass ratio of 1:4:32, stir and ultrasonically disperse to obtain a nano super anti-droplet antiviral superhydrophobic protective coating slurry. The solid content of aqueous fluorocarbon resin DF-M05 in this slurry is 5%, and the volume ratio of anhydrous ethanol to water in the anhydrous ethanol / water solution is 10:3. Figure 1 The SEM image of the nano super anti-droplet antiviral superhydrophobic protective coating slurry of this example is shown.

[0067] (4) Dissolve chitosan quaternary ammonium salt in water, and after high-speed mechanical stirring and uniform dispersion, obtain a chitosan quaternary ammonium salt aqueous solution. The solid content of chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt aqueous solution is 6%; mix the chitosan quaternary ammonium salt aqueous solution and the aqueous polyurethane resin PU-2944 solution in a mass ratio of 204:35, and stir evenly to obtain a nano adsorption disinfection superhydrophilic protective coating slurry. The solid content of the aqueous polyurethane resin PU-2944 in this slurry is 1%.

[0068] (5) Uniformly spray the nano super anti-droplet antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, with a coating thickness of 10 μm. Uniformly spray the nano adsorption disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, with a coating thickness of 10 μm. Leave it to dry at room temperature for 2 days.

[0069] (6) As Figure 2 、 3 shown, stack the skin-friendly layer coated with the nano adsorption disinfection superhydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano super anti-droplet antiviral superhydrophobic protective coating in sequence from the inside to the outside, and then perform hot rolling treatment under the conditions of 50 °C and 0.3 MPa to obtain a superwetting antiviral protective mask. In this example, the skin-friendly layer is made of ordinary sanitary gauze, the isolation and filtration layer is made of a meltblown material layer of ultra-fine polypropylene fibers, and the antibacterial layer is made of non-woven fabric.

[0070] Example 2:

[0071] A preparation method of a superwetting antiviral protective mask in this example includes the following steps:

[0072] (1) Prepare an inorganic nanowire mixture: After mixing anhydrous ethanol and ammonia water with a mass concentration of 25% in a volume ratio of 8:0.5, mix the anhydrous ethanol / ammonia water solution and silica nanowires in a mass ratio of 6767:850, stir and then ultrasonically disperse for 20 min to prepare a silica nanowire mixture; the solid content of silica nanowires in the silica nanowire mixture is 10%. The size of the silica nanowires is 50 nm.

[0073] (2) Preparation of low surface energy inorganic nanowires: A mixed solution of (pentafluoroethyl)trimethylsilane, tetraethyl orthosilicate, and silicon dioxide nanowires was mixed in a mass ratio of 325:13:500 to prepare a precursor solution. The solid content of (pentafluoroethyl)trimethylsilane in the precursor solution was 6.5%, and the solid content of tetraethyl orthosilicate was 0.26%. After stirring evenly, white precipitate was collected by centrifugation, and the white precipitate was washed with absolute ethanol and dried to prepare low surface energy silicon dioxide nanowires;

[0074] (3) The low surface energy silicon dioxide nanowires, aqueous fluorocarbon resin DF-01L, and absolute ethanol / water solution were mixed in a mass ratio of 1:7:15.4, and stirred and ultrasonically dispersed to obtain a nano super anti-droplet antiviral superhydrophobic protective coating slurry; the solid content of the aqueous fluorocarbon resin DF-01L in the slurry was 15%, and the volume ratio of absolute ethanol to water in the absolute ethanol / water solution was 10:9.

[0075] (4) Chitosan quaternary ammonium salt was dissolved in water, and after being dispersed evenly by high-speed mechanical stirring, a chitosan quaternary ammonium salt aqueous solution was obtained; the solid content of chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt aqueous solution was 10%. The chitosan quaternary ammonium salt aqueous solution and the aqueous polyurethane resin 1500F solution were mixed in a mass ratio of 17:12, and stirred evenly to obtain a nano adsorption disinfection superhydrophilic protective coating slurry. The solid content of the aqueous polyurethane resin 1500F in the slurry was 6%.

[0076] (5) The nano super anti-droplet antiviral superhydrophobic protective coating slurry prepared in step (3) was evenly spin-coated on the outer side of the antibacterial layer, and the coating thickness was 10 μm. The nano adsorption disinfection superhydrophilic protective coating slurry prepared in step (4) was evenly spin-coated on the inner side of the skin-friendly layer, and the coating thickness was 10 μm. It was left to dry at room temperature for 4 days.

[0077] (6) The skin-friendly layer coated with the nano adsorption disinfection superhydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano super anti-droplet antiviral superhydrophobic protective coating were stacked in sequence from the inside to the outside, and then hot rolling treatment was carried out under the conditions of 50 °C and 0.3 MPa to obtain a superwetting antiviral protective mask. In this embodiment, the skin-friendly layer was prepared from non-woven fabric, the isolation and filtration layer was prepared from a fine polypropylene fiber melt-blown material layer, and the antibacterial layer was prepared from an ultra-thin polypropylene melt-blown material layer.

[0078] Example 3:

[0079] The preparation method of a superwetting antiviral protective mask in this embodiment includes the following steps:

[0080] (1) Preparation of inorganic nanowire mixture: After mixing absolute ethanol and ammonia water with a mass concentration of 25% according to a volume ratio of 8:1.5, the absolute ethanol / ammonia water solution and titanium dioxide nanowires are mixed according to a mass ratio of 7677:1330, stirred and then ultrasonically dispersed for 40 min to prepare a titanium dioxide nanowire mixture; the solid content of titanium dioxide nanowires in the titanium dioxide nanowire mixture is 14%. The size of the titanium dioxide nanowires is 100 nm.

[0081] (2) Preparation of low surface energy inorganic nanowires: 1H,1H,2H,2H-perfluorohexyltrichlorosilane, tetraethyl orthosilicate, and the titanium dioxide nanowire mixture are mixed according to a mass ratio of 275:21:350 to prepare a precursor solution. The solid content of 1H,1H,2H,2H-perfluorohexyltrichlorosilane in the precursor solution is 11%, and the solid content of tetraethyl orthosilicate is 0.84%. After stirring evenly, white precipitate is collected by centrifugation, and the white precipitate is washed with absolute ethanol and dried to prepare low surface energy titanium dioxide nanowires;

[0082] (3) Mix low surface energy titanium dioxide nanowires, waterborne fluorocarbon resin FEM-101, and absolute ethanol / aqueous solution according to a mass ratio of 1:12:6, stir and ultrasonically disperse to obtain a nano super anti-droplet antiviral superhydrophobic protective coating slurry; the solid content of waterborne fluorocarbon resin FEM-101 in the slurry is 30%, and the volume ratio of absolute ethanol to water in the absolute ethanol / aqueous solution is 10:19.

[0083] (4) Dissolve chitosan quaternary ammonium salt in water, and after high-speed mechanical stirring and uniform dispersion, a chitosan quaternary ammonium salt aqueous solution is obtained. The solid content of chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt aqueous solution is 20%; the chitosan quaternary ammonium salt aqueous solution and the waterborne polyurethane resin 1402F solution are mixed according to a mass ratio of 8:5, stirred evenly to obtain a nano adsorption disinfection superhydrophilic protective coating slurry. The solid content of the waterborne polyurethane resin 1402F in the slurry is 10%.

[0084] (5) Uniformly coat the nano super anti-droplet antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, with a coating thickness of 10 μm. Uniformly brush the nano adsorption disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, with a coating thickness of 10 μm. Place it at room temperature to dry for 5 days.

[0085] (6) Stack the skin-friendly layer coated with the nano-adsorption disinfection super-hydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano-super anti-droplet and antiviral super-hydrophobic protective coating in sequence from the inside to the outside, and then perform hot rolling treatment under the conditions of 50 °C and 0.3 MPa to obtain the super-infiltration antiviral protective mask. In this embodiment, the skin-friendly layer is prepared from non-woven fabric, the isolation and filtration layer is prepared from a melt-blown material layer of ultra-fine polypropylene fibers, and the antibacterial layer is prepared from non-woven fabric.

[0086] Example 4:

[0087] A preparation method of a super-infiltration antiviral protective mask in this embodiment includes the following steps:

[0088] (1) Prepare an inorganic nanowire mixture: After mixing anhydrous ethanol and ammonia water with a mass concentration of 25% according to a volume ratio of 8:5, mix the anhydrous ethanol / ammonia water solution and aluminum oxide nanowires according to a mass ratio of 5431:1430, stir, and then perform ultrasonic dispersion for 15 minutes to prepare an aluminum oxide nanowire mixture; the solid content of aluminum oxide nanowires in the aluminum oxide nanowire mixture is 22%. The size of the aluminum oxide nanowires is 40 nm.

[0089] (2) Prepare low-surface-energy inorganic nanowires: Mix 3,3,3-trifluoropropyltriethoxysilane, tetraethyl orthosilicate, and the aluminum oxide nanowire mixture according to a mass ratio of 145:14:220 to prepare a precursor solution. The solid content of 3,3,3-trifluoropropyltriethoxysilane in the precursor solution is 14.5%, and the solid content of tetraethyl orthosilicate is 1.4%. After stirring evenly, centrifuge to collect the white precipitate, wash the white precipitate with anhydrous ethanol, and dry it to prepare low-surface-energy aluminum oxide nanowires;

[0090] (3) Mix the low-surface-energy aluminum oxide nanowires, water-based fluorocarbon resin HT-610FY, and anhydrous ethanol / water solution according to a mass ratio of 1:15:22.5, stir, and perform ultrasonic dispersion to obtain a nano-super anti-droplet and antiviral super-hydrophobic protective coating slurry; the solid content of the water-based fluorocarbon resin HT-610FY in the slurry is 20%, and the volume ratio of ethanol to water in the anhydrous ethanol / water solution is 10:25.

[0091] (4) Dissolve chitosan quaternary ammonium salt in water, and after high-speed mechanical stirring and uniform dispersion, obtain a chitosan quaternary ammonium salt aqueous solution; the solid content of chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt aqueous solution is 24%. Mix the chitosan quaternary ammonium salt aqueous solution and the water-based polyurethane resin DB-716 solution according to a mass ratio of 256:35, stir evenly, and obtain a nano-adsorption disinfection super-hydrophilic protective coating slurry. The solid content of the water-based polyurethane resin DB-716 in the slurry is 3%.

[0092] (5) Uniformly roll-coat the nano super anti-droplet antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, with a coating thickness of 10 μm. Uniformly roll-coat the nano adsorptive disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, with a coating thickness of 10 μm. Leave it to dry at room temperature for 4 days.

[0093] (6) Stack the skin-friendly layer coated with the nano adsorptive disinfection superhydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano super anti-droplet antiviral superhydrophobic protective coating in sequence from the inside to the outside, and then perform hot rolling treatment under the conditions of 50 °C and 0.3 MPa to obtain the super-wetting antiviral protective mask. In this embodiment, the skin-friendly layer is prepared from ordinary hygienic yarn, the isolation and filtration layer is prepared from an ultra-fine polypropylene fiber meltblown material layer, and the antibacterial layer is prepared from an ultra-thin polypropylene meltblown material layer.

[0094] Example 5:

[0095] A preparation method of a super-wetting antiviral protective mask in this embodiment includes the following steps:

[0096] (1) Prepare an inorganic nanowire mixture: After mixing anhydrous ethanol and ammonia water with a mass concentration of 25% according to a volume ratio of 8:10, mix the anhydrous ethanol / ammonia water solution and silicon dioxide nanowires according to a mass ratio of 7706:2700, stir, and then perform ultrasonic dispersion for 25 min to prepare a silicon dioxide nanowire mixture; the solid content of silicon dioxide nanowires in the silicon dioxide nanowire mixture is 30%. The size of the silicon dioxide nanowires is 70 nm.

[0097] (2) Prepare low-surface-energy inorganic nanowires: Mix a mixture of 1H,1H,2H,2H-perfluorohexyltrichlorosilane, tetraethyl orthosilicate, and silicon dioxide nanowires according to a mass ratio of 10:1:15 to prepare a precursor solution. The solid content of 1H,1H,2H,2H-perfluorohexyltrichlorosilane in the precursor solution is 20%, and the solid content of tetraethyl orthosilicate is 2%. After stirring evenly, centrifuge to collect the white precipitate, wash the white precipitate with anhydrous ethanol, and dry it to prepare low-surface-energy silicon dioxide nanowires;

[0098] (3) Mix low-surface-energy silicon dioxide nanowires, waterborne fluorocarbon resin 121A, and anhydrous ethanol / water solution according to a mass ratio of 1:20:80, stir, and perform ultrasonic dispersion to obtain a nano super anti-droplet antiviral superhydrophobic protective coating slurry; the solid content of waterborne fluorocarbon resin 121A in this slurry is 10%, and the volume ratio of anhydrous ethanol to water in the anhydrous ethanol / water solution is 10:40;

[0099] (4) Dissolve the quaternary ammonium salt of chitosan in water. After high-speed mechanical stirring and uniform dispersion, an aqueous solution of the quaternary ammonium salt of chitosan is obtained. The solid content of the quaternary ammonium salt of chitosan in the aqueous solution of the quaternary ammonium salt of chitosan is 40%. Mix the aqueous solution of the quaternary ammonium salt of chitosan and the aqueous polyurethane resin 1402F solution in a mass ratio of 88:15, and stir evenly to obtain a nano-adsorption disinfection super-hydrophilic protective coating slurry. The solid content of the aqueous polyurethane resin 1402F in this slurry is 6%.

[0100] (5) Uniformly spray the nano-super anti-droplet and anti-virus super-hydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, with a coating thickness of 10 μm. Uniformly spray the nano-adsorption disinfection super-hydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, with a coating thickness of 10 μm. Place it at room temperature to dry for 3 days.

[0101] (6) Stack the skin-friendly layer coated with the nano-adsorption disinfection super-hydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano-super anti-droplet and anti-virus super-hydrophobic protective coating in sequence from the inside to the outside, and then perform hot rolling treatment under the conditions of 50 °C and 0.3 MPa to obtain a super-infiltration anti-virus protective mask. In this embodiment, the skin-friendly layer is prepared from ordinary sanitary gauze, the isolation and filtration layer is prepared from a melt-blown material layer of ultra-fine polypropylene fibers, and the antibacterial layer is prepared from non-woven fabric.

[0102] Example 6:

[0103] A preparation method of a super-infiltration anti-virus protective mask in this embodiment includes the following steps:

[0104] (1) Prepare an inorganic nanowire mixture: After mixing anhydrous ethanol and ammonia water with a mass concentration of 25% in a volume ratio of 8:7, mix the anhydrous ethanol / ammonia water solution and silicon dioxide nanowires in a mass ratio of 6341:2625, stir, and then perform ultrasonic dispersion for 10 min to prepare a silicon dioxide nanowire mixture. The solid content of silicon dioxide nanowires in the silicon dioxide nanowire mixture is 35%. The size of the silicon dioxide nanowires is 30 nm.

[0105] (2) Prepare low-surface-energy inorganic nanowires: Mix 3,3,3-trifluoropropyltriethoxysilane, tetraethyl orthosilicate, and the silicon dioxide nanowire mixture in a mass ratio of 10:1:350 to prepare a precursor solution. The solid content of 3,3,3-trifluoropropyltriethoxysilane in the precursor solution is 1%, and the solid content of tetraethyl orthosilicate is 0.1%. After stirring evenly, centrifuge to collect the white precipitate, wash the white precipitate with anhydrous ethanol, and dry it to prepare low-surface-energy silicon dioxide nanowires;

[0106] (3) Mix low surface energy silica nanowires, aqueous fluorocarbon resin DF-M05, and an ethanol / water solution in a mass ratio of 1:4:32, and stir and ultrasonically disperse to obtain a nano super anti-droplet and antiviral superhydrophobic protective coating slurry; the solid content of the aqueous fluorocarbon resin DF-M05 in the slurry is 5%, and the volume ratio of ethanol to water in the ethanol / water solution is 10:1;

[0107] (4) Dissolve chitosan quaternary ammonium salt in water, and after high-speed mechanical stirring and uniform dispersion, obtain a chitosan quaternary ammonium salt aqueous solution; the solid content of chitosan quaternary ammonium salt in the chitosan quaternary ammonium salt aqueous solution is 5%; mix the chitosan quaternary ammonium salt aqueous solution and an aqueous polyurethane resin PU-2944 solution in a mass ratio of 170:35, and stir evenly to obtain a nano adsorption and disinfection superhydrophilic protective coating slurry. The solid content of the aqueous polyurethane resin PU-2944 in the slurry is 1%.

[0108] (5) Uniformly spray the nano super anti-droplet and antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, with a coating thickness of 10 μm. Uniformly spray the nano adsorption and disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, with a coating thickness of 10 μm. Leave it to dry at room temperature for 2 days.

[0109] (6) Stack the skin-friendly layer coated with the nano adsorption and disinfection superhydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano super anti-droplet and antiviral superhydrophobic protective coating in sequence from the inside to the outside, and then perform hot rolling treatment under the conditions of 50 °C and 0.3 MPa to obtain a superwetting antiviral protective mask. In this embodiment, the skin-friendly layer is made of non-woven fabric, the isolation and filtration layer is made of a fine polypropylene fiber meltblown material layer, and the antibacterial layer is made of an ultra-thin polypropylene meltblown material layer.

[0110] Antibacterial effect test of the superwetting antiviral protective mask:

[0111] Test method: Refer to GB / T 20944

[0112] Test materials: Superwetting antiviral protective mask, control: ordinary medical mask;

[0113] Test bacteria: Staphylococcus aureus, Escherichia coli;

[0114] Test results:

[0115] (1) The antibacterial rate of the superwetting antiviral protective mask against Staphylococcus aureus > 99.9%, and the action time is 24 h; the antibacterial rate of the superwetting antiviral protective mask against Escherichia coli > 99.9%, and the action time is 24 h;

[0116] (2) The antibacterial rate of ordinary medical masks against Staphylococcus aureus is < 70%, and the action time is 24 hours; the antibacterial rate of ordinary medical masks against Escherichia coli is < 50%, and the action time is 24 hours.

[0117] Antiviral effect test of superwetting antiviral protective masks:

[0118] Test method: Refer to "Disinfection Technical Specification" 2002 Edition - 2.1.1.10.7

[0119] Test materials: Superwetting antiviral protective masks, control: ordinary medical masks;

[0120] Test virus: Influenza A virus H1N1;

[0121] Test results:

[0122] (1) The inactivation rate of superwetting antiviral protective masks against Influenza A virus H1N1 is > 99.99%, and the action time is 5 minutes;

[0123] (2) The inactivation rate of ordinary medical masks against Influenza A virus H1N1 is < 40%, and the action time is 5 minutes;

[0124] The above-described embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the present invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made. For example, spraying the nano super anti-droplet antiviral superhydrophobic protective coating slurry evenly on the outer side of the existing mask, and spraying the nano adsorption disinfection superhydrophilic protective coating slurry evenly on the inner side of the existing mask, and a superwetting antiviral protective mask can also be prepared. These all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A super-hydrophilic and antiviral protective mask, which successively has a skin-friendly layer, an isolation and filtration layer, and an antibacterial layer from the inside to the outside, and is characterized in that: The inner side of the skin-friendly layer is coated with a nano-adsorption disinfection super-hydrophilic protective coating, and the outer side of the antibacterial layer is coated with a nano-super anti-droplet and anti-virus super-hydrophobic protective coating. The nano-super anti-droplet and anti-virus super-hydrophobic protective coating comprises the following components: Polar group fluoropolymer, waterborne fluorocarbon resin, inorganic nanowires, tetraethyl orthosilicate, absolute ethanol and ammonia water; The nano-adsorption disinfection super-hydrophilic protective coating comprises the following components: chitosan quaternary ammonium salt, waterborne polyurethane resin; The preparation method of the super-infiltration anti-virus protective mask comprises the following steps: (1) Prepare an inorganic nanowire mixture: After mixing absolute ethanol and ammonia water, mix the absolute ethanol / ammonia water solution with inorganic nanowires, stir and ultrasonically disperse to prepare an inorganic nanowire mixture; (2) Prepare low-surface-energy inorganic nanowires: Add polar group fluoropolymer and tetraethyl orthosilicate to the inorganic nanowire mixture prepared in step (1) to prepare a precursor solution, stir evenly, centrifuge to collect the white precipitate, wash the white precipitate, and finally dry it to prepare low-surface-energy inorganic nanowires; (3) Weigh the low-surface-energy inorganic nanowires prepared in step (2) and waterborne fluorocarbon resin according to a mass ratio of 1:4 to 20, then add a mixed solution of absolute ethanol and water, stir and ultrasonically disperse to obtain a nano-super anti-droplet and anti-virus super-hydrophobic protective coating slurry; (4) Dissolve chitosan quaternary ammonium salt in water and stir at high speed to obtain a chitosan quaternary ammonium salt aqueous solution, then add it to the waterborne polyurethane resin solution, stir evenly to prepare a nano-adsorption disinfection super-hydrophilic protective coating slurry; (5) Uniformly coat the nano-super anti-droplet and anti-virus super-hydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, and uniformly coat the nano-adsorption disinfection super-hydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, and leave it to dry at room temperature; (6) Stack the skin-friendly layer coated with the nano-adsorption disinfection super-hydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano-super anti-droplet and anti-virus super-hydrophobic protective coating in sequence from the inside to the outside, and perform hot rolling treatment to obtain a super-infiltration anti-virus protective mask.

2. The super-infiltration anti-virus protective mask according to claim 1, wherein: The polar group fluoropolymer is one of 3,3,3-trifluoropropyltriethoxysilane, (pentafluoroethyl)trimethylsilane or 1H,1H,2H,2H-perfluorohexyltrichlorosilane.

3. The super-infiltration anti-virus protective mask according to claim 1, wherein: The inorganic nanowires are one of silicon dioxide nanowires, titanium dioxide nanowires or aluminum oxide nanowires.

4. The super-infiltration anti-virus protective mask according to claim 1, wherein: The waterborne fluorocarbon resin is one of DF-01L, FEM-101, HT-610FY or 121A.

5. The super-infiltration anti-virus protective mask according to claim 1, wherein: The waterborne polyurethane resin is one of PU-2944, 1500F, 1402F or DB-716.

6. The preparation method of a superwetting antiviral protective mask according to any one of claims 1-5, characterized in that, Comprising the following steps: (1) Preparation of inorganic nanowire mixture: After mixing absolute ethanol and ammonia water, the absolute ethanol / ammonia water solution is mixed with inorganic nanowires, stirred and ultrasonically dispersed to prepare an inorganic nanowire mixture; (2) Preparation of low surface energy inorganic nanowires: A polar group fluoropolymer and tetraethyl orthosilicate are added to the inorganic nanowire mixture prepared in step (1) to prepare a precursor solution, which is stirred evenly, centrifuged to collect a white precipitate, and the white precipitate is washed and finally dried to prepare low surface energy inorganic nanowires; (3) Weigh the low surface energy inorganic nanowires prepared in step (2) and the waterborne fluorocarbon resin according to a mass ratio of 1:4 - 20, then add a mixed solution of absolute ethanol and water, and stir and ultrasonically disperse to obtain a nano super anti-droplet antiviral superhydrophobic protective coating slurry; (4) Dissolve chitosan quaternary ammonium salt in water and stir at high speed to obtain a chitosan quaternary ammonium salt aqueous solution, and then add it to the waterborne polyurethane resin solution and stir evenly to prepare a nano adsorption disinfection superhydrophilic protective coating slurry; (5) Uniformly coat the nano super anti-droplet antiviral superhydrophobic protective coating slurry prepared in step (3) on the outer side of the antibacterial layer, and uniformly coat the nano adsorption disinfection superhydrophilic protective coating slurry prepared in step (4) on the inner side of the skin-friendly layer, and leave it to dry at room temperature; (6) Stack the skin-friendly layer coated with the nano adsorption disinfection superhydrophilic protective coating, the isolation and filtration layer, and the antibacterial layer coated with the nano super anti-droplet antiviral superhydrophobic protective coating in sequence from the inside to the outside, and perform hot rolling treatment to obtain a super-infiltration antiviral protective mask.

7. The preparation method of a super-wettable antiviral protective mask according to claim 6, characterized in that: In step (1), the absolute ethanol / ammonia water solution and the inorganic nanowires are mixed according to a mass ratio of 5431 - 7706:162 - 2700; the volume ratio of absolute ethanol to ammonia water in the absolute ethanol / ammonia water solution is 8:0.1 - 10.

8. The preparation method of a super-wetting antiviral protective mask according to claim 6, characterized in that: In step (2), the polar group fluoropolymer, tetraethyl orthosilicate, and inorganic nanowire mixture are mixed according to a mass ratio of 10 - 325:1 - 21:15 - 350.

9. The preparation method of a super-wettable antiviral protective mask according to claim 6, characterized in that: In step (3), the low surface energy inorganic nanowires, waterborne fluorocarbon resin, and mixed solution of absolute ethanol and water are mixed according to a mass ratio of 1:4 - 20:6 - 80.

10. The preparation method of a superwetting antiviral protective mask according to claim 6, characterized in that: In step (4), the chitosan quaternary ammonium salt aqueous solution and the waterborne polyurethane resin solution are mixed according to a mass ratio of 8 - 256:5 - 35.

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