Inorganic nano antibacterial and mildew-proof spray and preparation method thereof

Abstract

The invention discloses an inorganic nano antibacterial and mildew-proof spray and a preparation method thereof. The preparation method of the inorganic nano antibacterial and mildew-proof spray adopts a centrifugal disperser, an auxiliary dispersing aid and a related dispersing treatment process, which can make the particle size D90 of the doped ZnO nanoparticles, that is, the particle size at which the cumulative distribution of ZnO nanoparticles is 90%, and the content of particles smaller than this particle size accounts for 90% of all particles below 110nm, and the lowest can reach below 50nm, effectively avoiding the agglomeration of nanoparticles, making the doped nanoparticles have high dispersion efficiency, narrow particle size distribution, and uniform particle distribution. The inorganic nano antibacterial and mildew-proof spray prepared by the preparation method can still have the characteristics of high sterilization efficiency, wide sterilization range, high safety, etc. under insufficient light conditions, and has a non-migrating nanoscale with long-term effectiveness.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial materials, and in particular to an inorganic nano antibacterial and anti-mildew spray and a preparation method thereof. Background Art

[0002] For a long time, the spread of various germs in life has caused various health problems for humans. Microorganisms such as bacteria and molds can enter the human body through certain ways (contact, breathing, diet, air flow, etc.), affecting health and spreading diseases. With the development of society and the improvement of awareness, people are paying more and more attention to hygiene issues in daily life. A clean living environment can make humans healthier. The most effective way to maintain a clean living environment is to sterilize and remove mold to limit the spread of bacteria and microorganisms.

[0003] Because of this, the research and development and application of antimicrobial agents are receiving more and more attention. Existing antimicrobial agents can be divided into organic antimicrobial agents, inorganic antimicrobial agents and natural plant antimicrobial agents. Inorganic antimicrobial agents have been widely used in recent years because of their long-lasting antibacterial properties, good antibacterial effects, heat resistance and stable properties.

[0004] Studies have shown that by refining and dispersing the effective ingredients of inorganic antibacterial materials into nano-sized inorganic nano antibacterial materials, the nano-size effect can be effectively used to kill bacteria. Inorganic nano antibacterial materials are generally divided into two categories: metal nanoparticle antibacterial materials (such as nano silver, nano copper, nano zinc, etc.) and inorganic non-metal oxide nano antibacterial materials (such as nano silicon dioxide, nano zinc oxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide and nano iron oxide, etc.). The silver, copper and other components in the commonly used metal nanoparticle antibacterial materials can make bacterial cells inactive, but after the bacteria are killed, they will release harmful substances such as their internal toxins; while inorganic non-metal oxide nano antibacterial materials can not only affect the reproduction of bacteria, but also attack the outer layer of bacterial cells, penetrate the cell membrane, completely destroy bacteria, and prevent them from producing endotoxins and causing secondary pollution. In contrast, inorganic non-metal oxide nano antibacterial materials have attracted much attention due to their high safety, thorough sterilization, wide sources, and long-lasting antibacterial properties.

[0005] Chinese invention patent CN109893539A (invention name: A composite antibacterial aerosol and its preparation method) mixes chitosan diquaternary ammonium salt, nano-scale titanium dioxide, and sea salt, adds them to an ethanol solution, adds a surfactant, stirs them thoroughly, then adds a film-forming agent and a lubricant, stirs them evenly, and then the obtained mixture is sealed with a metering valve system, and a propellant is pressed into the aerosol. The antibacterial aerosol only uses a stirring and mixing method to mix the nanoparticles evenly, but cannot keep them at the nanoscale, and is prone to agglomeration, which affects the antibacterial effect; and the antibacterial spray material can only play an antibacterial role under strong light conditions, and its antibacterial effect is not good under weak light conditions.

[0006] Chinese invention patent CN 1772375A (invention title: doped nano zinc oxide and its preparation method and photocatalytic degradation of organic matter and antibacterial application) relates to a preparation method of nano zinc oxide doped with silver and rare earth metals and its photocatalytic degradation of organic matter and antibacterial application. By doping silver, rare earth metals, etc. into nano zinc oxide, the photocatalytic activity of nano zinc oxide is improved, and it is used to degrade harmful chemicals and fight bacteria. Under light, it produces higher photocatalytic activity than ordinary zinc oxide, and improves the antibacterial ability; when there is no light, due to the action of antibacterial ions such as silver, zinc, and rare earth metals, it still has a strong antibacterial effect. However, the doped nano zinc oxide antibacterial agent only uses a mixing method to mix the nanoparticles evenly. This processing technology does not perform corresponding surface treatment on the doped nano zinc oxide, so it cannot achieve a good nano dispersion effect. It is easy to agglomerate itself, and the doped nano zinc oxide cannot always maintain the nano size, thereby affecting its antibacterial effect.

[0007] 《M 2+ Antibacterial Properties of (M=Cu, Cd, Ag, Fe)-doped ZnO Nanopowders (Ding Yan et al., Journal of Inorganic Chemistry, 2014.2, 30(2)) ZnO and M were prepared by citric acid sol-gel method. 2+ The composition, structure and morphology of the samples were characterized by doping ZnO nanopowder (M = Cu, Cd, Ag, Fe) with testing technology. The antibacterial activity of the samples under sunlight was studied with Escherichia coli, Staphylococcus aureus and Candida albicans as test strains. The results showed that the antibacterial properties of the samples doped with Cu, Ag and Cd were significantly enhanced compared with the parent ZnO, which may be due to the replacement of Zn by doped metal ions. 2+ Lattice defects and charge defects are generated, which prevent the recombination of photogenerated electrons and photogenerated hole pairs, thereby enhancing the photocatalytic activity and antibacterial activity. However, the doped zinc oxide nanopowder crystals do not adopt any nanoparticle dispersion measures. This processing technology does not perform corresponding surface treatment on the doped nano zinc oxide, so the nano dispersion effect cannot be achieved. The doped zinc oxide nanopowder crystal particles exist in the form of agglomeration and cannot maintain the nano size, which affects its antibacterial effect.

[0008] Chinese invention patent CN 102417220 A (invention name: Application of tantalum-doped zinc oxide nanopowder photocatalyst in water treatment antibacterial) discloses the application of tantalum-doped zinc oxide nanopowder photocatalyst in water treatment antibacterial. The bacterial species include Gram-positive bacteria Bacillus subtilis, Staphylococcus aureus, Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa, indicating that tantalum-doped zinc oxide nanopowder can inhibit bacterial growth in dark environment and visible light, and its antibacterial property is better than pure zinc oxide nanopowder; and photocatalysis can effectively reduce the minimum inhibitory concentration (MIC) in dark environment, and a smaller addition amount can achieve a higher antibacterial effect. However, the tantalum-doped zinc oxide nanopowder antibacterial agent does not adopt any nanoparticle dispersion measures, and its powder particles still exist in the form of agglomeration, which cannot keep its nano size, affecting its antibacterial effect.

[0009] Generally speaking, even if nanoparticles are dispersed in a matrix material, they will still aggregate during the subsequent storage process and no longer maintain the nanosize effect, which will affect the antibacterial effect of antimicrobial agents. Therefore, it is necessary to find a material that can stably maintain its nanosize for a long time.

[0010] Among many inorganic metal oxide nanomaterials, zinc oxide (ZnO) has attracted extensive attention due to its advantages of simple preparation process, diverse preparation methods, and easy doping. Moreover, ZnO is a direct bandgap wide bandgap semiconductor with high electron mobility (115-155cm 2 / (V·s)), the present invention disperses and modifies the ZnO nano material so that it can stably maintain its nano size for a long time, and uses it to make an inorganic nano antibacterial and antifungal spray. Summary of the invention

[0011] In order to overcome the deficiencies and shortcomings of the prior art, the primary purpose of the present invention is to provide a centrifugal disperser, which can be used to physically disperse inorganic metal particles in a solution.

[0012] The second purpose of the present invention is to provide a method for preparing an inorganic nano antibacterial and mildew proof spray. In the preparation method, a centrifugal disperser is used to uniformly disperse the mixed liquid to be dispersed by combining physical dispersion and chemical dispersion to prepare an inorganic nano antibacterial and mildew proof spray with excellent antibacterial and mildew proof properties.

[0013] Due to the large specific surface area, high surface energy and insufficient coordination number of surface atoms of nanoparticles, these surface atoms are highly active and extremely unstable, and surface electrons are easily separated from holes. Traditional inorganic metal oxide nanoparticles achieve antibacterial properties by separating electrons from holes. However, electrons and holes often recombine, which reduces the antibacterial effect. It is necessary to introduce another ion to prevent the combination of electrons and holes and improve the catalytic efficiency. The commonly used method is transition metal doping. Studies have shown (Singh, Sarika, Barick, et al. Novel and Efficient Three Dimensional Mesoporous ZnO Nanoassemblies For Envirnomental Remediation [J]. International Journal of Nanoscience, 2011) iron ions (Fe 3+ ) has a radius close to that of zinc ions (Zn 2+ ), non-toxic, easy to dope, and can effectively improve the catalytic performance of inorganic nano-oxides. 3+ The ability of the valence d orbital to capture electrons is basically the same as the ability to capture holes. By capturing electrons and holes, the recombination of electron-hole pairs generated on the ZnO surface can be prevented, and energy can be continuously released and absorbed, thereby improving the antibacterial activity of inorganic metal oxide nanomaterials, thereby greatly improving the bactericidal effect. 3+ )'s inorganic nano antibacterial and anti-mildew spray can effectively kill bacteria even in low light conditions.

[0014] The third object of the present invention is to provide an inorganic nano antibacterial and antifungal spray prepared by the above preparation method.

[0015] The primary purpose of the present invention is achieved through the following technical solutions:

[0016] A centrifugal disperser, such as Figure 1 As shown, it is composed of a feeding port, a pressure building bin, a high-pressure pump and a centrifugal dispersion device; the feeding port and the high-pressure pump are respectively connected to the pressure building bin through valves; the centrifugal dispersion device is arranged at the lower end of the pressure building bin and is connected to the pressure building bin through a closed valve; the centrifugal dispersion device includes a coarse pipeline, an acceleration pipeline and a centrifugal dispersion pipeline connected in sequence, the diameter of the coarse pipeline is the same as the maximum diameter of the acceleration pipeline, and the diameter of the centrifugal dispersion pipeline is the same as the minimum diameter of the acceleration pipeline.

[0017] Preferably, the centrifugal disperser further comprises a disperser outlet arranged at the tail end of the centrifugal dispersion pipeline.

[0018] Preferably, the accelerating pipe is an annular accelerating pipe with a gradually decreasing diameter, and the ratio of the maximum diameter to the minimum diameter of the accelerating pipe is 4:1.

[0019] The high-pressure pump is an external device that can increase the pressure in the pressure-building chamber to 40-50 MPa; the inner walls of the acceleration pipe and the centrifugal dispersion pipe are both frosted pipe walls, and their surface roughness reaches 3000 meshes.

[0020] The key dimensions of the centrifugal disperser include: the diameter of the thick pipe is 20mm; the ratio of the maximum diameter to the minimum diameter of the acceleration pipe is 4:1; the length of the acceleration pipe is 40mm; the diameter of the centrifugal dispersion pipe is 5mm; the total length of the centrifugal dispersion pipe is 2m, the maximum winding diameter is 0.3m, and the number of windings is 4.

[0021] Preferably, the specific working process of the centrifugal disperser dispersing the nanoparticle mixture is as follows:

[0022] 1) First, add the nanoparticle mixture to be dispersed into the pressure building bin through the feeding port, close the valve between the feeding port and the pressure building bin and the airtight valve between the pressure building bin and the rough pipeline, open the high-pressure pump and the valve between the high-pressure pump and the pressure building bin to start pressure building, and set the pressure target value of the pressure building to 40-50MPa;

[0023] 2) After the pressure reaches the target set value, the airtight valve connecting the pressure building chamber and the thick pipeline is opened, and the nanoparticle mixture that is easy to agglomerate reaches the acceleration pipeline through the thick pipeline. The pipeline of the acceleration pipeline gradually becomes thinner. In the process of flowing through the thinning pipeline, the volume flow rate of the nanoparticle mixture that is easy to agglomerate remains unchanged. Therefore, the linear velocity of the nanoparticle mixture that is easy to agglomerate in the thin pipeline is relatively high, while the linear velocity of the nanoparticle mixture to be dispersed in the thick pipeline is relatively low. The speed difference under high speed and pressure causes the nanoparticle mixture to be dispersed to be stretched in the flow velocity direction, thereby generating stretching rheology; this stretching rheology causes the particles in the nanoparticle mixture to be dispersed to be strongly stretched, and the agglomerated particles are gradually dispersed under the action of this stretching rheology to form nano-scale particles;

[0024] 3) After being accelerated, the nanoparticle mixture that is easy to agglomerate enters the centrifugal dispersion pipe. Since the nanoparticle mixture has a high speed, the annular pipe makes the nanoparticle mixture subject to a large centrifugal force, and this centrifugal force is provided by the outer side of the inner wall of the centrifugal dispersion pipe (outer side a of the inner wall of the pipe). There, a high force and high-speed friction are generated between the 3000-mesh frosted wall surface and the nanoparticle mixture that is easy to agglomerate, which can further disperse the agglomerated nanoparticles and make them free in the water.

[0025] During the entire dispersion process, the pressure applied by the high-pressure pump directly acts on the easily agglomerated nanoparticle mixture, keeping it in a high-pressure state; the easily agglomerated nanoparticle mixture produces a high flow rate under high pressure, which causes the easily agglomerated nanoparticles in the acceleration pipe to be stretched by the higher flow rate difference, and the agglomerated nanoparticles are gradually broken up and dispersed into nanoparticles; on the other hand, the annular pipe gives the high-flow-rate nanoparticle mixture a certain centrifugal force, which is balanced by the pressure of the nanoparticle mixture on the pipe wall. Under this pressure and the rough pipe wall, the nanoparticle mixture is subjected to high shear, and this high shear again shears and tears the agglomerated nanoparticles, further breaking up their agglomeration to form nano-scale particles.

[0026] Compared with ordinary nano-dispersing equipment, the centrifugal disperser provided by the present invention has the advantages of high speed, high pressure, high stretching and high shearing. The commonly used dispersion equipment on the market generally relies on the shearing force generated by the high-speed operation of the equipment to grind the nanoparticles, such as ball mills, high-speed grinders, etc.; in addition, there are also equipment that relies on high pressure on the material to disperse the particles, such as spray drying dispersers. These devices only disperse the agglomerated nanoparticles by generating high-speed shearing or high pressure, and the effect is not good. The centrifugal disperser provided by the present invention combines high speed, high pressure, high stretching and high shearing to act on the nanoparticles that are easy to agglomerate, so as to better disperse them evenly.

[0027] The second object of the present invention is achieved by the following technical solutions:

[0028] A method for preparing an inorganic nano antibacterial and antifungal spray comprises the following steps: uniformly mixing the following raw material components by mass: 0.5-10 parts of inorganic metal oxide nanoparticles, 20-80 parts of deionized water, 1-20 parts of a dispersant, and 1-40 parts of an auxiliary dispersing aid to obtain a nanoparticle mixed solution, and adding the nanoparticle mixed solution to Figure 1 The inorganic nano antibacterial and antifungal spray is obtained by centrifugation in the centrifugal disperser shown in the figure, and the water-soluble nano mixed liquid after dispersion treatment is obtained, and the propellant is added, mixed and bottled. Among them, the amount of propellant used depends on the situation, and the pressure in the bottle can reach 2-5Mpa when bottling.

[0029] Preferably, the nanoparticle mixture reaches the accelerating pipe 6 through the thick pipe 5 of the centrifugal dispersing instrument, where the pipe gradually becomes thinner, forcing the nanoparticle mixture to undergo extensional rheology, and the dispersant in the nanoparticle mixture together with the ZnO particles and the auxiliary dispersing aid are stretched and oriented, and the agglomerated ZnO particles are gradually dispersed under the action of this stretching force, and mixed in the solvent together with the dispersant molecular chain, to achieve a better dispersion effect. In addition, the inner wall of the annular pipe in the centrifugal dispersing instrument also provides a large centrifugal force for the high-speed flowing ZnO mixture, so that the nanoparticles in the mixture are subjected to high shearing to achieve the purpose of uniform dispersion.

[0030] Preferably, the molecular formula of the inorganic metal oxide nanoparticles is Zn 1-x Fe x O 1+0.5x , where 0.05≤x≤0.15.

[0031] Preferably, the molecular formula of the inorganic metal oxide nanoparticles is Zn 0.95 Fe 0.05 O 1.025 .

[0032] Preferably, the molecular formula of the inorganic metal oxide nanoparticles is Zn 0.85 Fe 0.15 O 1.075 .

[0033] Preferably, the method for preparing the inorganic metal oxide nanoparticles comprises the following steps:

[0034] (1) Zinc chloride (ZnCl 2 ) was dissolved in hydrochloric acid (HCl) solution, and ammonia (NH 3 ·H 2 O), adjust the pH to 1-4, stir evenly to obtain a mixed solution, ZnCl 2 The mass volume ratio of the mixed solution is 1g:80-100mL;

[0035] (2) adding the mixed solution in step (1) into deionized water, wherein the volume ratio of the mixed solution to deionized water is 1:(20-25), and performing a hydrothermal reaction at 120-200° C. for 2-10 h;

[0036] (3) Add the product obtained in step (2) to ferric chloride hexahydrate (FeCl 3 6H 2 O) stirred and mixed, microwaved for 1-2 h, and then ultrasonicated for 30-50 min, wherein the added FeCl 3 6H 2 O and ZnCl 2The mass ratio is 1:10-50;

[0037] (4) The product obtained in step (3) is stirred and reacted at 150-160° C. for 8-12 hours, and then centrifuged. The precipitate is washed with deionized water and anhydrous ethanol for 5 times each, and then dried to obtain inorganic metal oxide nanoparticles.

[0038] The present invention uses iron ions (Fe 3+ ) doping zinc oxide (ZnO) to improve the antibacterial activity of inorganic metal oxide nanomaterials. Physical dispersion method (centrifugal disperser) and chemical dispersion method (dispersant) are combined to evenly disperse the particles in the mixed liquid to completely reach the nanometer size state. The inorganic metal oxide nanoparticles dispersed in the nanometer size state have excellent antibacterial and antifungal effects.

[0039] The inorganic metal oxide nanoparticles (Zn 1-x Fe x O 1+0.5x , 0.05≤x≤0.15) is Fe 3+ After preliminary grinding, the doped ZnO particles can be obtained into powdery Fe 3+ Doped ZnO particles (Zn 1-x Fe x O 1+0.5x ), at this time, the ZnO particles have not yet reached the nano-size state and need to be dispersed.

[0040] Preferably, the dispersant includes anionic dispersants, cationic dispersants, nonionic dispersants, amphoteric dispersants, electrically neutral dispersants and polymer dispersants; the anionic dispersant is one of sodium oleate, carboxylate, sulfate or sulfonate; the cationic dispersant is one of octadecylamine acetate, ammonium salt, aminopropylamine dioleate, quaternary ammonium salt, polyaminoamide phosphate or pyridinium salt; the nonionic dispersant is one of the adducts of fatty acid ethylene oxide, polyethyleneimine derivatives, ethylene glycol type or polyol type; the amphoteric dispersant is a phosphate ester type polymer; the electrically neutral dispersant is an oleyl amino oleate; the polymer dispersant is one of the polycaprolactone polyol-polyethyleneimine block copolymer type, acrylate polymer type or polyurethane or polyester polymer dispersant.

[0041] Preferably, the auxiliary dispersing aid is polyethylene glycol grafted glycidyl methacrylate (PEG-g-GMA), which can be prepared by the method described in patent CN201710959226.8 (polyethylene glycol-modified glycidyl methacrylate resin and preparation method and application) (using polyethylene glycol diacrylate and glycidyl methacrylate as monomers, tetraethylthiuram disulfide as a precursor, azobisisobutyronitrile as an initiator, using a one-pot reaction system, and reacting at 70°C for 6h).

[0042] Preferably, the propellant is at least one of compressed carbon dioxide, compressed nitrous oxide, trichlorofluoromethane, and difluoromethane.

[0043] By passing Fe 3+ The mixed solution consisting of doped ZnO particles (hereinafter referred to as ZnO particles), deionized water, dispersant and auxiliary dispersing agent is added to Figure 1 In the centrifugal disperser shown, the mixed liquid reaches the accelerating pipe through a thick pipe, where the pipe gradually becomes thinner, forcing the mixed liquid to undergo extensional rheology. The dispersant in the mixed liquid, together with the ZnO particles and auxiliary dispersing aids, are stretched and oriented. The agglomerated ZnO particles gradually disperse under the action of this stretching force and mix with the dispersant molecular chains in the solvent to achieve a better dispersion effect. In addition, the inner wall of the annular pipe in the centrifugal disperser also provides a large centrifugal force for the high-speed flowing ZnO mixed liquid, so that the nanoparticles in the mixed liquid are subjected to high shearing to achieve the purpose of uniform dispersion.

[0044] The particle size of the ZnO nanoparticles treated by the physical dispersion and chemical dispersion methods proposed by the present invention is maintained at about 110nm, and can be as low as 50nm or less, and can be uniformly dispersed in an aqueous solution for a long time by being wrapped with a dispersing aid. The water-soluble nano mixed liquid after the dispersion treatment is added with a propellant, mixed and bottled to obtain an inorganic nano antibacterial and antifungal spray. The spray has excellent antibacterial and antifungal effects and a long-lasting antibacterial property.

[0045] In addition, Fe 3+A large number of hydroxyl groups are adsorbed on the surface of the doped ZnO nanoparticles, and the glycidyl methacrylate (-GMA) molecules in the auxiliary dispersant molecular chains free in water contain epoxy groups. The two can form hydrogen bonds and produce partial chemical reactions to be modified, and the modified ZnO nanoparticles are connected to the dispersing agent; at the same time, the polyethylene glycol molecular chains in the dispersing agent are easily soluble in water. Under the shearing and grinding action of the centrifugal disperser, the dispersed nanoparticles are wrapped by the dispersing agent and can be evenly dispersed in the aqueous solution; on the other hand, the ZnO nanoparticles are connected to the dispersing agent, which is equivalent to dragging a long molecular chain, and their migration and movement ability is hindered by the dispersant molecular chain. Therefore, they will not re-agglomerate due to contact with other nanoparticles for a long time after dispersion.

[0046] The third object of the present invention is achieved by the following technical solutions:

[0047] An inorganic nano antibacterial and mildew-proof spray prepared by the above preparation method has the characteristics of high sterilization efficiency, wide sterilization range, high safety, etc. under insufficient light conditions, and has a non-migrating nanoscale with long-term effectiveness.

[0048] Compared with the prior art, the present invention has the following advantages:

[0049] (1) When preparing the inorganic nano antibacterial and mildew-proof spray, the present invention adopts a centrifugal disperser, an auxiliary dispersing aid and a related dispersion treatment process, which can make the particle size D90 (i.e., the particle size at which the cumulative distribution of particles is 90%, and the content of particles smaller than this particle size accounts for 90% of all particles) of the doped ZnO nanoparticles below 110nm, and can be as low as below 50nm, thereby effectively avoiding the agglomeration of nanoparticles, and making the doped nanoparticles have high dispersion efficiency, narrow particle size distribution and uniform particle distribution.

[0050] (2) In the preparation of the inorganic nano antibacterial and antifungal spray, a centrifugal disperser is used to 3+ The doped ZnO particles are subjected to high-speed, high-pressure, high-stretching and high-shear dispersion treatment. The ZnO aqueous solution undergoes extensional rheology in the centrifugal disperser, and the dispersant, ZnO particles and auxiliary dispersing aids are stretched and oriented together. The agglomerated ZnO particles are dispersed under the action of this stretching force and mixed in the solvent together with the dispersant molecular chains. In addition, the acceleration pipe is an annular pipe, and the radius of the annular pipe gradually decreases, so that the nano solution and the outer wall of the tube form a higher pressure (the centrifugal force is getting stronger and stronger). The inner wall of the acceleration pipe collides with the ZnO nanoparticles under high speed and high pressure, and the agglomerated particles are subjected to strong shear force, which further receives good dispersion. In the centrifugal disperser, the Fe 3+The doped ZnO particles are simultaneously subjected to high speed, high pressure, high stretching, and high shear dispersion. These four effects can disperse the particles to the greatest extent, making them dispersed into nano-sized particles, which has advantages that other dispersion equipment on the market currently does not have. This ensures the uniform dispersion of nanoparticles and the final spray has excellent antibacterial and anti-mildew effects.

[0051] In the centrifugal disperser, Fe 3+ The doped ZnO nanoparticles have hydroxyl groups on their surfaces, and can be connected to the auxiliary dispersing agent polyethylene glycol grafted glycidyl methacrylate through hydrogen bonds, or can undergo a chemical reaction to connect the two, thereby forming a state in which the auxiliary dispersing agent molecules wrap the ZnO nanoparticles; at the same time, since the ZnO nanoparticles are connected to one or more long molecular chains, their migration and movement capabilities are hindered by the dispersant molecular chains, and they will not re-agglomerate due to contact with other nanoparticles for a long time after dispersion, so the dispersed ZnO nanoparticles can remain in a nano-size state for a long time, so that the finally prepared spray has a long-lasting antibacterial and anti-mildew effect.

[0052] The two important features of the method for preparing the antibacterial and mildew-proof spray of the present invention are that the nanoparticles are mechanically and physically dispersed by a centrifugal disperser and chemically dispersed by a dispersing aid. Only by combining these two dispersion methods can the size of the nanoparticles in the antibacterial and mildew-proof spray be minimized, and the nanoparticles are evenly dispersed and can be placed for a long time without agglomeration, so that the nanomaterial can give full play to its nanometer size effect and realize its nanometer antibacterial mechanism, so that the spray finally prepared has excellent and lasting antibacterial and mildew-proof effects. If one of these two important dispersion methods is missing, the antibacterial and mildew-proof effects of the spray will be deteriorated.

[0053] (3) The inorganic nano antibacterial and antifungal spray prepared by the present invention can still have the characteristics of high sterilization efficiency, wide sterilization range, high safety, etc. under insufficient light conditions, and has a non-migrating nanoscale with long-term effectiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 This is a schematic diagram of the structure of the centrifugal disperser in Example 1,

[0055] Among them, 1-feeding port; 2-high pressure pump; 3-valve; 4-pressurization chamber; 5-rough pipeline; 6-acceleration pipeline;

[0056] 7-centrifugal dispersion pipeline; 8-disperser outlet (a-outside of the inner wall of the pipeline; b-inside of the inner wall of the pipeline);

[0057] Figure 2 The particle size and distribution diagram of ZnO particles in Example 2;

[0058] Figure 3 The particle size and distribution diagram of ZnO particles in Example 3;

[0059] Figure 4 The particle size and distribution diagram of ZnO particles in Example 4;

[0060] Figure 5 The particle size and distribution diagram of ZnO particles in Example 5;

[0061] Figure 6 This is a graph of the particle size of the grinding particles for the comparative example. DETAILED DESCRIPTION

[0062] The present invention is further described in detail below in conjunction with embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0063] Example 1

[0064] like Figure 1 The centrifugal disperser shown is composed of a feeding port 1, a pressure building bin 4, a high-pressure pump 2 and a centrifugal dispersion device; the feeding port 1 and the high-pressure pump 2 are respectively connected to the pressure building bin 4 through valves; the centrifugal dispersion device is arranged at the lower end of the pressure building bin 4 and is connected to the pressure building bin 4 through a closed valve; the centrifugal dispersion device includes a coarse pipeline 5, an acceleration pipeline 6 and a centrifugal dispersion pipeline 7 connected in sequence, the diameter of the coarse pipeline 5 is the same as the maximum diameter of the acceleration pipeline 6, and the diameter of the centrifugal dispersion pipeline 7 is the same as the minimum diameter of the acceleration pipeline 6.

[0065] Furthermore, the centrifugal disperser also includes a disperser outlet 8 arranged at the tail end of the centrifugal dispersion pipeline 7.

[0066] Furthermore, the accelerating pipe 6 is an annular accelerating pipe with a gradually decreasing diameter, and the ratio of the maximum diameter to the minimum diameter of the accelerating pipe 6 is 4:1.

[0067] The high-pressure pump 2 is an external device that can increase the pressure in the pressure-building chamber to 40 MPa; the inner wall of the acceleration pipe 6 and the inner wall of the centrifugal dispersion pipe 7 are both frosted pipe walls, and their surface roughness reaches 3000 meshes.

[0068] The key dimensions of the centrifugal disperser in this embodiment include: the diameter of the coarse pipe 5 is 20 mm; the ratio of the maximum diameter to the minimum diameter of the acceleration pipe 6 is 4:1; the length of the acceleration pipe 6 is 40 mm; the diameter of the centrifugal dispersion pipe 7 is 5 mm; the total length of the centrifugal dispersion pipe 7 is 2 m, the maximum winding diameter is 0.3 m, and the number of windings is 4.

[0069] In this embodiment, the specific working process of the centrifugal disperser dispersing the nanoparticle mixture is as follows:

[0070] 1) First, add the nanoparticle mixture to be dispersed into the pressure building bin 4 through the feed port 1, close the valve between the feed port 1 and the pressure building bin 4 and the airtight valve between the pressure building bin 4 and the rough pipeline, open the high-pressure pump 2 and the valve between the high-pressure pump and the pressure building bin to start pressure building, and set the pressure target value of the pressure building to 40MPa;

[0071] 2) After the pressure reaches the target set value, the airtight valve connecting the pressure building chamber 4 and the thick pipe 5 is opened, and the nanoparticle mixture that is easy to agglomerate reaches the acceleration pipe 6 through the thick pipe 5. The pipe of the acceleration pipe 6 gradually becomes thinner. In the process of flowing through the thinning pipe, the volume flow rate of the nanoparticle mixture that is easy to agglomerate remains unchanged. Therefore, the linear velocity of the nanoparticle mixture that is easy to agglomerate in the thin pipe is relatively high, while the linear velocity of the nanoparticle mixture to be dispersed in the thick pipe is relatively low. The speed difference under high speed and pressure causes the nanoparticle mixture to be dispersed to be stretched in the direction of the flow velocity, thereby generating stretching rheology; this stretching rheology causes the particles in the nanoparticle mixture to be dispersed to be strongly stretched, and the agglomerated particles are gradually dispersed under the action of this stretching rheology to form nano-scale particles;

[0072] 3) After being accelerated, the nanoparticle mixture that is easy to agglomerate enters the centrifugal dispersion pipe 7. Since the nanoparticle mixture has a high speed, the annular pipe causes the nanoparticle mixture to be subjected to a large centrifugal force, and this centrifugal force is provided by the outer side of the inner wall of the centrifugal dispersion pipe 7 (outer side a of the inner wall of the pipe). A high force and high-speed friction are generated between the 3000-mesh frosted wall and the nanoparticle mixture that is easy to agglomerate, so that the agglomerated nanoparticles can be further dispersed and freed in the water.

[0073] During the entire dispersion process, the pressure applied by the high-pressure pump 2 directly acts on the easily agglomerated nanoparticle mixture, so that it is always in a high-pressure state; the easily agglomerated nanoparticle mixture produces a high flow rate under high pressure, which makes the easily agglomerated nanoparticles at the acceleration pipe 6 stretched by the higher flow rate difference, and the agglomerated nanoparticles are gradually broken up and dispersed into nanoparticles; on the other hand, the annular pipe gives the high-flow-rate nanoparticle mixture a certain centrifugal force, which is balanced with the pressure of the nanoparticle mixture on the pipe wall. Under this pressure and the rough pipe wall, the nanoparticle mixture is subjected to high shear, and this high shear again shears and tears the agglomerated nanoparticles, further breaking up their agglomeration phenomenon to form nano-scale particles.

[0074] Compared with ordinary nano-dispersion equipment, the centrifugal disperser provided in the embodiment of the present invention has the advantages of high speed, high pressure, high stretching and high shearing. The commonly used dispersion equipment on the market generally relies on the shearing force generated by the high-speed operation of the equipment to grind the nanoparticles, such as ball mills, high-speed grinders, etc.; in addition, there are also equipment that relies on high pressure on the material to disperse the particles, such as spray drying dispersers. These devices only disperse the agglomerated nanoparticles by generating high-speed shearing or high pressure, and the effect is not good. The centrifugal disperser provided by the present invention combines high speed, high pressure, high stretching and high shearing to act on nanoparticles that are easy to agglomerate, so as to better disperse them evenly.

[0075] Table 1 is a comparison of the main performances of the centrifugal disperser provided by the present invention and two common dispersion devices on the market. It can be seen that the centrifugal disperser provided by the present invention combines speed and pressure to disperse particles; ordinary nano-dispersing devices mainly rely on the effect of high-speed shear force, while the centrifugal disperser provided by the present invention not only applies high-speed shear force to particles, but also has the effect of tensile force.

[0076] Table 1 Comparison of main performances of various dispersion equipment

[0077]

[0078] The centrifugal disperser provided by the invention is used for physically dispersing inorganic metal oxide particles in a solution.

[0079] Example 2

[0080] 1. Fe 3+ Doping ZnO nanomaterials to prepare inorganic metal oxide nanoparticles, the modification process is as follows:

[0081] (1) ZnCl 2 (ZnCl 2 , model: German LANXESS 1050, Guangzhou Pengyuan Chemical Co., Ltd.) was dissolved in HCl solution (model: 0.1-1.0MOL, Shenzhen Jinyi Trading Co., Ltd.), and an appropriate amount of NH 3 ·H 2 O (Model: A801005, McLean), adjust the pH to 2, stir evenly, and it is a mixed solution, ZnCl 2 The ratio of mixed solution is 1g:80mL;

[0082] (2) adding the above solution into deionized water, wherein the volume ratio of the solution to deionized water is 1:20, and hydrothermally reacting at 150° C. for 8 h;

[0083] (3) Add FeCl to the product in (2) 3 6H 2O (model: I809489, McLean) was stirred and mixed, microwaved for 2 h, and then ultrasonicated for 50 min. 3 6H 2 O and ZnCl 2 The mass ratio is 1:50;

[0084] (4) The product of step (3) was stirred at 160° C. for 10 h, then centrifuged, and the precipitate was washed 5 times with deionized water and 5 times with anhydrous ethanol, and dried to obtain Fe 3+ Doped ZnO nanoparticles to form Zn 0.95 Fe 0.05 O 1.025 After preliminary grinding, powdery doped inorganic metal oxide nanoparticles can be obtained.

[0085] 2. An inorganic nano antibacterial and antifungal spray, the composition ratio (mass ratio) and its preparation method are as follows:

[0086] Deionized water (Model: 0003, Shanghai Dingyuan Water Treatment Technology Co., Ltd.) 60 parts

[0087] 1 part of inorganic metal oxide nanoparticles Dispersant sodium carboxylate (model: ph01, Wujiang Puhua Chemical Light Industry Co., Ltd.) 14 parts

[0088] Auxiliary dispersing agent PEG-GMA (prepared according to the method in the aforementioned patent CN201710959226.8) 25 parts;

[0089] The doped inorganic metal oxide nanoparticles are added to the centrifugal disperser described in Example 1 together with deionized water, a dispersant and an auxiliary dispersing agent for treatment, so that the average particle size of the nanoparticles is maintained below 96 nm (e.g. Figure 2 As shown, the left arrow indicates the percentage of content corresponding to each nanometer size shown in the curve in the figure, corresponding to the scale on the left; the right arrow indicates the cumulative distribution of nanoparticle sizes shown in the curve in the figure, corresponding to the scale on the right. ) and dispersed in water for a long time and evenly. Finally, the above Fe 3+ The doped and dispersed ZnO dispersion is compressed and bottled with propellant carbon dioxide (3MPa) to obtain an inorganic nano antibacterial and antifungal spray.

[0090] Example 3

[0091] Fe doping 3+ Nano ZnO material is used to prepare inorganic metal oxide nanoparticles. The specific operation is as follows, wherein the composition ratio (mass ratio) is the same as that in Example 2, except that in step (3), the nano ZnO is treated with different contents of Fe3+ Doping modification. Fe 3+ Doping ZnO nanomaterials, the modification process is as follows:

[0092] (1) ZnCl 2 (ZnCl 2 , model: German LANXESS 1050, Guangzhou Pengyuan Chemical Co., Ltd.) was dissolved in HCl solution (model: 0.1-1.0MOL, Shenzhen Jinyi Trading Co., Ltd.), and an appropriate amount of NH 3 ·H 2 O (Model: A801005, McLean), adjust the pH to 2, stir evenly, and it is a mixed solution, ZnCl 2 The ratio of mixed solution is 1g:80mL;

[0093] (2) adding the above solution into deionized water, wherein the volume ratio of the solution to deionized water is 1:20, and hydrothermally reacting at 150° C. for 8 h;

[0094] (3) Add FeCl to the product in (2) 3 6H 2 O (model: I809489, McLean) was stirred and mixed, microwaved for 2 h, and then ultrasonicated for 50 min. 3 6H 2 O and ZnCl 2 The mass ratio is 1:30;

[0095] (4) The product of step (3) was stirred at 160° C. for 10 h, then centrifuged, and the precipitate was washed 5 times with deionized water and 5 times with anhydrous ethanol, and dried to obtain Fe 3+ Doped ZnO nanoparticles to form Zn 0.9 Fe 0.1 O 1.05 After preliminary grinding, powdery doped inorganic metal oxide nanoparticles can be obtained.

[0096] 2. The inorganic metal oxide nanoparticles are added together with deionized water, a dispersant and an auxiliary dispersing agent into a centrifugal disperser for dispersion treatment, wherein the composition ratio (mass ratio) is the same as that of Example 1, except that in step (3), the inorganic metal oxide nanoparticles are subjected to nano ZnO and Fe 3+ Doping modification keeps the average particle size of nanoparticles below 101nm (such as Figure 3 As shown), and dispersed in water for a long time and evenly. 3+ The doped and dispersed ZnO dispersion is compressed and bottled with carbon dioxide (4MPa) to obtain an inorganic nano antibacterial and antifungal spray.

[0097] Example 4

[0098] 1. Fe 3+ Doping ZnO nanomaterials to prepare inorganic metal oxide nanoparticles, the modification process is as follows:

[0099] (1) ZnCl 2 (ZnCl 2 , model: German LANXESS 1050, Guangzhou Pengyuan Chemical Co., Ltd.) was dissolved in HCl solution (model: 0.1-1.0MOL, Shenzhen Jinyi Trading Co., Ltd.), and an appropriate amount of NH 3 ·H 2 O (Model: A801005, McLean), adjust the pH to 2, stir evenly, and it is a mixed solution, ZnCl 2 The ratio of mixed solution is 1g:100mL;

[0100] (2) adding the above solution into deionized water, wherein the volume ratio of the solution to deionized water is 1:25, and subjecting to hydrothermal reaction at 190° C. for 10 h;

[0101] (3) Add FeCl to the product in (2) 3 6H 2 O (model: I809489, McLean) was stirred and mixed, microwaved for 1 h, and then ultrasonicated for 50 min. 3 6H 2 O and ZnCl 2 The mass ratio is 1:10;

[0102] (4) The product of step (3) was stirred at 160° C. for 8 h, then centrifuged, and the precipitate was washed 5 times with deionized water and 5 times with anhydrous ethanol, and dried to obtain Fe 3+ Doped ZnO nanoparticles to form Zn 0.85 Fe 0.15 O 1.075 After preliminary grinding, powdery doped inorganic metal oxide nanoparticles can be obtained.

[0103] 2. An inorganic nano antibacterial and antifungal spray, the composition ratio (mass ratio) and its preparation method are as follows:

[0104] Deionized water (Model: 0003, Shanghai Dingyuan Water Treatment Technology Co., Ltd.) 60 parts 6 parts of inorganic metal oxide nanoparticles

[0105] Dispersant pyridinium salt (Model: LG-20210308012, Shandong Linguan Fine Chemical Co., Ltd.) 14 parts

[0106] Auxiliary dispersing agent PEG-GMA (prepared according to the method in the aforementioned patent CN201710959226.8) 20 parts

[0107] The doped nanomaterials are added to a centrifugal disperser together with deionized water, a dispersant and an auxiliary dispersing agent for dispersion treatment. After testing, the average particle size of the nanoparticles is kept below 102 nm (e.g. Figure 4 As shown), and can be dispersed in water evenly and permanently. 3+ The doped and dispersed ZnO dispersion is bottled with carbon dioxide compression (3MPa) to obtain an inorganic nano antibacterial and antifungal spray.

[0108] Example 5

[0109] 1. Fe 3+ The doped ZnO nanomaterial was used to prepare inorganic metal oxide nanoparticles. The doping process and doping amount were the same as those in Example 3, that is, ZnO nanoparticles were formed. 0.85 Fe 0.15 O 1.075 .

[0110] 2. An inorganic nano antibacterial and antifungal spray, the composition ratio (mass ratio) and its preparation method are as follows:

[0111] Deionized water (Model: 0003, Shanghai Dingyuan Water Treatment Technology Co., Ltd.) 70 parts

[0112] Inorganic metal oxide nanoparticles (ZnO, model: Germany Lanxess 1050, Guangzhou Pengyuan Chemical Co., Ltd.) 10 parts

[0113] Dispersant sodium carboxylate (model: ph01, Wujiang Puhua Chemical Light Industry Co., Ltd.) 8 parts

[0114] Auxiliary dispersing agent PEG-GMA (prepared according to the method in the aforementioned patent CN201710959226.8) 12 parts;

[0115] The doped nanomaterials are added to a centrifugal disperser together with deionized water, a dispersant and an auxiliary dispersing agent for dispersion treatment. After testing, the average particle size of the nanoparticles is kept below 89 nm (e.g. Figure 5 As shown), and can be dispersed in water for a long time and evenly; finally, the above Fe 3+ The doped and dispersed ZnO dispersion is compressed and bottled with carbon dioxide (3MPa) to obtain an inorganic nano antibacterial and antifungal spray.

[0116] Comparative Example

[0117] 1. The Fe3+ The doped ZnO nanomaterial is used to prepare inorganic metal oxide nanoparticles. The doping process and doping amount are the same as those in Example 2, that is, Zn 0.95 Fe 0.05 O 1.025 .

[0118] 2. An inorganic nano antibacterial and antifungal spray, the composition ratio (mass ratio) and its preparation method are as follows:

[0119] Deionized water (Model: 0003, Shanghai Dingyuan Water Treatment Technology Co., Ltd.) 60 parts Fe 3+ Doped ZnO nanomaterial (ZnO, model: Germany Lanxess 1050, Guangzhou Pengyuan Chemical Co., Ltd.) 1 part

[0120] Dispersant sodium carboxylate (article number: ph01, Wujiang Puhua Chemical Light Industry Co., Ltd.) 14 parts

[0121] Auxiliary dispersing agent PEG-GMA (prepared according to the method in the aforementioned patent CN201710959226.8) 25 parts

[0122] The preparation method of the inorganic nano antibacterial and antifungal spray is as follows:

[0123] The inorganic metal oxide nanoparticles are mixed with deionized water, a dispersant and an auxiliary dispersing agent, and then dispersed using a high-speed grinder. The average particle size of the nanoparticles is less than 140 nm (e.g. Figure 6 As shown). It can be seen that the high-speed grinder does not have the advantages of combining the physical dispersion of the centrifugal disperser and the chemical dispersion method of the dispersant as described in the present invention.

[0124] Antibacterial performance test

[0125] The spray obtained in the above examples and comparative examples was placed at room temperature for one year, and a comparative test of the sterilization rate was conducted with inorganic nano antibacterial and mildew-proof materials under insufficient light conditions. The test was conducted using the method specified in the national standard GB / T21866-2008, and the main test strains were Escherichia coli and Staphylococcus aureus. The test results are shown in Table 2, where the "x value" represents the doped nanomaterial Zn 1-x Fe x O 1+0.5x The value of x in the figure refers to the amount of Zn added when preparing the antibacterial spray material. 1- x Fe x O 1+0.5x The number of copies.

[0126] Table 2 Antibacterial rate of nanomaterials with different doping amounts and different numbers (under insufficient light conditions)

[0127]

[0128] It can be seen that Fe 3+ After being placed for one year, the inorganic metal oxide nano antibacterial and mildew-proof spray material doped and treated by the preparation method of the present invention still has excellent antibacterial properties under insufficient light conditions; the comparative antibacterial spray product that has not been treated by the preparation method of the present invention has a larger nanoparticle size and a poorer antibacterial effect after being placed for one year.

[0129] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing an inorganic nano antibacterial and antifungal spray, characterized in that: The method comprises the following steps: uniformly mixing the following raw material components by weight: 0.5-10 parts of inorganic metal oxide nanoparticles, 20-80 parts of deionized water, 1-20 parts of a dispersant, and 1-40 parts of an auxiliary dispersing aid to obtain a nanoparticle mixed solution; adding the nanoparticle mixed solution into a centrifugal disperser for centrifugal dispersion to obtain a water-soluble nanoparticle mixed solution after dispersion treatment; adding a propellant, mixing, and bottling to obtain an inorganic nano antibacterial and antifungal spray; The molecular formula of the inorganic metal oxide nanoparticles is Zn 1-x Fe x O 1+0.5x , where 0.05≤x≤0.15; The method for preparing the inorganic metal oxide nanoparticles comprises the following steps: (1) dissolving ZnCl2 in HCl solution, adding NH3·H2O, adjusting the pH to 1-4, stirring evenly, and preparing a mixed solution, wherein the mass volume ratio of ZnCl2 to the mixed solution is 1g:80-100mL; (2) adding the mixed solution in step (1) into deionized water, wherein the volume ratio of the mixed solution to deionized water is 1:20-25, and performing a hydrothermal reaction at 120-200° C. for 2-10 h; (3) adding FeCl3·6H2O to the product obtained in step (2), stirring and mixing, microwave reaction for 1-2h, and then ultrasonic treatment for 30-50min to obtain a product, wherein the mass ratio of the added FeCl3·6H2O to ZnCl2 is 1:10-50; (4) stirring the product obtained in step (3) at 150-160° C. for 8-12 h, then centrifuging, washing the precipitate with deionized water and anhydrous ethanol 5 times each, and drying to obtain inorganic metal oxide nanoparticles; The centrifugal disperser comprises a feed port, a pressure building bin, a high-pressure pump and a centrifugal dispersion device; the feed port and the high-pressure pump are respectively connected to the pressure building bin through valves; the centrifugal dispersion device is arranged at the lower end of the pressure building bin and is connected to the pressure building bin through a closed valve; the centrifugal dispersion device comprises a coarse pipeline, an acceleration pipeline and a centrifugal dispersion pipeline connected in sequence, the diameter of the coarse pipeline is the same as the maximum diameter of the acceleration pipeline, and the diameter of the centrifugal dispersion pipeline is the same as the minimum diameter of the acceleration pipeline; The specific working process of the centrifugal disperser dispersing the nanoparticle mixture is as follows: 1) First, add the nanoparticle mixture to be dispersed into the pressure building bin through the feeding port, close the valve between the feeding port and the pressure building bin and the airtight valve between the pressure building bin and the rough pipeline, open the high-pressure pump and the valve between the high-pressure pump and the pressure building bin to start pressure building; 2) After the pressure reaches the set value, the airtight valve connecting the pressure building bin and the thick pipeline is opened, and the nanoparticle mixture that is easy to agglomerate reaches the acceleration pipeline through the thick pipeline. The pipeline of the acceleration pipeline gradually becomes thinner. In the process of flowing through the thinning pipeline, the volume flow rate of the nanoparticle mixture that is easy to agglomerate remains unchanged. Therefore, the linear velocity of the nanoparticle mixture that is easy to agglomerate in the thin pipeline is relatively high, while the linear velocity of the nanoparticle mixture to be dispersed in the thick pipeline is relatively low. The speed difference under high speed and pressure causes the nanoparticle mixture to be dispersed to be stretched in the flow velocity direction, thereby generating stretching rheology; this stretching rheology causes the particles in the nanoparticle mixture to be dispersed to be strongly stretched, and the agglomerated particles are gradually dispersed under the action of this stretching rheology to form nano-scale particles; 3) After being accelerated, the nanoparticle mixture that is easy to agglomerate enters the centrifugal dispersion pipe. Since the nanoparticle mixture has a high speed, the annular acceleration pipe causes the nanoparticle mixture to be subjected to a large centrifugal force, and this centrifugal force is provided by the outer side of the inner wall of the centrifugal dispersion pipe. A high force and high-speed friction are generated between the wall of the centrifugal dispersion pipe and the nanoparticle mixture that is easy to agglomerate, so that the agglomerated nanoparticles are further dispersed and free in the water, thereby obtaining a dispersed nanoparticle mixture; The dispersant is sodium carboxylate or pyridinium salt; The auxiliary dispersing aid is polyethylene glycol grafted glycidyl methacrylate.

2. The method for preparing the inorganic nano antibacterial and antifungal spray according to claim 1, characterized in that: The centrifugal disperser also includes a disperser outlet arranged at the tail end of the centrifugal dispersion pipeline.

3. The method for preparing the inorganic nano antibacterial and antifungal spray according to claim 1, characterized in that: The accelerating pipe is an annular accelerating pipe with a gradually decreasing diameter, and the ratio of the maximum diameter to the minimum diameter of the accelerating pipe is 4:

1.

4. The method for preparing the inorganic nano antibacterial and antifungal spray according to claim 1, characterized in that: The molecular formula of the inorganic metal oxide nanoparticles is Zn 0.95 Fe 0.05 O 1.025 .

5. The method for preparing the inorganic nano antibacterial and antifungal spray according to claim 1, characterized in that: The molecular formula of the inorganic metal oxide nanoparticles is Zn 0.85 Fe 0.15 O 1.075 .

6. An inorganic nano antibacterial and antifungal spray prepared according to the preparation method according to any one of claims 1 to 5.

Images