Microsphere-based antibacterial and antifogging additive, preparation method thereof, multifunctional coating and application

Abstract

The invention relates to the technical field of sterilization and antifogging, in particular to a microsphere-based antibacterial and antifogging additive, a preparation method thereof, a multifunctional coating and application. The microsphere-based antibacterial and antifogging additive is a liposome vesicle microsphere, and the liposome vesicle microsphere is prepared from an oil-phase raw material and a water-phase raw material; the oil phase raw material comprises one or more of distearoyl phosphatidylcholine, hydrogenated lecithin and cholesterol; the water-phase raw material is a mixture of polyhexamethylene biguanide, polyethyleneimine and benzalkonium chloride; in the water phase raw material, the content of the polyhexamethylene biguanide is 25wt%-45wt%. By optimizing the formula of the microspheres, the efficiency and effect of killing nucleic acid can be remarkably improved, and the fog-resistant and anti-fog effects are achieved.

Description

Technical Field

[0001] This invention relates to the field of sterilization and anti-fogging technology, and in particular to a microsphere-based antibacterial and anti-fogging additive, its preparation method, multifunctional coating, and its application. Background Technology

[0002] In daily life and industrial production, many scenarios require the use of anti-fogging agents to prevent fogging of object surfaces, such as car windows, eyeglasses, and medical devices. Traditional anti-fogging agents mainly work by reducing surface tension and altering surface hydrophilicity, allowing water vapor to spread evenly on the surface, thus preventing water droplets from forming fog. However, most of these anti-fogging agents only have a single anti-fogging function and cannot meet the needs of some special scenarios that require sterilization.

[0003] For example, in the medical field, medical mirrors and protective face shields need to prevent fogging to ensure clear vision, while also needing sterilization functions to prevent the spread of bacteria and cross-infection. In daily life, especially in crowded environments where masks are required, the demand for glasses that combine anti-fogging and disinfection functions is also increasing for people who need to wear glasses.

[0004] Currently, most anti-fogging agents on the market prevent water vapor from condensing into fog by reducing surface tension or altering surface hydrophilicity; however, most of these products lack bactericidal properties. Although some anti-fogging agents contain small amounts of antibacterial agents in their formulations, their bactericidal effect is limited, and the type and amount of antibacterial agents added need to be strictly controlled to avoid adverse effects on the environment and human health. Therefore, developing an additive that combines highly efficient anti-fogging and bactericidal / disinfecting functions is of great significance for meeting market demands and improving product performance.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] This invention provides a microsphere-based antibacterial and anti-fogging additive, its preparation method, a multifunctional coating, and its application, in order to solve the problem that existing technologies cannot simultaneously achieve efficient disinfection, sterilization, and anti-fogging functions.

[0007] This invention provides a microsphere-based antibacterial and anti-fogging additive, wherein the microsphere-based antibacterial and anti-fogging additive is a liposome vesicle microsphere, which is prepared from an oil phase raw material and an aqueous phase raw material; the oil phase raw material includes one or more of distearate, hydrogenated lecithin, and cholesterol; the aqueous phase raw material is a mixture of polyhexamethylene biguanide, polyethyleneimine, and benzalkonium chloride; and the content of polyhexamethylene biguanide in the aqueous phase raw material is 25wt%~45wt%.

[0008] In the aqueous raw material, the content of polyhexamethylene biguanide can be any value among 25wt%, 30wt%, 35wt%, 40wt%, and 45wt%, or a range of values ​​with any two of the above values ​​as endpoints.

[0009] This invention optimizes the disinfectant formulation to ensure efficient and effective nucleic acid killing. Furthermore, this invention unexpectedly discovered that the liposome vesicle microspheres also possess anti-fogging properties, forming a uniform protective film on the surface of an object. This protective film can alter the surface's hydrophilicity or hydrophobicity, effectively preventing water vapor condensation into fog. Specifically, this invention found that polyhexamethylene biguanide plays a dual role in the aqueous raw material, both synergistically killing nucleic acids with polyethyleneimine and benzalkonium chloride, and imparting anti-fogging effects to the microspheres. This invention further enhances the anti-fogging performance by controlling the content of polyhexamethylene biguanide in the aqueous raw material within the aforementioned range.

[0010] In this invention, the molecular weight of polyethyleneimine can be 3000~20000, for example, it can be any value among 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, or a range of values ​​with any two of the above values ​​as endpoints.

[0011] According to the present invention, the liposome-based antibacterial and anti-fogging additive has a particle size of 135nm to 152nm, for example, any value among 135nm, 136nm, 137nm, 138nm, 139nm, 140nm, 141nm, 142nm, 143nm, 144nm, 145nm, 146nm, 147nm, 148nm, 149nm, 150nm, 151nm, and 152nm, or a range of values ​​with any two of the above values ​​as endpoints, and a PDI of less than 0.2.

[0012] The microsphere size within the aforementioned range helps the microspheres form a dense protective film on the object's surface, uniformly covering the surface. It also helps balance surface area and stability, preventing excessively small microspheres from becoming too reactive or excessively large microspheres from causing sedimentation, thus ensuring the stability of the microspheres in the coating. A PDI of less than 0.2 indicates uniform particle size distribution, ensuring even coverage of the protective film and preventing areas from being unable to effectively prevent fogging.

[0013] According to the present invention, a microsphere-based antibacterial and antifogging additive is provided, wherein the mass ratio of polyhexamethylene biguanide to polyethyleneimine is (1~4):(1~4).

[0014] According to the present invention, in a microsphere-based antibacterial and antifogging additive, the mass ratio of the mixture of polyhexamethylene biguanide and polyethyleneimine to benzalkonium chloride in the aqueous phase raw material is (1~3):(1~3).

[0015] Through further formulation optimization, this invention enables the microspheres to have a more stable structure, making them less prone to failure due to changes in the external environment (such as temperature and humidity), thus enhancing their stability and reliability in different usage scenarios and further improving their anti-fogging and disinfection functions.

[0016] According to the present invention, in a microsphere-based antibacterial and antifogging additive, the molar ratio of distearate, hydrogenated lecithin and cholesterol in the oil phase raw material is 1:(4~6):(3~5).

[0017] According to the microsphere-based antibacterial and antifogging additive provided by the present invention, in the aqueous phase raw material, the volume ratio of the oil phase raw material to the aqueous phase raw material is 1:(2~4). In some specific embodiments, the volume ratio of the oil phase raw material to the aqueous phase raw material can be any ratio among 1:2, 1:3, and 1:4, or a range of ratios with any two of the above ratios as endpoints.

[0018] Secondly, the present invention provides a preparation system for the aforementioned microsphere-based antibacterial and anti-fogging additive. Jet mixer 310; The jet mixer 310 includes; The collision mixing unit 311 has a mixing chamber, and at least one liquid outlet channel and at least two liquid inlet channels are formed in the collision mixing unit 311; the liquid inlet channels and the liquid outlet channels are both connected to the mixing chamber. At least two Laval nozzles 312 are arranged in the inlet channel in a one-to-one correspondence; along the fluid flow direction, the Laval nozzles 312 are divided into a constriction section, a throat section and an expansion section connected in sequence.

[0019] Preferably, the collision mixing unit 311 has one liquid outlet channel and two liquid inlet channels; the liquid outlet channel and the two liquid inlet channels are arranged at circumferential intervals along the collision mixing unit 311; the two liquid inlet channels are arranged symmetrically along the central axis of the liquid outlet channel.

[0020] Preferably, it further includes: An oil phase supply device 320 is used to store an oil phase solution; the oil phase supply device 320 is connected to an inlet of one of the Laval nozzles 312; Aqueous phase supply device 330 is used to store aqueous phase solution; the aqueous phase supply device 330 is connected to the inlet of another Laval nozzle 312.

[0021] Compared to microfluidic systems, collisional jet mixers offer significant advantages in improving mixing efficiency and enabling large-scale preparation. These mixers use high-speed jets to propel aqueous and oil solutions into a mixing chamber from different directions. The intense collisions of the jets within the chamber generate strong turbulence, significantly enhancing mixing efficiency. During this process, positively charged liposomes rapidly and efficiently encapsulate negatively charged biomolecules through electrostatic adsorption, forming structurally stable and uniformly sized microsphere disinfectants. This collision-induced turbulent mixing allows for thorough mixing of the two fluids in a very short time and space, providing an effective method for the mass production of microsphere disinfectants.

[0022] The core advantage of impact jet mixers lies in their ability to generate intense turbulence through jet collisions. Unlike microfluidic technologies that rely primarily on laminar diffusion for mixing, jet mixers use jet ejection to cause fluids to collide within the mixing chamber, creating complex turbulent and shear flows. This turbulent mixing effect significantly increases the contact area between fluids and dramatically shortens the mixing time, allowing aqueous and oil solutions to mix thoroughly within milliseconds. Furthermore, the high jet velocity and inertial force of the jet significantly enhance the convective mixing effect, further improving the binding efficiency of liposomes and biomolecules. In contrast, diffusion mixing in microfluidic systems relies on molecular diffusion at the fluid interface, which is typically slow, thus limiting mixing efficiency due to the diffusion path and the fluid diffusion coefficient. Microfluidic chips require extremely complex channel designs (such as stacked structures and herringbone mixers) to increase the fluid contact area and flow complexity to enhance mixing; however, these designs are often difficult to implement for mass production.

[0023] Another significant advantage is that the processing capacity of impact jet mixers is significantly superior to that of microfluidics. Microfluidic chips, due to their small channel size, have limited fluid throughput, making large-scale production difficult in a short time. In contrast, jet mixers, through high-speed jet ejection, can handle larger volumes of fluid, significantly increasing the microsphere production rate per unit time. This is particularly crucial in microsphere fabrication, as large-scale production requires equipment capable of processing large volumes of solution quickly while ensuring uniform and consistent mixing. Impact jet mixers, through their simple structural design, can achieve high-throughput production while maintaining effective mixing, meeting the demands of industrial-grade production. Furthermore, impact jet mixers offer better operability compared to microfluidics. Microfluidic chips typically impose extremely high demands on manufacturing processes due to the complexity of their channel structure and their tiny size, and are highly sensitive to changes in parameters such as flow rate, pressure, and fluid viscosity during practical use. Therefore, the production and operation of microfluidic chips are challenging and costly. In contrast, jet mixers are relatively simple in design, with easily adjustable jet nozzle sizes, lower manufacturing costs, and more flexible operation, adaptable to the physicochemical properties of different solutions.

[0024] In the preparation of microsphere disinfectants, the impact jet mixer can flexibly control the mixing efficiency and physical properties of particles by adjusting parameters such as jet velocity, thereby realizing personalized and customized preparation of microsphere nanoparticles. This flexibility makes the jet mixer more advantageous in industrial applications.

[0025] According to the microsphere-based antibacterial and antifogging additive preparation system provided by the present invention, the expansion ratio of the expansion sections of the Laval nozzle 312 for conveying the oil phase solution and another Laval nozzle 312 for conveying the aqueous phase solution is the same or different from 2 to 5. For example, it can be any value among 2, 3, 4, and 5, or a range of values ​​with any two of the above values ​​as endpoints.

[0026] More preferably, the expansion ratio of the expansion section of the Laval nozzle 312 for conveying the oil phase solution and another Laval nozzle 312 for conveying the aqueous phase solution is the same or different, and is 2 to 3.

[0027] It is understandable that the expansion ratio of the expansion section of the Laval nozzle 312 is the ratio of the area of ​​the cross-section at the exit of the expansion section to the area of ​​the minimum cross-section at the throat of the Laval nozzle 312.

[0028] This invention discovers that controlling the expansion ratio of the expansion section of a Laval nozzle helps alleviate back pressure generated by high-speed jets. Typically, high-speed jets in a mixer lead to increased local pressure, affecting the flow of subsequent fluids and mixing efficiency. Through the gradually expanding section design of the Laval nozzle 312, back pressure can be eliminated to some extent, resulting in smoother fluid flow and more uniform mixing.

[0029] Thirdly, the present invention provides a method for preparing the microsphere-based antibacterial and anti-fogging additive, wherein the microsphere-based antibacterial and anti-fogging additive preparation system described above is used, and the preparation method includes: The aqueous phase raw material is dissolved in water, and the oil phase raw material is dissolved in an organic solvent to obtain an aqueous phase solution and an oil phase solution, respectively; preferably, the organic solvent includes ethanol; An oil phase solution is delivered to one Laval nozzle 312, and an aqueous phase solution is delivered to another Laval nozzle 312; the oil phase solution and the aqueous phase solution form a high-speed jet through the corresponding Laval nozzle 312, and the two high-speed jets collide and mix in the mixing chamber to obtain liposome vesicle microspheres.

[0030] According to the preparation method of the microsphere-based antibacterial and antifogging additive provided by the present invention, and / or, the inlet pressure of the Laval nozzle 312 for conveying the oil phase solution and the other Laval nozzle 312 for conveying the aqueous phase solution are the same or different, ranging from 0.1 MPa to 15 MPa, more preferably from 1 MPa to 1.5 MPa; for example, it can be any value among 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, and 1.5 MPa, or a range of values ​​with any two of the above values ​​as endpoints.

[0031] In this invention, the microsphere disinfectant prepared by the above system and method is beneficial for precise control of particle size and particle size distribution, with a PDI much lower than the pharmaceutical standard requirement of 0.2, and can realize the batch synthesis of liposome microspheres, breaking through the bottleneck of large-scale microsphere preparation.

[0032] Furthermore, the flow rate of the oil phase feedstock is 2 mL / min to 10 mL / min; for example, it can be any value among 2 mL / min, 3 mL / min, 4 mL / min, 5 mL / min, 6 mL / min, 7 mL / min, 8 mL / min, 9 mL / min, and 10 mL / min, or a range of values ​​with any two of the above values ​​as endpoints. The flow rate of the aqueous phase feedstock is 13 mL / min to 20 mL / min; for example, it can be any value among 13 mL / min, 14 mL / min, 15 mL / min, 16 mL / min, 17 mL / min, 18 mL / min, 19 mL / min, and 20 mL / min, or a range of values ​​with any two of the above values ​​as endpoints. Appropriate flow rates ensure thorough mixing of the oil and aqueous phase feedstocks in the impact jet mixer, avoiding problems such as uneven mixing caused by excessively fast or slow flow rates. By precisely controlling the flow rate of raw materials, the preparation process of microsphere disinfectants can be further optimized, improving the quality and performance of microsphere disinfectants and enabling them to achieve better disinfection effects in practical applications.

[0033] Furthermore, the mixing time is 2 to 5 minutes, for example, any value among 2, 3, 4, and 5 minutes, or a range of values ​​with any two of the above values ​​as endpoints. Controlling the mixing time has a significant impact on the formation and performance of the microsphere disinfectant. A suitable mixing time ensures sufficient reaction between the oil-phase and aqueous-phase raw materials, forming a stable microsphere structure. If the mixing time is too short, the raw materials may not be fully mixed, affecting the quality and performance of the microsphere disinfectant; while if the mixing time is too long, it may increase production costs and energy consumption. By limiting the mixing time range, the preparation process of the microsphere disinfectant can be ensured to be completed within a reasonable time, while guaranteeing the stability of its quality and performance, thus achieving efficient preparation of the microsphere disinfectant.

[0034] Fourthly, the present invention provides a multifunctional coating containing the aforementioned microsphere-based antibacterial and anti-fogging additive.

[0035] Preferably, in the multifunctional coating, the concentration of the microsphere-based antibacterial and antifogging additive is 0.001wt% to 0.1wt%, for example, it can be any value among 0.001wt%, 0.002wt%, 0.003wt%, 0.004wt%, 0.005wt%, 0.006wt%, 0.007wt%, 0.008wt%, 0.009wt%, 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, and 0.1wt%, or a range of values ​​with any two of the above values ​​as endpoints.

[0036] According to the present invention, a multifunctional coating further comprises polyacrylate; more preferably, the concentration of polyacrylate in the multifunctional coating is 0.001wt% to 0.4wt%, for example, it can be any value among 0.001wt%, 0.005wt%, 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.1wt%, 0.2wt%, 0.3wt%, and 0.4wt%, or a range of values ​​with any two of the above values ​​as endpoints.

[0037] In this invention, polyacrylate serves as a film-forming agent, enabling the formation of a continuous, transparent film on the substrate surface. This film structure facilitates rapid water spread and prevents water droplet formation, thereby enhancing the anti-fogging effect. Simultaneously, its excellent adhesion ensures the coating's durability in various environments.

[0038] According to the present invention, a multifunctional coating comprises the following components in parts by weight: Microsphere-based antibacterial and antifogging additive, 0.001~0.01 parts; Water 0.99~0.995 parts; Polyacrylate 0.001~0.04 parts.

[0039] In this invention, the microsphere-based antibacterial and anti-fogging additive, water, and polyacrylate are mixed evenly according to a certain ratio to prepare the multifunctional coating. Water is used as a solvent, and polyacrylate can synergistically enhance the anti-fogging function with liposome vesicle microspheres.

[0040] Fifthly, the present invention provides the application of the microsphere-based antibacterial and antifogging additive or the multifunctional coating in the sterilization and antifogging of glass products and eyeglass lenses.

[0041] Preferably, in application, the multifunctional coating is sprayed onto the surface of glass products, eyeglass lenses, or electronic displays, or the surface of glass products, eyeglass lenses, or electronic displays is wiped with a cloth impregnated with the multifunctional coating.

[0042] The microsphere-based antibacterial and anti-fogging additive or the multifunctional coating described in this invention can be applied to various devices such as window glass, windshields, reflectors, myopia glasses, hyperopia glasses, sunglasses, surveillance cameras, vehicle cameras, and optical sensors, effectively combining sterilization and disinfection with anti-fogging functions, avoiding health risks while improving the user experience.

[0043] The microsphere-based antibacterial and anti-fogging additive, its preparation method, multifunctional coating, and application provided by this invention can significantly improve the efficiency and effect of killing nucleic acids by controlling the particle size and particle size distribution of the microsphere disinfectant and further optimizing the disinfectant formulation, while also achieving anti-fogging and anti-fogging effects. Attached Figure Description

[0044] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0045] Figure 1 This is a schematic diagram of the microsphere disinfectant preparation system provided by the present invention.

[0046] Figure 2 This is one of the schematic diagrams of the jet mixer in the microsphere disinfectant preparation system provided by the present invention.

[0047] Figure 3 This is the second schematic diagram of the jet mixer structure of the microsphere disinfectant preparation system provided by the present invention.

[0048] Figure 4 This is a transmission electron microscope image of a microsphere-based antibacterial and antifogging additive provided in Embodiment 1 of the present invention.

[0049] Figure 5 This is a comparison of the anti-fogging effects of the multifunctional coating and the positive control in Example 1 of this invention within 30 minutes.

[0050] Figure 6 This is a comparison of the anti-fogging effect of the multifunctional coatings prepared in the embodiments and comparative examples provided by the present invention for more than 30 minutes.

[0051] Figure 7 This is one of the diagrams showing the bactericidal effect of the microsphere-based antibacterial and anti-fogging additive obtained in Example 1 of the present invention on Escherichia coli.

[0052] Figure 8 This is the second diagram showing the bactericidal effect of the microsphere-based antibacterial and anti-fogging additive obtained in Example 1 of the present invention on Escherichia coli. Detailed Implementation

[0053] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0054] like Figures 1 to 3 As shown, a specific embodiment of the present invention provides a preparation system for microsphere-based antibacterial and anti-fogging additives (hereinafter sometimes referred to as "microsphere disinfectants" or "liposome vesicle microspheres"). The preparation system includes a jet mixer 310; the jet mixer 310 includes a collision mixing unit 311 and two Laval nozzles 312; the collision mixing unit 311 has a mixing chamber, and forms an outlet channel and two inlet channels within the collision mixing unit 311; both the inlet and outlet channels are connected to the mixing chamber; the two Laval nozzles 312 are correspondingly arranged in the inlet channels.

[0055] In the following embodiment, by incorporating a Laval nozzle 312 in the inlet channel, the Laval nozzle 312 accelerates the passing fluid to supersonic speeds through its own contraction-expansion structure, forming a high-energy jet. Two high-speed jets are ejected from different jet outlets and collide violently within the mixing chamber. This not only increases the fluid contact area but also significantly enhances the mixing uniformity by rapidly disrupting stable interfaces in laminar flow through shear force and turbulence effects. Furthermore, the instantaneous jet mixing (completed in milliseconds) avoids batch variations inherent in traditional droplet-based mixing, making it suitable for continuous production. Therefore, the preparation system of this embodiment can produce microsphere disinfectants with uniform particle size, solving the problem of uneven particle size that exists in existing microfluidic systems for preparing microsphere disinfectants.

[0056] By directly embedding the Laval nozzle 312 into the inlet channel, external pressurization equipment (such as a high-pressure pump) is eliminated, reducing pipeline connection points, lowering the risk of leakage, and improving system compactness. With at least two inlet channels, each corresponding to a specific inlet channel and positioned within it, flexible configuration of multiple inlet channels is possible. This allows for the simultaneous processing of multiple raw materials (such as oil phase and aqueous phase) to meet complex formulation requirements.

[0057] The Laval Nozzle 312 utilizes fluid pressure energy to convert it into kinetic energy, making it more energy-efficient than mechanical stirring and reducing maintenance costs due to the absence of moving parts and wear. The improved mixing efficiency also reduces the amount of surfactant needed, meeting the demands of low-cost pharmaceutical manufacturing. The jet mixing process generates no significant temperature rise, preventing the inactivation of heat-sensitive drugs (such as proteins), and the reduced metal contact area lowers the risk of heavy metal contamination.

[0058] Furthermore, the design of the Laval nozzle 312 allows for precise control of the fluid flow state as needed. For example, the conversion between subsonic and supersonic flow can be achieved by changing the geometric parameters of the Laval nozzle 312 (such as throat diameter, inlet and outlet cross-sectional area ratio, etc.). Through precise control, the jet mixer 310 can optimize jet velocity and turbulence intensity, thereby optimizing the mixing and formation process of microspheres. The expanding section of the Laval nozzle 312 helps alleviate the back pressure generated by the high-speed jet. Typically, high-speed jets in a mixer lead to an increase in local pressure, thus affecting the flow of subsequent fluids and mixing efficiency. Through the gradually expanding section design of the Laval nozzle 312, the back pressure can be eliminated to a certain extent, resulting in smoother fluid flow and more uniform mixing. Therefore, the preparation system of this embodiment can produce microsphere disinfectant particles with uniform particle size.

[0059] Furthermore, the collision mixing unit 311 comprises one outlet channel and two inlet channels; the outlet channel and the two inlet channels are arranged circumferentially around the collision mixing unit 311; the two inlet channels are symmetrically arranged along the central axis of the outlet channel. The symmetrical circumferential distribution and symmetrical arrangement of the two inlet channels along the central axis of the outlet channel allow the high-speed jet to collide head-on within the mixing chamber, generating stronger turbulence and shear force, significantly improving the dispersion uniformity of lipids and polymers. The outlet channel and the inlet channel are at a certain angle, allowing for rapid removal of the mixed product, preventing the retention of insufficiently mixed materials, and ensuring the stability of continuous flow. The circumferential layout shortens the path of the jet from inlet to collision, reducing pressure loss and lowering energy consumption compared to a straight channel. The symmetrical inlet channels balance the jet pressure, avoiding uneven mixing caused by unilateral flow deviation. By independently controlling the flow rates of the two inlet jets, gradient mixing can be achieved, adapting to complex process requirements. The circumferential liquid outlet design shortens the residence time of the product in the cavity.

[0060] Preferably, the expansion ratio of the expansion section of the Laval nozzle 312 is 2 to 3. It should be noted that the expansion ratio of the expansion section of the Laval nozzle 312 used for jet oil phase can be the same as or different from the expansion ratio of the expansion section of the Laval nozzle 312 used for jet water phase.

[0061] This design not only directly affects the maximum Mach number achievable within the Laval nozzle 312, but also influences the distribution of the Mach number, as well as the stability of the axial Mach number and velocity variations. Under these conditions, the flow field within the Laval nozzle 312 will exhibit relatively good results; the greater the deviation of the expansion ratio from this value, the worse the overall flow field quality.

[0062] In the following embodiments, two Laval tubes with an expansion ratio of 3 are used. The expansion section connection radius Y3 of the Laval tube is 7.50 mm, the outlet radius Y2 is 9.00 mm, and the inlet radius Y1 is 24 mm; the contraction section length L1 is 36.00 mm; the contraction ratio n=Y1 / Y* is 8.00; the length-to-diameter ratio of the contraction section L1 / 2Y1 is 0.75; the throat radius Y* is 3.00 mm; the throat surface curvature radius R is 24.00 mm; and the throat curvature radius / throat radius is 8.00.

[0063] Example 1 This embodiment provides a microsphere-based antibacterial and antifogging additive, which is prepared from oil-phase raw materials and aqueous-phase raw materials; wherein, the oil-phase raw materials are hydrogenated lecithin, distearate phosphatidylcholine and cholesterol in a molar ratio of 5:1:4; the aqueous-phase raw materials are polyethyleneimine, polyhexamethylene biguanide and benzalkonium chloride in a mass ratio of 1:1:2; the volume ratio of oil-phase raw materials to aqueous-phase raw materials is 1:3; the molecular weight of polyethyleneimine is 18000.

[0064] 0.6 g of aqueous phase feedstock was dissolved in 300 mL of water, and 2 g of oil phase feedstock was dissolved in 100 mL of ethanol to obtain aqueous and oil phase solutions, respectively. The oil phase solution was fed into one Laval nozzle 312, and the aqueous phase solution was fed into another Laval nozzle 312. The oil phase solution and the aqueous phase solution were mixed at a flow ratio of 1:3 through the corresponding Laval nozzle 312 to form a high-speed jet. The mixture was mixed in the mixing chamber for 3 min. The inlet flow rate of the oil phase feedstock was 6 mL / min, and the inlet flow rate of the aqueous phase feedstock was 18 mL / min. The inlet pressure of both Laval nozzles 312 was adjusted to 1.5 MPa. After mixing, the synthesized liposome vesicle microspheres were collected. Figure 4 As shown, the microspheres have a particle size of 146.2 ± 5.4 nm and a PDI of 0.12.

[0065] This embodiment further provides a multifunctional coating, which is composed of the following components in parts by weight: 0.001 parts of microsphere-based antibacterial and antifogging additive; 0.995 parts ultrapure water; 0.004 parts of polyacrylate.

[0066] The preparation method of the multifunctional coating includes: mixing the above raw materials evenly according to the above proportions to obtain the multifunctional coating.

[0067] Example 2 This embodiment provides a microsphere-based antibacterial and antifogging additive, which differs from Example 1 in that the aqueous phase raw materials are polyethyleneimine, polyhexamethylene biguanide, and benzalkonium chloride in a mass ratio of 1:4:4. The resulting microspheres have a particle size of 143.2±3.6 nm and a PDI of 0.1.

[0068] This embodiment further provides a multifunctional coating, the formulation and preparation method of which are the same as those in Example 1.

[0069] Example 3 This embodiment provides a microsphere-based antibacterial and antifogging additive, which differs from Example 1 in that the aqueous phase raw materials are polyethyleneimine, polyhexamethylene biguanide, and benzalkonium chloride in a mass ratio of 1:1:1. The resulting microspheres have a particle size of 139.41±2.4 nm and a PDI of 0.09.

[0070] This embodiment further provides a multifunctional coating, the formulation and preparation method of which are the same as those in Example 1.

[0071] Example 4 This embodiment provides a microsphere-based antibacterial and anti-fogging additive, which differs from Example 1 in that the inlet pressure of both Laval nozzles 312 is 1 MPa. The resulting microspheres have a particle size of 140.32 ± 1.4 nm and a PDI of 0.09.

[0072] This embodiment further provides a multifunctional coating, the formulation and preparation method of which are the same as those in Example 1.

[0073] Example 5 This embodiment provides a multifunctional coating, which differs from Embodiment 1 in that it does not contain polyacrylate. The coating is composed of liposome vesicle microspheres and ultrapure water, with a microsphere concentration of 0.002 wt%.

[0074] Comparative Example 1 This comparative example provides a microsphere-based antibacterial and antifogging additive, which differs from Example 1 in that: the preparation method of the microspheres includes: passing an oil phase solution and an aqueous phase solution into a microfluidic chip at a flow rate ratio of 1:3, wherein the flow rate of the oil phase raw material is 10 mL / min and the flow rate of the aqueous phase raw material is 1 mL / min, and the synthesized microspheres are collected after mixing.

[0075] The final microspheres had a particle size of 95.26 ± 3.5 nm and a PDI of 0.1.

[0076] Comparative Example 2 This comparative example provides a microsphere-based antibacterial and antifogging additive, which differs from Example 1 in that polyhexamethylene biguanide is replaced with benzalkonium chloride in an equal amount, meaning that the aqueous raw material does not contain polyhexamethylene biguanide. The resulting microspheres have a particle size of 141.33 ± 4.3 nm and a PDI of 0.12.

[0077] Comparative Example 3 This comparative example provides a microsphere-based antibacterial and antifogging additive, which differs from Example 1 in that polyethyleneimine is replaced with chitosan in an equal amount. The resulting microspheres have a particle size of 144.43 ± 4.3 nm and a PDI of 0.11.

[0078] This comparative example further provides a multifunctional coating, the formulation and preparation method of which are the same as those in Example 1.

[0079] Test case 1. Anti-fog performance Application method: Spray the multifunctional coating prepared in Example 1 directly onto the eyeglass lens.

[0080] Step 1: Add 200mL of ultrapure water to a flat-mouthed beaker and seal the mouth of the beaker with sealing film; Step 2: Make a hole in the sealing film and place the eyeglass lens in the hole; Step 3: Place the beaker in a 60℃ water bath and observe the anti-fog performance of the eyeglass lenses at 0, 1, 5, 15 and 30 minutes respectively.

[0081] according to Figure 5 It is evident that the coating prepared in Example 1 exhibits superior anti-fogging performance on eyeglass lenses. It should be noted that experiments demonstrate that the coatings prepared in Examples 2-4 have comparable anti-fogging effects to Example 1. Examples 5 and Comparative Example 3 show slightly weaker anti-fogging effects compared to Examples 1-4, but still maintain visible anti-fogging performance within 30 minutes. Comparative Example 1 demonstrates anti-fogging effects comparable to the examples; Comparative Example 2 shows anti-fogging effects only slightly better than the positive control group, but the anti-fogging effect is very poor.

[0082] See the anti-fog effect after 30 minutes. Figure 6 .

[0083] 2. Instant sterilization performance Experimental methods: 1. Dilute the microsphere-based antibacterial and anti-fogging additive prepared in Example 1 to a disinfectant solution with a mass concentration of 0.002 wt%. Take 100 μL of Escherichia coli (10 μL) and... 6 The CFU suspension was added dropwise perpendicular to the center of the glass support, and the filter paper was held by tweezers to absorb and spread the film. The film was dried at room temperature for 15 minutes to form a uniform film. 2. Using a calibration spray bottle (output 0.8mL / s), spray the surface at a uniform speed in a Z-shaped trajectory from a distance of 30cm, using 1mL of the spray, and let it stand until the specified time point.

[0084] 3. Three sampling areas were selected using the nine-square grid method, and samples were taken at 1 and 5 minutes respectively. After sampling, the samples were placed in a neutralizing agent (1L PBS with 1g sodium thiosulfate + 10g Tween 80 + 5g lecithin). 4. Then centrifuge at 6000 rpm for 5 min, resuspend in 100 μL LB medium, spread onto solid culture medium, and incubate overnight. Take photos and perform counting and analysis. (For example...) Figure 7 As shown, the disinfectant solution (0.002 wt%) prepared with the additive in Example 1 killed all Escherichia coli in a short time of 1 minute.

[0085] 3. Long-lasting bactericidal performance Experimental methods: 1. Dilute the microsphere-based antibacterial and antifogging additive prepared in Example 1 to a disinfectant solution with a mass concentration of 0.002 wt%. Take 1 ml of the disinfectant solution and spread it on the eyeglass lens, then let it stand at room temperature. 2. On days 1, 3, 5, and 7, 100 μL of E. coli (10 μL) was added to the solution. 6 CFU is applied to the lens of the eye. 3. After 1 minute, the sample was placed in a neutralizing agent (1L PBS with 1g sodium thiosulfate + 10g Tween 80 + 5g lecithin); 4. Then centrifuge at 6000 rpm for 5 min, resuspend in 100 μL LB medium, spread onto solid culture medium, and incubate overnight. Take photos and perform counting and analysis. (For example...) Figure 8 As shown, the disinfectant solution (0.002 wt%) prepared with the additive in Example 1 can stably kill all Escherichia coli within 7 days.

[0086] 4. Virus killing effect Experimental methods: 1. Dilute the microsphere-based antibacterial and anti-fogging additives prepared in Examples 1 and 3 to a disinfectant solution with a mass concentration of 0.002%. Take 100 μL of African swine fever (>10 CT) suspension and drop it vertically to the center of the glass carrier. Use tweezers to hold the edge of the filter paper to adsorb and spread it. Dry at room temperature for 15 min to form a uniform film layer. 2. Using a calibration spray bottle (output 0.8mL / s), spray the surface at a uniform speed in a Z-shaped trajectory from a distance of 30cm, using 1mL of the spray, and let it stand until the specified time point.

[0087] 3. Three sampling areas were selected using the nine-square grid method, and samples were taken at 10, 20, and 30 minutes respectively. After sampling, the samples were placed in a neutralizing agent (1L PBS with 1g sodium thiosulfate + 10g Tween 80 + 5g lecithin). 4. Viral DNA was then directly extracted for RT-PCR, and the results are shown in Table 5. The results indicate that the disinfectant solution prepared in Example 1 essentially killed all African swine fever.

[0088] Table 5

[0089] This invention reveals that while the microsphere disinfectant prepared using a microfluidic chip in Comparative Example 1 can also control the PDI of the microspheres to be less than 0.2, the PDI of the microspheres fluctuates significantly during continuous batch preparation. In contrast, the preparation method of this invention can continuously prepare microsphere disinfectants with a PDI less than 0.2 for up to 100 hours, exhibiting good batch reproducibility and successfully achieving the batch synthesis of liposome microspheres. Specific results are shown in Table 6. Table 6 PDI 1h 2h 10h 50h 100h Example 1 0.11 0.1 0.09 0.11 0.12 Comparative Example 1 0.11 0.15 - - - Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A microsphere-based antibacterial and antifogging additive, characterized in that, The microsphere-based antibacterial and anti-fogging additive is a liposome vesicle microsphere, which is prepared from an oil phase raw material and an aqueous phase raw material. The oil phase raw material includes one or more of distearate, hydrogenated lecithin, and cholesterol. The aqueous phase raw material is a mixture of polyhexamethylene biguanide, polyethyleneimine, and benzalkonium chloride. The content of polyhexamethylene biguanide in the aqueous phase raw material is 25wt%~45wt%.

2. The microsphere-based antibacterial and antifogging additive according to claim 1, characterized in that, The liposome vesicle microspheres have a particle size of 135nm~152nm and a PDI of less than 0.

2.

3. The microsphere-based antibacterial and antifogging additive according to claim 1, characterized in that, The mass ratio of polyhexamethylene biguanide to polyethyleneimine is (1~4):(1~4). And / or, in the aqueous phase raw material, the mass ratio of the mixture of polyhexamethylene biguanide and polyethyleneimine to benzalkonium chloride is (1~3):(1~3).

4. The microsphere-based antibacterial and antifogging additive according to any one of claims 1 to 3, characterized in that, In the oil phase feedstock, the molar ratio of distearate phosphatidylcholine, hydrogenated lecithin, and cholesterol is 1:(4~6):(3~5). And / or, the volume ratio of the oil phase raw material to the aqueous phase raw material is 1:(2~4).

5. The method for preparing the microsphere-based antibacterial and antifogging additive according to any one of claims 1 to 4, characterized in that, The preparation system for the microsphere-based antibacterial and antifogging additive includes: Jet mixer (310); The jet mixer (310) includes; The collision mixing unit (311) has a mixing chamber and at least one liquid outlet channel and at least two liquid inlet channels are formed in the collision mixing unit (311); the liquid inlet channels and the liquid outlet channels are both connected to the mixing chamber. At least two Laval nozzles (312) are arranged in the inlet channel in a one-to-one correspondence; along the fluid flow direction, the Laval nozzles (312) are divided into a constriction section, a throat section and an expansion section connected in sequence; The preparation method of the microsphere-based antibacterial and antifogging additive includes: The aqueous phase raw material is dissolved in water, and the oil phase raw material is dissolved in an organic solvent to obtain an aqueous phase solution and an oil phase solution, respectively; preferably, the organic solvent includes ethanol; An oil phase solution is delivered to one Laval nozzle (312), and an aqueous phase solution is delivered to another Laval nozzle (312); the oil phase solution and the aqueous phase solution form a high-speed jet through the corresponding Laval nozzle (312), and the two high-speed jets collide and mix in the mixing chamber to obtain liposome vesicle microspheres; And / or, the flow rate of the oil phase solution is 2 mL / min to 10 mL / min; And / or, the flow rate of the aqueous solution is 13 mL / min to 20 mL / min; And / or, the inlet pressure of the Laval nozzle (312) used for conveying the oil phase solution and another Laval nozzle (312) used for conveying the aqueous phase solution is the same or different, ranging from 0.1 MPa to 15 MPa.

6. The preparation method of the microsphere-based antibacterial and antifogging additive according to claim 5, characterized in that, The expansion ratio of the expansion section of the Laval nozzle (312) used for conveying oil phase solution and another Laval nozzle (312) used for conveying aqueous phase solution is the same or different, ranging from 2 to 5.

7. A multifunctional coating, characterized in that, The multifunctional coating contains the microsphere-based antibacterial and antifogging additive as described in any one of claims 1 to 4 or the microsphere-based antibacterial and antifogging additive prepared by the preparation method described in claim 5 or 6, wherein the concentration of the microsphere-based antibacterial and antifogging additive in the multifunctional coating is 0.001 wt% to 0.1 wt%.

8. The multifunctional coating according to claim 7, characterized in that, The multifunctional coating also contains polyacrylate; the concentration of the polyacrylate in the multifunctional coating is 0.001wt%~0.4wt%.

9. The multifunctional coating according to claim 8, characterized in that, The multifunctional coating comprises the following components in parts by weight: Microsphere-based antibacterial and antifogging additive, 0.001~0.01 parts; Water 0.99~0.995 parts; Polyacrylate 0.001~0.04 parts.

10. The application of the microsphere-based antibacterial and antifogging additive according to any one of claims 1 to 4, the microsphere-based antibacterial and antifogging additive prepared by the preparation method according to claim 5 or 6, or the multifunctional coating according to any one of claims 7 to 9 in the sterilization and antifogging of glass products and eyeglass lenses; preferably, in application, the multifunctional coating is sprayed onto the surface of the glass product, eyeglass lens, or electronic display, or the surface of the glass product, eyeglass lens, or electronic display is wiped with a cloth impregnated with the multifunctional coating.

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