TWI807276B - Air filtration system, antiviral face mask, coating obtained by drying of a solution and coated object - Google Patents

Abstract

The present invention provides an air filtration system comprising one or more first layers, one or more second layers and one or more third layers, wherein the one or more second layers are located between the one or more first layers and one or more third layers, and each of the one or more first layers and each of the one or more third layers comprises a hydrophobic gas-permeable composite material, and each of the one or more second layers comprises a polycationic anti-viral and anti-bacterial gas-permeable composite material.

Description

Air filter systems, antiviral masks, paints obtained by drying solutions, and objects to be plated

The present invention relates to an air filter system, especially an air filter system with anti-virus and anti-bacteria and its manufacturing method, which can effectively filter viruses and bacteria such as coronavirus in the air. The present invention can be used with any device, tool, equipment, object and instrument that needs to filter air.

It is known that the 2019 coronavirus (COVID-19) has spread widely, and there are more and more confirmed cases of coronavirus in different countries. More and more people are wearing anti-viral masks to protect themselves from infection, thus there is a high demand for anti-bacterial and anti-viral masks that can effectively filter the air in different countries. Known antiviral masks can protect humans from bacterial and viral infections, but there is no experimental evidence that the air filter materials of these known antiviral masks can effectively prevent humans from contracting COVID-19 or other similar viruses.

In order to solve the above problems, the object of the present invention is to provide an antibacterial and antiviral air filtration system, which has been proved by experiments to effectively protect human cells from COVID-19 or other similar virus attacks, and can be successfully applied to face masks.

[Prior Technical Literature] 〔Non-patent literature〕

1. Wiegand C., Heinze T., Hipler U.C. (2009) Comparative in vitro study on cytotoxicity, antimicrobial activity and binding capacity for pathophysiological factors in chronic wounds of alginate and silver-containing alginate. Wound Repair Regen., 17, 5 11-521.

An improved antiviral mask is provided below through the description of different embodiments of the present invention.

An air filtration system characterized by comprising one or more first layers, one or more second layers and one or more third layers, wherein the one or more second layers are located between the one or more first layers and one or more third layers, and each of the one or more first layers and each of the one or more third layers comprises a hydrophobic gas-permeable composite material, and each of the one or more second layers comprises a polycationic anti-viral and anti-bacterial gas-permeable composite material.

Ideally, the aforementioned polycationic antiviral and antibacterial breathable composite material comprises a breathable substrate, an antiviral agent, an antibacterial agent and a binder. The aforementioned antiviral agent comprises a polymer having polycationic properties. The aforementioned polymers with polycationic properties include polyethyleneimine (PEI), poly-L-lysine (PLL), diethylamineethyldextran (DEAE-dextran) or polyamidoamine (PAMAM) dendrimers.

Ideally, the aforementioned air-permeable substrate includes nonwoven fabric or cellulose nonwoven fabric.

Ideally, the aforementioned binder comprises a thermoplastic elastomer.

Ideally, the aforementioned antibacterial agent comprises silver nanowires.

Ideally, the aforementioned hydrophobic and gas-permeable composite material includes a gas-permeable base material, a hydrophobic binder and a photocatalyst reaction component.

Ideally, the aforementioned hydrophobic binder comprises a synthetic polymer having hydrophobic properties.

Ideally, the aforementioned photocatalyst reaction components include titanium dioxide nanoparticles.

An antiviral mask is characterized by comprising an air filter system, a pair of straps and a wire, wherein the pair of straps are respectively arranged on both sides of the air filter system, and the wire is arranged above the inside of the air filter system.

The following descriptions enable one skilled in the art to make or use the various embodiments, and descriptions of specific devices, techniques, and applications are provided as examples only. Various adjustments to the examples described in this specification are obvious to those skilled in the art, and the principles defined in this specification can be applied to other examples and applications without departing from the spirit of the present invention and the scope of the patent application. Therefore, the content disclosed in the present invention is not intended to be limited to the examples described and shown in the specification, but should be consistent with the scope of the patent application.

Figure 1 shows a cross-sectional view of an air filtration system/air filter material according to various embodiments of the present invention. The air filtration system 100 may comprise one, two, three or more layers, and the present invention may be used with any devices, tools, equipment, objects and instruments that need to filter air.

The air filtration system 100 may include one or more first layers 102 , one or more second layers 104 and one or more third layers 106 . In this embodiment, the second layer 104 is located between the first layer 102 and the third layer 106, the second layer 104 is also considered as an intermediate layer, and the first layer 102 and the third layer 106 are meant to be hydrophobic and breathable layers. The first layer 102 and the third layer 106 are used for waterproofing and allowing air to pass through, and the hydrophobic air-permeable layer comprises a hydrophobic air-permeable composite material. The second layer 104 is meant to be a multifunctional breathable layer, which includes polycationic antiviral and antibacterial breathable composite materials.

In one example, the aforementioned multifunctional breathable layer comprises a polycationic antiviral and antibacterial breathable composite material formed based on, including but not limited to, a breathable substrate (for example: woven/cellulose woven fabric with hydrophilic properties, knitted or non-woven/cellulose non-woven fabric), an antiviral agent (for example: a polymer with polycationic properties such as polyethyleneimine (PEI), poly-L-lysine (PLL), diethylaminoethyl dextran (DEAE-dextran) or polyamide Aminoamine (PAMAM) dendrimers), antibacterial agents (eg silver nanowires) and/or binders (eg thermoplastic elastomers) obtained by surface coating technology with aqueous liquids. The adhesive is suitable for reducing the pore size of the air-permeable substrate so that the antiviral agent (such as: PEI) can be closely combined with the air-permeable substrate. In the present invention, the breathable substrate is non-woven/cellulose non-woven fabric and the antiviral agent is polyethyleneimine (PEI), and the multifunctional breathable layer (second layer 104) is used to capture and/or filter bacteria and viruses (especially COVID-19) in the air.

The aforementioned hydrophobic air-permeable layer includes a hydrophobic air-permeable composite material, which is formed based on, including but not limited to, an air-permeable substrate (for example: woven/cellulose woven fabric with hydrophobic properties, knitted or non-woven/cellulose non-woven fabric), a binder/hydrophobic binder with hydrophobic properties (for example: synthetic polymers with hydrophobic properties, such as silicon-containing polymers, fluorine-containing polymers, and polyolefins) and/or components that have photocatalytic reactions/components that have photocatalytic reactions (such as: titanium dioxide nanoparticles), It is obtained by surface coating technology with the aid of liquids. In the present invention, the air-permeable substrate is non-woven/cellulose non-woven fabric, and air can pass through the hydrophobic air-permeable layer (the first layer 102 and the third layer 106 ).

It is known that coating materials (such as binders, antiviral agents, and antibacterial agents) can be coated on the surface of non-woven fabric fibers (breathable substrate) by surface coating technology, which can reduce the pore size of non-woven fabrics and maintain its unique texture (structure) and inherent properties (ie, softness and air permeability), and can also introduce new functions/properties of coating materials and significantly reduce their usage.

A polymer with polycationic properties such as polyethyleneimine (PEI) can be used as an active agent for filtering suspended particles, viruses and bacteria or as an antiviral agent. Polyethyleneimine (PEI)

A polymer with polycationic properties such as polyethyleneimine (PEI) can be successfully grown in aminated solutions. By coating this polymer with polycationic properties such as polyethyleneimine (PEI) on the fabric, the T4D phage adsorption, which represents the virus filtration efficiency (VFE), can be more effectively increased by 15 times. By coating this polymer with polycationic properties such as polyethyleneimine (PEI) on the fabric, the adsorption of Staphylococcus aureus, which represents bacterial filtration efficiency (BFE), can be more effectively increased by 25 times. The use of such polymers with polycationic properties such as polyethyleneimine (PEI) can highly improve its affinity for bacteria and viruses in the air.

The aforementioned fabrics can be air-permeable substrates and can include fibrous substrates, which can be woven or non-woven materials. Examples of woven materials include natural and synthetic polymers such as cotton, cellulose, wool, polyolefins, polyesters, polyamides (such as nylon), rayon, polyacrylonitrile, cellulose acetate, polystyrene, polyethylene, and any other synthetic polymers that can be processed into fibers. Examples of nonwoven materials include polypropylene, polyethylene, polyester, nylon, PET and PLA.

In one embodiment, the aforementioned non-woven fabric used in the present invention may be in the form of a non-woven fabric sheet or gasket. Ideally, polyester nonwovens are used as the breathable substrate, as it has been found that the aminated coatings of polycationic polymers such as polyethyleneimine (PEI) described in this specification adhere better to polyester materials, and the aminated coatings of polycationic polymers such as polyethyleneimine (PEI) appear to be less likely to peel off or be rubbed off polyester substrates. Polyester fibers and fabrics therefrom are well known. The term "polyester" described in the present invention is a general term for fibers made by linking polymer monomers with ester groups. Polyester-based polyethylene terephthalate is generally used in the manufacture of woven fibers and non-woven fibers.

Known masks have an air-filtering middle layer, which is suitable for capturing and neutralizing viruses and bacteria. The middle layer is made of a melt-blown material that can capture viruses and bacteria with electrostatic attraction. When the melt-blown material encounters the water vapor exhaled by the user from the mouth, the electrostatic attraction will gradually disappear, causing the melt-blown material to lose most of the electrostatic attraction, causing the Bacterial Filtration Efficiency (BFE) and Virus Filtration Efficiency (VFE) of the mask to drop significantly after several hours of use.

In the present invention, the second layer 104 is a multi-functional air-permeable layer, which includes polycationic anti-virus and anti-bacterial air-permeable composite materials. One of its advantages is that when the ionic strength varies greatly, it can still substantially maintain stability in capturing and neutralizing viruses and bacteria. When the cellulose surface is treated with polymer species with polycationic properties such as polyethyleneimine (PEI), it can capture phages up to 15 times more efficiently. The affinity that exists between viruses and bacteria and polymer species with polycationic properties such as polyethyleneimine (PEI) is due to the strong electrostatic attraction between polymer species with polycationic properties such as polyethyleneimine (PEI) and negatively charged viruses, which increases with humidity and conductivity in the fabric structure. The PEI-coated non-woven fabric is used as a filter material for air purifiers in confined spaces (aircraft, ships, offices, hospitals), antiviral masks, surface cleaning wipes or protective clothing.

One of the advantages is reduced manufacturing costs. PEI has two physical structures. Linear PEI is solid at room temperature, and it is easy to coat on fabric structures, but it costs as much as US$1,000 per gram. Branched-chain PEI is liquid at room temperature and incompatible with fabric materials, but costs only $17.96 per kilogram.

By improving the industrial process and applying a suitable chemical carrier, PEI was successfully laminated on the surface of the fabric in a branched chain structure, and the cost of manufacturing polycationic anti-virus and anti-bacterial breathable composite materials was reduced by 99.998204%, making it commercially feasible to manufacture polycation-type anti-virus and anti-bacteria breathable composite materials.

In another embodiment of the present invention, the aforementioned polycationic antiviral and antibacterial gas-permeable composite materials of the second layer 104 are further improved with multi-arm polytelechelic compounds, such as oligomers, polymers and/or particles, which have high-density multifunctional cationic end groups and have strong affinity with the virus surface through the combined effects of electrostatic force, hydrogen bonding, van der Waals force and chain entanglement.

The aforementioned multi-armed poly-telechelic component can be directly, densely, uniformly and evenly spread on the hydrophilic surface of the target through electrostatic interaction, hydrogen bond interaction and/or ion complexation of some multifunctional functional cationic end groups.

When the polytelechelic component is coated on the material, it can be tightly, evenly and evenly spread on the surface of the material with or without the help of the amphiphilic coupling agent. The inclusion of the coupling agent allows the polytelechelic component to be closely linked to the reactive end groups of the polymeric component through electrostatic interaction, hydrogen bonding and/or ion complexation. When no coupling agent is contained, the polytelechelic component can be directly attached to the target surface through chemical bonds, ionic bonds, hydrogen bonds and/or van der Waals forces.

The polytelechelic compound structure of the present invention includes hyperbranched, star or brush oligomers and polymers, or oligomers and polymer-modified nanoparticles. On the other hand, the alkylated polycation groups can be evenly distributed on the surface of the material. The uniform and persistent distribution of the polycation groups leaves insufficient space for small-sized viruses and bacteria to attach and survive on the modified surface. The multifunctional cationic end groups can also lead to electrostatic forces, hydrogen bonding, ion complexation, van der Waals forces and/or chain entanglement with bacteria and viruses. Such a high-density, uniform and average distribution can further make constructive interference between the dipole-dipole force between the multifunctional cationic end groups and the protein structure in viruses and bacteria, and more effectively and efficiently capture and destroy viruses and bacteria.

In one embodiment, the number of arms of the aforementioned polytelechelic compound exceeds 14 arms. In one embodiment, the density of the aforementioned polyfunctional cationic end groups is greater than 1.37×10 ²² g ^-1 .

In one embodiment, a method of preparing a material having a multi-armed polytelechelic compound dispersed therein comprises the steps of: (a) dissolving (i) at least one cationic polymer; and (ii) ammonium polyphosphate (APP) in water to prepare an aqueous solution; (b) spraying the solution onto the material or immersing the material in the solution; and (c) removing water from the material. After removing the water, there should be 0.5 to 100 g/m ² of solids remaining on the fabric or fiber surface.

In another embodiment, the aqueous solution in step (a) further includes (iii) quaternary ammonium salt; and (iv) nonionic hydrophilic polymer.

In one embodiment, the aforementioned dissolving step is carried out at a temperature between 250°C and 350°C. In one embodiment, the aforementioned dissolving step is performed at a pressure between 5 Pa and 10 Pa. In one embodiment, the total mass fraction of nitrogen in the prepared aqueous solution is greater than 25 wt%. In another embodiment, the total mass fraction of nitrogen in the prepared aqueous solution is between 10 wt% and 35 wt%.

In one embodiment, the aforementioned cationic polymer is selected from the group consisting of branched/linear polyethyleneimine (PEI), chitosan and polylysine. In one embodiment, the aforementioned quaternary ammonium salt is selected from the group consisting of polydiallyldimethylammonium chloride (PDADMAC) and ethoxylated quaternary ammonium hydroxyethylcellulose (Quaternized Hydroxyethylcellulose ethoxylate). In one embodiment, the aforementioned nonionic hydrophilic polymer is selected from the group consisting of polyacrylamide (PAM), poly(N-isopropylacrylamide) and polyethylene glycol.

In one embodiment, the aforementioned aqueous solution includes 10 wt % to 80 wt % of the aforementioned at least one cationic polymer and 20 wt % to 90 wt % of the aforementioned ammonium polyphosphate. In another embodiment, the aforementioned aqueous solution comprises 6.5 parts of PEI, 3.0 parts of PDADMAC, 1.0 part of PAM, 0.5 parts of APP and 490 parts of water by weight.

Materials used

The multifunctional breathable layer comprises polycationic antiviral and antibacterial breathable composite materials, which are formed based on, including but not limited to, breathable substrates (such as woven, knitted or non-woven fabrics with hydrophilic properties), antiviral agents (such as polymers with polycationic properties such as polyethyleneimine (PEI), poly-L-lysine (PLL), diethylamineethyldextran (DEAE-dextran) and polyamidoamine (PAMAM) dendrimers), Antibacterial agents (eg silver nanowires) and/or binders (eg thermoplastic elastomers) are obtained by surface coating techniques with aqueous liquids. The adhesive is suitable for reducing the pore size of the air-permeable substrate so that the antiviral agent (eg: PEI) can be closely combined with the air-permeable substrate. thermoplastic elastomer

The term "polymer species having polycationic properties such as polyethyleneimine (PEI)" as used in this specification includes polymers having polyethyleneimine groups along their main chain, eg as pendant groups. A suitable group is a polyethyleneimine group. Fabrics coated with polymer species of polycationic character such as polyethyleneimine (PEI), which may be branched or linear. Generally speaking, the current application of the present invention is ideally branched, such as: branched polymers. In addition, the branched structure has relatively more amine groups for use, and the branched polymer is also more soluble, so it can be used in the preparation process described in this specification.

Polyethyleneimine (PEI) is a polymer consisting of repeating units consisting of amine groups and dicarbon aliphatic CH2CH2 spacers. Branched polyethyleneimines contain primary, secondary and tertiary amine groups compared to linear polyethyleneimines which contain all secondary amines. PEI is produced on an industrial scale, and most of the applications found for PEI are generally derived from its polycationic properties. Linear Polyethyleneimine (PEI)

Branched polyethyleneimines can be synthesized by ring-opening polymerization of aziridine, depending on the reaction conditions, different degrees of branching can be achieved. Linear polyethyleneimine can be obtained by post-modification of other polymers such as poly(2-oxazoline) or N-substituted aziridine. Linear polyethyleneimine is synthesized by hydrolysis of poly(2-ethyl-2-oxazoline) and sold as jetPEI. The current generation of in-vivo-jetPEI uses a custom-made poly(2-ethyl-2-oxazoline) polymer as a precursor. Branched Polyethyleneimine (PEI)

For example, the filter material can be combined with one or more surfactants, which can promote wetting of the filter material. It is known that pathogens such as viruses in the air can attach to small water droplets, so increasing the humidity of the filter material can make the pathogens more effectively contact the active materials on the filter material. In addition, surfactants are known to effectively disrupt the membranes of viruses and bacteria. Ideally a nonionic surfactant, since ionic surfactants tend to gel aminated coatings, especially polyethyleneimine. Select an ideal nonionic surfactant.

Generally speaking, high-loaded polymers with polycationic properties, such as polyethyleneimine (PEI), can achieve satisfactory high anti-pathogen effects on the substrate, but it is found that too high a load will hinder air from passing through the filter material. A balance should be struck between the two.

In order to achieve an appropriate amount of immobilized viruses in the air passing through the air filtration system 100, combined with an appropriate air permeability, if there is a polymer type with polycationic properties such as polyethyleneimine (PEI), plus any surfactant on any filter material substrate, the total loading range is ideally 20~50 g/m ² , more preferably 25~45 g/m ² .

The standard weight per square meter of substrate discussed in this specification can correspond to the total loading of any surfactant on any filter substrate if there is a polymer species with polycationic properties such as polyethyleneimine (PEI), generally 10~30 wt% (based on 100% of the weight of the substrate itself).

For example, the aforementioned filter material can contain one or more metal salts, such as salts selected from silver, zinc, iron, copper, tin and mixtures thereof. The salts can have antibacterial activity, which can be organic salts or inorganic salts such as inorganic acids, such as chlorides, nitrates or sulfates, wherein the metal salt of this type is zinc chloride.

For example, the aforementioned filter material may contain one or more antimicrobial compounds. Suitable examples of such compounds include quaternary ammonium compounds (such as: benzalkonium chloride, cetrimide), phenolic compounds (such as: triclosan, benzoic acid), biguanides (such as: chlorhexidine (chlorhexidine), alexidine (alexidine)) and mixtures thereof.

On the whole, the filter material ideally includes branched polyethyleneimine (PEI) and non-ionic surfactants in the proportion described in this manual, and deposits them on the non-woven polyester fiber substrate.

One particular type of filter material described above comprises a fibrous substrate (as previously described) on which an aminated coating, particularly PEI, is deposited. The filter material described in this specification can be produced by various methods, including the method of combining an air-permeable substrate with an aminated coating, especially PEI.

In one approach, PEI may be deposited on a gas permeable substrate as a full or partial film on the substrate (eg, on fibers). In another method, PEI may be combined with materials in air-permeable substrates (eg, fibers). This method can be done during the process of forming fibers, such as: non-woven materials formed by spunbonding and meltblowing.

In another method, the filter material of the present invention can be produced by the conventional electrospinning process, and the polymer forms a charged liquid column in solution or melted form and deposits on the fibers of the grounded collecting plate.

The aforementioned hydrophobic air-permeable layer includes hydrophobic air-permeable composite materials, which are formed based on, including but not limited to, air-permeable substrates (for example: woven, knitted or non-woven fabrics with hydrophobic properties), adhesives with hydrophobic properties/hydrophobic adhesives (for example: synthetic polymers with hydrophobic properties, such as silicon-containing polymers, fluorine-containing polymers, and polyolefins) and/or components that have photocatalytic reactions/components that have photocatalytic reactions (such as: titanium dioxide nanoparticles), and by using liquid surface coating technology And get.

The aforementioned air-permeable substrate may include a fibrous substrate, which may be a woven or non-woven material. Examples of woven materials include natural and synthetic polymers such as cotton, cellulose, wool, polyolefins, polyesters, polyamides (eg nylon), rayon, polyacrylonitrile, cellulose acetate, polystyrene, polyethylene, and any other synthetic polymer that can be processed into fibers. Examples of nonwoven materials include polypropylene, polyethylene, polyester, nylon, PET and PLA. Ideally for the present invention is a nonwoven, this material may be in the form of a nonwoven sheet or gasket. Polyester nonwovens are ideal breathable substrates as aminated coatings, particularly the polyethyleneimines (PEI) described in this specification, have been found to adhere better to polyester materials and the aminated coatings, particularly the polyethyleneimines (PEI) described in this specification, appear to be less prone to peeling or being rubbed off polyester substrates. Polyester fibers and the fabrics therefrom are well known. The term "polyester" described in the present invention is a general term for fibers made by linking polymer monomers with ester groups. Polyester-based polyethylene terephthalate is generally used in the manufacture of woven fibers and non-woven fibers.

The grade of fibrous substrate that can be used can depend on the practice to achieve proper air flow, and its density can be known in the mask art to provide a comfortable mask weight.

Typical nonwoven polypropylene materials found to be suitable for use in the present invention have weights of 10-40 g/ ^m2 , although weights of other suitable materials can be determined empirically.

Typical nonwoven polyester materials found to be suitable for use in the present invention have a weight of 10 to 200 g/m ² , although materials near the upper end of this weight range may be too heavy for use in face masks. For example, the ideal weight of the material is 20~200 g/m ² , eg about 60 g/m ² . This material is commercially available and other suitable materials can be determined empirically.

The breathable substrate can be replaced by other types such as open foam. For example: polyurethane foam is also used in air filters, such as filtering air nasal plugs. It has been found that especially aminated coatings of polyethyleneimine (PEI) can effectively capture and neutralize airborne viruses and bacteria passing through the material. Without being limited to a specific theory of action, it is generally believed that once the virus touches the surface of the substrate, it will interact with the polymer and be captured and fixed by polyethyleneimine (PEI), thereby inactivating and neutralizing the virus. It is generally believed that the filter material of the present invention can resist viruses that cause colds, influenza, SARS, RSV, bird flu, COVID-19 and serotype mutants thereof in this type.

Manufacturing method

Two breathable substrates with suitable thickness, porosity, and surface wettability are selected for making the multifunctional breathable layer (MAL), the second layer 104, and the hydrophobic breathable layers HALs, the first layer 102 and the third layer 106, respectively.

In FIG. 15A, a process example 1500A is used to fabricate one or more multifunctional breathable layers (MALs). In some examples, process 1500A is applied to cleaning devices. As shown in FIG. 15A , the step 1501 of the process 1500A includes dipping and stirring the nonwoven fabric in a solvent containing a carrier in a container for a period of time ranging from 20 seconds to 180 seconds, ideally 60 seconds, and at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and the nonwoven fabric. For example, the carrier is carboxymethyl. Carboxymethyl

The aforementioned carboxymethyl group is suitable for combining with the hydroxyl group of the glucopyranose monomer forming the cellulose skeleton, such as carboxymethyl cellulose (CMC), cellulose gum, sodium carboxymethyl cellulose, filler or SE filler, and its concentration ranges from 0.1% to 2%, ideally 0.5%.

In step 1502, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

In step 1503, the non-woven fabric is dipped and stirred in a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI), and its concentration ranges from 0.1% to 10%, ideally 2%, and lasts for a period of time, the time range falls from 20 seconds to 180 seconds, ideally 60 seconds, and is carried out at room temperature to optimize the affinity between the virus and/or bacteria and the non-woven fabric (optimize the capture and blocking of viruses and/or bacteria).

In step 1504, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

Alternatively, as shown in FIG. 15B , in step 1505 , the process 1500B includes dipping and stirring the nonwoven fabric in a solvent containing another carrier for a period of time, the time ranges from 20 seconds to 180 seconds, ideally 60 seconds, and at room temperature to optimize the affinity between the polymer with polycationic properties such as polyethyleneimine (PEI) and the nonwoven fabric. The carrier is alginic acid. Alginic acid

The aforementioned solvents include straight-chain copolymers, which contain homopolymeric blocks of (1-4)-linked β-D-mannuronic acid (M) and its C-5 epiisomer α-L-guluronic acid (G) residues, which are covalently linked in different sequences or blocks, and its monomers may be homopolymeric blocks of continuous G-residues (G-blocks), homopolymeric blocks of continuous M-residues (M-blocks), or blocks in which M-residues and G-residues alternately occur ( MG-block) such as alginic acid, alginate or alginate, its concentration ranges from 0.1% to 2%, ideally 0.5%.

In step 1506, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

In step 1507, the non-woven fabric is soaked and stirred in a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI), the concentration ranges from 0.1% to 10%, ideally 2%, and lasts for a period of time, the time range falls from 20 seconds to 180 seconds, ideally 60 seconds, and is performed at room temperature to optimize the affinity between the virus and/or bacteria and the non-woven fabric (optimize the capture and blocking of viruses and/or bacteria).

In step 1508, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

By way of example only, an alternate process 1600A for fabricating one or more multifunctional air-permeable layers (MALs) is illustrated in FIG. 16A. In some examples, process 1700A is applied to spraying machines. As shown in FIG. 16A , in step 1601, the process 1600A includes spraying a solvent containing carboxymethyl (-CH2-COOH) on the nonwoven fabric for a period of time, the time ranges from 20 seconds to 180 seconds, ideally 60 seconds, and at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and the nonwoven fabric. The carboxymethyl group is suitable for combining with the hydroxyl group of the glucopyranose monomer forming the cellulose backbone, such as carboxymethyl cellulose (CMC), hexamin, sodium carboxymethyl cellulose, filler or SE filler, and its concentration ranges from 0.1% to 2%, ideally 0.5%.

In step 1602, spray a polymer with polycationic properties such as polyethyleneimine (PEI) solvent on the non-woven fabric, the concentration ranges from 0.1% to 10%, ideally 2%, and lasts for a period of time, the time range falls from 20 seconds to 180 seconds, ideally 60 seconds, and it is carried out at room temperature to optimize the affinity between the virus and/or bacteria and the non-woven fabric (optimize the capture and blocking of viruses and/or bacteria).

In step 1603, dry the non-woven fabric at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, ideally 10 minutes.

Alternatively, as shown in FIG. 16B, in step 1604, the process 1600B includes spraying a solvent containing another carrier on the nonwoven fabric for a period of time ranging from 20 seconds to 180 seconds, ideally 60 seconds, and at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and the nonwoven fabric. The solvent is the same as in Figure 16B, and the carrier is alginic acid, the concentration of which falls within the range of 0.1% to 2%, ideally 0.5%.

In step 1605, spray a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI) on the non-woven fabric. The concentration ranges from 0.1% to 10%, ideally 2%, and the time range falls from 20 seconds to 180 seconds, ideally 60 seconds. It is carried out at room temperature to optimize the affinity between the virus and/or bacteria and the non-woven fabric (optimize the capture and blocking of viruses and/or bacteria).

In step 1606, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

By way of example only, an alternate process 1700A for fabricating one or more multifunctional breathable layers (MALs) is illustrated in FIG. 17A. In some examples, process 1800A is applied to a printing machine. As shown in Figure 17A, in step 1701, the process 1700A includes printing a solvent containing carboxymethyl (-CH2-COOH) on the non-woven fabric for a period of time, the time range is 20 seconds to 180 seconds, ideally 60 seconds, and it is carried out at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and the non-woven fabric. The carboxymethyl group is suitable for combining with the hydroxyl group of the glucopyranose monomer forming the cellulose backbone, such as carboxymethyl cellulose (CMC), hexamin, sodium carboxymethyl cellulose, filler or SE filler, and its concentration ranges from 0.1% to 2%, ideally 0.5%.

In step 1702, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

In step 1703, the non-woven fabric is soaked and stirred in a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI), and its concentration ranges from 0.1% to 10%, ideally 2%, and lasts for a period of time, the time range falls from 20 seconds to 180 seconds, ideally 60 seconds, and is carried out at room temperature to optimize the affinity between the virus and/or bacteria and the non-woven fabric (optimize the capture and blocking of viruses and/or bacteria).

In step 1704, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

Alternatively as shown in FIG. 17B , in step 1705 , process 1700B includes printing a solvent containing another carrier on the nonwoven fabric for a period of time ranging from 20 seconds to 180 seconds, ideally 60 seconds, and at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and the nonwoven fabric. The solvent is the same as in Figure 16B, and the carrier is alginic acid, the concentration of which falls within the range of 0.1% to 2%, ideally 0.5%.

In step 1706, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

In step 1707, the non-woven fabric is soaked and stirred in a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI), and its concentration ranges from 0.1% to 10%, ideally 2%, and lasts for a period of time, the time range falls from 20 seconds to 180 seconds, ideally 60 seconds, and is carried out at room temperature to optimize the affinity between the virus and/or bacteria and the non-woven fabric (optimize the capture and blocking of viruses and/or bacteria).

In step 1708, the non-woven fabric is dried at a temperature ranging from 40°C to 90°C, ideally at 70°C, for a period of time ranging from 2 minutes to 12 minutes, preferably 10 minutes.

Hydrophobic air-permeable layers (HALs) can be prepared by a conventional process. For example, conventional processes include forming a web and curing the web. The forming webs include carding, air-laid, wet-laid, spunbonded, meltblown, and electrospinning.

The air filtration system 100 is formed by sandwiching one MAL (second layer) between two HALs (first layer and third layer) by conventional lamination methods such as ultrasonic welding, heat-press lamination, and cold-press lamination.

The invention provides an air filtering system. In one embodiment, the air filtration system comprises: one or more first layers; one or more second layers; and one or more third layers; wherein the one or more second layers are located between the one or more first layers and the one or more third layers, and each of the one or more first layers and each of the one or more third layers comprises a hydrophobic gas-permeable composite material, and each of the one or more second layers comprises a polycationic anti-viral and anti-bacterial gas-permeable composite material.

In one embodiment, the aforementioned one or more second layers comprise: ( ^a ) a hollow hydrophilic fiber substrate; and (b) a coating obtained by drying a solution comprising: (i) a polycationic polymer; (ii) a ^quaternary ammonium salt; ⁽ iii) a nonionic hydrophilic polymer; 25 wt%.

In one embodiment, the aforementioned air filtration system comprises one or more of the following: (a) the polycationic polymer is selected from the group consisting of branched/linear polyethyleneimine, chitosan, poly-L-lysine and poly-D-lysine; (b) the quaternary ammonium salt is polydiallyldimethylammonium chloride or ethoxylated quaternary ammonium hydroxyethyl cellulose (QuaternizedHydroxyethylcelluloseethoxylate); or (c) the non- The ionic hydrophilic polymer is selected from the group consisting of polyacrylamide, poly(N-isopropylacrylamide) and polyethylene glycol.

In one embodiment, the aforementioned solution is a 2 wt% solution comprising 31.8% polyethyleneimine, 8.7% polydiallyldimethylammonium chloride, 19.7% polyacrylamide and 13.1% ammonium polyphosphate.

In one embodiment, the mass fraction of the aforementioned nitrogen is 26.56 wt%.

In one embodiment, the aforementioned polycationic polymer is a multi-armed polytelechelic polymer, comprising >14 arms.

In one embodiment, the aforementioned hollow hydrophilic fiber matrix includes cotton or cellulose.

In one embodiment, the one or more second layers have a pressure drop of 0.5 to 10 Pa at a physiological respiratory flow rate and have a virus filtration efficiency (VFE) of >99.9%.

In one embodiment, the aforementioned polycationic anti-viral and anti-bacterial air-permeable composite material includes an air-permeable substrate, an anti-viral agent, an anti-bacterial agent and a binder.

In one embodiment, the aforementioned antiviral agent comprises a polymer with polycationic properties.

In one embodiment, the aforementioned polymers with polycationic properties include polyethyleneimine (PEI), poly-L-lysine (PLL), diethylamineethyldextran (DEAE-dextran) or polyamidoamine (PAMAM) dendrimers.

In one embodiment, the aforementioned air-permeable substrate includes non-woven fabric or cellulose non-woven fabric.

In one embodiment, the aforementioned binder includes thermoplastic elastomer.

In one embodiment, the aforementioned antibacterial agent includes silver nanowires.

In one embodiment, the aforementioned hydrophobic and gas-permeable composite material includes a gas-permeable base material, a hydrophobic binder, and a photocatalyst reaction component.

In one embodiment, the aforementioned hydrophobic binder includes a synthetic polymer with hydrophobic properties.

In one embodiment, the aforementioned photocatalyst reaction components include titanium dioxide nanoparticles.

The present invention also provides an antiviral mask. In one embodiment, the antiviral mask includes: (a) the air filter system described in the embodiment of the present invention; (b) a pair of straps; and (c) a wire; wherein, the pair of straps are respectively arranged on both sides of the air filter system, and the wire is arranged above the inside of the air filter system.

The present invention further provides a coating obtained by drying the solution. In one embodiment, the solution comprises: (a) polycationic polymer; (b) quaternary ammonium salt; (c) non-ionic hydrophilic polymer; and (d) ammonium polyphosphate; wherein the coating contains >1.37×10 ²² g ^-1 cationic groups, dry mass >2 g/m ² and the total mass fraction of nitrogen >25 wt%.

In one embodiment, the aforementioned coating comprises one or more of the following: (a) the polycationic polymer is selected from the group consisting of branched/linear polyethyleneimine, chitosan, poly-L-lysine and poly-D-lysine; (b) the quaternary ammonium salt is polydiallyldimethylammonium chloride or ethoxylated quaternary ammonium hydroxyethylcellulose (Quaternized Hydroxyethylcellulose ethoxylate); or (c) the nonionic The type hydrophilic polymer is selected from the group consisting of polyacrylamide, poly(N-isopropylacrylamide) and polyethylene glycol.

In one embodiment, the aforementioned solution is a 2 wt% solution comprising 31.8% polyethyleneimine, 8.7% polydiallyldimethylammonium chloride, 19.7% polyacrylamide and 13.1% ammonium polyphosphate.

In one embodiment, the mass fraction of nitrogen in the aforementioned paint is 26.56 wt%.

In one embodiment, the aforementioned polycationic polymer is a multi-armed polytelechelic polymer, comprising >14 arms.

The present invention also provides an object to be plated comprising: (a) a substrate; and (b) the coating as described in the embodiment of the present invention.

In one embodiment, the aforementioned coating is plated on the hydrophobic surface of the substrate that has been treated with an amphiphilic coupling agent. [Example]

In order to obtain the results, results and findings described above, many tests were carried out. For example, performing an air permeability test, a virus filtration efficiency test, and a bacteria filtration efficiency test, all three tests are known. Figures 4 to 14 illustrate the different results and findings of these three tests.

Example 1: Air permeability test

Refer to Figure 4 to illustrate the air permeability pressure measurement of different fabric materials with or without coating. Based on the test results, the cellulose woven/woven fabric coated with HALs and the cellulose non-woven/non-woven fabric coated with HALs are compared with traditional melt blown materials. Compared with the former, the former has higher air permeability.

Embodiment 2: Virus filtration efficiency test

Referring to Figures 5-12, the Virus Filtration Efficiency (VFE) test was carried out on fabric materials with or without coating. The results show that the fabric material with coating shows that its VFE is 15 times higher than that of fabric material without coating, and the VFE of fabric material with coating reaches 99.999%.

Cellulose woven fabric coated with HALs According to "Polyethyleneimine surface layer for enhanced virus immobilization on cellulose, Ghania Tiliket, Guy Ladam, Quang Trong Nguyen, Laurent Lebrun, 2016", it shows that the FTIR spectrum of the regenerated cellulose substrate coated with HALs is compared with the FTIR spectrum of the hydrolyzed cellulose surface and the KWL of the pure cellulose non-woven fabric. , which proves that the fiber fabric is effectively modified into cellulose (Figure 5A). In addition, the unmodified surface of the substrate maintains the spectral characteristics of the fiber fabric with a strong band at 1700 cm ^-1 consistent with the ester C=O group (Figure 5B). The effect of hydrolysis treatment on HALs-coated cellulose fabrics was also examined by water contact angle measurements. The water contact angle decreased significantly from 71° (± 6°) before hydrolysis to 48° (± 4°) after hydrolysis, consistent with the conversion of HALs-coated cellulose fabrics to more hydrophilic cellulose. As can be seen from the AFM data, the structure of the cellulose fabric does not change when it is transformed (Fig. 6). Both natural and modified paints have a flat and uniform main shape, but they have the disadvantage of being scattered. The disadvantage is that holes may be formed due to a small part of the material falling off, and the material needs to be redeposited on the paint. During the spin-coating, washing and drying process, nano-bubbles may be entrained, which may cause the coating to fall off at the position where the coating has weak adhesion to gold. The presence of holes allows the coating thickness (30±2 nm) to be measured. Hypothetically, the effect of the pores on the further measurement of PEI adsorption via QCM-D can be neglected, since the proportion of uncoated gold surface is very small (approximately 5%).

Adsorption of PEI on cellulose substrate The initial pH value of PEI 4.4% w/v solution is 11. When the pH value drops, the amine nitrogen atoms of PEI are protonated and the ability to support immobilization increases. Previous experiments with virus filtration showed better virus retention at pH=6. At pH = 6, the proportion of protonated amine groups was determined to be 75% ± 5. Therefore, the measurement of PEI adsorption was carried out at pH=6, and the adsorption of PEI on regenerated cellulose was studied by QCM-D. Three experiments were performed and averaged. Figure 7A shows the normalized frequency as a function of time after successive injections of PEI solutions at increasing concentrations. A decrease in Δf _n /n can be observed after each injection (after taking into account rinsing with NaCl 0.2 M reference medium), indicating that the mass absorbed by the cellulose fabric is due to the adsorption of PEI. As previously proposed by Swerin and Ahola et al., when highly charged cationic polyelectrolytes are layered on hydrolyzed cellulose (at a low salt concentration), the absorption of PEI (pKa = 7.7 and pKa = 9.7; cations at pH = 6) may be accompanied by the release of water from the cellulose substrate.

However, the QCM-D technique cannot distinguish between the two effects, and the normalized frequencies before and after washing are almost overlapping, indicating that the PEI-treated film has a rigid structure. The very small increase in the dissipation factor (measured in the reference medium of NaCl 0.2 M) (Fig. 7B) confirms the rigidity of the film (ΔDn = 8×10 ^-7 for the maximum concentration of PEI (1% w/v)), therefore, it can be calculated using the Sauerbrey equation. The first step of adsorption is to use 0.1% w/v PEI solution to obtain about 100 ng cm ^-2 of PEI adsorbed on the cellulose film (Fig. 8). With each subsequent injection of PEI (concentrations of 0.4, 0.7 and 1% w/v), the additional adsorption of PEI on the cellulose substrate was limited. In this way, a 10-fold increase in PEI concentration only resulted in a 1.4-fold increase in the mass of adsorption. The results indicated that high concentrations of PEI may not be required to cover the regenerated cellulose surface.

Effect of ionic strength on the structure of PEI layer deposited on cellulose substrate The stability of the adsorption layer was tested by studying the effect of ionic strength on the structure of adsorbed PEI by QCM-D. The regenerated cellulose fabric was first coated with PEI (PEI with a concentration of 0.1% w/v in 0.2M NaCl), and then put into NaCl solutions with increasing concentrations (0.05 M, 0.5 M, 1 M). The NaCl in the intermediate washing step was 0.2 M. The corresponding changes in the normalized frequency Δfn/n and the dissipation factor ΔDn were recorded during the entire experiment. As a control experiment, the same experiment was carried out with natural regenerated cellulose film (without adsorbed PEI) to understand the combined effects of (i) changes in solution viscosity and (ii) potential structural changes of the cellulose substrate on the QCM-D parameters. Then, according to the results of the control experiment, the QCM-D parameters obtained by measuring PEI were calibrated (via subtraction) to analyze the influence of the ionic strength on the structure of the PEI adsorption layer itself as shown in Figure 9. After the PEI injection and flushing steps, the absorbed mass was detected as indicated by the drop in resonance frequency. Decreasing the NaCl concentration to 0.05 M resulted in water uptake, as indicated by the decrease in the resonance frequency, and similar water release when the NaCl concentration was subsequently increased to 0.5 M or 1 M. This swelling and deswelling behavior is expected based on the well-established electrostatic shielding effect, which enhances or weakens intra-chain and inter-chain electrostatic repulsion of polyelectrolytes at low or high ionic strength, leading to chain elongation or chain curling, respectively. The dissipation factor decreased at high NaCl concentrations (0.5 M and 1 M), indicating that the hardening of the PEI layer was consistent with the deswelling effect. In contrast, no significant increase in the dissipation factor was measured in 0.05 M NaCl solution. If the underlying cellulose could not be accurately reproduced between the PEI-containing experiment and the control experiment, it could be due to slight deviations in calibrating the QCM-D parameters.

After replacing 0.05 M NaCl solution with 0.2 M NaCl solution, a slight increase in the dissipation factor was measured, confirming that the PEI layer would swell when washed in 0.05 M NaCl. The swelling effect of the PEI layer after treatment with lower ionic strength is irreversible, while the deswelling effect observed with higher ionic strength treatment is reversible, and after washing with 0.2 M NaCl, Δfn/n and ΔDn return to the previous values. By reducing the electrostatic shielding effect, thereby increasing the mutual repulsion between PEI chains and the mutual attraction between PEI chains and the underlying cellulose, low ionic strength treatment may enable the PEI chains on the surface of the cellulose film to reorganize to form a more firmly bonded PEI layer.

Adsorption of T4D bacteriophages on PEI- treated cellulose substrates First, AFM observations were carried out on silicon substrates in contact with T4D phage suspensions to confirm that the virus was completely adsorbed on the substrate through the filtration process, rather than just adsorbing residues such as proteins. The AFM images included in Figure 10 show the presence of many intact phages consisting of heads and tails with a size of 120 nm, some phages appear ruptured and the presence of aggregates (protein or non-structural virus) is also detected.

Next, QCM-D was used to compare the adsorption of T4D phage to natural and PEI-treated cellulose substrates. The concentration of PEI used for deposition was 1% w/v, which was consistent with the preparation method of PEI functional filters for antiviral masks. This concentration is higher than the recommended minimum concentration of 0.1% w/v for PEI partially adsorbed on cellulose fabric, since the filter is a porous non-woven material with a larger surface than the planar support. Figure 11 shows the corresponding changes in the QCM-D parameters. After the phage adsorption and washing steps, the frequency curves did not completely overlap, indicating the viscoelastic properties of the phage layer, confirmed by the increased dissipation factor, especially for PEI-treated cellulose (without PEI treatment Δ Dn = 4x10 ^-6 ; with PEI treatment Δ Dn = 27x10 ^-6 ). Therefore, the adsorption amount cannot be obtained from the frequency shift using the Sauerbrey linear equation, so the Q-Tools software (Q-Sense) was used to analyze the raw data within the framework of the Voigt viscoelastic model.

Figure 12 shows the evolution of the thickness derived from the data model for the adsorption of phage layers on non-PEI-treated and PEI-treated cellulose. The thickness of the PEI layer on the cellulose film (after taking into account the rinsing step) was approximately 3.5 nm. When the phage layer was deposited on PEI-treated cellulose substrates, it was 15 times thicker (93 nm) than that deposited on untreated cellulose substrates, demonstrating the strong affinity between phage and PEI-treated regenerated cellulose, which can be mainly explained by the strong electrostatic interaction between positively charged PEI and negatively charged viruses. For example, Anany et al. have prepared active membranes against E. coli and Listeria by immobilizing the head of T4 phage on a positively charged modified cellulose membrane. Li et al. also disclosed that T4 phage can be bound to cellulose by protein to prepare antibacterial paper. Adsorption of polyelectrolytes on charged surfaces leads to overcompensation of surface charge. Thus, when polycationic PEI chains are adsorbed on cellulose, the surface becomes positively charged and promotes electrostatic attraction to negatively charged sites on other materials. For example, PEI-treated cellulose microporous membrane captures glucose oxidase, amylase or heparin to form a highly active enzyme membrane. PEI is also currently used to bind RNA or DNA to adenovirus particles via electrostatic interactions.

In addition, the flexibility of PEI chains promotes chain folding, thereby optimizing local interactions on the virus surface, so PEI chains with large charge density and great chain extension length provide the best conditions for capturing viruses.

Embodiment 3: Virus filtration efficiency test Referring to Figures 13-14, Bacterial Filtration Efficiency (BFE) tests were carried out on fabric materials with and without paint. The results show that the bacterial filtration efficiency (BFE) of the coated fabric material is 25 times that of the uncoated fabric material, reaching 99.9703%.

For example, Staphylococcus aureus bioaerosol is used to measure the bacterial filtration efficiency (BFE) of medical mask materials, and the ratio of upstream attacking bacteria to downstream residual bacteria concentration is used to determine the filtration efficiency of medical mask materials.

By spraying 2250 Staphylococcus aureus with bioaerosol on the analyte, and measuring the number of bacteria, the BFE of different analytes can be obtained by comparing the number of bacteria.

Figure 13 shows that the BFE of cellulosic fabric with 2% PEI is 25 times higher than that of meltblown material and further demonstrates the efficiency of PEI on BFE.

Figure 14 shows the actual bacterial counts of cellulose fabrics with 2% PEI.

Example 4: Example of filtered air for use with an antiviral mask FIG. 3 shows an example of an antiviral mask with the air filtration system of FIG. 1 according to various embodiments of the present invention. In one embodiment, the face mask 300 includes an air filtration system/air filter material 302/100, a pair of straps 304 and wires 306. In this example, the straps 304 are made of elastomer such as rubber, and are arranged on both sides of the air filter system/air filter material 302 to support the mask 300 on the user's ears. The wire 306 is disposed above the inside of the air filter system/air filter 302, and the wire 306 is deformable to enhance the sealing of the mask along the user's nose and chin. The antiviral mask 300 further includes at least three pleats 308 in the horizontal direction of the air filter system/air filter material 302 to enhance the seal of the mask along the user's nose and lower chin. The shape of the air filter system/air filter material 302 is hemispherical, and the middle part of the filter 302 is concave.

The shape and structure of the antiviral mask 300 shows that it has a high seal with the user's face and facilitates the user's breathing.

The use of the air filter system/air filter material 302 is not limited here. In one example, the air filter system/air filter material 302 may be used for an air purifier or air conditioner. In another example, the air filtration system/media 302 may be used in a protective helmet or the like.

Example 5: Results of Coating Polytelelechelic Compound Materials

Impact on the virus

In order to test the affinity and antiviral effect of materials coated with polytelechelic compounds to viruses, other materials commonly used in laboratories or in the manufacture of face masks were used for testing. The following five different materials were tested: toilet paper used in the laboratory, filter material of FFP2 standard, sponge of FFP2 standard, needle material coated with polytelechelic compound and paper coated with polytelechelic compound.

A 2.5 x 2.5 cm piece of material was taken from each material and placed into individual 2ml Eppendorf tubes, and 200 µl of buffer solution containing about 50,000 PFU of HCoV-229E virus was added to each tube, each tube was incubated for 5 minutes, and then centrifuged to remove the buffer solution from the test material. The test material was removed from the tube and RT-qPCR was used to measure the residual virus concentration in the buffer solution. The same experiment was repeated, the incubation time was 60 minutes, and two groups of experiments were repeated using Coxsackievirus B6 instead of HCov-229E, and the experimental method is shown in FIG. 23 .

As shown in Figures 24A and 24B, the virus concentrations of HCoV-229E and Coxsackievirus B6 were higher in toilet paper, FFP2 filter material and FFP2 sponge. In each case, no matter whether the test material was incubated in the tube for 5 or 60 minutes, the concentration of the tested virus remaining in the buffer solution was reduced by more than half of the original concentration. This means that the affinity between toilet paper, FFP2 filter material and FFP2 sponge material and the test virus is low. On the contrary, for the water card clothing and paper treated with polytelechelic material, the virus concentration remaining in the buffer solution is very low. After incubation and centrifugation, only less than or equal to 10 virus copies remained in the buffer solution, so it can be inferred that both tested virus strains have strong affinity to the polytelechelic compound of the material.

Virus Filtration Efficiency ( VFE ) Test A further test was performed to determine the filtration efficiency of the polytelechelic compound coated textile material by comparing the control virus count upstream of the test article with the virus count downstream. The bacteriophage ΦΧ174 suspension was atomized with a nebulizer and delivered to the test object with a constant flow rate and a fixed air pressure. The test object was a white non-woven fabric coated with a polytelechelic compound. The challenge transmission object was maintained at 1.1~3.3×10 ⁶ spot forming units (PFU), and its average particle size (MPS) was 3.0±0.3 μm. The aerosol droplets were collected by an Anderson six-stage bioaerosol sampler. The results are shown in Table 1 below.

[Table 1] Results of antibacterial ability against Staphylococcus aureus Test object number VFE percentage (%) 1 >99.9 2 >99.9 3 >99.9 4 >99.9 5 >99.9

Using a test area of about 40 cm2, with the condition parameters of VFE flow rate of 28.3 liters/min, relative humidity of 85±5% and 21±5 °C for at least 4 hours, the results of each VFE test percentage in the 5 repeated experiments were more than 99.9%. Because no plaque was detected on the Anderson sampling plate of all test objects, all phages were captured under the fast airflow, indicating that the polytelechelic compound has a high affinity for the virus.

Effect on Bacteria Two samples of white fabric coated with polytelechelic compound were tested for antibacterial ability. Inoculate 1 ml of Staphylococcus aureus inoculum with a concentration of 1×10 ⁶ CFU/ml to 3×10 ⁶ CFU/ml onto the agar culture plate, wherein each sample is placed on the surface of the agar culture plate and pressed with a 200 g stainless steel weight for 60±5 seconds to transfer the microorganisms. Shake the bacteria with protein water before incubating one sample and after incubating the other. The results of the number of bacteria for each sample are shown in Table 2 below. Based on the results obtained, the samples showed effective antibacterial properties during the transfer phase of the experiment, killing Staphylococcus aureus.

[Table 2] Results of antibacterial ability against Staphylococcus aureus sample condition Bacteria count (CFU per sample) 1 shaking before incubation 0 2 shake after incubation 0

Under the same test conditions and methods, further experiments were carried out on 3 different types of materials coated with polytelechelic compounds: 100% cotton, 65% polyester + 35% cotton and 92% polyester + 8% spandex twill. Each material was tested without washing and after washing 60 times, the results are shown in Table 3:

[Table 3] The results of the antibacterial ability of different materials against Staphylococcus aureus sample condition Bacteria count (CFU per sample) Antibacterial activity value 100% cotton shaking before incubation 4 5.93 shake after incubation 1 100% cotton after 60 washes shaking before incubation 13 3.75 shake after incubation 494 65% polyester + 35% cotton shaking before incubation 11 6.37 shake after incubation 1 65% polyester + 35% cotton after 60 washes shaking before incubation 11 2.81 shake after incubation 3400 92% polyester + 8% spandex twill shaking before incubation 10 6.33 shake after incubation 1 92% polyester + 8% spandex twill after 60 washes shaking before incubation 12 4.00 shake after incubation 244

According to the literature records of Wiegand et al. (Wiegand C, Heinze T, Hipler UC. (2009) Comparative in vitro study on cytotoxicity, antimicrobial activity, and binding capacity for pathophysiological factors in chronic wounds of alginate and silver-containing alginate. Wound Repair Regen., 1 7, 511-521.), the antimicrobial activity value below 0.5 represents no antibacterial activity, the activity value between 0.5 and 1 represents slight antibacterial activity, the activity value greater than 1 and less than or equal to 3 represents significant antibacterial activity and the logarithm of the activity value reduction greater than 3 represents strong antibacterial activity. The experimental results showed that even after 60 washes, almost all samples showed strong antibacterial activity.

The present invention records different exemplary embodiments. These examples are used as a reference rather than limiting the present invention. The purpose is to provide a description of the wider application of the disclosed technology. Various changes and equivalent substitutions can be made without departing from the true spirit and scope of the various embodiments of the present invention. In addition, various modifications may be made to adapt a particular situation, material, constituent substance, process, process act or step to the purpose, spirit or scope of the various embodiments. In addition, those skilled in the art should understand that the individual changes described and recorded in the present invention have discrete elements and features, which can be easily separated from other embodiments and combined with any feature in other embodiments without departing from the spirit and scope of various embodiments of the present invention.

100: Air Filtration System 102: first floor 104: second floor 106: third layer 300: mask 302: Air filter material 304: Lace 306: wire 308: pleats

[FIG. 1] A cross-sectional view showing an air filter system according to various embodiments of the present invention. [FIG. 2] shows examples of silver nanowires according to various embodiments of the present invention. [FIG. 3] shows an example of a mask with the air filter system shown in FIG. 1 according to various embodiments of the present invention. [Figure 4] shows the air permeability pressure difference (KPasm ^-1 ) of different fabric materials according to various embodiments of the present invention in a graph, SNS refers to PET-1 fabric coated with hydrophobic air-permeable layer (HALs); VNV refers to PET-2 fabric coated with HALs; RN refers to RN cellulose nonwoven fabric coated with HALs; RS refers to RS cellulose nonwoven fabric coated with HALs; RV refers to RV cellulose nonwoven fabric coated with HALs; ltblown-I refers to the unused melt-blown fabric coated with HALs; Meltblown-II refers to the used melt-blown fabric coated with HALs. [Fig. 5] Figs. 5A-5B represent the virus filtration efficiency according to various embodiments of the present invention in a graph; in Fig. 5A, the dotted line shows the FTIR spectrum of the hydrolyzed polycationic anti-viral and anti-bacterial air-permeable composite material, and the solid line shows the spectrum of the pure non-woven fabric KWL; Fig. 5B shows the FTIR spectrum of the polycationic anti-viral and anti-bacterial air-permeable composite material. [Fig. 6] Fig. 6 shows atomic force microscope (AFM) images of polycationic antiviral and antibacterial gas-permeable composite materials according to various embodiments of the present invention; Fig. 6 (a) shows the composite material and cellulose, and Fig. 6 (b) shows the composite material layer (left: 20 x 20 μm, right: 5 x 5 μm), and the topographical image shows that the brightness increases with height. [FIG. 7] FIGS. 7A~7B are progressive graphs showing the (a) normalized frequency change fn / n and (b) loss factor change Dn of the third, fifth and seventh overtones during the adsorption of polyethyleneimine (PEI) on the regenerated fabric layer with increasing concentration according to various embodiments of the present invention. [Fig. 8] Fig. 8 graphically represents the hydration adsorption mass of PEI on cellulose according to various embodiments of the present invention as a function of PEI concentration, which is calculated from QCM-D data using the Sauerbrey equation, wherein the coefficient of determination has a value of 0.999. [FIG. 9] FIG. 9 graphically represents (a) the change in normalized frequency fn / n and (b) the change in loss factor Dn of the third, fifth, and seventh overtones in the rinsing steps performed with different NaCl solution concentrations during the deposition of PEI onto fabrics and subsequent processes according to various embodiments of the present invention. [Fig. 10] Fig. 10 shows AFM images of bacteriophage T4 deposited on a silicon substrate (5×5 μm) in a suspension according to various embodiments of the present invention, and the suspension was further used for immobilization testing on a QCM-D sensor coated with fabric. [FIG. 11] FIG. 11 graphically represents the variation fn / n of the normalized frequencies of the third, fifth and seventh harmonics and the difference of the loss factor variation Dn during the deposition of bacteriophage T4 on (a) natural fabrics and (b) PEI-treated fabrics according to various embodiments of the present invention. [Fig. 12] Fig. 12 graphically shows the difference in deposition thickness of T4D phage adsorbed to natural and PEI-treated fabrics according to various embodiments of the present invention, which are respectively obtained from the QCM-D data shown in Fig. 11, and adopts the Voigt (Voigt) viscoelastic model with a typical organic film density of 1 g cm ^-3 . [FIG. 13] FIG. 13 graphically represents the difference in the number of bacteria caused by spraying 2250 Staphylococcus aureus on test fabrics according to various embodiments of the present invention. [FIG. 14] FIG. 14 is a graph showing the number of bacteria caused by spraying 2250 Staphylococcus aureus to deposit on cellulose with 2% PEI according to various embodiments of the present invention. [FIG. 15] FIG. 15A is a process flow diagram of using a carrier to prepare one or more multifunctional air-permeable layers (MALs) according to various embodiments of the present invention; FIG. 15B is a process flow diagram of using another carrier in FIG. 15A according to various embodiments of the present invention. [FIG. 16] FIG. 16A is an alternative process flow diagram for preparing one or more multifunctional air-permeable layers (MALs) using a carrier according to various embodiments of the present invention; FIG. 16B is a process flow diagram for using another carrier in FIG. 16A according to various embodiments of the present invention. [FIG. 17] FIG. 17A is an alternative process flow diagram for preparing one or more multifunctional air-permeable layers (MALs) using a carrier according to various embodiments of the present invention; FIG. 17B is a process flow diagram for using another carrier in 17A in various embodiments of the present invention. [Figure 18] FIG. 18A is a picture of a multi -arm aggregation compound. Its multi -official energy cationic end base system is attached to the surface of the virus surface through static electricity interaction, hydrogen bonding, ionic mismatches, Vaedvali effects, and chain entanglement. The 18C is assisted by the coupling co -agent of the two groups, and the multi -arm clustering components are scattered on the surface of hydrophobic. [Fig. 19] Fig. 19 is a diagram of another armpoly-telechelic compound. [FIG. 20] FIG. 20A is a multi-armed telechelic component with many reactive end groups evenly distributed on the surface with the assistance of a coupling agent; FIG. 20B shows that the polyfunctional cationic end groups of the polytelechelic component lead to electrostatic interaction, hydrogen bonding, ion complexation, van der Waals effect and/or chain entanglement with the target (virus). [Fig. 21] Fig. 21 shows that the high-density, uniform and uniform distribution of polytelechelic compounds enables constructive interference of dipole-dipole forces between multifunctional cationic end groups and protein structures in viruses and bacteria. [FIG. 22] FIG. 22 is an electrostatic interaction diagram of an electrostatic field generated between a positively charged surface and a negatively charged surface of a virus. [Fig. 23] Fig. 23 shows the experimental procedure for testing the affinity between the polytelechelic compound-coated material and the virus. [Figure 24] Figure 24A is a diagram of the number of HCoV-229E virus copies remaining in the buffer solution after using, culturing and centrifuging the test materials; Figure 24B is a diagram of the number of copies of Coxsackievirus B6 remaining in the buffer solution after using, culturing and centrifuging the test materials.

100: Air Filtration System

102: first floor

104: second floor

106: third floor

Claims (24)

An air filtration system characterized by comprising: one or more first layers; one or more second layers; and one or more third layers; wherein the one or more second layers are located between the one or more first layers and one or more third layers, and each of the one or more first layers and each of the one or more third layers comprises a hydrophobic gas-permeable composite material, and each of the one or more second layers comprises a polycationic antiviral and antibacterial gas-permeable composite material; wherein the one or more second layers comprise: a. a hollow hydrophilic fiber matrix; and b. A coating obtained by drying a solution comprising: i. polycationic polymer; ii. quaternary ammonium salt; iii. nonionic hydrophilic polymer; and iv. ammonium polyphosphate; wherein the coating comprises >1.37×10^{twenty two}g^-1Cationic base, dry mass>2g/m²And the total mass fraction of nitrogen>25wt%. The air filtration system as described in Claim 1, wherein the coating comprises one or more of the following: a. the polycationic polymer is selected from the group consisting of branched/linear polyethyleneimine, chitosan, poly-L-lysine and poly-D-lysine; b. the quaternary ammonium salt is polydiallyldimethylammonium chloride or ethoxylated quaternary ammonium hydroxyethyl cellulose (Quaternized Hydroxyethylcellulose ethoxylate); or c. The non-ionic hydrophilic polymer is selected from the group consisting of polyacrylamide, poly(N-isopropylacrylamide) and polyethylene glycol. The air filtration system as claimed in claim 1, wherein the solution is a 2wt% solution comprising 31.8% polyethyleneimine, 8.7% polydiallyldimethylammonium chloride, 19.7% polyacrylamide and 13.1% ammonium polyphosphate. The air filtration system as described in Claim 3, wherein the mass fraction of the nitrogen is 26.56wt%. The air filtration system according to claim 1, wherein the polycationic polymer is a multi-armed polytelechelic polymer comprising >14 arms. The air filtration system according to claim 1, wherein the hollow hydrophilic fiber matrix comprises cotton or cellulose. The air filtration system according to claim 1, wherein the one or more second layers have a pressure drop of 0.5 to 10 Pa at a physiological respiratory flow rate and have a virus filtration efficiency (VFE) of >99.9%. The air filtration system according to claim 1, wherein the polycationic antiviral and antibacterial breathable composite material comprises a breathable substrate, an antiviral agent, an antibacterial agent, and a binder. The air filtration system of claim 8, wherein the antiviral agent comprises a polymer having polycationic properties. The air filtration system as claimed in item 9, wherein the polymer having polycationic properties comprises polyethyleneimine (PEI), poly-L-lysine (PLL), diethylamine ethyl dextran (DEAE-dextran) or polyamidoamine (PAMAM) dendrimers. The air filtration system according to claim 8, wherein the air-permeable substrate comprises non-woven fabric or cellulose non-woven fabric. The air filtration system as claimed in claim 8, wherein the binder comprises a thermoplastic elastomer. The air filtration system according to claim 8, wherein the antibacterial agent comprises silver nanowires. The air filtration system according to claim 1, wherein the hydrophobic and air-permeable composite material comprises an air-permeable substrate, a hydrophobic binder and a photocatalyst reaction component. The air filtration system according to claim 14, wherein the hydrophobic binder comprises a synthetic polymer having hydrophobic properties. The air filtration system according to claim 14, wherein the photocatalyst reaction component comprises titanium dioxide nanoparticles. An antiviral mask, characterized by comprising: a. the air filtration system as described in claim 1; b. a pair of straps; and c. a wire; wherein, the pair of straps are respectively arranged on both sides of the air filtration system, and the wire is arranged above the inside of the air filtration system. A coating obtained by drying a solution, characterized in that the ^solution comprises: ^a . polycationic polymer; b. ^quaternary ammonium salt; c. nonionic hydrophilic polymer; The coating according to claim 18, wherein the coating comprises one or more of the following: a. the polycationic polymer is selected from the group consisting of branched/linear polyethyleneimine, chitosan, poly-L-lysine and poly-D-lysine; b. the quaternary ammonium salt is polydiallyldimethylammonium chloride or ethoxylated quaternary ammonium hydroxyethylcellulose (Quaternized Hydroxyethylcellulose ethoxylate); or c. The ionic hydrophilic polymer is selected from the group consisting of polyacrylamide, (N-polyisopropylacrylamide) and polyethylene glycol. The coating as described in claim 19, wherein the solution is a 2wt% solution comprising 31.8% polyethyleneimine, 8.7% polydiallyldimethylammonium chloride, 19.7% polyacrylamide and 13.1% ammonium polyphosphate. The coating according to claim 20, wherein the mass fraction of nitrogen is 26.56wt%. The coating according to claim 18, wherein the polycationic polymer is a multi-armed polytelechelic polymer comprising >14 arms. An object to be plated, characterized by comprising: a. a substrate; and b. the coating as described in claim 18. The object to be plated according to claim 23, wherein the paint is plated on the hydrophobic surface of the base material which has been treated with an amphiphilic coupling agent.