TWM625350U - Air filtration system and antiviral face mask - 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 in the one or more first layers One layer and one or more third layers are intermediate, and each one or more first layers and each one or more third layers comprise a hydrophobic breathable composite material, and each one or more second layers comprise a polycation Anti-viral and anti-bacterial breathable composite material.

Description

Air filtration system and anti-viral mask

This creation is about an air filtration system, especially an air filtration system with anti-virus and anti-bacteria, which can effectively filter viruses and bacteria such as coronavirus in the air. This creation can be used with any device, tool, equipment, object and apparatus 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 wear anti-viral masks to protect themselves from infection, so there is a high demand for anti-bacterial and anti-viral masks that can effectively filter the air in different countries. Antiviral masks are known to protect humans from bacterial and viral infections, but there is no experimental evidence that the air filters 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 purpose of this creation 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 viruses, and can be successfully applied to face mask.

[Prior Art 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, 511- 521.

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

An air filtration system is 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 in the one or more first layers Layers and one or more third layers are intermediate, and each one or more first layers and each one or more third layers comprise a hydrophobic breathable composite material, and each one or more second layers comprise a polycationic Anti-viral and anti-bacterial breathable 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), diethylamine ethyl dextran (DEAE-dextran) or polyamidoamine ( PAMAM) dendrimers.

Desirably, the aforementioned breathable substrate comprises a non-woven fabric or a cellulosic non-woven fabric.

Ideally, the aforementioned binder comprises a thermoplastic elastomer.

Desirably, the aforementioned antibacterial agent comprises nanosilver wires.

Ideally, the aforementioned hydrophobic gas-permeable composite material comprises a gas-permeable substrate, a hydrophobic binder and a photocatalyst reactive component.

Ideally, the aforementioned hydrophobic binders comprise synthetic polymers having hydrophobic properties.

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

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

100: Air Filtration System

102: The first floor

104: Second floor

106: The third floor

201: Nano Silver Wire

300: mask

302: Air filter material

304: Lace

306: Wire

308: Pleated

601: Composites and Cellulose Layers

602: Composite Layer

1001: Silicon substrate with bacteriophage T4 deposited in suspension

1401: Medium for testing bacterial counts

1801: Multi-armed polytelechelic compounds

1802: Hydrophilic Surface

1803: Hydrophobic Surfaces

1901: Multi-armed polytelechelic compounds

2101: Constructive Intervention

2201: Virus

2202: Modified positively charged water injection material

[FIG. 1] shows a cross-sectional view of an air filtration system according to various embodiments of the present invention.

[FIG. 2] shows examples of nanosilver wires according to various embodiments of the present invention.

[FIG. 3] shows an example of a mask with the air filtration system of FIG. 1 according to various embodiments of the present invention.

[Fig. 4] The air permeability pressure difference (KPasm ^-1 ) of different fabric materials according to various embodiments of the present invention is shown in a graph, SNS refers to PET-1 fabric coated with hydrophobic air permeability layers (HALs); VNV refers to PET-2 fabrics coated with HALs; RN refers to RN cellulose nonwovens coated with HALs; RS refers to RS cellulose nonwovens coated with HALs; RV refers to RV cellulose nonwovens coated with HALs; Meltblown -I refers to unused meltblown fabric coated with HALs; Meltblown-II refers to used meltblown fabric coated with HALs.

[Fig. 5] Figs. 5A-5B graphically represent the virus filtration efficiency according to various embodiments of the present invention; in Fig. 5A, the dotted line shows the FTIR light of the hydrolyzed polycationic antiviral and antibacterial gas permeable composite material spectrum, while the solid line shows the spectrum of pure nonwoven KWL; Figure 5B shows the FTIR spectrum of the polycationic antiviral and antibacterial breathable composite.

[Fig. 6] Fig. 6 shows a scanning electron microscope (SEM) image of the gas-permeable composite material of polycationic antiviral and antibacterial according to various embodiments of the present invention; Fig. 6(a) shows the composite material and cellulose, While Fig. 6(b) shows the composite layer, the topographic image shows an increase in brightness with height.

[FIG. 7] FIGS. 7A-7B are progressive graphs showing the adsorption process of polyethyleneimine (PEI) on the regenerated fabric layer with increasing concentration according to various embodiments of the present invention, the (a) of the third, fifth and seventh overtones ) change in normalized frequency fn / n and (b) change in loss factor Dn .

[FIG. 8] FIG. 8 graphically represents the hydrated adsorption mass of PEI on cellulose as a function of PEI concentration according to various embodiments of the present invention, which is calculated from QCM-D data and using the Sauerbrey equation, where the coefficient of determination The value is 0.999.

[FIG. 9] FIG. 9 graphically represents the (3rd, 5th, and 7th overtones of the third, fifth, and seventh overtones in the rinsing steps at different NaCl solution concentrations during the deposition of PEI onto the fabric and subsequent processes, in accordance with various embodiments of the present invention). a) change in normalized frequency fn / n and (b) change in loss factor Dn .

[FIG. 10] FIG. 10 shows AFM images of phage T4 deposited on a silicon substrate (5 x 5 μm) in suspension according to various embodiments of the present invention, which was further used for QCM-D sensing of coated fabrics Do a fixed test on the device.

[FIG. 11] FIG. 11 is a graphical representation of the third, fifth and seventh overtone normalized frequencies during the deposition of phage T4 on (a) natural fabrics and (b) PEI-treated fabrics according to various embodiments of the present invention. Variation fn / n and loss factor variation Dn difference.

[Fig. 12] Fig. 12 graphically represents the difference in the thickness change of T4D phages adsorbed to native and PEI-treated fabrics according to various embodiments of the present invention, which were obtained from the QCM-D data shown in Fig. 11, respectively, and used The 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 the test fabric according to various embodiments of the present invention.

[Fig. 14] Fig. 14 shows pictures of bacterial counts 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 breathable layers (MALs) according to various embodiments of the present invention; FIG. 15B is according to various embodiments of the present invention when FIG. 15A is used Process flow diagram of another carrier.

[FIG. 16] FIG. 16A is an alternative process flow diagram of using a carrier to prepare one or more multifunctional breathable layers (MALs) according to various embodiments of the present invention; FIG. 16B is a flow chart of FIG. 16A according to various embodiments of the present invention Process flow diagram using another carrier.

[Fig. 17] Fig. 17A is a flow chart of an alternative process for preparing one or more multifunctional breathable layers (MALs) using a carrier according to various embodiments of the present invention; A process flow diagram of a carrier.

[Fig. 18] Fig. 18A is a diagram of the multi-armed polytelechelic compound created by the present invention, and its multifunctional cationic end groups are formed by electrostatic interaction, hydrogen bonding, ionic dislocation, Van der Waals force effect and chain entanglement. The combined effect is attached to the surface of the virus; Figure 18B shows that the multi-armed polytelechelic components are directly dispersed on the target with a hydrophilic surface; Figure 18C is assisted by the coupling agent of the amphiphilic group. The telechelic components are dispersed on a hydrophobic surface.

[Fig. 19] Fig. 19 is a diagram of another arm-polytelechelic compound.

：具有許多聚陽離子反應性端基之多臂聚遙爪 組份2001；

：耦合劑2002；

：任何表面/材料2003)；圖20B顯示聚遙爪組分之多官能性陽離子端基導致其與目標物(病毒)間之靜電交互作用、氫鍵作用、離子錯合作用、凡德瓦力效應及/或鏈纏結(

：具有許多聚陽離子反應性端基之多臂聚遙爪組份2001；

：耦合劑2002；

：任何表面/材料2003)。 [Fig. 20] Fig. 20A is a multi-armed polytelechelic assembly with many reactive end groups evenly distributed on the surface with the aid of a coupling agent (

: Multi-arm polytelechel component 2001 with many polycationic reactive end groups;

: Couplant 2002;

: Any Surface/Material 2003); Figure 20B shows that the polyfunctional cationic end groups of the polytelechel component lead to electrostatic interactions, hydrogen bonding, ionic dislocation, van der Waals forces with the target (virus) effects and/or chain tangles (

: Multi-arm polytelechel component 2001 with many polycationic reactive end groups;

: Couplant 2002;

: Any Surface/Material 2003).

[Fig. 21] Fig. 21 shows the high density, uniform and even distribution of polytelechelic compounds, allowing constructive interference of dipole-dipole forces between multifunctional cationic end groups and protein structures in viruses and bacteria.

[Fig. 22] Fig. 22 is a diagram of electrostatic interaction by generating an electrostatic field between the positively charged surface and the negatively charged surface of the virus.

[Fig. 23] Fig. 23 shows the experimental procedure for testing the affinity between the material coated with the polytelechel compound and the virus.

[Fig. 24] Fig. 24A shows the number of copies of HCoV-229E virus remaining in the buffer solution after using, culturing and centrifuging the test material; Fig. 24B shows the remaining cosa in the buffer solution after using, culturing and centrifuging the test material Coxsackievirus B6 (Coxsackievirus B6) replica number map.

The following descriptions enable one of ordinary skill in the art to implement or use the various embodiments, and descriptions of specific devices, techniques, and applications are provided by way of example only. Various modifications to the examples described in this specification will be readily apparent to those of ordinary skill in the art, and the principles defined in this specification may be applied to other examples and applications without departing from the spirit of the invention and the scope of the claims. Therefore, the content disclosed in this creation 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.

1 shows a cross-sectional view of an air filter system/air filter material according to various embodiments of the present invention. The air filter system 100 may include one, two, three or more layers. The present invention can be used with any device or tool that needs to filter air. , equipment, objects and instruments used together.

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 breathable layers . The first layer 102 and the third layer 106 are used to waterproof and allow air to pass through, and the hydrophobic breathable layer comprises a hydrophobic breathable composite material. The second layer 104 is meant to be a multifunctional breathable layer comprising a polycationic antiviral and antibacterial breathable composite material.

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 (eg, woven/fiber with hydrophilic properties) Plain woven fabric, knitted or non-woven/cellulose non-woven fabric), antiviral agent (for example: a polymer with polycationic properties such as polyethyleneimine (PEI), poly-L-lysine (PLL), diethyl ether aminoethyl dextran (DEAE-dextran) or polyamidoamine (PAMAM) dendrimers), antibacterial agents (eg: silver nanowires) and/or binders (eg: thermoplastic elastomers), It is obtained by surface coating technology with the aid of aqueous liquids. The adhesive is suitable for reducing the pore size of the air-permeable substrate so that the anti-viral agent (eg PEI) can be tightly combined with the air-permeable substrate. In this creation, the breathable substrate is non-woven/cellulose non-woven fabric and the antiviral agent is polyethyleneimine (PEI), and the multifunctional breathable layer (the second layer 104 ) is used to capture and/or filter air bacteria and viruses (especially COVID-19).

The aforementioned hydrophobic breathable layer comprises a hydrophobic breathable composite material, which is formed based on, including but not limited to, breathable substrates (eg: woven/cellulose woven fabrics with hydrophobic properties, knitted fabrics) or nonwoven/cellulose nonwoven), binders with hydrophobic properties/hydrophobic binders (for example: synthetic polymers with hydrophobic properties, such as silicon-containing polymers, fluoropolymers and polyolefins) and/or components with Photocatalytic reactions/components with photocatalytic reactions (eg: TiO2 nanoparticles), which are obtained by surface coating techniques by means of liquids. In the present invention, the breathable substrate is a non-woven/cellulose non-woven fabric, and air can pass through the hydrophobic breathable 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 the non-woven fabric and maintain its unique Texture (structure) and inherent properties (ie softness and breathability) 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 aerosols, viruses and bacteria or as an antiviral agent.

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

The aforementioned fabrics may be breathable substrates, may include fibrous substrates, which may be woven or non-woven materials, examples of woven materials include natural and synthetic polymers such as cotton, cellulose, wool, polyolefins, polyesters, polyamides Amines (eg 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 creation can be in the form of a non-woven fabric sheet or a spacer. Ideally, polyester nonwovens are used as breathable substrates, since the aminated coatings of polymers with polycationic properties such as polyethyleneimine (PEI) described in this specification have been found to adhere better to polyethylene. polyester materials, and the aminated coatings of polymers with polycationic properties such as polyethyleneimine (PEI) appear to be less prone to peeling or rubbing off polyester substrates. Polyester fibers and fabrics from which they are made are known. The term "polyester" described in this work is a general term for fibers made by linking polymer monomers with ester groups, and is generally used to manufacture polyester-based polyethylene terephthalate for woven fibers and non-woven fibers.

It is known that the mask has an air-filtering intermediate layer suitable for capturing and neutralizing viruses and bacteria, the intermediate layer is made of a melt-blown material capable of capturing viruses and bacteria by electrostatic attraction. After the material encounters the water vapor exhaled from the user's mouth, the electrostatic attraction will gradually disappear, causing the meltblown material to lose most of the electrostatic attraction, resulting in the bacterial filtration efficiency (BFE) and virus filtration efficiency (VFE) of the mask. ) decreased significantly after a few hours of use.

In this creation, the second layer 104 is a multifunctional breathable layer, which includes a polycationic antiviral and antibacterial breathable composite material. One of its advantages is that when the ionic strength variability is large, it can capture and neutralize Viruses and bacteria remain virtually stable. When the cellulose surface is treated with polymer species with polycationic properties, such as polyethyleneimine (PEI), it can capture phages more efficiently 15 times. The affinity that exists between viruses and bacteria and polymer species with polycationic properties such as polyethyleneimine (PEI) is due to the interaction between polymer species with polycationic properties such as polyethyleneimine (PEI) and negatively charged viruses. Strong electrostatic attraction, which increases with humidity and increases conductivity in the fabric structure. The PEI-coated non-woven fabric is used as a filter material for air purifiers in confined spaces (airplanes, ships, offices, hospitals), anti-virus 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, which is easy to coat on fabric structures, but costs as much as $1,000 per gram. Branched 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 suitable chemical carriers, PEI was successfully layered on the surface of the fabric in a branched structure, and the cost of manufacturing the polycationic antiviral and antibacterial breathable composite material was reduced by 99.998204%, making the manufacturing Polycationic antiviral and antibacterial breathable composites are commercially available.

In another embodiment of the present invention, the aforementioned polycationic antiviral and antibacterial breathable composite material of the second layer 104 is further modified with multi-armed polytelechelic compounds, such as oligomers, polymers and/or The microparticles, which have high-density multifunctional cationic end groups, have a 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 polytelechelic components can be directly, closely, uniformly and evenly distributed on the hydrophilic surface of the target by electrostatic interaction, hydrogen bonding and/or ionic mischelation of part of the multifunctional functional cationic end groups. .

When the polytelechelic component is coated on the material, with or without the aid of the amphiphilic coupling agent, It can also be densely, uniformly and evenly spread on the surface of the material. The inclusion of the coupling agent can make the polytelechelic components tightly bond with the reactive end groups of the polymeric components through electrostatic interaction, hydrogen bonding and/or ionic misalignment. In the absence of a coupling agent, 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 creation includes hyperbranched, star-shaped or brush-shaped oligomers and polymers, or oligomer and polymer-modified nanoparticles. On the other hand, the alkylated polycationic group can make It is evenly distributed on the surface of the material, and the polycationic groups are so uniformly and persistently distributed that there is insufficient space for microscopic viruses and bacteria to attach and live on the modified surface. The multifunctional cationic end groups can also lead to electrostatic forces, hydrogen bonding, ionic dislocation, Van der Waals forces and/or chain entanglement effects with bacteria and viruses. Such a high density, uniform and even distribution can further enable constructive interference of the dipole-dipole force between the polyfunctional cationic end groups and the protein structure in viruses and bacteria, and capture and destroy viruses and bacteria more effectively and efficiently. .

In one embodiment, the number of arms of the aforementioned polytelechelic compound exceeds 14 arms. In one embodiment, the density of the aforementioned multifunctional 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 An aqueous solution is prepared; (b) the solution is sprayed onto the material or the material is immersed in the solution; and (c) moisture is removed from the material. After the moisture is removed, 0.5 to 100 g/ ^m2 of solids should remain on the fabric or fiber surface.

In another embodiment, the aqueous solution of the aforementioned step (a) further comprises (iii) a quaternary ammonium salt; and (iv) a non-ionic hydrophilic polymer.

In one embodiment, the aforementioned dissolving step is performed at a temperature between 250°C and 350°C. one In the embodiment, the aforementioned dissolving step is performed at a pressure between 5Pa and 10Pa. 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 quaternary ammonium salt is selected from the group consisting of polydiallyl dimethyl ammonium chloride (PDADMAC) and ethoxylated quaternized hydroxyethylcellulose ethoxylate group. In one embodiment, the aforementioned non-ionic 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 to 80 wt % of the aforementioned at least one cationic polymer and 20 to 90 wt % of the aforementioned ammonium polyphosphate. In another embodiment, the aforementioned aqueous solution comprises, by weight, 6.5 parts of PEI, 3.0 parts of PDADMAC, 1.0 parts of PAM, 0.5 parts of APP and 490 parts of water.

Materials used

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

The term "polymeric species with polycationic properties such as polyethyleneimine (PEI)" as used in this specification includes polymers having polyethyleneimine groups along their backbone, eg, as pendant groups. Suitable groups are polyethyleneimine groups. Fabrics coated with polymeric species with polycationic properties such as polyethyleneimine (PEI), which may be branched or linear. Generally speaking, branched chains are ideal for current applications, such as branched chain polymers. In addition, the branched chain structure has relatively more amine groups for use, and the branched chain polymers are more soluble and thus can be used for the purposes of this specification. recorded in the preparation process.

Polyethyleneimine (PEI) is a polymer consisting of repeating units consisting of amine groups and dicarbon aliphatic CH2CH2 spacers. In contrast to linear polyethyleneimine which contains all secondary amines, branched polyethyleneimine contains primary, secondary and tertiary amine groups. PEI is produced on an industrial scale, and it is found that most applications of PEI generally derive from its polycationic properties.

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

For example, the filter media can be combined with one or more surfactants, which can promote wetting of the filter media. Airborne pathogens such as viruses are known to attach to small water droplets, so increasing the wetting of the filter media allows pathogens to more effectively contact the active material on the filter media. In addition, surfactants are known to effectively disrupt viral and bacterial membranes. A non-ionic surfactant is desirable, since ionic surfactants tend to gel aminated coatings, especially polyethyleneimine. Choose an ideal nonionic surfactant.

While generally high loadings of polymer species with polycationic properties such as polyethyleneimine (PEI) achieve satisfactorily high antipathogenic efficacy on substrates, it has been found that too high loadings can hinder air Through the shortcomings of filter media, a balance should be struck between the two.

In order to achieve a suitable amount of airborne immobilized virus passing through the air filtration system 100, combined with suitable air permeability, if a polymer species with polycationic properties such as polyethyleneimine (PEI) is present, plus any filter substrate For any of the above surfactants, 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 may correspond to the sum of the presence of polymer species with polycationic properties such as polyethyleneimine (PEI), plus any surfactant on any filter substrate The loading is 5~60wt%, generally 10~30wt% (based on 100% of the weight of the substrate itself).

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

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

In general, the filter material ideally has a structure comprising branched polyethyleneimine (PEI) and a nonionic surfactant in the proportions described in this specification, and is deposited on a non-woven polyester fiber substrate.

A specific type of filter media described above comprises a fibrous substrate (as previously described) on which an aminated coating, particularly PEI, is deposited. The filter media described in this specification can be made by a variety of methods, including a method of combining a breathable substrate with an aminated coating, particularly PEI.

In one approach, PEI may be deposited on a breathable substrate as a complete or partial film on the substrate (eg, on fibers). In another approach, PEI may be combined with a breathable substrate (e.g. Such as: material bonding in fibers), this method can be completed in the process of forming fibers, such as: forming non-woven materials by spun bonding and melt blowing.

In another method, the filter material of the present invention can be prepared by a conventional electrospinning process, and the polymer is formed in a solution or molten form into a charged liquid column and deposited on the grounded collecting plate fibers.

The aforementioned hydrophobic breathable layer comprises a hydrophobic breathable composite material, which is formed based on, including but not limited to, breathable substrates (eg: woven, knitted or non-woven fabrics with hydrophobic properties), binders/hydrophobic binders with hydrophobic properties (For example: synthetic polymers with hydrophobic properties, such as silicon-containing polymers, fluoropolymers and polyolefins) and/or components with photocatalytic reactions/components with photocatalytic reactions (for example: titanium dioxide nanoparticles), and by Obtained by means of liquid surface coating technology.

The aforementioned breathable substrates may comprise fibrous substrates, which may be woven or non-woven materials. 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 polymers that can be processed into fibers. Examples of nonwoven materials include polypropylene, polyethylene, polyester, nylon, PET, and PLA. For this creation, the ideal is non-woven fabric, and this material may be in the form of non-woven fabric sheets or spacers. Polyester non-woven fabrics are ideal breathable substrates, because it was found that aminated coatings, especially polyethyleneimine (PEI) described in this specification, can better adhere to polyester materials, and the aminated coatings, especially The polyethyleneimine (PEI) described in this specification appears to be less likely to peel or rub off from polyester substrates. Polyester fibers and fabrics from which they are made are known. The term "polyester" described in this work is a general term for fibers made by linking polymer monomers with ester groups, and is generally used to manufacture polyester-based polyethylene terephthalate for woven fibers and non-woven fibers.

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

Typical nonwoven polypropylene materials found to be suitable for use in this creation have a weight of 10-40 g/m ² , although the weight of other suitable materials can be determined empirically.

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

Breathable substrates can be substituted for other types such as open foams, for example: Polyurethane foams are also used in air filters, such as filtering air for nasal congestion, especially the amination of polyethyleneimine (PEI) has been found The coating effectively captures and neutralizes airborne viruses and bacteria that pass through the material. Without being limited to a particular theory of action, it is generally believed that once the virus contacts the surface of the substrate, it interacts with the polymer and is captured and immobilized by polyethyleneimine (PEI), thereby inactivating and neutralizing the virus. It is generally believed that the filter material of this creation can resist the viruses that cause colds, influenza, SARS, RSV, bird flu, COVID-19 and their serotype mutants.

Production method

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

In Figure 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, step 1501 of process 1500A includes immersing and stirring the nonwoven fabric in a carrier-containing solvent in a container for a period of time in the range of 20 seconds to 180 seconds, ideally 60 seconds, and at Conducted at room temperature to optimize the interaction between polymers with polycationic properties such as polyethyleneimine (PEI) and nonwovens Affinity. For example, the carrier is carboxymethyl.

The aforementioned carboxymethyl group is suitable for combining with the hydroxyl group of the glucopyranose monomer that forms the cellulose backbone, such as: carboxymethyl cellulose (CMC), tissue cellulose gum, sodium carboxymethyl cellulose, filler Bulk or SE filled body, its concentration range falls 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, ideally 10 minutes.

In step 1503, the non-woven fabric is then impregnated and stirred in a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI), the concentration of which ranges from 0.1% to 10%, ideally 2%, and continues. A period of time, the time range of which falls in the range of 20 seconds to 180 seconds, ideally 60 seconds, and is carried out at room temperature to optimize the affinity between viruses and/or bacteria and non-woven fabrics (optimized 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, ideally 10 minutes.

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

The aforementioned solvent comprises a linear copolymer containing homoblocks of (1-4)-linked β-D-mannuronic acid (M) and its C-5 epimer α-L-gulose, respectively Alkylic acid (G) residues, covalently linked in different sequences or blocks, the monomers may be homopolymeric blocks of consecutive G-residues (G-blocks), homopolymeric blocks of consecutive M-residues blocks (M-blocks) or alternating blocks of M-residues and G-residues (MG-blocks) such as alginic acid, alginate or alginate, in concentrations ranging from 0.1% to 2%, The ideal is 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, ideally 10 minutes.

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

In step 1508, the non-woven fabric is dried in the temperature range of 40°C to 90°C, ideally at 70°C, and lasted for a period of time, the time range being 2 minutes to 12 minutes, ideally 10 minutes.

By way of example only, an alternative process 1600A is illustrated in FIG. 16A for fabricating one or more multifunctional breathable layers (MALs). In some examples, process 1700A is used in spraying machines. As shown in FIG. 16A, in step 1601, the process 1600A includes spraying a solvent containing carboxymethyl (-CH2-COOH) on the non-woven fabric for a period of time, the time range being 20 seconds to 180 seconds, ideally 60 seconds , and carried out at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and nonwovens. The carboxymethyl group is suitable for combining with the hydroxyl group of the glucopyranose monomer that forms the cellulose backbone, such as: carboxymethyl cellulose (CMC), tissue cellulose gum, sodium carboxymethyl cellulose, filler Body or SE filled body, its concentration range falls from 0.1% to 2%, ideally 0.5%.

In step 1602, a solvent with a polycationic polymer such as polyethyleneimine (PEI) is sprayed on the non-woven fabric, and its concentration is in the range of 0.1% to 10%, ideally 2%, and continues for a period of time. The range falls from 20 seconds to 180 seconds, ideally 60 seconds, and is performed at room temperature to optimize the affinity between viruses and/or bacteria and the nonwoven (optimize capture and blocking of viruses and/or bacteria).

In step 1603, 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, ideally 10 minutes.

Alternatively, as shown in FIG. 16B, in step 1604, the process 1600B includes spraying a solvent containing another carrier on the non-woven fabric for a period of time in the range of 20 seconds to 180 seconds, ideally 60 seconds, and in It is carried out at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and nonwovens. The solvent is the same as in Figure 16B, and the carrier is seaweed Acid, whose concentration ranges from 0.1% to 2%, ideally 0.5%.

In step 1605, a solvent containing a polymer with polycationic properties such as polyethyleneimine (PEI) is sprayed on the non-woven fabric, the concentration of which is in the range of 0.1% to 10%, ideally 2%, and the time range is in 20 seconds to 180 seconds, ideally 60 seconds, and performed at room temperature to optimize the affinity between viruses and/or bacteria and nonwovens (optimize capture and blocking of viruses and/or bacteria).

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

By way of example only, an alternative process 1700A is illustrated in FIG. 17A to fabricate one or more multifunctional breathable layers (MALs). In some examples, process 1800A is used in a printing machine. As shown in FIG. 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, and the time range is 20 seconds to 180 seconds, ideally 60 seconds , and carried out at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and nonwovens. The carboxymethyl group is suitable for combining with the hydroxyl group of the glucopyranose monomer that forms the cellulose backbone, such as: carboxymethyl cellulose (CMC), tissue cellulose gum, sodium carboxymethyl cellulose, filler Bulk or SE filled body, its concentration range falls 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, ideally 10 minutes.

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

Alternatively, as shown in FIG. 17B, in step 1705, the process 1700B includes printing a solvent containing another carrier on the non-woven fabric for a period of time in the range of 20 seconds to 180 seconds, ideally 60 seconds, and in It is carried out at room temperature to optimize the affinity between polymers with polycationic properties such as polyethyleneimine (PEI) and nonwovens. The solvent is the same as in Figure 16B, and the carrier is alginic acid with a concentration ranging from 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, ideally 10 minutes.

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

Hydrophobic breathable layers (HALs) can be prepared by a known process. For example, conventional processes include forming a fibrous web and curing the fibrous web. The forming webs includes carding, air layers, wet layers, spunbonding, meltblowing, and electrospinning.

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

The present creation provides an air filtration 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 on the one or more A plurality of first layers and one or more third layers are intermediate, and each of the one or more first layers and each of the one or more third layers comprises a hydrophobic breathable composite material, and each of the one or more second layers comprises Polycationic antiviral and antibacterial breathable 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, the solution comprising: (i) a polycationic polymer (ii) quaternary ammonium salts; (iii) non-ionic hydrophilic polymers; and (iv) ammonium polyphosphates; wherein the coating comprises >1.37×10 ²² g ⁻¹ of cationic groups, dry mass >2 g/m ² and the total mass fraction of nitrogen>25wt%.

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 - the group consisting of lysine and poly-D-lysine; (b) the quaternary ammonium salt is polydiallyldimethylammonium chloride or ethoxylated quaternary ammonium hydroxyethyl fiber Quaternized Hydroxyethylcellulose ethoxylate; or (c) the non-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 2wt% 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 comprises cotton or cellulose.

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

In one embodiment, the aforementioned polycationic antiviral and antibacterial breathable composite material comprises a breathable substrate, an antiviral agent, an antibacterial agent and a binder.

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

In one embodiment, the aforementioned polymer species with polycationic properties comprises polyethyleneimine (PEI), poly-L-lysine (PLL), diethylaminoethyl dextran (DEAE-dextran) or polyethylenimine (DEAE-dextran). Amidoamine (PAMAM) dendrimer.

In one embodiment, the aforementioned breathable substrate comprises non-woven fabric or cellulose non-woven fabric.

In one embodiment, the aforementioned binder includes a thermoplastic elastomer.

In one embodiment, the aforementioned antibacterial agent comprises nanosilver wires.

In one embodiment, the above-mentioned hydrophobic air-permeable composite material includes an air-permeable substrate, a hydrophobic adhesive and a photocatalyst reactive component.

In one embodiment, the aforementioned hydrophobic binder comprises a synthetic polymer having hydrophobic properties compound.

In one embodiment, the photocatalyst reaction component includes titanium dioxide nanoparticles.

The present invention also provides an antiviral mask, in one embodiment, the antiviral mask comprises: (a) the air filtration 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 filtration system, and the wire is arranged above the interior of the air filtration system.

The present invention further provides a coating obtained by drying a solution. In one embodiment, the solution comprises: (a) a polycationic polymer; (b) a quaternary ammonium salt; (c) a nonionic hydrophilic polymer and (d) ammonium polyphosphate; wherein the coating comprises >1.37×10 ²² g ⁻¹ of cationic groups, a dry mass of > 2 g/m ² and a 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-ion The group consisting of amino acid and poly-D-lysine; (b) the quaternary ammonium salt is polydiallyl dimethyl ammonium 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.

In one embodiment, the aforementioned solution is a 2wt% 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 coating 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 embodiments of the present invention.

In one embodiment, the aforementioned coating is applied to the hydrophobic surface of the substrate which has been treated with an amphiphilic coupling agent.

[Example]

In order to obtain the above results, achievements and findings, a number of tests were performed. For example, it is conventional to conduct air permeability test, virus filtration efficiency test and bacterial filtration efficiency test. Figures 4-14 illustrate the different results and findings of these three tests.

Example 1: Air permeability test

Referring to Figure 4, the air permeability pressure measurement of different fabric materials with and without coatings is described. 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 meltblown materials, The former has higher air permeability.

Example 2: Viral Filtration Efficiency Test

Referring to Figures 5 to 12, the virus filtration efficiency (VFE) test was performed on fabric materials with or without coating, respectively. The results show that the VFE of the coated fabric material is 15 times higher than that of the non-coated fabric material, and the VFE of the coated fabric material reaches 99.999%.

Cellulose woven fabric coated with HALs

According to "Polyethylenimine surface layer for enhanced virus immobilization on cellulose, Ghania Tiliket, Guy Ladam, Quang Trong Nguyen, Laurent Lebrun, 2016", the FTIR spectra of the hydrolyzed cellulose surface of the regenerated cellulose substrate coated with HALs and the pure fiber were shown The comparison of KWL of plain non-woven fabrics, whose spectra almost overlap, proves to effectively modify the fiber fabric to cellulose (Fig. 5A), in addition, the unmodified side of the substrate maintains the fiber fabric with the esters C=O at 1700cm ^-1 The spectral features of the strong band of the base match (FIG. 5B). The effect of hydrolysis treatment of cellulosic fabrics coated with HALs 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 SEM data, when the cellulose fabric was converted, its structure did not change (Figure 6). Both natural and modified coatings have the main form of flat and uniform, but they have the disadvantage of scattering. 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 coating. During spin-coating, cleaning and drying operations, nano-bubbles may be entrapped, causing the coating to peel off where the coating has weak adhesion to gold. The presence of voids allows the coating thickness (30±2nm) to be measured. Hypothetically, the effect of voids on further measurements 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 Substrates

The initial pH value of PEI 4.4% w/v solution is 11. When the pH value decreases, the amine nitrogen atom of PEI is 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 amine groups protonated was determined to be 75%±5. Therefore, the measurement of PEI adsorption was performed 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 continuous injections of PEI solutions at increasing concentrations, a decrease in Δfn/ _n was observed after each injection (considering flushing with NaCl 0.2M reference medium), indicating cellulose The quality of fabric absorption is due to the absorption of PEI. When a highly charged cationic polyelectrolyte was layered on hydrolyzed cellulose (at a low salt concentration), as previously suggested by Swerin and Ahola et al., the uptake of PEI (pKa=7.7 and pKa=9.7; cation at pH=6) May be accompanied by the release of moisture from the cellulosic substrate.

However, the QCM-D technique was unable to distinguish between the two effects, and the normalized frequencies before and after rinsing almost overlapped, indicating that the PEI-treated film had a rigid structure. The very slight increase in dissipation factor (measured in a reference medium of NaCl 0.2M) (Fig. 7B) confirms the rigidity characteristic of the film (ΔDn=8× ^10-7 for maximum PEI concentration (1% w/v)), therefore, It can be calculated by applying the Sauerbrey equation. The first step for adsorption was to use a 0.1% w/v solution of PEI 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 will be limited. In this way, a 10-fold increase in PEI concentration will only result in adsorption The quality was improved by a factor of 1.4, and the results indicated that high concentrations of PEI may not be required to coat the regenerated cellulose surface.

Effect of ionic strength on the structure of PEI layers deposited on cellulose substrates

The effect of ionic strength on the structure of adsorbed PEI was investigated by QCM-D to test the stability of the adsorption layer. 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 (0.05M, 0.5M, 1M), and the NaCl in the intermediate rinse step was 0.2M, the corresponding changes of normalized frequency Δfn/n and dissipation factor ΔDn were recorded during the whole experiment. As a control experiment, the same experiment was performed with native regenerated cellulose film (without adsorbed PEI) to understand the synthesis of (i) changes in solution viscosity and (ii) potential structural changes of the cellulose substrate on QCM-D parameters Influence. Then, according to the results of the control experiment, the QCM-D parameters obtained with PEI were measured with correction (by subtraction) to analyze the influence of the ionic strength on the structure of the PEI adsorption layer as shown in FIG. 9 . After the injection of PEI and the rinse steps, the quality of the absorption was detected, as indicated by a drop in the resonance frequency. Decreasing the NaCl concentration to 0.05M induces moisture uptake, as shown by the decrease in the resonance frequency, while subsequent increases in the NaCl concentration to 0.5M or 1M induce similar water release. This swelling and de-swelling behavior is expected based on the well-established electrostatic shielding effect, which enhances or weakens the intrachain and interchain electrostatic repulsion of polyelectrolytes at low or low levels. At high ionic strength, chain elongation or chain coiling, respectively, results. The dissipation factor decreased at high NaCl concentrations (0.5M and 1M), indicating that the hardening of the PEI layer is consistent with the de-swelling effect. In contrast, in 0.05M NaCl solution, no significant increase in the dissipation factor was measured. If the cellulose in the bottom layer could not be accurately reproduced between the PEI-containing experiment and the control experiment, it may be due to a slight deviation in the calibration of the QCM-D parameters.

After replacing the 0.05M NaCl solution with the 0.2M NaCl solution, a slight increase in the dissipation factor was measured, confirming that the PEI layer would swell when washed in 0.05M NaCl. The swelling effect of the PEI layer treated with lower ionic strength was irreversible, while the de-swelling effect observed with the treatment with higher ionic strength was reversible. Dn returns to its previous value. 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, the low ionic strength treatment may enable the PEI chains on the surface of the cellulose film to reorganize to form more bonds. Solid PEI layer.

Adsorption of T4D bacteriophages on cellulose substrates treated with PEI

First, AFM observations of the silicon substrate in contact with the T4D phage suspension were performed to confirm that the virus was completely adsorbed onto the substrate through the filtration process, rather than only adsorbing residues such as proteins. The AFM images contained in Figure 10 show the presence of many intact phages consisting of heads and tails, 120 nm in size, some phages appear to be disrupted and the presence of aggregates (protein or non-structural viruses) is also detected.

QCM-D was then used to compare the adsorption of T4D phage to native and PEI-treated cellulose substrates, with a PEI concentration of 1% w/v for deposition and the preparation of PEI functional filters for antiviral face masks method is the same. This concentration is higher than the recommended minimum concentration of 0.1% w/v for PEI partially adsorbed on the cellulose fabric, because the filter is a porous non-woven material with a larger surface than a flat support. Figure 11 shows the corresponding changes in QCM-D parameters, the frequency curves of phages after adsorption and washing steps do not overlap completely, indicating the viscoelastic properties of the phage layer, confirmed by the increased dissipation factor, especially after PEI treatment Passed cellulose (without PEI treatment Δ Dn =4×10 ⁻⁶ ; with PEI treatment Δ Dn =27×10 ⁻⁶ ). Therefore, the Sauerbrey linear equation cannot be used to derive the adsorption amount from the frequency shift, so Q-Tools software (Q-Sense) was used to analyze the raw data within the framework of Voigt's viscoelastic model.

Figure 12 shows the evolution of thickness derived from data modeling of phage layer adsorption onto PEI-untreated and PEI-treated cellulose. The thickness of the PEI layer on the cellulose film (after taking into account the rinse step) was approximately 3.5 nm. When the phage layer was deposited on the PEI-treated cellulose substrate, its thickness was 15 times (93 nm) the thickness deposited on the untreated cellulose substrate, confirming that the phage and PEI-treated regenerated cellulose The strong affinity between the positively charged PEI and the negatively charged virus is mainly explained by the strong electrostatic interaction. 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 revealed that antibacterial paper can be prepared by protein binding of T4 phage to cellulose. Adsorption of polyelectrolytes on charged surfaces results in overcompensation of surface charges. Thus, when polycationic PEI chains are adsorbed on cellulose, the surface becomes positively charged and promotes electrostatic attraction of negatively charged sites on other materials. For example, PEI-treated cellulose microporous membranes capture glucose oxidase, amylase or heparin to form highly active enzyme membranes. PEI can also currently be used to bind RNA or DNA to adenoviral particles by electrostatic interaction.

In addition, the softness of PEI chains promotes chain folding, which in turn optimizes local interactions on the virus surface, so PEI chains with large charge densities and extremely large chain stretch lengths provide optimal conditions for virus capture.

Example 3: Viral Filtration Efficiency Test

Referring to Figures 13-14, bacterial filtration efficiency (BFE) tests were performed on fabric materials with and without paint, respectively. The results showed that the bacterial filtration efficiency (BFE) of the coated fabric was 25 times that of the non-coated fabric, reaching 99.9703%.

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

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

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

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

Example 4: Filtered Air Example for Use with Antiviral Face Masks

FIG. 3 shows an example of an antiviral mask having the air filtration system of FIG. 1 according to various embodiments of the present invention. In one embodiment, the mask 300 includes an air filter system/air filter material 302/100, a pair of straps 304 and wires 306. The two sides of the air filter system/air filter material 302 are used to support the mask 300 on the user's ears. The wire 306 is disposed above the interior 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 of the filter 302 is concave.

The shape and construction of the antiviral mask 300 shows a high density between it and the user's face. seal and facilitate the user's breathing.

The use of the air filter system/air filter material 302 is not limited herein. In one example, the air filter system/air filter material 302 may be used for air purifiers or air conditioners. In another example, the air filter system/air filter material 302 may be used in a protective helmet or the like.

Example 5: Results of coating polytelechelic material

impact on virus

In order to test the affinity and virucidal effect of the material coated with the polytelechel compound on viruses, other materials commonly used in the laboratory or in the manufacture of face masks were used for testing. The following five different materials were tested: toilet paper for laboratory use, FFP2 standard filter material, FFP2 standard sponge, polytelechel compound-coated water injection material, and poly-telechel compound-coated paper.

As in step 2301, take a piece of 2.5 x 2.5 cm from each material, put it into a separate 2ml Eppendorf tube, and add 200μl of HCoV-229E virus buffer solution containing about 50,000 PFU to each tube , as in step 2302, each tube is incubated for 5 minutes, as in step 2303, and then centrifuged to remove the buffer solution from the test material. As in step 2304, the test material is removed from the tube and RT-qPCR is used to measure the residual virus concentration in the buffer solution. The same experiment was repeated with an incubation time of 60 minutes and two sets of experiments were repeated using Coxsackie virus B6 instead of HCov-229E, as shown in Figure 23.

As shown in Figures 24A and 24B, virus concentrations of HCoV-229E and Coxsackievirus B6 were higher in toilet paper, FFP2 filter media, and FFP2 sponge, in each case regardless of whether the test materials were incubated in tubes for 5 or 60 minutes , the concentration of the tested virus remaining in the buffer solution is reduced by more than half of the original concentration. This means that the toilet paper, FFP2 filter material and FFP2 sponge material have low affinity with the tested virus. On the contrary, for the water card clothing and paper treated with polytelechelic material, the residual amount in the buffer solution The virus concentration 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 concluded that both tested virus strains have strong affinity for the polytelechelic compounds of the material.

Virus Filtration Efficiency (VFE) Test

The test was further performed to determine the filtration efficiency of the polytelechel-coated textile material by comparing the upstream and downstream virus counts of the test article. Use a sprayer to atomize the phage ΦX174 suspension, and transfer it to the test object at a constant flow rate and a fixed air pressure. The test object is a white non-woven fabric coated with polytelechel compound, and the challenge transmission material is maintained at 1.1~3.3× 10 ⁶ plaque forming units (PFU) with a mean particle size (MPS) of 3.0 ± 0.3 μm, aerosol droplets were collected through an Anderson six-stage bioaerosol sampler. The results are shown in Table 1 below.

Using a test area of about 40 square centimeters, with VFE flow rate of 28.3 liters/min and relative humidity of 85±5% and 21±5°C for at least 4 hours, the results of each VFE test percentage in 5 repeated experiments All were more than 99.9%, because no plaques were detected on the Anderson sampling plate of all the tested substances, and all phages were captured under fast airflow, indicating that the polytelechelic compounds have a high affinity for viruses.

effect on bacteria

Two white fabric samples coated with polytelechelic compounds were tested for their antibacterial ability. 1 ml of S. aureus inoculum at a concentration of 1 x 10 ⁶ CFU/ml to 3 x 10 ⁶ CFU/ml was inoculated onto an agar plate, where each sample was placed on the surface of the agar plate and weighed with a 200g stainless steel weight Code pressure for 60±5 seconds to transfer microorganisms. Before culturing one sample and after culturing another sample, the bacteria were shaken with protease water. The results of bacterial counts for each sample are shown in Table 2 below. Based on the results obtained, the samples exhibited potent antibacterial properties during the transfer phase of the experiment, killing Staphylococcus aureus.

Under the same test conditions and methods, further experiments were conducted 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 60 washes, and the results are shown in Table 3:

According to the literature 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., 17, 511-521.), antimicrobial activity values below 0.5 indicate no antibacterial activity, and activity values between 0.5 and 1 indicate Slight antibacterial activity, activity values greater than 1 and less than or equal to 3 represent significant antibacterial activity and log reduction of activity values greater than 3 represents strong antibacterial activity. The experimental results showed that almost all samples showed strong antibacterial activity even after 60 washes.

This creation describes different exemplary embodiments, and these examples are used as a reference rather than a limitation of this creation, and the purpose is to provide a description of the wider application of the disclosed technology without departing from the true spirit of the various embodiments of this creation. Various changes and equivalent substitutions can be made within the scope of the product. In addition, various modifications may be made to adapt a particular situation, material, composition of matter, process, process act or step to the purpose, spirit or scope of various embodiments. Furthermore, those of ordinary skill in the art will understand that the individual variations described and documented in this creation have discrete elements and features, which can be readily adapted from other embodiments without departing from the spirit and scope of the various embodiments of this creation Separate and combine with any of the features of the other embodiments.

100: Air Filtration System

102: The first floor

104: Second floor

106: The third floor

Claims (18)

An air filtration system is 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 in the one or more layers The first layer and the one or more third layers are intermediate, and each of the one or more first layers and each of the one or more third layers comprises a hydrophobic breathable composite material, and each of the one or more second layers comprises a polycation Anti-viral and anti-bacterial breathable composite material. The air filtration system of claim 1, wherein the one or more second layers comprise: a hollow hydrophilic fiber matrix; and a coating obtained by drying a solution, the solution comprising: a polycationic polymer; a quaternary Ammonium salt; nonionic hydrophilic polymer; and ammonium polyphosphate; wherein the coating comprises >1.37×10 ²² g ⁻¹ cationic groups, dry mass > 2 g/m ² and total nitrogen mass fraction > 25 wt %. The air filtration system of claim 2, wherein the coating comprises one or more of the following: the polycationic polymer is selected from the group consisting of branched/linear polyethyleneimine, chitosan, poly -The group consisting of L-lysine and poly-D-lysine; the quaternary ammonium salt is polydiallyldimethylammonium chloride or ethoxylated quaternary ammonium hydroxyethyl cellulose (Quaternized Hydroxyethylcellulose ethoxylate); or 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 2, wherein the solution is a 2wt% solution comprising 31.8% polyethyleneimine, 8.7% polydiallyldimethylammonium chloride, 19.7% poly Acrylamide and 13.1% ammonium polyphosphate. The air filtration system according to claim 4, wherein the mass fraction of the nitrogen is 26.56wt%. The air filtration system of claim 2, wherein the polycationic polymer is a multi-arm polytelechelic polymer comprising >14 arms. The air filtration system of claim 2, wherein the hollow hydrophilic fiber matrix comprises cotton or cellulose. The air filtration system of claim 2, wherein the one or more second layers have a pressure drop of 0.5 to 10 Pa at physiological respiratory flow rates while having a viral filtration efficiency (VFE) of >99.9%. The air filtration system of 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 9, wherein the antiviral agent comprises a polymer having polycationic properties. The air filtration system of claim 10, wherein the polymer with polycationic properties comprises polyethyleneimine (PEI), poly-L-lysine (PLL), diethylaminoethyl dextran (DEAE-dextran) or polyamidoamine (PAMAM) dendrimers. The air filtration system according to claim 9, wherein the breathable substrate comprises a non-woven fabric or a cellulose non-woven fabric. The air filtration system of claim 9, wherein the binder comprises a thermoplastic elastomer. The air filtration system of claim 9, wherein the antibacterial agent comprises silver nanowires. The air filtration system of claim 1, wherein the hydrophobic air-permeable composite material comprises an air-permeable substrate, a hydrophobic binder and a photocatalyst reactive component. The air filtration system of claim 15, wherein the hydrophobic binder comprises a synthetic polymer having hydrophobic properties. The air filtration system of claim 15, wherein the photocatalyst reaction component comprises titanium dioxide nanoparticles. An antiviral face mask, which is characterized by comprising: the air filtration system according to claim 1; a pair of straps; and a wire; wherein, the pair of straps are respectively arranged on both sides of the air filtration system, and the wire It is arranged above the interior of the air filtration system.

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