Antibacterial and antiviral film and method for preparing the same

Abstract

The application provides an antibacterial and antiviral film and a preparation method thereof. The antibacterial and antiviral film comprises a high polymer protective layer, a metal nanofiber network layer and a substrate which are sequentially stacked. The material of the high polymer protective layer is a high polymer protective liquid with sulfonated groups. The material of the metal nanofiber network layer comprises composite metal nanowires with a structured network.

Description

Technical Field

[0001] This invention belongs to the field of thin film materials technology, specifically relating to an antibacterial and antiviral thin film and its preparation method. Background Technology

[0002] In our daily lives, many items we frequently come into contact with carry a large number of bacteria or viruses harmful to health, especially furniture, home appliances, mobile phones, computers, or public items (such as handrails on buses and subways, interior parts of vehicles, and seats). People are very likely to cause cross-infection of bacteria through repeated touching of these items. Therefore, it is crucial to develop a convenient method to prepare antibacterial and antiviral films on the surfaces of these components.

[0003] Existing antibacterial materials include natural, inorganic, and organic antibacterial materials. However, these materials primarily inhibit bacteria and fungi, with few targeting viruses. Inorganic antibacterial materials mainly consist of nano-metal particles or nano-metal oxide particles. These are added to resins and solvents to form an antibacterial composition, which is then processed into an antibacterial film. This process is complex and time-consuming. Furthermore, inorganic antibacterial agents are prone to yellowing (e.g., silver ions) or causing decreased film transparency (e.g., nano-zinc oxide, copper oxide). Organic antibacterial agents suffer from short-lasting antibacterial effects and are prone to developing drug resistance. Solid antibacterial films have low bactericidal and virucidal efficiency and cannot quickly kill bacteria and viruses in high-traffic, high-frequency contact environments, still posing a risk of infection. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an antibacterial and antiviral film and its preparation method. The antibacterial and antiviral film exhibits broad-spectrum antibacterial properties, durability, high efficiency, and safety.

[0005] In a first aspect, the present invention provides an antibacterial and antiviral film comprising a polymer protective layer, a metal nanofiber network layer, and a substrate, which are sequentially stacked.

[0006] The polymer protective layer is made of a polymer protective liquid with sulfonated groups.

[0007] The material of the metal nanofiber network layer includes composite metal nanowires with a structured network;

[0008] The polymer protective layer contains ion channels.

[0009] Furthermore, the antibacterial and antiviral film comprises a first protective layer, a polymer protective layer, a metal nanofiber network layer, a substrate, an adhesive layer, and a second protective layer, which are sequentially stacked.

[0010] The polymer protective layer is made of a polymer protective liquid with sulfonated groups; the metal nanofiber network layer is made of composite metal nanowires with a structured network.

[0011] Furthermore, the polymer protective liquid includes sulfonated aromatic compounds, aqueous diluents, aqueous aliphatic resin dispersions, wetting and leveling agents, defoamers, and blocking curing agents.

[0012] Furthermore, the polymer protective liquid comprises the following raw materials expressed as a percentage by weight:

[0013] Sulfonated aromatic compounds 2-18%,

[0014] Waterborne aliphatic resin dispersion 30-70%,

[0015] Aqueous diluent 10-33%,

[0016] Wetting and leveling agent 0.1-1%,

[0017] Defoamer 0.1-1%,

[0018] 1-3% sealing and curing agent;

[0019] The total weight of all components in the polymer protective liquid is 100%.

[0020] Furthermore, the composite metal nanowire consists of metal A encapsulating metal B nanowires; metal B is located inside metal A, and metal B has exposed points;

[0021] Metal A includes one or more of the following: gold, silver, copper, iron, tin, titanium, nickel, cobalt, and platinum.

[0022] Metal B includes one or more of the following: silver, silver oxide, copper, copper oxide, zinc, zinc oxide, titanium, and titanium oxide.

[0023] In this invention, metal A-clad metal B nanowires refer to metal nanowires with metal A as the outer shell and metal B as the core, wherein the thickness of the outer shell of metal A can be 2 to 20 nm.

[0024] Furthermore, the substrate includes one or more of PET, PE, TPU, and PVC.

[0025] Furthermore, the adhesive layer is made of one or more of silicone and acrylic adhesives.

[0026] Furthermore, the material of the first protective layer includes one or more of PMMA release film, BOPP release film, PE release film, TPX release film, PVC release film, PTFE release film, and PET release film.

[0027] Furthermore, the material of the second protective layer includes one or more of PMMA release film, BOPP release film, PE release film, TPX release film, PVC release film, PTFE release film, and PET release film.

[0028] In this invention, the materials of the first protective layer and the second protective layer can be the same or different.

[0029] Further, the thickness of the first protective layer is 30-100 μm, the thickness of the adhesive layer is 0.5-2 μm, the thickness of the substrate is 25-180 μm, the thickness of the metal nanofiber network layer is 0.3-2 μm, the thickness of the polymer protective layer is 1-3 μm, and the thickness of the second protective layer is 10-60 μm.

[0030] Furthermore, the ratio of the thickness of the metal nanofiber network layer to the thickness of the polymer protective layer is 1:1 to 1:5. When the thickness ratio is 1:1 to 1:5, it ensures that the polymer protective layer completely encapsulates and covers the metal nanofiber network layer, and also ensures that when there are pathogenic microorganisms on the surface of the antibacterial film, the metal cations can quickly reach the surface and kill them.

[0031] Furthermore, the sheet resistance of the antibacterial and antiviral film is >10 Ω·cm. 8 Ω / □.

[0032] In this invention, composite metal nanowires are coated inside a polymer protective layer, resulting in a large sheet resistance of the antibacterial and antiviral film. It does not have conductive properties and can be applied to the surface of touch screens in computers, mobile phones, hospital registration and payment machines, which helps with signal reception.

[0033] Secondly, the present invention provides a method for preparing an antibacterial and antiviral film, comprising the following steps:

[0034] Provide base materials;

[0035] Composite metal nanowires with a structured network are deposited on one surface of the substrate to form a metal nanofiber network layer.

[0036] A polymer protective liquid is coated on the surface of the metal nanofiber network layer to form a polymer protective layer.

[0037] Furthermore, the method for preparing the antibacterial and antiviral film includes the following steps:

[0038] Provide base materials;

[0039] Composite metal nanowires with a structured network are deposited on the first surface of the substrate to form a metal nanofiber network layer.

[0040] A polymer protective liquid is coated on the surface of the metal nanofiber network layer to form a polymer protective layer.

[0041] A first protective layer is applied to the surface of the polymer protective layer;

[0042] An adhesive layer is formed on the second surface of the substrate;

[0043] A second protective layer is applied to the surface of the adhesive layer.

[0044] Furthermore, the preparation method of the polymer protective liquid includes the following steps:

[0045] The aromatic ring of an aromatic compound is sulfonated using a sulfonating agent to generate a sulfonated aromatic compound.

[0046] Mix 2-18% of the sulfonated aromatic compound with 10-33% of an aqueous diluent until homogeneous, then add 30-70% of an aqueous aliphatic resin dispersion, 0.1-1% of a wetting and leveling agent, 0.1-1% of a defoamer, and 1-3% of a blocking curing agent in proportion, and mix until homogeneous to obtain the polymer protective liquid.

[0047] The total weight of all components of the polymer protective liquid is 100%, and the amount of each component of the polymer protective liquid is by weight.

[0048] Among them, the wetting and leveling agent can be a silicone-based leveling agent, the defoamer can be a modified polysiloxane-based defoamer, and the closed-type curing agent can be an amine-based curing agent or / and an isocyanate-based curing agent.

[0049] In this invention, the sulfonated aromatic polyurethane resin contains -SO3H groups, which construct uniformly distributed cation channels within the protective layer. When pathogenic microorganisms appear on the surface, the metal cation generator utilizes the ion channels to target and release positive charges that combine with the negative charges of the thiol groups of the pathogenic microorganisms (bacteria, viruses), thereby attacking the pathogenic microorganisms and enhancing the efficiency, safety, and durability of antibacterial and antiviral treatments.

[0050] Furthermore, the preparation method of the polymer protective liquid includes the following steps:

[0051] The aromatic ring of an aromatic compound is sulfonated using a sulfonating agent to generate a sulfonated aromatic compound.

[0052] Mix 2-18% of a sulfonated aromatic compound with 10-33% of an aqueous diluent, ultrasonically disperse for 30-60 minutes, place under a stirring device and start stirring at 300-600 rpm. Then add 30-70% of an aqueous aliphatic resin dispersion, 0.1-1% of a wetting and leveling agent, 0.1-1% of a defoamer, and 1-3% of a blocking curing agent in proportion. Increase the stirring speed to 800-1000 rpm and stir for 15 minutes to obtain the polymer protective liquid. The total weight of all components in the polymer protective liquid is 100%, and the amounts of each component are by weight. The aqueous diluent can be deionized water.

[0053] Furthermore, the method for preparing the sulfonated aromatic compound includes the following steps:

[0054] Aromatic compounds are placed in a reactor, and slow stirring is started. A certain mass of sulfonating agent is added while stirring. The mixture is heated in a water bath to 65-95°C and stirred for 0.5-4 hours. Then, the heating is stopped, and the reactor is placed in an ice-water bath for rapid cooling to obtain a product containing sulfonated aromatic compounds.

[0055] Add an alkaline solution to the generated liquid to neutralize it, stir for 20-50 minutes and then filter. After the filtrate is allowed to stand and crystallize, it is rinsed with pure water, filtered again, and the product is placed in an oven at 50-80℃ to dry, thus obtaining the sulfonated aromatic compound.

[0056] The molar ratio of the aromatic compound to the sulfonating agent is 1:2 to 1:15.

[0057] The alkaline solution can be a concentrated sodium hydroxide solution.

[0058] Furthermore, the aromatic compound is one or more of aromatic polyurethane resin, aromatic epoxy resin, aromatic polyester, and aromatic acrylate.

[0059] Furthermore, the sulfonating agent is one or more of concentrated sulfuric acid, sulfur trioxide, fuming sulfuric acid, chlorosulfonic acid, sulfite, and sulfur dioxide. The concentrated sulfuric acid is concentrated sulfuric acid with a purity > 98%.

[0060] The beneficial effects of this invention are:

[0061] (1) The antibacterial and antiviral film prepared by the present invention has cation channels. Only when pathogenic microorganisms appear on the film surface, the metal cation generator uses the ion channels to release positive charges and combine them with the thiol negative charges of the pathogenic microorganisms (bacteria, viruses) to attack the pathogenic microorganisms, thereby improving the efficiency, safety and durability of antibacterial and antiviral treatment.

[0062] (2) The antibacterial and antiviral film of the present invention has composite metal nanowires coated inside a polymer protective layer, which makes the sheet resistance of the antibacterial and antiviral film relatively large and does not have conductive function. It can be applied to the surface of touch screens such as computers, mobile phones, and hospital registration and payment machines, which helps to receive signals. Attached Figure Description

[0063] Figure 1 This is a schematic diagram of the structure of an antibacterial and antiviral film according to an embodiment of the present invention;

[0064] Figure 2 This is a schematic diagram of the structure of an antibacterial and antiviral film according to another embodiment of the present invention.

[0065] Reference numerals: 100, 200—antibacterial and antiviral film; 101, 201—substrate; 102, 202—metal nanofiber mesh layer; 103, 203—polymer protective layer; 204—first protective layer; 205—adhesive layer; 206—second protective layer. Detailed Implementation

[0066] Unless otherwise specified, the experimental methods described in the following embodiments of the present invention are generally performed under conventional conditions. All commonly used chemical reagents used in the embodiments are commercially available products.

[0067] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0068] The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, apparatus, product, or device that includes a series of steps is not limited to the steps or modules listed, but may optionally include steps not listed, or may optionally include other steps inherent to such process, method, product, or device.

[0069] In this invention, "multiple" refers to two or more. "And / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0070] The specific technical solutions of the present invention will be described in detail below with reference to specific embodiments 1-4.

[0071] Example 1

[0072] (1) As Figure 1As shown, a substrate 101 is provided, wherein the substrate 101 is a PET substrate.

[0073] (2) A metal nanofiber mesh layer 102 is formed on one surface of the substrate 101, and the specific preparation method is shown below:

[0074] 6g of structured silver-coated copper nanowires (25μm in length, 20nm in diameter) were added to 4641.5g of deionized water and stirred at 300rpm. While stirring, 2.5g of modified polyether dispersant, 100g of ethylene glycol, and 250g of isopropanol were added. After stirring for 40min, a composite metal nanowire dispersion was obtained. A spray head was set on a coating device to spray the nano-metal dispersion onto the surface of substrate 101 at a linear velocity of 20m / min. The substrate was then heated and dried. The oven temperature was set to 5 segments, with temperatures of 75℃, 85℃, 100℃, 125℃, and 110℃ respectively. Through segmented temperature control, a metal nanofiber mesh layer 102 with a thickness of 0.8μm was formed on the surface of substrate 101.

[0075] (3) A polymer protective layer 103 is formed on the surface of the metal nanofiber mesh layer 102. The specific preparation method is as follows:

[0076] Place 200g of aromatic polyurethane resin in a 500ml reactor equipped with a condenser, turn on the stirring slowly, and slowly add 80ml of concentrated sulfuric acid (>98%) while stirring at a molar ratio of 1:4. Heat the water bath to 90℃, stir and react for 4 hours, then stop heating and place the reactor in an ice-water bath to cool it rapidly.

[0077] Add 50 ml of concentrated sodium hydroxide (60%) solution to the reactor, stir for 30 min and filter. After the filtrate has been allowed to stand for 8 h to crystallize, it is rinsed 3 times with pure water, filtered again and the product is placed in a 60 °C oven to dry for 24 h to obtain sulfonated aromatic polyurethane resin.

[0078] 250g of sulfonated aromatic compound was added to 1600g of deionized water and ultrasonically dispersed for 45min. The mixture was then placed under a stirring device and stirred. Under slow stirring, 3000g of aqueous aliphatic polyurethane dispersion, 25g of wetting and leveling agent (organosilicon leveling agent), 25g of defoamer (modified polysiloxane defoamer), and 100g of sealing and curing agent (amine curing agent) were added sequentially. The stirring speed was increased to 800rpm and stirred for 15min to obtain the polymer protective liquid.

[0079] The polymer protective liquid was coated onto the surface of the metal nanofiber mesh layer 102 by coating, and dried at 120℃ using a 140-mesh metal roller at a linear speed of 15m / min to obtain the polymer protective layer 103, which has a thickness of 2μm.

[0080] (4) The substrate 101, the metal nanofiber mesh layer 102 and the polymer protective layer 103 are stacked in sequence to form an antibacterial and antiviral film 100.

[0081] Example 2

[0082] (1) As Figure 1 As shown, a substrate 101 is provided, wherein the substrate 101 is a PET substrate.

[0083] (2) A metal nanofiber mesh layer 102 is formed on one surface of the substrate 101, and the specific preparation method is shown below:

[0084] 7.5g of silver-coated copper nanowires with structured overlapping points were added to 4640g of deionized water and stirred at 300rpm. While stirring, 2.5g of modified polyether dispersant, 100g of ethylene glycol, and 250g of isopropanol were added. After stirring for 40min, a composite metal nanowire dispersion was obtained. A spray head was set on a coating device to spray the nano-metal dispersion onto the surface of substrate 101 at a linear velocity of 15m / min. The substrate was then heated and dried. The oven temperature was set to 5 stages, with the temperatures of each stage being 80℃, 100℃, 120℃, 130℃, and 120℃ respectively. Through segmented temperature control, a metal nanofiber mesh layer 102 with a thickness of 1.2μm was formed on the surface of substrate 101.

[0085] (3) A polymer protective layer 103 is formed on the surface of the metal nanofiber mesh layer 102. The specific preparation method is as follows: 135g of aromatic polyurethane resin is placed in a 500ml reactor with a condenser. The stirring is turned on slowly. 100ml of concentrated sulfuric acid (>98%) is slowly added while stirring at a molar ratio of 1:6. The mixture is heated to 90°C in a water bath. After stirring and reacting for 3h, the heating is stopped. The reactor is placed in an ice-water bath for rapid cooling.

[0086] Add 65 ml of concentrated sodium hydroxide (60%) solution to the reactor, stir for 30 min and filter. After the filtrate has been allowed to stand for 8 h to crystallize, it is rinsed 3 times with pure water, filtered again and the product is placed in a 60 °C oven to dry for 24 h to obtain sulfonated aromatic polyurethane resin.

[0087] 150g of sulfonated aromatic compound was added to 2200g of deionized water and ultrasonically dispersed for 45min. The mixture was then placed under a stirring device and stirred slowly. In the following order, 2500g of aqueous aliphatic polyurethane dispersion, 25g of wetting and leveling agent (organosilicon leveling agent), 25g of defoamer (modified polysiloxane defoamer), and 100g of sealing and curing agent (isocyanate curing agent) were added. The stirring speed was increased to 800rpm and stirred for 15 minutes to obtain the polymer protective liquid.

[0088] The polymer protective liquid was coated onto the surface of the metal nanofiber mesh layer 102 by coating, and dried at 120℃ using a 140-mesh metal roller at a linear speed of 15m / min to obtain the polymer protective layer 103, which has a thickness of 1.8μm.

[0089] (4) The substrate 101, the metal nanofiber mesh layer 102 and the polymer protective layer 103 are stacked in sequence to form an antibacterial and antiviral film 100.

[0090] Example 3

[0091] (1) As Figure 2 As shown, a substrate 201 is provided, wherein the substrate 201 is a PET substrate;

[0092] (2) A metal nanofiber mesh layer 202 is formed on one surface of the substrate 201, and the specific preparation method is shown below:

[0093] Six g of structured silver-coated copper nanowires (25 μm in length, 20 nm in diameter) were added to 4641.5 g of deionized water and stirred at 300 rpm. While stirring, 2.5 g of modified polyether dispersant, 100 g of ethylene glycol, and 250 g of isopropanol were added. After stirring for another 40 min, a composite metal nanowire dispersion was obtained. A spray head was set on a coating device, and the nano-metal dispersion was sprayed onto the surface of substrate 101 at a linear velocity of 20 m / min. The substrate 201 was then heated and dried. The oven temperature was set to five stages, with the stage temperatures being 75℃, 85℃, 100℃, 125℃, and 110℃ respectively. The temperature was controlled by a segmented program to form a metal nanofiber mesh layer 202 with a thickness of 0.8 μm on the surface of substrate 201.

[0094] (3) A polymer protective layer 203 is formed on the surface of the metal nanofiber mesh layer 202. The specific preparation method is as follows:

[0095] Place 200g of aromatic polyurethane resin in a 500ml reactor equipped with a condenser, turn on the stirring slowly, and slowly add 80ml of concentrated sulfuric acid (>98%) while stirring at a molar ratio of 1:4. Heat the water bath to 90℃, stir and react for 4 hours, then stop heating and place the reactor in an ice-water bath to cool it rapidly.

[0096] Add 50 ml of concentrated sodium hydroxide (60%) solution to the reactor, stir for 30 min and filter. After the filtrate has been allowed to stand for 8 h to crystallize, it is rinsed 3 times with pure water, filtered again and the product is placed in a 60 °C oven to dry for 24 h to obtain sulfonated aromatic polyurethane resin.

[0097] 250g of sulfonated aromatic compound was added to 1600g of deionized water and ultrasonically dispersed for 45min. The mixture was then placed under a stirring device and stirred. Under slow stirring, 3000g of aqueous aliphatic polyurethane dispersion, 25g of wetting and leveling agent (organosilicon leveling agent), 25g of defoamer (modified polysiloxane defoamer), and 100g of sealing and curing agent (amine curing agent) were added sequentially. The stirring speed was increased to 800rpm and stirred for 15min to obtain the polymer protective liquid.

[0098] The polymer protective liquid was coated onto the surface of the metal nanofiber mesh layer 202 by coating. The polymer protective layer 203 was obtained by drying at 120℃ using a 160-mesh metal roller at a linear speed of 15m / min. The thickness of the obtained polymer protective layer 203 was 1.5μm.

[0099] (4) A first protective layer (release film) 204 is applied to the surface of the polymer protective layer 203 for protection, an adhesive layer 205 is formed by applying adhesive to the second surface of the substrate 201, and a second protective layer (release film) 206 is applied to the surface of the adhesive layer 205 for protection.

[0100] (5) The second protective layer 206, adhesive layer 205, substrate 201, metal nanofiber mesh layer 202, polymer protective layer 203 and first protective layer 204 are stacked in sequence to form an antibacterial and antiviral film 200.

[0101] Example 4

[0102] (1) As Figure 2 As shown, a substrate 101 is provided, wherein the substrate 101 is a PET substrate.

[0103] (2) A metal nanofiber mesh layer 102 is formed on one surface of the substrate 101, and the specific preparation method is shown below:

[0104] 7.5g of silver-coated copper nanowires with structured overlapping points were added to 4640g of deionized water and stirred at 300rpm. While stirring, 2.5g of modified polyether dispersant, 100g of ethylene glycol, and 250g of isopropanol were added. After stirring for 40min, a composite metal nanowire dispersion was obtained. A spray head was set on a coating device to spray the nano-metal dispersion onto the surface of substrate 101 at a linear velocity of 15m / min. The substrate was then heated and dried. The oven temperature was set to 5 stages, with the temperatures of each stage being 80℃, 100℃, 120℃, 130℃, and 120℃ respectively. Through segmented temperature control, a metal nanofiber mesh layer 102 with a thickness of 1.2μm was formed on the surface of substrate 101.

[0105] (3) A polymer protective layer 103 is formed on the surface of the metal nanofiber mesh layer 102. The specific preparation method is as follows: 135g of aromatic polyurethane resin is placed in a 500ml reactor with a condenser. The stirring is turned on slowly. 100ml of concentrated sulfuric acid (>98%) is slowly added while stirring at a molar ratio of 1:6. The mixture is heated to 90°C in a water bath. After stirring and reacting for 3h, the heating is stopped. The reactor is placed in an ice-water bath for rapid cooling.

[0106] Add 65 ml of concentrated sodium hydroxide (60%) solution to the reactor, stir for 30 min and filter. After the filtrate has been allowed to stand for 8 h to crystallize, it is rinsed 3 times with pure water, filtered again and the product is placed in a 60 °C oven to dry for 24 h to obtain sulfonated aromatic polyurethane resin.

[0107] 150g of sulfonated aromatic compound was added to 2200g of deionized water and ultrasonically dispersed for 45min. The mixture was then placed under a stirring device and stirred slowly. In the following order, 2500g of aqueous aliphatic polyurethane dispersion, 25g of wetting and leveling agent (organosilicon leveling agent), 25g of defoamer (modified polysiloxane defoamer), and 100g of sealing and curing agent (isocyanate curing agent) were added. The stirring speed was increased to 800rpm and stirred for 15 minutes to obtain the polymer protective liquid.

[0108] The polymer protective liquid was coated onto the surface of the metal nanofiber mesh layer 102 by coating, and dried at 120℃ using an 80-mesh metal roller at a linear speed of 14m / min to obtain the polymer protective layer 103, which has a thickness of 2.4μm.

[0109] (4) A first protective layer (release film) 204 is applied to the surface of the polymer protective layer 203 for protection, an adhesive layer 205 is formed by applying adhesive to the second surface of the substrate 201, and a second protective layer (release film) 206 is applied to the surface of the adhesive layer 205 for protection.

[0110] (5) The second protective layer 206, adhesive layer 205, substrate 201, metal nanofiber mesh layer 202, polymer protective layer 203 and first protective layer 204 are stacked in sequence to form an antibacterial and antiviral film 200.

[0111] Comparative Example 1

[0112] 8g of silver-coated copper nanowires were dispersed in 500g of deionized water, and 0.2g of dispersant was added. The mixture was stirred at 300rpm for 40min to obtain a silver-coated copper nanowire-aqueous dispersion.

[0113] 250g of sulfonated aromatic compound was added to 1300g of deionized water and ultrasonically dispersed for 45min. The mixture was then placed under a stirring device and stirred. Under slow stirring, 300g of silver-coated copper nanowire-water dispersion, 3000g of aqueous aliphatic polyurethane dispersion, 25g of wetting and leveling agent (organosilicon leveling agent), 25g of defoamer (modified polysiloxane defoamer), and 100g of sealing and curing agent (amine curing agent) were added sequentially. The stirring speed was increased to 800rpm and stirred for 15min to obtain a polymer protective liquid containing antibacterial agent.

[0114] An antibacterial film is obtained by coating a polymer protective liquid containing antibacterial agent onto the surface of a substrate using a 140-mesh metal roller at a linear speed of 15 m / min and drying at 120°C. The thickness of the antibacterial film layer is 2 μm.

[0115] Comparative Example 2

[0116] Except for using a commercially available glass-borne silver-zinc antibacterial agent to replace the silver-coated copper metal nanowire-aqueous dispersion, the preparation method for the antibacterial film was the same as that for Comparative Example 1.

[0117] Physical properties and antibacterial and antiviral properties were tested on Examples 1-4 and Comparative Examples 1-2. The physical property test results of the Examples and Comparative Examples are shown in Table 1.

[0118] Transmittance and haze were measured according to the method specified in "Determination of Transmittance and Haze of Transparent Plastics" and the method specified in "Cross-cut Test of Paint and Varnish Films". Pencil hardness was measured according to the method specified in "Determination of Hardness of Paint and Varnish Films by Pencil Method". Surface sheet resistance was measured using a four-probe sheet resistance meter.

[0119] Table 1

[0120]

[0121]

[0122] For Staphylococcus aureus, Escherichia coli, and Candida albicans, the antibacterial properties of the examples and comparative examples were tested according to the standard GB / T 21866-2008, and the test results are shown in Table 2.

[0123] Table 2

[0124]

[0125] The antibacterial film was applied to a high-traffic elevator for 3 months before its antibacterial activity was tested. The antibacterial films prepared in Examples 1-4 still had an antibacterial effect of over 99.9%, and Comparative Example 1 also had an antibacterial effect of over 99%, but its surface sheet resistance was [not specified]. This limited its application. The antibacterial membrane prepared in Comparative Example 2 showed a significantly reduced permeability and lost its antibacterial effectiveness after 3 months of use.

[0126] For poliomyelitis, H1N1, and COVID-19, the examples and comparative examples were tested according to the standard "ISO 21702:2019", and the test results of their antibacterial properties are shown in Table 3.

[0127] Table 3

[0128]

[0129]

[0130] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0131] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. An antibacterial and antiviral film, characterized in that, It includes a polymer protective layer, a metal nanofiber network layer, and a substrate, which are stacked sequentially. The polymer protective layer is made of a polymer protective liquid with sulfonated groups. The material of the metal nanofiber network layer includes composite metal nanowires with a structured network; The polymer protective layer has ion channels inside; The polymer protective liquid comprises the following raw materials, expressed as a percentage by weight: Sulfonated aromatic compounds 2-18%, Waterborne aliphatic resin dispersion 30-70%, Water-based diluent 10-33%, Wetting and leveling agent 0.1-1%, Defoamer 0.1~1%, Sealing and curing agent 1~3%; The sulfonated aromatic compound is an aromatic polyurethane resin; The total weight of all components in the polymer protective liquid is 100%. The composite metal nanowire consists of metal A encapsulating metal B nanowires; metal B is located inside metal A and has an exposed point; wherein metal A is silver and metal B is copper.

2. The antibacterial and antiviral film according to claim 1, characterized in that, The ratio of the thickness of the metal nanofiber network layer to the thickness of the polymer protective layer is 1:1 to 1:

5.

3. The antibacterial and antiviral film according to claim 1, characterized in that, The sheet resistance of the antibacterial and antiviral film is >10 Ω. 8 Ω / □.

4. The method for preparing the antibacterial and antiviral film according to any one of claims 1 to 3, characterized in that, Includes the following steps: Provide base materials; A composite metal nanowire with a structured network is deposited on one surface of the substrate to form a metal nanofiber network layer; A polymer protective liquid is coated on the surface of the metal nanofiber network layer to form a polymer protective layer.

5. The method for preparing the antibacterial and antiviral film according to claim 4, characterized in that, The preparation method of the polymer protective liquid includes the following steps: The aromatic ring of an aromatic compound is sulfonated using a sulfonating agent to generate a sulfonated aromatic compound. Mix 2-18% of the sulfonated aromatic compound with 10-33% of an aqueous diluent until homogeneous, then add 30-70% of an aqueous aliphatic resin dispersion, 0.1-1% of a wetting and leveling agent, 0.1-1% of a defoamer, and 1-3% of a blocking curing agent in proportion, and mix until homogeneous to obtain the polymer protective liquid. The total weight of all components of the polymer protective liquid is 100%, and the amount of each component of the polymer protective liquid is by weight.

6. The method for preparing the antibacterial and antiviral film according to claim 4, characterized in that, The method for preparing the sulfonated aromatic compound includes the following steps: The aromatic compound is placed in a reactor, and a slow stir is started. The sulfonating agent is added while stirring. The mixture is heated in a water bath to 65-95°C. After stirring and reacting for 0.5-4 hours, the heating is stopped, and the reactor is placed in an ice-water bath for rapid cooling to obtain a product containing the sulfonated aromatic compound. Add an alkaline solution to the generated liquid to neutralize it, stir for 20-50 minutes and then filter. After the filtrate is allowed to stand and crystallize, it is rinsed with pure water, filtered again, and the product is placed in an oven at 50-80℃ to dry, thus obtaining the sulfonated aromatic compound. The molar ratio of the aromatic compound to the sulfonating agent is 1:2 to 1:

15.

7. The method for preparing the antibacterial and antiviral film according to claim 4, characterized in that, The sulfonating agent is one or more of concentrated sulfuric acid, sulfur trioxide, fuming sulfuric acid, chlorosulfonic acid, sulfite, and sulfur dioxide.

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