CN115162023A - Long-acting antibacterial antiviral artificial leather and preparation method thereof - Google Patents

Long-acting antibacterial antiviral artificial leather and preparation method thereof Download PDF

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Publication number
CN115162023A
CN115162023A CN202210826466.1A CN202210826466A CN115162023A CN 115162023 A CN115162023 A CN 115162023A CN 202210826466 A CN202210826466 A CN 202210826466A CN 115162023 A CN115162023 A CN 115162023A
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parts
pvc
agent
antiviral
layer
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胡玉洁
张旭
刘洲
朱磊
李彬
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Dongfeng Motor Corp
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Dongfeng Motor Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation
    • D06N2211/261—Body finishing, e.g. headliners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Abstract

The application relates to a long-acting antibacterial antiviral artificial leather and a preparation method thereof, wherein the artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer; the preparation raw materials of the coating layer comprise the following components in parts by weight: 80-120 parts of waterborne polyurethane, 0.5-10 parts of antibacterial antiviral agent, 1-3 parts of flatting agent, 1-3 parts of hand feeling agent and 5-10 parts of cross-linking agent; wherein the antibacterial and antiviral agent is aqueous nano copper water solution. This application adopts the antibiotic antiviral structural design of individual layer, through giving the antibiotic antiviral performance of finish, can guarantee that the synthetic leather product that makes has obvious antibiotic antiviral performance, and after long-term harsh operating mode condition, still has antibiotic antiviral effect.

Description

Long-acting antibacterial antiviral artificial leather and preparation method thereof
Technical Field
The application relates to the technical field of artificial leather, in particular to long-acting antibacterial and antiviral artificial leather and a preparation method thereof.
Background
With the continuous development and growth of the automobile industry and the development of social economy, the preservation quantity of automobiles is increased year by year, and the automobiles become common transportation means in people's lives gradually. The automobile interior decoration also has the original single functional requirement, and is developed into a product with multiple requirements of comfort, safety, health and the like. At present, the parts of the automobile interior parts which are frequently contacted with drivers and passengers basically realize soft coating, so that the comfort of the drivers and passengers is greatly improved. Through the continuous development of the preparation technology and the surface treatment technology, the existing PVC artificial leather product has excellent wear resistance, mildew resistance, heat resistance and other properties, and has been widely used as an artificial leather material with strong cost competitiveness and excellent touch feeling in the interior parts of automobiles.
As a frequently used and exposed automobile, the closed cabin environment provides a favorable environment for the mass propagation and growth of bacteria and viruses. In view of the complexity of the use conditions of automobiles, the development of the PVC artificial leather material which is applied to the antibacterial and antiviral effects of the interior trims of automobiles and can meet various severe use conditions of automobiles is very necessary.
Disclosure of Invention
The embodiment of the application provides long-acting antibacterial and antiviral artificial leather and a preparation method thereof, a single-layer antibacterial and antiviral structural design is adopted, and the prepared artificial leather product can have obvious antibacterial and antiviral performance by endowing a coating layer with antibacterial and antiviral performance, and still has antibacterial and antiviral effects after long-term severe working conditions.
In a first aspect, the long-acting antibacterial and antiviral artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base fabric layer;
the preparation raw materials of the coating layer comprise the following components in parts by weight: 80-120 parts of waterborne polyurethane, 0.5-10 parts of antibacterial antiviral agent, 1-3 parts of flatting agent, 1-3 parts of hand feeling agent and 5-10 parts of cross-linking agent; wherein the antibacterial and antiviral agent is aqueous nano copper water solution.
In some embodiments, the aqueous nano-copper solution contains 30-150 ppm of nano-copper particles, the particle size distribution D50 of the nano-copper particles is 40-80nm, and the D90 is 70-120 nm.
In some embodiments, the aqueous nano-copper aqueous solution is prepared by the following preparation method:
adding a cupric salt aqueous solution into a mixed aqueous solution of a reducing agent and a coating agent under the stirring condition at the temperature of between 50 and 60 ℃, and preparing a solid after precipitation and washing;
adding the solid into a thiol aqueous solution containing carboxyl with the concentration of 0.01-0.1 mol/L, stirring for 30 min-1 h, washing through precipitation, and adding water to prepare the aqueous nano copper aqueous solution.
In some embodiments, the reducing agent is ascorbic acid, hydrazine hydrate, naBH 4 One of (a) and (b);
and/or the coating agent is one or more of citrate, PVP and PEI;
and/or the cupric salt is CuSO 4 、CuCl 2 、Cu(acac) 2 One or more of (a);
and/or, the thiol containing carboxyl is one or more of thioglycolic acid, 3-mercaptopropionic acid and 6-mercaptohexanoic acid.
In some embodiments, the preparation raw materials of the PVC surface layer comprise the following components in parts by weight: 100 to 150 parts of PVC resin powder, 35 to 75 parts of plasticizer, 5 to 10 parts of stabilizer and 1 to 5 parts of antioxidant.
In some embodiments, the preparation raw materials of the PVC foaming layer comprise the following components in parts by weight: 100 parts of PVC resin powder, 50-70 parts of plasticizer, 1-5 parts of foaming agent and 0.1-5 parts of dispersing agent.
In some embodiments, the polymerization degree of the PVC resin powder is 1250-1600, and the K value is 71-76;
and/or the plasticizer is selected from one or the combination of more than two of phthalate, phosphate, epoxy plasticizer and bio-based plasticizer.
In some embodiments, the stabilizer is selected from one or a combination of two or more of metal soaps, calcium and zinc species, organotin, epoxy compounds, rare earth stabilizers.
In some embodiments, the base fabric layer is made of natural fibers, regenerated fibers or synthetic fibers as a base material by a weaving or knitting process.
In a second aspect, there is provided a method for preparing artificial leather with long-lasting antibacterial and antiviral effects, comprising:
preparing a surface layer: preparing PVC surface layer slurry, uniformly coating the PVC surface layer slurry on release paper, and drying to form a PVC surface layer;
preparing a foaming layer: preparing PVC foaming layer slurry, uniformly coating the PVC foaming layer slurry on a PVC surface layer, and drying to form a PVC foaming layer;
the base cloth layer is attached to the PVC foaming layer and dried;
preparing a coating layer: mixing and stirring the waterborne polyurethane, the waterborne nano-copper aqueous solution, the flatting agent, the hand feeling agent and the cross-linking agent to obtain coating slurry, removing the release paper, uniformly coating the coating slurry on the PVC surface layer, and drying to obtain the long-acting antibacterial antiviral artificial leather.
The beneficial effect that technical scheme that this application provided brought includes:
the raw material with the antibacterial and antiviral effects is the aqueous nano copper aqueous solution, and has the advantage of low cost compared with a silver ion antibacterial agent. Meanwhile, the nano copper particles are combined with the sulfydryl at one end of the thiol micromolecules containing carboxyl, and the carboxyl at the other end of the molecule can improve the water solubility, so that the aqueous nano copper aqueous solution can be prepared, and the aqueous nano copper aqueous solution can be well dispersed in the aqueous polyurethane surface treating agent without using a carrier. Meanwhile, the small molecules are wrapped on the surfaces of the nano-copper particles, so that the problems of oxidation of the nano-copper-containing particles and long-term storage of the nano-copper-containing antibacterial agent can be effectively solved.
The long-acting antibacterial and antiviral artificial leather prepared by the application adopts a single-layer antibacterial and antiviral structural design, and can ensure that the prepared artificial leather product has obvious antibacterial and antiviral performance only by endowing a coating layer with antibacterial and antiviral performance, and still has antibacterial and antiviral effects after long-term harsh working conditions.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method of preparation provided in an embodiment of the present application;
fig. 2 is a flowchart of a method for preparing an aqueous nano copper aqueous solution according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a long-acting antibiotic antiviral synthetic leather can be applied to the soft cladding part of automotive interior, like on parts such as instrument panel, door guard board, seat, ceiling, it is including scribbling decorations layer, PVC surface course, PVC foaming layer and base cloth layer, scribbles decorations layer, PVC surface course, PVC foaming layer and base cloth layer and arranges in proper order.
The coating layer comprises the following raw materials in parts by weight: 80-120 parts of waterborne polyurethane, 0.5-10 parts of antibacterial antiviral agent, 1-3 parts of flatting agent, 1-3 parts of hand feeling agent and 5-10 parts of cross-linking agent; wherein the antibacterial and antiviral agent is aqueous nano copper water solution.
The PVC surface layer comprises the following raw materials in parts by weight: 100 to 150 parts of PVC resin powder, 35 to 75 parts of plasticizer, 5 to 10 parts of stabilizer and 1 to 5 parts of antioxidant.
The PVC foaming layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 50-70 parts of plasticizer, 1-5 parts of foaming agent and 0.1-5 parts of dispersing agent.
The base cloth layer is made of natural fiber, regenerated fiber or synthetic fiber as a base material by a weaving or spinning process.
The raw material with the antibacterial and antiviral effects is the aqueous nano copper aqueous solution, and has the advantage of low cost compared with a silver ion antibacterial agent. Meanwhile, the nano copper particles are combined with the sulfydryl at one end of the thiol micromolecules containing carboxyl, and the carboxyl at the other end of the molecule can improve the water solubility, so that the aqueous nano copper aqueous solution can be prepared, and the aqueous nano copper aqueous solution can be well dispersed in the aqueous polyurethane surface treating agent without using a carrier. Meanwhile, the small molecules are wrapped on the surfaces of the nano-copper particles, so that the problems of oxidation of the nano-copper-containing particles and long-term storage of the nano-copper-containing antibacterial agent can be effectively solved.
The long-acting antibacterial and antiviral artificial leather prepared by the application adopts a single-layer antibacterial and antiviral structural design, and can ensure that the prepared artificial leather product has obvious antibacterial and antiviral performance only by endowing a coating layer with antibacterial and antiviral performance, and still has antibacterial and antiviral effects after long-term harsh working conditions.
Referring to fig. 1, the long-acting antibacterial and antiviral artificial leather can be prepared by the following preparation method:
101. preparation of the facing layer
Selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 20-30 min at the stirring speed of 400 +/-50 rpm;
and uniformly coating the prepared PVC surface layer slurry on the selected release paper by adopting a coating method, and drying at 150-200 ℃ to form the PVC surface layer.
102. Preparation of foamed layer
Preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 30-40min at the stirring speed of 1000 +/-100 rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on a PVC surface layer by adopting a coating method, and drying at 160-200 ℃ to form a PVC foaming layer.
103. And (3) adhering the selected base cloth layer to the PVC foaming layer, and drying at 170 ℃.
104. Preparation of the coating
Preparing coating layer slurry: adding the waterborne polyurethane, the waterborne nano-copper aqueous solution, the flatting agent, the hand feeling agent and the crosslinking agent into a stirring barrel, mixing and stirring to obtain coating layer slurry, wherein the stirring time is 30-40min, and the stirring speed is 1100 +/-100 rpm;
removing the release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing platform, roll-coating the decorative layer slurry on the PVC surface layer, processing at the speed of 7m/min, and drying at the temperature of 100-150 ℃ to obtain the long-acting antibacterial antiviral artificial leather.
Wherein, the antibacterial and antiviral effect can be weakened when the content of the nano-copper is too small, the antibacterial and antiviral performance improving effect is not obvious when the content of the nano-copper is too large, and the preparation process and the dispersibility can be influenced, so that the content of the nano-copper particles in the aqueous nano-copper aqueous solution is 30-150 ppm; the nano-copper has too small particle size, poor stability, too large particle size and difficult dispersion, and the particle size can influence the antibacterial and antiviral properties, so the nano-copper particle has the particle size distribution D50 of 40-80nm and the particle size distribution D90 of 70-120 nm.
Referring to fig. 2, the aqueous nano-copper aqueous solution is prepared by the following preparation method:
201: slowly adding a cupric salt aqueous solution into a mixed aqueous solution of a reducing agent and a coating agent under the conditions of micro-heating at 50-60 ℃ and fully stirring, and preparing a solid after precipitation and washing.
202: adding the solid into a thiol aqueous solution containing carboxyl with the concentration of 0.01-0.1 mol/L, fully stirring for 30 min-1 h, washing by precipitation, and adding water to prepare an aqueous nano copper aqueous solution, wherein the water can adopt deionized water.
In the application, the combination of the sulfydryl at one end of the thiol containing carboxyl and the cupric salt can improve the stability, the carboxyl at the end can improve the dispersibility and the water compatibility, and the Cu belongs to an inorganic substance, can realize the antibacterial and antiviral effect by dissolving out trace ions, and can realize long-acting effect. Therefore, the water-based nano copper prepared by the method has the advantages of good dispersibility, high stability and long acting.
Wherein the reducing agent is ascorbic acid, hydrazine hydrate, naBH 4 (sodium borohydride).
The coating agent is one or more of citrate, PVP (polyvinylpyrrolidone) and PEI (polyethyleneimine).
The cupric salt is CuSO 4 、CuCl 2 、Cu(acac) 2 One or more of (a).
The thiol containing carboxyl is one or more of thioglycolic acid, 3-mercaptopropionic acid and 6-mercaptohexanoic acid.
The polymerization degree of the PVC resin powder is 1250-1600, and the K value is 71-76.
The plasticizer is selected from one or more of phthalate, phosphate, epoxy plasticizer and bio-based plasticizer.
The stabilizer is one or the combination of more than two of metal soap, calcium zinc, organic tin, epoxy compound and rare earth stabilizer.
The aqueous polyurethane is commercially available, and is selected from, for example, stahl WF-13-417 or Stahl EVO WF-3649/A.
The leveling agent is commercially available, and is selected from BYK 342 and BYK L9565.
The hand feeling agent is commercially available, and is selected from AC-629/A, HM-186.
The cross-linking agent is commercially available, and is selected from Starter XR-5580, XR-28-404.
The foaming agent is commercially available, and is selected from AC381 and AC2000.
The dispersant is commercially available, and is selected from BYK 182 and EFKA4010, for example.
The antioxidant is commercially available, such as 1010, 2246.
Example 1:
a long-acting antibacterial and antiviral artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer.
The coating layer comprises the following raw materials in parts by weight: 110 parts of waterborne polyurethane, 5 parts of antibacterial antiviral agent, 1 part of flatting agent, 3 parts of hand feeling agent and 5 parts of crosslinking agent.
The antibacterial and antiviral agent is an aqueous nano copper aqueous solution, and the preparation method comprises the following two steps: slowly adding CuSO (cupric oxide) salt into a mixed aqueous solution of an ascorbic acid reducing agent and a PVP (polyvinyl pyrrolidone) coating agent under the conditions of low heat at 60 ℃ and full stirring 4 Water solution, and solid is prepared after precipitation and washing. And then adding the solid into 0.05mol/L thioglycollic acid aqueous solution, fully stirring for 45min, washing through precipitation, and adding deionized water to prepare aqueous nano copper aqueous solution with the nano copper particle content of 150 ppm.
The PVC surface layer is formed by drying PVC surface layer slurry at 190 ℃, and the PVC surface layer comprises the following raw materials in parts by weight: 130 parts of PVC resin powder (polymerization degree 1350), 65 parts of phthalate plasticizer, 10 parts of metal soap stabilizer and 2 parts of antioxidant.
The PVC foaming layer is positioned between the PVC surface layer and the synthetic fiber base cloth layer, the PVC foaming layer is formed by drying PVC foaming layer slurry at 180 ℃, and the PVC foaming layer comprises the following preparation raw materials in parts by weight: 100 parts of PVC resin powder, 60 parts of plasticizer, 1 part of foaming agent and 1 part of dispersing agent.
The preparation method of the long-acting antibacterial and antiviral artificial leather comprises the following steps:
(1) Preparing a surface layer:
selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 30min at the stirring speed of 450rpm; uniformly coating the prepared PVC surface layer slurry on selected release paper by adopting a coating method, and drying at 190 ℃ to form a PVC surface layer;
(2) Preparing a foaming layer:
preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 30min at the stirring speed of 1000rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on the PVC surface layer prepared in the previous step by adopting a coating method, and drying at 180 ℃ to form a PVC foaming layer;
(3) The selected base cloth layer is adhered to the PVC foaming layer and then dried at 170 ℃;
(4) Preparing a coating layer:
preparing coating layer slurry: adding the waterborne polyurethane, the waterborne nano-copper aqueous solution, the leveling agent, the hand feeling agent and the crosslinking agent into a stirring barrel, stirring for 30min at the stirring speed of 1100rpm;
removing release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing platform, roll-coating the decorative layer slurry on the PVC surface layer, processing at the speed of 7m/min, and drying at the temperature of 140 ℃ to obtain the long-acting antibacterial antiviral artificial leather.
Example 2:
a long-acting antibacterial and antiviral artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer.
The coating layer comprises the following raw materials in parts by weight: 80 parts of waterborne polyurethane, 5 parts of antibacterial antiviral agent, 1 part of flatting agent, 2 parts of hand feeling agent and 5 parts of crosslinking agent.
The antibacterial and antiviral agent is an aqueous nano copper aqueous solution, and the preparation method comprises the following two steps: under the condition of 60 ℃ slight heat and full stirring, naBH is added 4 Slowly adding cupric salt Cu (acac) into mixed aqueous solution of reducing agent and PVP coating agent 2 Water solution, and solid is prepared after precipitation and washing. And then adding the solid into a 3-mercaptopropionic acid aqueous solution with the concentration of 0.05mol/L, fully stirring for 30min, washing through precipitation, and adding deionized water to prepare the aqueous nano-copper aqueous solution with the nano-copper particle content of 50 ppm.
The PVC surface layer is formed by drying PVC surface layer slurry at 170 ℃, and the PVC surface layer slurry comprises the following raw materials in parts by weight: 120 parts of PVC resin powder (polymerization degree 1600), 65 parts of phthalate plasticizer, 8 parts of calcium-zinc stabilizer and 5 parts of antioxidant.
The PVC foaming layer is positioned between the PVC surface layer and the synthetic fiber base cloth layer, the PVC foaming layer is formed by drying PVC foaming layer slurry at 200 ℃, and the preparation raw materials of the PVC foaming layer comprise the following components in parts by weight: 100 parts of PVC resin powder, 60 parts of plasticizer, 2 parts of foaming agent and 5 parts of dispersing agent.
The preparation method of the long-acting antibacterial antiviral artificial leather comprises the following steps:
(1) Preparing a surface layer: selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 20min at the stirring speed of 400rpm; uniformly coating the prepared PVC surface layer slurry on selected release paper by adopting a coating method, and drying at 170 ℃ to form a PVC surface layer;
(2) Preparing a foaming layer:
preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 40min at the stirring speed of 1000rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on the PVC surface layer prepared in the previous step by adopting a coating method, and drying at 200 ℃ to form a PVC foaming layer;
(3) The selected base cloth layer is adhered to the PVC foaming layer and then dried at 170 ℃;
(4) Preparing a coating layer:
preparing coating layer slurry: adding the waterborne polyurethane, the waterborne nano-copper aqueous solution, the flatting agent, the hand feeling agent and the crosslinking agent into a stirring barrel, stirring for 40min at the stirring speed of 1000rpm;
removing the release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing platform, roll-coating the decorative layer slurry on the PVC surface layer, processing at the speed of 7m/min, and drying at the temperature of 130 ℃ to obtain the long-acting antibacterial antiviral artificial leather.
Example 3:
a long-acting antibacterial and antiviral artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer.
The coating layer comprises the following raw materials in parts by weight: 120 parts of waterborne polyurethane, 5 parts of antibacterial antiviral agent, 1 part of flatting agent, 1 part of hand feeling agent and 8 parts of crosslinking agent.
The antibacterial antiviral agent is an aqueous nano copper aqueous solution, and the preparation method comprises the following two steps of chemical reduction and coating agent exchange: slowly adding cupric salt CuCl into the mixed water solution of hydrazine hydrate reducing agent and PVP coating agent under the conditions of 50 ℃ of low heat and full stirring 2 Water solution, and solid is prepared after precipitation and washing. And then adding the solid into a thioglycollic acid aqueous solution with the concentration of 0.05mol/L, fully stirring for 30min, washing through precipitation, and adding deionized water to prepare the aqueous nano copper aqueous solution with the nano copper particle content of 100 ppm.
The PVC surface layer is formed by drying PVC surface layer slurry at 180 ℃, and the PVC surface layer slurry comprises the following raw materials in parts by weight: 130 parts of PVC resin powder (with the polymerization degree of 1500), 70 parts of phthalate plasticizer, 8 parts of epoxy compound stabilizer and 5 parts of antioxidant.
The PVC foaming layer is positioned between the PVC surface layer and the synthetic fiber base cloth layer, the PVC foaming layer is formed by drying PVC foaming layer slurry at 180 ℃, and the preparation raw materials of the PVC foaming layer comprise the following components in parts by weight: 100 parts of PVC resin powder, 70 parts of plasticizer, 1 part of foaming agent and 0.1 part of dispersing agent.
The preparation method of the long-acting antibacterial antiviral artificial leather comprises the following steps:
(1) Preparing a surface layer: selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 20min at the stirring speed of 400rpm; uniformly coating the prepared PVC surface layer slurry on selected release paper by adopting a coating method, and drying at 180 ℃ to form a PVC surface layer;
(2) Preparing a foaming layer:
preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 40min at the stirring speed of 900rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on the PVC surface layer prepared in the previous step by adopting a coating method, and drying at 180 ℃ to form a PVC foaming layer;
(3) The selected base cloth layer is adhered to the PVC foaming layer and then dried at 170 ℃;
(4) Preparing a coating layer:
preparing coating layer slurry: adding the waterborne polyurethane, the waterborne nano-copper aqueous solution, the flatting agent, the hand feeling agent and the crosslinking agent into a stirring barrel, stirring for 30min at the stirring speed of 1000rpm;
removing release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing platform, roll-coating the decorative layer slurry on the PVC surface layer, processing at the speed of 7m/min, and drying at the temperature of 140 ℃ to obtain the long-acting antibacterial antiviral artificial leather.
Example 4:
a long-acting antibacterial and antiviral artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer.
The coating layer comprises the following raw materials in parts by weight: 120 parts of waterborne polyurethane, 1 part of antibacterial antiviral agent, 2 parts of flatting agent, 1 part of hand feeling agent and 10 parts of cross-linking agent.
The antibacterial antiviral agent is an aqueous nano copper aqueous solution, and the preparation method comprises the following two steps of chemical reduction and coating agent exchange: slowly adding cupric salt CuCl into mixed aqueous solution of hydrazine hydrate reducing agent and citrate coating agent under the conditions of 50 ℃ of slight heat and full stirring 2 Water solution, and solid is prepared after precipitation and washing. And then adding the solid into a 6-mercaptohexanoic acid aqueous solution with the concentration of 0.05mol/L, fully stirring for 45min, washing through precipitation, and adding deionized water to prepare a water-based nano copper aqueous solution with the nano copper particle content of 100 ppm.
The PVC surface layer is formed by drying PVC surface layer slurry at 170 ℃, and the PVC surface layer slurry comprises the following raw materials in parts by weight: 120 parts of PVC resin powder (with the polymerization degree of 1350), 40 parts of phthalate plasticizer, 8 parts of rare earth stabilizer and 4 parts of antioxidant.
The PVC foaming layer is positioned between the PVC surface layer and the regenerated fiber base cloth layer, is formed by drying PVC foaming layer slurry at 180 ℃, and comprises the following components in parts by weight: 100 parts of PVC resin powder, 50 parts of plasticizer, 1 part of foaming agent and 1.5 parts of dispersing agent.
The preparation method of the long-acting antibacterial antiviral artificial leather comprises the following steps:
(1) Preparing a surface layer: selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 20min at the stirring speed of 350rpm; uniformly coating the prepared PVC surface layer slurry on selected release paper by adopting a coating method, and drying at 170 ℃ to form a PVC surface layer;
(2) Preparing a foaming layer:
preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 30min at the stirring speed of 1100rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on the PVC surface layer prepared in the previous step by adopting a coating method, and drying at 180 ℃ to form a PVC foaming layer;
(3) The selected base cloth layer is adhered to the PVC foaming layer and then dried at 170 ℃;
(4) Preparing a coating layer:
preparing coating layer slurry: adding the waterborne polyurethane, the waterborne nano-copper aqueous solution, the flatting agent, the hand feeling agent and the crosslinking agent into a stirring barrel, stirring for 40min at the stirring speed of 1200rpm;
removing the release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing platform, roll-coating the decorative layer slurry on the PVC surface layer, processing at the speed of 7m/min, and drying at the temperature of 100 ℃ to obtain the long-acting antibacterial antiviral artificial leather.
Example 5:
a long-acting antibacterial and antiviral artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer.
The coating layer comprises the following raw materials in parts by weight: 120 parts of waterborne polyurethane, 5 parts of antibacterial antiviral agent, 3 parts of flatting agent, 2 parts of hand feeling agent and 8 parts of crosslinking agent.
The antibacterial and antiviral agent is an aqueous nano copper aqueous solution, and the preparation method comprises the following two steps: slowly adding cupric salt CuSO into mixed aqueous solution of hydrazine hydrate reducing agent and PVP coating agent under the conditions of 60 ℃ micro-heating and full stirring 4 Water solution, and solid is prepared after precipitation and washing. And then adding the solid into a 3-mercaptopropionic acid aqueous solution with the concentration of 0.02mol/L, fully stirring for 30min, washing through precipitation, and adding deionized water to prepare an aqueous nano-copper aqueous solution with the nano-copper particle content of 150 ppm.
The PVC surface layer is formed by drying PVC surface layer slurry at 170 ℃, and the PVC surface layer slurry comprises the following raw materials in parts by weight: 130 parts of PVC resin powder (polymerization degree 1250), 75 parts of phthalate plasticizer, 8 parts of epoxy compound stabilizer and 1 part of antioxidant.
The PVC foaming layer is positioned between the PVC surface layer and the regenerated fiber base cloth layer, is formed by drying PVC foaming layer slurry at 190 ℃, and comprises the following components in parts by weight: 100 parts of PVC resin powder, 50 parts of plasticizer, 2 parts of foaming agent and 1.5 parts of dispersing agent.
The preparation method of the long-acting antibacterial and antiviral artificial leather comprises the following steps:
(1) Preparing a surface layer: selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 20min at a stirring speed of 450rpm; uniformly coating the prepared PVC surface layer slurry on selected release paper by adopting a coating method, and drying at 170 ℃ to form a PVC surface layer;
(2) Preparing a foaming layer:
preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 40min at the stirring speed of 1000rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on the PVC surface layer prepared in the last step by adopting a coating method, and drying at 190 ℃ to form a PVC foaming layer;
(3) The selected base cloth layer is adhered to the PVC foaming layer and then dried at 170 ℃;
(4) Preparing a coating layer:
preparing coating layer slurry: adding the waterborne polyurethane, the waterborne nano-copper aqueous solution, the flatting agent, the hand feeling agent and the crosslinking agent into a stirring barrel, stirring for 30min at the stirring speed of 1100rpm;
removing the release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing platform, roll-coating the decorative layer slurry on the PVC surface layer, processing at the speed of 7m/min, and drying at the temperature of 110 ℃ to obtain the long-acting antibacterial antiviral artificial leather.
Comparative example:
a common artificial leather comprises a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer.
The coating layer comprises the following raw materials in parts by weight: 100 parts of waterborne polyurethane, 3 parts of a leveling agent, 2 parts of a hand feeling agent and 10 parts of a crosslinking agent.
The PVC surface layer is formed by drying PVC surface layer slurry at 160 ℃, and the PVC surface layer slurry comprises the following raw materials in parts by weight: 130 parts of PVC resin powder (polymerization degree 1350), 40 parts of phthalate plasticizer, 8 parts of calcium-zinc stabilizer and 5 parts of antioxidant.
The PVC foaming layer is positioned between the PVC surface layer and the natural fiber base cloth layer, the PVC foaming layer is formed by drying PVC foaming layer slurry at 160 ℃, and the preparation raw materials of the PVC foaming layer comprise the following components in parts by weight: 100 parts of PVC resin powder, 50 parts of plasticizer, 5 parts of foaming agent and 5 parts of dispersing agent.
The preparation method of the common artificial leather comprises the following steps:
(1) Preparing a surface layer:
selecting release paper, preparing PVC surface layer slurry: adding PVC resin powder, a plasticizer, a stabilizer and an antioxidant into a high-speed stirring barrel, and stirring for 30min at the stirring speed of 350rpm; uniformly coating the prepared PVC surface layer slurry on selected release paper by adopting a coating method, and drying at 160 ℃ to form a PVC surface layer;
(2) Preparing a foaming layer:
preparing PVC foaming layer slurry: adding PVC resin powder, a plasticizer, a foaming agent and a dispersing agent into a high-speed stirring barrel, and stirring for 30min at the stirring speed of 1000rpm; continuously introducing air into the slurry from the bottom of the stirring barrel in the stirring process;
uniformly coating the prepared PVC foaming layer slurry on the PVC surface layer prepared in the previous step by adopting a coating method, and drying at 160 ℃ to form a PVC foaming layer;
(3) The selected base cloth layer is adhered to the PVC foaming layer and then dried at 170 ℃;
(4) Preparing a coating layer:
preparing coating layer slurry: adding the waterborne polyurethane, the flatting agent, the hand feeling agent and the crosslinking agent into a stirring barrel, stirring for 40min at the stirring speed of 1200rpm;
removing release paper, performing surface treatment on the PVC surface layer by adopting a two-roll printing and brushing table, and rolling the coating slurry on the PVC surface layer at a processing speed of 7m/min and drying at 150 ℃ to obtain the common artificial leather.
Example of effects:
the artificial leather having antibacterial and antiviral effects and the general artificial leather prepared according to the comparative examples of examples 1 to 5 were subjected to photo-aging treatment (xenon lamp, black standard temperature 100 ℃, wavelength 420nm, irradiation intensity 1.4W/m2, treatment time 240 hours), heat aging treatment (85 ℃ X240 hours), taber abrasion treatment (CS 10/1000g/2000 rev), and martindale abrasion treatment (13.8 Kpa) of 1600g/20000 times.
The antibacterial performance is tested according to QB/T4715-2014 and QB/T4341-2012 standards, and the tested strains are staphylococcus aureus and escherichia coli. The antivirus test is that SARS-CoV-2 virus stock solution is contacted with the long-acting antibacterial antivirus artificial leather material according to a virus titer determination method, the virus titer is detected after incubation for 1h, and the virus inactivation rate is calculated.
The performance characteristics of the long-acting antibacterial and antiviral artificial leather manufactured in examples 1 to 5 and the general artificial leather manufactured in the comparative example are shown in table 1.
Table 1 results of performance test of examples and comparative examples
Figure BDA0003744137780000161
Figure BDA0003744137780000171
As can be seen from Table 1, the antibacterial and antiviral agent coating layer adopted by the application has better light stability, heat resistance and wear resistance, can meet the severe operating condition requirements of automotive interior parts, and has lasting antibacterial and antiviral properties.
In the description of the present application, it should be noted that the terms "upper", "lower", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are only for convenience in describing the present application and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and operate, and thus, should not be construed as limiting the present application. Unless expressly stated or limited otherwise, the terms "mounted," "connected," and "coupled" are to be construed broadly and encompass, for example, both fixed and removable coupling as well as integral coupling; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
It is noted that, in the present application, relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The long-acting antibacterial antiviral artificial leather is characterized by comprising a coating layer, a PVC surface layer, a PVC foaming layer and a base cloth layer;
the preparation raw materials of the coating layer comprise the following components in parts by weight: 80-120 parts of waterborne polyurethane, 0.5-10 parts of antibacterial antiviral agent, 1-3 parts of flatting agent, 1-3 parts of hand feeling agent and 5-10 parts of cross-linking agent; wherein the antibacterial and antiviral agent is aqueous nano copper water solution.
2. The long-acting antibacterial and antiviral artificial leather according to claim 1, wherein:
the content of nano-copper particles in the aqueous nano-copper aqueous solution is 30-150 ppm, the particle size distribution D50 of the nano-copper particles is 40-80nm, and the D90 is 70-120 nm.
3. The long-acting antibacterial and antiviral artificial leather according to claim 1, wherein the aqueous nano copper aqueous solution is obtained by the following preparation method:
adding a cupric salt aqueous solution into a mixed aqueous solution of a reducing agent and a coating agent under the stirring condition at the temperature of between 50 and 60 ℃, and preparing a solid after precipitation and washing;
and adding the solid into a thiol aqueous solution containing carboxyl with the concentration of 0.01-0.1 mol/L, stirring for 30 min-1 h, washing through precipitation, and adding water to prepare the aqueous nano-copper aqueous solution.
4. The long-acting antibacterial and antiviral artificial leather according to claim 3, wherein:
the reducing agent is ascorbic acid, hydrazine hydrate and NaBH 4 One of (1);
and/or the coating agent is one or more of citrate, PVP and PEI;
and/or the cupric salt is CuSO 4 、CuCl 2 、Cu(acac) 2 One or more of;
and/or, the thiol containing carboxyl is one or more of thioglycolic acid, 3-mercaptopropionic acid and 6-mercaptohexanoic acid.
5. The long-acting antibacterial and antiviral artificial leather according to claim 1, wherein:
the PVC surface layer is prepared from the following raw materials in parts by weight: 100 to 150 parts of PVC resin powder, 35 to 75 parts of plasticizer, 5 to 10 parts of stabilizer and 1 to 5 parts of antioxidant.
6. The long-acting antibacterial and antiviral artificial leather according to claim 1, wherein:
the PVC foaming layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 50-70 parts of plasticizer, 1-5 parts of foaming agent and 0.1-5 parts of dispersing agent.
7. The long-acting antibacterial and antiviral artificial leather according to claim 5 or 6, wherein:
the polymerization degree of the PVC resin powder is 1250-1600, and the K value is 71-76;
and/or the plasticizer is selected from one or the combination of more than two of phthalate, phosphate, epoxy plasticizer and bio-based plasticizer.
8. The long-acting antibacterial and antiviral artificial leather according to claim 5, wherein:
the stabilizer is selected from one or the combination of more than two of metal soap, calcium zinc, organic tin, epoxy compound and rare earth stabilizer.
9. The long-acting antibacterial and antiviral artificial leather according to claim 1, wherein:
the base cloth layer is made of natural fibers, regenerated fibers or synthetic fibers serving as base materials through a weaving or spinning process.
10. A method for preparing artificial leather having long-lasting antibacterial and antiviral effects as claimed in any one of claims 1 to 9, comprising:
preparing a surface layer: preparing PVC surface layer slurry, uniformly coating the PVC surface layer slurry on release paper, and drying to form a PVC surface layer;
preparing a foaming layer: preparing PVC foaming layer slurry, uniformly coating the PVC foaming layer slurry on a PVC surface layer, and drying to form a PVC foaming layer;
the base cloth layer is attached to the PVC foaming layer and dried;
preparing a coating layer: mixing and stirring the waterborne polyurethane, the waterborne nano copper aqueous solution, the flatting agent, the hand feeling agent and the cross-linking agent to obtain coating layer slurry, removing the release paper, uniformly coating the coating layer slurry on the PVC surface layer, and drying to obtain the long-acting antibacterial and antiviral artificial leather.
CN202210826466.1A 2022-07-13 2022-07-13 Long-acting antibacterial antiviral artificial leather and preparation method thereof Pending CN115162023A (en)

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