WO2022007430A1 - 一种抗菌材料及其制备方法和应用 - Google Patents

一种抗菌材料及其制备方法和应用 Download PDF

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WO2022007430A1
WO2022007430A1 PCT/CN2021/081563 CN2021081563W WO2022007430A1 WO 2022007430 A1 WO2022007430 A1 WO 2022007430A1 CN 2021081563 W CN2021081563 W CN 2021081563W WO 2022007430 A1 WO2022007430 A1 WO 2022007430A1
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antibacterial
quaternary ammonium
antibacterial material
antibacterial agent
ammonium salt
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PCT/CN2021/081563
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English (en)
French (fr)
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陈立
郑明�
毛逸宁
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中科鼎晟科技有限公司
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Publication of WO2022007430A1 publication Critical patent/WO2022007430A1/zh

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups

Definitions

  • the present application relates to the field of materials, in particular to an antibacterial material and a preparation method and application thereof.
  • the antibacterial properties of non-woven fabrics are often improved by adding inorganic antibacterial agents to non-woven fabrics.
  • inorganic antibacterial agents For example, silver, zinc, copper, titanium and its compounds are plated on non-woven fabrics, but when non-woven products with inorganic antibacterial agents are added to the human body, for example, the human body wears masks made of silver-plated non-woven fabrics.
  • the protective clothing is made of silver-plated non-woven fabrics, the metal particles on the non-woven fabrics are easy to fall off and enter the human body, which will cause potential harm to the human body.
  • the present application provides an antibacterial material and a preparation method and application thereof, so as to solve the problem that the existing antibacterial material is dangerous to the human body when it acts on the human body.
  • a first aspect of the present application provides an antibacterial material, the antibacterial material includes a non-woven substrate and an antibacterial agent cured on the nonwoven substrate, wherein the antibacterial agent includes a quaternary ammonium salt.
  • the quaternary ammonium salt includes tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.
  • a second aspect of the present application provides a method for preparing an antibacterial material, the method comprising:
  • the antibacterial agent solution is obtained by mixing at least a quaternary ammonium salt, an organic solvent, a surfactant and an inorganic solvent;
  • the impregnated substrate is dried to solidify the quaternary ammonium salt on the non-woven substrate to obtain an antibacterial material.
  • the quaternary ammonium salt includes tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.
  • the temperature of the drying treatment is 70°C to 180°C.
  • the duration of the drying treatment is 1 min to 10 min.
  • the antibacterial agent solution includes each component of the following mass percentages:
  • the surfactant is oleic acid amide.
  • the organic solvent is triethylene glycol monomethyl ether.
  • the third aspect of the present application provides an application of the antibacterial material prepared by any one of the methods provided in the second aspect of the present application in inhibiting or killing the 2019 novel coronavirus.
  • the antibacterial material provided in this application has a good adsorption and removal effect on the 2019 novel coronavirus.
  • the antibacterial agent solidified on the non-woven substrate is quaternary ammonium salt, which is a non-metallic substance, and when it acts on the human body, it will not cause harm to the human body.
  • the antibacterial agent can be stably cured on the non-woven fabric substrate, is not easy to fall off, and has low cost, which is easy to mass-produce and popularized and applied.
  • Fig. 1 is the flow chart of the preparation method embodiment 1 of the antibacterial material provided by the application;
  • FIG. 2 is a schematic diagram of the preparation of the antibacterial material provided by the application.
  • Figure 3 is a graph of amplification curves obtained by fluorescence quantitative PCR detection.
  • first, second, third, etc. may be used in this application to describe various information, such information should not be limited by these terms. These terms are only used to distinguish the same type of information from each other.
  • first information may also be referred to as the second information, and similarly, the second information may also be referred to as the first information without departing from the scope of the present application.
  • word "if” as used herein can be interpreted as "at the time of” or "when” or "in response to determining.”
  • the antibacterial properties of non-woven fabrics are often improved by adding inorganic antibacterial agents to non-woven fabrics.
  • inorganic antibacterial agents For example, silver, zinc, copper, titanium and its compounds are plated on non-woven fabrics, but when non-woven products with inorganic antibacterial agents are added to the human body, for example, the human body wears masks made of silver-plated non-woven fabrics.
  • the protective clothing is made of silver-plated non-woven fabrics, the metal particles on the non-woven fabrics are easy to fall off and enter the human body, which will cause potential harm to the human body.
  • the present application provides an antibacterial material and a preparation method and application thereof, so as to solve the problem that the existing antibacterial material is dangerous to the human body when it acts on the human body.
  • FIG. 1 is a flow chart of Embodiment 1 of the preparation method of the antibacterial material provided by the application.
  • FIG. 2 is a schematic diagram of the preparation of the antibacterial material provided by the application. Please refer to FIG. 1 and FIG. 2 at the same time, the preparation method of the antibacterial material provided in this embodiment may include:
  • S101 Prepare an antibacterial agent solution; wherein, the antibacterial agent solution is obtained by mixing at least a quaternary ammonium salt, an organic solvent, a surfactant and an inorganic solvent.
  • the organic solvent is mainly used as a solvent to be miscible with an inorganic solvent
  • the organic solvent can be alcohols such as methanol, isopropanol, propylene glycol, pentaerythritol and other solvents or ester solvents such as propylene carbonate.
  • the organic solvent may be triethylene glycol monomethyl ether (its molecular formula is C 7 H 16 O 4 ), and its mass fraction in the antibacterial agent solution may be 0.01% to 5%.
  • its mass fraction in the antibacterial agent solution can be 0.01%, 1%, 2%, 3% or 4%, etc.
  • the surfactant is mainly used to reduce the tension of the liquid surface, so that the fiber substrate can fully absorb the antibacterial agent solution.
  • the surfactant may be oleic acid amide (molecular formula is C 18 H 35 NO), and its mass fraction in the antibacterial agent solution may be 0.05% to 1%.
  • its mass fraction in the antibacterial agent solution can be 0.05%, 0.08%, 1% and the like.
  • the inorganic active agent may be pure water or deionized water.
  • quaternary ammonium salts are mainly used for adsorption and removal of viruses. It may include at least one of the following quaternary ammonium salts: chitosan quaternary ammonium salts, double-chain quaternary ammonium salts, multi-chain quaternary ammonium salts, and organosilicon quaternary ammonium salts. For example, it may be dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, cetyltrimethylammonium bromide, tetradecyldimethylbenzyl chloride ammonium chloride, cetyl pyridinium chloride and combinations thereof, etc.
  • the quaternary ammonium salt may be tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.
  • tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride also called tetraacetate dimethyl(3-3methoxysilylpropyl)ammonium or
  • the mass fraction of dimethyl (3-3 methoxysilylpropyl) ammonium tetraacetate 50% hydrochloric acid solution, the molecular formula is C 22 H 50 ClNO 3 Si, commonly known as multi-chain quaternary ammonium salt) in the antibacterial agent solution can be 1% to 20%.
  • its mass fraction in the antibacterial agent solution can be 4%, 10%, 15% and the like.
  • the mass fraction of quaternary ammonium salts in the antibacterial agent solution is too low or too high to improve its curing effect on non-woven fabrics.
  • the mass fraction of tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride in the antibacterial agent solution is 3% to 10%, it is on the non-woven fabric substrate.
  • the curing effect is the best (it should be noted that the better the curing effect, the better the stability of the quaternary ammonium salt that characterizes curing on the non-woven substrate, and the higher the concentration. Among them, the higher the concentration, the better the antibacterial properties of the antibacterial material. the better).
  • the antibacterial agent solution includes each component in the following mass percentages:
  • quaternary ammonium salt is tetradecyl dimethyl (3-3 methoxysilyl propyl)
  • organic solvent is triethylene glycol monomethyl ether
  • surfactant is oleic acid amide
  • inorganic solvent is deionized water
  • tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride commonly known as multi-chain quaternary ammonium salt
  • triethylene glycol monomethyl ether commonly known as multi-chain quaternary ammonium salt
  • Oleic acid amide and water are mixed according to the ratio shown in Table 1 to obtain an antibacterial agent solution:
  • multi-chain quaternary ammonium salt, triethylene glycol monomethyl ether, oleic acid amide and water can be mixed according to the ratio shown in Table 2 to obtain an antibacterial agent solution:
  • multi-chain quaternary ammonium salt, triethylene glycol monomethyl ether, oleic acid amide and water can be mixed according to the ratio shown in Table 3 to obtain an antibacterial agent solution:
  • the above four substances can be mixed under specified conditions.
  • the above four substances can be mixed with stirring.
  • the mixed solution can be heated at a specified temperature.
  • the mixed solution can be vibrated at a high speed. In this embodiment, this is not limited.
  • the content ratios in the above Tables 1 to 3 are only implementations shown in the exemplary embodiments. Of course, the present application may adopt different ratios according to specific circumstances.
  • a stabilizer may be added to increase the stability of the antibacterial agent solution.
  • the stabilizer may be a non-toxic antimony-based stabilizer.
  • the non-woven fabric substrate can be a non-woven fabric produced by various production processes. For example, it may be a spunbond nonwoven, a needle punched nonwoven, a meltblown nonwoven, and the like.
  • the non-woven fabric can be made of polypropylene (Polypropylene, referred to as PP), polyester (Polyester, referred to as PET), acrylic fiber, nylon, polyvinyl chloride (Polyvinyl Chloride, referred to as PVC) and polybutylene terephthalate (Polybutylene Terephthalate) , referred to as PBT) and other non-woven fabrics produced as raw materials.
  • the following is an example of a non-woven fabric made of PP as a raw material and produced by a spunbond process.
  • immersion refers to soaking in a liquid.
  • the rolled non-woven base material can be unrolled by an unwinding device, and then the unrolled non-woven fabric can enter a solution pool (in which an antibacterial agent solution is placed), and soak in a In the antibacterial agent solution, it is fully contacted with the antibacterial agent solution in the solution pool, soaked through, and the immersed base material is obtained.
  • the impregnated substrate can be put into an oven to be dried by an oven, so that the quaternary ammonium salt is cured on the non-woven substrate to obtain an antibacterial material. Finally, the obtained antibacterial material is wound into a roll shape by a winding device.
  • the drying temperature during the drying treatment can be determined according to the temperature tolerance of the non-woven fabric substrate.
  • the specific value of the drying temperature is not limited.
  • the drying temperature may be 70°C to 180°C.
  • the drying temperature may be 70°C, 100°C, 110°C or 160°C, etc.
  • the drying temperature is 110°C to 160°C.
  • the duration of the drying treatment may be 1 min to 10 min.
  • the duration of the drying treatment may be 1 min, 3 min, 5 min, or 10 min, or the like.
  • the impregnated substrate can be dried at 70° C. for 10 minutes to obtain the antibacterial material.
  • the impregnated substrate may be dried at 110° C. for 5 minutes to obtain the antibacterial material.
  • the impregnated substrate may be dried at 160° C. for 3 minutes to obtain the antibacterial material.
  • the oven has a certain length. At this time, the impregnated substrate can pass through the oven at a certain speed to ensure that the impregnated substrate stays in the oven for a specified time.
  • the antibacterial agent solidified on the fiber substrate includes quaternary ammonium salt, and the antibacterial agent is a non-metallic material and is harmless to the human body.
  • the antibacterial agent can be stably cured on the non-woven fabric substrate, is not easy to fall off, and has low cost, easy mass production, and popularization and application.
  • the antibacterial agent solution was prepared according to the components and contents shown in Table 4, and the anti-sticking non-woven fabric of PP material was dipped in the above-mentioned antibacterial agent solution to obtain the impregnated non-woven fabric, and the impregnated non-woven fabric was heated at 70 ° C After drying for 3 minutes, the No. 1 antibacterial material was obtained.
  • the antibacterial agent solution was prepared according to the components and contents shown in Table 4, and the anti-sticking non-woven fabric of PP material was dipped in the above-mentioned antibacterial agent solution to obtain the impregnated non-woven fabric.
  • the impregnated non-woven fabric was heated at 100 ° C Dry for 3Min to obtain No. 2 antibacterial material.
  • the antibacterial agent solution was prepared according to the components and contents shown in Table 4, and the anti-sticking non-woven fabric of PP material was dipped in the above-mentioned antibacterial agent solution to obtain the impregnated non-woven fabric. Dry for 3Min to obtain No. 3 antibacterial material.
  • the antibacterial materials No. 1 to No. 3 prepared in the above Examples 1 to 3 and the anti-sticking non-stick cloth made of PP material without any treatment (for the convenience of distinction, denoted as No. 4 material).
  • Vero-E6 cells after culture and passage.
  • cryopreserved Vero-E6 cells can be cultured for 2-3 days in MEM medium containing 10% fetal bovine serum in a cell culture incubator at 37°C and 5% CO 2 , and passaged once to obtain Vero-E6 cells after culture and passage.
  • 2019 Novel Coronavirus is the fourth generation of the virus isolated from throat swabs of 2019 Novel Coronavirus infection cases.
  • Vero-E6 cells were inoculated into a 96-well cell culture plate at 0.1 ml per well and cultured for 24 hours.
  • CCID50 Cell Culture Infective Dose 50%, referred to as CCID50
  • CCID50 Cell Culture Infective Dose 50%
  • the Spearman-Karber method or the Reed-Muench method can be used to calculate the half-infection dose of the cell culture. In the present application, this is not limited. In this example, the Spearman-Karber method is used to calculate the half-infection of the cell culture.
  • the half-cell infection amount of the 2019 new coronavirus is 10 -4.67 /ml (which means that each 1 ml of the virus solution contains 10 4.67 2019 new coronaviruses).
  • concentration of the virus is the concentration of the virus isolated in the laboratory, and such a high concentration of virus does not exist in nature.
  • the method for testing the adsorption or removal of antibacterial materials on the 2019 novel coronavirus may include the following steps: (1) Take 1 part of No. 1 antibacterial material, 1 part of No. 2 antibacterial material, and 1 part of No. 3 antibacterial material Antibacterial material and 5 parts of No. 4 material, put 8 parts of material into 8 sterile cryopreservation tubes respectively.
  • materials of a specified size can be put into a cryopreservation tube.
  • the specified size is set according to actual needs.
  • the specified size can be determined based on the capacity of the cryovial.
  • the volume of the cryovial is 5ml, and the designated size is 0.2cm x 0.2cm.
  • the capacity of the cryopreservation tube is 10ml, and the designated size is 0.4cm ⁇ 0.4cm.
  • the volume of the cryopreservation tube is 5 ml and the designated size is 0.2 cm ⁇ 0.2 cm as an example for description.
  • the first specified amount of antibacterial material and the second specified amount of non-woven fabric without any treatment can also be tested.
  • the first specified amount of antibacterial materials may be antibacterial materials prepared under the same preparation conditions, or may be antibacterial materials prepared under different preparation conditions, which are not limited in this application. In this example, three samples of antibacterial materials prepared under different preparation conditions are taken as an example for testing.
  • the 2019 new coronavirus is diluted 10-4.67 times to obtain the 2019 new coronavirus liquid, and then the 2019 new coronavirus liquid is added to the cryopreservation tube.
  • the amount of the 2019 novel coronavirus liquid to be added can be determined according to the capacity of the cryopreservation tube. For example, when the volume of the cryovial is 5 ml, 20 ⁇ l can be added to the cryovial.
  • the titer of the 2019 new coronavirus can be detected by the method described above, and then the 2019 new coronavirus liquid is prepared according to the obtained titer (the 2019 new coronavirus liquid is the dilution of the 2019 new coronavirus).
  • the cryovial can be stored at room temperature for a specified period of time (for example, it can be 40 min, 1 hour, 50 min, etc.), so that the material can fully absorb the virus.
  • the specified duration is 30 minutes.
  • a specified amount of MEM maintenance solution can be added to each cryovial to create conditions for virus survival and allow the virus to multiply sufficiently.
  • the specified amount is set according to actual needs, for example, in this example, the specified amount is 200 ⁇ l.
  • the MEM maintenance solution may be a MEM maintenance solution containing 2% fetal bovine serum.
  • the virus solution in the No. 1 cryovial can be inoculated into the No. 1 petri dish
  • the virus solution in the No. 2 cryopreservation tube can be inoculated into the No. 2 petri dish
  • the virus solution in the No. 3 cryopreservation tube can be inoculated.
  • Into the No. 3 petri dish suck the virus liquid in the No. 4 cryovial to inoculate the No. 4 petri dish, suck the virus liquid in the No. 5 cryo-tube and inoculate it into the No.
  • the virus liquid was inoculated into the No. 6 petri dish
  • the virus liquid in the No. 7 cryopreservation tube was inoculated into the No. 7 petri dish
  • the virus liquid in the No. 8 cryopreservation tube was inoculated into the No. 8 petri dish.
  • cryovials can be shaken at high speed.
  • the cryovial can be centrifuged at 4000 rpm for 3 min, or the cryovial can be centrifuged at 2000 rpm for 10 min, or the cryovial can be centrifuged at 2500 rpm for 8 min, etc.
  • the cryopreservation tube is centrifuged at 3000 rpm for 5 min as an example for description.
  • the incubation time can be set according to actual needs. For example, it can be 1h, 2h, etc.
  • the MEM medium can be a MEM medium containing 2% fetal bovine serum.
  • 1 ml of MEM medium can be added to the dish.
  • the culture dish was placed in a 37°C, 5% CO 2 incubator for 1 h and taken out.
  • step (6) In the experimental study of the adsorption effect of antibacterial materials on the 2019 new coronavirus, in step (6) to observe the cytopathic CPE, it was found that the liquid corresponding to 5 No. 4 materials were all inoculated on the third day after Vero-E6 cells. Obvious lesions occurred, and the liquid corresponding to No. 1, 2 and 3 antibacterial materials showed lesions on the 6th day after inoculation of Vero-E6 cells, and no obvious lesions were found.
  • the amount of virus contained in the liquid corresponding to No. 1, 2 and 3 antibacterial materials is less than the amount of virus contained in the liquid corresponding to No. 4 material, and No. 1, 2 and 3 antibacterial materials have obvious adsorption and removal effect on 2019 new coronavirus .
  • Figure 3 is a graph of amplification curves obtained by fluorescence quantitative PCR detection.
  • the CT value of the liquid corresponding to 5 pieces of No. 4 material (in this application, the CT value corresponds to the number of cycles when the fluorescence intensity is 11593.420726) is about 14, and the CT value of the liquid corresponding to No. 1 antibacterial material is about 17,
  • the CT value of the liquid corresponding to the No. 2 antibacterial material is about 28, and the CT value of the No. 3 antibacterial material corresponding to the liquid is about 28.
  • the CT value of the liquid corresponding to No. 4 material is much smaller than the CT value of the liquid corresponding to No. 1, 2, and 3 antibacterial materials.
  • the amount of virus contained in the liquid corresponding to 5 copies of No. 4 material is far greater than the amount of virus contained in the liquid corresponding to the antibacterial material (the smaller the CT value, the greater the amount of virus).
  • the virus has a good adsorption and removal effect.
  • the antibacterial material provided by the application has a good adsorption effect on the 2019 novel coronavirus, therefore, the application also provides an antibacterial material prepared by the preparation method of any one of the antibacterial materials provided by the application in the adsorption removal. 2019 Novel Coronavirus Application.
  • various protective articles can be made using the antibacterial materials provided in this application.
  • masks, protective clothing, etc. can be produced, and for example, filters for equipment such as air purifiers, air conditioner filters, and air filters can also be produced. In this embodiment, this is not limited.
  • the amount of virus contained in the liquid corresponding to No. 2 antibacterial material (drying temperature is 100°C) and No. 3 antibacterial material (drying temperature is 110°C) is less than 1
  • the amount of virus contained in the liquid corresponding to the antibacterial material No. 2 that is, the adsorption effect of the antibacterial material No. 2 and the antibacterial material No. 3 on the virus is better than the adsorption and removal effect of the antibacterial material No. have a certain impact.
  • the drying temperature is 110°C to 160°C.
  • the present application also provides examples of antibacterial materials.
  • the antibacterial material provided in this application is an antibacterial material prepared according to any method for preparing an antibacterial material provided in this application, and the antibacterial material includes a non-woven substrate and an antibacterial agent cured on the non-woven substrate, wherein , the antibacterial agent includes quaternary ammonium salt.
  • quaternary ammonium salts are mainly used for adsorption and removal of viruses. It may include at least one of the following quaternary ammonium salts: chitosan quaternary ammonium salts, double-chain quaternary ammonium salts, multi-chain quaternary ammonium salts, and organosilicon quaternary ammonium salts. For example, it may be dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, cetyltrimethylammonium bromide, tetradecyldimethylbenzyl chloride ammonium chloride, cetyl pyridinium chloride and combinations thereof, etc.
  • the quaternary ammonium salt includes tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride.
  • the non-woven fabric substrate can be a non-woven fabric produced by various production processes.
  • it may be a spunbond nonwoven, a needle punched nonwoven, a meltblown nonwoven, and the like.
  • the non-woven fabric can be made of polypropylene (Polypropylene, referred to as PP), polyester (Polyester, referred to as PET), acrylic fiber, nylon, polyvinyl chloride (PVC) and polybutylene terephthalate (Polybutylene Terephthalate, referred to as PBT) and other non-woven fabrics produced as raw materials.

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Abstract

本申请提供一种抗菌材料及其制备方法和应用。本申请提供的抗菌材料，包括无纺布基材和固化在所述无纺布基材上的抗菌剂，其中，所述抗菌剂包括季铵盐。本申请提供的抗菌材料，对2019新型冠状病毒具有良好的吸附去除作用。此外，本申请提供的抗菌材料，固化在无纺布基材上的抗菌剂为季铵盐，其是一种非金属物质，其作用于人体时，不会对人体造成伤害。

Description

一种抗菌材料及其制备方法和应用 技术领域
本申请涉及材料领域，尤其涉及一种抗菌材料及其制备方法和应用。
背景技术
近来，随着2019新型冠状病毒的爆发，各种防护用品的需求量逐渐增加。目前，绝大多数的防护用品均采用无纺布制作而成。相关研究表明，2019新型冠状病毒可以在无纺布上存活8小时以上，因此，如何提高无纺布的抗菌性能成为热点。
目前，常通过在无纺布上添加无机抗菌剂来提高无纺布的抗菌性能。例如，在无纺布上镀银、锌、铜、钛及其化合物等，但是，当添加无机抗菌剂的无纺布制品作用于人体时，例如，人体佩戴镀银的无纺布制备的口罩或镀银的无纺布制备的防护服时，无纺布上的金属微粒容易脱落进入人体，会对人体产生潜在的危害。
发明内容
有鉴于此，本申请提供一种抗菌材料及其制备方法和应用，以解决现有的抗菌材料作用于人体时，对人体存在危险的问题。
本申请第一方面提供一种抗菌材料，所述抗菌材料包括无纺布基材和固化在所述无纺布基材上的抗菌剂，其中，所述抗菌剂包括季铵盐。
进一步地，所述季铵盐包括十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵。
本申请第二方面提供一种抗菌材料的制备方法，所述方法包括：
制备抗菌剂溶液；其中，所述抗菌剂溶液至少由季铵盐、有机溶剂、表面活性剂和无机溶剂混合得到；
将无纺布基材浸渍在所述抗菌剂中，得到浸渍后的基材；
对所述浸渍后的基材进行烘干处理，使所述季铵盐固化在所述无纺布基材上，得到抗菌材料。
进一步地，所述季铵盐包括十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵。
进一步地，所述烘干处理的温度为70℃～180℃。
进一步地，所述烘干处理的时长为1min～10min。
进一步地，所述抗菌剂溶液包括以下质量百分比的各组分：
1％～20％的所述十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵、0.05％～1％的所述表面活性剂、0.01％～5％的所述有机溶剂和余量的所述无机溶剂。
进一步地，所述表面活性剂为油酸酰胺。
进一步地，所述有机溶剂为三甘醇单甲醚。
本申请第三方面提供一种如本申请第二方面提供的任一项所述的方法制备的抗菌材料在抑制或杀灭2019新型冠状病毒上的应用。
本申请提供的抗菌材料，对2019新型冠状病毒具有良好的吸附去除作用。此外，本申请提供的抗菌材料，固化在无纺布基材上的抗菌剂为季铵盐，其是一种非金属物质，其作用于人体时，不会对人体造成伤害。此外，本申请提供的抗菌材料，抗菌剂可稳定的固化在无纺布基材上，不容易脱落，且成本较低，易大量生产，推广应用。
附图说明
图1为本申请提供的抗菌材料的制备方法实施例一的流程图；
图2为本申请提供的抗菌材料的制备原理图；
图3为荧光定量PCR检测得到的扩增曲线图。
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本申请相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本申请的一些方面相一致的装置和方法的例子。
在本申请使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。还应当理解，本文中使用的术语“和/或”是指并包含一个或多个相关联的列出项目的任何或所有可能组合。
应当理解，尽管在本申请可能采用术语第一、第二、第三等来描述各种信息，但这些信息不应限于这些术语。这些术语仅用来将同一类型的信息彼此区分开。例如，在不脱离本申请范围的情况下，第一信息也可以被称为第二信息，类似地，第二信息也可以被称为第一信息。取决于语境，如在此所使用的词语“如果”可以被解释成为“在……时”或“当……时”或“响应于确定”。
近来，随着2019新型冠状病毒的爆发，各种防护用品的需求量逐渐增加。目前，绝大多数的防护用品均采用无纺布制作而成。相关研究表明，2019新型冠状病毒可以在无纺布上存活8小时以上，因此，如何提高无纺布的抗菌性能成为热点。
目前，常通过在无纺布上添加无机抗菌剂来提高无纺布的抗菌性能。例如，在无纺布上镀银、锌、铜、钛及其化合物等，但是，当添加无机抗菌剂的无纺布制品作用于人体时，例如，人体佩戴镀银的无纺布制备的口罩或镀银的无纺布制备的防护服时，无纺布上的金属微粒容易脱落进入人体，会对人体产生潜在的危害。本申请提供一种抗菌材料及其制备方法和应用，以解决现有的抗菌材料作用于人体时，对人体存在危险的问题。
下面给出几个具体的实施例，用以详细介绍本申请的技术方案，下面这几个具体的实施例可以相互结合，对于相同或相似的概念或过程可能在某些实施例中不再赘述。
图1为本申请提供的抗菌材料的制备方法实施例一的流程图。图2为本申请提供的抗菌材料的制备原理图。请同时参照图1和图2，本实施例提供的抗菌材料的制备方法，可以包括：
S101、制备抗菌剂溶液；其中，所述抗菌剂溶液至少由季铵盐、有机溶剂、表面活性剂和无机溶剂混合得到。
具体的，有机溶剂主要用于作为溶剂与无机溶剂混溶，该有机溶剂可以是甲醇、异丙醇、丙二醇、季戊四醇等醇等溶剂或碳酸丙稀酯等酯类溶剂。
例如，在一可能的实现方式中，有机溶剂可以为三甘醇单甲醚(其分子式为C 7H 16O 4)，其在抗菌剂溶液中的质量分数可以为0.01％～5％。例如，其在抗菌剂溶液中的质量分数可以为0.01％、1％、2％、3％或4％等。
表面活性剂主要用于降低液体表面的张力，使纤维基材充分吸收抗菌剂溶液。例如，在一可能的实现方式中，表面活性剂可以是油酸酰胺(分子式为C 18H 35NO)，其在抗菌剂溶液中的质量分数可以为0.05％～1％。例如，其在抗菌剂溶液中的质量分数可以为0.05％、0.08％、1％等。此外，无机活性剂可以为纯水或去离子水。
具体的，季铵盐主要用于吸附去除病毒。其可以包括以下至少一种季铵盐：壳聚糖季铵盐、双链季铵盐、多链季铵盐和有机硅季铵盐。例如，其可以是二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵、十六烷基三甲基溴化铵、十四烷基二甲基苄基氯化铵和十六烷基吡啶氯化铵及其组合等。
可选地，在本申请一可能的实现方式中，季铵盐可以是十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵。
需要说明的是，十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵(也叫四乙酸二甲基(3-3甲氧基硅基丙基)铵或四乙酸二甲基(3-3甲氧基硅基丙基)铵50％盐酸溶液，分子式为C 22H 50ClNO 3Si，俗称多链季铵盐)在抗菌剂溶液中的 质量分数可以为1％～20％。例如，其在抗菌剂溶液中的质量分数可以是4％、10％、15％等。
研究表明，季铵盐在抗菌剂溶液中的质量分数太低或太高，均不利用提高其在无纺布基材上的固化效果。具体的，当十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵在抗菌剂溶液中的质量分数为3％～10％，其在无纺布基材上的固化效果最好(需要说明的是，固化效果越好，表征固化在无纺布基材上的季铵盐的稳定性越好，浓度越高。其中，浓度越高，抗菌材料的抗菌性能越好)。
示例性地，抗菌剂溶液包括以下质量百分比的各组分：
3％～10％的十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵、0.08％～1％的表面活性剂、1％～5％的有机溶剂和余量的水。
下面以“季铵盐为十四烷基二甲基(3-3甲氧基硅基丙基)、有机溶剂为三甘醇单甲醚、表面活性剂为油酸酰胺和无机溶剂为去离子水”为例说明抗菌剂溶液的制备过程。
例如，一可能的实现方式中，可将十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵(俗称多链季铵盐)、三甘醇单甲醚、油酸酰胺和水按照表1所示配比混合，得到抗菌剂溶液：
表1抗菌剂溶液的组成
  组分 作用 含量(质量分数)
1 多链季铵盐 抑菌 8％
2 三甘醇单甲醚 溶剂 2％
3 油酸酰胺 表面活性剂 1％
4 去离子水 溶剂 89％
再例如，在另一可能的实现方式中，可将多链季铵盐、三甘醇单甲醚、油酸酰胺和水按照表2所示配比混合，得到抗菌剂溶液：
表2抗菌剂溶液的组成
  组分 作用 含量(质量分数)
1 多链季铵盐 抑菌 4％
2 三甘醇单甲醚 溶剂 1％
3 油酸酰胺 表面活性剂 0.08％
4 去离子水 溶剂 94.92％
再例如，在再一可能的实现方式中，可将多链季铵盐、三甘醇单甲醚、油酸酰胺和水按照表3所示配比混合，得到抗菌剂溶液：
表3抗菌剂溶液的组成
  组分 作用 含量(质量分数)
1 多链季铵盐 抑菌 14％
2 三甘醇单甲醚 溶剂 5％
3 油酸酰胺 表面活性剂 1％
4 去离子水 溶剂 80％
需要说明的是，在制备抗菌剂溶液时，为了使季铵盐充分溶解，可在指定条件下将上述四种物质混合。例如，可边搅拌边将上述四种物质混合。再例如，可将四种物质混合后，以指定温度对混合后的溶液进行加热。再例如，还可以将四种物质混合后，高速振动混合后的溶液。本实施例中，不对此进行限定。
可选地，上述表1至表3中的含量配比仅为示例性实施例示出的实现方式，当然，本申请可根据具体情况，采用不同的配比。另外，在本申请其他实施方式中，除了上述四种物质外，还可加入稳定剂，以增加抗菌剂溶液的稳定性。例如，一实施例中，该稳定剂可以是无毒的锑系稳定剂。
S102、将无纺布基材浸渍在所述抗菌剂溶液中，得到浸渍后的基材。
该无纺布基材可以是各种生产工艺制作的无纺布。例如，其可以是纺粘无纺布、针刺无纺布、熔喷无纺布等。此外，该无纺布可以是以丙纶(Polypropylene，简称PP)、涤纶(Polyester，简称PET)、腈纶、锦纶、氯纶(Polyvinyl Chloride， 简称PVC)和聚对苯甲酸丁二乙醇酯(Polybutylene Terephthalate，简称PBT)等为原料生产的无纺布。
下面以无纺布基材为以PP为原料、采用纺粘工艺生产的无纺布为例进行说明。
具体的，浸渍指的是浸在液体中泡透。本申请中，如图2所示，可将成卷的无纺布基材通过放卷装置展开，进而使展开后的无纺布进入溶液池(该溶液池中放置有抗菌剂溶液)，浸泡在抗菌剂溶液中，使其在溶液池中与抗菌剂溶液充分接触、泡透，得到浸渍后的基材。
S103、对所述浸渍后的材料进行烘干处理，使所述季铵盐固化在所述无纺布基材上，得到抗菌材料。
请继续参照图2，可使浸渍后的基材进入烘箱，以采用烘箱对其进行烘干处理，使季铵盐固化在无纺布基材上，得到抗菌材料。最后，再利用收卷装置将制得的抗菌材料收成卷状。
具体的，可根据无纺布基材对温度的耐受性确定烘干处理时的烘干温度。本实施例中，不对烘干温度的具体值进行限定。例如，在本申请一可能的实现方式中，烘干温度可以为70℃～180℃。例如，烘干温度可以为70℃、100℃、110℃或160℃等。
研究表明，随着烘干温度的提高，季铵盐在无纺布基材的固化效果逐渐提高。优选的，烘干温度为110℃～160℃。
此外，烘干处理的时长可以为1min～10min。例如，烘干处理的时长可以为1min、3min、5min或10min等。
具体的，例如，在一可能的实现方式中，可以将浸渍后的基材在70℃下烘干10min，得到抗菌材料。再例如，在另一可能的实现方式中，可以将浸渍后的基材在110℃下烘干5min，得到抗菌材料。再例如，在再一可能的实现方式中，可以将浸渍后的基材在160℃下烘干3min，得到抗菌材料。
进一步地，参照图2，烘箱具有一定的长度，此时，可使浸渍后的基材以一定速度通过烘箱，以保证浸渍后的基材在烘箱中停留指定时长。
需要说明的是，采用上述方法制备抗菌材料时，固化在纤维基材上的抗菌剂包括季铵盐，该抗菌剂为非金属材料，对人体无害。此外，本申请制备的抗菌材料，抗菌剂可稳定的固化在无纺布基材上，不容易脱落，且成本较低，易大量生产，推广应用。
下面给出几个具体的实施例，用以详细说明本申请提供的抗菌材料的制备方法：
实施例1
按照表4所示组分和含量制备抗菌剂溶液，将PP材质的防粘无纺布浸渍在上述抗菌剂溶液中，得到浸渍后的无纺布，将浸渍后的无纺布在70℃下烘干3min，得到1号抗菌材料。
表4抗菌剂溶液的组分和含量
  组分 含量
1 多链季铵盐 4％(质量分数)
2 三甘醇单甲醚 0.02mmol/l
3 油酸酰胺 0.1mmol/l
4 纯水  
实施例2
按照表4所示组分和含量制备抗菌剂溶液，将PP材质的防粘无纺布浸渍在上述抗菌剂溶液中，得到浸渍后的无纺布，将浸渍后的无纺布在100℃下烘干3Min，得到2号抗菌材料。
实施例3
按照表4所示组分和含量制备抗菌剂溶液，将PP材质的防粘无纺布浸渍在上述抗菌剂溶液中，得到浸渍后的无纺布，将浸渍后的无纺布在110℃下烘干3Min，得到3号抗菌材料。
上面对本申请提供的抗菌材料的制备方法进行了详细的介绍，下面对采用 本申请提供的方法制备的抗菌材料的抗菌性进行说明：
具体的，为了说明抗菌材料的抗菌性，本申请中，针对抗菌材料对2019新型冠状病毒的吸附去除作用进行了试验研究，具体研究过程如下：
一、材料
1、受试物
上述实施例1至实施例3制备的1至3号抗菌材料和无任何处理的PP材质的防粘无妨布(为了方便区别，记为4号材料)。
2、细胞
经培养、传代后的Vero-E6细胞。
需要说明的是，可以将冻存的Vero-E6细胞在37℃、5％CO 2的细胞培养箱中，用含10％胎牛血清的MEM培养基培养2-3天，并传代一次，得到经培养、传代后的Vero-E6细胞。
3、菌株
2019新型冠状病毒，该2019新型冠状病毒为从2019新型冠状病毒感染病例的咽拭子中分离出的病毒，第四代。
二、方法与结果
1、检测2019新型冠状病毒的滴度
具体步骤如下：
(1)将4ⅹ10 5/ml的Vero-E6细胞以每孔0.1ml接种到96孔细胞培养板上培养24小时。
(2)将2019新型冠状病毒用MEM培养液从10 -1到10 -10作连续10倍的稀释。
(3)将稀释好的不同浓度的2019新型冠状病毒接种到已长出单层Vero-E6细胞的96孔细胞培养板上；其中，每一稀释度接种4个孔，每孔接种0.1ml。
(4)设置正常细胞对照。
(5)继续培养细胞，连续观察细胞病变CPE(Cytopathic Effect，简称CPE)6天，记录结果。
(6)根据记录的结果计算细胞培养半数感染量CCID50(Cell Culture Infective Dose 50％，简称CCID50)，得到2019新型冠状病毒的滴度。
具体的，可以采用Spearman-Karber法或Reed-Muench法计算细胞培养半数感染量。本申请中，不对此进行限定，本实施例中，采用Spearman-Karber法来计算细胞培养半数感染量。
本申请中，通过检测2019新型冠状病毒的滴度，确定2019新型冠状病毒的半数细胞感染量为10 -4.67/ml(其表示每1ml病毒溶液中含有10 4.67个2019新型冠状病毒)。需要说明的是，该病毒浓度为实验室分离的病毒浓度，自然界中，并不存在这么高浓度的病毒。
2、抗菌材料对2019新型冠状病毒的吸附或去除作用的试验研究
具体的，本申请提供的测试抗菌材料对2019新型冠状病毒的吸附或去除作用的方法，可以包括如下步骤：(1)取1份1号抗菌材料、1份2号抗菌材料、1份3号抗菌材料和5份4号材料，将八份材料分别放入8个无菌的冻存管。
例如，将1号抗菌材料放入1号冻存管，将2号抗菌材料放入2号冻存管，将3号抗菌材料放入3号冻存管，在4至8号冻存管中各放入一份4号材料。
需要说明的是，具体实现时，可以将指定尺寸的材料放入冻存管。指定尺寸是根据实际需要设定的。例如，可根据冻存管的容量确定指定尺寸。例如，在一可能的实现方式中，冻存管的容量为5ml，指定尺寸为0.2cm×0.2cm。再例如，在另一可能的实现方式中，冻存管的容量为10ml，指定尺寸为0.4cm×0.4cm。本申请中，以冻存管的容量为5ml，指定尺寸为0.2cm×0.2cm为例进行说明。
此外，在具体测试，也可以取第一指定数量的抗菌材料和第二指定数量的无任何处理的无纺布进行试验。其中，第一指定数量的抗菌材料可以是相同的制备条件制备的抗菌材料，也可以是不同的制备条件制备的抗菌材料，本申请中，不对此进行限定。本例中，以取3份不同的制备条件制备的抗菌材料进行测试为例进行说明。
(2)在冻存管中加入上述滴度(10 -4.67/ml)的2019新型冠状病毒液。
即将2019新型冠状病毒稀释10 -4.67倍，得到2019新型冠状病毒液，之后将 2019新型冠状病毒液加入冻存管中。
具体实现时，可根据冻存管的容量确定加入的2019新型冠状病毒液的量。例如，当冻存管的容量为5ml时，可以向冻存管中加入20μl。
需要说明的是，在开始测试之前，可采用前面所述方法检测2019新型冠状病毒的滴度，进而根据得到的滴度制备2019新型冠状病毒液(2019新型冠状病毒液为将2019新型冠状病毒稀释确定的滴度倍后得到的病毒液)。
(3)先让材料充分吸附病毒，之后，再向冻存管中加入营养液，让病毒繁殖。
例如，在一可能的实现方式中，可先将冻存管在室温下保存指定时长(例如，可以是40min，1小时，50min等)，以让材料充分吸附病毒。本申请中，指定时长为30min。
进一步地，之后，可向各个冻存管中加入指定量的MEM维持液，以创造病毒生存的条件，让病毒充分繁殖。
需要说明的是，指定量是根据实际需要设定的，例如，本例中，指定量为200μl。此外，本例中，MEM维持液可以为含2％胎牛血清的MEM维持液。
(4)针对各个冻存管，吸取该冻存管中的病毒液接种到已培养好Vero-E6细胞的培养皿中。
例如，可吸取1号冻存管中的病毒液接种到1号培养皿中，吸取2号冻存管中的病毒液接种到2号培养皿中，吸取3号冻存管中的病毒液接种到3号培养皿中，吸取4号冻存管中的病毒液接种到4号培养皿，吸取5号冻存管中的病毒液接种到5号培养皿中，吸取6号冻存管中的病毒液接种到6号培养皿中,吸取7号冻存管中的病毒液接种到7号培养皿中，吸取8号冻存管中的病毒液接种到8号培养皿中。
需要说明的是，为了保证材料充分吸附病毒，在将冻存管中的病毒液接种到培养皿之前，可创造条件让材料充分吸附病毒。例如，可高速震荡冻存管。具体实现时，可将冻存管以4000rpm离心3min，或者是，将冻存管以2000rpm离心10min，或者是，将冻存管以2500rpm离心8min等。本申请中，以将冻存 管以3000rpm离心5min为例进行说明。
(5)将培养皿放置在37℃、5％CO 2的培养箱中温育后取出。
具体的，温育的时长可以根据实际需要设定。例如，可以为1h、2h等。
(6)向培养皿中加入MEM培养液继续培养。
具体的，MEM培养液可以为含2％的胎牛血清的MEM培养液。此外，可向培养皿加入1ml的MEM培养液。
(6)在继续培养的过程中，每天观察细胞病变CPE，连续培养6天后取出培养皿中的上清液进行荧光定量PCR检测。
下面给出一个更具体的例子，用以详细说明测试的过程，该过程可以包括：
(1)取1份0.2cm×0.2cm的1号抗菌材料、1份0.2cm×0.2cm的2号抗菌材料、1份0.2cm×0.2cm 3号抗菌材料和5份0.2cm×0.2cm的4号材料。
(2)针对每份材料，将该材料放入无菌的5ml冻存管。
(3)将2019新型冠状病毒稀释10 -4.67倍，得到2019新型冠状病毒液，在各个冻存管中加入20μl2019新型冠状病毒液。
(4)将冻存管在室温下放置30min，让材料充分吸附病毒。
(5)向冻存管中加入200μl含2％胎牛血清的MEM维持液，让病毒繁殖。
(6)将冻存管以3000rmp离心5min，让材料充分吸附病毒。
(7)针对每个冻存管，吸取该冻存管中的病毒液接种到已培养好Vero-E6细胞的培养皿中。
(8)将培养皿放置在37℃、5％CO 2的培养箱中温育1h后取出。
(9)向培养皿中加入1ml含2％胎牛血清的MEM培养液进行培养。
(10)在培养的过程中，每天观察细胞病变CPE，连续培养6天后取出培养皿中的上清液进行荧光定量PCR检测。
三、试验结果
1、细胞病变观察结果
在抗菌材料对2019新型冠状病毒的吸附作用的试验研究中，在步骤(6)观擦细胞病变CPE中发现，5份4号材料对应的液体均在接种Vero-E6细胞后的 第三天就发生了明显病变，而1、2和3号抗菌材料对应的液体在接种Vero-E6细胞后的第6天才出现了病变，且未见明显病变。
由此可知，1、2和3号抗菌材料对应的液体含有的病毒量小于4号材料对应的液体含有的病毒量，1、2和3号抗菌材料对2019新型冠状病毒有明显的吸附去除作用。
2、荧光定量PCR检测结果
图3为荧光定量PCR检测得到的扩增曲线图。参见图3，5份4号材料对应的液体的CT值(本申请中，CT值为荧光强度为11593.420726时对应的循环数)大概为14，1号抗菌材料对应液体的CT值大概为17，2号抗菌材料对应液体的CT值大概28，3号抗菌材料对应液体的CT值大概为28。
即4号材料对应的液体的CT值远远小于1、2、3号抗菌材料对应的液体的CT值。换言之，即5份4号材料对应的液体中含有的病毒量远远大于抗菌材料对应的液体含有的病毒量(CT值越小，病毒量越多)，由此可见，抗菌材料对2019新型冠状病毒有良好的吸附去除作用。
参见前面的描述，本申请提供的抗菌材料对2019新型冠状病毒有良好的吸附作用，因此，本申请还提供一种如本申请提供的任一项抗菌材料的制备方法制备的抗菌材料在吸附去除2019新型冠状病毒上的应用。
需要说明的是，可利用本申请提供的抗菌材料制作各种防护用品。例如，可制作口罩、防护服等，再例如，还可以制作空气净化器、空调滤清器或空气过滤器等设备用过滤网等。本实施例中，不对此进行限定。
进一步地，请继续参照图3，从图3可以看出，2号抗菌材料(烘干温度为100℃)和3号抗菌材料(烘干温度为110℃)对应的液体含有的病毒量小于1号抗菌材料对应的液体含有的病毒量，即2号抗菌材料和3号抗菌材料对病毒的吸附作用优于1号抗菌材料对病毒的吸附去除作用，这说明烘干温度对抗菌剂的固化效果有一定的影响。当温度升高时，抗菌剂的固化效果升高。本申请中，优选地，烘干温度为110℃～160℃。
与前述制备抗菌材料的方法的实施例相对应，本申请还提供了抗菌材料的 实施例。
本申请提供的抗菌材料，为按照本申请提供的任一抗菌材料的制备方法制备的抗菌材料，该抗菌材料包括无纺布基材和固化在所述无纺布基材上的抗菌剂，其中，所述抗菌剂包括季铵盐。
具体的，季铵盐主要用于吸附去除病毒。其可以包括以下至少一种季铵盐：壳聚糖季铵盐、双链季铵盐、多链季铵盐和有机硅季铵盐。例如，其可以是二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵、十六烷基三甲基溴化铵、十四烷基二甲基苄基氯化铵和十六烷基吡啶氯化铵及其组合等。
可选地，所述季铵盐包括十四烷基二甲基(3-三甲氧基硅基丙基)氯化铵。
需要说明的是，该无纺布基材可以是各种生产工艺制作的无纺布。例如，其可以是纺粘无纺布、针刺无纺布、熔喷无纺布等。此外，该无纺布可以是以丙纶(Polypropylene，简称PP)、涤纶(Polyester，简称PET)、腈纶、锦纶、氯纶(PVC)和聚对苯甲酸丁二乙醇酯(Polybutylene Terephthalate，简称PBT)等为原料生产的无纺布。
本申请上述各实施方式在不产生冲突的情况下，可互为补充。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (10)

  1. 一种抗菌材料，其特征在于，所述抗菌材料包括无纺布基材和固化在所述无纺布基材上的抗菌剂，其中，所述抗菌剂包括季铵盐。
  2. 根据权利要求1所述的抗菌材料，其特征在于，所述季铵盐包括十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵。
  3. 一种抗菌材料的制备方法，其特征在于，所述方法包括：
    制备抗菌剂溶液；其中，所述抗菌剂溶液至少由季铵盐、有机溶剂、表面活性剂和无机溶剂混合得到；
    将无纺布基材浸渍在所述抗菌剂溶液中，得到浸渍后的基材；
    对所述浸渍后的基材进行烘干处理，使所述季铵盐固化在所述无纺布基材上，得到抗菌材料。
  4. 根据权利要求3所述的方法，其特征在于，所述季铵盐包括十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵。
  5. 根据权利要求3所述的方法，其特征在于，所述烘干处理的温度为70℃～180℃。
  6. 根据权利要求3所述的方法，其特征在于，所述烘干处理的时长为1min～10min。
  7. 根据权利要求4所述的方法，其特征在于，所述抗菌剂溶液包括以下质量百分比的各组分：
    1％～20％的所述十四烷基二甲基[3-(三甲氧基硅基)丙基]氯化铵、0.05％～1％的所述表面活性剂、0.01％～5％的所述有机溶剂和余量的所述无机溶剂。
  8. 根据权利要求3所述的方法，其特征在于，所述表面活性剂为油酸酰胺。
  9. 根据权利要求3所述的方法，其特征在于，所述有机溶剂为三甘醇单甲醚。
  10. 一种如权利要求3至9任一项所述的方法制备的抗菌材料在吸附去除2019新型冠状病毒上的应用。
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