CN113914098A - Antibacterial material and preparation method and application thereof - Google Patents

Antibacterial material and preparation method and application thereof Download PDF

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Publication number
CN113914098A
CN113914098A CN202010647773.4A CN202010647773A CN113914098A CN 113914098 A CN113914098 A CN 113914098A CN 202010647773 A CN202010647773 A CN 202010647773A CN 113914098 A CN113914098 A CN 113914098A
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antibacterial
quaternary ammonium
ammonium salt
antibacterial agent
woven fabric
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陈立
郑明�
毛逸宁
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Zhongke Dingsheng Technology Co ltd
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Zhongke Dingsheng Technology Co ltd
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Priority to PCT/CN2021/081563 priority patent/WO2022007430A1/en
Publication of CN113914098A publication Critical patent/CN113914098A/en
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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
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    • 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
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    • 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
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    • 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
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    • 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

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Abstract

The application provides an antibacterial material and a preparation method and application thereof. The application provides an antibacterial material, including the non-woven fabrics substrate with solidify the antibacterial agent on the non-woven fabrics substrate, wherein, the antibacterial agent includes quaternary ammonium salt. The antibacterial material provided by the application has a good adsorption and removal effect on 2019 novel coronavirus. In addition, the antibacterial material provided by the application, the antibacterial agent solidified on the non-woven fabric substrate is quaternary ammonium salt, which is a non-metallic substance and cannot cause harm to human bodies when acting on the human bodies.

Description

Antibacterial material and preparation method and application thereof
Technical Field
The application relates to the field of materials, in particular to an antibacterial material and a preparation method and application thereof.
Background
Recently, with the outbreak of 2019 new coronaviruses, the demand for various protective articles has gradually increased. At present, most of protective articles are made of non-woven fabrics. Relevant studies show that 2019 novel coronavirus can survive on the non-woven fabric for more than 8 hours, and therefore, how to improve the antibacterial performance of the non-woven fabric becomes a hotspot.
At present, inorganic antibacterial agents are often added to nonwoven fabrics to improve the antibacterial performance of the nonwoven fabrics. For example, silver, zinc, copper, titanium, and compounds thereof are added to a nonwoven fabric, but when a nonwoven fabric product to which an inorganic antibacterial agent is added acts on a human body, for example, when a human body wears a mask made of silver-plated nonwoven fabric or a protective clothing made of silver-plated nonwoven fabric, metal particles on the nonwoven fabric easily fall off into the human body, and thus, the nonwoven fabric product may potentially cause harm to the human body.
Disclosure of Invention
In view of the above, the present application provides an antibacterial material, and a preparation method and an application thereof, so as to solve the problem that the existing antibacterial material is dangerous to a human body when acting on the human body.
The application provides an antibacterial material in a first aspect, the antibacterial material comprises a non-woven fabric substrate and an antibacterial agent solidified on the non-woven fabric substrate, wherein the antibacterial agent comprises quaternary ammonium salt.
Further, the quaternary ammonium salt includes tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
In a second aspect, the present application provides a method for preparing an antibacterial material, the method comprising:
preparing an antibacterial agent solution; wherein the antibacterial agent solution is obtained by mixing at least quaternary ammonium salt, an organic solvent, a surfactant and an inorganic solvent;
dipping a non-woven fabric substrate in the antibacterial agent to obtain a dipped substrate;
and drying the impregnated base material to enable the quaternary ammonium salt to be solidified on the non-woven fabric base material, so as to obtain the antibacterial material.
Further, the quaternary ammonium salt includes tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
Further, the temperature of the drying treatment is 70-180 ℃.
Further, the drying time is 1-10 min.
Further, the antibacterial agent solution comprises the following components in percentage by mass:
1 to 20 percent of tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 0.05 to 1 percent of surfactant, 0.01 to 5 percent of organic solvent and the balance of inorganic solvent.
Further, the surfactant is oleamide.
Further, the organic solvent is triethylene glycol monomethyl ether.
In a third aspect of the present application, there is provided a use of an antibacterial material prepared by any one of the methods provided in the second aspect of the present application for adsorbing and removing 2019 novel coronaviruses.
The antibacterial material provided by the application has a good adsorption and removal effect on 2019 novel coronavirus. In addition, the antibacterial material provided by the application, the antibacterial agent solidified on the non-woven fabric substrate is quaternary ammonium salt, which is a non-metallic substance and cannot cause harm to human bodies when acting on the human bodies. In addition, the antibacterial material that this application provided, the solidification that the antiseptic can be stable is on the non-woven fabrics substrate, is difficult to drop, and the cost is lower, easy bulk production, popularization and application.
Drawings
Fig. 1 is a flow chart of a first embodiment of a method for preparing an antibacterial material provided by the present application;
FIG. 2 is a schematic diagram of the preparation of the antibacterial material provided by the present application;
FIG. 3 is a graph showing the amplification curve obtained by the fluorescent quantitative PCR assay.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present application. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present application, as detailed in the appended claims.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
It is to be understood that although the terms first, second, third, etc. may be used herein to describe various information, such information should not be limited to these terms. These terms are only used to distinguish one type of information from another. For example, first information may also be referred to as second information, and similarly, second information may also be referred to as first information, without departing from the scope of the present application. The word "if" as used herein may be interpreted as "at … …" or "when … …" or "in response to a determination", depending on the context.
Recently, with the outbreak of 2019 new coronaviruses, the demand for various protective articles has gradually increased. At present, most of protective articles are made of non-woven fabrics. Relevant studies show that 2019 novel coronavirus can survive on the non-woven fabric for more than 8 hours, and therefore, how to improve the antibacterial performance of the non-woven fabric becomes a hotspot.
At present, inorganic antibacterial agents are often added to nonwoven fabrics to improve the antibacterial performance of the nonwoven fabrics. For example, silver, zinc, copper, titanium, and compounds thereof are applied to a nonwoven fabric, but when a nonwoven fabric product added with an inorganic antibacterial agent acts on a human body, for example, when a human body wears a mask made of silver-plated nonwoven fabric or a protective clothing made of silver-plated nonwoven fabric, metal particles on the nonwoven fabric easily fall off into the human body, and thus, the nonwoven fabric product may potentially cause damage to the human body.
The application provides an antibacterial material, and a preparation method and application thereof, which are used for solving the problem that the existing antibacterial material is dangerous to a human body when acting on the human body.
Several specific embodiments are given below to describe the technical solutions of the present application in detail, and these specific embodiments may be combined with each other, and details of the same or similar concepts or processes may not be repeated in some embodiments.
Fig. 1 is a flowchart of a first embodiment of a method for preparing an antibacterial material provided by the present application. Fig. 2 is a schematic diagram of the preparation of the antibacterial material provided by the present application. Referring to fig. 1 and fig. 2, the method for preparing the antibacterial material provided in this embodiment may include:
s101, preparing an antibacterial agent solution; wherein the antibacterial agent solution is obtained by mixing at least quaternary ammonium salt, an organic solvent, a surfactant and an inorganic solvent.
Specifically, the organic solvent is mainly used as a solvent to be miscible with the inorganic solvent, and the organic solvent can be an alcohol solvent such as methanol, isopropanol, propylene glycol, pentaerythritol and the like or an ester solvent such as propylene carbonate and the like.
For example, in one possible implementation, the organic solvent may be triethylene glycol monomethyl ether (formula C)7H16O4) The mass fraction of the antibacterial agent in the antibacterial agent solution can be 0.01-5%. For example, the mass fraction thereof in the antibacterial agent solution may be 0.01%, 1%, 2%, 3%, 4%, or the like.
The surfactant is mainly used for reducing the surface tension of the liquid, so that the non-woven fabric substrate can fully absorb the antibacterial agent solution. For example, in one possible implementation, the surfactant may be oleamide (formula C)18H35NO), the mass fraction of which in the antimicrobial solution may be 0.05% to 1%. For example, the mass fraction thereof in the antibacterial agent solution may be 0.05%, 0.08%, 1%, or the like. In addition, the inorganic active agent may be pure water or deionized water.
In particular, quaternary ammonium salts are used primarily for the adsorption removal of viruses. It may include at least one quaternary ammonium salt of: chitosan quaternary ammonium salt, double-chain quaternary ammonium salt, multi-chain quaternary ammonium salt and organosilicon quaternary ammonium salt. For example, it may comprise at least one quaternary ammonium salt of: dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, hexadecyltrimethylammonium bromide, tetradecyldimethylbenzylammonium chloride and hexadecylpyridinium ammonium chloride.
Alternatively, in one possible implementation of the present application, the quaternary ammonium salt may be tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
Specifically, tetradecyldimethyl [3- (trimethoxysilyl) propyl ] group]Ammonium chloride (also called tetraethylammonium dimethyl (3-3 methoxysilylpropyl) chloride or tetraethylammonium dimethyl (3-3 methoxysilylpropyl) chloride 50% hydrochloric acid solution, molecular formula C22H50ClNO3Si, commonly referred to as multi-chain quaternary ammonium salt) may be present in the antimicrobial solution in a mass fraction of 1% to 20%. For example, the mass fraction thereof in the antibacterial agent solution may be 4%, 10%, 15%, or the like.
Research shows that the mass fraction of the quaternary ammonium salt in the antibacterial agent solution is too low or too high, and the curing effect of the quaternary ammonium salt on the non-woven fabric substrate is not improved. Specifically, when the mass fraction of tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride in the antibacterial agent solution is 3% -10%, the curing effect on the non-woven fabric substrate is the best (it should be noted that the better the curing effect, the better the stability of the quaternary ammonium salt cured on the non-woven fabric substrate, and the higher the concentration, wherein the higher the concentration, the better the antibacterial performance of the antibacterial material).
Illustratively, the antibacterial agent solution comprises the following components in percentage by mass:
3 to 10 percent of tetradecyl dimethyl [3- (trimethoxy silicon) propyl ] ammonium chloride, 0.08 to 1 percent of surfactant, 1 to 5 percent of organic solvent and the balance of water.
The preparation process of the antibacterial agent solution is illustrated by the following example that quaternary ammonium salt is tetradecyldimethyl (3-3 methoxysilyl propyl) ammonium chloride, organic solvent is triethylene glycol monomethyl ether, surfactant is oleamide, and inorganic solvent is deionized water.
For example, in one possible implementation, tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride (commonly known as a multi-chain quaternary ammonium salt), triethylene glycol monomethyl ether, oleamide, and deionized water may be mixed in the proportions shown in Table 1 to provide an antimicrobial solution:
TABLE 1 composition of antimicrobial solutions
Components Function of Content (mass fraction)
1 Multi-chain quaternary ammonium salts Antibacterial 8％
2 Triethylene glycol monomethyl ether Solvent(s) 2％
3 Oleic acid amides Surface active agent 1％
4 Deionized water Solvent(s) 89％
For another example, in another possible implementation, the multi-chain quaternary ammonium salt, triethylene glycol monomethyl ether, oleic acid amide, and deionized water may be mixed according to the ratio shown in table 2 to obtain the antimicrobial solution:
TABLE 2 composition of antimicrobial solutions
Components Function of Content (mass fraction)
1 Multi-chain quaternary ammonium salts Antibacterial 4％
2 Triethylene glycol monomethyl ether Solvent(s) 1％
3 Oleic acid amides Surface active agent 0.08％
4 Deionized water Solvent(s) 94.92％
For another example, in another possible implementation, the multi-chain quaternary ammonium salt, triethylene glycol monomethyl ether, oleic acid amide, and deionized water may be mixed in the ratio shown in table 3 to obtain an antimicrobial solution:
TABLE 3 composition of antimicrobial solutions
Components Function of Content (mass fraction)
1 Multi-chain quaternary ammonium salts Antibacterial 14％
2 Triethylene glycol monomethyl ether Solvent(s) 5％
3 Oleic acid amides Surface active agent 1％
4 Deionized water Solvent(s) 80％
In order to sufficiently dissolve the quaternary ammonium salt in the preparation of the antibacterial agent solution, the above four substances may be mixed under predetermined conditions. For example, the above four substances may be mixed with stirring. For another example, the four substances may be mixed, and the mixed solution may be heated at a predetermined temperature. For another example, the four substances may be mixed, and the mixed solution may be vibrated at a high speed. In the present embodiment, this is not limited.
Optionally, the content ratios in tables 1 to 3 are only implementation manners shown in exemplary embodiments, and of course, different ratios may be adopted according to specific situations. In addition, in other embodiments of the present application, a stabilizer may be added in addition to the above four substances to increase the stability of the antimicrobial solution. For example, in one embodiment, the stabilizer may be a non-toxic antimony-based stabilizer.
S102, immersing the non-woven fabric substrate in the antibacterial agent solution to obtain an immersed substrate.
The non-woven fabric base material can be non-woven fabrics manufactured by various production processes. For example, it may be a spunbond nonwoven fabric, a needle-punched nonwoven fabric, a meltblown nonwoven fabric, or the like. In addition, the non-woven fabric may be a non-woven fabric produced by using Polypropylene (PP), Polyester (PET), acrylic, nylon, Polyvinyl Chloride (PVC), Polybutylene Terephthalate (PBT) and the like as raw materials.
The following description will be made by taking a nonwoven fabric base material as a nonwoven fabric produced by a spun-bonding process using PP as a raw material.
In particular, dipping refers to immersion in a liquid to soak through. In the application, as shown in fig. 2, the rolled non-woven fabric substrate can be unwound by the unwinding device, and then the unwound non-woven fabric enters the solution tank (where the antibacterial agent solution is placed), and is soaked in the antibacterial agent solution, so that the non-woven fabric is fully contacted with the antibacterial agent solution in the solution tank and is completely soaked, and the impregnated substrate is obtained.
S103, drying the impregnated material to enable the quaternary ammonium salt to be solidified on the non-woven fabric base material, and obtaining the antibacterial material.
With reference to fig. 2, the impregnated substrate may be put into an oven to be dried by the oven, so that the quaternary ammonium salt is cured on the nonwoven fabric substrate to obtain the antibacterial material. And finally, winding the prepared antibacterial material into a roll by using a winding device.
Specifically, the drying temperature during the drying treatment may be determined according to the temperature resistance of the nonwoven fabric base material. In this embodiment, the specific value of the drying temperature is not limited. For example, in one possible implementation of the present application, the drying temperature may be 70 ℃ to 180 ℃. For example, the drying temperature may be 70 ℃, 100 ℃, 110 ℃, 160 ℃, or the like.
Research shows that the curing effect of the quaternary ammonium salt on the non-woven fabric base material is gradually improved along with the increase of the drying temperature. Preferably, the drying temperature is 110-160 ℃.
In addition, the drying time can be 1-10 min. For example, the drying treatment time may be 1min, 3min, 5min, 10min, or the like.
Specifically, for example, in one possible implementation, the impregnated substrate may be dried at 70 ℃ for 10min to obtain the antibacterial material. For another example, in another possible implementation manner, the impregnated substrate may be dried at 110 ℃ for 5min to obtain the antibacterial material. For another example, in another possible implementation manner, the impregnated substrate may be dried at 160 ℃ for 3min to obtain the antibacterial material
Further, referring to FIG. 2, the oven has a length, wherein the impregnated substrate may be passed through the oven at a speed to ensure that the impregnated substrate remains in the oven for a specified period of time.
When the antibacterial material is prepared by the method, the antibacterial agent solidified on the non-woven fabric base material comprises quaternary ammonium salt, and the antibacterial agent is a non-metallic material and is harmless to human bodies. In addition, the antibacterial material prepared by the application can be stably solidified on the non-woven fabric substrate, is not easy to fall off, has low cost, and is easy for mass production, popularization and application.
Several specific examples are given below to illustrate in detail the preparation of the antibacterial material provided herein:
example 1
Preparing an antibacterial agent solution according to the components and contents shown in Table 4, soaking an anti-sticking non-woven fabric made of a PP material in the antibacterial agent solution to obtain a soaked non-woven fabric, and drying the soaked non-woven fabric at 70 ℃ for 3min to obtain the No. 1 antibacterial material.
TABLE 4 composition and content of antimicrobial solution
Components Content (wt.)
1 Multi-chain quaternary ammonium salts 4% (mass fraction)
2 Triethylene glycol monomethyl ether 0.02mmol/l
3 Oleic acid amides 0.1mmol/l
4 Pure water
Example 2
Preparing an antibacterial agent solution according to the components and contents shown in table 4, dipping a PP anti-sticking non-woven fabric into the antibacterial agent solution to obtain a dipped non-woven fabric, and drying the dipped non-woven fabric at 100 ℃ for 3min to obtain the No. 2 antibacterial material.
Example 3
Preparing an antibacterial agent solution according to the components and contents shown in table 4, dipping a PP anti-sticking non-woven fabric into the antibacterial agent solution to obtain a dipped non-woven fabric, and drying the dipped non-woven fabric at 110 ℃ for 3min to obtain the No. 3 antibacterial material.
The method for preparing the antibacterial material provided by the present application is described in detail above, and the antibacterial property of the antibacterial material prepared by the method provided by the present application is described below:
specifically, in order to illustrate the antibacterial property of the antibacterial material, in the application, experimental studies are performed on the adsorption removal effect of the antibacterial material on the 2019 novel coronavirus, and the specific research processes are as follows:
materials (I) and (II)
1. Test article
The above-mentioned antibacterial materials No. 1 to 3 prepared in examples 1 to 3 and the non-treated PP-based non-blocking cloth (for convenience of distinction, denoted as material No. 4) were used.
2. Cells
Vero-E6 cells after culture and passage.
Furthermore, the frozen Vero-E6 cells were incubated at 37 ℃ with 5% CO2The cell culture chamber of (3) was cultured in MEM medium containing 10% fetal bovine serum for 2 to 3 days and passaged once to obtain Vero-E6 cells after culturing and passaging.
3. Bacterial strains
2019A novel coronavirus, wherein the 2019 novel coronavirus is a virus isolated from a pharyngeal swab of a 2019 novel coronavirus infected case, and the fourth generation.
Second, method and results
1. Detecting 2019 novel coronavirus titer
The method comprises the following specific steps:
(1) will 4 x 105Vero-E6 cells/ml were seeded at 0.1ml per well in 96 well cell culture plates for 24 hours.
(2) Culturing 2019 new coronavirus in MEM (minimum essential oil) culture medium 10-1To 10-10Serial 10-fold dilutions were made.
(3) Inoculating the diluted 2019 novel coronavirus with different concentrations to a 96-well cell culture plate on which a monolayer of Vero-E6 cells grows; wherein 4 wells were inoculated per dilution, 0.1ml per well.
(4) A normal cell control was set.
(5) The cells were cultured and the Cytopathic CPE (CPE for short) was continuously observed for 6 days, and the results were recorded.
(6) From the recorded results, the Cell Culture median infectious Dose CCID50(Cell Culture infectious Dose 50%, abbreviated as CCID50) was calculated to obtain the titer of 2019 novel coronavirus.
Specifically, the amount of infection in half of the cell culture can be calculated by the Spearman-Karber method or the Reed-Muench method. In the present application, this is not limited, and in the present example, the Spearman-Karber method is used to calculate the half infection amount in cell culture.
In the application, the half cell infection amount of the 2019 novel coronavirus is determined to be 10 by detecting the titer of the 2019 novel coronavirus-4.67Perml (which means 10 per 1ml of virus solution)4.672019 new coronaviruses). The virus concentration is a concentration of a virus isolated in a laboratory, and the virus does not exist in such a high concentration in nature.
2. Experimental study on adsorption removal effect of antibacterial material on 2019 novel coronavirus
Specifically, the method for testing the adsorption removal effect of the antibacterial material on the 2019 novel coronavirus can comprise the following steps:
(1) taking 1 part of No. 1 antibacterial material, 1 part of No. 2 antibacterial material, 1 part of No. 3 antibacterial material and 5 parts of No. 4 material, and respectively putting eight parts of materials into 8 sterile freezing tubes.
For example, the number 1 antibacterial material is put into the number 1 cryopreservation tube, the number 2 antibacterial material is put into the number 2 cryopreservation tube, the number 3 antibacterial material is put into the number 3 cryopreservation tube, and a part of the number 4 material is put into each of the number 4 to 8 cryopreservation tubes.
It should be noted that, in specific implementation, a material with a specified size can be put into the cryopreservation tube. The specified size is set according to actual needs. For example, the specified size may be determined based on the volume of the vial. For example, in one possible implementation, the vial has a capacity of 5ml, with specified dimensions of 0.2cm by 0.2 cm. For another example, in another possible implementation, the vial has a capacity of 10ml, with specified dimensions of 0.4cm x 0.4 cm. In the present application, the description will be made by taking an example in which the volume of the vial for freezing is 5ml and the specified size is 0.2cm × 0.2 cm.
In addition, in the specific test, the test may be performed with the first specified amount of the antibacterial material and the second specified amount of the nonwoven fabric without any treatment. The first specified amount of the antibacterial material may be the antibacterial material prepared under the same preparation conditions, or the antibacterial material prepared under different preparation conditions, which is not limited in this application. In this example, 3 parts of the antibacterial material prepared under different preparation conditions were used for the test.
(2) The titer (10) was added to the vial-4.67/ml) 2019 of a novel coronavirus solution.
Namely diluting the 2019 novel coronavirus by 10-4.67Doubling to obtain 2019 novel coronavirus liquid, and adding the 2019 novel coronavirus liquid into a cryopreservation tube.
In specific implementation, the amount of 2019 novel coronary virus liquid added can be determined according to the capacity of the cryopreservation tube. For example, when the volume of the cryopreservation tube is 5ml, 20 μ l2019 of the novel coronary virus solution may be added to the cryopreservation tube.
Before starting the test, the titer of the 2019 novel coronavirus can be detected by the method described above, and then the 2019 novel coronavirus solution is prepared according to the obtained titer (the 2019 novel coronavirus solution is obtained by diluting the 2019 novel coronavirus to a determined titer which is doubled).
(3) The material is made to adsorb virus fully, and then nutrient solution is added into the freezing tube to propagate the virus.
For example, in one possible implementation, the vial may be first stored at room temperature for a specified length of time (e.g., 40min, 1 hour, 50min, etc.) to allow the material to sufficiently adsorb the virus. In the present application, the specified duration is 30 min.
Further, a predetermined amount of the MEM maintaining solution may be added to each of the freezing tubes to create conditions for virus to survive and allow the virus to propagate sufficiently.
The specified amount is set as needed, for example, 200 μ l in this example. In this example, the MEM retaining solution may be a MEM retaining solution containing 2% fetal bovine serum.
(4) And (4) sucking the virus liquid in each cryopreservation tube and inoculating the virus liquid into a culture dish in which Vero-E6 cells are cultured.
For example, the virus liquid in the number 1 cryopreservation tube can be sucked and inoculated into the number 1 culture dish, the virus liquid in the number 2 cryopreservation tube can be sucked and inoculated into the number 2 culture dish, the virus liquid in the number 3 cryopreservation tube can be sucked and inoculated into the number 3 culture dish, the virus liquid in the number 4 cryopreservation tube can be sucked and inoculated into the number 4 culture dish, the virus liquid in the number 5 cryopreservation tube can be sucked and inoculated into the number 5 culture dish, the virus liquid in the number 6 cryopreservation tube can be sucked and inoculated into the number 6 culture dish, the virus liquid in the number 7 cryopreservation tube can be sucked and inoculated into the number 7 culture dish, and the virus liquid in the number 8 cryopreservation tube can be sucked and inoculated into the number 8 culture dish.
In order to ensure that the material can sufficiently adsorb the virus, conditions can be created to allow the material to sufficiently adsorb the virus before the virus solution in the cryopreservation tube is inoculated to the culture dish. For example, the tube may be cryopreserved by shaking at high speed. Specifically, the frozen tube may be centrifuged at 4000rpm for 3min, or the frozen tube may be centrifuged at 2000rpm for 10min, or the frozen tube may be centrifuged at 2500rpm for 8min, etc. In this application, the frozen tube is centrifuged at 3000rpm for 5min as an example.
(5) The culture dish was placed at 37 ℃ in 5% CO2The incubator of (2) is taken out after incubation.
Specifically, the incubation time can be set according to actual needs. For example, it may be 1h, 2h, or the like.
(6) MEM was added to the culture dish to continue the culture.
Specifically, the MEM culture medium may be a MEM culture medium containing 2% fetal bovine serum. In addition, 1ml of MEM culture medium may be added to the culture dish.
(6) During the continuous culture process, the cytopathic CPE is observed every day, and after continuous culture for 6 days, the supernatant in the culture dish is taken out for fluorescent quantitative PCR detection.
A more specific example is given below to illustrate the process of testing, which may include:
(1) 1 part of No. 1 antibacterial material 0.2cm × 0.2cm, 1 part of No. 2 antibacterial material 0.2cm × 0.2cm, 1 part of No. 0.2cm × 0.2cm 3 antibacterial material and 5 parts of No. 4 material 0.2cm × 0.2cm are taken.
(2) For each material, the material was placed into a sterile 5ml cryopreservation tube.
(3) Diluting 2019 new coronavirus to 10-4.67Doubling to obtain 2019 novel coronary virus liquid, and adding 20 mu l of 2019 novel coronary virus liquid into each freezing storage tube.
(4) The frozen tube was left at room temperature for 30min to allow the material to fully adsorb the virus.
(5) To the frozen tube, 200. mu.l of MEM holding solution containing 2% fetal bovine serum was added to propagate the virus.
(6) The frozen tube was centrifuged at 3000rmp for 5min to allow the material to fully adsorb the virus.
(7) And (4) sucking the virus liquid in each cryopreservation tube and inoculating the virus liquid into a culture dish in which Vero-E6 cells are cultured.
(8) The culture dish was placed at 37 ℃ in 5% CO2The culture box is taken out after being incubated for 1 h.
(9) 1ml of MEM culture medium containing 2% fetal bovine serum was added to the culture dish to culture.
(10) During the culture process, the cytopathic CPE is observed every day, and after continuous culture for 6 days, the supernatant in the culture dish is taken out for fluorescent quantitative PCR detection.
Third, test results
1. Observation of cytopathic effects
In the experimental study on the adsorption removal effect of the antibacterial material on the 2019 novel coronavirus, in the step (6) of observing and wiping cytopathic CPE, 5 parts of liquid corresponding to the No. 4 material are found to have obvious lesions on the third day after the Vero-E6 cell is inoculated, and the liquids corresponding to the No. 1, 2 and 3 antibacterial materials have lesions on the 6 th day after the Vero-E6 cell is inoculated, and no obvious lesions are found.
Therefore, the amounts of viruses contained in the liquids corresponding to the antibacterial materials No. 1, 2 and 3 are smaller than the amount of viruses contained in the liquid corresponding to the antibacterial material No. 4, and the antibacterial materials No. 1, 2 and 3 have obvious adsorption and removal effects on the 2019 novel coronavirus.
2. Fluorescent quantitative PCR detection result
FIG. 3 is a graph showing the amplification curve obtained by the fluorescent quantitative PCR assay. Referring to fig. 3, the CT value of the liquid corresponding to 5 parts of the material No. 4 (in this application, the CT value is the number of cycles corresponding to 11593.420726 fluorescence intensity) is about 14, the CT value of the liquid corresponding to the antibacterial material No. 1 is about 17, the CT value of the liquid corresponding to the antibacterial material No. 2 is about 28, and the CT value of the liquid corresponding to the antibacterial material No. 3 is about 28.
Namely, the CT value of the liquid corresponding to the material No. 4 is far less than that of the liquid corresponding to the antibacterial materials No. 1, 2 and 3. In other words, the amount of viruses contained in the liquid corresponding to 5 parts of material No. 4 is much larger than the amount of viruses contained in the liquid corresponding to the antibacterial material (the smaller the CT value is, the larger the amount of viruses is), and thus it can be seen that the antibacterial material has a good adsorption and removal effect on the 2019 novel coronavirus.
Referring to the foregoing description, the antibacterial material provided by the present application has a good adsorption effect on the 2019 novel coronavirus, and therefore, the present application also provides an application of the antibacterial material prepared by the preparation method of any one of the antibacterial materials provided by the present application in adsorption removal of the 2019 novel coronavirus.
It should be noted that the antimicrobial materials provided herein can be used to make various protective articles. For example, a mask, a protective clothing, or the like can be produced, and for example, a filter net for equipment such as an air cleaner, an air conditioner filter, or an air filter can be produced. In the present embodiment, this is not limited.
Further, with continuing reference to fig. 3, it can be seen from fig. 3 that the amount of viruses contained in the liquid corresponding to the antibacterial material nos. 2 (drying temperature is 100 ℃) and 3 (drying temperature is 110 ℃) is less than the amount of viruses contained in the liquid corresponding to the antibacterial material nos. 1, that is, the adsorption and removal effects of the antibacterial material nos. 2 and 3 on the viruses are better than the adsorption and removal effects of the antibacterial material nos. 1 on the viruses, which indicates that the drying temperature has a certain influence on the curing effect of the antibacterial agent. When the temperature is increased, the curing effect of the antibacterial agent is increased. In this application, the drying temperature is preferably 110 ℃ to 160 ℃.
In correspondence with the foregoing examples of methods of making antimicrobial materials, the present application also provides examples of antimicrobial materials.
The antibacterial material provided by the application is prepared by any one of the preparation methods of the antibacterial material provided by the application, and comprises a non-woven fabric base material and an antibacterial agent solidified on the non-woven fabric base material, wherein the antibacterial agent comprises quaternary ammonium salt.
In particular, quaternary ammonium salts are used primarily for the adsorption removal of viruses. It may include at least one quaternary ammonium salt of: chitosan quaternary ammonium salt, double-chain quaternary ammonium salt, multi-chain quaternary ammonium salt and organosilicon quaternary ammonium salt. For example, it may be dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, hexadecyltrimethylammonium bromide, tetradecyldimethylbenzylammonium chloride or hexadecylpyridinium chloride, a combination of various quaternary ammonium salts, or the like.
Alternatively, the quaternary ammonium salt comprises tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride.
The nonwoven fabric substrate may be a nonwoven fabric produced by various production processes. For example, it may be a spunbond nonwoven fabric, a needle-punched nonwoven fabric, a meltblown nonwoven fabric, or the like. In addition, the non-woven fabric can be produced by using Polypropylene (PP), Polyester (PET), acrylic, nylon, polyvinyl chloride (PVC), Polybutylene Terephthalate (PBT) and the like as raw materials.
The above embodiments of the present application may be complementary to each other without conflict.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims (10)

1. The antibacterial material is characterized by comprising a non-woven fabric base material and an antibacterial agent solidified on the non-woven fabric base material, wherein the antibacterial agent comprises quaternary ammonium salt.
2. The antimicrobial material of claim 1, wherein the quaternary ammonium salt comprises tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
3. A method of preparing an antimicrobial material, the method comprising:
preparing an antibacterial agent solution; wherein the antibacterial agent solution is obtained by mixing at least quaternary ammonium salt, an organic solvent, a surfactant and an inorganic solvent;
dipping a non-woven fabric substrate in the antibacterial agent solution to obtain a dipped substrate;
and drying the impregnated base material to enable the quaternary ammonium salt to be solidified on the non-woven fabric base material, so as to obtain the antibacterial material.
4. The method of claim 3, wherein the quaternary ammonium salt comprises tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride.
5. The method according to claim 3, wherein the temperature of the drying process is 70 ℃ to 180 ℃.
6. The method according to claim 3, wherein the drying process is performed for a period of 1 to 10 min.
7. The method of claim 4, wherein the antimicrobial solution comprises the following components in mass percent:
1 to 20 percent of tetradecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride, 0.05 to 1 percent of surfactant, 0.01 to 5 percent of organic solvent and the balance of inorganic solvent.
8. The method of claim 3, wherein the surfactant is oleamide.
9. The method of claim 3, wherein the organic solvent is triethylene glycol monomethyl ether.
10. Use of an antimicrobial material prepared by the method of any one of claims 3 to 9 for the adsorptive removal of 2019 novel coronaviruses.
CN202010647773.4A 2020-07-07 2020-07-07 Antibacterial material and preparation method and application thereof Pending CN113914098A (en)

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Application publication date: 20220111