CN111534877B - Compound Chinese medicinal multifunctional antibacterial fiber for resisting coronavirus and influenza virus - Google Patents
Compound Chinese medicinal multifunctional antibacterial fiber for resisting coronavirus and influenza virus Download PDFInfo
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Abstract
The invention belongs to the field of functional fiber materials, and discloses a traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber. The fiber comprises traditional Chinese medicine antiviral particles, inorganic antibacterial particles, health-care functional particles and a fiber matrix; the traditional Chinese medicine antiviral particles are silica aerogel microspheres loaded with traditional Chinese medicine antiviral components, and the traditional Chinese medicine antiviral components comprise extracts of radix isatidis, dandelion, honeysuckle, wild chrysanthemum flower, folium isatidis, common andrographis herb, pericarpium citri reticulatae, ageratum and mint. The silica aerogel microspheres are innovatively used as carriers of traditional Chinese medicine antiviral components and are introduced into the fiber material, so that the traditional Chinese medicine antiviral functional components can be protected from being damaged in the fiber forming process, and a good antiviral effect is achieved. The anti-virus activity rate of the fiber product obtained by testing on coronavirus Hcov-229E and influenza A virus H1N1 can reach more than 99%.
Description
Technical Field
The invention belongs to the field of functional fiber materials, and particularly relates to a traditional Chinese medicine compound anti-coronavirus and anti-influenza composite antibacterial multifunctional fiber.
Background
The protection against infectious viruses is becoming more and more urgent due to outbreaks of new coronaviruses and the spread of infectious diseases caused by frequent viral infections. Since virus infection through the respiratory tract is mainly transmitted by droplets (sneezing, etc.) containing virus discharged from virus-infected persons, transmission of virus can be slowed to some extent by wearing a mask. The demand for fibrous materials for making masks is increasing. In addition, partial viral infection occurs not only when the droplets containing the virus discharged from a virus-infected person are directly contacted but also when the droplets are contacted with clothes, towels, and the like (indirect contact) that the virus-infected person has contacted. For example, when the mask is used for a long time, a source of viruses accumulates on the mask, and when the mask is removed and brought into contact with the mask body, the viruses adhere to the hands, and when the hands come into contact with a towel or clothes, the viruses adhere to the towel or clothes. Then, when a third person touches the place where the virus is attached, the virus attaches to the hands, causing secondary infection. In view of such problems, various techniques for suppressing or destroying viruses adhering to fiber products and the like have been proposed.
The loading of inorganic antiviral particles or antiviral agents into the fiber is an important direction.
Patent CN 200580006819.8 discloses an antiviral fiber, a method for producing the fiber, and a fiber product using the fiber. This patent discloses that fine particles of a metal and/or a metal compound having a virus inactivating effect and being hardly soluble in water are dispersed in a fiber having a crosslinked structure and having a carboxyl group in a molecule; a fiber having a carboxyl group in its molecule is provided with a fine particle of a metal and/or a metal compound deposited on the fiber by a reduction and/or substitution reaction after binding a metal ion of a metal having a inactivating effect on viruses and being hardly soluble in water to at least a part of the carboxyl group. The mechanism of viral inactivation by the antiviral fiber is not clear at present, and it is generally considered that the fine particles of the above-mentioned poorly soluble metal and/or metal compound dispersed in the fiber come into contact with the virus to stop or destroy the movement of proteins including an enzyme protein (envelope) and an S protein (spike) which surround the nucleic acid of the virus, thereby exerting an excellent viral inactivation effect.
Patent CN 200980100540.4 discloses an antiviral agent, an antiviral fiber and an antiviral fiber structure. The antiviral fiber is prepared by loading antiviral agent on fiber, and the effective component of the antiviral agent is metal (Fe, Co, Mn, Ti, V, Ni, Cu, Zn, Mo, W, Os) phthalo blue derivative. The method comprises the steps of putting rayon fibers into aqueous solution of metal sodium phthalocyaninedisulfonate with a certain concentration, dyeing the rayon fibers under the conditions of heating and stirring by using a dyeing auxiliary agent, and obtaining the antiviral fibers loaded with the metal sodium phthalocyaninedisulfonate through washing, dewatering and drying.
As a precious wealth in China, the traditional Chinese medicine plays an important role in the aspect of antivirus, and at present, through a large number of researches at home and abroad, some Chinese herbal medicines with a broad-spectrum inhibition effect on infectious viruses are discovered. If reported, pericarpium citri reticulatae, parasitic loranthus, wrinkled gianthyssop, perilla leaves, eupatorium and the like have the inhibiting effect on enteroviruses; scutellariae radix, Coptidis rhizoma, cortex Phellodendri, flos Lonicerae, bupleuri radix, rhizoma Osmundae, fructus forsythiae, folium Isatidis, radix Isatidis, herba Mimosae Pudicae, etc. have effect in inhibiting respiratory tract virus; the narcissus pseudonarcissus, elderberry and the like have an inhibitory effect on Japanese encephalitis virus; radix Isatidis, herba Schizonepetae, herba Menthae, etc. have effect in inhibiting parotitis virus; herba Taraxaci, and herba Ardisiae Japonicae have effect in inhibiting herpesvirus. And the traditional Chinese medicine functional components are added to the fiber material to obtain the corresponding fiber with the antiviral function, and the research is also widely carried out.
Patent CN 201610091214 discloses an indigowoad leaf cellulose fiber with antiviral, antibacterial, skin-care and health-care functions and a preparation method thereof. The paint comprises the following components in parts by weight: 2.0-8.0 parts of folium isatidis extract, 2.0-8.0 parts of sodium caseinate, 2-30 parts of porous starch and 2-50 parts of protein. The preparation method comprises the following steps: 1. preparing a folium isatidis extract-sodium caseinate composite microcapsule; 2. preparing a blended spinning solution; 3. spinning and post-processing. The obtained fiber has an inactivation rate of not less than 82.0% for influenza A virus, an inactivation rate of not less than 84.0% for herpes virus, a bacteriostatic activity value of not less than 2.0 and a bactericidal activity value of not less than 0.2.
Patent CN 201710183270 discloses a sarcandra glabra high-efficiency antibacterial antiviral cellulose fiber and a preparation method thereof. Comprises chitosan-functional component composite particles composed of chitosan, functional components (radix Isatidis extract, herba Pileae Scriptae extract, herba Menthae extract), and polyquaternary ammonium salt, and silicic acid composite colloid, and is obtained by mixing, spinning, and molding. The obtained fiber can effectively resist influenza A virus and influenza B virus, and has high inhibition rate on staphylococcus aureus, candida albicans and typhoid bacillus.
Patent CN 201710183744 discloses a viscose fiber containing isatis root extract and a preparation method thereof. The preparation method comprises the steps of firstly preparing isatis root microcapsules, then adding a modifier solution for modification to obtain the modified isatis root microcapsules, then adding an ionic liquid to prepare modified isatis root microcapsule emulsion, and then carrying out blending spinning with a viscose stock solution to obtain viscose containing isatis root extract. So as to reduce the loss of isatis root microcapsules in the fiber preparation process and reduce the bench-dismantling backwashing rate of the coagulation bath filter; improving the technical effect of the uniformity of the distribution of the isatis root microcapsules in the fiber.
However, it can be seen from the above prior art that the existing antiviral and antibacterial fibers only contain a single inorganic antiviral and antibacterial material or antiviral and antibacterial herbal ingredients. The development of artificial antibacterial fibers added with metal ion type antibacterial agents is rapid in recent years. The fiber has the characteristics of high safety, no drug resistance and the like, particularly has excellent heat resistance and chemical stability, and is widely applied to the fields of fibers and the like. The most commonly used metal ions for inorganic antimicrobial agents are primarily silver, copper and zinc. However, metals in ionic form have migratory properties and may enter the human body through the skin, causing accumulation and harm to human health. The simple substances and/or oxides of silver, copper and zinc can solve the defect and maintain certain antibacterial and antiviral effects. However, the simple substances and/or oxides of silver, copper and zinc have poor compatibility with the fiber base material, and a special pretreatment process is needed to improve the dispersibility of the simple substances and/or oxides in the fiber base material. In the earlier research process, functional master batch preparation and blending technology, specific silane coupling agent surface modification technology added and functional nanoparticle ball-milling erosion perforating pretreatment technology are developed to carry out pretreatment on inorganic functional materials, so that the technical effect of improving the dispersibility of the inorganic functional materials in a fiber base material is achieved. However, these methods are ineffective for introducing antiviral and antibacterial ingredients of Chinese medicinal materials. The prior art mainly comprises a microcapsule embedding blending method and a composite particle embedding blending method for introducing antiviral and antibacterial traditional Chinese medicine components into functional fibers. The methods can avoid the damage of the antiviral and antibacterial traditional Chinese medicine components in the fiber forming process, so that the corresponding antiviral and antibacterial functions can be exerted. However, these methods generally have the defects of complex process and low industrialization degree, and the compatibility between the microcapsule embedding or composite particle embedding and the fiber matrix is a big problem, and the poor dispersibility will seriously affect the exertion of the antiviral and antibacterial functions and reduce the fiber strength to a certain extent. For this reason, it is further desired to find a method capable of simultaneously introducing an inorganic antiviral and antibacterial material and an antiviral and antibacterial Chinese medicinal ingredient into a fiber matrix. Under the condition of not reducing the fiber strength, the inorganic antiviral and antibacterial effect and the traditional Chinese medicine antiviral and antibacterial effect can be well and stably exerted.
Silica aerogel microspheres are a new material that has been developed in recent years. It has the characteristics of light weight, porosity and high specific surface. The preparation method has wide application in the fields of heat insulation materials (CN 104231798A, modified silica aerogel microsphere heat insulation coatings), adsorption treatment of organic dye pollutants (such as methylene blue) (CN 106467304A, silica aerogel microspheres and a preparation method thereof), adsorption treatment of heavy metal pollution (CN 107043112A, modified silica aerogel microspheres and a preparation method and application thereof), high-temperature load catalysis and biological enzyme load catalysis (CN 108579705A, a preparation method of mesoporous silica microspheres), and building materials (CN 106699040A). The general idea for preparing the silica aerogel is to hydrolyze a silica precursor (organic silicon alkoxide, water glass or silicon tetrachloride) in an alcohol solvent to obtain an alcohol sol of silicon, then adjust the pH to be neutral to obtain wet gel, and then dry to obtain the aerogel. The silica aerogel can be controlled to form microspheres and adjust the particle size by adjusting the solvent or adding a dispersant, a template agent, an emulsifier and the like (CN 110683552A, a preparation method of nano silica microspheres with the particle size of 10-20 nm). Different reactive groups can be introduced by adding different silicon sources (cyanosilanes, aminosilanes, carboxysilanes, etc.). However, at present, no report of using silica aerogel microspheres for inorganic or traditional Chinese medicine antiviral and antibacterial fiber materials exists.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide the traditional Chinese medicine compound anti-coronavirus and anti-influenza composite antibacterial multifunctional fiber.
The invention also aims to provide a preparation method of the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus compound antibacterial multifunctional fiber.
The invention also aims to provide application of the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber in preparation of masks, clothes, bedding textile products, bath textile products, automobile textile products, plush toys and the like.
The purpose of the invention is realized by the following technical scheme:
a Chinese medicinal compound antibacterial multifunctional fiber for resisting coronavirus and influenza virus comprises Chinese medicinal antivirus particles, inorganic antibacterial particles, health promoting functional particles and fiber matrix; the traditional Chinese medicine antiviral particles are silica aerogel microspheres loaded with traditional Chinese medicine antiviral components, and the traditional Chinese medicine antiviral components comprise extracts of radix isatidis, dandelion, honeysuckle, wild chrysanthemum flower, folium isatidis, common andrographis herb, pericarpium citri reticulatae, ageratum and mint.
Further, the inorganic antibacterial particles comprise antibacterial copper or copper oxide powder, antibacterial zinc or zinc oxide powder, antibacterial silver or silver oxide powder, supported copper ion, copper or copper oxide antibacterial powder, supported zinc ion, zinc or zinc oxide antibacterial powder, supported silver ion, silver or silver oxide antibacterial powder, and graphene or supported graphene.
Further preferably, the supported copper ion, copper or copper oxide antibacterial powder, the supported zinc ion, zinc or zinc oxide antibacterial powder and the supported silver ion, silver or silver oxide antibacterial powder take silicon dioxide aerogel microspheres as carriers.
Further, the health care functional particles comprise at least one of nano negative ion powder, nano far infrared powder, nano antibacterial and anti-mite powder, nano magnetic powder, inorganic nano formaldehyde removing powder, inorganic nano peculiar smell removing powder and inorganic nano anti-radiation and anti-ultraviolet powder. The nano negative ion powder comprises at least one of tourmaline negative ion powder, natural opal mineral powder and titanium dioxide nano particles; the nano far infrared powder comprises at least one of vermiculite raw ore powder, medical stone raw ore powder, far infrared ceramic powder, zirconia nano powder, taiji stone powder, nano silicon dioxide, nano aluminum oxide, nano manganese oxide and nano calcium oxide; the nano antibacterial anti-mite powder comprises at least one of lanthanum oxide nano powder, zinc oxide nano powder, titanium dioxide nano powder, zeolite nano powder, silicon dioxide nano powder, aluminum oxide nano powder, copper oxide nano powder, magnesium oxide nano powder and silver iodide nano powder; the nano magnetic powder comprises magnetite nano powder; the inorganic nano formaldehyde-removing powder comprises at least one of nano mineral crystal and nano titanium dioxide; the inorganic nano peculiar smell removing powder comprises at least one of nano zinc oxide, nano titanium dioxide and nano kieselguhr; the inorganic nano anti-radiation ultraviolet-proof powder comprises at least one of nano titanium dioxide, nano zinc oxide and nano silicon dioxide.
Further, the health care functional particles are subjected to silane coupling agent surface modification pretreatment or ball milling erosion perforation pretreatment before use. To enhance its compatibility and bonding with the fibrous matrix.
Furthermore, the particle diameters of the traditional Chinese medicine antiviral particles, the inorganic antibacterial particles and the health care functional particles are less than 1.5 μm. A particle size greater than 1.5 μm will result in failure of the resulting fiber to spin properly.
Furthermore, the addition amount of the traditional Chinese medicine antiviral particles is 0.2-6% of the mass of the fiber matrix, the addition amount of the inorganic antibacterial particles is 0.2-5% of the mass of the fiber matrix, and the addition amount of the health care functional particles is 0.2-5% of the mass of the fiber matrix.
Further, the fiber matrix includes at least one of polypropylene fibers (PP, polypropylene), polyethylene fibers (PE, polyethylene), polyester fibers (PET, dacron), polyaramid fibers (aramid), polyamide fibers (chinlon), polyacrylonitrile fibers (acrylon), polyurethane fibers (spandex), and cellulose fibers (e.g., viscose).
A preparation method of a Chinese medicinal compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber comprises the following preparation steps:
(1) preparing the traditional Chinese medicine antiviral particles: adding radix Isatidis, herba Taraxaci, flos Lonicerae, flos Chrysanthemi Indici, folium Isatidis, herba Andrographitis, pericarpium Citri Tangerinae, herba Agastaches and herba Menthae into water, decocting, and filtering to obtain filtrate to obtain Chinese medicinal antiviral extractive solution; then adding silica aerogel microspheres for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the traditional Chinese medicine antiviral components to obtain traditional Chinese medicine antiviral particles;
(2) respectively grinding the traditional Chinese medicine antiviral particles, the inorganic antibacterial particles and the health care functional particles, and then adding the ground traditional Chinese medicine antiviral particles, the inorganic antibacterial particles and the health care functional particles into a mixer for mixing to obtain mixed particles;
(3) and (3) mixing the mixed particles obtained in the step (2) with a fiber matrix, and spinning to obtain the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber.
Further, the weight ratio of the traditional Chinese medicine components in the step (1) is as follows: 30-50 parts of isatis root, 20-40 parts of dandelion, 10-30 parts of honeysuckle, 5-20 parts of wild chrysanthemum flower, 3-15 parts of folium isatidis, 2-10 parts of common andrographis herb, 2-10 parts of pericarpium citri reticulatae, 2-6 parts of ageratum and 2-6 parts of mint.
Further, the particle size range of the silica aerogel microspheres in the step (1) is 20 nm-1.5 μm, and the pore size range is 2-50 nm.
Further, the inorganic antibacterial particles in the step (2) are prepared by the following method:
adding the silica aerogel microspheres into an inorganic antibacterial metal salt solution for adsorption treatment, drying and/or roasting the silica aerogel microspheres adsorbed with inorganic antibacterial metal ions, and grinding to obtain inorganic antibacterial particles; or adding the silicon dioxide aerogel microspheres adsorbed with the inorganic antibacterial metal ions into a dilute alkali solution for soaking reaction, washing the product with water, drying, optionally thermally decomposing, and grinding to obtain the inorganic antibacterial particles.
Further, the silica aerogel microspheres used in the preparation of the inorganic antibacterial particles refer to silica aerogel microspheres containing carboxyl groups, and can be prepared by the following method:
adjusting the pH value of silica sol to 1-4 by using an acid solution, adding 3- [ 3-carboxyl allylamido ] propyl triethoxysilane as a mixed silicon source, stirring and mixing uniformly, continuously stirring and adding absolute ethyl alcohol, adding the obtained mixed solution into an organic solvent, adding an emulsifier for homogenization to obtain an emulsion, adding ammonia water to adjust the pH value to 9-11, stirring and mixing uniformly, standing for layering, washing and drying the sediment on the lower layer, and crushing to obtain the silica aerogel microspheres containing carboxyl.
The organic solvent is preferably a mixture of an alkane solvent with 5-12 carbon atoms and a micromolecular alcohol solvent with 3-6 carbon atoms; the emulsifier is preferably a nonionic surfactant.
The silica aerogel microspheres prepared by the method contain two groups, namely carboxyl and amino, and have a better adsorption and fixation effect on antibacterial metal ions.
Further, the inorganic antibacterial metal salt solution is an aqueous solution containing at least one of silver salt, zinc salt and copper salt; the adsorption treatment is carried out under the ultrasonic condition, and the adsorption treatment time is 0.5-12 h. The ultrasonic condition can improve the adsorption effect.
Further, the drying temperature is 50-120 ℃; the temperature of the roasting treatment is 150-800 ℃; the thermal decomposition temperature is 125-800 ℃; the drying, the roasting treatment and the thermal decomposition are all carried out under the air condition.
The roasting treatment has the function of leading the migratory metal ions to generate metal simple substances and/or oxides with antibacterial function through in-situ pyrolysis/oxidation. Wherein the silica aerogel microspheres are used as a fixed carrier and a template. The metal ions are mainly adsorbed on the silica aerogelDrying the micro-pores and the mesopores of the gel microspheres to obtain the supported metal ion antibacterial material. And carrying out roasting treatment and in-situ pyrolysis/oxidation to generate a nano-sized metal simple substance and/or oxide, thereby obtaining the load type metal or metal oxide antibacterial material. Or adsorbing metal ions and dilute alkali solution (such as NaOH solution with concentration less than 0.1mol/L, KOH solution, Na solution)2CO3Solution, etc.) to generate hydroxide, oxide or carbonate precipitate in situ, and then the supported metal oxide antibacterial material is obtained through thermal decomposition treatment or not. Can avoid the generation of toxic and harmful gases containing N, Cl, S and the like.
The Chinese medicinal compound anti-coronavirus and anti-influenza composite antibacterial multifunctional fiber can be applied to preparation of masks, clothes, bedding textile products, bath textile products, automobile textile products, plush toys and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the silica aerogel microspheres are innovatively used as carriers of traditional Chinese medicine antiviral components, namely isatis roots, dandelion, honeysuckle, wild chrysanthemum flowers, dyers woad leaves, common andrographis herbs, citrus chachiensis peels, ageratum and mint extracts, and are introduced into the fiber material, so that the traditional Chinese medicine antiviral functional components can be protected from being damaged in the fiber forming process, and a good antiviral effect is achieved. The antiviral activity rate of the fiber product obtained by testing on coronavirus Hcov-229E and influenza A virus H1N1 can reach more than 99%.
(2) The invention can further use the silicon dioxide aerogel microspheres as carriers of inorganic antibacterial components, can adsorb and fix antibacterial metal ions by utilizing the adsorption, fixation and template functions of micropores and mesopores in the silicon dioxide aerogel microspheres, can further carry out in-situ pyrolysis/oxidation to generate nano-sized metal simple substances and/or oxides with antibacterial function, or can obtain nano-sized supported metal oxides with antibacterial function by dilute alkali in-situ precipitation/pyrolysis, thereby exerting good antibacterial effect. The fiber product obtained by tests has over 99 percent of bacteriostasis rate to staphylococcus aureus and escherichia coli.
(3) According to the invention, by utilizing the porous load fixed structure of the silica aerogel microspheres, the antiviral components and the inorganic antibacterial components of the traditional Chinese medicine are firmly combined, and the silica aerogel microspheres can resist washing and have long-lasting and long-acting corresponding antiviral and antibacterial effects.
(4) The silica aerogel microspheres adopted by the invention have a porous structure, can be well fused with a fiber base material, have excellent compatibility and dispersion stability, and have a certain reinforcing effect on a fiber material.
(5) The silica aerogel microspheres adopted by the invention have light weight and lower heat conduction efficiency, and have the advantages of light weight and good heat insulation effect when being used for fiber base materials.
(6) According to the invention, nano anion powder, nano far infrared powder, nano antibacterial and anti-mite powder, nano magnetic powder, inorganic nano formaldehyde removing powder, inorganic nano peculiar smell removing powder, inorganic nano anti-radiation and anti-ultraviolet powder and the like are added into a fiber base material, so that the fiber material is endowed with corresponding health care functions.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The compound anti-coronavirus and anti-influenza multifunctional traditional Chinese medicine PP fiber is prepared by the following steps:
(1) preparing the traditional Chinese medicine antiviral particles: adding 30 parts by mass of radix isatidis, 20 parts by mass of dandelion, 20 parts by mass of honeysuckle, 10 parts by mass of wild chrysanthemum flower, 10 parts by mass of folium isatidis, 10 parts by mass of andrographis paniculata, 5 parts by mass of pericarpium citri reticulatae, 5 parts by mass of ageratum and 5 parts by mass of mint into 500 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: will contain carboxyl groupsSilica aerogel microspheres (with 3- [ 3-carboxyl allylamide group)]Propyl triethoxy silane is prepared as a mixed silicon source, the particle size range is 0.1-1 mu m, the pore diameter range is 10-40 nm) is added into AgNO with the mass fraction of 6%3Performing ultrasonic adsorption treatment in an aqueous solution for 2h, roasting the silica aerogel microspheres adsorbed with Ag ions for 6h at 200 ℃, cooling and grinding to obtain the inorganic antibacterial particles.
(3) Respectively grinding 3 parts by mass of the traditional Chinese medicine antiviral particles in the step (1), 2 parts by mass of the inorganic antibacterial particles in the step (2) and 1 part by mass of the far infrared ceramic powder until the particle size is less than 1.5 mu m, and adding the mixture into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (4) extruding and mixing the mixed particles obtained in the step (3) and 94 parts by mass of PP slices by an extruder, and then carrying out melt spinning to obtain the traditional Chinese medicine compound coronavirus and influenza virus-resistant composite antibacterial multifunctional PP fiber.
Example 2
The compound anti-coronavirus and anti-influenza traditional Chinese medicine multifunctional PE fiber is prepared by the following method:
(1) preparing the traditional Chinese medicine antiviral particles: adding 40 parts by mass of radix isatidis, 30 parts by mass of dandelion, 10 parts by mass of honeysuckle, 10 parts by mass of wild chrysanthemum flower, 5 parts by mass of folium isatidis, 5 parts by mass of andrographis paniculata, 10 parts by mass of pericarpium citri reticulatae, 3 parts by mass of ageratum and 2 parts by mass of mint into 400 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: silica aerogel microspheres (3- [ 3-carboxyl allylamide) containing carboxyl]Propyltriethoxysilane as mixed silicon source with particle size of 0.1-1 μm and pore diameter of 10-40 nm) is added into 5 wt% Cu (NO)3)2Ultrasonic adsorption treatment in water solution for 2h to adsorbAnd roasting the silicon dioxide aerogel microspheres with Cu ions at 650 ℃ for 4 hours, cooling and grinding to obtain the inorganic antibacterial particles.
(3) Respectively grinding 6 parts by mass of the traditional Chinese medicine antiviral particles in the step (1), 5 parts by mass of the inorganic antibacterial particles in the step (2) and 5 parts by mass of tourmaline negative ion powder until the particle size is less than 1.5 mu m, and adding the ground particles into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (4) extruding and mixing the mixed particles obtained in the step (3) and 84 parts by mass of PE slices by an extruder, and then carrying out melt spinning to obtain the traditional Chinese medicine compound coronavirus and influenza virus-resistant composite antibacterial multifunctional PE fiber.
Example 3
The compound anti-coronavirus and anti-influenza multifunctional traditional Chinese medicine PET fiber is prepared by the following method:
(1) preparing the traditional Chinese medicine antiviral particles: adding 50 parts by mass of radix isatidis, 20 parts by mass of dandelion, 10 parts by mass of honeysuckle, 10 parts by mass of wild chrysanthemum flower, 5 parts by mass of folium isatidis, 5 parts by mass of andrographis paniculata, 10 parts by mass of pericarpium citri reticulatae, 5 parts by mass of ageratum and 5 parts by mass of mint into 500 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: silica aerogel microspheres (3- [ 3-carboxyl allylamide) containing carboxyl]Propyl triethoxy silane is prepared as a mixed silicon source, the particle size range is 0.1-1 mu m, the pore diameter range is 10-40 nm) is added into AgNO with the mass fraction of 4%3And Zn (NO) with the mass fraction of 4%3)2Performing ultrasonic adsorption treatment in an aqueous solution for 1h, roasting the silica aerogel microspheres adsorbed with Ag ions and Zn ions at 400 ℃ for 4h, cooling and grinding to obtain the inorganic antibacterial particles.
(3) Grinding 2 parts by mass of the traditional Chinese medicine antiviral particles in the step (1), 2 parts by mass of the inorganic antibacterial particles in the step (2) and 2 parts by mass of the taijishi powder respectively until the particle size is less than 1.5 mu m, and adding the ground particles into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (4) extruding and mixing the mixed particles obtained in the step (3) and 94 parts by mass of PET slices by an extruder, and then carrying out melt spinning to obtain the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional PET fiber.
Example 4
The compound anti-coronavirus and anti-influenza multifunctional Chinese medicinal nylon fiber is prepared by the following steps:
(1) preparing the traditional Chinese medicine antiviral particles: adding 40 parts by mass of radix isatidis, 20 parts by mass of dandelion, 10 parts by mass of honeysuckle, 15 parts by mass of wild chrysanthemum flower, 10 parts by mass of folium isatidis, 5 parts by mass of andrographis paniculata, 5 parts by mass of pericarpium citri reticulatae, 5 parts by mass of ageratum and 5 parts by mass of mint into 400 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: adding silicon dioxide aerogel microspheres (with the particle size range of 0.1-1 mu m and the mesoporous diameter range of 10-40 nm) into AgNO with the mass fraction of 6%3Ultrasonic adsorption treatment is carried out in the water solution for 2 hours, filtering is carried out, then, the silicon dioxide aerogel microspheres adsorbed with Ag ions are added into NaOH water solution with the concentration of 0.05mol/L for soaking reaction, and the product is washed, dried and ground to obtain the inorganic antibacterial particles.
(3) Grinding 4 parts by mass of the traditional Chinese medicine antiviral particles obtained in the step (1), 2 parts by mass of the inorganic antibacterial particles obtained in the step (2) and 3 parts by mass of the magnetite nano powder respectively until the particle size is less than 1.5 mu m, and adding the ground particles into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (3) extruding and mixing the mixed particles obtained in the step (3) and 91 parts by mass of nylon chips by an extruder, and then carrying out melt spinning to obtain the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional nylon fiber.
Example 5
The compound antibacterial multifunctional acrylic fiber for resisting coronavirus and influenza virus of the traditional Chinese medicine compound is prepared by the following method:
(1) preparing the traditional Chinese medicine antiviral particles: adding 30 parts by mass of radix isatidis, 40 parts by mass of dandelion, 10 parts by mass of honeysuckle, 15 parts by mass of wild chrysanthemum flower, 3 parts by mass of folium isatidis, 2 parts by mass of andrographis paniculata, 10 parts by mass of pericarpium citri reticulatae, 2 parts by mass of ageratum and 2 parts by mass of mint into 600 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: adding silicon dioxide aerogel microspheres (with the particle size range of 0.1-1 mu m and the mesoporous diameter range of 10-40 nm) into AgNO with the mass fraction of 6%3Ultrasonic adsorption treatment is carried out in the water solution for 2 hours, filtering is carried out, then, the silicon dioxide aerogel microspheres adsorbed with Ag ions are added into NaOH water solution with the concentration of 0.05mol/L for soaking reaction, and the product is washed, dried and ground to obtain the inorganic antibacterial particles.
(3) Respectively grinding 3 parts by mass of the traditional Chinese medicine antiviral particles in the step (1), 3 parts by mass of the inorganic antibacterial particles in the step (2) and 2 parts by mass of the nano-mineral crystal powder until the particle size is less than 1.5 mu m, and adding the ground particles into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (4) adding the mixed particles obtained in the step (3) into a spinning solution containing 92 parts by mass of polyacrylonitrile, uniformly stirring and mixing, and then carrying out wet spinning forming to obtain the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional acrylic fiber.
Example 6
The compound antibacterial multifunctional spandex fiber for resisting coronavirus and influenza virus of the traditional Chinese medicine compound is prepared by the following method:
(1) preparing the traditional Chinese medicine antiviral particles: adding 40 parts by mass of radix isatidis, 20 parts by mass of dandelion, 10 parts by mass of honeysuckle, 10 parts by mass of wild chrysanthemum flower, 10 parts by mass of folium isatidis, 10 parts by mass of andrographis paniculata, 2 parts by mass of pericarpium citri reticulatae, 6 parts by mass of ageratum and 6 parts by mass of mint into 800 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: adding silicon dioxide aerogel microspheres (mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 10-40 nm) into Cu (NO) with the mass fraction of 4%3)2And Zn (NO) with the mass fraction of 4%3)2Ultrasonic adsorption treatment is carried out in an aqueous solution for 2h, filtering is carried out, then, silicon dioxide aerogel microspheres adsorbed with Cu and Zn ions are added into NaOH aqueous solution with the concentration of 0.05mol/L for soaking reaction, products are washed, dried and thermally decomposed for 2h at 200 ℃ in the air atmosphere, and grinding is carried out, so that the inorganic antibacterial particles are obtained.
(3) Grinding 4 parts by mass of the traditional Chinese medicine antiviral particles in the step (1), 4 parts by mass of the inorganic antibacterial particles in the step (2) and 4 parts by mass of nano kieselguhr respectively until the particle size is less than 1.5 mu m, and adding the ground particles into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (4) extruding and mixing the mixed particles obtained in the step (3) and 88 parts by mass of spandex slices by an extruder, and then carrying out melt spinning to obtain the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional spandex fiber.
Example 7
The compound anti-coronavirus and anti-influenza virus multifunctional viscose fiber of the traditional Chinese medicine is prepared by the following method:
(1) preparing the traditional Chinese medicine antiviral particles: adding 30 parts by mass of radix isatidis, 30 parts by mass of dandelion, 15 parts by mass of honeysuckle, 15 parts by mass of wild chrysanthemum flower, 5 parts by mass of folium isatidis, 5 parts by mass of andrographis paniculata, 10 parts by mass of pericarpium citri reticulatae, 6 parts by mass of ageratum and 6 parts by mass of mint into 800 parts by mass of water for decoction, filtering, taking filtrate and concentrating to obtain a traditional Chinese medicine antiviral extract; then adding silica aerogel microspheres (micropores and mesopores with the particle size range of 0.1-1 mu m and the pore diameter range of 2-40 nm) into the antiviral extract of the traditional Chinese medicine for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the antiviral components of the traditional Chinese medicine to obtain the antiviral particles of the traditional Chinese medicine.
(2) Preparation of inorganic antibacterial particles: adding silicon dioxide aerogel microspheres (with the particle size range of 0.1-1 mu m and the mesoporous diameter range of 10-40 nm) into Cu (NO) with the mass fraction of 5%3)2Performing ultrasonic adsorption treatment in an aqueous solution for 2h, roasting the silica aerogel microspheres adsorbed with Cu ions for 4h at 650 ℃, cooling and grinding to obtain the inorganic antibacterial particles.
(3) Respectively grinding 3 parts by mass of the traditional Chinese medicine antiviral particles in the step (1), 3 parts by mass of the inorganic antibacterial particles in the step (2) and 3 parts by mass of tourmaline negative ion powder until the particle size is less than 1.5 mu m, and adding the ground particles into a high-speed dispersion mixer for mixing to obtain mixed particles.
(4) And (4) adding the mixed particles obtained in the step (3) into a spinning solution containing 91 parts by mass of viscose, uniformly stirring and mixing, and then carrying out wet spinning forming to obtain the traditional Chinese medicine compound coronavirus and influenza virus resistant composite antibacterial multifunctional viscose.
The Chinese herbal compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber obtained by the invention is subjected to performance test:
(1) testing the fiber strength: the tensile breaking strength and elongation at break of the individual fibers were measured by a fiber strength tester (the product obtained in example 1 was used as a test sample, and PP fibers to which the antiviral particles of the traditional Chinese medicine and the inorganic antibacterial particles were not added were used as a comparison). The results show that compared with the PP fiber without the antiviral and antibacterial particles, the PP fiber with the traditional Chinese medicine antiviral particles and the inorganic antibacterial particles has the advantages that the tensile breaking strength of the fiber is increased by 22 percent, and the breaking elongation is increased by 5 percent. The invention shows that the antiviral and antibacterial particles which adopt the silica aerogel microspheres with porous structures as carriers have certain reinforcing effect on the fiber base material.
(2) And (3) testing antiviral and antibacterial properties: the anti-viral activity was tested by the "detection center for microbiological analysis in Guangdong province" (using the fiber material obtained in example 2 as a test sample, the detection requirements and criteria: WS 628-2018; ISO 18184-. The national center for quality inspection of textile garment products (Guangzhou) was commissioned to perform tests for antibacterial performance in accordance with the GB/T20944.3-2008 oscillatory method (the fiber material obtained in example 1 was used as a test sample). The test result shows that the antiviral activity rate of the obtained fiber product on coronavirus Hcov-229E and influenza A virus H1N1 can reach more than 99%. The bacteriostasis rate to staphylococcus aureus and escherichia coli can reach more than 99%. After the washing for 10 times by oscillating water, the antiviral activity rate and the bacteriostatic rate are not obviously reduced. The Chinese medicinal compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber has good antiviral and antibacterial effects, and the Chinese medicinal antiviral components and the inorganic antibacterial components are firmly combined with the fiber matrix, so that the fiber can resist washing and has corresponding antiviral and antibacterial effects with lasting and long-acting effects.
(3) Testing far infrared performance and heat preservation performance: according to the standard of CAS115-2005, health care functional textiles, the corresponding far infrared wavelength range should be 4 μm-16 μm. Its normal emissivity should be not less than 0.80. According to the standard of GBT 30127 and 2013, detection and evaluation of far infrared performance of textiles, the temperature rise of corresponding far infrared radiation is not lower than 1.4 ℃. The far infrared emissivity refers to the ratio of the normal far infrared radiation intensity of the sample and the same temperature standard black board under the specified conditions; the temperature rise refers to the temperature rise value of the surface of the test sample measured after the far infrared radiation source irradiates the test sample for a certain time with constant radiation intensity. The far infrared radiation and heat preservation performance of the fiber material are represented by measuring the far infrared wavelength range, the far infrared emissivity and the temperature rise of the Chinese medicinal compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional PET fiber material obtained in the example 3, and the PET fiber material obtained without adding antiviral and antibacterial particles is used as a comparative example. The results are shown in the following table:
from the results, the addition of the traditional Chinese medicine antiviral particles and the inorganic antibacterial particles has no adverse effect on the far infrared radiation performance of the fiber, and the temperature rise is obviously improved, so that the silica aerogel microspheres have lower heat conduction efficiency, and the obtained fiber base material has better heat preservation effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber is characterized by comprising the following preparation steps:
(1) preparing the traditional Chinese medicine antiviral particles: adding radix Isatidis, herba Taraxaci, flos Lonicerae, flos Chrysanthemi Indici, folium Isatidis, herba Andrographitis, pericarpium Citri Tangerinae, herba Agastaches and herba Menthae into water, decocting, and filtering to obtain filtrate to obtain Chinese medicinal antiviral extractive solution; then adding silica aerogel microspheres for adsorption treatment, and freeze-drying the silica aerogel microspheres adsorbed with the traditional Chinese medicine antiviral components to obtain traditional Chinese medicine antiviral particles;
(2) respectively grinding the traditional Chinese medicine antiviral particles, the inorganic antibacterial particles and the health care functional particles, and then adding the ground traditional Chinese medicine antiviral particles, the inorganic antibacterial particles and the health care functional particles into a mixer for mixing to obtain mixed particles;
(3) mixing the mixed particles obtained in the step (2) with a fiber matrix and spinning to obtain the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber;
the inorganic antibacterial particles in the step (2) are prepared by the following method:
adding the silica aerogel microspheres into an inorganic antibacterial metal salt solution for adsorption treatment, drying and/or roasting the silica aerogel microspheres adsorbed with inorganic antibacterial metal ions, and grinding to obtain inorganic antibacterial particles; or adding the silicon dioxide aerogel microspheres adsorbed with inorganic antibacterial metal ions into a dilute alkali solution for soaking reaction, washing the product with water, drying, optionally thermally decomposing, and grinding to obtain inorganic antibacterial particles;
the inorganic antibacterial metal salt solution is an aqueous solution containing at least one of silver salt, zinc salt and copper salt; the adsorption treatment is carried out under the ultrasonic condition, and the adsorption treatment time is 0.5-12 h; the drying temperature is 50-120 ℃; the temperature of the roasting treatment is 150-800 ℃; the thermal decomposition temperature is 125-800 ℃; the drying, the roasting treatment and the thermal decomposition are all carried out under the air condition;
in the step (1) and the step (2), the particle size range of the silicon dioxide aerogel microspheres is 20 nm-1.5 mu m, and the pore size range is 2-50 nm.
2. The preparation method of the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber according to claim 1, which is characterized by comprising the following steps of: the health care functional particles comprise at least one of nano anion powder, nano far infrared powder, nano antibacterial and anti-mite powder, nano magnetic powder, inorganic nano formaldehyde-removing powder, inorganic nano peculiar smell-removing powder and inorganic nano anti-radiation and anti-ultraviolet powder; the nano negative ion powder comprises at least one of tourmaline negative ion powder, natural opal mineral powder and titanium dioxide nano particles; the nano far infrared powder comprises at least one of vermiculite raw ore powder, medical stone raw ore powder, far infrared ceramic powder, zirconia nano powder, taiji stone powder, nano silicon dioxide, nano aluminum oxide, nano manganese oxide and nano calcium oxide; the nano antibacterial anti-mite powder comprises at least one of lanthanum oxide nano powder, zinc oxide nano powder, titanium dioxide nano powder, zeolite nano powder, silicon dioxide nano powder, aluminum oxide nano powder, copper oxide nano powder, magnesium oxide nano powder and silver iodide nano powder; the nano magnetic powder comprises magnetite nano powder; the inorganic nano formaldehyde-removing powder comprises at least one of nano mineral crystal and nano titanium dioxide; the inorganic nano peculiar smell removing powder comprises at least one of nano zinc oxide, nano titanium dioxide and nano kieselguhr; the inorganic nano anti-radiation ultraviolet-proof powder comprises at least one of nano titanium dioxide, nano zinc oxide and nano silicon dioxide.
3. The preparation method of the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber according to claim 1, which is characterized by comprising the following steps of: the particle diameters of the traditional Chinese medicine antiviral particles, the inorganic antibacterial particles and the health care functional particles are less than 1.5 mu m;
the addition amount of the traditional Chinese medicine antiviral particles is 0.2-6% of the mass of the fiber matrix, the addition amount of the inorganic antibacterial particles is 0.2-5% of the mass of the fiber matrix, and the addition amount of the health care functional particles is 0.2-5% of the mass of the fiber matrix;
the fiber matrix includes at least one of polypropylene fibers, polyethylene fibers, polyester fibers, polyaramide fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, and cellulose fibers.
4. The preparation method of the traditional Chinese medicine compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber according to claim 1, which is characterized by comprising the following steps of: the weight ratio of the traditional Chinese medicine components in the step (1) is as follows: 30-50 parts of isatis root, 20-40 parts of dandelion, 10-30 parts of honeysuckle, 5-20 parts of wild chrysanthemum flower, 3-15 parts of folium isatidis, 2-10 parts of common andrographis herb, 2-10 parts of pericarpium citri reticulatae, 2-6 parts of ageratum and 2-6 parts of mint.
5. A Chinese herbal compound anti-coronavirus and anti-influenza virus composite antibacterial multifunctional fiber is characterized in that: prepared by the method of any one of claims 1 to 4.
6. The use of the compound anti-coronavirus and anti-influenza multifunctional fiber as defined in claim 5 for the manufacture of masks, clothes, bedding textiles, bath textiles, automotive textiles, and plush toys.
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| CN112011851A (en) * | 2020-09-10 | 2020-12-01 | 江苏宝恒纺织科技发展有限公司 | Anti-influenza virus fiber and preparation method thereof |
| CN112323176A (en) * | 2020-09-21 | 2021-02-05 | 连云港杜钟新奥神氨纶有限公司 | Antiviral and antibacterial spandex fiber and application thereof |
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