HK40040784B

HK40040784B - Multilayer copper-based zeolite fiber medical material, medical protective article and manufacturing method thereof

Info

Publication number: HK40040784B
Application number: HK42021031165.0A
Authority: HK
Inventors: 范杰; 肖丽萍; 余丽莎; 李丹; 施益峰; 姚航平
Original assignee: 浙江大学; 杭州沸创生命科技股份有限公司
Filing date: 2021-05-14
Publication date: 2021-12-03

Description

Multilayer copper-based zeolite fiber medical material, medical protective product and manufacturing method thereof

Technical Field

The invention relates to the field of epidemic prevention sanitary appliances, in particular to a medical material with sufficiently low cytotoxicity and sufficiently high antibacterial and antiviral performances, which is particularly suitable for being used as a biosafety medical material for killing new coronavirus and a medical protective article.

Background

The new outbreak of infectious diseases causes great harm to the health of human beings, social politics, economy and the like. Coronavirus is a large virus family, and can cause infectious diseases such as cold, Middle East Respiratory Syndrome (MERS), Severe Acute Respiratory Syndrome (SARS), and novel coronavirus pneumonia (COVID-19). Among them, the main retransmission routes of the novel coronavirus (SARS-CoV-2) are: direct transmission, aerosol transmission, contact transmission, and the like. Thus, wearing personal protective equipment is one of the most effective protective measures against viral infections.

For dangerous bacteria and viruses, small contact/inhalations are both dangerous and scary. In fact, medical staff and epidemic prevention staff face the problems that patients are diagnosed and high-risk and easily-infected environments are prone to infection, the number of bacteria and viruses is high, and the patients are prone to infection due to improper protection.

At present, a common medical mask is composed of three layers, wherein an outer layer and an inner layer are both made of non-woven fabrics, and a middle layer is made of melt-blown non-woven fabrics. The outermost layer of the mask is designed to prevent spray, the middle layer is a core functional layer and is used for filtering spray, particles or bacteria, and the inner layer mainly absorbs moisture. The mask utilizes the principle of filtration, and can block partial pathogens such as virus and bacteria to a certain extent to the physical barrier of virus, thereby reducing the risk of being infected by the virus. However, it is inevitable that a small number of viruses and bacteria are attached to the surface of the mask. Studies have demonstrated that the new coronavirus (SARS-CoV-2) trapped or trapped on the mask survives for up to 7 days. The viruses which are attached to the surface of the mask and have the vitality are likely to become cross infection sources, so that the viruses are spread again. Therefore, how to eradicate the virus residue on the surface of the mask or the filter layer is a key problem in the whole epidemic prevention system.

Masks are classified into a civil mask and a medical mask according to the type of use of the mask. The medical masks are mainly classified into 3 types, namely, a common medical mask, a medical surgical mask and a medical protective mask (Sun Xingchun, etc. the patent and technology research of the medical protective mask, new material industry 2020, (2) 13-15). The medical mask utilizes the filtering function of the mask to separate or protect bacteria and viruses, and pays attention to the protection function, so that the national standard or the industrial standard of the medical mask puts forward the requirements on the filtering efficiency, and the filtering effect of the medical mask is the highest in the sequence of common medical masks < medical surgical masks < medical protective masks. However, the above three types of medical masks do not set the technical standards of antibacterial and antiviral, wherein the common medical mask or the medical surgical mask sets the biological safety standard of cytotoxicity (cytotoxicity should not be greater than level 2), but the medical protective mask does not set the biological safety standard of cytotoxicity.

The civil mask has short wearing time and low protection requirement, and does not regulate cytotoxicity. Common medical masks or surgical masks must meet the regulations of the industry standards regarding cytotoxicity: namely, the cytotoxicity of the mask must meet the cytotoxicity regulations of the medical industry standard YY/T0969-2013 Disposable medical mask and YY0469-2011 medical surgical mask issued by the State food and drug administration, wherein the cytotoxicity of the mask is not more than grade 2, namely, no more than 50% of cell inhibition phenomenon (namely, the cell survival rate is more than 50%) can be observed. Furthermore, cytotoxicity must be strictly in accordance with the national standard "biological evaluation of medical devices part 5: in vitro cytotoxicity test GB/T16886.5-2017/ISO 10993-5: 2009. In addition, the medical protective mask needs to meet the standard of GB19083-2010 medical protective mask technical requirement, important indexes of the medical protective mask mainly include filtering efficiency and air suction resistance, and biological safety problems related to cytotoxicity are not specified. The medical protective mask meeting the N95 standard in the prior art adopts a passive protection technology (the filtration efficiency of particles with aerodynamic diameters of 0.075 μm +/-0.020 μm reaches more than 95%), only provides simple filtration and barrier properties, and is difficult to ensure the use safety of professionals for medical protection, disease control, epidemic prevention and control and the like of infectious diseases.

With the diffusion and continuous variation of the new coronavirus, the survival ability of the virus is stronger, and the effect of filtering the virus through the mask cannot meet the protection requirement of the new coronavirus, so that higher requirements are provided for the performance of the medical mask, and the medical mask is required to have the function of killing bacteria and viruses. The existing medical mask mainly adopts nano materials (nano zinc oxide, graphene and silver ions), a photocatalyst technology (such as peptide dioxide), traditional Chinese medicines and a mode of adding an antibacterial functional layer to realize better antibacterial and antiviral performances. At present, the antibacterial and antiviral performances of medical masks in the market are different and the standards are not unified, and the technical standards of antibacterial and antiviral and the biological safety standards of cytotoxicity are not set for the medical masks at the same time in the current national or industrial standards. At present, in order to achieve the function of killing bacteria and viruses of the medical mask, the medical mask is realized by destroying cell membranes/walls of the bacteria or the viruses, and the cell structures of the bacteria or the viruses are also destroyed, so that the biological safety evaluation of the mask, particularly the cytotoxicity is very undesirable and the cytotoxicity is very high. Therefore, the antibacterial and antiviral effects of the medical mask are obtained at the cost of sacrificing biological safety in the prior art, and particularly for the medical protective mask with the highest requirement on the protection level, the better the antibacterial and antiviral effects are, the greater the cytotoxicity is, so that the related technical standards cannot be set for the cytotoxicity of the medical protective mask, and the antibacterial and antiviral technical standards and the biological safety standards for the cytotoxicity cannot be set for all types of medical masks at the same time.

The copper element can kill bacteria and viruses and can be used for an antibacterial and antiviral mask, but the copper element needs to be loaded on a mask material in a proper form, and the flexibility of the mask is kept and the biological safety of the mask is ensured. Among them, biological safety is one of the most important indexes of medical masks. Biosafety refers to cytotoxicity, skin irritation, and delayed hypersensitivity, wherein cytotoxicity is the most critical technical index for biosafety evaluation. Cytotoxicity (cytotoxicity) refers to the destruction of cellular structures by extracellular chemicals, which ultimately leads to apoptosis or necrosis of cells, resulting in decreased cell survival in vitro experiments.

At present, the application of copper element in medical mask materials has two potential safety hazards based on the cytotoxicity problem: 1) although copper (particularly, divalent copper ions) has a good bactericidal and virucidal effect, it has a strong cytotoxicity (Chendexan. evaluation of cytotoxicity of nine metal ions [ J ] J. oral Material instruments, 1993,000(002): 12-13.). The cytotoxicity and the antibacterial and antiviral performances of the copper element are positively correlated, namely the higher the content of the copper element is, the better the antibacterial and antiviral performances are, but the higher the cytotoxicity is. When the concentration of the divalent copper ions in the solution is 0.5ppm or 5ppm, the cytotoxicity is grade 1, but the divalent copper ions have no antibacterial and antiviral functions; when the concentration of the divalent copper ions in the solution is 10ppm, the cytotoxicity is grade 4, the solution has certain antibacterial and antiviral functions, but the cytotoxicity is far higher than the cytotoxicity regulation in the industry standard, and the requirements of a medical mask or a medical surgical mask cannot be met. 2) In the wearing process of the mask, when the spray or the aerosol passes through the mask layer with the copper element, as the copper ions are very easily dissolved in the water solution, the aerosol is very easy to exchange substances (including ion exchange) with the copper element of the mask fiber layer, so that the copper element enters the nose, the mask with the copper element is worn for a long time, certain damage is caused to the body, and particularly, the harm to medical staff and epidemic prevention staff who wear the mask all the time is more serious.

Therefore, the content of copper element is low, and the antibacterial and antiviral performance effect cannot be realized; on the contrary, in order to achieve high-efficiency antibacterial and antiviral properties, the content of copper element is high, and the cytotoxicity of copper element is inevitably sacrificed, so that the copper element cannot meet the regulation of cytotoxicity in the industrial standard of medical masks (see the correlation between the copper ion amount, the cytotoxicity and the antiviral property in comparative examples 1 to 4 in table 1 of the specification).

At present, the copper element used for preparing the mask mainly comprises 3 forms of a copper simple substance, a monovalent copper ion compound and a divalent copper ion compound, and the 3 forms have inherent defects when being used for preparing a medical mask or a medical surgical mask: (1) in the form of nano-sized, micron-sized copper particles, copper wires, etc. Although the cytotoxicity of the simple copper substance is lower than that of the divalent copper ions, the antiviral and antibacterial effects of the simple copper substance are obviously inferior to that of the divalent copper ions, and the simple copper substance cannot meet the high-standard antibacterial and antiviral protection requirements, and is not suitable for being used as a material of a medical or medical surgical mask. (2) In the form of monovalent copper ion compounds, such as cuprous oxide, cuprous iodide, etc. Among them, cuprous oxide (risk term R22: harmful to swallowing; R50/53: extremely toxic to aquatic organisms, possibly having an adverse effect on the water environment; safety term S61: avoidance of release into the environment). The safety of cuprous iodide (S24/25) should be avoided from contacting skin and eyes, and the hazard class code (R36/37/38) is eye, respiratory and skin irritation. The monovalent copper ion compound is highly irritating to eyes, respiratory system and skin, and is not suitable for use as a material for medical or surgical masks. (3) In the form of a cupric ionic compound such as copper sulfate, copper chloride, copper nitrate, copper carbonate, etc. The antiviral and antibacterial effects of the divalent copper ions are better than that of the simple substance copper, but the divalent copper ions are easy to fall off and dissolve in water, so that the finally synthesized copper fiber has extremely low divalent copper ion content and poor antiviral and antibacterial effects. In order to enhance the antibacterial and antiviral functions, more divalent copper ion compounds need to be added, but the cytotoxicity of the mask material is enhanced at the same time, and the mask material does not meet the cytotoxicity regulation in the medical mask industry standard. In addition, excessive divalent copper ion compounds are added, so that when medical workers wear the mask for a long time, a large amount of divalent copper ions are easily dissolved in water vapor on the mask and easily enter the body, and the health of the body is harmed. In addition, copper element is mainly used for preparing copper fiber in a spinning mode, elemental copper has no affinity to fabric, and the spinning difficulty is high; the monovalent copper ion compound generally has color and is not suitable for weaving the mask fabric; the divalent copper ion compound is easy to lose a large amount in the spinning preparation process, and the fiber with high content of divalent copper ions cannot be prepared. At present, the three forms of the copper element can not realize low cytotoxicity and high antibacterial and antiviral property at the same time, can not meet the cytotoxicity regulation of the medical mask or the medical surgical mask, and the material containing the copper element can not be used for the medical mask or the medical surgical mask.

The copper element-containing material also includes copper ion-modified zeolite material, which is an aqueous alkali or alkaline earth aluminosilicate compound. The chemical composition formula of the zeolite is as follows: (M)_2/nO·xAl₂O₃·ySiO₂·pH₂O, M represent metal ions (e.g. K)⁺、Na⁺、Ca²⁺、Ba²⁺Etc.), n represents the valence of the metal ion, and x represents Al₂O₃Y represents SiO₂P represents H₂The number of moles of O. The zeolite can be X-type zeolite, Y-type zeolite, A-type zeolite, chabazite, mordenite, L-type zeolite, P-type zeolite, and merlino zeolite. The metal ions with balance charges outside the framework of the zeolite can be replaced by copper ions through an ion exchange part, so that the zeolite modified by the copper ions has the capability of killing bacteria and viruses and can control the release of the copper ions to a certain extent; however, to achieve a sufficiently high effect of killing bacteria and viruses, the cytotoxicity is inevitably increased to a level higher than that of the second level, and the cytotoxicity cannot satisfy the specification of the medical mask or the medical surgical mask, and cannot be used as a material for the medical mask or the medical surgical mask (see results of comparative example 1 and table 1).

Chinese patent CN 111227345a discloses an antibacterial and antiviral mask and a preparation method thereof, which sequentially comprises a surface layer, a core layer and an inner layer from outside to inside, wherein the surface layer is a water-repellent polypropylene spun-bonded nonwoven fabric, the core layer is an antibacterial and antiviral nonwoven fabric, the antibacterial and antiviral staple fibers prepared by blending silver-copper-loaded nano zeolite material and fibers are mixed with common PET staple fibers, and finally the antibacterial and antiviral nonwoven fabric is formed. Although the mask prepared by the invention has higher antiviral activity rate on SARS, H1N1, H7N9 and H3N2 and higher antibacterial activity on escherichia coli and staphylococcus aureus, the specification also refers to that 'copper ions are refined by protein/amino acid attacking cell walls so that silver ions easily invade cells and are jointly attacked in the cells', so that the structure of the cells is inevitably damaged by the copper ions in the antibacterial and antiviral process, and the mask has very strong cytotoxicity; in order to achieve the antiviral effect, the cytotoxicity of the mask cannot be guaranteed; can not meet the cytotoxicity requirement of the medical mask or the medical surgical mask, and is not suitable for being worn by medical care personnel for a long time. On the other hand, the antibacterial and antiviral nonwoven fabric of the mask of the invention is arranged in the middle layer, and the polypropylene spun-bonded nonwoven fabric with the water repellency on the outermost layer prevents bacteria and virus droplets from entering the body, but the bacteria and virus droplets attached to the outermost layer of the mask still keep activity and are likely to become a cross infection source, so that the virus can be transmitted again. The middle layer antibacterial and antiviral non-woven fabric can inactivate bacteria and viruses entering from the outermost layer, but cannot inactivate the bacteria and viruses on the outermost layer of the mask.

An article (anti Research,2012,93(2): 225-. The paper shows that the copper-containing zeolite cotton textile has the effect of inactivating high-pathogenicity H5N1 and low-pathogenicity H5N3 viruses. It is mentioned that the copper zeolite cotton textile does not show cytotoxicity in the cytotoxicity test, and the experimental operation is that the copper zeolite cotton textile is only soaked in the culture solution for 1min, and then the leaching solution is diluted by 10 times and used for detecting the cytotoxicity of the material, so that the false conclusion that the copper zeolite cotton textile does not show cytotoxicity is obtained. According to the national standard "biological evaluation of medical devices part 5: in vitro cytotoxicity test GB/T16886.5-2017/ISO 10993-5:2009 states that for the leaching liquor test of medical devices (8.2.9), samples were incubated for at least 24h before the leaching liquor could be used to determine cytotoxicity. The paper only cultures the copper zeolite cotton fabric and the culture solution for 1min, and the leaching solution is diluted by 10 times for the detection of cytotoxicity, which far fails to meet the requirements of national standard detection, has very strong cytotoxicity, and does not meet the biological evaluation standard of cytotoxicity of YYT 0969 + 2013 disposable medical mask and YY0469 + 2011 medical surgical mask in China (see the results of comparative example 1 and table 1).

Chinese patent CN 111469498A discloses a medical protective material containing a copper ion antibacterial fabric, which consists of a primary filter layer, an antibacterial fabric layer, a precision filter layer and a skin-friendly comfortable layer which are sequentially arranged from outside to inside, wherein the antibacterial fabric layer contains a copper ion antibacterial fabric layer. The medical protective material is used as a medical mask, only the indexes related to filtration efficiency and air suction resistance in the standard of GB/T19083-2010 medical protective mask technical requirement are required to be met, in order to realize the antibacterial and antiviral functions of the medical protective mask, the patent specification mentions that 'copper ions are positively charged, when reaching bacterial cell membranes, metal ions can firmly adsorb the cell membranes by means of coulomb attraction and further penetrate through the cell walls, so that cytoplasm outflows are caused by the rupture of the cell walls, the propagation of bacteria is hindered, and finally the bacteria die', because the cell membranes are negatively charged. Similarly, the copper ions can also act on the cell membrane with negative charges of human cells to achieve the effect of damaging the cell structure, which indicates that the medical protective mask has strong cytotoxicity and cannot meet the requirement of biological safety. The patent specification mentions that the statement that copper is the only metal element which is harmless to human body, does not pollute the environment and has good antibacterial property is wrong, and various authoritative documents prove that copper has strong cytotoxicity (Wataha J C. effect of cell line on visual basis [ J ] fractional Materials,1994,10(3): 156. 161; Wataha J C, Hanks C T, crack R G. the in visual effects of metallic on ecological cell methodology [ J ] of Journal of biological Materials Research partial A2010, 25.). Therefore, the medical protective mask related to the invention obtains the antibacterial and antiviral effects at the cost of sacrificing biological safety, is not suitable for medical workers to wear the medical protective mask for a long time for resisting the new coronavirus, and is not suitable for the medical protective mask for resisting the new coronavirus.

In addition, in the mask material containing copper element in the prior art, for example, patent CN 100490925C (a bactericidal and antiviral mask and a preparation method thereof), patent CN 102171322B (a dry disinfection patch for reducing the spread of virosomes), patent CN 111235871a (an antiviral filter layer made of copper-containing chitosan fibers and an application thereof), patent CN111264932A (a novel antibacterial surgical protective mask), etc., the copper element inevitably damages the cell structure to increase the cytotoxicity to achieve high antibacterial and antiviral properties.

In summary, the prior art has the following problems: materials containing copper elements (copper simple substances, monovalent copper ion compounds, divalent copper ion compounds, including copper ion-modified zeolite materials) can be used for civil masks, but cannot be used for medical masks with high requirements on biological safety. For example, a common medical mask or a medical surgical mask must meet related regulations on cytotoxicity in the industry standards (YYT 0969-: in vitro cytotoxicity test GB/T16886.5-2017/ISO 10993-5: 2009; in addition, the cytotoxicity and the antibacterial and antiviral properties of copper are positively correlated, and in order to achieve a sufficiently good antibacterial and antiviral property, the content of copper must be sufficiently high, but the cytotoxicity is also increased accordingly. That is, in order to achieve the biological safety index of cytotoxicity of the medical mask or the surgical mask, the antibacterial and antiviral properties cannot be necessarily achieved; on the contrary, to achieve high-efficiency antibacterial and antiviral properties, the requirements of cytotoxicity must be sacrificed inevitably, and the requirements of biological safety of the medical mask cannot be met. That is, the prior art cannot simultaneously satisfy the requirements of the copper-containing material on high enough antibacterial and antiviral performance and low enough cytotoxicity, that is, the copper-containing material cannot simultaneously realize the safety of biological evaluation of copper on the mask and the high efficiency of killing bacteria and viruses, and cannot satisfy the requirements of medical masks on cytotoxicity. Furthermore, according to the structure of the mask body of the existing mask, the mask made of copper-containing materials cannot be used for medical masks with high requirements on biological safety.

Disclosure of Invention

In view of the defects of the prior art, the first object of the invention is to provide a multilayer copper-based zeolite fiber medical material, which contains copper element, has sufficiently low cytotoxicity and sufficiently high antibacterial and antiviral properties, can be used as a medical material with high requirements on biological safety, and is particularly suitable for being used as a biological safety medical material for killing new coronavirus.

Based on the problems in the prior art, the inventor surprisingly finds that, by means of repeated and unrelenting experimental researches, a copper-based zeolite fiber layer with a specific structure and a specific layer are laminated according to a specific sequence, the relative size of the pore sizes of the copper-based zeolite fiber layer at the outermost layer and a first intermediate layer is controlled, and the quality of copper-based zeolite is controlled to be distributed in a gradient manner from outside to inside along a radial interface, so that the prepared medical material can kill bacteria or viruses by utilizing the action of copper ions locked on the surface of the copper-based zeolite fiber layer and biomacromolecules such as proteins/amino acids of the bacteria or viruses after the bacteria or the viruses are adsorbed, the cytotoxicity of the medical material is greatly reduced, the biological safety of the medical material is ensured, the technical requirement of the cytotoxicity of the medical material is met, and the copper-based zeolite fiber with the cytotoxicity is enabled to be under a specific macroscopic structure, the prepared medical material containing the copper element material has high enough antibacterial and antiviral property and low enough cytotoxicity, meets the regulation related to cytotoxicity in the industrial standard of the medical mask, breaks through the traditional academic thinking formula, breaks through the technical obstruction of the prior art, and overcomes the technical bias of the application of the copper element material in the medical material.

It should be noted that the cytotoxicity of the present invention is determined strictly according to the national standard "biological evaluation of medical devices part 5: the in vitro cytotoxicity test GB/T16886.5-2017/ISO 10993-5:2009 regulates the obtained detection results.

The invention adopts the following technical scheme: the multilayer copper-based zeolite fiber medical material comprises a four-layer structure, wherein the medical material sequentially comprises an outermost layer, a first intermediate layer, a second intermediate layer and an innermost layer; the outermost layer and the second middle layer are copper-based zeolite fiber layers, the first middle layer is a hydrophobic fiber layer, and the innermost layer is a hydrophilic fiber layer; the pore size of the copper-based zeolite fiber layer of the outermost layer is larger than that of the hydrophobic fiber layer of the first intermediate layer; the copper-based zeolite fiber layer comprises copper-based zeolite and fiber wires, and the fiber wires are formed by winding fibers; the copper-based zeolite is independently dispersed on the surface of the fiber, and the mass of the copper-based zeolite is reduced in a gradient manner from outside to inside along the radial interface of the fiber line (as shown in figures 1, 2 and 3).

The innermost layer of the medical material is the surface attached to the human body of a wearer.

The outermost layer of the medical material is the side furthest from the wearer's body.

The copper-based zeolite refers to that the surface or the internal/external of the zeolite framework contains copper ions, and the copper ions are selected from Cu¹⁺And/or Cu²⁺。

The metal ions for balancing charges outside the copper-based zeolite framework: is formed by [ SiO ] as cation balance₄]⁰And [ AlO ]₄]^-The anion framework structure of tetrahedrally structured zeolites.

The hydrophilic fiber layer is composed of hydrophilic fibers; the hydrophilic fiber refers to a fiber with a certain number of groups (such as-OH, -NH) with stronger polarity on the macromolecular chain₂and-C ═ O, etc.).

The hydrophobic fiber layer is composed of fibers with low density and strong hydrophobicity or water resistance; the hydrophobic fiber is selected from any one or more of polyethylene, polypropylene, polyester, modified polyethylene, modified polypropylene and modified polyester. Typically, a low-density point-bonded nonwoven fabric layer containing polyethylene terephthalate fibers and polyethylene and subjected to a point-bonding process under pressure can be used.

The mechanism of the medical material of the present invention having sufficiently high antibacterial and antiviral properties and sufficiently low cytotoxicity is as follows:

the hydrophobic fiber layer has smaller pore size than the copper-based zeolite fiber layer and has water locking effect on the surface, namely, the water locking is extremely small water drops formed on the surface of the hydrophobic fiber layer (close to the copper-based zeolite fiber layer), so that the method is favorable for the water lockingThe copper ions dissolved out from a small amount of the copper-based zeolite are limited in the local range of the copper-based zeolite fiber layer. The mass of the copper-based zeolite is reduced from the outer periphery to the inner periphery of the fiber line along the radial interface of the fiber line by a gradient (the mass of the copper-based zeolite is larger, the concentration of copper ions contained in the copper-based zeolite is higher), and because the ions in the solution have a diffusion effect from high concentration to low concentration, when the water vapor exhaled during the wearing process of the mask infiltrates the copper-based zeolite fiber layer, the copper ions locked in the zeolite pore channels on the surface layer of the fiber line have a tendency to move towards the inner part of the fiber line, but due to the limitation of the internal framework structure of the zeolite, although the copper ions have a tendency to move from the outer periphery to the inner part of the fiber line, the copper ions are still locked in the pore channels of the zeolite on the surface of the fiber line¹⁺And/or Cu²⁺. The size of the cells is generally 5-200 μm, while the size of the bacteria is generally 0.2-5 μm and the size of the viruses is generally below 200 nm. Because copper ions are limited in the pore channels of the copper-based zeolite and copper ions dissolved out by a small amount of the copper-based zeolite are limited in a local range of the copper-based zeolite fiber layer, the copper-based zeolite fiber layer is difficult to contact with cells with large sizes, the possibility of action with the cells is reduced, and the cytotoxicity is greatly reduced. Because the size of the bacteria and the viruses is smaller, the bacteria and the viruses can be adsorbed by the copper-based zeolite of the copper-based zeolite fiber layer, and at the moment, copper ions locked in zeolite pore channels and distributed in a small amount in the local range of the fiber layer can act on the bacteria and the viruses, so that the excellent performance of killing the bacteria and the viruses is achieved.

Preferably, the copper-based zeolite contains a copper element having an electron acceptor.

The electron acceptor refers to the ability of copper element in the copper-based zeolite to accept the surface group of the copper-based zeolite to donate electrons.

Preferably, the metal ions for balancing charges outside the copper-based zeolite framework comprise Cu²⁺。

Preferably, the copper-based zeolite comprises groups containing lone electron pairs and/or groups containing conjugation effects.

The group containing the lone pair of electrons means that non-bonding electrons which are not used for forming covalent bonds exist in the outermost electron layer of at least one atom of the group.

The group containing the conjugation effect contains pi electrons and can change the electron cloud distribution in a conjugation system.

The copper-based zeolite contains-COOH groups and/or-COO^-A group.

Preferably, the copper-based zeolite comprises N groups containing lone pairs of electrons; preferably, the lone pair of electron-containing N group comprises-NH₂A group.

Preferably, a melt-blown non-woven fabric layer can be added between the first middle layer and the second middle layer.

The composition of the melt-blown non-woven fabric comprises one or more of polyethylene, polypropylene, polyester, modified polyethylene, modified polypropylene and modified polyester.

Preferably, the pore size of the copper-based zeolite fiber layer of the second intermediate layer is larger than the pore size of the hydrophilic fiber layer of the innermost layer.

Preferably, the particle size D90 of the copper-based zeolite is 0.5-20 μm; preferably, the particle size D90 of the copper-based zeolite is 1-15 μm; more preferably, the particle size D90 of the copper-based zeolite is 5-10 μm.

D90 means: the cumulative particle size distribution percentage of the microscopic particles of the copper-based zeolite on the fiber surface reaches 90 percent. Its physical meaning is that the microscopic particles of copper-based zeolite with a particle size larger than that of the copper-based zeolite account for 10% and the microscopic particles of copper-based zeolite with a particle size smaller than that of the copper-based zeolite account for 90%. The microscopic particles of the copper-based zeolite are zeolite geometries having a shape and a size of less than 50 microns that retain the boundaries of the original copper-based zeolite growth shapes.

Preferably, the mass fraction of the copper element in the copper-based zeolite fiber layer is 0.02-4 wt%; preferably, the mass fraction of the copper element in the copper-based zeolite fiber layer is 0.5-2 wt%; more preferably, the mass fraction of the copper element in the copper-based zeolite fiber layer is 1-1.5 wt%.

Preferably, the Cu is²⁺The content of metal ions which account for the balance charges outside the framework of the copper-based zeolite is 5 to 40 percent; preferably, the Cu²⁺Gold occupying the extra-framework charge balance of copper-based zeoliteThe content of the metal ions is 10 to 30 percent; preferably, the Cu²⁺The content of metal ions which account for the balance charges outside the framework of the copper-based zeolite is 15 to 20 percent.

The content of the metal ions refers to the ratio of the number of the metal ions.

Preferably, the Si/Al ratio of the copper-based zeolite is 1.5-5; preferably, the Si/Al ratio of the copper-based zeolite is 1.8-3; preferably, the Si/Al ratio of the copper-based zeolite is 2-2.5.

The Si/Al ratio of the copper-based zeolite is the ratio of the two atomic numbers.

Preferably, the copper-based zeolite independently dispersed on the surface of the fiber has its own independent boundary for each microscopic particle of the copper-based zeolite.

Preferably, the independent dispersion means that the minimum distance between the copper-based zeolite microparticles and the copper-based zeolite microparticles which are most adjacent to the copper-based zeolite microparticles is more than or equal to one half of the sum of the particle sizes of the two copper-based zeolite microparticles, namely: d is more than or equal to r₁+r₂(ii) a Wherein r is₁,r₂Respectively representing one half of the grain diameter of two adjacent copper-based zeolite microparticles; d represents the minimum distance between two adjacent copper-based zeolite microparticles (as shown in fig. 4).

Preferably, the copper-based zeolite is composed of zeolite nanoparticles.

Preferably, the copper-based zeolite is selected from any one or more of X-type zeolite, Y-type zeolite, a-type zeolite, chabazite, L-type zeolite, and P-type zeolite.

Preferably, the fibers of the copper-based zeolite fiber layer are selected from any one or more of rayon fibers, acetate fibers, carboxymethyl cellulose, bamboo fibers, cotton fibers, wood fibers, polypropylene fibers and polyethylene fibers.

The second object of the present invention is: the method for manufacturing the multilayer copper-based zeolite fiber medical material comprises the following steps:

1) preparing a hydrophobic fiber layer and a hydrophilic fiber layer;

2) preparing a copper-based zeolite fiber layer, the manufacturing method of the copper-based zeolite fiber layer comprising:

(a) forming fiber threads by the fibers in a winding mode, and synthesizing the fiber threads containing the copper-based zeolite by taking the fiber threads as a scaffold for zeolite nucleation and growth; wherein the content of the copper-based zeolite has a small gradient from outside to inside along the radial interface of the fiber line;

(b) weaving the copper-based zeolite fiber wires as warp and weft to form a copper-based zeolite fiber layer;

3) preparing a four-layer antibacterial and antiviral medical material by using a copper-based zeolite fiber layer, a hydrophobic fiber layer, a copper-based zeolite fiber layer and a hydrophilic fiber layer in sequence; wherein the pore size of the copper-based zeolite fiber layer of the outermost layer is larger than the pore size of the hydrophobic fiber layer.

Preferably, a melt-blown non-woven fabric layer can be added between the water fiber layer and the hydrophilic fiber layer.

Preferably, the hydrophilic fiber layer is made of hydrophilic fibers; the hydrophilic fiber refers to a fiber with a certain number of groups (such as-OH, -NH) with stronger polarity on the macromolecular chain₂and-C ═ O, etc.).

Preferably, the hydrophobic fiber layer is composed of fibers with low density and strong hydrophobicity or water resistance; the hydrophobic fiber is selected from any one or more of polyethylene, polypropylene, polyester, modified polyethylene, modified polypropylene and modified polyester. Typically, a low-density point-bonded nonwoven fabric layer containing polyethylene terephthalate fibers and polyethylene and subjected to a point-bonding process under pressure can be used.

The third purpose of the invention is to provide a medical mask, which comprises the multilayer copper-based zeolite fiber medical material in any form or the multilayer copper-based zeolite fiber medical material prepared by the preparation method in any form.

The innermost layer of the mask is the face attached to the face of the wearer.

The outermost layer of the mask is the side furthest from the face of the wearer.

The mask comprises a mask body and ear bands connected to two sides of the mask body.

The mask can be a medical mask or a civil mask. The medical mask can be a common medical mask, a medical surgical mask and a medical protective mask.

It is a fourth object of the present invention to provide a respirator that contains a medical material that is a multilayer copper-based zeolite fiber in any of the forms described above or a medical material that is a multilayer copper-based zeolite fiber produced by the manufacturing process in any of the forms described above.

A fifth object of the present invention is to provide a medical protective article comprising the multilayered copper-based zeolite fiber medical material in any one of the forms described above or the multilayered copper-based zeolite fiber medical material obtained by the manufacturing method in any one of the forms described above.

Further, the medical protective article refers to a wearing article for professional safety protection of medical personnel, and includes but is not limited to protective clothing, a face screen, gloves, shoes, boots, caps, earmuffs and the like.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention solves the problems of the safety (cytotoxicity) and the effectiveness (antibacterial and antiviral property) of the medical material based on the copper-based zeolite fiber layer for the first time, and overcomes the technical bias that the medical material can not be prepared by using the material containing copper element in the prior art. The medical material provided by the invention comprises four layers, which are formed by sequentially laminating a copper-based zeolite fiber layer, a hydrophobic fiber layer, a copper-based zeolite fiber layer and a hydrophilic fiber layer, wherein the copper-based zeolite fiber layer comprises copper-based zeolite and fiber threads, the fiber threads are formed by winding fibers, the copper-based zeolite is independently dispersed on the surface of the fibers, and the content of the copper-based zeolite is reduced in a gradient manner from outside to inside along the radial interface of the fiber threads; the microstructure and the macrostructure of the medical material have a synergistic effect on the whole through the overall design and control of the macrostructure (a four-layer fiber composite structure) based on the copper-based zeolite fiber layer and the microstructure of the copper-based zeolite fiber layer, so that the medical material which has low enough cytotoxicity and high enough antibacterial and antiviral performances is prepared, and the specification of related cytotoxicity in the industrial standard of medical masks is met. The invention ensures that medical staff and epidemic prevention staff have very effective protective measures when facing to the accurate diagnosis of patients and high-risk infection-prone environment and environment with higher quantity of bacteria and viruses, thereby greatly reducing the possibility of bacterial and viral infection.

2. Furthermore, the invention not only controls the release of copper ions through zeolite, but also introduces groups containing lone electron pairs and/or groups containing conjugate effect on the surface of the copper-based zeolite, thereby further reducing the cytotoxicity of medical materials, improving the efficiency of killing bacteria and viruses through the action of copper ions locked with the surface of the copper-based zeolite, further limiting the dissolution of the copper ions in water vapor, and avoiding the potential safety hazard of medical personnel wearing the medical materials for a long time.

3. Furthermore, the melt-blown cloth not only can improve the filtering effect of the medical material, but also has the electrostatic charge effect. The electrostatic charge effect can further regulate and lock the activity interval of copper ions, and has a certain balance effect on the high antibacterial and antiviral performance and the low enough cytotoxicity of the invention.

4. The invention provides a medical material with double inactivated bacteria and viruses for the first time, and the medical material provided by the invention comprises a four-layer structure and a copper-based zeolite fiber layer comprising two layers. Wherein, the outermost copper-based zeolite fiber layer can kill bacteria and viruses efficiently for the droplets carrying the bacteria and viruses to be attached to the outermost medical material layer. Therefore, on one hand, the design scheme of the invention can not only prevent bacteria and viruses carried in the body from entering the body, but also completely kill the bacteria and viruses attached to the outer layer of the medical material, prevent the contaminated medical material from becoming cross-infected and eliminate the risk of bacterial and virus re-transmission. According to the invention, the second middle layer is the copper-based zeolite fiber layer, the innermost layer is the hydrophilic fiber layer, if a person wearing the medical material carries a virus source, saliva carrying virus bacteria is exhaled, and passes through the hydrophilic fiber layer to the copper-based zeolite fiber layer, the virus bacteria in the saliva are efficiently inactivated in the copper-based zeolite fiber layer, and the person carrying the virus source can be prevented from spreading the virus bacteria outwards. Therefore, the multilayer copper-based zeolite fiber medical material can double inactivate viruses, and has high-efficiency protection for both healthy people and patients.

5. The medical material and the medical protective product prepared by the medical material have the technical advantages of low cytotoxicity and high antibacterial and antiviral property, and the high performance of killing bacteria and viruses is ensured without sacrificing the cytotoxicity. The technology of the invention has high-efficiency virus (especially new coronavirus) killing effect and enough biological safety for the new coronavirus with strong survival ability and fast variation, is expected to remold the industrial standard of the medical mask, breaks through the thinking and definition in the traditional academia, breaks through the technical defect of medical protection in the traditional practice, and has high theoretical and industrial practical values.

Drawings

FIG. 1 is a schematic view showing an arrangement of layers of a multilayer copper-based zeolite fiber medical material according to the present invention; 1-copper-based zeolite fiber layer, 2-hydrophobic fiber layer, 3-copper-based zeolite fiber layer and 4-hydrophilic fiber layer;

FIG. 2 is a scanning electron micrograph of a fiber line containing a copper-based zeolite in a fibrous layer of a copper-based zeolite according to the present invention;

FIG. 3 is a schematic representation of the radial interfacial distribution of the copper-based zeolite of the present invention along the fiber lines; 5-fiber thread; 6-radial interface of fiber strands; 7-copper based zeolite; the radial interface of the fiber thread refers to the cross section of the fiber thread; the mass of the copper-based zeolite decreases in a gradient from outside to inside along the radial interface of the fiber line (the mass of the copper-based zeolite decreases in a gradient in the direction of the arrow shown in the figure);

FIG. 4 is a schematic diagram showing the positional relationship between the copper-based zeolite microparticles adjacent to the fiber surface of the copper-based zeolite fiber layer of the multilayer copper-based zeolite fiber medical material of the present invention, wherein the copper-based zeolite microparticles are independently dispersed on the fiber surface.

Detailed Description

As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and singular forms of elements or components also include plural forms unless the number clearly indicates the singular form.

Determination of copper ion elution amount: soaking the medical material in MEM culture solution at a ratio of 0.1g/mL for 24h to obtain leaching solution of the medical material; detecting the obtained leaching liquor by a finger-induction coupling plasma emission spectrometer to obtain Cu in the leaching liquor²⁺And (4) concentration.

Cytotoxicity assay (see national standard "biological evaluation of medical devices part 5: in vitro cytotoxicity test" GB/T16886.5-2017/ISO 10993-5: 2009): the medical material is soaked in MEM culture solution for 24h according to the proportion of 0.1g/mL to obtain the leaching liquor of the medical material. Vero cell culture medium (1X 10)⁵) In (C) is placed in CO₂The incubator is used for 22-26 h. Removing culture medium, adding medical material leaching solution, and placing in CO₂The incubator is used for 24 h. Observing morphological change of Vero cells with microscope, removing culture medium, adding 50 μ L MTT solution, and placing in CO₂Incubate for 2h, remove MTT solution, add 100. mu.L of isopropanol per well, shake the plate, and measure absorbance at 570 nm. And converting the measured absorbance into the corresponding survival rate of the cells.

The method for testing the antibacterial performance of the material comprises the following steps: gram-negative Escherichia coli (Escherichia coli) ATCC25922, gram-negative Klebsiella pneumoniae (Klesiella pneumoniae) ATCC70063, and gram-positive Staphylococcus aureus (Staphylococcus aureus) ATCC 6538. a) And (4) preparing a bacterial suspension. The nutrient broth was diluted 500 times with distilled water and used as a diluent after autoclaving. After the ring flame sterilization, taking a ring of strains on the slant nutrient agar culture mediumDiluting the bacterial liquid to a suitable concentration (about (1-9) × 10) in a test tube containing a diluent by a 10-fold dilution method⁵CFU/mL]This is the experimental bacterial liquid. b) The medical material to be tested is paved in a sterilized culture dish, 0.15mL of bacterial suspension is absorbed and dropped on the medical material, a covering film with the square size of 400mm +/-2 mm is covered on the medical material, the bacterial suspension is uniformly covered on the medical material but cannot exceed the edge of the thin film, and the culture dish is covered for 1 hour at room temperature to carry out viable count treatment. c) And counting live bacteria. The medical material and cover were repeatedly rinsed with 10mL of SCDLP broth. Diluting 1mL of washing solution and 9mL of phosphate buffer solution by 10 times after being uniform, sucking 1mL of washing solution into a culture dish, adding 15mL to 20mL of plate counting agar (46 ℃ to 48 ℃) for mixing, putting the mixture into a biochemical incubator (36 +/-1 ℃) for culturing for 40h to 48h after solidification, counting the number of viable bacteria, namely the number in the plate, according to the method of GB4889.2, and calculating the sterilization rate.

Test method for inactivation of New coronavirus (SARS-CoV-2): the medical material was placed in a 6-well plate in a bowl with a concave middle, 0.5mL of virus solution was slowly dropped onto the medical material (30s) to ensure that the virus solution was not dropped by the mask, and incubated for a period of time (15 min). Adding 2mL of culture solution into each well, soaking for 2min, discarding the mask, and adding 1mL of Vero cell culture solution (5 × 10)⁵) Mixing, and placing in CO₂The incubator is used for 72 h. Cytopathic effect was observed and viral nucleic acid (PCR) was detected. And (3) sucking 200 mu L of cell culture supernatant, extracting virus nucleic acid by using a magnetic bead method nucleic acid extraction kit (MVR01) and a full-automatic nucleic acid extractor, and finally eluting the virus nucleic acid into 50 mu L of elution volume. Taking 5 mu L of nucleic acid extract, adopting a novel one-step method coronavirus nucleic acid detection kit to detect the virus nucleic acid level, and calculating the inhibition rate of the material to the virus according to the Ct value.

The embodiment of the invention takes a mask as an example to illustrate the preparation method, the structural characteristics, the biological safety (such as cytotoxicity) and the antibacterial and antiviral performances of the multilayer copper-based zeolite fiber medical material and the mask prepared from the same.

Example 1

The preparation method of the mask 1 comprises the following steps:

the mask comprises an outermost layer, a first middle layer, a second middle layer and an innermost layer; the outermost layer and the second intermediate layer are composed of copper-based zeolite fiber layers; the first middle layer is a hydrophobic fiber layer; the innermost layer is a hydrophilic fiber layer.

The first intermediate layer is composed of a low-density fiber having high hydrophobicity or water resistance, and typically a low-density point-bonded nonwoven fabric layer containing polyethylene terephthalate fiber and polyethylene and subjected to point bonding processing under pressure; the pore size of the first intermediate layer is set to be 40-60 μm;

the innermost layer is a water-absorbent non-woven fabric layer;

the preparation method of the copper-based zeolite fiber layers of the outermost layer and the second intermediate layer comprises the following steps:

(1) preparing a zeolite precursor solution according to the following molar ratio of 8Na₂O:Al₂O₃:9SiO₂:180H₂And O is used as a starting material to synthesize the zeolite precursor solution. And twisting 60 cotton fibers into fiber yarns, winding the cotton fibers to form the fiber yarns, uniformly mixing the zeolite precursor solution and the fiber yarns, and carrying out heat treatment at 110 ℃ for 36 hours to obtain the Y-type zeolite fiber yarns. Soaking for 3 times by 5M copper sulfate solution, each time for 3h, and washing with deionized water for multiple times to form the fiber line containing copper-based zeolite.

(2) The fiber line containing copper-based zeolite is used as warp and weft to be woven into a copper-based zeolite fiber layer. The pore size of the copper-based zeolite fiber layer was set to 100 μm.

The Si/Al ratio of the copper-based zeolite is 2; cu²⁺The content of metal ions which account for the balance charge outside the framework of the copper-based zeolite is 20 percent; the mass fraction of the copper element in the copper-based zeolite fiber layer is 2 wt%.

The prepared copper-based zeolite fiber wire is observed by a scanning electron microscope, the fiber wire is formed by spirally winding fibers, the hemispherical copper-based zeolite with the average particle size of 7 mu m is independently dispersed on the surfaces of the fibers, and the content of the copper-based zeolite is reduced in a gradient manner from outside to inside along the radial interface of the fiber wire. The obtained copper-based zeolite is observed by a scanning electron microscope, and the copper-based zeolite is microscopic particles consisting of nano particles, so that the copper-based zeolite is tightly combined with fibers. Wherein the pore size of the copper-based zeolite fiber layer of the outermost layer is larger than the pore size of the hydrophobic fiber layer of the first intermediate layer; the pore size of the copper-based zeolite fiber layer of the second intermediate layer is larger than the pore size of the innermost layer fibers.

The mask body of the mask 1 of the present invention is prepared by heat-sealing the above-mentioned sequence of the copper-based zeolite fiber layer, the hydrophobic fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer.

Comparative example 1

The copper-based zeolite fiber layer obtained in example 1 was used as comparative example 1 and was compared with example 1.

Comparative example 2

The mask body 1 of the comparative mask was prepared by heat-sealing the sequence of the hydrophobic fiber layer, the copper-based zeolite fiber layer, and the hydrophilic fiber layer, and was compared with example 1.

Comparative example 3

The mask body 2 of the comparative mask was prepared by heat-sealing the order of the copper-based zeolite fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer, and was compared with example 1.

Comparative example 4

The mask body 3 of the comparative mask was prepared by heat-sealing the order of the copper-based zeolite fiber layer, the hydrophobic fiber layer, and the copper-based zeolite fiber layer, and was compared with example 1.

Comparative example 5

Referring to the preparation method of the medical protective material containing the copper ion antibacterial fabric of the invention CN 111469498A in China.

The "antibacterial fabric layer" in the primary filter layer, the antibacterial fabric layer, the precision filter layer and the skin-friendly comfortable layer, which are sequentially arranged from the outside to the inside, is replaced by the "copper-based zeolite fiber layer" of the invention, and the medical protective material of the comparative example 5 is integrated again.

According to the above method of the present invention, the medical protective materials prepared in example 1 and comparative examples 1 to 5 were tested for copper ion elution amount, antibacterial activity, antiviral activity, and cytotoxicity, and the results are shown in Table 1.

TABLE 1 comparison of cytotoxicity of mask materials

As can be seen from the comparison of example 1 with comparative examples 1 to 4 (Table 1), the copper-based zeolite fiber layer had strong cytotoxicity; however, the mask body formed by sequentially stacking the copper-based zeolite fiber layer, the hydrophobic fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer has low cytotoxicity and meets the cytotoxicity regulation in the industrial standard of medical masks. In addition, if the hydrophobic fiber layer, the hydrophilic fiber layer, or the relative position of the hydrophobic fiber layer is changed (comparative example 1) in the mask of the present invention, the amount of copper ions eluted is increased, the cytotoxicity of the mask body is increased, and the mask body does not meet the biosafety standard of medical masks. According to the invention, the copper-based zeolite fiber layer and the specific mask layer are laminated according to a specific sequence, the relative size of the pore sizes of the copper-based zeolite fiber layer at the outermost layer and the first intermediate layer is controlled, the quality of the copper-based zeolite is controlled to be distributed in a gradient manner from outside to inside along the radial interface, and copper ions are locked by virtue of various synergistic effects such as surface water locking of the hydrophobic fiber layer, electrostatic adsorption to the copper ions and the like, so that the dissolution amount of the copper ions is limited, the possibility of acting on cells is reduced, and the cytotoxicity is greatly reduced; the zeolite adsorbs bacteria and viruses, and the high-concentration locked copper ions on the surface of the copper zeolite inhibit the activity of the bacteria and viruses, thereby playing a role in efficiently resisting the bacteria and viruses.

From comparative examples 1 to 4, correlation between the amount of eluted copper ions and cytotoxicity, antibacterial activity and antiviral activity was found. The content of copper element is low, and good antibacterial and antiviral performance effect (less than 70 percent) cannot be realized; on the contrary, in order to achieve high-efficiency antibacterial and antiviral performance (> 90%), the content of copper is high, so that the cytotoxicity of the copper is inevitably sacrificed, and the specification of the cytotoxicity in the industrial standard of the medical mask cannot be met.

Compared with the medical protective material of the comparative example 5, even if the antibacterial and antiviral functional layer in the medical protective material is replaced by the copper-based zeolite fiber layer of the present invention in the prior art, the medical protective material of the present invention still cannot achieve low cytotoxicity and high antibacterial and antiviral properties at the same time. Therefore, the macrostructure based on the copper-based zeolite fiber layer and the overall design and control of the microstructure of the copper-based zeolite fiber layer, which are discovered unexpectedly, enable the microstructure and the macrostructure of the mask to play a synergistic effect on the whole, so that the mask has high antibacterial and antiviral properties and low cytotoxicity.

Comparative example 6

The difference from example 1 is that the content of the copper-based zeolite in the prepared copper-based zeolite fiber layer is equal from outside to inside along the radial interface of the fiber line, and the rest manufacturing steps are the same, so as to form the mask body 4 of the comparative mask.

(1) preparing a zeolite precursor solution according to the following molar ratio of 8Na₂O:Al₂O₃:9SiO₂:180H₂And O is used as a starting material to synthesize the zeolite precursor solution. Uniformly mixing the cotton fiber and the zeolite precursor solution, and carrying out heat treatment at 110 ℃ for 36h to obtain the Y-type zeolite fiber. Soaking in 5M copper sulfate solution for 3 times, each for 3h, and washing with deionized water for several times to obtain fiber containing copper-based zeolite.

60 fibers containing copper-based zeolite were twined into a fiber yarn containing copper-based zeolite.

(2) Weaving the copper-based zeolite fiber wires as warp and weft to form a copper-based zeolite fiber layer; the content of the copper-based zeolite is equal everywhere from outside to inside along the radial interface of the fiber line.

Comparative example 7

The difference from example 1 is that in the prepared copper-based zeolite fiber layer, the content of copper-based zeolite is increased in a gradient manner from outside to inside along the radial interface of the fiber line, and the rest manufacturing steps are the same, so that the mask body 5 of the comparative mask is formed.

(1) preparing a zeolite precursor solution,according to the following mol ratio of 8Na₂O:Al₂O₃:9SiO₂:180H₂And O is used as a starting material to synthesize the zeolite precursor solution. And twisting 60 cotton fibers into fiber yarns, winding the cotton fibers to form the fiber yarns, uniformly mixing the zeolite precursor solution and the fiber yarns, and carrying out heat treatment at 110 ℃ for 36 hours to obtain the Y-type zeolite fiber yarns. Soaking in 5M copper sulfate solution for 3 times (each for 3 hr), and washing with deionized water for several times to obtain fiber line containing copper-based zeolite.

(2) Untwisting the fiber line containing the copper-based zeolite, rearranging the fibers containing the copper-based zeolite to increase the content of the copper-based zeolite from outside to inside in a gradient manner, and twisting 60 fibers containing the copper-based zeolite again to form the fiber line containing the copper-based zeolite.

Weaving the obtained fiber thread containing the copper-based zeolite into a copper-based zeolite fiber layer by using the fiber thread as warp and weft; the content of the copper-based zeolite is increased along the radial interface of the fiber line from outside to inside in a gradient manner.

TABLE 2 comparison of cytotoxicity and antiviral Properties of mask Material

As can be seen from comparison of example 1 with comparative examples 6 and 7 (table 2), the content of the copper-based zeolite according to the present invention decreases in a gradient from outside to inside along the radial interface of the fiber line, which is a synergistic effect in balancing cytotoxicity and inactivating the efficiency of the new coronavirus, so that the whole mask material has low cytotoxicity (high cell survival rate) and high inactivated virus. Conversely, the distribution of other two copper-based zeolites on the fiber line is either high cytotoxicity and high inactivated virus or slightly low cytotoxicity and low inactivated virus, so that the low cytotoxicity and the high inactivated virus cannot be realized at the same time, and the requirements on cytotoxicity in the industrial standard of the medical mask cannot be met.

Example 2

The preparation method of the mask 2 comprises the following steps:

(2) The fiber line containing copper-based zeolite is used as warp and weft to be woven into a copper-based zeolite fiber layer.

(3) Modifying the surface of copper-based zeolite with-COO^-A group.

The mask body of the mask 2 of the invention is prepared by heat-sealing the sequence of the copper-based zeolite fiber layer, the hydrophobic fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer.

Modifying the above-mentioned-COO^-Copper-based zeolite fiber layer, hydrophobic fiber layer, modified-COO^-The mask body of the mask 2 of the invention is prepared by the sequence of the copper-based zeolite fiber layer and the hydrophilic fiber layer through heat sealing.

Example 3

The preparation method of the mask 3 comprises the following steps:

(3) Modifying the surface of copper-based zeolite with-NH₂A group.

The mask body of the mask 3 of the present invention is prepared by heat-sealing the above-mentioned sequence of the copper-based zeolite fiber layer, the hydrophobic fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer.

Modifying the above-mentioned-NH₂Copper-based zeolite fiber layer, hydrophobic fiber layer, modified-NH of group₂The mask body of the mask 3 of the invention is prepared by the sequence of the copper-based zeolite fiber layer and the hydrophilic fiber layer through heat sealing.

Example 4

The preparation method of the mask 4 comprises the following steps:

(3) The surface of the copper-based zeolite is treatedSimultaneous surface modification of-NH₂A radical and-COO^-A group.

The mask body of the mask 4 of the present invention is prepared by heat-sealing the above-mentioned sequence of the copper-based zeolite fiber layer, the hydrophobic fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer.

Modifying the above-mentioned-NH₂、-COO^-Copper-based zeolite fiber layer, hydrophobic fiber layer, modified-NH of group₂、-COO^-The mask body of the mask 4 of the present invention is prepared by heat-sealing the sequence of the copper-based zeolite fiber layer and the hydrophilic fiber layer of the group.

TABLE 3 cytotoxicity and antiviral, antibacterial efficacy of mask materials

As can be seen from examples 1, 2, 3 and 4 (Table 3), the copper-based zeolite fiber layer was very cytotoxicHowever, the mask body formed by stacking the copper-based zeolite fiber layer, the hydrophobic fiber layer, the copper-based zeolite fiber layer and the hydrophilic fiber layer in sequence has low cytotoxicity. Furthermore, if the surface of the copper-based zeolite in the copper-based zeolite fiber layer is modified with-NH₂A radical or-COO^-A group capable of locking Cu by coordinating with copper ion having an electron acceptor on the surface of copper-based zeolite²⁺Reduce Cu²⁺Elution amount, reducing the possibility of interaction with cells; the zeolite adsorbs bacteria or viruses, and the high-concentration copper ions on the surface of the copper zeolite inhibit the activity of the viruses and bacteria. The technical characteristics not only further improve the cell survival rate, but also increase the efficiency of inactivating the new coronavirus.

Example 5

The preparation method of the mask 5 comprises the following steps:

the mask comprises a copper-based zeolite fiber layer, a hydrophobic fiber layer, a melt-blown non-woven fabric, a copper-based zeolite fiber layer and a hydrophilic fiber layer. The preparation method of the copper-based zeolite fiber layer comprises the following steps:

The mask body of the mask 5 of the invention is prepared by heat-sealing the sequence of the copper-based zeolite fiber layer, the hydrophobic fiber layer, the melt-blown non-woven fabric, the copper-based zeolite fiber layer and the hydrophilic fiber layer. In cytotoxicity detection, the copper ion elution amount of the mask body of the mask 5 is 0.98ppm, and the cell survival rate is 83%; in the anti-new coronavirus (SARS-CoV-2) test, the virus inactivation rate is 99.92%.

Examples 6 to 11

The mask 6-11 comprises a copper-based zeolite fiber layer, a hydrophobic fiber layer, a copper-based zeolite fiber layer and a hydrophilic fiber layer. The preparation steps are the same as those of example 1, and masks of examples 6 to 11 (tables 4 and 5) were prepared by changing the composition of the copper-based zeolite fiber layer, specifically as follows:

TABLE 4 composition of copper-based zeolite fiber layer of mask material

TABLE 5 cytotoxic and antiviral, antibacterial effects of the mask Material

The above examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Although the mask is taken as an example to illustrate the preparation method, the structural characteristics, the biological safety (such as cytotoxicity) and the antibacterial and antiviral performances of the medical material of the invention in examples 1 to 11, the technical scheme of the invention can also be applied to various medical protective articles, which refer to wearing articles for professional safety protection of medical personnel, including but not limited to protective clothing, masks, gloves, shoes, boots, caps, earmuffs and the like. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Claims

1. The multilayer copper-based zeolite fiber medical material is characterized by comprising a four-layer structure, wherein the medical material sequentially comprises an outermost layer, a first intermediate layer, a second intermediate layer and an innermost layer; the outermost layer and the second middle layer are copper-based zeolite fiber layers, the first middle layer is a hydrophobic fiber layer, and the innermost layer is a hydrophilic fiber layer; the pore size of the copper-based zeolite fiber layer of the outermost layer is larger than that of the hydrophobic fiber layer of the first intermediate layer; the copper-based zeolite fiber layer comprises copper-based zeolite and fiber wires, and the fiber wires are formed by winding fibers; the copper-based zeolite is independently dispersed on the surface of the fiber, and the mass of the copper-based zeolite is reduced in a gradient manner from outside to inside along the radial interface of the fiber line.

2. The multilayer copper-based zeolite fiber medical material according to claim 1, wherein a melt-blown non-woven fabric layer is interposed between the first intermediate layer and the second intermediate layer.

3. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the copper-based zeolite comprises copper element with an electron acceptor.

4. Multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the charge-balancing metal ions outside the copper-based zeolite framework comprise Cu²⁺。

5. Multilayer copper-based zeolite fiber medical material according to claim 1 or 2, characterized in that the copper-based zeolite contains groups containing lone pair electrons and/or groups containing conjugation effect.

6. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the copper-based zeolite comprises-COOH groups and/or-COO groups^-A group.

7. The multilayer copper-based zeolite fiber medical material of claim 1 or 2, wherein the copper-based zeolite comprises N groups containing lone pairs of electrons.

8. The multilayer copper-based zeolite fiber medical material of claim 7, wherein said lone pair electron-containing N group comprises-NH₂A group.

9. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the pore size of the copper-based zeolite fiber layer of the second intermediate layer is larger than the pore size of the hydrophilic fiber layer of the innermost layer.

10. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the particle size D90 of the copper-based zeolite is 0.5-20 μm.

11. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the particle size D90 of the copper-based zeolite is 1-15 μm.

12. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the particle size D90 of the copper-based zeolite is 5-10 μm.

13. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the mass fraction of copper in the copper-based zeolite fiber layer is 0.02-4 wt%.

14. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the mass fraction of copper element in the copper-based zeolite fiber layer is 0.5-2 wt%.

15. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the mass fraction of copper in the copper-based zeolite fiber layer is 1 to 1.5 wt%.

16. The multilayer copper-based zeolite fiber medical material of claim 4, wherein the Cu is²⁺The content of metal ions which account for the balance charges outside the framework of the copper-based zeolite is 5 to 40 percent.

17. The multilayer copper-based zeolite fiber medical material of claim 4, wherein the Cu is²⁺The content of metal ions which account for the balance charge outside the framework of the copper-based zeolite is 10 to 30 percent.

18. The multilayer copper-based zeolite fiber medical material of claim 4, wherein the Cu is²⁺The content of metal ions which account for the balance charges outside the framework of the copper-based zeolite is 15 to 20 percent.

19. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the Si/Al ratio of the copper-based zeolite is 1.5 to 5.

20. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the Si/Al ratio of the copper-based zeolite is 1.8 to 3.

21. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the Si/Al ratio of the copper-based zeolite is 2 to 2.5.

22. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the copper-based zeolite independently dispersed on the fiber surface, each microscopic particle of copper-based zeolite has its own independent boundary.

23. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein said separate components areThe dispersion means that the minimum distance between the copper-based zeolite micro-particles and the most adjacent copper-based zeolite micro-particles is more than or equal to one half of the sum of the particle sizes of the two copper-based zeolite micro-particles, namely: d is more than or equal to r₁+r₂(ii) a Wherein r is₁, r₂Respectively representing one half of the grain diameter of two adjacent copper-based zeolite microparticles; d represents the minimum distance between two adjacent copper-based zeolite microparticles.

24. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the copper-based zeolite is comprised of zeolite nanoparticles.

25. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the copper-based zeolite is selected from any one or more of X-type zeolite, Y-type zeolite, a-type zeolite, chabazite, L-type zeolite, P-type zeolite.

26. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the fibers of the copper-based zeolite fiber layer are selected from any one or more of acetate fibers, carboxymethyl cellulose, bamboo fibers, cotton fibers, wood fibers, polypropylene fibers, and polyethylene fibers.

27. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the fibers of the copper-based zeolite fiber layer are rayon fibers.

28. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the hydrophilic fiber layer is composed of hydrophilic fibers, and the hydrophilic fibers are groups having polarity on the macromolecular chains of the fibers.

29. The multilayer copper-based zeolite fiber medical material of claim 28, wherein the polar groups are selected from-OH, -NH₂、-C=O。

30. The multilayer copper-based zeolite fiber medical material according to claim 1 or 2, wherein the hydrophobic fiber layer is composed of hydrophobic fibers with low density and strong hydrophobicity or water resistance.

31. The multilayer copper-based zeolite fiber medical material of claim 30, wherein the hydrophobic fibers are selected from any one or more of polyethylene, polypropylene, polyester, modified polyethylene, modified polypropylene, and modified polyester.

32. The medical material of claim 30, wherein the hydrophobic fiber is a low-density point-bonded nonwoven fabric layer containing polyethylene terephthalate fibers and polyethylene and processed by point bonding under pressure.

33. The method for manufacturing the multilayer copper-based zeolite fiber medical material is characterized by comprising the following steps of:

1) preparing a hydrophobic fiber layer and a hydrophilic fiber layer;

34. The method of claim 33, wherein a meltblown nonwoven layer is interposed between the hydrophobic fiber layer and the hydrophilic fiber layer.

35. The production method according to claim 33 or 34, wherein the hydrophilic fiber layer is formed of hydrophilic fibers, and the hydrophilic fibers are groups having polarity on macromolecular chains of the fibers.

36. The method of claim 35, wherein the polar group is selected from the group consisting of-OH, -NH₂、-C=O。

37. The method of claim 33 or 34, wherein the hydrophobic fiber layer is composed of hydrophobic fibers having low density and strong hydrophobicity or water resistance.

38. The method according to claim 37, wherein the hydrophobic fiber is selected from one or more of polyethylene, polypropylene, polyester, modified polyethylene, modified polypropylene, and modified polyester.

39. The method of claim 37, wherein the hydrophobic fiber is a low-density point-bonded nonwoven fabric layer containing polyethylene terephthalate fiber and polyethylene and subjected to point bonding processing under pressure.

40. A medical mask, characterized in that the mask body of the medical mask comprises the multilayer copper-based zeolite fiber medical material according to any one of claims 1 to 32 or the multilayer copper-based zeolite fiber medical material obtained by the manufacturing method according to any one of claims 33 to 39.

41. A respirator comprising a multilayered copper-based zeolite fiber medical material according to any one of claims 1 to 32 or a multilayered copper-based zeolite fiber medical material obtained by the process of any one of claims 33 to 39.

42. A medical protective article comprising the multilayer copper-based zeolite fiber medical material according to any one of claims 1 to 32 or the multilayer copper-based zeolite fiber medical material obtained by the production method according to any one of claims 33 to 39.

43. The medical protective article according to claim 42, wherein said medical protective article is a garment for occupational safety protection of medical personnel.

44. The medical protective article according to claim 43, wherein said article of wear is selected from the group consisting of protective clothing, a face screen, gloves, shoes, hats, and earmuffs.