Multilayer Copper-based Zeolite Fiber Medical Material, Protective Equipment and Manufacturing Method

Abstract

The present disclosure is to provide a medical material, medical protective equipment with both low cytotoxicity and high-efficiency antibacterial, antiviral properties and its manufacturing method. The multi-layer copper-based zeolite fiber medical material of the present disclosure includes a four-layer structure, including the outermost layer, the first intermediate layer, the second intermediate layer, and the innermost layer in sequence; the outermost layer and the second intermediate layer are copper-based zeolite fiber layer, the first intermediate 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 greater than the pore size of the hydrophobic fiber layer of the first intermediate layer; the copper-based zeolite fiber layer contains copper-based zeolite and fiber threads, the fiber threads are formed by twisting fibers; the copper-based zeolite is independently dispersed on the fiber surface.

Claims

1. A multilayer copper-based zeolite fiber medical material, comprising an outermost layer, a first intermediate layer, a second intermediate layer, and an innermost layer in sequence; wherein the outermost layer and the second intermediate layer are copper-based zeolite fiber layers; the first intermediate layer is a hydrophobic fiber layer, and the innermost layer is a hydrophilic fiber layer; a pore size of the copper-based zeolite fiber layer of the outermost layer is greater than that of the hydrophobic fiber layer of the first intermediate layer; the copper-based zeolite fiber layer contains copper-based zeolite and fiber threads; the fiber threads are formed by twisting fibers; the copper-based zeolite is independently dispersed on the fiber surface, and a mass of the copper-based zeolite decreases in a gradient from outside to inside along a radial interface of the fiber thread.

2. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the copper-based zeolite contains copper element with electron acceptor.

3. The multi-layer copper-based zeolite fiber medical material of claim 1, wherein the surface or the inside/outside of the zeolite framework of the copper-based zeolite contains copper ions.

4. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the copper-based zeolite includes a group containing a lone electron pair and/or a group containing a conjugation effect.

5. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the copper-based zeolite contains a —COOH group and/or a —COO— group.

6. The multi-layer copper-based zeolite fiber medical material of claim 1, wherein the copper-based zeolite includes N group containing a lone pair of electrons.

7. The multilayer copper-based zeolite fiber medical material of claim 1, wherein a melt-blown non-woven fabric layer can be added between the first intermediate layer and the second intermediate layer.

8. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the pore size of the copper-based zeolite fiber layer of the second intermediate layer is greater than that of the hydrophilic fiber layer of the innermost layer.

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

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

11. The multilayer copper-based zeolite fiber medical material of claim 3, wherein the Cu2+ accounts for 5% to 40% of the charge-balanced metal ion content outside the framework of the copper-based zeolite.

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

13. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the copper-based zeolite is selected from the group consisting of X-type zeolite, Y-type zeolite, A-type zeolite, chabazite, L-type zeolite and P-type zeolite.

14. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the fibers of the copper-based zeolite fiber layer are selected from the group consisting of rayon fibers, acetate fibers, carboxymethyl cellulose, bamboo fibers, cotton fibers, wood fibers, polypropylene fibers, and polyethylene fibers.

15. The multilayer copper-based zeolite fiber medical material of claim 1, wherein the hydrophilic fiber layer is composed of hydrophilic fibers.

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

17. A manufacturing method of a multilayer copper-based zeolite fiber medical material, wherein the following steps comprises: 1) preparing a hydrophobic fiber layer and a hydrophilic fiber layer; 2) preparing a copper-based zeolite fiber layer, wherein the manufacturing method of the copper-based zeolite fiber layer comprises: (a) twisting the fibers to form a fiber thread, and synthesizing a fiber thread containing copper-based zeolite by using the fiber thread as a scaffold for zeolite nucleation and growth; wherein the content of copper-based zeolite decreases along the radial interface of the fiber thread from the outside to the inside in a gradient; (b) forming a copper-based zeolite fiber layer by weaving the copper-based zeolite-containing fiber threads as warp and weft; 3) preparing a four-layer antibacterial and antiviral medical material in the order of a copper-based zeolite fiber layer, a hydrophobic fiber layer, a copper-based zeolite fiber layer, and a hydrophilic fiber layer; wherein a pore size of the outermost copper-based zeolite fiber layer is greater than that of the hydrophobic fiber layer.

18. The manufacturing method of claim 17, wherein a melt-blown non-woven fabric layer is added between the hydrophobic fiber layer and the hydrophilic fiber layer.

19. A protective equipment, wherein the protective equipment comprises the multilayer copper-based zeolite fiber medical material according to claim 1.

20. The protective equipment of claim 19, wherein the protective equipment refers to wearables used for safety protection from virus and bacteria, and the wearables are selected from the group consisting of masks, protective masks, protective clothing, face screens, gloves, shoes, boots, hats, and earmuffs.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0079] FIG. 1 is a schematic diagram of the arrangement of the layers of the multilayer copper-based zeolite fiber medical material of the present disclosure; 1—copper-based zeolite fiber layer, 2—hydrophobic fiber layer, 3—copper-based zeolite fiber layer, 4—hydrophilic fiber layer;

[0080] FIG. 2 is a scanning electron micrograph of fiber threads containing copper-based zeolite in the copper-based zeolite fiber layer of the present disclosure;

[0081] FIG. 3 is a schematic diagram showing the distribution of the copper-based zeolite of the present disclosure along the radial interface of the fiber thread; 5—fiber thread; 6—fiber thread radial interface; 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 the inside along the radial interface of the fiber thread (the mass of the copper-based zeolite shown in the figure decreases in the direction of the arrow);

[0082] FIG. 4 is a schematic diagram of the positional relationship between the copper-based zeolite microparticles on the fiber surface of the copper-based zeolite fiber layer of the present disclosure, and the copper-based zeolite microparticles are independently dispersed on the fiber surface.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0083] The terms “comprising”, “including”, “having”, “containing” or any other variations as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, product, or device containing the listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent elements in the composition, step, method, product, or device.

[0084] In addition, the indefinite articles “a” and “an” before an element or component of the present disclosure have no limitation on the quantity requirement (that is, the number of occurrences) of the element or component. Therefore, “a” or “an” should be interpreted as including one or at least one, and a singular form of an element or component also includes a plural form, unless the number clearly refers to the singular form.

[0085] Determination of the amount of copper ions dissolved: the medical material is immersed in MEM culture solution at a ratio of 0.1 g/mL for 24 hours to obtain an extract of the medical material. The obtained extract is detected with Inductively Coupled Plasma Emission Spectrometer to obtain Cu.sup.2+ concentration in the extract.

[0086] Cytotoxicity test (refer to the national standard “Biological Evaluation of Medical Devices Part 5: In Vitro Cytotoxicity Test” GB/T 16886.5-2017/ISO 10993-5:2009): After immersing the medical material in MEM culture solution at a ratio of 0.1 g/mL for 24 hours, an extract of the medical material is obtained. Place the Vero cell culture medium (1×10.sup.5) in a CO.sub.2 incubator for 22 to 26 h. The culture medium is replaced by the extract of medical materials, and incubated for another 24 hours. Observe the morphological changes of Vero cells with a microscope. Then remove the medium and add 50 μL of MTT solution, incubate in a CO.sub.2 incubator for 2 hours. The MTT solution is removed and 100 μL of isopropanol is added to each well. Shake the titer plate, and measure the absorbance at 570 nm. According to the measured absorbance, it is converted into the survival rate of the cell.

[0087] Material antibacterial performance test method: Preparation of a suspension of Gram-negative Escherichia coli (ATCC25922), Gram-negative Klebsiella pneumoniae (ATCC70063), Gram-positive Staphylococcus aureus (ATCC6538). a). Dilute the nutrient broth 500 times with distilled water and use it as a diluent after autoclaving. After the inoculation loop is flame-sterilized, take a loop of slant nutrient agar medium in a test tube containing the dilution solution, and use a 10-fold dilution method to dilute the bacteria solution to an appropriate concentration [about (1˜9)×10.sup.5 CFU/mL], which is the experimental bacterial solution. b) Spread the medical material to be tested in a sterilized petri dish, draw 0.15 mL of the bacterial suspension drop on the medical material, and use the 400 mm±2 mm square covering film to make the bacterial suspension evenly cover the medical materials, but not beyond the edge of the film. Cover the petri dish and place it at room temperature for 1 h to count the viable bacteria. c) Live bacteria count. Rinse the medical materials and coverings repeatedly with 10 mL of SCDLP broth. Dilute 1 mL washing solution 10 times with 9 mL phosphate buffer solution and mix well, pipette 1 mL into a petri dish. Add 15 mL-20 mL agar (46° C.-48° C.) to mix, and put it in a biochemical incubator (36±1° C.) and cultivate in for 40 h to 48 h after solidification. Count the number of viable bacteria in the plate according to the method of GB4889.2, and calculate the sterilization rate.

[0088] The test method for the inactivation of SARS-CoV-2: Place the medical material in a 6-well plate with a concave bowl in the middle, and slowly drop 0.5 mL of the virus onto the medical material (30 s) to ensure the virus liquid is absorbed by the mask and will not drip. Incubate for a certain period of time (15 minutes). Add 2 mL of culture medium to each well, fully infiltrate for 2 minutes, and then discard the mask. 1 mL of Vero cell culture medium (5×10.sup.5) is added to each well and mixed, then placed in a CO.sub.2 incubator for 72 h. Observe cell pathology and detect viral nucleic acid (PCR). Aspirate 200 μL of the cell culture supernatant, and extract the viral nucleic acid with a magnetic bead method nucleic acid extraction kit (MVR01) and an automatic nucleic acid extractor. The final elution volume is 50 μL. Take 5 μL of nucleic acid extract, use a one-step novel coronavirus nucleic acid detection kit to detect the level of viral nucleic acid, and calculate the material's inhibition rate against the virus based on the Ct value.

[0089] The embodiment of the present disclosure uses a mask as an example to illustrate the manufacturing method, structural characteristics, biological safety (such as cytotoxicity), and antibacterial and antiviral performance of the multilayer copper-based zeolite fiber medical material and the prepared mask.

Example 1

[0090] The manufacturing method of the mask 1 of the present disclosure includes the following steps:

[0091] The mask includes the outermost layer, the first intermediate layer, the second intermediate layer and the innermost layer; the outermost layer and the second intermediate layer are composed of copper-based zeolite fiber layers; the first intermediate layer is a hydrophobic fiber layer; the innermost layer is a hydrophilic fiber layer.

[0092] Among them, the first intermediate layer is composed of low-density and hydrophobic or water-resistant fibers. Typically, a low-density point-bonded non-woven fabric layer made of polyethylene terephthalate fiber and polyethylene subjected to pressure point bonding processing can be used. The pore size of the first intermediate layer is set at 40-60 μm.

[0093] The innermost layer is a layer of water-absorbing non-woven fabric.

[0094] Among them, the manufacturing methods of the copper-based zeolite fiber layer of the outermost layer and the second intermediate layer are as follows:

[0095] (1) Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. 60 cotton fiber were twisted and spun into fiber threads. The zeolite precursor solution and the fiber threads were mixed uniformly and heat treated at 110° C. for 36 h to obtain Y-type zeolite fiber threads. After soaking in a 5 M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained.

[0096] (2) Knitting up a copper-based zeolite fiber layer by using the copper-based zeolite-containing fiber thread as warp and weft. The pore size of the copper-based zeolite fiber layer was set to 100 μm.

[0097] The Si/Al ratio of the copper-based zeolite is 2; Cu.sup.2+ accounts for 20% of the charge-balanced metal ion content outside the framework of the copper-based zeolite; and the mass fraction of copper in the fiber layer of the copper-based zeolite is 2 wt %.

[0098] Through observation of the prepared copper-based zeolite fiber thread by scanning electron microscope, the fiber thread is formed by spirally winding fibers, and the copper-based zeolite with an average particle size of 7 μm hemispherical is independently dispersed on the surface of the fiber, and the content of copper-based zeolite decreases gradually along the radial interface of the fiber thread from the outside to the inside. Observing the obtained copper-based zeolite through a scanning electron microscope, the copper-based zeolite is a microscopic particle composed of nanoparticles, which makes the copper-based zeolite and the fiber tightly combined. Among them, the pore size of the copper-based zeolite fiber layer of the outermost layer is greater than that 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 greater than that of the innermost fiber layer.

[0099] The copper-based zeolite fiber layer, hydrophobic fiber layer, copper-based zeolite fiber layer, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover of the mask 1 of the present disclosure.

Comparative Example 1

[0100] The copper-based zeolite fiber layer prepared in Example 1 was used as Comparative Example 1, and was compared with Example 1.

Comparative Example 2

[0101] The hydrophobic fiber layer, copper-based zeolite fiber layer, copper-based zeolite fiber layer, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover 1 of the comparative mask, which was compared with Example 1.

Comparative Example 3

[0102] The copper-based zeolite fiber layer, the copper-based zeolite fiber layer, and the hydrophilic fiber layer are sequentially heat-sealed to prepare the cover 2 of the comparative mask, which was compared with Example 1.

Comparative Example 4

[0103] The copper-based zeolite fiber layer, the hydrophobic fiber layer, and the copper-based zeolite fiber layer was sequentially heat-sealed to prepare the cover 3 of the comparative mask, which was compared with Example 1.

Comparative Example 5

[0104] Refer to the Chinese publication No. 111469498A for the manufacturing method of the medical protective material containing copper ion antibacterial fabric.

[0105] The “antibacterial fabric layer” of the primary filter layer, the antibacterial fabric layer, the precision filter layer, and the skin-friendly comfort layer arranged in sequence from outside in is replaced with the “copper-based zeolite fiber layer” described in the present disclosure, and reintegrated into a medical protective material of Comparative Example 5

[0106] According to the above method of the present disclosure, the medical protective materials prepared in Example 1 and Comparative Examples 1-5 were tested for copper ion elution, antibacterial, antiviral, and cytotoxicity. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Comparison of cytotoxicity of mask materials. Antibacterial Antiviral rate/% rate/% Copper ion Cell survival (Escherichia (SARS- Number Material elution/ppm rate/% coli) CoV-2) Example 1 Cover of the mask 1 1 80 99.97 99.95 in the present disclosure Comparative Copper-based 80 0.5 99.99 99.99 Example 1 zeolite fiber layer Comparative Cover 1 of 8 45 56.67 60.98 Example 2 comparative mask Comparative Cover 2 of 40 1.0 99.95 99.99 Example 3 comparative mask Comparative Cover 3 of 10 20 89.78 93.99 Example 4 comparative mask Comparative Medical protective 20 5 90.68 95.64 Example 5 material of comparative Example 5

[0107] Comparing Example 1 with Comparative Examples 1-4 (Table 1), the copper-based zeolite fiber layer has strong cytotoxicity; however, the mask cover composed of copper-based zeolite fiber layer, hydrophobic fiber layer, copper-based zeolite fiber layer and hydrophilic fiber layer stacked in sequence has less cytotoxicity and meets the cytotoxicity regulations in the medical mask industry standard. In addition, if the hydrophobic fiber layer and hydrophilic fiber layer of the present disclosure are reduced, or the relative position of the hydrophobic fiber layer is changed (Comparative Example 1), the amount of copper ions leached out will increase, and the cytotoxicity of the mask body will increase, which does not meet the biosafety standards of medical masks. By laminating the copper-based zeolite fiber layer and the specific mask layer of the present disclosure in a specific order, controlling the relative pore size of the outermost copper-based zeolite fiber layer and the first intermediate layer and the quality of the copper-based zeolite along the radial interface gradient distribution from the outside to the inside, locking water by the surface of the hydrophobic fiber layer and the electrostatic adsorption of copper ions and other synergistic effects, the amount of copper ions eluted is limited and the possibility of interaction with cells is reduced, thus the cytotoxicity is greatly reduced; bacterial and viruses are adsorbed by the zeolite, and then the activity of the bacterial and virus is inhibited by the high concentration of copper ions on the surface of the copper zeolite, which has an effective anti-bacterial and anti-virus effect.

[0108] It can be obtained from Comparative Examples 1-4 that the amount of copper ions dissolved out is related to cytotoxicity, antibacterial and antiviral rate. The low content of copper element cannot achieve good antibacterial and antiviral performance effects (<70%); on the contrary, in order to achieve high antibacterial and antiviral performance (>90%), the high content of copper element is required, which is unable to meet the cytotoxicity regulations in the medical mask industry standard.

[0109] From the comparison of the medical protective materials of Example 1 and Comparative Example 5, even if the prior art replaces the antibacterial and antiviral functional layer in the medical protective material with the copper-based zeolite fiber layer of the present disclosure, it still cannot achieve low cells toxicity and high antibacterial and antiviral performance at the same time. This shows that the overall design and control of macrostructure and microstructure of the copper-based zeolite fiber layer unexpectedly discovered by the present disclosure make the microstructure and macrostructure of the mask play a synergistic effect on the whole, making it have high antibacterial and antiviral performance and low cytotoxicity.

Comparative Example 6

[0110] The difference from Example 1 is that the content of the copper-based zeolite is equal from outside to inside along the radial interface of the fiber thread in the prepared copper-based zeolite fiber layer. And the rest of the manufacturing steps are the same. The cover 4 of the comparative mask is obtained.

[0111] Among them, the manufacturing methods of the copper-based zeolite fiber layer of the outermost layer and the second intermediate layer are as follows:

[0112] (1) Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. The cotton fiber and the zeolite precursor solution were mixed uniformly and heat-treated at 110° C. for 36 h to obtain Y-type zeolite fiber. After soaking in a 5M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained.

[0113] 60 fibers containing copper-based zeolite are twist-spun into fiber threads containing copper-based zeolite.

[0114] (2) The copper-based zeolite-containing fiber threads are used as warp and weft to weave a copper-based zeolite fiber layer; the content of the copper-based zeolite is equal everywhere along the radial interface of the fiber thread from outside in.

Comparative Example 7

[0115] The difference from Example 1 is that the content of the copper-based zeolite increases gradually along the radial interface of the fiber line from outside to inside in the prepared copper-based zeolite fiber layer. The rest of the manufacturing steps are the same. The cover 5 of the comparative mask is obtained.

[0116] Among them, the manufacturing methods of the copper-based zeolite fiber layer of the outermost layer and the second intermediate layer are as follows:

[0117] (1) Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. 60 cotton fibers were twisted and spun into fiber threads. The zeolite precursor solution and the fiber threads were mixed uniformly and heat treated at 110° C. for 36 h to obtain Y-type zeolite fiber threads. After soaking in 5 M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained (before).

[0118] (2) Untying the fiber thread containing copper-based zeolite (before), re-arrange the fiber containing copper-based zeolite, so that the content of copper-based zeolite gradually increases from the outside to the inside. 60 copper-based zeolite-containing fibers are re-twisted into fiber threads containing copper-based zeolite.

[0119] The fiber thread containing the copper-based zeolite obtained above is used as warp and weft to knit into a copper-based zeolite fiber layer; the content of the copper-based zeolite increases gradually along the radial interface of the fiber thread from outside to inside.

TABLE-US-00002 TABLE 2 Comparison of cytotoxicity and antiviral performance of mask materials Copper Antiviral ion Cell rate/% elution/ survival (SARS- Number Material ppm rate/% CoV-2) Example 1 Cover of the mask 1 1 80 99.95 in this disclosure Comparative Cover 4 of 9 20 95.35 Example 6 comparative mask Comparative Cover 5 of 8 45 30.45 Example 7 comparative mask

[0120] From the comparison of Example 1 with Comparative Examples 6 and 7 (Table 2), the content of the copper-based zeolite of the present disclosure decreases gradually from the outside to the inside along the radial interface of the fiber thread, which plays a coordinated role in balancing the cytotoxicity and efficiency of inactivating SARS-CoV-2, so that the overall mask material has low cytotoxicity (high cell survival rate) and high virus inactivation. In contrast, for the other two types of copper-based zeolite distribution in the fiber thread, either high cytotoxicity and high virus inactivation, or slightly lower cytotoxicity and low virus inactivation, low cytotoxicity and high inactivation of the virus cannot be achieved at the same time, which cannot meet the cytotoxicity regulations in the medical mask industry standard.

Example 2

[0121] The manufacturing method of the mask 2 of the present disclosure includes the following steps:

[0122] The mask includes the outermost layer, the first intermediate layer, the second intermediate layer and the innermost layer; the outermost layer and the second intermediate layer are composed of copper-based zeolite fiber layers; the first intermediate layer is a hydrophobic fiber layer; the innermost layer is a hydrophilic fiber layer.

[0123] Among them, the manufacturing methods of the copper-based zeolite fiber layer of the outermost layer and the second intermediate layer are as follows:

[0124] (1) Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. 60 cotton fiber were twisted and spun into fiber threads. The zeolite precursor solution and the fiber threads were mixed uniformly and heat treated at 110° C. for 36 h to obtain Y-type zeolite fiber threads. After soaking in a 5M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained.

[0125] (2) The copper-based zeolite-containing fiber threads are used as warp and weft to knit into a copper-based zeolite fiber layer.

[0126] (3) Surface modification of copper-based zeolite with —COO— groups.

[0127] The Si/Al ratio of the copper-based zeolite is 2; Cu.sup.2+ accounts for 20% of the charge-balanced metal ion content outside the framework of the copper-based zeolite; the mass fraction of copper in the fiber layer of the copper-based zeolite is 2 wt %.

[0128] Through observation of the prepared copper-based zeolite fiber thread by scanning electron microscope, the fiber thread is formed by spirally winding fibers, and the copper-based zeolite with an average particle size of 7 μm hemispherical is independently dispersed on the surface of the fiber, and the content of copper-based zeolite decreases gradually along the radial interface of the fiber line from the outside to the inside. Observing the obtained copper-based zeolite through a scanning electron microscope, the copper-based zeolite is a microscopic particle composed of nanoparticles, which makes the copper-based zeolite and the fiber tightly combined. Among them, the pore size of the copper-based zeolite fiber layer of the outermost layer is greater than that 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 greater than that of the innermost fiber layer.

[0129] The above-mentioned copper-based zeolite fiber layer, hydrophobic fiber layer, copper-based zeolite fiber layer, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover of the mask 2 of the present disclosure.

[0130] The copper-based zeolite fiber layer modified with —COO.sup.− groups, a hydrophobic fiber layer, a copper-based zeolite fiber layer modified with —COO.sup.− groups, and a hydrophilic fiber layer are prepared by heat sealing to obtain the cover of mask 2 of the present disclosure.

Example 3

[0131] The manufacturing method of the mask 3 of the present disclosure includes the following steps:

[0132] The mask includes the outermost layer, the first intermediate layer, the second intermediate layer and the innermost layer; the outermost layer and the second intermediate layer are composed of copper-based zeolite fiber layers; the first intermediate layer is a hydrophobic fiber layer; the innermost layer is a hydrophilic fiber layer.

[0133] Among them, the manufacturing methods of the copper-based zeolite fiber layer of the outermost layer and the second intermediate layer are as follows:

[0134] (1) Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. 60 cotton fiber were twisted and spun into fiber threads. The zeolite precursor solution and the fiber threads were mixed uniformly and heat treated at 110° C. for 36 h to obtain Y-type zeolite fiber threads. After soaking in a 5 M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained.

[0135] (2) The copper-based zeolite-containing fiber threads are used as warp and weft to knit into a copper-based zeolite fiber layer.

[0136] (3) Surface modification of copper-based zeolite with —NH.sub.2 groups.

[0137] The Si/Al ratio of the copper-based zeolite is 2; Cu.sup.2+ accounts for 20% of the charge-balanced metal ion content outside the framework of the copper-based zeolite; the mass fraction of copper in the fiber layer of the copper-based zeolite is 2 wt %.

[0138] Through observation of the prepared copper-based zeolite fiber thread by scanning electron microscope, the fiber thread is formed by spirally winding fibers, and the copper-based zeolite with an average particle size of 7 μm hemispherical is independently dispersed on the surface of the fiber, and the content of copper-based zeolite decreases gradually along the radial interface of the fiber line from the outside to the inside. Observing the obtained copper-based zeolite through a scanning electron microscope, the copper-based zeolite is a microscopic particle composed of nanoparticles, which makes the copper-based zeolite and the fiber tightly combined. Among them, the pore size of the copper-based zeolite fiber layer of the outermost layer is greater than that 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 greater than that of the innermost fiber layer.

[0139] The above-mentioned copper-based zeolite fiber layer, hydrophobic fiber layer, copper-based zeolite fiber layer, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover body of the mask 3 of the present disclosure.

[0140] The copper-based zeolite fiber layer modified with —NH.sub.2 groups, the hydrophobic fiber layer, the copper-based zeolite fiber layer modified with —NH.sub.2 groups, and the hydrophilic fiber layer are sequentially heat-sealed to prepare the cover of the mask 3 of the present disclosure.

Example 4

[0141] The manufacturing method of the mask 4 of the present disclosure includes the following steps:

[0142] The mask includes the outermost layer, the first intermediate layer, the second intermediate layer and the innermost layer; the outermost layer and the second intermediate layer are composed of copper-based zeolite fiber layers; the first intermediate layer is a hydrophobic fiber layer; the innermost layer is a hydrophilic fiber layer.

[0143] Among them, the manufacturing methods of the copper-based zeolite fiber layer of the outermost layer and the second intermediate layer are as follows:

[0144] Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. 60 cotton fiber were twisted and spun into fiber threads. The zeolite precursor solution and the fiber threads were mixed uniformly and heat treated at 110° C. for 36 h to obtain Y-type zeolite fiber threads. After soaking in a 5 M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained.

[0145] The copper-based zeolite-containing fiber threads are used as warp and weft to knit into a copper-based zeolite fiber layer.

[0146] Surface modification of copper-based zeolite with —NH.sub.2 group and —COO.sup.− group at the same time.

[0147] The Si/Al ratio of the copper-based zeolite is 2; Cu.sup.2+ accounts for 20% of the charge-balanced metal ion content outside the framework of the copper-based zeolite; and the mass fraction of copper in the fiber layer of the copper-based zeolite is 2 wt %.

[0148] Through observation of the prepared copper-based zeolite fiber thread by scanning electron microscope, the fiber thread is formed by spirally winding fibers, and the copper-based zeolite with an average particle size of 7 μm hemispherical is independently dispersed on the surface of the fiber, and the content of copper-based zeolite decreases gradually along the radial interface of the fiber line from the outside to the inside. Observing the obtained copper-based zeolite through a scanning electron microscope, the copper-based zeolite is a microscopic particle composed of nanoparticles, which makes the copper-based zeolite and the fiber tightly combined. Among them, the pore size of the copper-based zeolite fiber layer of the outermost layer is greater than that 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 greater than that of the innermost fiber layer.

[0149] The copper-based zeolite fiber layer, hydrophobic fiber layer, copper-based zeolite fiber layer, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover body of the mask 4 of the present disclosure.

[0150] The copper-based zeolite fiber layer modified with —NH.sub.2, —COO.sup.− groups, hydrophobic fiber layer, copper-based zeolite fiber layer modified with —NH.sub.2, —COO.sup.− groups, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover of the mask 4 of the present disclosure.

TABLE-US-00003 TABLE 3 Comparison of cytotoxicity and antiviral, antibacterial performance of mask materials Cell Antibacterial rate Antiviral rate Copper ion survival Antibacterial rate Antibacterial rate (Staphylococcus (SARS- Number elution/ppm rate/% (E. coli)/% (Pneumoniae)/% aureus)/% CoV-2)/% Example 1 80 >99.99 >99.99 >99.99 99.95 1 Example 0.5 92 >99.99 >99.99 >99.99 99.99 2 Example 0.5 93 >99.99 >99.99 >99.99 99.98 3 Example 0.05 97 >99.99 >99.99 >99.99 99.999 4

[0151] It can be obtained from Examples 1, 2, 3, and 4 (Table 3) that although the copper-based zeolite fiber layer has strong cytotoxicity, the mask sequentially stacked by copper-based zeolite fiber layer, hydrophobic fiber layer, copper-based zeolite fiber layer and hydrophilic fiber layer has less cytotoxicity. In addition, if the surface of the copper-based zeolite in the copper-based zeolite fiber layer is modified with —NH.sub.2 groups or —COO.sup.− groups, it can be coordinated with copper ions with electron acceptors on the copper-based zeolite surface to lock Cu.sup.2+, reduce the dissolution of Cu.sup.2+ and the possibility of interaction with cells; bacteria or viruses are adsorbed by the zeolite, and then the activity of viruses and bacteria is inhibited by the high concentration of copper ions on the surface of the copper zeolite. This technical feature not only further improves the cell survival rate, but also increases the efficiency of inactivating SARS-CoV-2.

Example 5

[0152] The manufacturing method of the mask 5 of the present disclosure includes the following steps:

[0153] The mask includes 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. Among them, the manufacturing method of the copper-based zeolite fiber layer is as follows:

[0154] Preparing the zeolite precursor solution according to the following molar ratio of 8Na.sub.2O:Al.sub.2O.sub.3:9SiO.sub.2:180H.sub.2O. 60 cotton fiber were twisted and spun into fiber threads. The zeolite precursor solution and the fiber threads were mixed uniformly and heat treated at 110° C. for 36 h to obtain Y-type zeolite fiber threads. After soaking in a 5 M copper sulfate solution for 3 times, each time for 3 h, rinsing with deionized water several times, fiber threads containing copper-based zeolite are obtained.

[0155] The copper-based zeolite-containing fiber threads are used as warp and weft to knit into a copper-based zeolite fiber layer.

[0156] The Si/Al ratio of the copper-based zeolite is 2; Cu.sup.2+ accounts for 20% of the charge-balanced metal ion content outside the framework of the copper-based zeolite; and the mass fraction of copper in the fiber layer of the copper-based zeolite is 2 wt %.

[0157] The copper-based zeolite fiber layer, hydrophobic fiber layer, melt-blown non-woven fabric, copper-based zeolite fiber layer, and hydrophilic fiber layer are sequentially heat-sealed to prepare the cover of the mask 5 of the present disclosure. In the cytotoxicity test, the dissolution of copper ions from the cover of mask 5 was 0.98 ppm, and the cell survival rate was 83%; in the anti-SARS-CoV-2 test, the virus inactivation rate was 99.92%.

Examples 6-11

[0158] Masks 6-11 include a copper-based zeolite fiber layer, a hydrophobic fiber layer, a copper-based zeolite fiber layer, and a hydrophilic fiber layer. The described manufacturing steps are the same as in Example 1, except that the composition of the copper-based zeolite fiber layer is changed to prepare the masks of Examples 6-11 (Tables 4 and 5). The details are as follows.

TABLE-US-00004 TABLE 4 Composition of copper-based zeolite fiber layers of mask materials The ratio of Copper accounts Copper- Quality ratio for a metal based of copper in ion of the outer Si/Al zeolite copper- balanced ratio of particle based charge of copper- size zeolite copper-based based Number Example D90/μm fibers/wt % zeolite/% zeolite 1 Example 6 0.5 0.02 5 1.5 2 Example 7 1 0.5 10 1.8 3 Example 8 5 1 15 2 4 Example 9 10 1.5 20 2.5 5 Example 10 15 2 30 3 6 Example 11 20 4 40 5

TABLE-US-00005 TABLE 5 cytotoxicity and antiviral, antibacterial performance of mask materials Cell Antibacterial Antibacterial Antibacterial rate Antiviral rate survival rate rate (Staphylococcus (SARS- rate/% (E. coli)/% (Pneumoniae)/% aureus)/% CoV-2)/% Example 6 97 95 96 95 99.95 Example 7 93 98 98 97 99.89 Example 8 90 >99.99 >99.99 >99.99 99.98 Example 9 92 >99.99 >99.99 >99.99 99.99 Example 10 80 >99.99 >99.99 >99.99 99.99 Example 11 70 >99.99 >99.99 >99.99 99.99

[0159] The above embodiments are only used to illustrate the present disclosure and not to limit the scope of the present disclosure. Although Examples 1-11 use masks as an example to illustrate the manufacturing method, structural characteristics, biological safety (such as cytotoxicity), and antibacterial and antiviral performance of the medical materials of the present disclosure, the technical solutions of the present disclosure can also be applied to various protective equipment. The protective equipment refers to wearable product medical staff occupational safety, and the wearables are selected from the group consisting of protective clothing, face screens, gloves, shoes, boots, caps, earmuffs. In addition, it should be understood that after reading the teachings of the present disclosure, those skilled in the art can make various changes or modifications to the present disclosure, and these equivalent forms also fall within the scope defined by the appended claims of the present application.