Kaolin composite piezoelectric antibacterial fabric and mask product thereof

Abstract

The invention relates to the technical field of antibacterial fabrics, in particular to a kaolin composite piezoelectric antibacterial fabric and a mask product thereof. According to the kaolin composite piezoelectric antibacterial fabric disclosed by the invention, a fabric is used as a carrier and is loaded with a kaolin composite antibacterial material; the preparation method of the kaolin composite antibacterial material comprises the steps that kaolin, anhydrous Zn (NO3) 2, anhydrous Na2CO3 and anhydrous NaCl are subjected to high-speed ball milling at the room temperature for 0.5-1 h, an obtained solid ball milling product is calcined, the kaolin composite antibacterial material is prepared, the loading capacity of ZnO is not smaller than 25%, and ZnO is embedded into the kaolin. According to the kaolin composite antibacterial material prepared by the invention, the nano ZnO is of a surface embedded configuration, so that the piezoelectric property of the kaolin composite antibacterial material is enhanced, and efficient interface charge transfer is ensured, so that efficient antibacterial property of the fabric under the action of external force is realized.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial fabrics, and in particular to a kaolin-compounded piezoelectric antibacterial fabric and a mask product thereof. Background Art

[0002] Nowadays, bacterial infection and multidrug resistance have brought great challenges to public health. The increase in bacterial resistance has prompted people to develop new strategies and materials to deal with this crisis. Therefore, the research and development of materials and products with antibacterial functions is of great significance to social production and people's lives. In recent years, antibacterial nanomaterials have become a research hotspot in the field of antibacterial because they can avoid the problem of bacterial resistance. Membrane respiration, as a necessary activity of bacterial cells, can provide energy for metabolism. Electrons play a key role in membrane respiration. Therefore, electron transfer is a common behavior of bacteria. Since the respiratory chain is located on the cell membrane, single-cell bacteria often exchange electrons with the medium when in contact. If the normal electron transfer process is disturbed, membrane respiration will be inhibited, leading to bacterial death. At the same time, it has nothing to do with the chemical composition of the materials used, and it also effectively avoids the production of drug resistance and toxic byproducts. In addition, it is reported that 80% of bacteria are transmitted through surface contact. Flexible bactericidal fabrics can interfere with electron transfer within bacteria and inactivate bacteria, which is of great significance to prevent bacterial contamination and spread.

[0003] Medical protective masks can prevent the spread of respiratory diseases and effectively block respiratory droplets in daily life. They play an important role in preventing respiratory infectious diseases such as influenza and colds. However, ordinary medical protective masks have a single function and do not have antibacterial function. They can only protect but not effectively kill bacteria. Therefore, how to make ordinary medical masks have antibacterial properties, with low production costs and simple process routes, is an urgent problem to be solved in the current research process of medical antibacterial masks. Summary of the invention

[0004] The object of the present invention is to provide a kaolin-compounded piezoelectric antibacterial fabric and a mask product thereof in view of the above-mentioned deficiencies in the prior art.

[0005] The present invention discloses a kaolin-composite piezoelectric antibacterial fabric, in which the kaolin-composite antibacterial material is loaded on the fabric as a carrier; the preparation method of the kaolin-composite antibacterial material is as follows: kaolin, anhydrous Zn(NO3)2, anhydrous Na2CO3 and anhydrous NaCl are subjected to high-speed ball milling at room temperature for 0.5-1h to obtain a solid ball milling product, and then the solid ball milling product is calcined, wherein the loading amount of ZnO is not less than 25%, and ZnO is embedded in the kaolin.

[0006] Furthermore, the calcination temperature is 400°C.

[0007] Furthermore, the kaolin-compounded piezoelectric antibacterial fabric generates a strong piezoelectric effect under external force.

[0008] Furthermore, the method of using fabric as a carrier to load the kaolin composite antibacterial material is as follows: the kaolin composite antibacterial material, PVP and deionized water are prepared into a suspension in proportion, and then the fabric is immersed in the suspension, and then rolled, dried and cut.

[0009] Furthermore, the concentration range of the kaolin antibacterial material in the suspension is 0.01-0.5 g / mL.

[0010] Furthermore, the concentration of PVP in the suspension ranges from 0.005 to 0.01 g / mL.

[0011] Furthermore, the fabric is immersed in the suspension for 5-10 minutes.

[0012] A mask product comprises a mask outer layer and a mask inner layer, wherein a meltblown antibacterial layer is arranged between the mask outer layer and the mask inner layer, the meltblown antibacterial layer is the kaolin composite piezoelectric antibacterial fabric as described above, and the fabric is meltblown fabric.

[0013] Furthermore, the force generated by breathing in and out during wearing of the mask product causes the antibacterial layer of the meltblown fabric to produce a strong piezoelectric effect.

[0014] The kaolin composite antibacterial material prepared by the present invention has nano ZnO in a surface embedded configuration, which enhances the piezoelectric properties of the kaolin composite antibacterial material and ensures efficient interface charge transfer, thereby achieving efficient antibacterial properties of the fabric when subjected to external forces.

[0015] The mask product of the present invention has significant antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), solving the problem that common medical masks do not have antibacterial properties. After testing, the antibacterial rate is greater than 99%.

[0016] The mask product of the present invention utilizes the force generated by breathing during wearing to make the antibacterial layer have a piezoelectric effect to generate interface electrons. The transmission of electrons between bacteria and kaolin antibacterial material will hinder the growth of bacteria and lead to the death of bacteria.

[0017] The medical protective antibacterial mask provided by the invention has strong antibacterial performance, low cost, simple preparation process, and is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a scanning electron microscope image of kaolin;

[0019] Figure 2 This is a high-resolution transmission electron microscopy image of kaolin composite antibacterial material;

[0020] Figure 3 This is the X-ray diffraction pattern of kaolin composite antibacterial material;

[0021] Figure 4 is the piezoelectric coefficient of the ZnO and kaolin composite antibacterial material;

[0022] Figure 5 The antibacterial effect of oscillating kaolin composite antibacterial materials prepared at different ball milling times in Example 4 on Escherichia coli and Staphylococcus aureus;

[0023] Figure 6 The antibacterial effect of oscillation of ZnO kaolin composite antibacterial materials with different embedded amounts on Escherichia coli and Staphylococcus aureus;

[0024] Figure 7 The scanning electron microscope image and corresponding element mapping image of the antibacterial layer of the meltblown fabric prepared in Example 7;

[0025] Figure 8 This is a diagram showing the antibacterial effect of applying external force to the kaolin-composite piezoelectric antibacterial fabric prepared in Example 8 on Escherichia coli and Staphylococcus aureus;

[0026] Fig. 9 This is a diagram showing the antibacterial effect of the kaolin-composite piezoelectric antibacterial fabric prepared in Example 7 on Escherichia coli and Staphylococcus aureus. DETAILED DESCRIPTION

[0027] The following are specific embodiments of the present invention and the accompanying drawings to further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0028] Example 1

[0029] This embodiment provides a method for preparing a kaolin composite antibacterial material. 0.675 g of uniform powdered kaolin, 1.5 g of anhydrous Zn(NO3)2, 1.5 g of anhydrous Na2CO3, and 3.85 g of anhydrous NaCl are weighed and added into a ball mill for high-speed ball milling for 0.5 h at room temperature to obtain a solid ball-milled product, which is calcined at 400°C. After the calcination, the calcined product is taken out, washed and dried to obtain a kaolin composite antibacterial material.

[0030] Example 2

[0031] This embodiment provides a method for preparing a kaolin composite antibacterial material. 1.35 g of uniform powdered kaolin, 1.5 g of anhydrous Zn(NO3)2, 1.5 g of anhydrous Na2CO3, and 3.85 g of anhydrous NaCl are weighed and added into a ball mill for high-speed ball milling for 0.5 h at room temperature to obtain a solid ball-milled product, which is calcined at 400°C. After the calcination, the calcined product is taken out, washed and dried to obtain a kaolin composite antibacterial material.

[0032] Example 3

[0033] This embodiment provides a method for preparing a kaolin composite antibacterial material. 2.7 g of uniform powdered kaolin, 1.5 g of anhydrous Zn(NO3)2, 1.5 g of anhydrous Na2CO3, and 3.85 g of anhydrous NaCl are weighed and added into a ball mill for high-speed ball milling for 0.5 h at room temperature to obtain a solid ball-milled product, which is calcined at 400°C. After the calcination, the calcined product is taken out, washed, and dried to obtain a kaolin composite antibacterial material.

[0034] Example 4

[0035] The present embodiment provides a method for preparing a kaolin composite antibacterial material with different ball milling times. 2.7 g of uniform powdered kaolin, 1.5 g of anhydrous Zn(NO3)2, 1.5 g of anhydrous Na2CO3, and 3.85 g of anhydrous NaCl are weighed and added into a ball mill at room temperature for high-speed ball milling for different times (0.5 h, 1.0 h, 2.0 h, 4.0 h, 6.0 h, and 8.0 h) to obtain solid ball milled products prepared at different ball milling times and calcined at 400°C. After the calcination, the calcined products are taken out, washed, and dried to obtain the kaolin composite antibacterial material.

[0036] Example 5

[0037] This embodiment provides a method for preparing a kaolin composite antibacterial material. 5.4 g of uniform powdered kaolin, 1.5 g of anhydrous Zn(NO3)2, 1.5 g of anhydrous Na2CO3, and 3.85 g of anhydrous NaCl are weighed and added into a ball mill for high-speed ball milling for 0.5 h at room temperature to obtain a solid ball-milled product, which is calcined at 400°C. After the calcination, the calcined product is taken out, washed, and dried to obtain a kaolin composite antibacterial material.

[0038] Example 6

[0039] This embodiment provides a method for preparing a kaolin composite antibacterial material. 8.1 g of uniform powdered kaolin, 1.5 g of anhydrous Zn(NO3)2, 1.5 g of anhydrous Na2CO3, and 3.85 g of anhydrous NaCl are weighed and added into a ball mill for high-speed ball milling for 0.5 h at room temperature to obtain a solid ball-milled product, which is calcined at 400°C. After the calcination, the calcined product is taken out, washed and dried to obtain a kaolin composite antibacterial material.

[0040] Example 7

[0041] A method for preparing kaolin-compounded piezoelectric antibacterial fabric

[0042] Weigh 1 g of the kaolin composite antibacterial material prepared in Example 1, 0.5 g of PVP and 100 mL of deionized water to make a uniform suspension, and then immerse the meltblown cloth in the uniform suspension for 10 minutes, and roll and dry to obtain the meltblown cloth antibacterial layer, i.e., kaolin composite piezoelectric antibacterial fabric.

[0043] Example 8

[0044] A method for preparing kaolin-compounded piezoelectric antibacterial fabric

[0045] Weigh 2.0 g of the kaolin composite antibacterial material prepared in Example 1, 1.0 g of PVP and 100 mL of deionized water to make a uniform suspension, then immerse the meltblown cloth in the uniform suspension for 10 minutes, and roll and dry to obtain the meltblown cloth antibacterial layer, i.e., kaolin composite piezoelectric antibacterial fabric.

[0046] Applying external force by oscillation: The kaolin composite antibacterial materials prepared in Examples 1-6 and the kaolin composite piezoelectric antibacterial fabric prepared in Example 7 were used to carry out antibacterial experiments on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus).

[0047] (1) Bacterial activation: Take out the preserved E. coli and S. aureus from the 4°C refrigerator and place them in the microbiological safety cabinet. Use an inoculation loop to pick up a colony from each and add it to 5 mL of liquid culture medium. Incubate the culture in a constant temperature shaker for 12 h at a speed of 180 r / min and a temperature of 37°C.

[0048] (2) Bacterial solution dilution: Take out the two bacterial solutions that have been revived for 12 h, mark them as E0 and S0, take the required 1.5 mL sterile centrifuge tubes and mark them respectively, add 900 μL of LB liquid culture medium to the first centrifuge tube, take 100 μL of the 12 h activated bacterial solution to the 1.5 mL centrifuge tube, mix well with a pipette, and perform gradient dilution. Dilute the bacterial solution to 10 5 -10 6 CFU mL -1 That's it.

[0049] (3) Addition of antibacterial material components: Prepare the required 50 mL sterile centrifuge tubes and mark them one by one. No antibacterial material is added to the centrifuge tube of the control group, only 10 mL of LB culture medium is added; 50 mg of antibacterial material is added to the centrifuge tube of the experimental group. Then take 100 μL of the diluted bacterial solution in (2) and add it to the control group and experimental group test tubes respectively, place them in a 37°C constant temperature shaker, rotate at 180 r / min, and culture for 4 hours.

[0050] Plate coating: Sterilize the prepared culture dishes and place them in a safety cabinet, mark them, take 50 μL of the control group and experimental group bacterial solution that have been cultured for 4 hours and drop them into the culture dishes, then add 4 sterile glass beads to each culture dish, roll in each direction for 2 minutes, and coat 3 culture dishes for each sample as a parallel group. Finally, place the coated culture dishes in a constant temperature incubator and culture them for 15 hours at 37°C.

[0051] Plate counting and photographing: calculate the antibacterial rate and compare the antibacterial properties.

[0052] The above antibacterial experiments were all carried out in the biological safety cabinet of the microbiology laboratory.

[0053] External force was applied by slight hand pinching: antibacterial experiments on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were carried out using kaolin-compounded piezoelectric antibacterial fabrics.

[0054] (1) Activation of bacterial culture: Take out the preserved E. coli and S. aureus from the 4°C refrigerator and place them in a microbiological safety cabinet. Use an inoculation loop to take one colony from each and add it to 5 mL of liquid culture medium. Incubate the culture in a constant temperature shaker for 12 h at a speed of 180 r / min and a temperature of 37°C.

[0055] (2) Dilution of bacterial solution: Take out the bacterial solution that has been revived for 12 hours and mark it as E0 and S0. Then take the required 1.5 mL sterile centrifuge tubes and mark them separately. Add 900 μL of LB liquid culture medium to the first centrifuge tube. Take 100 μL of the bacterial solution that has been activated for 12 hours and transfer it to the 1.5 mL centrifuge tube. Use a pipette to mix well and then perform gradient dilution. Dilute the bacterial solution to 10 5 -10 6 CFU mL -1 That's it.

[0056] (3) Interaction between the antibacterial layer of meltblown fabric and bacterial solution: The antibacterial layer of meltblown fabric was pre-cut into 2 cm x 2 cm squares, and 100 μL of bacterial (Staphylococcus aureus and Escherichia coli) suspension diluted in (2) was dripped onto its surface (10 5 ~10 6 CFU / mL). Then, each sample was subjected to 300 gentle bends for 3 minutes.

[0057] Plate coating: Sterilize the prepared culture dishes in advance and place them in a safety cabinet, mark them, take 50 μL of the bacterial solution of the control group and the experimental group and drop them into the culture dishes, then add 4 sterile glass beads to each culture dish, roll in each direction for 2 minutes, and coat 3 culture dishes for each sample as a parallel group. Finally, place the coated culture dishes in a constant temperature incubator and culture them for 15 hours at 37°C.

[0058] Plate counting and photographing: calculate the antibacterial rate and compare the antibacterial properties.

[0059] The above antibacterial experiments were all carried out in the biological safety cabinet of the microbiology laboratory.

[0060] Figure 1 This is a scanning electron microscope image of kaolin. From the image, we can clearly see that the kaolin is in the form of flakes and tubes, with uneven sizes, irregular flake edges, and aggregates in the form of stacked flakes or worms.

[0061] Figure 2 The high-resolution transmission electron microscopy image and corresponding element mapping image of the kaolin composite antibacterial material show that ZnO is embedded in kaolin.

[0062] Figure 3 This is the X-ray diffraction spectrum of the kaolin composite antibacterial material prepared in Example 1. It can be seen from the figure that the main phases in the composite antibacterial material are kaolinite, halloysite and zinc oxide, which proves the successful preparation of the kaolin composite antibacterial material.

[0063] Figure 4 : The piezoelectric coefficients of ZnO and the kaolin composite antibacterial material prepared in Example 3. As can be seen from the figure, the piezoelectric coefficient of the kaolin composite antibacterial material is higher than that of pure ZnO, indicating that the kaolin composite antibacterial material has stronger piezoelectric properties.

[0064] Figure 5 The antibacterial effect of the kaolin composite antibacterial material prepared by different ball milling times in Example 4 on Escherichia coli and Staphylococcus aureus is shown in the figure. It can be seen from the figure that the antibacterial effect on Escherichia coli and Staphylococcus aureus is very significant when the ball milling time is 0.5h and 1.0h.

[0065] Figure 6 The figure shows the antibacterial effect of oscillation of ZnO kaolin composite antibacterial materials with different embedded amounts on Escherichia coli and Staphylococcus aureus. From the figure, we can see that when the kaolin addition amount is 2.7g and the ZnO loading amount is 25%, the antibacterial rate against Escherichia coli and Staphylococcus aureus is >99%.

[0066] Figure 7The scanning electron microscope image and corresponding element mapping image of the antibacterial layer of the meltblown cloth prepared in Example 7. It can be seen that the kaolin composite antibacterial material is evenly distributed on the surface of the meltblown cloth fiber.

[0067] Figure 8 This is a diagram of the antibacterial effect of the meltblown antibacterial layer prepared in Example 8 on Escherichia coli and Staphylococcus aureus when an external force is applied. It can be seen from the figure that when no external force is applied, there is almost no antibacterial effect compared with the blank control, but after applying an external force, it has strong antibacterial properties against Escherichia coli and Staphylococcus aureus.

[0068] Fig. 9 This is a diagram showing the antibacterial effect of the antibacterial layer of the meltblown fabric prepared in Example 7 on Escherichia coli and Staphylococcus aureus. Compared with the blank control, the antibacterial rate of Escherichia coli and Staphylococcus aureus after oscillation reached 100%.

[0069] For matters not mentioned above, the prior art applies.

[0070] Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and are not intended to limit the scope of the present invention. Those skilled in the art to which the present invention belongs may make various modifications or supplements to the specific embodiments described or replace them in a similar manner, but they will not deviate from the direction of the present invention or exceed the scope defined by the attached claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc. made to the above embodiments based on the technical essence of the present invention should be included in the protection scope of the present invention.

Claims

1. A kaolin-compounded piezoelectric antibacterial fabric, characterized in that: A kaolin composite antibacterial material is loaded on fabric as a carrier; the preparation method of the kaolin composite antibacterial material is as follows: kaolin, anhydrous Zn(NO3)2, anhydrous Na2CO3, and anhydrous NaCl are ball-milled at high speed for 0.5-1h at room temperature to obtain a solid ball-milled product and calcined, wherein the loading amount of ZnO is not less than 25%, and ZnO is embedded in the kaolin.

2. The kaolin-composite piezoelectric antibacterial fabric according to claim 1, characterized in that: The calcination temperature is 400°C.

3. The kaolin-composite piezoelectric antibacterial fabric according to claim 1, characterized in that: The kaolin-compounded piezoelectric antibacterial fabric generates a strong piezoelectric effect under external force.

4. A kaolin-composite piezoelectric antibacterial fabric as claimed in any one of claims 1 to 3, characterized in that: The method of using fabric as a carrier to load the kaolin composite antibacterial material is as follows: the kaolin composite antibacterial material, PVP and deionized water are prepared into a suspension in proportion, and then the fabric is immersed in the suspension, and then rolled, dried and cut.

5. The kaolin-compounded piezoelectric antibacterial fabric according to claim 4, characterized in that: The concentration range of the kaolin antibacterial material in the suspension is 0.01-0.5 g / mL.

6. The kaolin-compounded piezoelectric antibacterial fabric according to claim 4, characterized in that: The concentration of PVP in the suspension ranged from 0.005 to 0.01 g / mL.

7. The kaolin-compounded piezoelectric antibacterial fabric according to claim 4, characterized in that: The fabric is immersed in the suspension for 5-10 minutes.

8. A mask product, characterized in that: It comprises a mask outer layer and a mask inner layer, wherein a meltblown antibacterial layer is arranged between the mask outer layer and the mask inner layer, and the meltblown antibacterial layer is the kaolin composite piezoelectric antibacterial fabric as described in any one of claims 1 to 3, and the fabric is meltblown fabric.

9. A mask product according to claim 8, characterized in that: The force generated by breathing in and out during wearing of the mask product causes the antibacterial layer of the meltblown fabric to produce a strong piezoelectric effect.

Images