Preparation method and application of antibacterial paper with super-biphobic property against bacteria adhesion

Abstract

The present invention relates to super-hydrophobic functional paper and food packaging technology field, and more particularly to a kind of preparation method and application of antibacterial adhesion super-double sparse antibacterial paper. The method includes: (1) nano-silicon dioxide particles are added in the mixed solution of absolute ethanol and ammonia, dispersed by ultrasonic dispersion instrument, and suspension is obtained; (2) the suspension obtained by step (1) is stirred at high speed, and 1H, 1H, 2H, 2H-perfluorodecyl triethoxysilane and tetraethyl silicate are added, and reacted at room temperature; (3) polyvinylidene fluoride is added to the suspension obtained by step (2) in proportion; (4) the suspension obtained by step (3) is added in spray gun spray pot, in 200KPa N2 atmosphere, sprayed on paper; (5) the paper obtained by step (4) is thoroughly dried, to obtain final product. The antibacterial adhesion super-double sparse antibacterial paper has excellent super-double sparse surface, compared with existing wrapping paper, has higher sterilization efficiency, acid and alkali corrosion resistance, is not easily contaminated and anti-ultraviolet radiation aging performance.

Description

Technical Field

[0001] The present invention relates to the technical field of super-hydrophobic functional paper and food packaging, and in particular to a preparation method and application of super-amphiphobic antibacterial paper that prevents bacterial adhesion. Background Art

[0002] Inspired by the structures of plant leaves, insect wings, and animal skin, researchers have discovered that insect wings possess specific nanostructures. The presence of these structures, such as hairs, pillars, needles, and plates, endows the surface with natural anti-wetting and anti-biofouling properties. They have also discovered that surfaces containing high-aspect-ratio nanopillars can resist bacterial adhesion and proliferation. One antibacterial mechanism currently recognized by researchers is that mechanical deformation causes the rupture of cellular components such as the cell wall, and that high-aspect-ratio nanostructures penetrate bacterial cells, causing the loss of bacterial cell contents and leading to cell death. Today, micro-nanostructures have become a solution for preventing bacterial adhesion and biofilm formation, addressing the problem of bacterial resistance to antibiotics.

[0003] Paper-based materials have advantages such as excellent physical and chemical properties, sufficient tensile strength, renewability, biodegradability and low price, and play an important role in all aspects of our daily lives. However, the hydrophilic nature of paper makes it susceptible to the adhesion of pollutants and the erosion and growth of bacteria. Therefore, in the past decade, super-amphiphobic paper-based surfaces with both superhydrophobic and superoleophobic properties have attracted widespread attention from researchers. Unlike superhydrophobic surfaces that only repel water, super-amphiphobic surfaces require that the contact angle of water and oil on the paper-based surface exceeds 150° and the sliding angle is less than 10°. Super-amphiphobic paper-based surfaces have micro-nanostructures. The trapped air layer between the rough micro-nanostructures greatly reduces the contact area between bacteria and the substrate surface, thereby greatly reducing the adhesion of bacteria on its surface and preventing bacterial adhesion; the rough micro-nanostructures can also penetrate into the interior of bacterial cells, causing the loss of bacterial cell contents and leading to bacterial cell death. Therefore, super-amphiphobic surfaces have the effect of preventing bacterial adhesion and proliferation.

[0004] Currently, there are reports on the preparation methods of nano-superhydrophobic materials and super-amphiphobic materials, but there is little research on their antibacterial and other functional properties. This application has developed a method for preparing antibacterial super-amphiphobic antibacterial paper, which can modify the surface of the paper base to construct micro-nanostructures over a large area. While achieving the super-amphiphobic surface of the paper, it also gives the paper base material moisture resistance, waterproofness, oil resistance, antibacterial adhesion, antibacterial properties, as well as good acid and alkali corrosion resistance and UV aging resistance. Summary of the Invention

[0005] The present invention relates to a preparation method and application of antibacterial super-amphiphobic antibacterial paper. The prepared super-amphiphobic paper-based material has excellent antibacterial adhesion, antibacterial, acid and alkali corrosion resistance and ultraviolet aging resistance, solving the problems of low sterilization efficiency, difficult preparation and easy contamination of existing paper-based single-performance surfaces.

[0006] One of the technical solutions adopted by the present invention is:

[0007] Provided is a method for preparing a super-amphiphobic antibacterial paper that prevents bacterial adhesion, comprising the following steps:

[0008] (1) adding nano-silica particles to a mixed solution of an appropriate amount of anhydrous ethanol and ammonia water, and dispersing the mixture using an ultrasonic disperser to obtain a suspension;

[0009] (2) stirring the suspension obtained in step (1) at high speed, adding 1H,1H,2H,2H-perfluorodecyltriethoxysilane and tetraethyl silicate, and reacting at room temperature;

[0010] (3) adding polyvinylidene fluoride to the suspension prepared in step (2) in proportion;

[0011] (4) spraying the suspension obtained in step (3) onto paper under a 200 kPa N2 atmosphere;

[0012] (5) The paper prepared in step (4) is dried thoroughly to obtain a super-amphiphobic antibacterial paper that prevents bacterial adhesion.

[0013] Furthermore, in step (1), the amount of nano-silica particles used is 0.1 g; the particle size of the nano-silica particles is 15 nm-200 nm; and the ultrasonic time is 10 min-30 min.

[0014] Furthermore, in step (2), the stirring speed is 600 r / min-800 r / min; the amount of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added is 120 μL; the amount of tetraethyl silicate added is 30 μL; and the reaction period is 2 h.

[0015] Furthermore, in step (3), the mass ratio of polyvinylidene fluoride to nano-silicon dioxide is 1:4-1:1.

[0016] Furthermore, the drying method in step (5) is a blast oven; the drying temperature is 80°C

[0017] Furthermore, the paper is filter paper, cardboard, corrugated paper or kraft paper.

[0018] The second technical solution adopted by the present invention is:

[0019] Provided is the use of the antibacterial adhesion super-amphiphobic antibacterial paper prepared by the above-mentioned preparation method in antibacterial and hydrophobic paper for food and medical use.

[0020] Beneficial effects of the present invention:

[0021] The present invention adopts a large-scale preparation process - spraying method to modify the paper base surface to construct a micro-nano structure, thereby achieving super-amphiphobic performance on the surface, while also having antibacterial properties, good acid and alkali corrosion resistance and ultraviolet aging resistance. The surface of the super-amphiphobic antibacterial paper prepared by the present invention can achieve a 4μl water droplet static contact angle of 162° and a propylene glycol contact angle of 158.1°; the trapped air layer between the rough micro-nanostructures greatly reduces the contact area between the bacteria and the substrate surface, thereby greatly reducing the adhesion of bacteria on its surface; the surface microstructure of the rough structure can also penetrate into the interior of the bacterial cells, causing the loss of bacterial cell contents, leading to bacterial cell death. The super-amphiphobic antibacterial paper prepared by the present invention has an antibacterial and bactericidal rate of more than 95% against Gram-negative Escherichia coli, which shows excellent antibacterial properties compared to existing kraft paper (commonly used packaging paper), milk cartons (antibacterial paper, with an antibacterial rate of 90.24%) and other packaging papers and antibacterial papers. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1 of the present invention has a magnification of 1000 times ( Figure 1 c) and 5000 times ( Figure 1 Scanning electron microscopy image of (d)

[0023] Figure 2 For blank kraft paper ( Figure 2 a and b) and Example 1 ( Figure 2 c and d), Example 2 ( Figure 2 e and f) and Example 3 ( Figure 2 g and h) Scanning electron micrographs of the prepared antibacterial super-amphiphobic antibacterial paper at magnifications of 1000x and 5000x;

[0024] Figure 3 The antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1 was diluted 10 3 ( Figure 3 e) and 10 4 ( Figure 3 f) The number of colonies after fold increase;

[0025] Figure 4 For blank kraft paper ( Figure 4 a and b), milk carton ( Figure 4 c and d) and Example 1 ( Figure 4 e and f), Example 2 ( Figure 4 g and h) and Example 2 ( Figure 4 The antibacterial adhesion super-amphiphobic antibacterial paper prepared in (i) and (j) was diluted with 10 3 times and 10 4 Figure of colony count afterward;

[0026] Figure 5 The ratio of polyvinylidene fluoride to nano-silica affects the contact angle of the surface of the super-amphiphobic antibacterial paper for preventing bacterial adhesion;

[0027] Figure 6 For blank kraft paper ( Figure 6 a) and Example 1 ( Figure 6 b), Example 2 ( Figure 6 c) and Example 3 ( Figure 6 d) Atomic force microscopy 3D morphology of the prepared antibacterial super-amphiphobic antibacterial paper;

[0028] Figure 7 Moisture-proof performance diagram of blank kraft paper and antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1, Example 2 and Example 3 (P1-P3);

[0029] Figure 8 The contact angle changes of the super-amphiphobic antibacterial paper under different pH conditions in Example 1 of the present invention;

[0030] Figure 9 This is the ultraviolet aging resistance test result of the super-amphiphobic antibacterial paper in Example 1 of the present invention;

[0031] Figure 10 This is the self-cleaning test result of the super-amphiphobic antibacterial paper of Example 1 of the present invention. DETAILED DESCRIPTION

[0032] In order to clearly illustrate the technical features of this solution, the present invention is described in detail below through specific implementation methods in conjunction with the accompanying drawings.

[0033] Example 1

[0034] A method for preparing a super-amphiphobic antibacterial paper that prevents bacterial adhesion comprises the following steps:

[0035] Step 1: Weigh 0.1 g of nano-silica particles, add them to a mixed solution of 44 ml of anhydrous ethanol and 6 ml of ammonia water, and disperse them using an ultrasonic disperser for 30 minutes to obtain a suspension;

[0036] Step 2: The suspension prepared in step 1 was stirred at a high speed of 600 r / min, and 120 μL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane and 30 μL of tetraethyl silicate were added, and the mixture was stirred and reacted at room temperature for 2 h;

[0037] Step 3: According to the mass ratio of polyvinylidene fluoride to nano-silica of 1:4, 25 mg of polyvinylidene fluoride was weighed and added to the suspension prepared in step 2;

[0038] Step 4: Add the suspension prepared in step 3 to a spray gun and spray it on the paper under a 200 kPa N2 atmosphere;

[0039] Step 5: The paper prepared in step 4 is dried thoroughly in a forced air oven at 80° C. to obtain a super-amphiphobic antibacterial paper that prevents bacterial adhesion.

[0040] like Figure 1 The electron micrographs shown in the figure show that the surface of the antibacterial super-amphiphobic antibacterial paper prepared in Example 1 has a rough microstructure, resulting in excellent superhydrophobic properties. Furthermore, the micro-nanostructure of the super-amphiphobic coating subjects the bacterial cell wall to physical tearing forces exceeding its tolerance, leading to significant mechanical deformation and cell death. Furthermore, the high-aspect-ratio micro-nanoprotrusions penetrate the E. coli cell wall, causing the loss of bacterial cell contents and resulting in cell death.

[0041] like Figure 3 As shown, the dilution was 10 3 and 10 4 The figure shows the number of Escherichia coli colonies grown on the anti-bacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1. This shows that it exhibits excellent antibacterial performance in the culture test of Escherichia coli.

[0042] Example 2

[0043] A method for preparing a super-amphiphobic antibacterial paper that prevents bacterial adhesion comprises the following steps:

[0044] Step 1: Weigh 0.1 g of nano-silica particles, add them to a mixed solution of 44 ml of anhydrous ethanol and 6 ml of ammonia water, and disperse them using an ultrasonic disperser for 30 minutes to obtain a suspension;

[0045] Step 2: The suspension prepared in step 1 was stirred at a high speed of 600 r / min, and 120 μL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane and 30 μL of tetraethyl silicate were added, and the mixture was stirred and reacted at room temperature for 2 h;

[0046] Step 3: According to the mass ratio of polyvinylidene fluoride to nano-silica of 1:2, 50 mg of polyvinylidene fluoride was weighed and added to the suspension prepared in step 2;

[0047] Step 4: Add the suspension prepared in step 3 to a spray gun and spray it on the paper under a 200 kPa N2 atmosphere;

[0048] Step 5: The paper prepared in step 4 is dried thoroughly in a forced air oven at 80° C. to obtain a super-amphiphobic antibacterial paper that prevents bacterial adhesion.

[0049] Example 3

[0050] A method for preparing a super-amphiphobic antibacterial paper that prevents bacterial adhesion comprises the following steps:

[0051] Step 1: Weigh 0.1 g of nano-silica particles, add them to a mixed solution of 44 ml of anhydrous ethanol and 6 ml of ammonia water, and disperse them using an ultrasonic disperser for 30 minutes to obtain a suspension;

[0052] Step 2: The suspension prepared in step 1 was stirred at a high speed of 600 r / min, and 120 μL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane and 30 μL of tetraethyl silicate were added, and the mixture was stirred and reacted at room temperature for 2 h;

[0053] Step 3: According to the mass ratio of polyvinylidene fluoride to nano-silica of 1:1, 100 mg of polyvinylidene fluoride was weighed and added to the suspension prepared in step 2;

[0054] Step 4: Add the suspension prepared in step 3 to a spray gun and spray it on the paper under a 200 kPa N2 atmosphere;

[0055] Step 5: The paper prepared in step 4 is dried thoroughly in a forced air oven at 80° C. to obtain a super-amphiphobic antibacterial paper that prevents bacterial adhesion.

[0056] like Figure 5 The figures show the contact angles of the antibacterial super-amphiphobic antibacterial paper produced in various embodiments of the present invention. This demonstrates that the super-amphiphobic antibacterial paper exhibits excellent hydrophobicity and oleophobicity for water, ethylene glycol, glycerol, and other liquids, with contact angles exceeding 150°, achieving both super-hydrophobicity and super-oleophobicity. Example 1 exhibits the highest contact angles for all three liquids, demonstrating the strongest hydrophobicity and oleophobicity.

[0057] like Figure 2 As shown, compared with blank kraft paper ( Figure 2 Surface morphologies of the substrates a and b) and Examples 1-3 of the present invention are shown in the figures. As can be seen, the surfaces of Examples 1-3 exhibit surface microstructures compared to the blank paper substrate, resulting in superhydrophobicity and superoleophobicity. Furthermore, for Examples 1-3, increasing the polyvinylidene fluoride content reduces surface roughness and weakens the hydrophobicity and oleophobicity.

[0058] like Figure 4 As shown, compared with blank kraft paper ( Figure 4 a and b), milk carton ( Figure 4 c and d) and Example 1 ( Figure 4e and f), Example 2 ( Figure 4 g and h) and Example 2 ( Figure 4 The results of the Escherichia coli culture on the antibacterial adhesion super-amphiphobic antibacterial paper prepared in (i) and (j) above are shown. Milk cartons are a commonly used antibacterial packaging, and the antibacterial ability and hydrophobicity and oleophobicity are improved compared to blank paper or kraft paper. Examples 1 to 3 significantly improved the antibacterial ability compared to blank kraft paper and milk cartons. The antibacterial rates of the super-amphiphobic antibacterial paper prepared in milk cartons and Examples 1-3 against Escherichia coli were 90.24%, 99.5%, 97.6%, and 95.2%, respectively. Among them, the antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1 had the strongest antibacterial ability.

[0059] like Figure 6 As shown in a, the surface of kraft paper is smooth and flat, and the corresponding surface roughness is (Ra=56.520). Figure 6 b is the antibacterial and antimicrobial paper prepared in Example 1, with Ra=128.686. Its high roughness and low surface energy give it excellent superhydrophobic and superoleophobic properties. Figure 6 Figure c is the antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 2, with Ra=92.726; Figure 6 Figure d is the antibacterial antibacterial paper with an Ra value of 79.389 obtained in Example 3. As the proportion of PVDF increases, the surface roughness of the antibacterial paper decreases, and its hydrophobic and oleophobic properties decrease.

[0060] 1. Moisture-proof performance test

[0061] The antibacterial adhesion super-amphiphobic antibacterial paper prepared in Examples 1, 2 and 3 of the present invention was used as an experimental group; and ordinary kraft paper was used as a control group to perform moisture-proof performance testing.

[0062] Experimental Method: Kraft paper and antibacterial paper samples of the present invention were placed under different relative humidity conditions for 24 hours. The moisture gain of the paper samples was recorded to obtain the relationship between the moisture gain of the paper samples at different relative humidity conditions. The moisture content (MC) and relative moisture content (RMC) of the sample paper were calculated as follows:

[0063] MC (%) = (M1-M0) / M×100%

[0064] RMC(%)=MC / MC(50%RH)×100%

[0065] Where M0 and M1 are the initial mass and mass of the sample paper after 24 hours, respectively, MC is the moisture content of the sample, and RMC is the relative moisture content.

[0066] The results are as follows Figure 7As shown, kraft paper, used as food packaging paper, experiences a rapid increase in relative moisture content with increasing humidity. At relative humidity levels of 80% and 100%, the relative moisture content of kraft paper reaches approximately 150% and 180%, respectively. The relative moisture content of the antibacterial super-amphiphobic antibacterial paper also gradually increases with humidity changes, albeit at a slower rate. The relative moisture content of the antibacterial paper in Example 1 increases to over 110% at 100% humidity, while the relative moisture content of the antibacterial paper in Examples 2 and 3 remains below 110%. Compared to kraft paper, the antibacterial paper produced by the present invention exhibits significantly improved moisture resistance.

[0067] 2. Acid and alkali corrosion resistance test

[0068] The antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1 of the present invention was immersed in a solution with a pH value of 1 to 13 for 3-5 seconds and then taken out. The water contact angle of the antibacterial adhesion super-amphiphobic antibacterial paper was measured using a contact angle meter.

[0069] The pH stability of super-amphiphobic antibacterial paper was studied, with the change of contact angle as the indicator. The results are as follows Figure 8 Whether the super-amphiphobic antibacterial paper is immersed in a strong acid solution or a strong alkaline solution, the surface contact angle of the super-amphiphobic antibacterial paper remains near 156.7°, indicating that the super-amphiphobic antibacterial paper has excellent pH stability, which may be related to the good acid and alkali resistance of PVDF. The superhydrophobic structure also prevents the penetration of acid and alkali molecules, indicating that the super-amphiphobic antibacterial paper has good chemical stability and can withstand harsh external environments. It has application prospects in the chemical corrosion protection of food packaging.

[0070] 3. UV aging resistance test

[0071] The antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1 of the present invention was irradiated with ultraviolet light for 1 to 10 hours in a dark environment, and then taken out and the water contact angle of the antibacterial adhesion super-amphiphobic antibacterial paper was measured using a contact angle meter.

[0072] like Figure 9 As shown in the figure, after long-term ultraviolet irradiation, the surface contact angle of the super-amphiphobic antibacterial paper has basically not changed, and the contact angle is still greater than 155°, which proves that the surface of the super-amphiphobic antibacterial paper is not damaged and has excellent anti-ultraviolet aging performance. It shows that the super-amphiphobic antibacterial paper can maintain excellent superhydrophobic properties for a long time under sunlight and can be used in food packaging.

[0073] 4. Self-cleaning test

[0074] Some sand was sprinkled on the antibacterial adhesion super-amphiphobic antibacterial paper prepared in Example 1 of the present invention, and then washed with deionized water.

[0075] like Figure 10As shown in the figure, the sand is easily carried away from the surface of the super-amphiphobic antibacterial paper by the rolling water droplets. Finally, the sand on the paper surface is thoroughly cleaned, and the surface of the super-amphiphobic antibacterial paper is as clean as before, which proves that the super-amphiphobic antibacterial paper can effectively prevent bacteria and other pollutants from adhering to its surface.

[0076] The above specific implementation manner cannot be used as a limitation on the protection scope of the present invention. For those skilled in the art, any replacement, improvement or transformation made to the implementation manner of the present invention falls within the protection scope of the present invention.

[0077] Any matters not described in detail in the present invention are well-known technologies to those skilled in the art.

Claims

1. A method for preparing a super-amphiphobic antibacterial paper that prevents bacterial adhesion, characterized in that: The steps are as follows: (1) Add 0.1 g of nano-silica particles to a mixed solution of an appropriate amount of anhydrous ethanol and ammonia water, and disperse them using an ultrasonic disperser for 10 min to 30 min to obtain a suspension; (2) The suspension prepared in step (1) was stirred at a high speed of 600 r / min-800 r / min, and 120 μL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane and 30 μL of tetraethyl silicate were added, and the mixture was reacted at room temperature for 2 h; (3) adding polyvinylidene fluoride to the suspension prepared in step (2) at a mass ratio of 1:4-1:1; (4) spraying the suspension prepared in step (3) onto paper under a 200 kPa N2 atmosphere; (5) The paper prepared in step (4) is dried thoroughly to obtain a super-amphiphobic antibacterial paper that prevents bacterial adhesion.

2. The method for preparing a super-amphiphobic antibacterial paper for preventing bacterial adhesion according to claim 1, wherein: The particle size of nano-silica particles is 15 nm-200 nm.

3. The method for preparing a super-amphiphobic antibacterial paper for preventing bacterial adhesion according to claim 1, wherein: The drying method in step (5) is a forced air oven; the drying temperature is 80°C.

4. The method for preparing a super-amphiphobic antibacterial paper for preventing bacterial adhesion according to claim 1, wherein: The paper is filter paper, cardboard, corrugated paper or kraft paper.

5. Application of the antibacterial adhesion super-amphiphobic antibacterial paper obtained by the arbitrary preparation method of claims 1-4 in food and medical antibacterial hydrophobic paper.

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