Preparation method of improved super-hydrophobic antibacterial fabric with photothermal effect

Abstract

The application discloses an improved super-hydrophobic antibacterial fabric with illumination heat production and metal sterilization and a preparation method thereof. The application first prepares nano-particles with photo-thermal and sterilization effects, makes the nano-particles adhere to a fabric substrate through an immersion method, modifies the surface of the material by using a silane coupling agent with an alkane chain, introduces a substance for reducing surface energy, constructs high roughness, and prepares a super-hydrophobic material with excellent photo-thermal and active antibacterial properties. The water contact angle of the fabric surface of the prepared super-hydrophobic antibacterial fabric is 152.4 degrees, the surface temperature is increased to 54.7 DEG C and 105 DEG C under the irradiation of sunlight and near-infrared light respectively, excellent photo-thermal cycle stability and super-hydrophobic high-temperature resistance are shown, the super-hydrophobic antibacterial fabric has good antibacterial effects on staphylococcus aureus and escherichia coli, the bacteriostatic rate of the super-hydrophobic antibacterial fabric on staphylococcus aureus and escherichia coli can reach 100% under the condition of near-infrared light. The antibacterial efficiency is strong and the antibacterial range is wide.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of super-hydrophobic antibacterial fabrics, in particular to a preparation method of an improved super-hydrophobic antibacterial fabric with photothermal effect. BACKGROUND

[0002] To solve the defects of the disclosed technical solutions of CN116219763B and CN115928441B, aiming at the problems in the prior art that passive super-hydrophobic sterilization cannot maintain 100% sterile surface conditions for a long time, active sterilization materials have limited antibacterial life, and the like, the applicant combines the special wetting performance of the super-hydrophobic material with the excellent sterilization performance of the antibacterial material, and develops a super-hydrophobic antibacterial fabric with photothermal effect which can maintain high antibacterial efficiency for a long time and is safe, as shown in the patent application No. 202510047210.4 of the applicant, but the applicant further develops on the basis to obtain a super-hydrophobic antibacterial fabric with better high-temperature performance, longer high-efficiency antibacterial time, higher safety and better comprehensive performance. SUMMARY

[0003] The application aims to develop a preparation method of an antibacterial super-hydrophobic coating with active sterilization activity, which is simple in process, and the super-hydrophobic antibacterial fabric not only has excellent photothermal cycle stability and super-hydrophobic high-temperature resistance, but also can maintain high-efficiency antibacterial effect for a long time and has high safety.

[0004] To achieve the above-mentioned purpose, the technical scheme adopted by the application is as follows: a preparation method of an improved super-hydrophobic antibacterial fabric with photothermal effect, comprising the following steps,

[0005] Step S1, after the chemical fiber fabric is cleaned, the chemical fiber fabric is placed in a photothermal preparation aqueous dispersion for soaking treatment, then the chemical fiber fabric is taken out and subjected to drying treatment, and the soaking treatment and the drying treatment are repeated for multiple times to obtain a photothermal fabric with the photothermal preparation attached to the surface of the fabric;

[0006] Step S2, 2-3 parts of ammonia water are added into 98 parts of ethanol to mix uniformly, and 100 parts of ethanol is taken out, 0.5-4 g of a silane coupling agent with a fluorine atom and 0.5-4 g of a silicate compound are added into the ethanol to mix respectively to obtain a mixed solution, and the mixed solution is stirred and mixed at a temperature of 25-60 DEG C for 2-8 h to obtain a super-hydrophobic modified dispersion;

[0007] Step S3, the photo-thermal fabric treated in step S1 is put into the super-hydrophobic modification dispersion solution prepared in step S2, and after stirring at 60-80℃ for 0.5-3h, the photo-thermal fabric is taken out and put into an oven at 80-120℃ for cross-linking and curing treatment for 0.5-2h, to obtain a super-hydrophobic antibacterial fabric with photo-thermal effect,

[0008] The surface of the fabric substrate of the super-hydrophobic antibacterial fabric is attached with a fluoralkyl coupling agent / hydrophobic silica nanoparticle cross-linked composite coating.

[0009] In step S3, the fluoralkyl coupling agent / hydrophobic silica nanoparticle cross-linked composite coating is formed by partial self-condensation and polymerization of silicate under high temperature conditions at 80-120℃ to generate hydrophobic silica nanoparticles, and the fluoralkyl coupling agent is a silane coupling agent containing a fluoralkyl group, which has low surface energy and good chemical stability, and can condense with the carboxyl or hydroxyl groups of the photo-thermal preparation under high temperature conditions at 80-120℃, and can also bind with the hydroxyl groups between fibers through electrostatic or hydrogen bonding, and the synergistic effect of chemical bonding and physical force makes the fluoralkyl coupling agent / hydrophobic silica nanoparticle composite coating, the fabric substrate of the super-hydrophobic antibacterial fabric and the photo-thermal preparation layer have good adhesion.

[0010] In step S1, the chemical fiber fabric is put into an ethanol solution and ultrasonically cleaned for 2-5min, taken out and dried in an oven at 60-100℃, and then the front and back surfaces of the chemical fiber fabric are respectively subjected to surface cleaning treatment using vacuum plasma for 60-90s, and after the surface cleaning treatment, the chemical fiber fabric is immersed in a photo-thermal preparation aqueous dispersion solution with a volume concentration of 2-8mg / mL for 2-5min, and then taken out and dried in an oven at 60-100℃, and the immersion treatment and drying treatment are repeated for 2-5times, to obtain the photo-thermal fabric with the photo-thermal preparation attached to the surface;

[0011] In step S1, the photo-thermal preparation aqueous dispersion solution is a uniformly dispersed solution obtained by putting the photo-thermal preparation into water and ultrasonic dispersion treatment, and the photo-thermal preparation is selected from dopamine.

[0012] During the photo-thermal preparation treatment, the hydrogen bonding and / or electrostatic interaction between the hydroxyl and carboxyl groups in the molecules of the photo-thermal preparation and the fibers of the chemical fiber fabric can make the fiber surface of the chemical fiber fabric rough, to enhance the physical adhesion of the photo-thermal preparation to the fiber surface, improve the surface properties of the chemical fiber fabric and endow the chemical fiber fabric with excellent photo-thermal performance.

[0013] The fabric material is one of polyester, nylon, spandex, and cellulose; and the fabric type is melt-blown fabric, non-woven fabric, or woven fabric.

[0014] The silane coupling agent with fluorine atom and the silicate compound are subjected to hydrolysis reaction in ethanol under the promotion of ammonia and water, to obtain hydrolysis reaction products and hydrophobic silica nanoparticles with good compatibility; and the modified dispersion liquid is uniformly dispersed and stable in solution after ultrasonic treatment.

[0015] The silane coupling agent with fluorine atom is at least one of trimethoxy(1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, tridecafluorooctyltrimethoxysilane, and perfluorodecyltrimethoxysilane.

[0016] The mass concentration of the silane coupling agent with fluorine atom in the solvent composed of ethanol, ammonia, and water is 0.005-0.04 mg / mL.

[0017] The hydrophobic silica nanoparticles are generated by hydrolysis of the silicate compound, and the particle size of the hydrophobic silica nanoparticles is 0.5-0.8 μm; and the mass ratio of the silicate compound to the silane coupling agent with fluorine atom is 1:1.

[0018] The silicate compound is at least one of tetraethyl silicate, tetrapropyl silicate, and tetraisopropyl silicate.

[0019] An improved super-hydrophobic antibacterial fabric with photothermal effect is prepared according to the above method, and the fabric substrate of the super-hydrophobic antibacterial fabric is attached with a cross-linked composite coating of fluoralkyl coupling agent and hydrophobic silica nanoparticles. The super-hydrophobic antibacterial fabric with photothermal effect combines passive super-hydrophobic antibacterial adhesion and active photothermal sterilization in antibacterial applications, and the inhibition rate of Staphylococcus aureus and Escherichia coli under near-infrared light can reach 100%. The antibacterial performance is strong and the antibacterial range is wide.

[0020] Compared with the prior art, the present application has the advantages that: the present application loads the photothermal preparation on the surface of the chemical fiber fabric through repeated immersion-drying, then coats the mixed solution of silicate and silane coupling agent with fluorine atoms on the fabric under alkaline conditions, and after thermal crosslinking, the super-hydrophobic antibacterial fabric with photothermal effect is prepared, the nanometer silicon dioxide generated by the hydrolysis of the photothermal preparation and the silicate on the fabric surface cooperatively constructs a uniform micro-nano rough structure, and the silane coupling agent with fluorine atoms hydrolyzes under alkaline conditions, then condenses with the carboxyl and hydroxyl groups of the photothermal preparation and is grafted on the surface of the photothermal preparation layer, and due to the characteristics of the fluorine atom itself, the fabric is endowed with low surface energy. The combination of the rough morphology and the special chemical structure enables the fabric surface to achieve super-hydrophobicity. The introduction of the photothermal preparation significantly improves the photothermal conversion performance of the fabric, under the synergistic effect of the passive antibacterial adhesion of the super-hydrophobic surface and the active sterilization effect of the photothermal preparation, the fabric exhibits excellent antibacterial efficiency on various bacteria, in addition, the self-cleaning effect of the super-hydrophobic surface can effectively remove the attached dead bacteria, reduce their adhesion on the surface of the antibacterial material, and significantly prolong the service life of the antibacterial material, the preparation process adopted by the present application is simple, efficient and low in cost, the prepared photothermal super-hydrophobic antibacterial fabric not only has excellent stability, wide antibacterial range, but also has high safety and no drug resistance problem.

[0021] The preparation process of the present application is more simple and efficient, and has good scalability, which is suitable for large-scale industrial production and effectively reduces the comprehensive production cost. The prepared super-hydrophobic antibacterial fabric exhibits excellent photothermal cycle stability and super-hydrophobic high-temperature resistance, and can maintain high-efficiency antibacterial effect for a long time, and has high safety. In addition, the raw material cost adopted by the present application is low, and the super-hydrophobic antibacterial fabric has the advantages of low energy consumption, environmental friendliness, etc., and has significant application value and broad application prospect in the field of medical protective materials.

[0022] The present application constructs a fabric with excellent super-hydrophobicity through the binary synergistic effect of the uniform micro-nano rough structure on the fabric surface generated by the hydrolysis of the photothermal preparation and the silicate and the low-surface-energy fluoralkane chain silane coupling agent with fluorine atoms, the obtained micro-nano rough structure is smaller than that of the prior application 202510047210.4, and the surface is more delicate; at the same time, dehydration condensation reaction occurs between the photothermal preparation and the silane coupling agent to form a chemical crosslinking structure, in addition, the present application introduces a photothermal preparation layer, so that the fabric has excellent heat generation performance under the irradiation of sunlight or near-infrared light, and the surface temperature can reach 105 DEG C, benefiting from its structural stability, the super-hydrophobic antibacterial fabric of the present application can maintain super-hydrophobicity under high temperature conditions of 105 DEG C for a long time, significantly enhancing the heat resistance and antibacterial durability of the fabric, that is, the fabric still has longer and effective antibacterial performance at a relatively lower temperature, and has higher safety.

[0023] The application firstly loads a photothermal preparation on the surface of the fabric to endow the fabric with photothermal performance, and then introduces a composite coating formed by silicate and fluoroalkane chain silane coupling agent to reduce the surface energy of the material and construct a micro-nano scale rough structure, thereby preparing a super-hydrophobic antibacterial fabric with excellent photothermal and super-hydrophobic performance.

[0024] The super-hydrophobic antibacterial fabric prepared by the preparation method has the advantages of excellent antibacterial performance. On the one hand, the super-hydrophobic property of the fabric significantly reduces the probability of bacterial adhesion on the surface of the material; on the other hand, the photothermal preparation layer can quickly kill a small amount of bacteria adhering to the surface of the material under light conditions, thereby realizing a double protection mechanism. The fabric not only has high antibacterial efficiency, wide antibacterial range, long antibacterial life, safety and reliability, and no drug resistance problem. In the application of antibacterial, the photothermal super-hydrophobic fabric combines passive super-hydrophobic antibacterial with active photothermal sterilization, has strong antibacterial effect, and has long-lasting effect. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The scanning electron microscope image of the super-hydrophobic antibacterial fabric with photothermal effect prepared in Example 1, Fig. a is 600 times magnification, and Fig. b is 5000 times magnification.

[0026] Figure 2 The X-ray energy spectrum analysis of the super-hydrophobic antibacterial fabric with photothermal effect prepared in Example 1.

[0027] Figure 3 The photothermal conversion ability of the super-hydrophobic antibacterial fabric with photothermal effect prepared in Example 1 under different light intensities of near-infrared light.

[0028] Figure 4 The resistance effect of the original fabric and the super-hydrophobic antibacterial fabric with photothermal effect prepared in Example 1 on E. coli and S. aureus before and after near-infrared light irradiation. DETAILED DESCRIPTION

[0029] Example 1

[0030] A preparation method of an improved super-hydrophobic antibacterial fabric with photothermal effect,

[0031] First, the synthetic fiber fabric was placed in a vacuum plasma treatment instrument for plasma cleaning for 60 seconds, with each side cleaned once. Then, it was immersed in a 3.8 mg / mL PDA@ZIF solution for 2 minutes, removed, and dried in a 50°C oven. This immersion-drying process was repeated 5 times. Subsequently, a mixed solution of 1 g of trimethoxy(1H,1H,2H,2H-heptadecyl)silane, 1 g of tetraethyl silicate, and 50 mL of ethanol was added to 49 mL of ethanol and 1 mL of ammonia water. The solution was heated and stirred at 60°C for 3 hours to obtain a superhydrophobic modified solution. Finally, the fabric loaded with PDA@ZIF particles (a polydopamine-coated zeolite imidazole framework solution) was placed in the modified solution and stirred at 60°C for 1 hour. It was then removed and placed in a 100°C oven for a crosslinking reaction for 1 hour to prepare a superhydrophobic antibacterial fabric with photothermal effects.

[0032] Figure 1 The image shows a scanning electron microscope (SEM) image of the photothermal superhydrophobic antibacterial fabric prepared in Example 1. It can be clearly seen that a cross-linked coating (FAS-SiO2 coating) of low surface energy fluorine-containing material and silica particles is clearly coated onto the antibacterial fabric. The silica particles are generated by the hydrolysis of tetraethyl silicate and have a particle size between 0.5 and 0.8 μm. Not only was the low surface energy fluorine-containing material successfully grafted, but the surface roughness of the fabric was also further increased, endowing the fabric with superhydrophobic properties and a surface contact angle of 152.4°. Furthermore, due to the stable cross-linked structure formed between trimethoxy(1H,1H,2H,2H-heptadecyl)silane and PDA@ZIF, the fabric exhibits good thermal stability, maintaining its superhydrophobicity and a contact angle of 151.5° even after treatment at 120°C for 72 hours.

[0033] Figure 2 X-ray energy dispersive spectroscopy (EDS) analysis was performed on the photothermal superhydrophobic antibacterial fabric prepared in Example 1. Elemental surface scanning and EDS analysis revealed that the prepared photothermal superhydrophobic antibacterial fabric contained not only carbon, oxygen, nitrogen, and zinc, but also silicon and fluorine elements on its surface, and these elements were uniformly distributed across the fiber surface. Figure 2 As shown, this indicates that the superhydrophobic modification of the PDA@ZIF fabric was successful. The atomic percentages of C, O, F, Si, N, and Zn on the surface of the F-PDA@ZIF fabric are 58.8%, 22.1%, 11.7%, 4.9%, 1.9%, and 0.5%, respectively.

[0034] Figure 3 The photothermal conversion ability of the superhydrophobic antibacterial fabric with photothermal effect prepared in Example 1 under near-infrared light of different intensities was measured. At 0.25 W / cm²... 2 0.50W / cm 2 and 0.75W / cm 2The surface temperature of the fabric reached 48.1℃, 74.6℃ and 96.9℃ respectively at the 10th second under the irradiation of near-infrared light with power; the temperature tended to be stable at the 1st minute, and reached 58.2℃, 98.7℃ and 129℃ respectively; the temperature reached 62.6℃, 105℃ and 139℃ respectively at the 4th minute. The temperature of the fabric could be stably maintained above 100℃ under the irradiation of near-infrared light with power of 0.50W / cm 2 The research shows that most bacteria, such as E. coli and Staphylococcus aureus, are difficult to survive at the temperature of 100℃, thereby achieving good antibacterial effect.

[0035] Figure 4 The antibacterial effect of the photo-thermal super-hydrophobic antibacterial fabric prepared in Example 1 on E. coli and Staphylococcus aureus before and after irradiation of near-infrared light can be seen. It can be seen that the bacterial colonies cultured on the original fabric are very dense on the agar plate; and the photo-thermal super-hydrophobic antibacterial fabric prepared in this example is difficult for bacteria to adhere to the surface of the sample due to its special wettability, thereby greatly reducing the amount of bacteria on the agar plate in this experimental group. However, due to the rough structure of the surface of the super-hydrophobic antibacterial fabric, it is inevitable to be reduced during storage, so there are still some colonies on the surface of the fabric. In addition, the photo-thermal super-hydrophobic antibacterial fabric is irradiated with near-infrared light with power of 0.5W / cm 2 The PDA rapidly heats up under near-infrared light, which can promote the release of zinc ions, and high temperature can also kill bacteria at the same time, achieving stronger antibacterial effect. Therefore, there is no bacterial colony on the agar plate, and the antibacterial rate on E. coli and Staphylococcus aureus is as high as 100%.

[0036] The test results of the hydrophobicity, high-temperature stability and photo-thermal conversion performance of the fabric are shown in Table 1, and the test results of the antibacterial performance of the fabric are shown in Table 2.

[0037] Example 2

[0038] A preparation method of an improved super-hydrophobic antibacterial fabric with photo-thermal effect,

[0039] Firstly, the polyurethane non-woven fabric was placed in a vacuum plasma treatment instrument for plasma cleaning, with a cleaning time of 60 s, and each side was cleaned once. Then it was immersed in a 2 mg / mL PDA@ZIF solution for 2 minutes, taken out and dried in a 50°C oven, and the immersion-drying process was repeated 5 times. Subsequently, a mixed solution of 0.5 g trimethoxy(1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, 0.5 g tetraethyl orthosilicate and 50 mL ethanol was added to 49 mL ethanol and 1 mL ammonia water, and heated and stirred at 60°C for 3 h to obtain a super-hydrophobic modification solution. Finally, the fabric loaded with PDA@ZIF particles was placed in the modification solution and stirred at 60°C for 1 h, and then taken out and placed in a 100°C oven for crosslinking reaction for 1 h to prepare a super-hydrophobic antibacterial fabric with photothermal effect.

[0040] The test results of the hydrophobicity, high-temperature stability and photothermal conversion performance of the fabric are shown in Table 1, and the test results of the antibacterial performance of the fabric are shown in Table 2.

[0041] Example 3

[0042] A method for preparing an improved super-hydrophobic antibacterial fabric with photothermal effect,

[0043] Firstly, the polyurethane non-woven fabric was placed in a vacuum plasma treatment instrument for plasma cleaning, with a cleaning time of 60 s, and each side was cleaned once. Then it was immersed in a 2 mg / mL PDA@ZIF solution for 2 minutes, taken out and dried in a 50°C oven, and the immersion-drying process was repeated 5 times. Subsequently, a mixed solution of 0.5 g trimethoxy(1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, 0.5 g tetraethyl orthosilicate and 50 mL ethanol was added to 49 mL ethanol and 1 mL ammonia water, and heated and stirred at 60°C for 3 h to obtain a super-hydrophobic modification solution. Finally, the fabric loaded with PDA@ZIF particles was placed in the modification solution and stirred at 60°C for 1 h, and then taken out and placed in a 100°C oven for crosslinking reaction for 1 h to prepare a super-hydrophobic antibacterial fabric with photothermal effect.

[0044] The test results of the hydrophobicity, high-temperature stability and photothermal conversion performance of the fabric are shown in Table 1, and the test results of the antibacterial performance of the fabric are shown in Table 2.

[0045] Example 4

[0046] A method for preparing an improved super-hydrophobic antibacterial fabric with photothermal effect,

[0047] Firstly, the polyester fabric was placed in a vacuum plasma treatment instrument for plasma cleaning, the cleaning time was 60 s, and each side was cleaned once. Then it was immersed in a 6 mg / mL PDA@ZIF solution for 2 minutes, taken out and dried in a 50°C oven, and the immersion-drying process was repeated 5 times. Subsequently, a mixed solution of 3 g of trimethoxy(1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, 3 g of tetraethyl silicate and 50 mL of ethanol was added to 49 mL of ethanol and 1 mL of ammonia water, and heated and stirred at 60°C for 3 h to obtain a super-hydrophobic modification solution. Finally, the fabric loaded with PDA@ZIF particles was placed in the modification solution and stirred at 60°C for 1 h, and then placed in a 100°C oven for crosslinking reaction for 1 h to prepare a super-hydrophobic antibacterial fabric with photothermal effect.

[0048] The test results of the hydrophobicity, high-temperature stability and photothermal conversion performance of the fabric are shown in Table 1, and the test results of the antibacterial performance of the fabric are shown in Table 2.

[0049] Comparative Example 1

[0050] In order to verify the key role of the rough structure in the photothermal super-hydrophobic antibacterial fabric prepared by the present application in realizing super-hydrophobicity, and to explore the significance of the super-hydrophobic surface in improving the antibacterial efficiency, the fabric without adding silicate was used as a control group for comparison.

[0051] Firstly, the fabric was placed in a vacuum plasma treatment instrument for plasma cleaning, the cleaning time was 60 s, and each side was cleaned once. Then it was immersed in a 3.8 mg / mL PDA@ZIF solution for 2 minutes, taken out and dried in a 50°C oven, and the immersion-drying process was repeated 5 times. Subsequently, a mixed solution of 1 g of trimethoxy(1H, 1H, 2H, 2H-heptadecafluorodecyl) silane and 50 mL of ethanol was added to 49 mL of ethanol and 1 mL of ammonia water, and heated and stirred at 60°C for 3 h to obtain a super-hydrophobic modification solution. Finally, the fabric loaded with PDA@ZIF particles was placed in the modification solution and stirred at 60°C for 1 h, and then placed in a 100°C oven for crosslinking reaction for 1 h to prepare a super-hydrophobic antibacterial fabric with photothermal effect.

[0052] The test results of the hydrophobicity and photothermal conversion performance of the fabric are shown in Table 1, and the test results of the antibacterial performance of the fabric are shown in Table 2.

[0053] Comparative Example 2

[0054] In order to verify the key role of the surface energy and rough structure in the photothermal super-hydrophobic antibacterial fabric prepared by the present application in realizing super-hydrophobicity, and to explore the influence of the fabric morphology, the fabric added with a common silane coupling agent and directly added with hydrophobic silica nanoparticles was used as a control group for comparison.

[0055] First, the chemical fabric was placed in a vacuum plasma treatment instrument for plasma cleaning, with a cleaning time of 60 s, and each side was cleaned once. Then it was immersed in a 3.8 mg / mL PDA@ZIF solution for 2 minutes, and then taken out and dried in a 50°C oven. The immersion-drying process was repeated 5 times. Subsequently, 1 g of hexadecyl trimethoxysilane, 1 g of hydrophobic nano-silica with a particle size distribution of 0.5-0.8 μm, and 50 mL of ethanol were added to a mixed solution of 49 mL of ethanol and 1 mL of ammonia water, and the mixture was heated and stirred at 60°C for 3 h to obtain a super-hydrophobic modification solution. Finally, the fabric loaded with PDA@ZIF particles was placed in the modification solution and stirred at 60°C for 1 h, and then taken out and placed in a 100°C oven for cross-linking reaction for 1 h to prepare a super-hydrophobic antibacterial fabric with a photo-thermal effect.

[0056] Performance test

[0057] (1) Scanning electron microscope test

[0058] A scanning electron microscope (Zeiss sigma300, Germany) was used for morphology observation, with an acceleration voltage of 10 kV. Before testing, the chemical fabric was fixed on the sample table with conductive glue and was subjected to gold spraying treatment.

[0059] (2) Contact angle test

[0060] A contact angle instrument (SDC-200S, Dongguan Shengding Precision Instrument Co., Ltd.) was used to test the water droplet contact angle on the surface of the coating. The water droplet size was 5 μL, and the contact angle value was calculated as the average value of 5 positions on the fabric surface.

[0061] (3) X-ray photoelectron spectroscopy test

[0062] An X-ray photoelectron spectrometer (Escalab 250Xi, Thermo Fisher Corporation, USA) was used to analyze the surface elements of the antibacterial fabric and the super-hydrophobic antibacterial fabric. The laser source used during testing was Al-Kα X-ray (hv = 1486.6 eV), the testing power was 300 W, the testing voltage was 15 kV, and the analysis area was 0.6 mm2.

[0063] (4) Photo-thermal performance test

[0064] In order to evaluate the photo-thermal conversion performance of the fabric, an 808 nm near-infrared light with a power of 0.75 W / cm 2 was used to irradiate the fabric, and an infrared thermal imager was used for detection, and the surface temperature of the fabric after 4 min of irradiation was recorded.

[0065] (5) Super-hydrophobic heat-resistant stability test

[0066] To evaluate the heat-resistant stability of the fabric, the chemical fiber fabric was heated in a 120 °C oven for 72 h, and then the super-hydrophobic antibacterial fabric was taken out for contact angle testing.

[0067] (6) Antibacterial test

[0068] To study the antibacterial effect of the fabric, the original fabric and the prepared polydopamine fabric, antibacterial fabric and super-hydrophobic antibacterial fabric were used for antibacterial test, in which the original fabric was used as the control group, the polydopamine fabric, the antibacterial fabric, the super-hydrophobic antibacterial fabric and the super-hydrophobic antibacterial fabric treated by near-infrared light were used as four experimental groups, and 1 mL of bacterial suspension with an initial concentration of 1 x 10 6 CFU / mL was incubated at 37 °C for 24 h. After that, the light-heat treatment group was treated under 808 nm near-infrared light at 0.5 W / cm 2 for 5 min. Then, the above-mentioned fabrics were treated by ultrasonic wave for 5 min (40 kHz, 320 W), 20 μL was taken and spread on a sterile agar plate, and after incubation at 37 °C for 18 h, the optical photograph of the plate was recorded, and the number of bacterial colonies was counted. The calculation formula of the antibacterial rate is: antibacterial rate (%) = [(number of bacterial colonies of the control group-number of bacterial colonies of the experimental group) / number of bacterial colonies of the control group] x 100%.

[0069]

[0070] Table 1 - Test results of fabric hydrophobicity, high-temperature stability and light-heat conversion performance

[0071]

[0072] Table 2 - Test results of fabric antibacterial performance

[0073] From the performance test results in Tables 1 and 2, it can be found that the light-heat super-hydrophobic antibacterial fabric prepared in Examples 1 to 4 not only exhibits excellent super-hydrophobicity, but also can maintain its super-hydrophobicity after 72 hours of treatment in a high-temperature environment, thereby effectively improving the antibacterial adhesion capacity of the material. At the same time, the light-heat conversion performance of the fabric is outstanding, and the combination of the super-hydrophobic surface further enhances the antibacterial effect, so that the antibacterial rate reaches 100%.

[0074] In the performance test of Table 1, the fabric of Comparative Example 1 failed to exhibit superhydrophobicity compared with Example 1. Although the fabric still had good light-heat conversion performance, and the surface temperature could be raised to 114℃ due to the absence of silicate substances, its antibacterial rate against E. coli and S. aureus was significantly reduced. This is because the lack of silicate components in the coating resulted in the inability to form hydrophobic silica, and the fibers were difficult to build sufficient roughness, with a fabric surface contact angle of only 140°. When bacteria come into contact with the fabric and reproduce on its surface, adhesion is likely to occur. Even if the surface bacteria are killed by simulated sunlight irradiation, the small amount of residual inactive bacteria will still affect the sterilization effect, causing the fabric to have a lower antibacterial rate under light and dark conditions.

[0075] In the performance test of Table 1, the fabric of Comparative Example 2 had significantly lower surface smoothness compared with Example 1. Comparative Example 2 used a silane coupling agent with an alkane chain, which had less hydrophobicity than fluorine atoms, and formed a porous structure with undulations, increasing the roughness of the fabric surface. At the same time, the directly added silica particles could form a porous structure with undulations with the silane coupling agent, increasing the roughness of the fabric surface, but due to the high surface roughness, the contact angle was 155°, slightly higher than Example 1. In contrast, the fabric of Example 1 not only had excellent superhydrophobicity, but also exhibited higher efficiency in light-heat conversion (surface temperature 105℃). This indicates that the fabric of Example 1 has a smoother surface, which can more effectively promote light-heat conversion while maintaining good superhydrophobic properties.

[0076] The light-heat effect superhydrophobic antibacterial fabric of the present application is composed of a light-heat preparation layer, a low-surface-energy fluorosilane coupling agent, and hydrophobic nanosilica, and is realized through a chemical cross-linking structure. The fabric has excellent superhydrophobicity, heat-resistant stability, light-heat conversion performance, and light-heat cycle stability. Its superhydrophobicity effectively reduces bacterial adhesion on the fabric surface, and at the same time, the light-heat effect can quickly kill the attached bacteria, achieving the integration of superhydrophobicity and antibacterial properties. In addition, the fabric also has the advantages of high antibacterial efficiency, wide antibacterial spectrum, long antibacterial life, and safety and reliability, and no drug resistance.

[0077] The above-described examples only express several embodiments of the present application, which are described in more detail and in detail, but should not be construed as limiting the scope of the present patent. It should be noted that for those skilled in the art, without departing from the concept of the present application, a number of modifications and modifications can be made, which are within the scope of the present application. Therefore, the scope of protection of the present patent should be subject to the attached claims.

Claims

1. A method for preparing an improved super-hydrophobic antibacterial fabric with photothermal effect, characterized in that: It comprises the following steps, Step S1, after the chemical fiber fabric is cleaned, it is placed in a photo-thermal preparation aqueous dispersion for soaking treatment, then taken out and dried, and the soaking treatment and drying treatment are repeated for multiple times to obtain a photo-thermal fabric with photo-thermal preparation attached to the surface; The photo-thermal preparation aqueous dispersion is a uniformly dispersed solution obtained by putting photo-thermal preparation into water and treating by ultrasonic dispersion, and the photo-thermal preparation is selected from dopamine; Step S2, 2-3 parts of ammonia water are added into 98 parts of ethanol to mix uniformly, and then 100 parts of ethanol are taken, 0.5-4 g of silane coupling agent with fluorine atom and 0.5-4 g of silicate compound are added into the ethanol to mix respectively to obtain a mixed solution, the mixed solution is stirred and mixed at a temperature of 25-60℃ for 2-8 h to obtain a super-hydrophobic modification dispersion; The silane coupling agent with fluorine atom is at least one of trimethoxy(1H, 1H, 2H, 2H-heptadecafluorodecyl)silane, tridecafluorooctyltrimethoxysilane and perfluorodecyltrimethoxysilane; Step S3, the photo-thermal fabric treated by step S1 is placed into the super-hydrophobic modification dispersion prepared by step S2, stirred at a temperature of 60-80℃ for 0.5-3 h, then taken out and placed into an oven at a temperature of 80-120℃ for cross-linking and curing treatment for 0.5-2 h to obtain a super-hydrophobic antibacterial fabric with photo-thermal effect, The surface of the fabric substrate of the super-hydrophobic antibacterial fabric is attached with a fluoralkyl coupling agent / hydrophobic silica nanoparticle cross-linked composite coating.

2. The method for preparing the improved super-hydrophobic antibacterial fabric with photothermal effect according to claim 1, characterized in that: In the step S3, the fluoralkyl coupling agent / hydrophobic silica nanoparticle cross-linked composite coating is obtained by condensation and polymerization of the hydrolyzed silicate at a high temperature of 80-120℃ to generate hydrophobic silica nanoparticles, and the fluoralkyl coupling agent is a silane coupling agent containing fluoralkyl group, which has low surface energy and good chemical stability, and can condense with carboxyl or hydroxyl group of the photo-thermal preparation and also can be combined with the hydroxyl group between fibers through electrostatic or hydrogen bonding at a high temperature of 80-120℃, and the synergistic effect of the chemical bonding and physical force makes the fluoralkyl coupling agent / hydrophobic silica nanoparticle composite coating, the fabric substrate of the super-hydrophobic antibacterial fabric and the photo-thermal preparation layer have good adhesion.

3. The method for preparing the improved super-hydrophobic antibacterial fabric with photothermal effect according to claim 2, characterized in that: In the step S1, the chemical fiber fabric is placed into an ethanol solution and ultrasonically cleaned for 2-5 min, then taken out and placed into an oven at a temperature of 60-100℃ for drying treatment, then the front and back surfaces of the chemical fiber fabric are respectively subjected to surface cleaning treatment by vacuum plasma for 1 time, the surface cleaning treatment time is 60-90 s, after the surface cleaning treatment is completed, the chemical fiber fabric is placed into a photo-thermal preparation aqueous dispersion with a volume concentration of 2-8 mg / mL for soaking treatment for 2-5 min, then taken out and placed into an oven at a temperature of 60-100℃ for drying treatment, and the soaking treatment and drying treatment are repeated for 2-5 times to obtain the photo-thermal fabric with photo-thermal preparation attached to the surface.

4. The method for preparing the improved super-hydrophobic antibacterial fabric with photothermal effect according to claim 1, characterized in that: The fabric material is one of polyester, nylon and spandex; and the fabric type is non-woven fabric or woven fabric.

5. The method for preparing the improved super-hydrophobic antibacterial fabric with photothermal effect according to claim 1, characterized in that: The silane coupling agent with fluorine atom and the silicate are subjected to hydrolysis reaction in ethanol under the promotion of ammonia and water, to obtain hydrolysis reaction products and silicate to generate hydrophobic silica nanoparticles with good compatibility, and the modified dispersion liquid is uniformly dispersed and kept stable in solution after ultrasonic treatment.

6. The method for preparing the improved super-hydrophobic antibacterial fabric with photothermal effect according to any one of claims 1 to 5, characterized in that: The mass concentration of the silane coupling agent with fluorine atom in the solvent composed of ethanol, ammonia and water is 0.005-0.04 mg / mL.

7. The method for preparing the improved super-hydrophobic antibacterial fabric with photothermal effect according to claim 6, characterized in that: The hydrophobic silica nanoparticles are generated by hydrolysis of silicate compounds, and the particle size of the hydrophobic silica nanoparticles is 0.5-0.8 μm; the mass ratio of the silicate compound and the silane coupling agent with fluorine atom is 1:

1. The silicate compound is at least one of tetraethyl silicate, tetrapropyl silicate and tetraisopropyl silicate.

8. An improved super-hydrophobic antibacterial fabric with photothermal effect, characterized in that: The preparation method of the improved super-hydrophobic antibacterial fabric with photothermal effect is prepared by the preparation method of the improved super-hydrophobic antibacterial fabric with photothermal effect according to any one of claims 1 to 7, the fabric substrate of the super-hydrophobic antibacterial fabric is attached with a cross-linked composite coating of fluorine alkyl coupling agent and hydrophobic silica nanoparticles, the super-hydrophobic antibacterial fabric with photothermal effect combines passive super-hydrophobic antibacterial adhesion and active photothermal sterilization in antibacterial application, and the antibacterial rate of the super-hydrophobic antibacterial fabric with photothermal effect to Staphylococcus aureus and Escherichia coli under near-infrared light conditions can reach 100%, the antibacterial performance is strong, and the antibacterial range is wide.

Images