Near-infrared light-induced antibacterial fabrics, their preparation methods and applications

Abstract

This invention prepares a near-infrared phthalocyanine derivative photosensitive material, ZnPc-NA. By preparing a finishing solution from ZnPc-NA and BPTCD, and then using this solution to finish fabrics, a fabric capable of synergistically achieving infrared-induced antibacterial effects was obtained, broadening the spectral range for BPTCD's antibacterial activity. The finishing process involves placing the fabric in the finishing solution, performing two dips and two nips (90% nipping rate), removing it, and placing it in an oven. The oven is heated at a rate of 1℃ / min until it reaches 130-170℃, held for 60 minutes, and then cooled to room temperature. Through optimized finishing processes, the antibacterial material exhibits high adhesion durability, good abrasion and wash resistance, and a pleasant hand feel, making it suitable for various applications requiring fabric sterilization.

Description

Technical Field

[0001] This application belongs to the technical field of home textile fabrics, specifically relating to a near-infrared photodynamic (photoinduced) antibacterial home textile fabric. Background Technology

[0002] With the development of home textile fabrics and the improvement of people's understanding of viral and bacterial infections, it has become clear that developing home textiles with highly efficient, convenient, antibacterial, antiviral, and green safety functions is of great significance. As an important place for people's lives and activities, indoor spaces contain a large number of home textiles, such as bedding, bathroom supplies, loungewear, sofas, curtains, and various fabrics. Microorganisms (including pathogenic bacteria, fungi, and viruses) easily adhere to the surfaces of these textiles. Due to their prominent reproductive capacity, survival ability, and transmissibility, these microorganisms greatly increase the spread of pathogens and the harm to human health. Therefore, developing home textiles with highly efficient antibacterial, antiviral, and green functions has significant research and development value and social significance.

[0003] Currently, various chemical disinfection and radiation sterilization methods are used for deep cleaning of object surfaces or living spaces. However, this requires labor input and strict adherence to operating procedures. These methods may cause damage to human cells and environmental pollution, and their effectiveness is short-lived. Traditional antibacterial products mainly involve adding antibacterial agents, but chemical antibacterial agents have a series of problems such as narrow antibacterial spectrum, large dosage, and safety concerns. Currently, the main approaches to endowing traditional textile surfaces with antimicrobial properties using antibacterial technology focus on two aspects: surface loading of metal (Ag or Cu) or various metal oxide nanoparticles, and surface grafting or embedding of antibacterial compounds, such as quaternary ammonium compounds and quaternary phosphorus compounds. However, under certain conditions, pathogens can develop tolerance to the toxicity of metal nanoparticles, and these metals can enter our environment and then pose a serious threat to human survival through bioaccumulation in the food chain. Similarly, quaternary ammonium compounds can also have similar negative environmental impacts. In addition, metals (oxides) and quaternary ammonium salts dissolve negatively charged cell membranes by disrupting cell structures or through electrostatic interactions. These two mechanisms are effective only for enveloped viruses with phospholipid membranes covering their surfaces, and are ineffective for non-enveloped viruses.

[0004] In recent years, research on photodynamic antibacterial technology has begun both domestically and internationally. This technology utilizes the conversion of light energy into chemical energy for antibacterial purposes. Current research primarily focuses on using photocatalysts for antibacterial disinfection under ultraviolet light. Japan is a leading country in this field, with Toshiba developing a new generation of advanced photocatalyst products, photodynamic functional fibers, and promoting the slogan "Wherever there is light, there is sterilization," which has had a significant impact. Photodynamic materials, represented by titanium dioxide, are widely used in antibacterial and indoor environmental purification research due to their excellent photocatalytic oxidation properties. These materials are deposited or composited onto textile substrates using methods such as finishing, magnetron sputtering, and surface grafting polymerization. However, photocatalysts, represented by titanium dioxide, have several problems in textiles. First, their spectral utilization is low, mainly operating in the ultraviolet region, resulting in a narrow spectrum and low antibacterial efficiency. Second, they cannot permanently adhere to fiber surfaces, requiring coatings or other methods for application, leading to poor wear and wash resistance, a poor hand feel, and low product quality. Some research has extended their spectrum to the visible spectrum region, but the efficiency and effectiveness remain low.

[0005] Utilizing sunlight for antibacterial and antiviral treatments offers a series of advantages compared to traditional chemical antibacterial agents. Chemical antibacterial agents suffer from a range of problems, including narrow antibacterial spectrum, high dosage requirements, and safety concerns. Photodynamic therapy generates free radicals on material surfaces, enabling highly efficient antibacterial and antiviral activity, representing a significant direction for functional product development. The target product of this project is a light-driven, highly efficient, broad-spectrum antibacterial and antiviral healthy home textile that effectively exerts its antibacterial effect, thereby meeting people's pursuit of healthy, safe, green, and environmentally friendly home textiles. The promotion of this technology will significantly enhance the technological level and core competitiveness of the home textile industry. Summary of the Invention

[0006] To address the problems of low spectral utilization, narrow effective spectral range, low antibacterial efficiency, low durability of photocatalysts on textiles, poor abrasion and washability, and poor hand feel in existing technologies, this invention prepares an antibacterial fabric with infrared light induction. It has high spectral utilization and strong antibacterial effect. Through improved finishing methods, the antibacterial material adheres to the fabric surface with high durability, abrasion and washability, and a good hand feel.

[0007] This invention proposes an infrared light-induced antibacterial fabric, characterized in that the preparation method of the infrared light-induced antibacterial fabric includes the following steps:

[0008] Step (1): Prepare phthalocyanine derivative photosensitive materials;

[0009] Step (2): Prepare an antibacterial material that can generate free radicals under light irradiation;

[0010] Step (3): Mix the materials prepared in steps (1) and (2) and prepare a finishing solution with infrared light-induced sterilization function;

[0011] Step (4) involves treating the cotton-containing fabric in the finishing solution described in step (3) to obtain the finished product of infrared light-induced antibacterial fabric.

[0012] The infrared light-induced antibacterial fabric proposed according to the present invention is characterized in that: the phthalocyanine derivative photosensitive material is tetrakis[N-hydroxyethyl-4-(N,N-dimethylpropanediamine)-1,8-naphthalimide]zinc phthalocyanine ZnPc-NA, and the antibacterial material capable of generating free radicals under light irradiation is 3,3',4,4'-benzophenone tetracarboxylic dianhydride BPTCD.

[0013] The infrared light-induced antibacterial fabric proposed according to the present invention is characterized in that: the concentration of ZnPc-NA in the finishing solution in step (4) is greater than or equal to 5 g / L, the concentration of BPTCD is greater than or equal to 5 g / L, and the mass ratio of ZnPc-NA to BPTCD added in the finishing solution is (1~5):4.

[0014] The method for preparing the ZnPc-NA in the infrared light-induced antibacterial fabric proposed according to the present invention includes:

[0015] Step a, Preparation of NA-OH: Pure 4-bromo-N-hydroxyethyl-1,8-naphthalenediamine was dissolved in 30 mL of ethylene glycol monomethyl ether, stirred and heated to reflux temperature; N,N'-dimethyl-1,3-propanediamine was added to the solution, and the reaction mixture was stirred at reflux temperature for 4 h; after completion, the resulting mixture was cooled to room temperature, washed with distilled water, and then extracted with dichloromethane. The organic layer was collected and dried with anhydrous Na2SO4, and then the solvent was evaporated under reduced pressure. The crude product was purified by recrystallization in a dichloromethane-ethyl acetate mixed solvent to obtain pure product NA-OH.

[0016] Step b, Preparation of NA-C: 4-nitrophthalonitrile, NA-OH, and anhydrous dimethylformamide were added to a reaction vessel, and then anhydrous potassium carbonate was added in batches. Under nitrogen protection, the mixture was stirred at 50°C for 45 hours. The mixture was then poured into 200 mL of ice water, the precipitated solid was filtered, and the solid was washed with water. The crude solid was recrystallized from ethanol to obtain pure yellow solid NA-C.

[0017] Step c, Preparation of ZnPc-NA: NA-C, zinc acetate dihydrate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and n-pentanol were refluxed under nitrogen protection for 24 h. After the reaction was completed, the mixture was cooled to room temperature, and then methanol was added. The resulting green precipitate was filtered and washed with methanol. The crude product was stirred in 1M hot hydrochloric acid and then stirred in hot sodium hydroxide solution. The residual solid was washed with boiling water, dried, and recrystallized with a DMF-CH2Cl2 mixed solvent to obtain the green solid ZnPc-NA.

[0018] The infrared light-induced antibacterial fabric proposed according to the present invention is characterized in that the finishing method in step (4) includes:

[0019] The fabric was placed in the finishing solution at 30°C and subjected to two dips and two nips, with a nipsing rate of 90%.

[0020] After removing them from the oven, heat them at a rate of 1℃ / min until they reach 130-170℃, hold for 60 minutes, and then cool them to room temperature.

[0021] This invention also proposes a method for preparing infrared light-induced antibacterial fabrics, characterized in that the preparation method includes the following steps:

[0022] Step (1): Prepare phthalocyanine derivative photosensitive materials;

[0023] Step (2): Prepare an antibacterial material that can generate free radicals under light irradiation;

[0024] Step (3): Mix the materials prepared in steps (1) and (2) and prepare a finishing solution with infrared light-induced sterilization function;

[0025] Step (4) involves treating the cotton-containing fabric in the finishing solution described in step (3) to obtain the finished product of infrared light-induced antibacterial fabric.

[0026] According to the above preparation method, the characteristic is that: the phthalocyanine derivative photosensitive material is tetrakis[N-hydroxyethyl-4-(N,N-dimethylpropanediamine)-1,8-naphthalimide]zinc phthalocyanine ZnPc-NA, and the antibacterial material that can generate free radicals under light irradiation is 3,3',4,4'-benzophenone tetracarboxylic dianhydride BPTCD.

[0027] According to the preparation method proposed in this invention, the concentration of ZnPc-NA in the finishing solution in step (4) is greater than or equal to 5 g / L, the concentration of BPTCD is greater than or equal to 5 g / L, and the mass ratio of ZnPc-NA to BPTCD added in the finishing solution is (1~5):4.

[0028] According to the preparation method proposed in this invention, the method for finishing in step (4) includes:

[0029] The fabric was placed in the finishing solution at 30°C and subjected to two dips and two nips, with a nipsing rate of 90%.

[0030] After removing them from the oven, heat them at a rate of 1℃ / min until they reach 130-170℃, hold for 60 minutes, and then cool them to room temperature.

[0031] According to the preparation method proposed in this invention, the fabric is a cotton-containing fabric.

[0032] According to the preparation method proposed in this invention, the finishing solution further includes sodium hypophosphite, and the concentration of sodium hypophosphite is 2 g / L.

[0033] The beneficial effects of this invention are as follows: A photosensitive material ZnPc-NA, a phthalocyanine derivative with near-infrared absorption, is prepared. ZnPc-NA absorbs near-infrared light, thereby photo-inducing BPTCD to achieve antibacterial activity, broadening the spectral range for inducing BPTCD to achieve antibacterial effects. A finishing solution with infrared light-induced bactericidal function is prepared by compounding ZnPc-NA and BPTCD, which is then applied to the fabric. The highly efficient near-infrared light-induced antibacterial function is achieved by adjusting the ratio of the two materials. Through optimized finishing processes, the bactericidal material exhibits high adhesion durability, good abrasion and wash resistance, and a pleasant hand feel, making it suitable for various applications requiring fabric sterilization. Attached Figure Description

[0034] Figure 1 Schematic diagram of the preparation of phthalocyanine derivative photosensitive materials

[0035] Figure 2 Effect of BPTCD concentration on hydroxyl radicals

[0036] Figure 3 Organize the process flow diagram Detailed Implementation

[0037] Example 1:

[0038] A simplified flowchart for preparing ZnPc-NA is attached. Figure 1 The specific method is as follows:

[0039] Step a, Preparation of NA-OH: Pure 4-bromo-N-hydroxyethyl-1,8-naphthalenediamine was dissolved in 30 mL of ethylene glycol monomethyl ether, stirred and heated to reflux temperature; N,N'-dimethyl-1,3-propanediamine was added to the solution, and the reaction mixture was stirred at reflux temperature for 4 h; after completion, the resulting mixture was cooled to room temperature, washed with distilled water, and then extracted with dichloromethane. The organic layer was collected and dried with anhydrous Na2SO4, and then the solvent was evaporated under reduced pressure. The crude product was purified by recrystallization in a dichloromethane-ethyl acetate mixed solvent to obtain pure product NA-OH.

[0040] Step b, Preparation of NA-C: 4-nitrophthalonitrile, NA-OH, and anhydrous dimethylformamide were added to a reaction vessel, and then anhydrous potassium carbonate was added in batches. Under nitrogen protection, the mixture was stirred at 50°C for 45 hours. The mixture was then poured into 200 mL of ice water, the precipitated solid was filtered, and the solid was washed with water. The crude solid was recrystallized from ethanol to obtain pure yellow solid NA-C.

[0041] Step c, Preparation of ZnPc-NA: NA-C, zinc acetate dihydrate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and n-pentanol were refluxed under nitrogen protection for 24 h. After the reaction was completed, the mixture was cooled to room temperature, and then methanol was added. The resulting green precipitate was filtered and washed with methanol. The crude product was stirred in 1M hot hydrochloric acid and then stirred in hot sodium hydroxide solution. The residual solid was washed with boiling water, dried, and recrystallized with a DMF-CH2Cl2 mixed solvent to obtain the green solid ZnPc-NA.

[0042] In the optimized scheme, in step a, the molar ratio of 4-bromo-N-hydroxyethyl-1,8-naphthalenediamine to N,N'-dimethyl-1,3-propanediamine is 1:5; the volume ratio of dichloromethane to ethyl acetate is 1:5; in step b, the mass ratio of 4-nitrophthalonitrile to NA-OH is 1:2; in step c, the molar ratio of NA-C, zinc acetate dihydrate, and DBU is 2:1:4, and the concentrations of hot hydrochloric acid and hot sodium hydroxide are both 1 mol / L.

[0043] The obtained ZnPc-NA photosensitive material exhibits near-infrared absorption and can emit various types of fluorescence under illumination.

[0044] Example 2:

[0045] The concentrations of p-nitrosodimethylaniline (p-NDA) were selected as 20 μmol / L, and the concentrations of BPTCD were 1 g / L, 5 g / L, 10 g / L, 20 g / L, and 30 g / L, respectively. The cotton fabric was subjected to two dips and two nips, with a nip-out rate of 90%. It was then dried at 90℃ for 3 min and baked at 160℃ for 3 min. A 3×3 cm sample was cut from the finished product.2 The sample was placed in a centrifuge tube containing 20 mL of the scavenging agent solution and irradiated under a 365 nm UV lamp for 60 min to investigate the effect of BPTCD concentration on the generation of hydroxyl radicals. The results are shown in [Figure number missing]. Figure 2 .

[0046] Depend on Figure 2 It can be seen that the amount of BPTCD material used increases with increasing concentration, and the amount of hydroxyl radicals generated also increases accordingly. When the BPTCD concentration increases to 20 g / L, the amount of free radicals generated does not change significantly. This may be because the fabric treated with 20 g / L can already generate a large amount of ·OH, and the quantitative p-NDA is completely reacted by the ·OH. With further increases in concentration, the content of ·OH cannot be detected further. Therefore, it is evident that fabrics made with BPTCD material under ultraviolet light can generate free radicals and have a strong bactericidal effect.

[0047] Example 3:

[0048] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The process flow is as follows: Figure 3 Specifically, ZnPc-NA and BPTCD are prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA is 0 g / L and the concentration of BPTCD is 20 g / L. The fabric is placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric is placed in an oven and heated at a rate of 1℃ / min until the temperature reaches 130℃. The temperature is maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0049] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0050] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0051] Example 4:

[0052] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 5 g / L and the concentration of BPTCD was 20 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0053] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0054] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0055] Example 5:

[0056] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 10 g / L and the concentration of BPTCD was 20 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0057] Take 3×3cm respectively 2Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0058] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0059] Example 6:

[0060] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 15 g / L and the concentration of BPTCD was 20 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0061] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0062] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0063] Example 7:

[0064] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 20 g / L and the concentration of BPTCD was 20 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0065] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0066] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0067] Example 8:

[0068] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 25 g / L and the concentration of BPTCD was 20 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0069] Take 3×3cm respectively 2Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0070] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0071] Example 9:

[0072] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 5 g / L and the concentration of BPTCD was 0 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0073] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution and the mixture was vigorously shaken for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37°C for 18 hours. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control. The bacterial reduction rate was calculated based on the number of colony-forming units on the agar plate according to the following formula:

[0074] Antibacterial rate (%) = (Number of colony-forming units in the dark sample - Number of colony-forming units in the light sample) / Number of colony-forming units in the dark sample.

[0075] The experimental results for each group in Examples 3-9 are shown in the table below:

[0076] ZnPc-NA concentration (g / L) BPTCD (g / L) <![CDATA[Inhibitory rate (Escherichia coli (10 5 CFU / mL) %)]]> Example 3 0 20 45.35 Example 4 5 20 95.78 Example 5 10 20 97.55 Example 6 15 20 99.99 Example 7 20 20 99.99 Example 8 25 20 99.99 Example 9 5 0 23.26

[0077] When the finishing solution contains neither ZnPc-NA nor BPTCD, the sterilization rate of the fabric under infrared light irradiation is poor. However, when the finishing solution contains both BPTCD and ZnPc-NA, the antibacterial rate is significantly improved, exceeding the effect of either alone. This demonstrates that the two substances can produce a synergistic effect to achieve a strong sterilization effect under infrared light induction. Furthermore, as the ZnPc-NA concentration increases, thanks to the synergistic effect of ZnPc-NA and BPTCD, it enhances the sterilization effect of the fabric under infrared light induction, improving the application wavelength range of the BPTCD photo-induced sterilization material. A sterilization rate of 99.99% is achieved when the ZnPc-NA concentration reaches 15 g / L.

[0078] Example 10:

[0079] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were prepared into a finishing solution at a certain concentration, wherein the concentration of ZnPc-NA was 15 g / L and the concentration of BPTCD was 20 g / L. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips with a nip-out rate of 90%. After removal, the fabric was placed in an oven and heated at a rate of 1℃ / min until the temperature reached 130℃. The temperature was maintained for 60 min and then cooled to room temperature to obtain the final fabric (modified fabric).

[0080] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution, followed by vigorous shaking of the mixture for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37 °C for 18 h. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control, and the inhibition rate was calculated.

[0081] Take another 3×3cm 2 The modified fabric was washed at room temperature and then dried at room temperature. After five washes and 5 dries, an antibacterial test was performed using the same procedure as described above. The durability of the modified fabric was evaluated by the degree of reduction in the antibacterial rate. A reduction of more than 10% in the antibacterial rate was considered unqualified, while a reduction of less than 10% was considered qualified.

[0082] Example 11:

[0083] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were mixed at a certain concentration to prepare the finishing solution, wherein the concentration of ZnPc-NA was 15 g / L, the concentration of BPTCD was 20 g / L, and the finishing solution also contained 2 g / L of sodium hypophosphite. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips, with a nipping rate of 90%. After removal, the fabric was placed in an oven, and the oven temperature was increased at a rate of 1℃ / min until it reached 130℃, which was maintained for 60 min. Then, the temperature was lowered to room temperature to obtain the final fabric (modified fabric).

[0084] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution, followed by vigorous shaking of the mixture for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37 °C for 18 h. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control, and the inhibition rate was calculated.

[0085] Take another 3×3cm 2 The modified fabric was washed at room temperature and then dried at room temperature. After five washes and 5 dries, an antibacterial test was performed using the same procedure as described above. The durability of the modified fabric was evaluated by the degree of reduction in the antibacterial rate. A reduction of more than 10% in the antibacterial rate was considered unqualified, while a reduction of less than 10% was considered qualified.

[0086] Example 12:

[0087] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were mixed at a certain concentration (ZnPc-NA concentration: 15 g / L, BPTCD concentration: 20 g / L), and the finishing solution also contained 2 g / L of sodium hypophosphite. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips, with a nipping rate of 90%. After removal, the fabric was placed in an oven, and the oven temperature was increased at a rate of 1℃ / min until it reached 140℃, which was maintained for 60 minutes. The temperature was then lowered to room temperature to obtain the final fabric (modified fabric).

[0088] Take 3×3cm respectively 2Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution, followed by vigorous shaking of the mixture for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37 °C for 18 h. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control, and the inhibition rate was calculated.

[0089] Take another 3×3cm 2 The modified fabric was washed at room temperature and then dried at room temperature. After five washes and 5 dries, an antibacterial test was performed using the same procedure as described above. The durability of the modified fabric was evaluated by the degree of reduction in the antibacterial rate. A reduction of more than 10% in the antibacterial rate was considered unqualified, while a reduction of less than 10% was considered qualified.

[0090] Example 13:

[0091] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were mixed at a certain concentration (ZnPc-NA concentration: 15 g / L, BPTCD concentration: 20 g / L), and the finishing solution also contained 2 g / L of sodium hypophosphite. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips, with a nipping rate of 90%. After removal, the fabric was placed in an oven, and the oven temperature was increased at a rate of 1℃ / min until it reached 150℃, which was maintained for 60 minutes. The temperature was then lowered to room temperature to obtain the final fabric (modified fabric).

[0092] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution, followed by vigorous shaking of the mixture for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37 °C for 18 h. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control, and the inhibition rate was calculated.

[0093] Take another 3×3cm 2The modified fabric was washed at room temperature and then dried at room temperature. After five washes and 5 dries, an antibacterial test was performed using the same procedure as described above. The durability of the modified fabric was evaluated by the degree of reduction in the antibacterial rate. A reduction of more than 10% in the antibacterial rate was considered unqualified, while a reduction of less than 10% was considered qualified.

[0094] Example 14:

[0095] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were mixed at a certain concentration (ZnPc-NA concentration: 15 g / L, BPTCD concentration: 20 g / L), and the finishing solution also contained 2 g / L of sodium hypophosphite. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips, with a nipping rate of 90%. After removal, the fabric was placed in an oven, and the oven temperature was increased at a rate of 1℃ / min until it reached 160℃, which was maintained for 60 minutes. The temperature was then lowered to room temperature to obtain the final fabric (modified fabric).

[0096] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution, followed by vigorous shaking of the mixture for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37 °C for 18 h. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control, and the inhibition rate was calculated.

[0097] Take another 3×3cm 2 The modified fabric was washed at room temperature and then dried at room temperature. After five washes and 5 dries, an antibacterial test was performed using the same procedure as described above. The durability of the modified fabric was evaluated by the degree of reduction in the antibacterial rate. A reduction of more than 10% in the antibacterial rate was considered unqualified, while a reduction of less than 10% was considered qualified.

[0098] Example 15:

[0099] A finishing solution with near-infrared light-induced bactericidal function was prepared for finishing fabrics. The specific method was as follows: ZnPc-NA and BPTCD were mixed at a certain concentration (ZnPc-NA concentration: 15 g / L, BPTCD concentration: 20 g / L), and the finishing solution also contained 2 g / L of sodium hypophosphite. The fabric was placed in the finishing solution at 30℃ and subjected to two dips and two nips, with a nipping rate of 90%. After removal, the fabric was placed in an oven, and the oven temperature was increased at a rate of 1℃ / min until it reached 160℃, which was maintained for 60 minutes. The temperature was then lowered to room temperature to obtain the final fabric (modified fabric).

[0100] Take 3×3cm respectively 2 Samples of both the original and modified fabrics were placed in separate sterile petri dishes and inoculated with 200 μL of diluted bacterial suspension. All samples were exposed to infrared light (780 nm) for 60 min, while control samples were covered and stored in the dark for the same duration. The fabrics were then immersed in 30 mL of sterile buffer solution, followed by vigorous shaking of the mixture for 1 minute. Aliquots of the mixture (0.1 mL each) were taken, diluted, and placed on agar plates and incubated at 37 °C for 18 h. The same test procedure was used for the bacterial solution of the unmodified cotton fabric as the original control, and the inhibition rate was calculated.

[0101] Take another 3×3cm 2 The modified fabric was washed at room temperature and then dried at room temperature. After five washes and 5 dries, an antibacterial test was performed using the same procedure as described above. The durability of the modified fabric was evaluated by the degree of reduction in the antibacterial rate. A reduction of more than 10% in the antibacterial rate was considered unqualified, while a reduction of less than 10% was considered qualified.

[0102] The test results of Examples 10-15 are shown in the table below:

[0103]

[0104] Compared with Example 11, Example 10's finishing solution contains sodium hypophosphite, which can promote the hydrolysis of BPTCD and promote its reaction with hydroxyl groups on cotton fabric to form ester bonds, thereby achieving cross-linking and better fixing to the fabric, increasing its durability and improving the hand feel.

[0105] As can be seen from Examples 11-15, fabrics with good sterilization effects can be obtained when the finishing temperature is increased from 130 degrees Celsius to 170 degrees Celsius, but the washability of the fabric is best when the finishing temperature is 130-160 degrees Celsius.

[0106] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims. The present invention illustrates the detailed process flow of the invention through the above embodiments, but the invention is not limited to the above process flow, i.e., it does not mean that the invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An infrared light-induced antibacterial fabric, characterized by, The preparation method of the infrared light-induced antibacterial fabric comprises the following steps: Step (1), preparing a phthalocyanine derivative photosensitive material; Step (2), preparing an antibacterial material capable of generating free radicals under the action of light; Step (3), mixing and formulating the materials prepared in steps (1) and (2) into a finishing liquid with infrared light-induced sterilization function; Step (4), finishing the cotton-containing fabric in the finishing liquid in step (3) to obtain an infrared light-induced antibacterial fabric product; The phthalocyanine derivative photosensitive material is zinc tetra [N-hydroxyethyl-4-(N,N-dimethylpropylenediamine)-1,8-naphthalimide] phthalocyanine ZnPc-NA, and the antibacterial material capable of generating free radicals under the action of light is 3,3',4,4'-benzophenone tetracarboxylic dianhydride BPTCD; The concentration of ZnPc-NA in the finishing liquid in step (4) is greater than or equal to 5 g / L, the concentration of BPTCD is greater than or equal to 5 g / L, and the mass ratio of ZnPc-NA to BPTCD added in the finishing liquid is (1-5):4; The finishing liquid further comprises sodium hypophosphite.

2. The infrared light-induced antibacterial fabric according to claim 1, wherein the preparation method of the ZnPc-NA comprises: Step a, preparing NA-OH: dissolve pure 4-bromo-N-hydroxyethyl-1,8-naphthalene dicarboxylic imide in 30 mL ethylene glycol monomethyl ether, stir and heat to reflux temperature; add N,N'-dimethyl-1,3-propanediamine to the solution, and stir the reaction mixture at reflux temperature for 4 h; after completion, cool the obtained mixture to room temperature, wash with distilled water, then extract with dichloromethane, collect the organic layer and dry with anhydrous Na2SO4, then evaporate the solvent under reduced pressure, and purify the crude product by recrystallization in a dichloromethane-ethyl acetate mixed solvent to obtain pure product NA-OH; Step b, preparing NA-C: add 4-nitrophthalonitrile, NA-OH, and anhydrous dimethylformamide to a reaction container, then add anhydrous potassium carbonate in batches, stir at 50°C for 45 hours under nitrogen protection, then pour the mixture into 200 mL ice water, filter the precipitated solid, and wash with water, recrystallize the crude solid with ethanol to obtain pure yellow solid NA-C; Step c, preparing ZnPc-NA: reflux react NA-C, zinc acetate dihydrate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and n-pentanol under nitrogen protection for 24 h, after the reaction is completed, cool the mixture to room temperature, then add methanol, filter the generated green precipitate, and wash with methanol, stir the obtained crude product with 1M hot hydrochloric acid, then stir in hot sodium hydroxide solution, wash the residual solid with boiling water, dry, and recrystallize with a DMF-CH2Cl2 mixed solvent to obtain green solid ZnPc-NA.

3. The infrared light-induced antibacterial fabric according to claim 1, wherein, The finishing method in step (4) comprises: Place the fabric in the finishing liquid at a temperature of 30°C, and perform double-dipping and double-padding with a pick-up rate of 90%. After taking out, the sample is placed in an oven, and the oven is heated at a heating rate of 1℃ / min until the temperature reaches 130-170℃, and then kept for 60 min, and then cooled to room temperature.

4. A method for preparing an infrared light-induced antibacterial fabric, characterized by, The preparation method comprises the following steps: Step (1), preparing a phthalocyanine derivative photosensitive material; Step (2), preparing an antibacterial material capable of generating free radicals under the action of light; Step (3), mixing the materials prepared in steps (1) and (2) and preparing a finishing liquid; Step (4), finishing the cotton-containing fabric in the finishing liquid described in step (3) to obtain an infrared light-induced antibacterial fabric product; The phthalocyanine derivative photosensitive material is zinc phthalocyanine ZnPc-NA, and the antibacterial material capable of generating free radicals under the action of light is 3,3',4,4'-benzophenone tetracarboxylic dianhydride BPTCD. In the finishing liquid in step (4), the concentration of ZnPc-NA is greater than or equal to 5 g / L, the concentration of BPTCD is greater than or equal to 5 g / L, and the mass ratio of ZnPc-NA to BPTCD added in the finishing liquid is (1-5):

4. The finishing liquid further comprises sodium hypophosphite.

5. The production method according to claim 4, characterized by, The finishing method in step (4) comprises: The fabric is placed in the finishing liquid at a temperature of 30℃, and is subjected to two-dip-two-nip, with a pick-up rate of 90%; After taking out, the sample is placed in an oven, and the oven is heated at a heating rate of 1℃ / min until the temperature reaches 130-170℃, and then kept for 60 min, and then cooled to room temperature.

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