Preparation method of antibacterial fabric based on cationic phthalocyanine-benzophenone compound

Abstract

The invention discloses a preparation method of an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound. The method comprises the following steps: compounding a novel cationic photoactive compound with a phthalocyanine and benzophenone structure with an auxiliary agent to prepare a finishing working solution, and finishing the silk fabric by using the finishing working solution to develop a novel multifunctional high-grade silk product with anti-ultraviolet performance, photothermal conversion performance and photothermal and photodynamic synergistic antibacterial performance.

Description

Technical Field

[0001] The invention relates to a method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound, and belongs to the technical field of textile materials. Background Art

[0002] As people's awareness of health and hygiene increases, the demand for antibacterial materials in the fields of medical treatment, textiles, food packaging, etc. is growing rapidly. Silk, as a natural fiber, is widely used in the field of high-end textiles due to its excellent biocompatibility, breathability and comfort. However, silk itself lacks antibacterial properties, so the development of silk materials with antibacterial functions can significantly enhance its application value and market competitiveness. At present, there have been some studies on antibacterial silk fabrics, but most of them rely on the addition of nanomaterials, which may have toxic residues and environmental pollution problems. In addition, these modified silk fabrics often lose antibacterial agents due to physical friction and washing during long-term use, thereby weakening their antibacterial effects. How to enhance the antibacterial and UV protection properties of silk fabrics in a stable and non-toxic way while maintaining their soft and comfortable feel is a technical problem that needs to be solved urgently.

[0003] Photothermal therapy and photodynamic therapy are two new antibacterial technologies that have emerged in recent years. Photothermal therapy generates heat energy through light-induced materials, thereby destroying the living environment of bacteria; photodynamic therapy generates active oxygen species under light of a specific wavelength through photosensitizers to kill pathogenic microorganisms. Combining these two mechanisms in the same material can effectively enhance the antibacterial effect and reduce the risk of bacterial resistance. Phthalocyanine compounds have been widely studied due to their good optical properties and stability, and through structural modification, they can produce photothermal and photodynamic effects under visible or near-infrared light. The introduction of cationic groups can both increase their water solubility and enhance their interaction with negatively charged bacterial cell membranes, thereby improving the antibacterial effect. Benzophenone, as a type of photosensitizer, can effectively generate singlet oxygen, which forms a synergistic effect with the photothermal effect of phthalocyanine and greatly improves the antibacterial performance. Therefore, the introduction of cationic phthalocyanine-benzophenone compounds on natural silk can endow silk with multiple functions such as photothermal, antibacterial, and UV protection, which has broad application prospects and important social significance. Summary of the invention

[0004] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing a photothermal-photodynamic synergistic antibacterial silk multifunctional fabric based on a cationic phthalocyanine-benzophenone compound. By introducing a cationic phthalocyanine-benzophenone compound into a silk fabric, the photothermal and photodynamic properties thereof are utilized to give the fabric excellent antibacterial properties and photothermal conversion properties. The invention has a novel structure, a simple preparation method, is easy to operate, and does not require special equipment. The obtained silk fabric has excellent UV protection and high-efficiency, broad-spectrum antibacterial properties.

[0005] The technical solution adopted by the present invention to solve the technical problem is: a method for preparing antibacterial fabrics based on cationic phthalocyanine-benzophenone compounds, including the preparation of cationic phthalocyanine-benzophenone compound antibacterial finishing liquid and the finishing of silk fabrics. Specifically, the following steps are included:

[0006] (1) preparing a certain concentration of cationic phthalocyanine-benzophenone compound aqueous solution, adding a certain amount of penetrant, and adjusting the pH value of the solution with a small amount of acetic acid to obtain an antibacterial finishing working solution;

[0007] (2) using the antibacterial finishing working solution prepared in step (1) to perform padding, drying and baking treatments on the silk fabric;

[0008] (3) The fabric treated in the above step (2) is cold-washed, washed, dried, shaped, and stretched to obtain a new high-end silk multifunctional fabric with UV protection, photothermal conversion, and photothermal-photodynamic synergistic antibacterial properties.

[0009] The silk fabric in step (1) includes fibers, yarns, and fabrics.

[0010] In the step (1), the finishing working solution is composed of a cationic phthalocyanine-benzophenone compound aqueous solution, a penetrant and acetic acid.

[0011] The structure of the cationic phthalocyanine-benzophenone compound in step (1) is shown below.

[0012]

[0013] The antibacterial agent was provided by the National Dyeing and Finishing Engineering Center of Donghua University.

[0014] The penetrant in step (1) is JFC.

[0015] In the step (1), the concentration of the cationic phthalocyanine-benzophenone compound aqueous solution is 0.5 g / L to 40 g / L, the concentration of the penetrant is 1 to 5 g / L, and the pH value of the solution is adjusted to about 5.0 with acetic acid.

[0016] In the step (2), the fabric padding bath ratio is 1:10-50.

[0017] The dipping and rolling process in step (2) is one dipping and one rolling or two dipping and two rolling, and the rolling rate is 70-85%.

[0018] In the step (3), the drying temperature is 60-100° C. and the drying time is 1-5 min.

[0019] In the step (2), the baking temperature is 120-160° C. and the baking time is 1-3 minutes.

[0020] The anti-ultraviolet, photothermal and photodynamic synergistic antibacterial silk fabric can be used in the fields of daily life and medical materials.

[0021] The beneficial effects of the present invention are as follows: compared with the prior art, the method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound provided by the present invention has the following advantages:

[0022] (1) The antibacterial silk multifunctional fabric of the present invention has a novel structure and a simple preparation method, does not require the addition of other chemicals, is easy to operate, has no special requirements on the reaction equipment, is easy to meet the requirements of industrial production, and the raw materials used in the preparation process are all conventionally used and have not been processed in any way, so the cost is low;

[0023] (2) The antibacterial silk multifunctional fabric prepared by the present invention has good active oxygen generation ability and high-efficiency, long-lasting and broad-spectrum photodynamic antibacterial performance.

[0024] (3) The antibacterial silk multifunctional fabric prepared by the present invention also has excellent light-to-heat conversion performance;

[0025] (4) The antibacterial silk multifunctional fabric prepared by the present invention also has excellent ultraviolet protection function. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The light-to-heat conversion performance of the silk multifunctional fabrics of Examples 1 to 4;

[0027] Figure 2 The active oxygen generation performance of the silk multifunctional fabrics of Examples 1 to 4;

[0028] Figure 3 These are photos showing the antibacterial effects of the silk multifunctional fabric of Example 2 on Escherichia coli and Staphylococcus aureus under different lighting conditions. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example 1

[0031] Prepare 1000mL of 5.0g / L cationic phthalocyanine-benzophenone compound aqueous solution, add penetrant JFC at a concentration of 3.0g / L, and adjust the solution pH to about 5.0 with acetic acid. Cut 20g silk fabric, immerse the silk fabric in the phthalocyanine-benzophenone compound aqueous solution, immerse twice and roll twice, and the rolling rate is 75%. Dry at 80℃ for 3min, bake at 120℃ for 3min, wash with cold water, wash with water, dry at 60℃, and obtain silk multifunctional fabric after shaping and stenting.

[0032] Example 2

[0033] Prepare 200mL of 3.0g / L cationic phthalocyanine-benzophenone compound aqueous solution, add penetrant JFC at a concentration of 2.0g / L, and adjust the solution pH to about 5.0 with acetic acid. Cut 10g silk fabric, immerse the silk fabric in the phthalocyanine-benzophenone compound aqueous solution, immerse twice and roll twice, and the rolling rate is 80%. Dry at 70℃ for 5min, bake at 130℃ for 3min, wash with cold water, wash with water, dry at 60℃, and obtain silk multifunctional fabric after shaping and stenting.

[0034] Example 3

[0035] Prepare 500mL of 1.0g / L cationic phthalocyanine-benzophenone compound aqueous solution, add penetrant JFC at a concentration of 2.0g / L, and adjust the solution pH to about 5.0 with acetic acid. Cut 20g silk fabric, immerse the silk fabric in the phthalocyanine-benzophenone compound aqueous solution, immerse twice and roll twice, and the rolling rate is 70%. Dry at 80℃ for 3min, bake at 120℃ for 3min, wash with cold water, wash with water, dry at 60℃, and obtain silk multifunctional fabric after shaping and stenting.

[0036] Example 4

[0037] Prepare 200mL of 0.5g / L cationic phthalocyanine-benzophenone compound aqueous solution, add penetrant JFC at a concentration of 1.0g / L, and adjust the solution pH to about 5.0 with acetic acid. Cut 10g silk fabric, immerse the silk fabric in the phthalocyanine-benzophenone compound aqueous solution, immerse and roll, and the rolling rate is 85%. Dry at 60℃ for 5min, bake at 120℃ for 3min, wash with cold water, wash with water, dry at 60℃, and obtain silk multifunctional fabric after shaping and stenting.

[0038] Test Example 1

[0039] The silk multifunctional fabrics of Examples 1 to 4 were cut into square fabric samples with a side length of 3 cm and evenly spread on white A4 paper. In a closed light box, a FLIR thermal imager from Filier, USA, was used, and an 8W red light / ultraviolet light / visible light flashlight was used to illuminate the fabric samples for 5 minutes at a distance of 5 cm from the product, and the temperature changes of the fabric samples were recorded. The results are shown in the attached Figure 1 As can be seen from the figure, under the irradiation of red light, ultraviolet light and visible light, the temperature of the silk multifunctional fabrics of Examples 1 to 4 increased significantly, showing good light-to-heat conversion performance.

[0040] Test Example 2

[0041] The multifunctional silk fabrics of Examples 1 to 4 were tested for the generation of active oxygen. The generation of active oxygen of the antibacterial agent was detected by spectrophotometry.

[0042] The silk multifunctional fabrics of Examples 1 to 4 were cut into square fabric samples with a side length of 3 cm, and further shredded. 20 mL of a 20 μmol / L p-NDA solution and a 1 mmol / L L-histidine solution were added to a 50 mL centrifuge tube, and the shredded fabrics were added and placed in the prepared p-NDA and L-histidine solutions. Under different light sources, the absorbance of the solution at 438 nm was measured for different irradiation times, and the production of active oxygen was calculated according to the following formula.

[0043] ΔC=CC t

[0044] p-NDA bleaching rate = ΔC / C

[0045] Where C is the initial concentration of p-NDA, C t is the concentration of p-NDA remaining in the solution after 30 min of irradiation.

[0046] See attached for the results Figure 2 As can be seen from the figure, the silk multifunctional fabrics of Examples 1 to 4 can generate a large amount of active oxygen free radicals under the irradiation of red light, ultraviolet light and visible light.

[0047] Test Example 3

[0048] The antibacterial properties of the silk multifunctional fabric of Example 2 were measured by the oscillation method according to the AATCC100-2012 standard. A square fabric with a side length of 2.5 cm was placed on LB medium and inoculated with 0.1 mL of 10 5 -10 6 (CFU) / mL of Escherichia coli solution and Staphylococcus aureus solution, wait until the bacterial solution completely wets the fabric, and place the fabric under ultraviolet light, red light, visible light, and darkness for 30 minutes. After 30 minutes, immerse the fabric in 0.9mL buffer and shake for 3 minutes, then take out 0.1mL from these solutions. Dilute 10, 10 2 , 10 3 After folding, drop them on different areas of the agar plate and then culture them at 37°C for 10 hours. The final bacterial reduction number can be calculated based on the number of surviving bacterial colonies on the agar plate according to the following formula:

[0049] Bacterial reduction percentage (%) = (BA) / B*100

[0050] Where B is the number of bacteria on the blank agar plate, and A is the number of colonies on the agar plates of other samples.

[0051] The antibacterial rate data are shown in Table 1, and the antibacterial photos are shown in Figure 3 .

[0052] Table 1 Antibacterial rate of the silk multifunctional fabric of Example 2 against Escherichia coli and Staphylococcus aureus under different illumination

[0053]

[0054] The antibacterial rate of the silk multifunctional fabric of Example 2 against Escherichia coli is 69.09% under dark conditions, and the antibacterial rate against Staphylococcus aureus is 85.45%. After irradiation with red light, ultraviolet light and visible light for 30 minutes, the antibacterial rate of the silk multifunctional fabric of Example 2 against Escherichia coli and Staphylococcus aureus can reach 99.99%. And compared with the unfinished silk, the antibacterial performance is significantly improved. The test data show that the silk multifunctional fabric based on cationic phthalocyanine-benzophenone compounds in the present invention has good photodynamic antibacterial performance.

[0055] Test Example 4

[0056] According to GB / T18830-2002 "Evaluation of UV Protection Performance of Textiles", the UV protection performance of the silk multifunctional fabrics of Examples 1 to 4 was tested using a UV protection transmission and sun protection tester, and the UV protection factor UPF value, T (UVA), and T (UVB) values ​​were used to represent the test results. See Table 2.

[0057] Table 2 UV protection performance of the silk multifunctional fabrics of Examples 1 to 4

[0058] Silk fabric Example 1 Example 2 Example 3 Example 4 UPF 251 162 124 85 T(UVA) 1.29％ 1.72％ 2.15％ 2.49％ T(UVB) 0.34％ 0.51％ 0.76％ 0.86％

[0059] It can be seen from the data in Table 2 that the UPF values ​​of the silk multifunctional fabrics of Examples 1 to 4 are all above 85, and the T(UVA) and T(UVB) values ​​are both low, indicating that the silk multifunctional fabrics in the present invention have the performance of protecting against ultraviolet radiation.

Claims

1. A method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound, characterized in that: The preparation method includes the preparation of a cationic phthalocyanine-benzophenone compound antibacterial finishing liquid and the finishing of silk fabrics by the liquid; specifically, the following steps: 1) preparing a certain concentration of a cationic phthalocyanine-benzophenone compound aqueous solution, adding a certain amount of a penetrant, and adjusting the pH value of the solution with a small amount of acetic acid to obtain an antibacterial finishing working solution; 2) using the antibacterial finishing solution prepared in step 1) to pad, dry, and bake the silk fabric; 3) The fabric treated in step 2) is cold-washed, washed, dried, shaped, and stretched to obtain a multifunctional silk fabric with UV protection, photothermal conversion, and photothermal-photodynamic synergistic antibacterial properties.

2. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 1, characterized in that: The silk fabrics include fibers, yarns and fabrics.

3. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 1, characterized in that: The antibacterial finishing working solution in step 1) is composed of a cationic phthalocyanine-benzophenone compound aqueous solution, a penetrant and acetic acid.

4. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 3, characterized in that: The structure of the cationic phthalocyanine-benzophenone compound in step 1) is shown below:

5. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 3, characterized in that: In the step 1), the penetrant is JFC.

6. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 3, characterized in that: In step 1), the concentration of the cationic phthalocyanine-benzophenone compound aqueous solution is 0.5 g / L to 40 g / L, the concentration of the penetrant is 1 to 5 g / L, and the pH value of the solution is adjusted to about 5.0 with acetic acid.

7. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 1, characterized in that: In the step 2), the fabric padding bath ratio is 1:10-50.

8. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 1, characterized in that: In the step 2), the dipping and rolling process is one dipping and one rolling or two dipping and two rolling, and the rolling rate is 70-85%.

9. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 1, characterized in that: In the step 2), the baking temperature is 120-160° C., and the baking time is 1-3 minutes; in the step 3), the drying temperature is 60-100° C., and the drying time is 1-5 minutes.

10. The method for preparing an antibacterial fabric based on a cationic phthalocyanine-benzophenone compound according to claim 1, characterized in that: The anti-ultraviolet, photothermal and photodynamic synergistic antibacterial silk fabric is used in the fields of daily life and medical materials.

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