An antibacterial method for apparel fabric

Abstract

The application relates to the technical field of clothing fabric, and discloses an antibacterial method for clothing fabric, which uses 4-aldehyde-3-hydroxyphenyl acrylate and 2-amino-5-sulfhydryl-1, 3, 4-thiadiazole as raw materials to synthesize a Schiff base compound, grafts and modifies the Schiff base compound containing an alkenyl group on terylene fabric, introduces a salicylaldehyde Schiff base and a sulfhydryl triazole structure on the surface of the terylene fabric, coordinates and complexes a large amount of silver ions on the surface of the terylene fabric, and then reduces a large amount of nano silver on the surface of the fabric. The nano silver realizes a higher bacteriostatic rate on escherichia coli and staphylococcus aureus, achieves better antibacterial performance, significantly improves the bacteriostatic rate of the fabric on the escherichia coli and the staphylococcus aureus, and the nano silver is tightly attached to the surface of the fabric through coordination, does not fall off during washing, still has a high bacteriostatic rate on the escherichia coli and the staphylococcus aureus, and realizes high washing resistance.

Description

Technical Field

[0001] This invention relates to the field of clothing fabric technology, specifically to an antibacterial method for clothing fabrics. Background Technology

[0002] Polyester is the most widely used and lowest-cost chemical fiber, and it has always been a major focus of research and development in new fiber materials. Encouraged by relevant national industry policies, the domestic polyester fiber manufacturing industry has flourished. Polyester is a condensation polymer of terephthalic acid and ethylene glycol, scientifically known as polyethylene terephthalate fiber, and is one of the most widely used synthetic fibers. Polyester has high strength, good elasticity, excellent wrinkle resistance and shape retention, making fabrics strong, durable, wrinkle-resistant, and easy to care for. It is mainly used in textiles such as clothing, interior decoration fabrics, and carpets. However, polyester itself has poor moisture absorption and breathability, which easily leads to sweat retention, providing a breeding ground for microorganisms (such as bacteria and fungi), thus producing odors, triggering allergies, and even accelerating material degradation.

[0003] In modern life, the demand for textiles with durable and highly effective antibacterial properties is increasing, especially in the fields of intimate apparel, medical protective clothing, and sportswear. The growth of microorganisms (such as Escherichia coli and Staphylococcus aureus) not only leads to odors and degradation in fabrics but can also pose health risks. Among numerous antibacterial agents, nano-silver is considered a promising option due to its broad-spectrum antibacterial properties, low drug resistance, and ability to destroy multiple targets of microbial cells. Traditional nano-silver loading methods (such as physical adsorption and coating) often suffer from drawbacks such as weak binding force, uneven distribution, and poor wash resistance.

[0004] Schiff bases, formed by the condensation of an aldehyde group and an amino group (-C=N-), are a class of organic ligands with excellent coordination ability. The nitrogen, oxygen, sulfur, and other heteroatoms in their structure can form stable coordination complexes with various metal ions (including Ag). This coordination not only enables high-density adsorption of silver ions, but also makes Schiff base silver and other metal complexes widely used in antibacterial applications in fiber fabrics, plastics, and other materials. Summary of the Invention

[0005] (a) Technical problems to be solved:

[0006] In view of the shortcomings of the prior art, the present invention provides an antibacterial method for clothing fabrics, which solves the problems of poor antibacterial properties and low washability of clothing fabrics.

[0007] (II) Technical Solution:

[0008] An antibacterial method for use in clothing fabrics is as follows:

[0009] Step (1): Add polyester fabric and m-cresol to the flask, with a bath ratio of 1:(10-15), heat to 40-50℃, swell for 3-5 hours, filter, wash with water, and bake to obtain swollen polyester fabric.

[0010] Step (2): Add 4-aldehyde-3-hydroxyphenyl acrylate, 2-amino-5-mercapto-1,3,4-thiadiazole, and ethanol to a flask equipped with a reflux condenser. Heat to 70-80℃ and react for 2-3 hours. Distill under reduced pressure until a precipitate forms. Filter and recrystallize the precipitate in ethanol to obtain a Schiff base compound. The synthetic reaction formula for the Schiff base compound is:

[0011]

[0012] Step (3): Under a nitrogen atmosphere, add Schiff base compound, benzoyl peroxide, Pingping O-20 and water to the flask, mix well, add the swollen polyester fabric, heat to 70-85℃, react for 3-5 hours, wash the fabric with boiling water, dry, and obtain the modified polyester fabric.

[0013] Step (4): Add silver nitrate, ascorbic acid, and sodium dodecyl sulfonate to water, stir, add modified polyester fabric, heat to 35-45℃, react for 5-8 hours, filter, wash with water, pre-dry at 100-120℃ for 20-30 minutes, bake at 160-180℃ for 5-10 minutes to obtain antibacterial clothing fabric.

[0014] Furthermore, in step (2), the molar ratio of 4-aldehyde-3-hydroxyphenyl acrylate and 2-amino-5-mercapto-1,3,4-thiadiazole is 1:(1.6-2).

[0015] Furthermore, in step (3), the ratio of Schiff base compound, benzoyl peroxide, phenoxylate O-20, and water is (120-250)g:(1.4-2)g:(5-15):1L.

[0016] Furthermore, in step (4), the ratio of silver nitrate, ascorbic acid, sodium dodecyl sulfonate, and water is (8-15)g:(15-32)g:(0.5-1)g:1L.

[0017] (III) Beneficial Technical Effects:

[0018] Using benzoyl peroxide as an initiator, a Schiff base compound containing an alkenyl group was grafted onto polyester fabric to modify it. This introduced salicylaldehyde Schiff base and mercaptotriazole structures onto the polyester fabric surface, exhibiting strong coordination with silver ions. A large number of silver ions were then coordinated and complexed onto the polyester fabric surface, subsequently reducing to generate a large amount of nano-silver. Nano-silver inhibits cell wall synthesis, membrane transport, nucleic acid synthesis, and electron transport processes by disrupting bacterial cell membranes and penetrating into the cells to bind to the sulfhydryl groups of enzymes, nucleic acids, and proteins. This leads to lipid, protein, and DNA damage, achieving a high antibacterial rate against *Escherichia coli* and *Staphylococcus aureus*, resulting in superior antibacterial performance. The fabric's antibacterial rate against these bacteria was significantly improved. Furthermore, the nano-silver adhered tightly to the fabric surface through coordination and did not detach during washing. After 30 washes, the fabric still maintained a high antibacterial rate against *E. coli* and *Staphylococcus aureus*, demonstrating high wash resistance. Detailed Implementation

[0019] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0020] According to the journal Chem. Commun. 2013, 49, 4833, the paper "A reusable nanofibrous film chemosensor for highly selective and sensitive optical signaling of Cu 2+ 4-Aldehyde-3-hydroxyphenyl acrylate was prepared by the method described in "inaqueous media": 6.90 g of 2,4-dihydroxybenzaldehyde, 6.8 mL of triethylamine, and 1.50 g of hydroxyquinone were added to 500 mL of 2-tert-butanone. 4.5 mL of acryloyl chloride was added dropwise at 0 °C, and the mixture was stirred at 25 °C for 2 h. The mixture was filtered, the filtrate was washed with water, dried over anhydrous MgSO4, rotary evaporated, and recrystallized in an aqueous ethanol solution to obtain 4-aldehyde-3-hydroxyphenyl acrylate.

[0021] Example 1:

[0022] Step (1): Add 1 kg of polyester fabric and 15 L of m-cresol to the flask, heat to 40°C, swell for 5 h, filter, wash with water, and bake to obtain swollen polyester fabric.

[0023] Step (2): Add 1.2 mol of 4-aldehyde-3-hydroxyphenyl acrylate, 1.92 mol of 2-amino-5-mercapto-1,3,4-thiadiazole (CAS No. 2349-67-9), and 3 L of ethanol to a flask equipped with a reflux condenser. Heat to 80 °C and react for 3 h. Distill under reduced pressure until a large amount of precipitate is formed. Filter and recrystallize the precipitate in ethanol to obtain a Schiff base compound.

[0024] Step (3): Under a nitrogen atmosphere, add 216g Schiff base compound, 3g benzoyl peroxide, 14g Pingpingjia O-20 and 1.8L water to a flask, mix well, add the swollen polyester fabric, the bath ratio is 1:30, heat to 80℃, react for 4h, wash the fabric with boiling water, dry, and obtain the modified polyester fabric.

[0025] Step (4): Add 80g silver nitrate, 260g ascorbic acid and 5g sodium dodecyl sulfonate to 10L of water, stir and then add modified polyester fabric. The bath ratio is 1:30. Heat to 40℃ and react for 6 hours. Filter, wash with water, pre-dry at 110℃ for 20 minutes, and bake at 160℃ for 10 minutes to obtain antibacterial clothing fabric.

[0026] Example 2:

[0027] Step (1): Add 1 kg of polyester fabric and 10 L of m-cresol to the flask, heat to 50°C, swell for 3 hours, filter, wash with water, and bake to obtain swollen polyester fabric.

[0028] Step (2): Add 1.2 mol of 4-aldehyde-3-hydroxyphenyl acrylate, 2.4 mol of 2-amino-5-mercapto-1,3,4-thiadiazole (CAS No. 2349-67-9), and 5 L of ethanol to a flask equipped with a reflux condenser. Heat to 70 °C and react for 2 h. Distill under reduced pressure until a large amount of precipitate is formed. Filter and recrystallize the precipitate in ethanol to obtain a Schiff base compound.

[0029] Step (3): Under a nitrogen atmosphere, add 294g Schiff base compound, 2.5g benzoyl peroxide, 20g Pingpingjia O-20 and 1.8L water to a flask, mix well, add swollen polyester fabric, the bath ratio is 1:40, heat to 70℃, react for 5h, wash the fabric with boiling water, dry, and obtain modified polyester fabric.

[0030] Step (4): Add 104g silver nitrate, 150g ascorbic acid, and 8g sodium dodecyl sulfonate to 10L of water, stir, add modified polyester fabric, bath ratio of 1:40, heat to 35℃, react for 8h, filter, wash with water, pre-dry at 100℃ for 30min, bake at 180℃ for 5min to obtain antibacterial clothing fabric.

[0031] Example 3:

[0032] Step (1): Under a nitrogen atmosphere, add 372g of Schiff base compound (obtained by the preparation method in Example 1), 3.6g of benzoyl peroxide, 9g of Pingpingjia O-20, and 1.8L of water to a flask, mix well, add the swollen polyester fabric, the bath ratio is 1:30, heat to 85°C, react for 3h, wash the fabric with boiling water, and dry to obtain the modified polyester fabric.

[0033] Step (2): Add 126g silver nitrate, 320g ascorbic acid, and 10g sodium dodecyl sulfonate to 10L of water, stir, add modified polyester fabric, bath ratio of 1:30, heat to 45℃, react for 5h, filter, wash with water, pre-dry at 120℃ for 20min, bake at 160℃ for 5min to obtain antibacterial clothing fabric.

[0034] Example 4:

[0035] Step (1): Under a nitrogen atmosphere, add 450g of Schiff base compound (obtained by the preparation method in Example 1), 3.6g of benzoyl peroxide, 27g of Pingpingjia O-20, and 1.8L of water to a flask, mix well, add the swollen polyester fabric, the bath ratio is 1:40, heat to 80℃, react for 4h, wash the fabric with boiling water, dry, and obtain the modified polyester fabric.

[0036] Step (2): Add 150g silver nitrate, 280g ascorbic acid, and 6g sodium dodecyl sulfonate to 10L of water, stir, add modified polyester fabric, bath ratio is 1:40, heat to 45℃, react for 6h, filter, wash with water, pre-dry at 100℃ for 30min, bake at 180℃ for 10min to obtain antibacterial clothing fabric.

[0037] Comparative Example 1 differs from Example 1 in that it does not use Schiff base compounds to graft and modify the polyester fabric.

[0038] Step (1): Add 80g silver nitrate, 260g ascorbic acid and 5g sodium dodecyl sulfonate to 10L of water, stir and then add polyester fabric. The bath ratio is 1:30. Heat to 40℃ and react for 6 hours. Filter, wash with water, pre-dry at 110℃ for 20 minutes, and bake at 160℃ for 10 minutes to obtain clothing fabric.

[0039] Comparative Example 2 differs from Example 1 in that nano-silver is not added to the fabric.

[0040] Step (1): Under a nitrogen atmosphere, add 216g of Schiff base compound (obtained by the preparation method in Example 1), 3g of benzoyl peroxide, 14g of Pingpingjia O-20, and 1.8L of water to a flask, mix well, add the swollen polyester fabric, the bath ratio is 1:30, heat to 80℃, react for 4h, wash the fabric with boiling water, and dry to obtain the modified polyester fabric.

[0041] Comparative Example 3 differs from Example 1 in that 4-aldehyde-3-hydroxyphenyl acrylate is used instead of the Schiff base compound.

[0042] Step (1): Under a nitrogen atmosphere, add 216g of 4-aldehyde-3-hydroxyphenyl acrylate, 3g of benzoyl peroxide, 14g of Pingpingjia O-20, and 1.8L of water to a flask, mix well, add the swollen polyester fabric, the bath ratio is 1:30, heat to 80℃, react for 4h, wash the fabric with boiling water, and dry to obtain the modified polyester fabric.

[0043] Step (2): Add 80g silver nitrate, 260g ascorbic acid and 5g sodium dodecyl sulfonate to 10L of water, stir and then add modified polyester fabric. The bath ratio is 1:30. Heat to 40℃ and react for 6 hours. Filter, wash with water, pre-dry at 110℃ for 20 minutes, and bake at 160℃ for 10 minutes to obtain the clothing fabric.

[0044] Following the method in GB / T 20944.3-2008, *Escherichia coli* and *Staphylococcus aureus* strains were selected, and the antibacterial properties of the clothing fabric were determined using the shaking method. Antibacterial rate = (W...) t -Q t ) / W t ×100%, W t Q represents the average active concentration (CFU / mL) in the flasks after 18 hours of shaking contact with three control samples. t The average concentration of viable bacteria (CFU / m³) in the flasks after 18 hours of shaking contact with three clothing fabric samples was recorded, with ordinary polyester fabric used as a control sample.

[0045] Wash the garment fabric 30 times according to the method standard of GB / T 8629-2017, and then test its antibacterial properties.

[0046] Table 1 Antibacterial rate of clothing fabrics

[0047]

[0048]

[0049] Compared to Comparative Example 1, the antibacterial clothing fabrics of Examples 1-4 were modified with Schiff base compounds and incorporated nano-silver. After modification of the polyester fabric with Schiff base compounds, salicylaldehyde Schiff base and mercaptotriazole structures were introduced onto the polyester fiber surface, exhibiting a strong coordination effect on silver ions. This resulted in a large number of silver ions being coordinated and complexed onto the polyester fabric surface, subsequently reducing to generate a large amount of nano-silver. Nano-silver inhibits cell wall synthesis, membrane transport, nucleic acid synthesis, and electron transport processes by disrupting bacterial cell membranes and penetrating into the cells to bind with the sulfhydryl groups of enzymes, nucleic acids, and proteins. This leads to lipid, protein, and DNA damage, achieving a high antibacterial rate against *Escherichia coli* and *Staphylococcus aureus*, thus achieving good antibacterial performance. The fabric's antibacterial rate against *E. coli* and *Staphylococcus aureus* was significantly improved. Furthermore, the nano-silver adhered tightly to the fabric surface through coordination and did not detach during washing. After 30 washes, the fabric still maintained a high antibacterial rate against *E. coli* and *Staphylococcus aureus*, achieving high wash resistance.

[0050] Comparative Example 2 did not use Schiff base compounds to modify the polyester fabric. Only a small amount of silver ions and nano silver adhered to the polyester surface, and the nano silver was easy to wash off, resulting in a low antibacterial rate of the fabric before and after washing.

[0051] The clothing fabric in Comparative Example 3 did not incorporate nano-silver, resulting in poor antibacterial properties.

[0052] Comparative Example 4 uses 4-aldehyde-3-hydroxyphenyl acrylate to graft and modify polyester fabric. Since it does not contain salicylaldehyde Schiff base and mercaptotriazole structure, it has a low coordination effect on silver ions, making it difficult to coordinate and complex a large number of silver ions onto the surface of polyester fabric, resulting in low antibacterial rate of the fabric before and after washing.

[0053] The above description is only a preferred embodiment of the present invention, but the present invention is not limited to the scope of implementation shown. Any changes made in accordance with the concept of the present invention, or equivalent embodiments modified to have equivalent changes, shall be within the protection scope of the present invention as long as they do not exceed the spirit covered by the specification.

Claims

1. An antibacterial method for clothing fabrics, characterized in that, The antibacterial method: Step (1): Under a nitrogen atmosphere, add Schiff base compound, benzoyl peroxide, Pingping O-20 and water to the flask, mix well, add the swollen polyester fabric, wash the fabric with boiling water after the reaction, and dry it to obtain the modified polyester fabric. The structural formula of the Schiff base compound is: Step (2): Add silver nitrate, ascorbic acid, and sodium dodecyl sulfonate to water, stir, add modified polyester fabric, heat and stir to react, filter, wash, and bake to obtain antibacterial clothing fabric.

2. The antibacterial method for clothing fabrics according to claim 1, characterized in that, In step (1), the ratio of Schiff base compound, benzoyl peroxide, Pingpingjia O-20, and water is (120-250)g:(1.4-2)g:(5-15):1L.

3. The antibacterial method for clothing fabrics according to claim 1, characterized in that, The reaction temperature in step (1) is 70-85℃, and the reaction time is 3-5h.

4. The antibacterial method for clothing fabrics according to claim 1, characterized in that, The preparation method of the swelling polyester fabric in step (1) is as follows: add polyester fabric and m-cresol to a flask, with a bath ratio of 1:(10-15), heat to 40-50℃, swell for 3-5 hours, filter, wash with water, and bake to obtain the swelling polyester fabric.

5. The antibacterial method for clothing fabrics according to claim 1, characterized in that, In step (2), the ratio of silver nitrate, ascorbic acid, sodium dodecyl sulfonate, and water is (8-15)g:(15-32)g:(0.5-1)g:1L.

6. The antibacterial method for clothing fabrics according to claim 1, characterized in that, The heating temperature in step (2) is 35-45℃, and the reaction time is 5-8h.

7. The antibacterial method for clothing fabrics according to claim 1, characterized in that, The baking conditions for step (2) are: pre-baking at 100-120℃ for 20-30 minutes and baking at 160-180℃ for 5-10 minutes.

8. The antibacterial method for clothing fabrics according to claim 1, characterized in that, The Schiff base compound is prepared by adding 4-aldehyde-3-hydroxyphenyl acrylate, 2-amino-5-mercapto-1,3,4-thiadiazole, and ethanol to a flask equipped with a reflux condenser. The mixture is heated to react, and then distilled under reduced pressure until a precipitate is formed. The precipitate is filtered and recrystallized in ethanol to obtain the Schiff base compound.

9. The antibacterial method for clothing fabrics according to claim 8, characterized in that, The molar ratio of the 4-aldehyde-3-hydroxyphenyl acrylate and the 2-amino-5-mercapto-1,3,4-thiadiazole is 1:(1.6-2).

10. The antibacterial method for clothing fabrics according to claim 8, characterized in that, The heating temperature is 70-80℃, and the reaction time is 2-3 hours.

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