Skin-friendly antibacterial polyester blended fabric and preparation method thereof

Abstract

The application relates to the technical field of fabrics, and discloses a skin-friendly antibacterial polyester blended fabric and a preparation method thereof. 4-isothiazolinone formate-based phthalic anhydride and chitosan are reacted to obtain a chitosan antibacterial finishing agent, which is then added into water, stirred and dissolved to prepare a finishing liquid. The modal / polyester blended fabric is subjected to two-dip-two-roll treatment, pre-drying, baking, washing and drying to obtain the skin-friendly antibacterial polyester blended fabric. The finishing agent contains a chitosan biological macromolecule antibacterial agent and an isothiazolinone antibacterial group, so that better antibacterial performance is achieved. The finishing agent contains hydrophilic carboxyl groups, amide bonds, hydroxyl groups and other functional groups, so that the fabric has better moisture absorption performance and good water resistance.

Description

Technical Field

[0001] This invention relates to the field of fabric technology, specifically to a skin-friendly and antibacterial polyester blended fabric and its preparation method. Background Technology

[0002] Polyester fabric possesses excellent mechanical strength, elasticity, and heat resistance; however, its moisture absorption is poor. Modal fabric, primarily composed of regenerated cellulose fibers, offers superior moisture absorption, breathability, and wearing comfort. However, modal fabric is prone to absorbing moisture, easily harboring bacteria and microorganisms, and has poor antibacterial properties. Blending modal and polyester fibers can leverage the advantages of both, leading to its wide application in high-end apparel fabrics.

[0003] Finishing agents can impart unique antibacterial, moisture-wicking, and soft properties to fabrics. Chitosan is inexpensive, readily available, biocompatible, non-toxic, and environmentally friendly, and it also possesses good antibacterial and hydrophilic properties, making it widely applicable. Patent CN118422499B discloses a method of impregnating surface-activated polyester fabric with a hydroxypropyltrimethylammonium chloride chitosan solution, followed by atomized spraying with reactive biomass antistatic ink and plasma treatment. The resulting fabric exhibits good antistatic properties, but this patent does not improve the fabric's moisture-wicking and antibacterial properties. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention solves the problem of low antibacterial properties of fabrics such as modal and polyester.

[0005] The technical solution of this invention is: a method for preparing a skin-friendly and antibacterial polyester blended fabric. (1) Add solvent, 2-hydroxymethylisothiazolinone, and pyridine to the reaction flask, add trimellitic anhydride acyl chloride dropwise, filter after reaction, evaporate the filtrate by rotary evaporation, wash the product with petroleum ether, and then recrystallize in ethyl acetate to obtain 4-isothiazolinone carbamate phthalic anhydride, the reaction formula is: .

[0006] (2) Add acetic acid solution and chitosan to the reaction flask, stir to dissolve, then add dropwise an acetone solution containing 4-isothiazolinone carbamate phthalic anhydride. After stirring and reacting, pour the solution into ethanol for precipitation. Filter, wash the product with ethanol, and dry to obtain chitosan antibacterial finishing agent. The reaction formula is: .

[0007] (3) Add chitosan antibacterial finishing agent to water, stir to dissolve and make finishing solution, and perform two dips and two nips on modal / polyester blended fabric. After pre-drying, baking, washing and drying, skin-friendly antibacterial polyester blended fabric is obtained.

[0008] Preferably, the solvent in (1) is tetrahydrofuran or toluene.

[0009] Preferably, the reaction in (1) is carried out at 15-40℃ for 8-12 hours.

[0010] Preferably, the ratio of 2-hydroxymethylisothiazolinone, pyridine, and trimellitic anhydride acyl chloride in (1) is 1 mol: (1-1.2) mol: (1-1.1) mol.

[0011] Preferably, the mass fraction of the acetic acid solution in (2) is 2-3%.

[0012] Preferably, in (2), the ratio of chitosan to 4-isothiazolinone carbamate phthalic anhydride is 100g: (15-40)g.

[0013] Preferably, the reaction in (2) is carried out at 15-25℃ for 12-24h.

[0014] Preferably, the ratio of water to chitosan antibacterial finishing agent in (3) is 1L:(5-20)g.

[0015] Preferably, in (3), the residual rate of the two dips and two rolls is 70-85%.

[0016] (III) Beneficial technical effects: The anhydride group of 4-isothiazolinone carbamate phthalic anhydride reacts with the amino group of chitosan to undergo an amidation ring-opening reaction, generating amide bonds and carboxyl groups, to obtain a chitosan antibacterial finishing agent containing isothiazolinone. Then, the modal / polyester blended fabric is finished. The finishing agent contains chitosan biomacromolecule antibacterial agent, and at the same time, an isothiazolinone antibacterial group is introduced, which contains active NS bonds. It can react irreversibly with key enzymes and proteins containing sulfhydryl groups in bacterial microbial cells, causing enzyme inactivation and disrupting cell metabolism, ultimately leading to the death of microorganisms, thus achieving better antibacterial performance.

[0017] The chitosan finishing agent of the present invention contains hydrophilic carboxyl groups, amide bonds, hydroxyl groups and other functional groups, which can reduce the good water diffusion time of the fabric, make the fabric have better moisture absorption properties, improve the moisture permeability and cooling effect of the fabric, and improve the skin-friendliness and wearing comfort of the fabric.

[0018] The finishing agent of this invention contains benzoic acid ester groups similar to those of polyester, which gives the finishing agent a high affinity with blended fabrics. The carboxyl groups it contains can form hydrogen bonds with the hydroxyl groups of cellulose fibers in modal, improving the bonding force between the finishing agent and the fabric, making the finishing agent adhere more firmly to the fabric surface. After washing, the fabric also has a lower drip diffusion time, a higher antibacterial rate, and excellent water resistance. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0020] 2-Hydroxymethylisothiazolinone was prepared according to the method described in the journal article "Preparation and Application of Isothiazolinone Antibacterial Finishing Agents" (Volume 26, Issue 10) of the journal *Dyeing and Finishing Auxiliaries*. The structural formula is: .

[0021] Example 1: (1) Add 200 mL of toluene, 60 mmol of 2-hydroxymethylisothiazolinone, and 66 mmol of pyridine to the reaction flask, and add 60 mmol of trimellitic anhydride acyl chloride dropwise. Stir the reaction at 25 °C for 12 h, filter, evaporate the filtrate by rotary evaporation, wash the product with petroleum ether, and then recrystallize in ethyl acetate to obtain 4-isothiazolinone carbamate phthalic anhydride.

[0022] (2) Add 5L of 3% acetic acid solution and 100g of chitosan to the reaction flask, stir to dissolve, and then add 40mL of acetone solution containing 15g of 4-isothiazolinone carbamate phthalic anhydride. Stir the reaction at 20℃ for 12h, pour the solution into ethanol for precipitation, filter, wash the product with ethanol, and dry to obtain chitosan antibacterial finishing agent.

[0023] (3) Add 50g of chitosan antibacterial finishing agent to 10L of water, stir and dissolve to make finishing solution, and perform two dips and two nips on modal / polyester blended fabric (the blending ratio of modal and polyester is 70:30, the same below), with a nips rate of 80%; pre-dry at 9℃ for 3min, bake at 150℃ for 2min, wash with water and dry at 90℃ to obtain skin-friendly antibacterial polyester blended fabric.

[0024] Example 2: (1) Add 250 mL of tetrahydrofuran, 60 mmol of 2-hydroxymethylisothiazolinone, and 72 mmol of pyridine to the reaction flask, and add 60 mmol of trimellitic anhydride acyl chloride dropwise. Stir the reaction at 15 °C for 12 h, filter, evaporate the filtrate by rotary evaporation, wash the product with petroleum ether, and then recrystallize in ethyl acetate to obtain 4-isothiazolinone carbamate phthalic anhydride.

[0025] (2) Add 5L of 3% acetic acid solution and 100g of chitosan to the reaction flask, stir to dissolve, and then add 60mL of acetone solution containing 22g of 4-isothiazolinone carbamate phthalic anhydride. Stir the reaction at 20℃ for 18h, pour the solution into ethanol for precipitation, filter, wash the product with ethanol, and dry to obtain chitosan antibacterial finishing agent.

[0026] (3) Add 100g of chitosan antibacterial finishing agent to 10L of water, stir and dissolve to make finishing solution, and perform two dips and two nips on modal / polyester blended fabric with a nipsing rate of 85%; pre-dry at 90℃ for 2min, bake at 140℃ for 3min, wash with water and dry at 90℃ to obtain skin-friendly antibacterial polyester blended fabric.

[0027] Example 3: (1) Add 250 mL of toluene, 60 mmol of 2-hydroxymethylisothiazolinone, and 60 mmol of pyridine to the reaction flask, and add 60 mmol of trimellitic anhydride acyl chloride dropwise. Stir the reaction at 40 °C for 8 h. After filtration, evaporate the filtrate by rotary evaporation. Wash the product with petroleum ether and then recrystallize it in ethyl acetate to obtain 4-isothiazolinone carbamate phthalic anhydride.

[0028] (2) Add 6L of 2% acetic acid solution and 100g of chitosan to the reaction flask, stir to dissolve, and then add 80mL of acetone solution containing 30g of 4-isothiazolinone carbamate phthalic anhydride. Stir the reaction at 15℃ for 24h, pour the solution into ethanol for precipitation, filter, wash the product with ethanol, and dry to obtain chitosan antibacterial finishing agent.

[0029] (3) Add 150g of chitosan antibacterial finishing agent to 10L of water, stir and dissolve to make finishing solution, and perform two dips and two nips on modal / polyester blended fabric with a nipsing rate of 85%; pre-dry at 95℃ for 2min, bake at 140℃ for 3min, wash with water and dry at 90℃ to obtain skin-friendly antibacterial polyester blended fabric.

[0030] Example 4: (1) Add 250 mL of tetrahydrofuran, 60 mmol of 2-hydroxymethylisothiazolinone, and 60 mmol of pyridine to the reaction flask, and add 66 mmol of trimellitic anhydride acyl chloride dropwise. Stir the reaction at 30 °C for 10 h, filter, evaporate the filtrate by rotary evaporation, wash the product with petroleum ether, and then recrystallize in ethyl acetate to obtain 4-isothiazolinone carbamate phthalic anhydride.

[0031] (2) Add 6L of 2% acetic acid solution and 100g of chitosan to the reaction flask, stir to dissolve, and then add 100mL of acetone solution containing 40g of 4-isothiazolinone carbamate phthalic anhydride. Stir the reaction at 25℃ for 18h, pour the solution into ethanol for precipitation, filter, wash the product with ethanol, and dry to obtain chitosan antibacterial finishing agent.

[0032] (3) Add 200g of chitosan antibacterial finishing agent to 10L of water, stir and dissolve to make finishing solution, and perform two dips and two nips on modal / polyester blended fabric with a nips rate of 70%; pre-dry at 90℃ for 3min, bake at 150℃ for 2min, wash with water and dry at 90℃ to obtain skin-friendly antibacterial polyester blended fabric.

[0033] Comparative Example 1 is an unfinished modal / polyester blended fabric.

[0034] Comparative Example 2: (1) Add 50g of chitosan to 10L of water and stir to make a finishing solution. The Modal / polyester blended fabric (the blending ratio of Modal and polyester is 70:30, the same below) is subjected to two dips and two nips, with a nips rate of 80%. It is pre-dried at 9℃ for 3min, baked at 150℃ for 2min, washed with water and dried at 90℃ to obtain the polyester blended fabric.

[0035] Comparative Example 3: (1) Add 5L of 3% acetic acid solution and 100g of chitosan to the reaction flask, stir to dissolve, then add 40mL of acetone solution containing 15g of phthalic anhydride. Stir the reaction at 20℃ for 12h, pour the solution into ethanol for precipitation, filter, wash the product with ethanol, and dry to obtain chitosan finishing agent.

[0036] (2) Add 50g of chitosan finishing agent to 10L of water, stir and dissolve to make finishing solution, and perform two dip and two nibble treatment on modal / polyester blended fabric (the blending ratio of modal and polyester is 70:30, the same below), with a nibble rate of 80%; pre-dry at 9℃ for 3min, bake at 150℃ for 2min, wash with water and dry at 90℃ to obtain polyester blended fabric.

[0037] Comparative Example 4: (1) Mix 100g of chitosan and 30g of 2-hydroxymethylisothiazolinone to obtain chitosan-isothiazolinone antibacterial finishing agent.

[0038] (2) Add 150g of chitosan-isothiazolinone antibacterial finishing agent to 10L of water, stir to make finishing solution, and perform two dips and two nips on modal / polyester blended fabric with a nips rate of 85%; pre-dry at 95℃ for 2min, bake at 140℃ for 3min, wash with water and dry at 90℃ to obtain polyester blended fabric.

[0039] The water droplet diffusion time of the fabric was tested according to GB / T 21655.1-2023. The fabric was washed and dried 20 times according to GB / T 8629-2017, and then the water droplet diffusion time was tested again.

[0040] The antibacterial properties of the fabric were tested according to GB / T 20944.3-2008 standard, with Escherichia coli as the test strain. The fabric was washed and dried 20 times according to GB / T 8629-2017 method, and then the water droplet diffusion time was tested.

[0041] Table 1 Fabric Performance

[0042] Compared with the modal / polyester blended fabric of Comparative Example 1, Examples 1-4 used chitosan finishing agents to finish the blended fabrics. The finishing agents contained chitosan biomacromolecule antibacterial agents and introduced isothiazolinone antibacterial groups, which contain active NS bonds. These can undergo irreversible reactions with key enzymes and proteins containing sulfhydryl groups in bacterial microbial cells, causing enzyme inactivation and disrupting cell metabolism, ultimately leading to microbial death, thus achieving better antibacterial performance. In addition, the finishing agents contain hydrophilic carboxyl groups, amide bonds, hydroxyl groups, and other functional groups, which reduce the good water-drip diffusion time of the fabric and have better moisture absorption properties. Furthermore, the finishing agents contain benzoic acid ester groups similar to polyester, which gives the finishing agents a high affinity with the blended fabric. The carboxyl groups can form hydrogen bonds with the hydroxyl groups of cellulose fibers in modal, improving the binding force between the finishing agents and the fabric, making the finishing agents adhere more firmly to the fabric surface. After washing, the fabric also has a lower water-drip diffusion time, a higher antibacterial rate, and excellent water resistance.

[0043] Comparative Example 2's chitosan does not contain isothiazolinone antibacterial groups, hydrophilic carboxyl groups, amide bonds, etc., nor does it contain ester groups. The fabric has a longer drip diffusion time and a lower antibacterial rate. After washing, the fabric's drip diffusion time increases significantly, and the antibacterial rate decreases significantly. The finishing agent has poor water resistance.

[0044] Comparative Example 3 chitosan does not contain isothiazolinone antibacterial groups and has a low antibacterial rate.

[0045] Comparative Example 4 used a blend of chitosan and 2-hydroxymethylisothiazolinone as a finishing agent. 2-hydroxymethylisothiazolinone is a small molecule compound, which has poor adhesion to the fabric surface and is easily washed off, resulting in a significant decrease in antibacterial rate. Furthermore, the fabric exhibits a long water droplet diffusion time and poor moisture absorption.

[0046] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A skin-friendly and antibacterial polyester blended fabric, characterized in that, The raw materials of the skin-friendly antibacterial polyester blended fabric include modal / polyester blended fabric and chitosan antibacterial finishing agent; The preparation method of the chitosan antibacterial finishing agent is as follows: add acetic acid solution and chitosan to a reaction flask, stir to dissolve, then add dropwise an acetone solution containing 4-isothiazolinone carbamate phthalic anhydride, stir to react, pour the solution into ethanol for precipitation, filter, wash the product, and dry to obtain the chitosan antibacterial finishing agent.

2. The skin-friendly antibacterial polyester blended fabric according to claim 1, characterized in that, The acetic acid solution has a mass fraction of 2-3%.

3. The skin-friendly antibacterial polyester blended fabric according to claim 1, characterized in that, The ratio of chitosan to 4-isothiazolinone carbamate-phthalic anhydride is 100g:(15-40)g.

4. The skin-friendly antibacterial polyester blended fabric according to claim 1, characterized in that, The reaction was carried out at 15-25°C for 12-24 hours.

5. The skin-friendly antibacterial polyester blended fabric according to claim 1, characterized in that, The preparation method of the 4-isothiazolinone carbamate phthalic anhydride is as follows: add solvent, 2-hydroxymethylisothiazolinone, and pyridine to a reaction flask, add trimellitic anhydride acyl chloride dropwise, stir the reaction at 15-40℃ for 8-12 h, filter, evaporate the filtrate by rotary evaporation, wash the product and recrystallize to obtain 4-isothiazolinone carbamate phthalic anhydride.

6. The skin-friendly antibacterial polyester blended fabric according to claim 5, characterized in that, The solvent is tetrahydrofuran or toluene.

7. The skin-friendly antibacterial polyester blended fabric according to claim 5, characterized in that, The ratio of 2-hydroxymethylisothiazolinone, pyridine, and trimellitic anhydride acyl chloride is 1 mol: (1-1.2) mol: (1-1.1) mol.

8. A method for preparing a skin-friendly antibacterial polyester blended fabric as described in any one of claims 1-7, characterized in that, The preparation method is as follows: chitosan antibacterial finishing agent is added to water, stirred and dissolved to prepare a finishing solution, and modal / polyester blended fabric is subjected to two dips and two nips, pre-drying, baking, washing and drying to obtain skin-friendly antibacterial polyester blended fabric.

9. The method for preparing the skin-friendly antibacterial polyester blended fabric according to claim 8, characterized in that, The ratio of water to chitosan antibacterial finishing agent is 1L:(5-20)g.

10. The method for preparing the skin-friendly antibacterial polyester blended fabric according to claim 8, characterized in that, The residual rate of the two dips and two rolls is 70-85%.

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