Antibacterial self-cleaning textile fabric and production process thereof
Patent Information
- Application Number
- CN202611123391.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-28
- Publication Date
- 2026-10-16
AI Technical Summary
[0002]随着人们生活水平的提高以及对健康和环境保护意识的增强，对于纺织品的要求已经不仅仅局限于基本的保暖和美观，还扩展到了功能性需求，例如抗菌、自清洁等功能，传统的纺织面料缺乏有效的抗菌和自清洁能力，容易滋生细菌和真菌，这对人体健康构成了潜在威胁
本发明的改性粘黏剂表面含有羧基，在与涤纶纺织面料共混时，羧基与酯基能够通过氢键作用，将改性粘黏剂接枝在涤纶纺织面料表面，并在表面形成致密的三维网状包覆层，有效避免了细菌等有机微生物的入侵，提高了纺织面料的抗菌性能，并且改性粘黏剂分子结构中含有高分子季铵盐，与小分子季铵盐相比，高分子季铵盐不仅不易被人体皮肤吸收，还具有更强的抗菌的效果，并在有机酸的协同作用下能够有效避免生物膜的生成，进一步提高了纺织面料的抗菌性能；与此同时，本发明的改性抗菌剂为聚甲基丙烯酸甲酯微球掺杂纳米二氧化钛，一方面聚甲基丙烯酸甲酯微球上的羧基能够与改性面料通过氢键结合，将改性抗菌剂均匀地负载在纺织面料表面，提高了改性抗菌剂与改性面料的相容性，另一方面，聚甲基丙烯酸甲酯微球能够捕捉光照下纳米二氧化钛产生的电子，有效促进了“电子-空穴”对的分离，提高了改性抗菌剂的光催化活性，将细菌等有机微生物分解成二氧化碳和水，赋予了纺织面料良好的光催化自清洁性能，此外聚甲基丙烯酸甲酯微球还能够吸收可见光，从而提高改性抗菌剂的光响应范围，进一步增强了纺织面料的抗菌自清洁性能；
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of textile fabric preparation technology, specifically relating to an antibacterial self-cleaning textile fabric and its production process. Background Technology
[0002] As people's living standards improve and their awareness of health and environmental protection increases, the requirements for textiles are no longer limited to basic warmth and aesthetics, but have expanded to functional needs, such as antibacterial and self-cleaning functions. Traditional textile fabrics lack effective antibacterial and self-cleaning capabilities, making them prone to the growth of bacteria and fungi, which poses a potential threat to human health.
[0003] Currently, nano-titanium dioxide is often added when preparing antibacterial and self-cleaning fabrics. Nano-titanium dioxide can use light sources to catalyze reactions, decomposing organic matter into harmless carbon dioxide and water, exhibiting good antibacterial and self-cleaning properties. However, pure nano-titanium dioxide has a high probability of photogenerated electron-hole recombination, and its light response range is limited to the near-ultraviolet band, resulting in low light energy utilization. Furthermore, due to its lack of highly active groups, it is difficult to firmly graft onto the surface of textile fabrics, greatly limiting the application of nano-titanium dioxide in the antibacterial and self-cleaning properties of textile fabrics. Therefore, how to improve the photocatalytic efficiency of nano-titanium dioxide and firmly graft it onto textile fabrics is a technical problem that needs to be solved. Summary of the Invention
[0004] The purpose of this invention is to provide an antibacterial self-cleaning textile fabric and its production process to solve the problems in the background art.
[0005] The objective of this invention can be achieved through the following technical solutions: A manufacturing process for an antibacterial self-cleaning textile fabric includes the following steps: Step S1: Add the modified adhesive to a 10wt% ethanol solution, stir and mix, add polyester textile fabric, and shake and react at 50-60℃ for 2-3 hours. After filtration, washing and drying, the modified fabric is obtained. Step S2: Add 10wt% dilute hydrochloric acid to deionized water to adjust the pH to 3-4, then add the modified antibacterial agent, stir and mix, add the modified fabric, and react at 30-40℃ for 2-3 hours. Take out the fabric, pre-dry it at 50℃ for 20 minutes, then bake it at 120℃ for 4 minutes, and finally dry it at 80℃ for 2 hours to obtain the antibacterial self-cleaning textile fabric.
[0006] Furthermore, the ratio of the ethanol solution, modified adhesive, and polyester textile fabric is 300mL: 2-8g: 10-12g.
[0007] Furthermore, the ratio of the deionized water, modified antibacterial agent, and modified fabric is 400mL: 2-3g: 10-12g.
[0008] Furthermore, the modified adhesive is prepared by the following steps: A1. Chitosan is added to isopropanol and stirred at 50-60℃. Then, an aqueous solution of glycidyltrimethylammonium chloride is added and stirred. After stirring, the mixture is refluxed at 85℃ for 22-24 hours. After filtration, washing, and drying, a chitosan derivative is obtained. Using isopropanol as a solvent and glycidyltrimethylammonium chloride as a quaternary ammonium salt reagent, glycidyltrimethylammonium chloride is grafted onto the chitosan molecule through a ring-opening reaction to obtain a chitosan derivative containing quaternary ammonium groups. A2. Add chitosan derivative to deionized water, stir to dissolve, add citric acid, mix well, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride aqueous solution and N-hydroxysuccinimide aqueous solution dropwise, react at 20-25℃ for 22-28h, then filter, wash and dry to obtain modified adhesive; using 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide as crosslinking system, link citric acid to chitosan derivative molecules through amide bonds to obtain modified adhesive with antibacterial properties.
[0009] Furthermore, the ratio of isopropanol, chitosan, and glycidyltrimethylammonium chloride aqueous solution is 40mL:2-6g:10mL; the concentration of glycidyltrimethylammonium chloride aqueous solution is 16-25wt%.
[0010] Further, the ratio of the amount of deionized water, chitosan derivative, citric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride aqueous solution and N-hydroxysuccinimide aqueous solution is 100mL:4-12g:0.1-1mL:15mL:10mL; the concentration of the 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride aqueous solution is 0.38-0.81g / mL; and the concentration of the N-hydroxysuccinimide aqueous solution is 0.12-0.37g / mL.
[0011] Furthermore, the modified antibacterial agent is prepared through the following steps: Methyl methacrylate was added to deionized water and stirred to dissolve at 70-75℃. Then, azobisisobutylamidine hydrochloride was added under a nitrogen atmosphere, and the mixture was stirred for 2-3 hours. After cooling, the mixture was filtered three times through a 400-mesh standard sieve. The pH value was then adjusted to 2-3 with 8wt% dilute hydrochloric acid. A nano-titanium dioxide dispersion was then added, and the mixture was ultrasonically reacted for 20-30 minutes. After filtration, washing with deionized water, and drying, a modified antibacterial agent was obtained. Polymethyl methacrylate microspheres were prepared by soap-free emulsion polymerization using azobisisobutylamidine hydrochloride as an initiator and methyl methacrylate as a monomer. The carboxyl groups on the surface of the microspheres could be covalently bonded to titanium dioxide, resulting in a modified antibacterial agent of polymethyl methacrylate microspheres doped with nano-titanium dioxide. Furthermore, the ratio of the amount of deionized water, methyl methacrylate, azobisisobutylamidine hydrochloride, and nano-titanium dioxide dispersion is 200mL: 11-16mL: 0.5-1g: 10mL.
[0012] Furthermore, the concentration of the nano-titanium dioxide dispersion is 0.3-0.5 g / mL; the particle diameter of the nano-titanium dioxide is 5-8 nm, and the low nanoscale titanium dioxide can promote the separation of "electron-hole" pairs.
[0013] An antibacterial self-cleaning textile fabric is produced by the above-mentioned production process.
[0014] The beneficial effects of this invention are: The modified adhesive of this invention contains carboxyl groups on its surface. When blended with polyester textile fabric, the carboxyl and ester groups can graft the modified adhesive onto the surface of the polyester textile fabric through hydrogen bonding, forming a dense three-dimensional network coating layer on the surface. This effectively prevents the invasion of bacteria and other organic microorganisms, improving the antibacterial properties of the textile fabric. Furthermore, the modified adhesive molecular structure contains a high-molecular-weight quaternary ammonium salt. Compared with small-molecular-weight quaternary ammonium salts, high-molecular-weight quaternary ammonium salts are not only less easily absorbed by human skin, but also have a stronger antibacterial effect. Under the synergistic effect of organic acids, they can effectively prevent the formation of biofilms, further improving the antibacterial properties of the textile fabric. Meanwhile, the modified antibacterial agent of this invention is a polymethyl methacrylate microsphere doped with polymethyl methacrylate. Nano-titanium dioxide has two main advantages. First, the carboxyl groups on polymethyl methacrylate (PMMA) microspheres can bond with the modified fabric through hydrogen bonds, uniformly loading the modified antibacterial agent onto the textile surface and improving the compatibility between the modified antibacterial agent and the modified fabric. Second, PMMA microspheres can capture electrons generated by nano-titanium dioxide under light, effectively promoting the separation of electron-hole pairs and improving the photocatalytic activity of the modified antibacterial agent. This decomposes bacteria and other organic microorganisms into carbon dioxide and water, giving the textile fabric excellent photocatalytic self-cleaning properties. In addition, PMMA microspheres can also absorb visible light, thereby increasing the light response range of the modified antibacterial agent and further enhancing the antibacterial and self-cleaning properties of the textile fabric. This invention introduces a compatible modified adhesive onto the surface of polyester fibers. On one hand, it provides chemical reaction sites for the grafting reaction of the modified antibacterial agent, enhances the intermolecular forces between the modified antibacterial agent and the textile fabric, and improves the wash fastness of the modified antibacterial agent. On the other hand, the modified adhesive can exert its own antibacterial properties under dark conditions, thereby enabling the textile fabric to have good antibacterial properties even in the absence of light. Under the synergistic effect of the two, the antibacterial and self-cleaning properties of the textile fabric are further improved. Detailed Implementation
[0015] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0016] Example 1
[0017] This embodiment provides a modified adhesive, which is prepared through the following steps: A1. Add 2g of chitosan to 40mL of isopropanol and stir at 50℃. Then add 10mL of 16wt% glycidyltrimethylammonium chloride aqueous solution and stir. After stirring, reflux at 85℃ for 22h. After filtration, washing and drying, chitosan derivative is obtained. A2. Add 4g of chitosan derivative to 100mL of deionized water, stir to dissolve, add 0.1mL of citric acid, mix well, then add 15mL of 0.38g / mL aqueous solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 10mL of 0.12g / mL aqueous solution of N-hydroxysuccinimide. React at 20℃ for 22h, then filter, wash and dry to obtain the modified adhesive.
[0018] Example 2
[0019] This embodiment provides a modified adhesive, which is prepared through the following steps: A1. Add 4g of chitosan to 40mL of isopropanol and stir at 55℃. Then add 10mL of 18wt% glycidyltrimethylammonium chloride aqueous solution and stir. After stirring, reflux at 85℃ for 23h. After filtration, washing and drying, chitosan derivative is obtained. A2. Add 8g of chitosan derivative to 100mL of deionized water, stir to dissolve, add 0.8mL of citric acid, mix well, then add 15mL of 0.51g / mL aqueous solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 10mL of 0.27g / mL aqueous solution of N-hydroxysuccinimide. React at 23℃ for 26h, then filter, wash and dry to obtain the modified adhesive.
[0020] Example 3
[0021] This embodiment provides a modified adhesive, which is prepared through the following steps: A1. Add 6g of chitosan to 40mL of isopropanol and stir at 60℃. Then add 10mL of 25wt% glycidyltrimethylammonium chloride aqueous solution and stir. After stirring, reflux at 85℃ for 24h. After filtration, washing and drying, chitosan derivative is obtained. A2. Add 12g of chitosan derivative to 100mL of deionized water, stir to dissolve, add 1mL of citric acid, mix well, then add 15mL of 0.81g / mL aqueous solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 10mL of 0.37g / mL aqueous solution of N-hydroxysuccinimide, react at 25℃ for 28h, then filter, wash and dry to obtain the modified adhesive.
[0022] Example 4
[0023] This embodiment provides a modified antibacterial agent, which is prepared through the following steps: 11 mL of methyl methacrylate was added to 200 mL of deionized water and stirred to dissolve at 70 °C. Then, 0.5 g of azobisisobutylamidine hydrochloride was added under a nitrogen atmosphere and stirred for 2 h. After cooling, the mixture was filtered three times through a 400-mesh standard sieve. The pH value was then adjusted to 2 with 8 wt% dilute hydrochloric acid. 10 mL of 0.3 g / mL nano-titanium dioxide dispersion was added and the mixture was sonicated for 20 min. After filtration, washing with deionized water, and drying, the modified antibacterial agent was obtained.
[0024] Example 5
[0025] This embodiment provides a modified antibacterial agent, which is prepared through the following steps: Add 14 mL of methyl methacrylate to 200 mL of deionized water and stir to dissolve at 73 °C. Then add 0.8 g of azobisisobutylamidine hydrochloride under a nitrogen atmosphere and stir to react for 2.5 h. After cooling, filter three times through a 400-mesh standard sieve. Adjust the pH value to 2.5 with 8 wt% dilute hydrochloric acid. Then add 10 mL of 0.4 g / mL nano titanium dioxide dispersion and sonicate for 25 min. After filtration, washing with deionized water, and drying, the modified antibacterial agent is obtained.
[0026] Example 6
[0027] This embodiment provides a modified antibacterial agent, which is prepared through the following steps: Add 16 mL of methyl methacrylate to 200 mL of deionized water and stir to dissolve at 75 °C. Then add 0.5-1 g of azobisisobutylamidine hydrochloride under a nitrogen atmosphere and stir to react for 3 h. After cooling, filter three times through a 400-mesh standard sieve. Adjust the pH value to 3 with 8 wt% dilute hydrochloric acid. Add 10 mL of 0.5 g / mL nano titanium dioxide dispersion and sonicate for 30 min. After filtration, washing with deionized water, and drying, the modified antibacterial agent is obtained.
[0028] Example 7
[0029] This embodiment provides a production process for antibacterial self-cleaning textile fabric, including the following steps: Step S1: Add 2g of modified adhesive to 300mL of 10wt% ethanol solution, stir and mix, add 10g of polyester textile fabric, and shake and react at 50℃ for 2h. After filtration, washing and drying, the modified fabric is obtained. Step S2: Add a 10wt% hydrochloric acid solution to 400mL of deionized water, adjust the pH to 3, add 2g of modified antibacterial agent, stir and mix, add 10g of modified fabric, and react at 30℃ for 2h. Take out the fabric, and after washing and drying, obtain antibacterial self-cleaning textile fabric.
[0030] Example 8
[0031] This embodiment provides a production process for antibacterial self-cleaning textile fabric, including the following steps: Step S1: Add 5g of modified adhesive to 300mL of 10wt% ethanol solution, stir and mix, add 11g of polyester textile fabric, and shake and react at 55℃ for 2.5h. After filtration, washing and drying, the modified fabric is obtained. Step S2: Add a 10wt% hydrochloric acid solution to 400mL of deionized water, adjust the pH to 3.5, then add 2.6g of modified antibacterial agent, stir and mix, then add 11g of modified fabric, and react at 35℃ for 2.5h. Take out the fabric, and after washing and drying, obtain antibacterial self-cleaning textile fabric.
[0032] Example 9
[0033] This embodiment provides a production process for antibacterial self-cleaning textile fabric, including the following steps: Step S1: Add 8g of modified adhesive to 300mL of 10wt% ethanol solution, stir and mix, add 12g of polyester textile fabric, and shake and react at 60℃ for 3h. After filtration, washing and drying, the modified fabric is obtained. Step S2: Add a 10wt% hydrochloric acid solution to 400mL of deionized water, adjust the pH to 4, add 3g of modified antibacterial agent, stir and mix, add 12g of modified fabric, and react at 40℃ for 3h. Take out the fabric, and after washing and drying, obtain antibacterial self-cleaning textile fabric.
[0034] Comparative Example 1: Compared with Example 7, the modified adhesive was replaced with chitosan in equal amounts, and the rest were the same.
[0035] Comparative Example 2: Compared with Example 7, no modified adhesive was added, and all other aspects were the same.
[0036] Comparative Example 3: Compared with Example 7, the modified antibacterial agent was replaced with an equal amount of nano-titanium dioxide, and the rest were the same.
[0037] Performance tests were conducted on Examples 7-9 and Comparative Examples 1-3. Wash fastness test: Following GB / T3921-2008, the textile fabric was tested for wash fastness, and the antibacterial properties against Escherichia coli before and after washing were also tested. The antibacterial properties were also tested according to GB / T 20944.3-2008. Self-cleaning performance test: Following GB / T23764-2009, 0.1 mL of a 0.1% gentian violet solution was vertically dropped onto the surface of the textile fabric sample, and the sample was then irradiated with visible light for 12 hours. The discoloration of the gentian violet stain was observed. The results are shown in Table 1. Table 1
[0038] As shown in Table 1, the antibacterial rates of the textile fabrics prepared by the modified adhesive and modified antibacterial agent in Examples 7-9 before and after washing are all greater than those in Comparative Examples 1-3, indicating good antibacterial properties and wash fastness. At the same time, under light conditions, gentian violet stains can be catalytically decolorized, demonstrating good photocatalytic self-cleaning properties. Furthermore, compared with Comparative Examples 2 and 3, Example 7 has higher antibacterial properties, indicating that the textile fabric prepared by the synergistic effect of modified adhesive and modified antibacterial agent has higher antibacterial and self-cleaning properties.
[0039] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0040] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A production process for an antibacterial self-cleaning textile fabric, characterized in that, Includes the following steps: Step S1: Add the modified adhesive to the ethanol solution, stir and mix, add the polyester textile fabric, and shake and react at 50-60℃ for 2-3 hours. After filtration, washing and drying, the modified fabric is obtained. Step S2: Add dilute hydrochloric acid to deionized water to adjust the pH value to 3-4, then add the modified antibacterial agent, stir and mix, add the modified fabric, and react at 30-40℃ for 2-3 hours. Take out the fabric, and after washing and drying, obtain the antibacterial self-cleaning textile fabric.
2. The production process of an antibacterial self-cleaning textile fabric according to claim 1, characterized in that, The ratio of the ethanol solution, modified adhesive, and polyester textile fabric used is 300mL: 2-8g: 10-12g.
3. The production process of an antibacterial self-cleaning textile fabric according to claim 1, characterized in that, The modified adhesive is prepared by the following steps: A1. Add chitosan to isopropanol and stir and mix at 50-60℃. Then add glycidyltrimethylammonium chloride aqueous solution and stir and mix. Reflux at 85℃ for 22-24h. After filtration, washing and drying, obtain chitosan derivative. A2. Add chitosan derivative to deionized water, stir to dissolve, add citric acid, mix well, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride aqueous solution and N-hydroxysuccinimide aqueous solution dropwise, react at 20-25℃ for 22-28h, then filter, wash and dry to obtain modified adhesive.
4. The production process of an antibacterial self-cleaning textile fabric according to claim 3, characterized in that, The ratio of isopropanol, chitosan, and glycidyltrimethylammonium chloride aqueous solution is 40 mL: 2-6 g: 10 mL; the concentration of the glycidyltrimethylammonium chloride aqueous solution is 16-25 wt%.
5. The production process of an antibacterial self-cleaning textile fabric according to claim 3, characterized in that, The ratio of deionized water, chitosan derivative, citric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride aqueous solution, and N-hydroxysuccinimide aqueous solution is 100mL:4-12g:0.1-1mL:15mL:10mL; the concentration of the 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride aqueous solution is 0.38-0.81g / mL; and the concentration of the N-hydroxysuccinimide aqueous solution is 0.12-0.37g / mL.
6. The production process of an antibacterial self-cleaning textile fabric according to claim 1, characterized in that, The ratio of deionized water, modified antibacterial agent, and modified fabric is 400mL: 2-3g: 10-12g.
7. The production process of an antibacterial self-cleaning textile fabric according to claim 1, characterized in that, The modified antibacterial agent is prepared through the following steps: Methyl methacrylate was added to deionized water and stirred to dissolve at 70-75℃. Then, azobisisobutylamidine hydrochloride was added under a nitrogen atmosphere and stirred for 2-3 hours. After cooling, the mixture was filtered multiple times through a 400-mesh standard sieve. The pH value was then adjusted to 2-3 with dilute hydrochloric acid. Nano-titanium dioxide dispersion was then added and the mixture was sonicated for 20-30 minutes. After filtration, washing with deionized water, and drying, the modified antibacterial agent was obtained.
8. The production process of an antibacterial self-cleaning textile fabric according to claim 7, characterized in that, The ratio of deionized water, methyl methacrylate, azobisisobutylamidine hydrochloride, and nano-titanium dioxide dispersion is 200mL: 11-16mL: 0.5-1g: 10mL.
9. The production process of an antibacterial self-cleaning textile fabric according to claim 7, characterized in that, The concentration of the nano-titanium dioxide dispersion is 0.3-0.5 g / mL; the particle diameter of the nano-titanium dioxide is 5-8 nm.
10. An antibacterial self-cleaning textile fabric, characterized in that, It is produced by the manufacturing process according to any one of claims 1-9.