Washable antibacterial agent

Abstract

The invention discloses a washable antibacterial agent which comprises one or more halogenated triazine compounds and integrates multiple functional groups: high-reaction-activity groups such as halogen s-triazine or vinyl sulfone and the like can be subjected to nucleophilic substitution reaction with hydroxyl groups on the surfaces of cellulose fibers such as cotton, hemp and the like under a mild alkaline condition to form stable covalent ether bonds; antibacterial molecules are firmly anchored on the fibers, so that the key defects that a traditional antibacterial agent is easy to fall off and is not washable only by physical adsorption are fundamentally overcome; in addition, phenolic hydroxyl groups, sulfonamide, carboxyl phenyl, chitosan and other antibacterial groups are introduced into molecules, after the antibacterial groups are fixed through covalent bonds, the original biological activity is kept, the risks of environmental pollution and skin irritation caused by a dissoluble antibacterial agent are avoided, the long-acting antibacterial effect is achieved, and after multiple times of washing, the antibacterial effect is slightly reduced.

Description

Technical Field

[0001] This invention relates to the field of antibacterial agents for textiles, and more particularly to a washable antibacterial agent. Background Technology

[0002] In the field of functional finishing of textiles, endowing cellulose fibers (such as cotton, linen, viscose, and their blends) with durable and washable antibacterial properties has always been a pressing technical challenge for the industry. Traditional antibacterial finishing processes generally employ antibacterial components such as quaternary ammonium salts, nano-silver, or chitosan to be fixed onto the fiber surface. However, these antibacterial agents are mainly fixed to the fiber surface through physical adsorption or weak interactions such as hydrogen bonds and van der Waals forces, lacking the ability to form covalent bonds with cellulose molecular chains. Therefore, during repeated wear and washing, the antibacterial active ingredients gradually swell, migrate, or fall off due to mechanical forces, detergents, and water rinsing, resulting in insufficient wash resistance. After 20 washes, the antibacterial rate of commonly commercially available antibacterial fabrics generally decreases from an initial ≥99% to below 65%.

[0003] To improve wash resistance, existing conventional technologies enhance the binding strength of antibacterial agents to fibers through adhesive film-forming, microencapsulation for sustained release, or plasma pretreatment. However, this often results in issues such as stiffer fabric feel, reduced air permeability, lengthy processing steps, and significantly increased costs. Some studies have used epoxy- or carboxymethylated cellulose, followed by cross-linking with amino / carboxylic antibacterial agents. While this improves wash resistance, it requires stringent pre-chemical modification of the fibers, disrupting their inherent structure and leading to strength loss, color variation, and reduced wearability. Therefore, current technologies have not yet achieved the goal of durable antibacterial properties and long-lasting wash resistance in textiles under mild conditions. Summary of the Invention

[0005] Purpose of the invention: The purpose of this invention is to provide an antibacterial agent that can achieve long-lasting antibacterial and wash-resistant properties in textiles under mild conditions.

[0006] Technical solution: This invention provides a water-resistant antibacterial agent, comprising one or more compounds selected from the structure shown in Formula 1:

[0007] Formula 1;

[0008] Where D1 is ;

[0009] D2 is selected from , Any one of chitosan;

[0010] D3 is selected from any one of -H, -C2H5, and -CH3;

[0011] X is selected from halogens;

[0012] In D1, R1, R2, and R3 are each independently selected from any one of -H, -SO3M1, -OCH3, -CH3, -SO2CH=CH2, and -SO2C2H4OSO3M2; and M1 and M2 are each independently selected from any one of hydrogen, potassium, sodium, lithium, and ammonium.

[0013] In D2, R4 is selected from -H or -OH; R5 is selected from -NH; and R6 is selected from... , Or -H.

[0014] Under alkaline conditions, the active groups of the antibacterial agent react with the fiber to form covalent bonds, thus fixing it onto the fiber. Under alkaline conditions, the hydroxyl groups on the cellulose fiber are deprotonated, forming cellulose anions with stronger nucleophilicity. The halogen in this application is a strong electron-withdrawing group, which reduces the electron cloud density of the carbon atom attached to the halogen in the triazine ring through an inductive effect, making the carbon atom attached to the halogen a reaction center that is easily attacked by the cellulose anion. After the attack occurs, the halogen atom is replaced as a leaving group, forming a stable ether covalent bond between the antibacterial agent and cellulose, thus forming a strong covalent bond between the antibacterial agent and the fiber.

[0015] The D2 group contains antibacterial or auxiliary groups such as hydroxyl, sulfonamide, carboxyl, or chitosan. Hydroxyl groups, especially phenolic hydroxyl groups, can disrupt the cell membrane integrity of pathogenic microorganisms and inhibit enzyme activity by binding to the sulfhydryl groups of microbial enzymes. Sulfonamides, when combined with pyridine or thiazole rings, can inhibit dihydropteroate synthase, blocking folic acid synthesis, exhibiting strong antibacterial activity and the ability to bind with heterocycles to broaden the antibacterial spectrum. Carboxyl groups can act as coordinating groups, binding to metal ions to enhance the overall antibacterial properties of the material. Carboxyphenyl groups can disrupt membrane structural integrity, binding to key enzymes through electrostatic interactions or hydrogen bonds to inhibit their activity. Positively charged amino groups in chitosan bind to the bacterial cell wall through electrostatic interactions, altering cell wall permeability, penetrating the cell membrane, entering the cell, binding to DNA, preventing transcription, and leading to bacterial death.

[0016] When D1 contains -SO2CH=CH2 or -SO2C2H4OSO3M2 groups, the strong electron-withdrawing effect of the sulfone group reduces the electron cloud density of the double bond, making the β-carbon more susceptible to nucleophilic attack by cellulose anions. After the β-carbon is attacked, the double bond electron cloud transfers to the α-carbon, forming a carbanion intermediate on the α-carbon. The carbanion acquires a proton from the water, ultimately forming a stable β-ether bond covalently, thus covalently binding the vinyl sulfone group with the cellulose fiber. Furthermore, halogens and vinyl sulfones exhibit a synergistic effect when reacting with fabric fibers. The two different reactive groups, halogens and vinyl sulfones, can provide different reaction pathways, increasing the probability of collision reactions with the hydroxyl groups on the fabric fibers. When one group reacts or becomes inactive, the other unreacted group can continue to bind to the fabric fibers, forming multi-point anchoring, enhancing the stability of the antibacterial agent-fiber bond, and effectively improving the fixation rate. Both groups can be activated under different reaction conditions, expanding the applicable pH and temperature range of the dye. For example, the optimal reaction temperature between monochlorotriazine and fabric fibers is 80-100 degrees Celsius, while the optimal reaction temperature between vinyl sulfone and fabric fibers is 60 degrees Celsius. When monochlorotriazine is compounded with vinyl sulfone, the reaction conversion rate with fabric can be increased to over 85% at 60-70 degrees Celsius.

[0017] Optionally, X is selected from -Cl or -F. Halogens are strong electron-withdrawing groups. In nucleophilic aromatic substitution reactions, the stronger the electronegativity, the stronger the electron-withdrawing inductive effect, which is more conducive to stabilizing the intermediate and increasing reactivity. Therefore, fluorine and chlorine substituents are more reactive than bromine and iodine substituents.

[0018] Alternatively, Equation 1 can be any of the following structural formulas:

[0019] Equation 1-1;

[0020] Equation 1-2;

[0021] Equation 1-3;

[0022] Equation 1-4;

[0023] Equations 1-5;

[0024] Equations 1-6;

[0025] Equations 1-7;

[0026] Equations 1-8;

[0027] Equations 1-9;

[0028] Equation 1-10;

[0029] Equation 1-11;

[0030] Equation 1-12;

[0031] Equation 1-13;

[0032] Equation 1-14;

[0033] Equation 1-15;

[0034] Equation 1-16;

[0035] Equation 1-17;

[0036] Equation 1-18;

[0037] Equation 1-19.

[0038] Preferably, the compounds shown in Formulas 1-5, 1-6, 1-14, 1-15, and 1-18 have a long-lasting antibacterial effect, and the antibacterial effect decreases only slightly after repeated washing.

[0039] Specifically, Formulas 1-5, 1-6, 1-14, and 1-15 all contain phenolic hydroxyl groups, sulfonamides, carboxyphenyl groups, and -SO2C2H4OSO3M2. The phenolic hydroxyl group can disrupt the cell membrane and inhibit enzyme activity for rapid sterilization; the sulfonamide group blocks the bacterial folic acid metabolism pathway for precise inhibition; the carboxyphenyl group provides a local acidic microenvironment, enhancing the permeability of the phenolic hydroxyl group and interfering with energy metabolism; and the -SO2C2H4OSO3M2 group improves water solubility and dispersibility. These groups synergistically form multi-target contact and attack, enhancing antibacterial properties. Through synergistic effects, these groups significantly reduce the risk of bacterial resistance through multi-target synergistic attack via membrane disruption, metabolic inhibition, and acidification.

[0040] Optionally, the antibacterial agent is of formula 1-6, and the content of formula 1-6 is 100 wt%.

[0041] Optionally, the antimicrobial agent includes formulas 1-10, 1-14 and 1-15, and the mass ratio of formula 1-15: formula 1-14: formula 1-10 is 40:40:20.

[0042] Optionally, the antimicrobial agent includes formulas 1-17 and 1-18, and the mass ratio of formulas 1-17 and 1-18 is 45:55.

[0043] Optionally, the antimicrobial agent includes formulas 1-5, 1-13 and 1-15, and the mass ratio of formulas 1-13, 1-5 and 1-15 is 65:25:10.

[0044] Optionally, the antimicrobial agent includes formulas 1-5, 1-9 and 1-11, and the mass ratio of formulas 1-5, 1-11 and 1-9 is 68:25:7.

[0045] Optionally, the antimicrobial agent includes formulas 1-16, 1-18 and 1-19, and the mass ratio of formulas 1-18, 1-19 and 1-16 is 40:35:25.

[0046] Optionally, the antimicrobial agent includes Formula 1-1, Formula 1-6 and Formula 1-9, and the mass ratio of Formula 1-9, Formula 1-1 and Formula 1-6 is 79:11:10.

[0047] Beneficial Effects: The washable antibacterial agent provided by this invention cleverly integrates multiple functional groups: On the one hand, highly reactive groups such as halogenated triazine or vinyl sulfone can undergo nucleophilic substitution reactions with the hydroxyl groups on the surface of cellulose fibers such as cotton and linen under mild alkaline conditions to form stable covalent ether bonds, firmly anchoring the antibacterial molecules to the fibers. This fundamentally solves the key defects of traditional antibacterial agents, which rely solely on physical adsorption and are prone to detachment and are not wash-resistant. On the other hand, the antibacterial groups such as phenolic hydroxyl, sulfonamide, and carboxyphenyl introduced into the molecule achieve highly efficient and broad-spectrum bactericidal effects through multiple mechanisms, including disrupting the integrity of bacterial cell membranes, inhibiting the activity of key enzymes in folic acid synthesis, and interfering with energy metabolism and DNA replication. Meanwhile, the amino cations of natural polysaccharides such as chitosan act on the negatively charged bacterial cell walls through electrostatic adsorption, causing cytoplasmic leakage and exudation of contents. After these antibacterial groups are fixed by covalent bonds, they not only maintain their original biological activity but also avoid the environmental pollution and skin irritation risks of leaching antibacterial agents, achieving a long-lasting antibacterial effect with minimal decrease in antibacterial efficacy after multiple washes. Detailed Implementation

[0049] To make the technical solution of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments.

[0050] Antimicrobial agents include one or more compounds selected from the following structural formulas:

[0051] Equation 1-1;

[0052] Equation 1-2;

[0053] Equation 1-3;

[0054] Equation 1-4;

[0055] Equations 1-5;

[0056] Equations 1-6;

[0057] Equations 1-7;

[0058] Equations 1-8;

[0059] Equations 1-9;

[0060] Equation 1-10;

[0061] Equation 1-11;

[0062] Equation 1-12;

[0063] Equation 1-13;

[0064] Equation 1-14;

[0065] Equation 1-15;

[0066] Equation 1-16;

[0067] Equation 1-17;

[0068] Equation 1-18;

[0069] Equation 1-19.

[0070] Example 1

[0071] The antibacterial agent is of formula 1-1, wherein the content of formula 1-1 is 100 wt%.

[0072] Example 2

[0073] The antibacterial agent includes formulas 1-2 and 1-3, wherein formulas 1-2 and 1-3 are compounded in a mass ratio of 50:50.

[0074] Example 3

[0075] The antibacterial agents include formulas 1-3, 1-4 and 1-5, wherein formulas 1-3, 1-4 and 1-5 are compounded in a mass ratio of 65:20:15.

[0076] Example 4

[0077] The antibacterial agent is of formula 1-6, wherein the content of formula 1-6 is 100wt%.

[0078] Example 5

[0079] The antibacterial agents include Formula 1-7 and Formula 1-8, wherein Formula 1-7 and Formula 1-8 are compounded in a mass ratio of 80:20.

[0080] Example 6

[0081] The antibacterial agents include Formula 1-1, Formula 1-6 and Formula 1-9, wherein Formula 1-9, Formula 1-1 and Formula 1-6 are compounded in a mass ratio of 79:11:10.

[0082] Example 7

[0083] The antibacterial agents include Formula 1-2, Formula 1-7 and Formula 1-10, wherein Formula 1-10, Formula 1-2 and Formula 1-7 are compounded in a mass ratio of 78:12:10.

[0084] Example 8

[0085] The antibacterial agents include formulas 1-3, 1-4 and 1-8, wherein formulas 1-4, 1-3 and 1-8 are compounded in a mass ratio of 66:19:15.

[0086] Example 9

[0087] The antibacterial agents include formulas 1-5, 1-9 and 1-11, wherein formulas 1-5, 1-11 and 1-9 are compounded in a mass ratio of 68:25:7.

[0088] Example 10

[0089] The antibacterial agents include formulas 1-3, 1-12 and 1-16, wherein formulas 1-12, 1-3 and 1-16 are compounded in a mass ratio of 40:40:20.

[0090] Example 11

[0091] The antibacterial agent includes formulas 1-10, 1-14 and 1-15, wherein formula 1-15, formula 1-14 and formula 1-10 are compounded in a mass ratio of 40:40:20.

[0092] Example 12

[0093] The antibacterial agents include formulas 1-5, 1-13, and 1-15, wherein formulas 1-13, 1-5, and 1-15 are compounded in a mass ratio of 65:25:10.

[0094] Example 13

[0095] The antibacterial agent includes formula 1-17 and formula 1-18, wherein formula 1-17 and formula 1-18 are compounded in a mass ratio of 45:55.

[0096] Example 14

[0097] The antibacterial agents include formulas 1-16, 1-18 and 1-19, wherein formulas 1-18, 1-19 and 1-16 are compounded in a mass ratio of 40:35:25.

[0098] Comparative Example 1 used 100 wt% 2-aminophenol-4-(2'-carboxyl)sulfonylaniline (CAS No. 91-35-0) as an antibacterial agent; Comparative Example 2 used 100 wt% 2-aminophenol-4-sulfonylaniline (CAS No. 80-20-6) as an antibacterial agent; Comparative Example 3 used 100 wt% sulfapyridine (CAS No. 144-83-2) as an antibacterial agent; Comparative Example 4 used 100 wt% chitosan as an antibacterial agent; Comparative Example 5 used 100 wt% p-aminobenzenesulfonamide (CAS No. 63-74-1) as an antibacterial agent; and Comparative Example 6 used 4-chloro-3-cresol (CAS No. 59-50-7) as an antibacterial agent.

[0099] The antibacterial effects of the antibacterial agents in all the above examples and comparative examples (Examples 1-14 and Comparative Examples 1-6) were tested. Five parallel tests were set up for each example, and the average value was taken after removing the highest and lowest values ​​to obtain the antibacterial rate. For each example and comparative example as an antibacterial agent, the specific operations were as follows: 5g of cotton fabric was taken as a sample and placed in a 100ml dye bath containing 0.2g of antibacterial agent at 40℃. The mixture was run for 10 minutes, then 4g of sodium sulfate was added, and the mixture was run for 10 minutes. Then, 1g of sodium carbonate was added, and the mixture was run for 10 minutes. The temperature was increased to 60℃ at a rate of 1℃ / min, and the mixture was run for 40 minutes. Afterward, the mixture was washed with water, soaped, washed again, and dried to test its antibacterial effect. The initial antibacterial effect, the antibacterial effect after 10 washes, and the antibacterial effect after 20 washes are shown in Tables 1, 2, and 3, respectively.

[0100] Table 1 Initial antibacterial effect

[0101]

[0102] Table 2. Antibacterial effect after 10 water washes

[0103]

[0104] Table 3. Antibacterial effect after 20 water washes

[0105]

[0106] As shown in Tables 1, 2, and 3 above, the antibacterial effect of Comparative Examples 1-6 decreased significantly after multiple washes, with a total attenuation of 30-35 percentage points after 20 washes. The antibacterial rates against Candida albicans, Escherichia coli, and Staphylococcus aureus all fell below 65.1%, no longer meeting the requirement of FZ / T 73023-2006 "Antibacterial Knitted Fabrics" that the antibacterial rate after 20 washes for Grade AA should not be less than 70%. In contrast, the total attenuation of all embodiments of this application after 20 washes was 6-13 percentage points, and the antibacterial rates against Candida albicans, Escherichia coli, and Staphylococcus aureus all reached above 78.6%. The wash resistance of the embodiments of this application is significantly better than that of the comparative examples, maintaining high activity even after 20 washes, while the comparative examples have essentially failed (antibacterial rate below 65%).

[0107] Examples 4, 11, and 13 exhibit excellent washability, with an inhibition rate of >80% against all bacterial species after 20 washes, far exceeding the comparative examples. Examples 6, 7, 9, 12, and 14 demonstrate good washability. Examples 1, 2, 3, 5, 8, and 10 show poorer washability compared to the other examples, with a relatively faster degradation.

[0108] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A wash-resistant antibacterial agent, characterized by comprising: comprises one or more compounds selected from the group consisting of compounds of formula 1: Formula 1; wherein D1 is ; D2 is selected from , , any of chitosan; D3 is selected from any one of -H, , . X is selected from halogen; wherein R1, R2, and R3 in D1 are each independently selected from any one of -H, -SO3M1, -OCH3, -CH3, -SO2CH=CH2, -SO2C2H4OSO3M2; wherein M1 and M2 are each independently selected from any one of hydrogen, potassium, sodium, lithium, ammonium; wherein R4in D2 is selected from -H or -OH; R5is selected from -NH; R6is selected from , , , or -H.

2. The antimicrobial agent of claim 1, wherein X is selected from -Cl or -F.

3. The antimicrobial agent of claim 2, wherein The formula 1 is any one of the following structural formulae: Formula 1-1; Equation 1-2; Equation 1-3; Equation 1-4; Equations 1-5; Equations 1-6; Equations 1-7; Equations 1-8; Equations 1-9; Equation 1-10; Equation 1-11; Equation 1-12; Formula 1-13; Equation 1-14; Equation 1-15; Equation 1-16; Equation 1-17; Equation 1-18; Formula 1-19.

4. The antimicrobial agent of claim 3, wherein, The antibacterial agent is the formula 1-6, and the content of the formula 1-6 is 100wt%.

5. The antimicrobial agent of claim 3, wherein The antibacterial agent comprises the formula 1-10, the formula 1-14, and the formula 1-15, and the mass ratio of the formula 1-15: formula 1-14: formula 1-10 is 40:40:

20.

6. The antimicrobial agent of claim 3, wherein The antibacterial agent comprises the formula 1-17 and the formula 1-18, and the mass ratio of the formula 1-17 and the formula 1-18 is 45:

55.

7. The antimicrobial agent of claim 3, wherein The antibacterial agent comprises the formula 1-5, the formula 1-13, and the formula 1-15, and the mass ratio of the formula 1-13, the formula 1-5, and the formula 1-15 is 65:25:

10.

8. The antimicrobial agent of claim 3, wherein The antibacterial agent comprises the formula 1-5, the formula 1-9, and the formula 1-11, and the mass ratio of the formula 1-5, the formula 1-11, and the formula 1-9 is 68:25:

7.

9. The antimicrobial agent of claim 3, wherein, The antibacterial agent comprises the formula 1-16, the formula 1-18, and the formula 1-19, and the mass ratio of the formula 1-18, the formula 1-19, and the formula 1-16 is 40:35:

25.

10. The antimicrobial agent of claim 3, wherein, The antibacterial agent comprises the formula 1-1, the formula 1-6, and the formula 1-9, and the mass ratio of the formula 1-9, the formula 1-1, and the formula 1-6 is 79:11:10.

Images