An antibacterial, moisture-permeable, waterproof finishing agent for fabrics and a preparation method thereof

Abstract

The application discloses an antibacterial, moisture-permeable and waterproof finishing agent for fabrics and a preparation method thereof. According to mass fraction, the antibacterial, moisture-permeable and waterproof finishing agent comprises the following raw materials: 3-15 parts of alkyl dimethyl tertiary amine antibacterial agent, 6-9 parts of high-boiling-point solvent, 13-16 parts of organic silicon, 5-7 parts of isobutyl acetate, 20-25 parts of diisocyanate, 3-7 parts of polyhydric alcohol, 0.5-2 parts of small-molecule chain extender, 0.5-5 parts of hydrophilic chain extender, 0.5-2 parts of salt-forming agent, and pure water added to 100 parts. The application simplifies the synthesis experiment steps, reduces the production cost, reduces the pollution to the ecological environment and the damage to the health of the first-line production workers, conforms to the current green environmental protection and sustainable development production concept, and guarantees the non-toxicity and safety in use.

Description

Technical Field

[0001] This invention relates to an antibacterial, breathable, and waterproof finishing agent for fabrics and its preparation method, belonging to the field of functional finishing technology for fabrics. Background Technology

[0002] With the improvement of living standards and health awareness, people's demand for the multifunctionality of textile products is increasing. Clothing fabrics with antibacterial, breathable and waterproof properties are more likely to be favored by people. Therefore, it is necessary to develop such multifunctional fabric finishing agents.

[0003] Existing patent CN108676143A discloses a method for preparing a waterborne synergistic antibacterial polyurethane. Compared to a single antibacterial mechanism, the resulting antibacterial polyurethane emulsion can better inhibit or delay the development of bacterial resistance, but it fails to impart a certain degree of waterproof and breathable properties to the finished fabric. Another patent, CN104727150A, discloses a method for preparing a waterproof, breathable, antibacterial, and UV-resistant waterborne polyurethane material. It utilizes silver-loaded nano-titanium dioxide to improve the antibacterial and UV-resistant properties of the waterborne polyurethane resin. However, the silver-loaded nano-titanium dioxide uses ethanol as a solvent, and the hydroxyl groups (-OH) in ethanol readily react with isocyanate groups (-NCO), affecting the synthesis of the target product. Another patent, CN103420868A, discloses a method for preparing an aqueous, non-toxic, antibacterial polyurethane emulsion containing bisquaternary ammonium diamine or diol monomers. This emulsion exhibits good biocompatibility, anti-adhesion, anti-biofilm formation, and bactericidal properties. However, its synthesis steps are complex, the reaction time is too long, and it cannot impart waterproof and breathable functions to fabrics during finishing. Furthermore, the bisquaternary ammonium diamine or diol monomers carrying antibacterial functional groups contain halogen elements that pose potential hazards to the environment or human health. Yet another patent, CN113684694A, discloses a method for preparing a waterproof, breathable, and antibacterial aqueous polyurethane. The resulting emulsion possesses excellent antibacterial and waterproof / breathable properties. However, during the synthesis of the desired emulsion, low-boiling-point solvents such as acetone are used to reduce the viscosity of the reaction system. In the later stages of synthesis, vacuum distillation of acetone is still required. Due to the volatile nature of acetone and the fact that its recovered liquid contains impurities and cannot be reused, this increases production costs during large-scale production. More seriously, it causes incalculable harm to the health of frontline workers.

[0004] In summary, considering performance, cost, environmental protection, and sustainable development, an antibacterial, breathable, and waterproof finishing agent for fabrics should not only enable the treated fabrics to possess excellent antibacterial, waterproof, and breathable properties, but also have basic characteristics such as being environmentally friendly, non-toxic to the human body, having a low effective concentration, excellent stability, not affecting the original properties of the fabric, being easy to process, and having low cost. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides an antibacterial, breathable, and waterproof finishing agent for fabrics and its preparation method.

[0006] To achieve the above objectives, the present invention employs an antibacterial, breathable, and waterproof finishing agent for fabrics, comprising, by weight, the following raw materials: 3-15 parts of alkyl dimethyl tertiary amine antibacterial agent, 6-9 parts of high-boiling-point solvent, 13-16 parts of organosilicon, 5-7 parts of isobutyl acetate, 20-25 parts of diisocyanate, 3-7 parts of polydiol, 0.5-2 parts of small molecule chain extender, 0.5-5 parts of hydrophilic chain extender, 0.5-2 parts of salt-forming agent, and pure water to a total of 100 parts.

[0007] As one embodiment, the alkyl dimethyl tertiary amine antibacterial agent is at least one selected from dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, and octadecyl dimethyl tertiary amine.

[0008] As one embodiment, the high-boiling-point solvent is at least one selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, toluene, and xylene.

[0009] As one embodiment, the organosilicon is at least one of aminoalkyl organosilicon, hydroxyalkyl polyether organosilicon, and dihydroxyalkyl organosilicon.

[0010] As one embodiment, the diisocyanate is at least one selected from isophorone diisocyanate, 1,6-hexane diisocyanate, toluene diisocyanate, trimethylhexane diisocyanate, and diphenylmethane diisocyanate.

[0011] As one embodiment, the polydiol is at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, and polycarbonate glycol.

[0012] As one embodiment, the small molecule chain extender is at least one selected from 1,2-propanediol, 1,4-butanediol, 1,6-ethylenediol, and trimethylolpropane.

[0013] As one embodiment, the hydrophilic chain extender is at least one of N-methyldiethanolamine, diethylenetriamine, diethanolamine, and triethanolamine.

[0014] As one embodiment, the salt-forming agent is at least one of hydrochloric acid, acetic acid, CH3I, (CH3)2SO4, and epichlorohydrin.

[0015] Finally, the present invention also provides a method for preparing the aforementioned antibacterial, breathable, and waterproof finishing agent for fabrics, comprising the following steps:

[0016] (1) Add the formulated amounts of alkyl dimethyl tertiary amine antibacterial agent, organosilicon, and polydiol to a dry four-necked round-bottom flask, and dehydrate them by vacuum distillation at 110℃~120℃ and a vacuum degree of -0.08~-0.1MPA to obtain anhydrous alkyl dimethyl tertiary amine antibacterial agent, anhydrous organosilicon, and anhydrous polydiol for later use.

[0017] (2) Place the anhydrous polydiol obtained in step (1) into a dry four-necked round-bottom flask, slowly add diisocyanate to the flask, stir evenly in a water bath and keep warm, and then carry out a prepolymer reaction to obtain a prepolymer with isocyanate groups at both ends.

[0018] (3) Dissolve the anhydrous organosilicon from step (1) in the prescribed amount of isobutyl acetate, add it to the prepolymer obtained in step (2), stir evenly in a water bath, and keep warm to obtain the preliminary modified emulsion for later use.

[0019] (4) The small molecule chain extender and hydrophilic chain extender in the formula amount are slowly added dropwise to the preliminary modified emulsion obtained in step (3) in sequence, stirred evenly in a water bath, and the chain extension reaction is carried out to obtain the chain extended mixture.

[0020] (5) Add the prescribed amount of salt-forming agent to the chain-extending mixture obtained in step (4), stir evenly in a water bath to obtain an ionized neutralized modified mixture, and then add the prescribed amount of pure water for full emulsification to obtain a water-based polyurethane waterproof and breathable finishing agent.

[0021] (6) Add the anhydrous alkyl dimethyl tertiary amine antibacterial agent from step (1) to the formula amount of high boiling point solvent, stir thoroughly and then perform ultrasonic treatment to obtain an alkyl dimethyl tertiary amine antibacterial agent solution.

[0022] (7) Add the alkyl dimethyl tertiary amine antibacterial agent solution obtained in step (6) to the water-based polyurethane waterproof and breathable finishing agent obtained in step (5), stir for 1 h to 1.5 h, and then perform ultrasonic treatment for 0.5 h to 2.5 h to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0023] Compared with the prior art, the antibacterial, breathable, and waterproof finishing agent for fabrics of the present invention has the following beneficial effects:

[0024] (1) Using high-boiling-point solvents as co-solvents and diluents avoids the need for vacuum distillation to remove low-boiling-point solvents (such as acetone) in the later stages of the reaction. This not only greatly simplifies the synthesis experimental steps and reduces production costs, but also reduces pollution to the ecological environment and harm to the health of front-line production workers, which is in line with the current green, environmentally friendly and sustainable development production concept.

[0025] (2) This invention combines an alkyl dimethyl tertiary amine antibacterial agent solution with an aqueous polyurethane waterproof and breathable finishing agent. The two work together to enhance the overall performance of the finishing agent, giving it superior comprehensive properties. Fabrics treated with this antibacterial, breathable and waterproof finishing agent have excellent waterproof and breathable effects. It also gives full play to the good antibacterial properties of alkyl dimethyl tertiary amine (it has a strong inhibitory and killing effect on various bacteria such as Staphylococcus aureus, Escherichia coli and Candida albicans), ensuring that it is non-toxic and safe to use during operation.

[0026] (3) Using high-boiling-point solvents as co-solvents and diluents can also improve the uniform dispersion of alkyl dimethyl tertiary amine antibacterial agents in antibacterial, breathable and waterproof finishing agents, so as to achieve the purpose of stable storage and convenient construction. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the water contact angle in various embodiments of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below. However, it should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the scope of the invention.

[0029] Example 1

[0030] An antibacterial, breathable, and waterproof finishing agent for fabrics, comprising the following raw materials by weight: 12 parts of dodecyl dimethyl tertiary amine antibacterial agent, 7 parts of N,N-dimethylformamide, 5.1 parts of isobutyl acetate, 14.4 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 21.7 parts of isophorone diisocyanate, 5.4 parts of polyoxypropylene glycol, 1.4 parts of 1,4-butanediol, 4.8 parts of N-methyldiethanolamine, 1.3 parts of acetic acid, and 26.9 parts of pure water, the total weight of the above components being 100 parts;

[0031] The preparation method of the antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps:

[0032] (1) The formulated amounts of polyoxypropylene glycol, hydroxyalkyl polyether silicone, and dodecyl dimethyl tertiary amine antibacterial agent are added to a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is subjected to vacuum distillation for 1.5 h at 110 °C and a vacuum degree of -0.1 MPa to obtain anhydrous polyoxypropylene glycol, anhydrous hydroxyalkyl polyether silicone, and anhydrous dodecyl dimethyl tertiary amine antibacterial agent for later use.

[0033] (2) The anhydrous polyoxypropylene glycol obtained in step (1) is placed in a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Isophorone diisocyanate is slowly added dropwise to the flask in the presence of the catalyst dibutyltin dilaurate. The mixture is stirred evenly in a water bath and kept at 75°C for 1.5 h to carry out the prepolymerization reaction and obtain a prepolymer with isocyanate groups at both ends.

[0034] (3) Dissolve the anhydrous hydroxyl polyether organosilicon from step (1) in isobutyl acetate and add it to the prepolymer obtained in step (2). Stir evenly in a water bath and keep warm at 75°C for 1.5 hours to obtain a preliminary modified emulsion for later use.

[0035] (4) The 1,4-butanediol and N-methyldiethanolamine of the formulation amount are slowly added dropwise to the preliminary modified emulsion obtained in step (3) in sequence, stirred evenly in a water bath, and chain extension reaction is carried out to obtain chain extension mixture; wherein, the chain extension reaction temperature is controlled at 55℃ and the chain extension time is 2h.

[0036] (5) At 35°C, add the prescribed amount of acetic acid to the chain-extended mixture obtained in step (4), stir evenly in a water bath to obtain an ionized neutralized modified mixture, and then add the prescribed amount of pure water for full emulsification to obtain a water-based polyurethane waterproof and breathable finishing agent.

[0037] (6) Add the anhydrous dodecyl dimethyl tertiary amine antibacterial agent from step (1) to N,N-dimethylformamide, stir thoroughly and then perform ultrasonic treatment for 1.5 hours to obtain a dodecyl dimethyl tertiary amine antibacterial agent solution.

[0038] (7) Add the dodecyl dimethyl tertiary amine antibacterial agent solution obtained in step (6) to the water-based polyurethane waterproof and breathable finishing agent obtained in step (5), stir for 1 hour, and then perform ultrasonic treatment for 2.5 hours to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0039] Example 2

[0040] An antibacterial, breathable, and waterproof finishing agent for fabrics, comprising the following raw materials by weight: 11 parts tetradecyl dimethyl tertiary amine antibacterial agent, 6.5 parts N,N-dimethylacetamide, 5.4 parts isobutyl acetate, 14.7 parts hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 22.2 parts isophorone diisocyanate, 5.7 parts polyoxypropylene glycol, 1.2 parts 1,4-butanediol, 4.3 parts N-methyldiethanolamine, 1.1 parts epichlorohydrin, and 27.9 parts pure water, the total weight fraction of the above components being 100.

[0041] The preparation method of the antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps:

[0042] (1) Add the prescribed amounts of tetradecyl dimethyl tertiary amine antibacterial agent, hydroxyalkyl polyether organosilicon, and polyoxypropylene glycol to a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Perform vacuum distillation dehydration treatment at 115°C and a vacuum degree of -0.1MPA for 1.5 hours to obtain anhydrous tetradecyl dimethyl tertiary amine antibacterial agent, anhydrous hydroxyalkyl polyether organosilicon, and anhydrous polyoxypropylene glycol for later use.

[0043] (2) The anhydrous polyoxypropylene glycol obtained in step (1) is placed in a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Isophorone diisocyanate is slowly added dropwise to the flask in the presence of the catalyst dibutyltin dilaurate. The mixture is stirred evenly in a water bath and kept at 80°C for 1 hour to carry out the prepolymerization reaction and obtain a prepolymer with isocyanate groups at both ends.

[0044] (3) Dissolve the anhydrous hydroxyl polyether organosilicon from step (1) in isobutyl acetate and add it to the prepolymer obtained in step (2). Stir evenly in a water bath and keep warm at 80°C for 1.5 hours to obtain a preliminary modified emulsion for later use.

[0045] (4) The 1,4-butanediol and N-methyldiethanolamine of the formulation amount are slowly added dropwise to the preliminary modified emulsion obtained in step (3) in sequence, stirred evenly in a water bath, and chain extension reaction is carried out to obtain chain extension mixture; wherein, the chain extension reaction temperature is controlled at 60℃ and the chain extension time is 3h.

[0046] (5) At 45°C, the formula amount of epichlorohydrin is added dropwise to the chain-extended mixture obtained in step (4), and after stirring evenly in a water bath, an ionized neutralized modified mixture is obtained. Then, the formula amount of pure water is added for full emulsification to obtain a waterborne polyurethane waterproof and breathable finishing agent.

[0047] (6) Add the anhydrous tetradecyl dimethyl tertiary amine antibacterial agent from step (1) to N,N-dimethylacetamide, stir thoroughly and then perform ultrasonic treatment for 2 hours to obtain a tetradecyl dimethyl tertiary amine antibacterial agent solution.

[0048] (7) Add the tetradecyl dimethyl tertiary amine antibacterial agent solution obtained in step (6) to the water-based polyurethane waterproof and breathable finishing agent obtained in step (5), stir for 1.5 h, and then perform ultrasonic treatment for 2.5 h to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0049] Example 3

[0050] A method for preparing an antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps:

[0051] (1) Weigh the following raw materials according to the mass percentages: 11 parts hexadecyl dimethyl tertiary amine antibacterial agent, 6 parts N,N-dimethylformamide, 5.7 parts isobutyl acetate, 15.4 parts hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 23.1 parts isophorone diisocyanate, 5.1 parts polytetrahydrofuran glycol, 1.1 parts 1,4-butanediol, 3.9 parts N-methyldiethanolamine, 1.1 parts acetic acid, and 27.6 parts pure water. The total mass percentages of the above components are 100 parts.

[0052] (2) The hexadecyl dimethyl tertiary amine antibacterial agent, hydroxyalkyl polyether organosilicon and polytetrahydrofuran diol described in step (1) are added to a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser and an outlet. The flask is subjected to vacuum distillation and dehydration treatment at 110°C and a vacuum degree of -0.08MPA for 1.5 hours to obtain anhydrous hexadecyl dimethyl tertiary amine antibacterial agent, anhydrous hydroxyalkyl polyether organosilicon and anhydrous polytetrahydrofuran diol.

[0053] (3) Place the anhydrous polytetrahydrofuran diol from step (2) into a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Slowly add isophorone diisocyanate to the flask, stir evenly in a water bath, and keep warm at 80°C for 1.5 h to carry out the prepolymerization reaction and obtain a prepolymer with isocyanate groups at both ends.

[0054] (4) Dissolve the anhydrous hydroxyl polyether organosilicon in step (2) in isobutyl acetate, add it to the prepolymer in step (3), stir evenly in a water bath, and keep warm at 80°C for 1.5 hours to obtain the preliminary modified emulsion.

[0055] (5) The 1,4-butanediol and N-methyldiethanolamine in step (1) are slowly added dropwise to the pre-modified emulsion in step (4) in sequence, stirred evenly in a water bath, and chain extension reaction is carried out to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 60°C and the chain extension time is 1.5h.

[0056] (6) Add the acetic acid weighed in step (1) to the chain extension mixture in step (5) at 45°C. After stirring evenly in a water bath, an ionized neutralized modified mixture is obtained. Then, pure water is added for full emulsification, and finally, a water-based polyurethane waterproof and breathable finishing agent is obtained.

[0057] (7) Add the anhydrous hexadecyl dimethyl tertiary amine antibacterial agent from step (2) to N,N-dimethylformamide, stir thoroughly and then perform ultrasonic treatment for 1.5h to obtain a hexadecyl dimethyl tertiary amine antibacterial agent solution.

[0058] (8) Add the hexadecyl dimethyl tertiary amine antibacterial agent solution described in step (7) to the water-based polyurethane waterproof and breathable finishing agent described in step (6), stir for 1.5 h and then perform ultrasonic treatment for 2.5 h to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0059] Example 4

[0060] A method for preparing an antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps:

[0061] (1) Weigh the following raw materials according to the following mass percentages: 12 parts of octadecyl dimethyl tertiary amine antibacterial agent, 8.8 parts of N-methylpyrrolidone, 5.4 parts of isobutyl acetate, 14.8 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 22.1 parts of isophorone diisocyanate, 4.2 parts of polyoxypropylene glycol, 1.2 parts of 1,4-butanediol, 4.8 parts of N-methyldiethanolamine, 1.3 parts of acetic acid, and 25.4 parts of pure water. The total mass percentage of the above components is 100 parts.

[0062] (2) Add the octadecyl dimethyl tertiary amine antibacterial agent, hydroxyalkyl polyether organosilicon and polyoxypropylene glycol described in step (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser and a gas outlet, and perform vacuum distillation dehydration treatment at 120°C and a vacuum degree of -0.1MPA for 1.5h to obtain anhydrous octadecyl dimethyl tertiary amine antibacterial agent, anhydrous hydroxyalkyl polyether organosilicon and anhydrous polyoxypropylene glycol;

[0063] (3) The anhydrous polyoxypropylene glycol described in step (2) is placed in a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Isophorone diisocyanate is slowly added dropwise to the flask. The mixture is stirred evenly in a water bath and kept at 80°C for 2 hours to carry out the prepolymerization reaction, thereby obtaining a prepolymer with isocyanate groups at both ends.

[0064] (4) Dissolve the anhydrous hydroxyl polyether organosilicon in step (2) in isobutyl acetate, then add it to the prepolymer in step (3), stir evenly in a water bath, and keep warm at 80°C for 1.5 hours to obtain the preliminary modified emulsion.

[0065] (5) The 1,4-butanediol and N-methyldiethanolamine described in step (1) are slowly added dropwise to the preliminarily modified emulsion in step (4) in sequence, stirred evenly in a water bath, and chain extension reaction is carried out to obtain a chain extension mixture; wherein, the chain extension reaction temperature is controlled at 55°C and the chain extension time is 2.5h.

[0066] (6) Add the acetic acid weighed in step (1) to the chain extension mixture in step (5) at 35°C. After stirring evenly in a water bath, an ionized neutralized modified mixture is obtained. Then, pure water is added for full emulsification, and finally, a water-based polyurethane waterproof and breathable finishing agent is obtained.

[0067] (7) Add the anhydrous octadecyl dimethyl tertiary amine antibacterial agent from step (2) to N-methylpyrrolidone, stir thoroughly and then perform ultrasonic treatment for 1.5 hours to obtain an octadecyl dimethyl tertiary amine antibacterial agent solution.

[0068] (8) Add the octadecyl dimethyl tertiary amine antibacterial agent solution from step (7) to the water-based polyurethane waterproof and breathable finishing agent from step (6), stir for 1.5 hours and then perform ultrasonic treatment for 2 hours to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0069] Example 5

[0070] A method for preparing an antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps:

[0071] (1) Weigh the following raw materials according to the mass percentages: 3 parts of dodecyl dimethyl tertiary amine antibacterial agent, 7 parts of tetradecyl dimethyl tertiary amine antibacterial agent, 6.7 parts of N,N-dimethylformamide, 5.9 parts of isobutyl acetate, 14.8 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 21.4 parts of isophorone diisocyanate, 5.6 parts of polyoxypropylene glycol, 1.5 parts of 1,4-butanediol, 5 parts of N-methyldiethanolamine, 1.4 parts of acetic acid, and 27.7 parts of pure water. The total mass percentages of the above components are 100 parts.

[0072] (2) The dodecyl dimethyl tertiary amine antibacterial agent, tetradecyl dimethyl tertiary amine antibacterial agent, hydroxyalkyl polyether organosilicon, and polyoxypropylene glycol from step (1) are respectively added to a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is subjected to vacuum distillation and dehydration treatment at 120°C and a vacuum degree of -0.08MPA for 1.5 hours to obtain anhydrous dodecyl dimethyl tertiary amine antibacterial agent, anhydrous tetradecyl dimethyl tertiary amine antibacterial agent, anhydrous hydroxyalkyl polyether organosilicon, and anhydrous polyoxypropylene glycol.

[0073] (3) Add the anhydrous polyoxypropylene glycol from step (2) into a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Slowly add isophorone diisocyanate to the flask, stir evenly in a water bath, and keep warm at 75°C for 2 hours to carry out the prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0074] (4) Dissolve the anhydrous hydroxyl polyether organosilicon from step (2) in isobutyl acetate, then add it to the prepolymer from step (3), stir evenly in a water bath, and keep warm at 80°C for 1.5 hours to obtain the preliminary modified emulsion.

[0075] (5) The 1,4-butanediol and N-methyldiethanolamine from step (1) are slowly added dropwise to the preliminary modified emulsion from step (4) in sequence, stirred evenly in a water bath, and chain extension reaction is carried out to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 65°C and the chain extension time is 2.5h.

[0076] (6) Add the acetic acid weighed in step (1) to the chain extension mixture in step (5) at 35°C. After stirring evenly in a water bath, an ionized neutralized modified mixture is obtained. Then, pure water is added for full emulsification, and finally, a water-based polyurethane waterproof and breathable finishing agent is obtained.

[0077] (7) Add the anhydrous dodecyl dimethyl tertiary amine antibacterial agent and the anhydrous tetradecyl dimethyl tertiary amine antibacterial agent from step (2) to N,N-dimethylformamide, stir thoroughly and then perform ultrasonic treatment for 1.5h to obtain a mixed alkyl dimethyl tertiary amine antibacterial agent solution.

[0078] (8) Add the mixed alkyl dimethyl tertiary amine antibacterial agent solution from step (7) to the water-based polyurethane waterproof and breathable finishing agent from step (6), stir for 1.5 hours and then perform ultrasonic treatment for 2 hours to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0079] Example 6

[0080] A method for preparing an antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps:

[0081] (1) Weigh the following raw materials according to the mass fractions: 3 parts of dodecyl dimethyl tertiary amine antibacterial agent, 9 parts of hexadecyl dimethyl tertiary amine antibacterial agent, 6.6 parts of N-methylpyrrolidone, 5.8 parts of isobutyl acetate, 14.9 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 22.3 parts of isophorone diisocyanate, 5.1 parts of polytetrahydrofuran diol, 1.5 parts of 1,4-butanediol, 5 parts of N-methyldiethanolamine, 1.4 parts of acetic acid, and 25.4 parts of pure water. The total mass fraction of the above components is 100.

[0082] (2) The dodecyl dimethyl tertiary amine antibacterial agent, hexadecyl dimethyl tertiary amine antibacterial agent, hydroxyalkyl polyether organosilicon, and polytetrahydrofuran diol from step (1) are respectively added to a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is subjected to vacuum distillation and dehydration treatment at 120°C and a vacuum degree of -0.1MPA for 1.5 hours to obtain anhydrous dodecyl dimethyl tertiary amine antibacterial agent, anhydrous hexadecyl dimethyl tertiary amine antibacterial agent, anhydrous hydroxyalkyl polyether organosilicon, and anhydrous polytetrahydrofuran diol.

[0083] (3) Place the anhydrous polytetrahydrofuran diol from step (2) into a dry four-necked round-bottom flask equipped with a thermocouple, a shear emulsifying stirrer, a nitrogen inlet, a condenser, and a gas outlet. Slowly add isophorone diisocyanate to the flask, stir evenly in a water bath, and keep warm at 85°C for 2 hours to carry out the prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0084] (4) Dissolve the anhydrous hydroxyl polyether organosilicon from step (2) in isobutyl acetate, then add it to the prepolymer from step (3), stir evenly in a water bath, and keep warm at 75°C for 1.5 hours to obtain the preliminary modified emulsion.

[0085] (5) The 1,4-butanediol and N-methyldiethanolamine from step (1) are slowly added dropwise to the preliminary modified emulsion from step (4) in sequence, stirred evenly in a water bath, and chain extension reaction is carried out to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 65°C and the chain extension time is 2.5h.

[0086] (6) Add the acetic acid weighed in step (1) to the chain-extended mixture in step (5) at 35°C. After stirring evenly in a water bath, an ionized neutralized modified mixture is obtained. Then, pure water is added for full emulsification to finally obtain a waterborne polyurethane waterproof and breathable finishing agent.

[0087] (7) Add the anhydrous dodecyl dimethyl tertiary amine antibacterial agent and anhydrous hexadecyl dimethyl tertiary amine antibacterial agent from step (2) to N-methylpyrrolidone, stir thoroughly and then perform ultrasonic treatment for 2 hours to obtain a mixed alkyl dimethyl tertiary amine antibacterial agent solution.

[0088] (8) Add the mixed alkyl dimethyl tertiary amine antibacterial agent solution from step (7) to the water-based polyurethane waterproof and breathable finishing agent from step (6), stir for 1.5 hours and then perform ultrasonic treatment for 2 hours to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

[0089] Comparative Example 1

[0090] The preparation method of the antibacterial, breathable and waterproof finishing agent for fabric provided in Comparative Example 1 differs from that in Example 5 in that the alkyl dimethyl tertiary amine antibacterial agent solution was not added to the waterborne polyurethane waterproof and breathable finishing agent obtained in Example 5, while the other conditions were the same.

[0091] Comparative Example 2

[0092] The preparation method of the antibacterial, breathable and waterproof finishing agent for fabric provided in Comparative Example 2 differs from that in Example 6 in that the alkyl dimethyl tertiary amine antibacterial agent solution was not added to the waterborne polyurethane waterproof and breathable finishing agent obtained in Example 6, while the other conditions were the same.

[0093] Product application performance testing

[0094] 1. Fabric finishing methods:

[0095] Antibacterial, breathable, and waterproof finishing agent concentration: 60g / L; Finished material: white knitted cotton fabric;

[0096] Finishing process: two dips and two rolls, 80% roll-up, rolling (2kg), drying (160℃ for 60 seconds), and sealing the fabric sample.

[0097] (1) Test antibacterial properties.

[0098] Test method: FZ / T 73023-2006 "Antibacterial Knitted Fabrics Appendix D.8 Test Method for Antibacterial Fabrics - Vibration Method"

[0099] Sample pretreatment: autoclaving (121℃, 15min); test sample: 0.75g±0.05g; contact conditions: (24±1)℃, 150r / min, 18h; incubation conditions: (37±1)℃, (24-72)h.

[0100] Tested bacterial strains: Staphylococcus aureus (ATCC 6538), Escherichia coli (8099), Candida albicans (ATCC10231);

[0101] The samples underwent 50 standard washes before testing;

[0102] The antibacterial test results of the antimicrobial fabrics are shown in the table below.

[0103] Table 1. Antibacterial rate index of antibacterial fabrics

[0104]

[0105] Table 2 shows the antibacterial rates of fabrics treated with and untreated with the finishing agents prepared in each example and comparative example.

[0106]

[0107] Table 3 shows the antibacterial levels of fabrics treated with and untreated with the finishing agents prepared in each example and comparative example.

[0108]

[0109] (2) Test waterproof and breathable properties

[0110] At room temperature, add water to a beaker, weigh out a piece of fabric with a mass of m0, immerse it in the water, remove it after 60 seconds, quickly wipe off the water on the surface of the fabric with filter paper, and weigh it as m1. Repeat the above steps 3 times, take the average value, and then calculate the water absorption rate of the fabric using formula (1);

[0111] Water absorption rate = (m1-m0) / m0×100% Equation (1);

[0112] The treated fabric was tested at room temperature using a water contact angle meter. Each sample was tested in triplicate, and the average value was taken.

[0113] Referring to the standard GB / T 12704.1—2009 "Textiles - Test Methods for Moisture Permeability of Fabrics - Part 1: Moisture Absorption Method", a moisture permeation cup containing desiccant and sealed with fabric is placed in a sealed environment with specified temperature and humidity. The moisture permeability of the fabric is calculated based on the change in mass of the moisture permeation cup over a certain period of time.

[0114] The water absorption rate, water contact angle, and moisture permeability of the fabrics treated with the finishing agents prepared in each embodiment and comparative example are shown in Table 4. Figure 1 As shown.

[0115] Table 4 shows the water absorption rate, water contact angle, and moisture permeability of the fabrics treated with the finishing agents prepared in each example and comparative example.

[0116]

[0117] Analysis of Tables 1, 2, and 3 shows that, compared with the untreated fabric, the fabric of Comparative Example 1, and the fabric of Comparative Example 2, the antibacterial properties of the fabrics treated in Examples 1 to 6 of the present invention are significantly improved. The antibacterial level of the test samples in Examples 1 to 6 is AAA, which indicates that the antibacterial, breathable, and waterproof finishing agent obtained by the present invention has a strong inhibitory and killing effect on Staphylococcus aureus, Escherichia coli, and Candida albicans.

[0118] From Table 4, Figure 1 It can be seen that the fabrics treated in each embodiment have lower water absorption, larger water contact angle, and higher moisture permeability compared to the untreated fabric and the comparative fabric. This indicates that the fabrics treated with the antibacterial, breathable, and waterproof finishing agent obtained in this invention have good waterproof and breathable properties.

[0119] The foregoing description of specific exemplary embodiments of the present invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and those skilled in the art can make various corresponding changes and modifications based on the above technical solutions and concepts. The exemplary embodiments were chosen and described to reveal the specific principles and practical applications of the invention, thereby enabling those skilled in the art to implement and utilize various different exemplary experimental schemes and various choices and modifications of the invention. All such changes and modifications are defined by the claims and their equivalents.

Claims

1. An antibacterial, breathable, and waterproof finishing agent for fabrics, characterized in that, By weight, it includes the following raw materials: 3-15 parts of alkyl dimethyl tertiary amine antibacterial agent, 6-9 parts of high-boiling-point solvent, 13-16 parts of organosilicon, 5-7 parts of isobutyl acetate, 20-25 parts of diisocyanate, 3-7 parts of polydiol, 0.5-2 parts of small molecule chain extender, 0.5-5 parts of hydrophilic chain extender, 0.5-2 parts of salt forming agent, and pure water to 100 parts; The alkyl dimethyl tertiary amine antibacterial agent is at least one selected from dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, and octadecyl dimethyl tertiary amine; the high-boiling-point solvent is at least one selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, toluene, and xylene; the organosilicon is at least one selected from aminoalkyl organosilicon, hydroxyalkyl polyether organosilicon, and dihydroxyalkyl organosilicon. The preparation method of the antibacterial, breathable, and waterproof finishing agent for fabrics includes the following steps: (1) Add the formulated amounts of alkyl dimethyl tertiary amine antibacterial agent, organosilicon, and polydiol to a dry four-necked round-bottom flask, and perform vacuum distillation dehydration treatment at 110℃~120℃ and a vacuum degree of -0.08~-0.1MPA to obtain anhydrous alkyl dimethyl tertiary amine antibacterial agent, anhydrous organosilicon, and anhydrous polydiol for later use; (2) Place the anhydrous polydiol obtained in step (1) into a dry four-necked round-bottom flask, slowly add diisocyanate to the flask, stir evenly in a water bath and keep warm, and then carry out a prepolymer reaction to obtain a prepolymer with isocyanate groups at both ends. (3) Dissolve the anhydrous organosilicon from step (1) in the prescribed amount of isobutyl acetate, add it to the prepolymer obtained in step (2), stir evenly in a water bath, and keep warm to obtain the preliminary modified emulsion for later use. (4) The small molecule chain extender and hydrophilic chain extender in the formula amount are slowly added dropwise to the preliminary modified emulsion obtained in step (3) in sequence, stirred evenly in a water bath, and the chain extension reaction is carried out to obtain the chain extended mixture. (5) Add the prescribed amount of salt-forming agent to the chain extender mixture obtained in step (4), stir evenly in a water bath to obtain an ionized neutralized modified mixture, and then add the prescribed amount of pure water for full emulsification to obtain a water-based polyurethane waterproof and breathable finishing agent. (6) Add the anhydrous alkyl dimethyl tertiary amine antibacterial agent from step (1) to the formula amount of high boiling point solvent, stir thoroughly and then perform ultrasonic treatment to obtain an alkyl dimethyl tertiary amine antibacterial agent solution. (7) Add the alkyl dimethyl tertiary amine antibacterial agent solution obtained in step (6) to the water-based polyurethane waterproof and breathable finishing agent obtained in step (5), stir for 1 h to 1.5 h, and then perform ultrasonic treatment for 0.5 h to 2.5 h to obtain a stable and dispersed antibacterial, breathable and waterproof finishing agent for fabrics.

2. The antibacterial, breathable, and waterproof finishing agent for fabrics according to claim 1, characterized in that, The diisocyanate is at least one selected from isophorone diisocyanate, 1,6-hexane diisocyanate, toluene diisocyanate, trimethylhexane diisocyanate, and diphenylmethane diisocyanate.

3. The antibacterial, breathable, and waterproof finishing agent for fabrics according to claim 1, characterized in that, The polydiol is at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, and polycarbonate glycol.

4. The antibacterial, breathable, and waterproof finishing agent for fabrics according to claim 1, characterized in that, The small molecule chain extender is at least one of 1,2-propanediol, 1,4-butanediol, 1,6-ethylenediol, and trimethylolpropane.

5. The antibacterial, breathable, and waterproof finishing agent for fabrics according to claim 1, characterized in that, The hydrophilic chain extender is at least one of N-methyldiethanolamine, diethylenetriamine, diethanolamine, and triethanolamine.

6. The antibacterial, breathable, and waterproof finishing agent for fabrics according to claim 1, characterized in that, The salt-forming agent is at least one of hydrochloric acid, acetic acid, CH3I, (CH3)2SO4, and epichlorohydrin.

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