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CN-121975414-A - Antibacterial coating for leather shoes and preparation method thereof

CN121975414ACN 121975414 ACN121975414 ACN 121975414ACN-121975414-A

Abstract

The invention discloses an antibacterial coating for leather shoes and a preparation method thereof, belonging to the technical field of leather chemical industry, wherein the coating takes aqueous polyurethane dispersoid as a film forming matrix and is matched with two antibacterial compounds with brand new designs: the vinyl functional biguanide silane quaternary ammonium salt and nano zinc loaded pyrithione silicon spheres are prepared by adding a cross-linking agent, a wetting leveling agent, a thickening agent, a film forming auxiliary agent and deionized water. The vinyl functional biguanidine silane quaternary ammonium salt is prepared by reacting isocyanate silane with biguanidine salt, then sequentially carrying out quaternization and epoxy ring opening modification, and integrating multiple antibacterial functional groups and polymerizable groups, wherein the nano zinc loaded pyridine thioketone silicon spheres are prepared by carrying out sulfhydrylation modification on mesoporous silicon dioxide nanospheres and then reacting with pyridine oxide and zinc salt, and have the physical cutting and ion releasing sterilization mechanism. The obtained coating has strong adhesion with leather shoe materials, is wash-resistant and friction-resistant, does not influence the air permeability and comfort of leather, and has good application prospect.

Inventors

  • WU LONGWEI
  • MA YUE
  • CHEN ZHIGUO
  • CHEN MIN

Assignees

  • 瑞安市大虎鞋业有限公司

Dates

Publication Date
20260505
Application Date
20260208

Claims (10)

  1. 1. The preparation method of the antibacterial coating for the leather shoes is characterized by comprising the following steps of: S1, stirring and mixing aqueous polyurethane dispersoid with deionized water, then adding polyether modified siloxane and polyurethane thickener, stirring and dispersing; s2, adding vinyl functionalized biguanide silane quaternary ammonium salt and nano zinc loaded pyrithione silicon spheres, stirring, and finally adding an aziridine cross-linking agent and dipropylene glycol methyl ether, and continuously stirring.
  2. 2. The method for preparing an antimicrobial coating for leather shoes according to claim 1, wherein in the step S1, the stirring and dispersing time is 10-20min.
  3. 3. The method for preparing an antimicrobial coating for leather shoes according to claim 1, wherein in the step S2, the stirring is continued for 20-40min.
  4. 4. The preparation method of the antibacterial coating for leather shoes according to claim 1 is characterized in that the preparation method of the vinyl functional biguanide silane quaternary ammonium salt comprises the steps of A1, adding 3-isocyanate propyl triethoxysilane and absolute ethyl alcohol into a three-neck flask, stirring under the protection of nitrogen, heating to 58-60 ℃, dropwise adding an ethanol solution containing 1, 1-dimethyl biguanide hydrochloride and triethylamine, reacting at 70-75 ℃, A2, then adding bromohexadecane, reacting at 78-82 ℃, finally adding glycidyl methacrylate, continuing to react at 78-80 ℃, and distilling under reduced pressure after the reaction is finished.
  5. 5. The method for preparing an antimicrobial coating for leather shoes according to claim 4, wherein in the step A1, the mass ratio of 3-isocyanatopropyl triethoxysilane, 1-dimethylbiguanide hydrochloride and triethylamine is 10:5:8.
  6. 6. The method for preparing an antimicrobial coating for leather shoes according to claim 4, wherein in the step A2, the reaction is continued for 3-4 hours at 78-80 ℃.
  7. 7. The preparation method of the antibacterial coating for leather shoes, which is characterized by comprising the steps of B1, dropwise adding tetraethoxysilane into a mixed solution consisting of ethanol, water and ammonia water, stirring and reacting at 28-32 ℃, centrifugally collecting precipitate, washing the precipitate to be neutral by deionized water, vacuum drying at 68-72 ℃ to obtain mesoporous silica nanospheres, B2, dispersing the mesoporous silica nanospheres in toluene, adding 3-mercaptopropyl triethoxysilane, reacting at 108-112 ℃ under reflux, centrifugally recovering a product after the reaction is finished, washing the product by ethanol to obtain mercaptosilicon spheres, finally dispersing the mercaptosilicon spheres into a phosphoric acid buffer solution with pH=8.0-8.5, sequentially adding 2-bromopyridine-1-oxide and zinc sulfate, stirring and reacting at 58-62 ℃, centrifugally collecting a product, washing the product by deionized water, and drying.
  8. 8. The method for preparing an antimicrobial coating for leather shoes according to claim 7, wherein in the step B1, the stirring reaction is carried out for 6-8 hours at 28-32 ℃.
  9. 9. The method for preparing an antimicrobial coating for leather shoes according to claim 7, wherein in the step B2, the reaction time is 12-14 hours under the reflux condition of 108-112 ℃.
  10. 10. The antibacterial coating for leather shoes prepared by the preparation method of the antibacterial coating for leather shoes according to any one of claims 1-9 is characterized by comprising the following raw materials, by weight, 60-85 parts of an aqueous polyurethane dispersion, 5-15 parts of vinyl functional biguanide silane quaternary ammonium salt, 3-10 parts of nano zinc-loaded pyrithione silicon spheres, 1-5 parts of an aziridine cross-linking agent, 0.3-1 part of polyether modified siloxane, 0.5-2 parts of a polyurethane thickener, 2-5 parts of dipropylene glycol methyl ether and 10-25 parts of deionized water.

Description

Antibacterial coating for leather shoes and preparation method thereof Technical Field The invention relates to the technical field of leather chemical industry, in particular to an antibacterial coating for leather shoes and a preparation method thereof. Background As a daily wearing article, the leather shoes are often in a damp-heat state due to factors such as tightness, sweat secretion of human bodies and the like in the internal environment, and become a hotbed for breeding various microorganisms. The porous structure of the leather and the rich protein components provide good living conditions for bacteria and fungi, and common pathogenic bacteria such as staphylococcus aureus, escherichia coli, trichophyton rubrum which is easy to cause beriberi and the like can be greatly propagated in the shoe cavity. The leather shoes not only generate bad smell, shorten the service life of the products, but also are more likely to cause foot skin diseases, and influence the health of consumers. The traditional leather shoe products generally lack effective antibacterial protection, and the conventional cleaning mode is difficult to thoroughly eliminate the hidden microorganisms in the shoe cavity, so that the defect becomes one of key factors for restricting the quality improvement of the leather shoe products. The existing antibacterial leather shoes technology on the market mainly depends on adding various antibacterial agents in the tanning or finishing process, but the methods have obvious limitations. Although the silver antibacterial agent has a certain broad-spectrum antibacterial property, the cost is high, migration and inactivation are easy to occur in leather matrix, bacterial drug resistance can be caused by long-term use, the organic antibacterial agents such as triclosan and the like are limited in a plurality of fields due to potential ecological toxicity, and the natural antibacterial agents such as chitosan derivatives have better safety, but have limited antibacterial efficacy and poor washing resistance, so that the long-term use requirement of leather shoes is difficult to meet. More importantly, most of the prior art adopts a single antibacterial mechanism, so that the growth of bacteria and fungi cannot be effectively inhibited at the same time, the binding force between antibacterial components and leather fibers is weak, and the antibacterial components are rapidly lost due to repeated bending friction in the wearing process, so that the antibacterial performance is rapidly attenuated. Although the partial coating technology can realize the initial antibacterial effect, the inherent air permeability and flexibility of leather are seriously damaged, and the wearing comfort is affected. In view of the above technical drawbacks, there is a need in the industry to develop a novel antimicrobial coating that can be firmly combined with leather shoe materials, has multiple antimicrobial mechanisms, and does not affect the natural properties of leather. The ideal coating should form a durable and effective protective layer on the leather surface, have broad-spectrum inhibition effect on common pathogenic microorganisms, and simultaneously maintain the water vapor permeability and soft touch of the leather. In recent years, a new thought is brought to the field by a modification technology based on silane chemistry and the appearance of a nanocomposite, different antibacterial functional groups are integrated into a stable carrier through molecular structure design, and the durability of a coating is enhanced by utilizing a crosslinking technology, so that the development of the functional coating has become a mainstream direction. Under the background, the invention successfully develops the antibacterial coating for leather shoes with high-efficiency antibacterial property and good application performance by innovatively designing two modified compounds with synergistic effect and optimizing the coating formula and the preparation process, and effectively solves a plurality of problems faced by the traditional technology. Disclosure of Invention The invention aims to provide an antibacterial coating for leather shoes and a preparation method thereof, which solve the technical problems that the conventional antibacterial coating for leather shoes has narrow antibacterial spectrum, is easy to migrate and fall off, has poor durability and affects the air permeability and flexibility of leather due to the addition of an antibacterial agent. The invention realizes the above purpose through the following technical scheme: the preparation method of the antibacterial coating for the leather shoes comprises the following steps: S1, stirring and mixing aqueous polyurethane dispersoid with deionized water, then adding polyether modified siloxane and polyurethane thickener, stirring and dispersing; s2, adding vinyl functionalized biguanide silane quaternary ammonium salt and nano zinc loaded pyrithione sili