Private part washing-free antibacterial liquid and preparation method thereof
By combining ingredients such as polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer, a no-wash antibacterial solution for private parts was prepared, which solved the problems of insufficient antibacterial durability and incomplete mucosal repair, and achieved the effects of immediate antibacterial, long-lasting protection and microecological balance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LIONSER MEDICAL DISINFECTANT (HANGZHOU) CO LTD
- Filing Date
- 2026-01-21
- Publication Date
- 2026-04-17
AI Technical Summary
Existing feminine washes lack the lasting antibacterial effect to effectively inhibit the growth of harmful bacteria, and some products disrupt the normal microecological balance or lack mucosal repair and protection.
Using polyhexamethylene biguanide hydrochloride as the core antibacterial ingredient, combined with chitosan-lactoferrin-lactate graft copolymer, sodium alginate-coated nano zinc-plant prebiotic microcapsules, mucosal repair agents, microecological regulators, moisturizing and soothing agents, thickening and stabilizing agents, and pH adjusters, a synergistic antibacterial solution for the intimate area is formed.
It achieves immediate antibacterial effect, long-lasting protection, mucosal repair and microecological balance, resulting in a safe, gentle and effective feminine hygiene care effect.
Abstract
Description
Technical Field
[0001] This invention relates to the field of nursing care products technology, specifically to a feminine wash-free antibacterial solution and its preparation method. Background Technology
[0002] The mucous membrane of the private parts is fragile and in a special physiological environment, making it susceptible to invasion by pathogens and causing discomfort. No-rinse antibacterial solutions have become commonly used care products for daily care and special occasions (such as after surgery or during menstruation) due to their convenient use and the fact that they do not require rinsing with water. Their research and development needs to take into account both antibacterial effectiveness and mucous membrane gentleness, and often involves the rational application of chemical raw materials or pharmaceutical excipients to achieve functional compatibility.
[0003] While existing general-purpose feminine washes can achieve short-term sterilization through basic antibacterial ingredients, most products suffer from insufficient duration of antibacterial effect, making it difficult to inhibit the growth of harmful bacteria in the long term. Furthermore, some products may disrupt the normal microecological balance of the private area when exerting their antibacterial effect, or lack targeted repair and protection for damaged mucous membranes, thus failing to meet users' core needs for both highly effective antibacterial and gentle care. Summary of the Invention
[0004] To address the problems existing in the prior art, the present invention provides a vaginal wash-free antibacterial solution and its preparation method, providing a safe and mild vaginal wash-free antibacterial solution that combines immediate antibacterial action, long-lasting protection, mucosal repair, and microecological balance.
[0005] To achieve the above objectives, the present invention provides the following technical solution: This application discloses a feminine wash-free antibacterial solution, which, by weight percentage, comprises: 0.08-0.16% polyhexamethylene biguanide hydrochloride, 0.9-1.9% chitosan-lactoferrin-lactate graft copolymer, 1.3-2.3% sodium alginate-coated nano-zinc-plant prebiotic microcapsules, 0.1-0.3% mucosal repair agent, 1.2-2.2% microecological regulator, 2.8-5.2% moisturizing and soothing agent, 0.35-0.75% thickening and stabilizing agent, 1.4-2.8% preservative, 0.6-1.4% pH adjuster, 1.2-2.6% emulsifier, with the balance being deionized water.
[0006] By employing the aforementioned technical solution, polyhexamethylene biguanide hydrochloride, as the core antibacterial ingredient, can rapidly disrupt the cell membranes of pathogenic bacteria. Chitosan-lactoferrin-lactate graft copolymer provides mucosal adsorption (prolonging the residence time of the antibacterial ingredient), anti-allergic and anti-inflammatory functions, and pH regulation. Sodium alginate-encapsulated nano-zinc-plant prebiotic microcapsules assist in antibacterial action, provide antioxidant effects, and protect the active ingredients. Mucosal repair agents promote epithelial cell healing; microecological regulators promote the proliferation of beneficial bacteria; moisturizing and soothing agents relieve dryness and itching; thickening and stabilizing agents enhance mucosal adhesion; pH regulators maintain the physiologically acidic environment of the intimate area; and emulsifiers improve system stability. The synergistic effect of these components achieves multiple benefits, including immediate antibacterial action, long-lasting protection, mucosal repair, and microecological balance, forming a safe, gentle, and highly effective no-rinse antibacterial solution for the intimate area.
[0007] Preferably, the mucosal repair agent is ceramide, the microecological regulator is one or more of xylooligosaccharides and fructooligosaccharides, the moisturizing and soothing agent is one or more of erythritol or allantoin, the thickening and stabilizing agent is one or more of xanthan gum or hydroxyethyl cellulose, the preservative is a compound of chlorphenesin and hexanediol in a mass ratio of 1:10-1:12, the pH adjuster is a citrate-sodium citrate buffer pair, and the emulsifier is one or more of polyglycerol-10 laurate or PEG-8 cetyl ether.
[0008] By setting up the above technical solutions, ceramides, as a mucosal repair agent, can effectively repair the mucosal barrier of the private parts; one or more of xylooligosaccharides and fructooligosaccharides, as microecological regulators, can promote the proliferation of beneficial bacteria to maintain microecological balance; one or more of erythritol or allantoin, as a moisturizing and soothing agent, can lock in moisture and relieve dryness and discomfort; one or more of xanthan gum or hydroxyethyl cellulose, as a thickening and stabilizing agent, can enhance the stability of the system and the adhesion of the mucosa; a preservative composed of chlorphenesin and hexanediol in a mass ratio of 1:10-1:12 can synergistically inhibit the growth of microorganisms in the product itself to extend the shelf life; a citrate-sodium citrate buffer pair, as a pH regulator, can maintain the system matching the physiological acidic environment of the private parts; and one or more of polyglycerol-10 laurate or PEG-8 cetyl ether, as an emulsifier, can promote the uniform dispersion of each component and optimize the skin feel; the synergistic effect of each component, while achieving the effects of mucosal repair, microecological regulation and moisturizing and soothing, ensures the stability, safety and user experience of the product.
[0009] Preferably, the raw materials comprising the chitosan-lactoferrin-lactate graft copolymer by weight parts include: 8-12 parts chitosan, 3.8-6.0 parts lactoferrin, 6.8-9.0 parts lactate, 0.55-0.85 parts 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 120-180 parts acetic acid solution with a volume fraction of 1.0-1.2%.
[0010] By setting up the above technical solution, chitosan is used as the main body of the grafting reaction. A volume fraction of 1.0-1.2% acetic acid solution can ensure its full dissolution to provide a homogeneous reaction system. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is used as an activator to efficiently activate the functional group reaction between chitosan, lactoferrin and lactate, and promote the successful grafting of the three to form a chitosan-lactoferrin-lactate graft copolymer. This copolymer can simultaneously possess the mucosal adsorption properties of chitosan, the anti-allergic effect of lactoferrin and the pH regulation function of lactate, thus realizing the synergistic integration of the functions of each raw material.
[0011] Preferably, the preparation method of the chitosan-lactoferrin-lactate graft copolymer includes the following steps: 1) Take chitosan, add acetic acid solution, and stir at 320-420 r / min at 42-52℃ for 32-42 min to dissolve it; 2) Add lactoferrin to the solution obtained in 1), stir well, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, activate for 32-42 min, then add lactate dropwise at a rate of 1.2-2.2 mL / min, stir well, then raise the temperature to 62-72℃ and react at this temperature for 2.2-3.2 h; 3) Adjust the pH of the mixture obtained in 2) to 7.1-7.6 with a 10-12% sodium hydroxide solution to produce a precipitate. Centrifuge the precipitate at 8200-10200 r / min for 16-22 min and collect the precipitate. 4) Wash the precipitate 3-4 times with anhydrous ethanol, then dry it under vacuum conditions of 52-62℃ and -0.092~-0.082MPa for 4.2-6.2h, pulverize it and pass it through a 200-300 mesh sieve to obtain chitosan-lactoferrin-lactate graft copolymer.
[0012] By setting up the above technical solution, stirring and dissolving at 42-52℃ ensures that chitosan is fully dispersed to form a uniform reaction system. The activation effect of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and the isothermal reaction at 62-72℃ synergistically promote the grafting reaction of chitosan, lactoferrin and lactate. pH adjustment and high-speed centrifugation can efficiently collect the target precipitate. Anhydrous ethanol washing combined with vacuum drying can remove unreacted monomers and avoid product oxidation. Sieving ensures uniform product particle size. Finally, through the synergistic effect of each process step, a chitosan-lactoferrin-lactate graft copolymer with high purity and stable performance is efficiently prepared.
[0013] Preferably, the chitosan has a degree of deacetylation of 91-99% and a weight-average molecular weight of 80-120 kDa; the lactoferrin has a weight-average molecular weight of 80-85 kDa; and the lactate is either ethyl lactate or butyl lactate.
[0014] By setting the above technical solutions, the parameters of chitosan are limited to ensure its good solubility in the reaction system and its excellent mucosal adsorption potential; the weight-average molecular weight of lactoferrin (80-85 kDa) ensures the stable performance of its anti-allergic activity; ethyl lactate or butyl lactate, as specific types of lactate esters, have strong structural compatibility with chitosan and lactoferrin, which is conducive to the efficient grafting reaction. Through the synergistic matching of structure and performance, the three components jointly promote the chitosan-lactoferrin-lactate graft copolymer to have comprehensive functions of mucosal adsorption, anti-allergy and anti-inflammatory and pH regulation.
[0015] Preferably, the raw materials of sodium alginate-coated nano-zinc-plant prebiotic microcapsules, by weight, include: 28-36 parts of active Lactobacillus acidophilus fermentation concentrate, 1.0-1.4 parts of nano-zinc powder, 4-5 parts of inulin, 4.8-6.0 parts of fructooligosaccharides, 1.0-1.7 parts of sodium alginate, and 80-120 parts of calcium chloride solution with a mass fraction of 2.2-3.2%.
[0016] By setting up the above technical solution, the active Lactobacillus acidophilus fermentation concentrate can enhance the basic function of microecological regulation, the nano zinc powder can play an auxiliary role in antibacterial and antioxidant effects, the inulin and fructooligosaccharides can promote the proliferation of beneficial bacteria as plant prebiotics, and the sodium alginate as a coating matrix can form a stable microcapsule structure under the cross-linking effect of calcium chloride solution with a mass fraction of 2.2-3.2%. The synergistic effect of each raw material not only protects the internal active ingredients from being destroyed through the coating structure, but also realizes the comprehensive functions of auxiliary antibacterial, antioxidant and microecological regulation, ensuring that the microcapsules can play a stable role in application.
[0017] Preferably, the preparation method of sodium alginate-coated nano-zinc-plant prebiotic microcapsules includes the following steps: a. Mix inulin and fructooligosaccharides, add deionized water, and stir at 220-320 r / min at 32-42℃ for 22-32 min to prepare a mixed solution with a total solute mass fraction of 8-13%; b. Add the nano zinc powder to the mixture obtained in step a, and ultrasonically disperse it for 12-17 minutes at a power of 220-320W to obtain the nano zinc-prebiotic dispersion; c. Mix the active Lactobacillus acidophilus fermentation concentrate with the nano zinc-prebiotic dispersion, add sodium alginate, and stir at 220-320 r / min for 22-32 min to obtain the mixture; d. The mixture was added dropwise to the calcium chloride solution at a rate of 0.6-1.1 mL / min, and stirred and solidified at a speed of 160-210 r / min for 16-22 min to obtain microcapsules. The microcapsules were washed with deionized water 3-4 times and then freeze-dried under vacuum at a temperature of -42~-32℃ and a pressure of -0.10~-0.09 MPa for 8-12 h to obtain sodium alginate-coated nano zinc-plant prebiotic microcapsules with a particle size of 1.2-2.2 μm.
[0018] By setting up the above technical solution, stirring and dissolving at appropriate temperature and speed ensures that inulin and fructooligosaccharides are fully dispersed, ultrasonic dispersion can effectively avoid the aggregation of nano-zinc, stirring and mixing can fully emulsify and fuse the active Lactobacillus acidophilus fermentation concentrate, nano-zinc-prebiotic dispersion and sodium alginate, dropwise addition and solidification form a stable sodium alginate coating structure, washing to remove impurities and vacuum freeze drying can retain the active ingredients to the greatest extent, and finally prepare sodium alginate-coated nano-zinc-plant prebiotic microcapsules with uniform particle size and stable structure, ensuring the stable performance of its auxiliary antibacterial, antioxidant and microecological regulation functions.
[0019] Preferably, the solid content of the active Lactobacillus acidophilus fermentation concentrate is 11-16%, wherein the viable count is 1×10⁻⁶. 8 -5×10 8 CFU / g; the particle size of the nano zinc powder is 40-90nm, the weight average molecular weight of inulin is 3-6kDa, and the weight average molecular weight of fructooligosaccharides is 1-1.5kDa.
[0020] By setting the above technical solutions, the limitation of parameters of the active Lactobacillus acidophilus fermentation concentrate can ensure the concentration of its active ingredients, providing a basis for microecological regulation; the particle size of 40-90nm of nano zinc powder can avoid agglomeration and ensure its uniform dispersion to fully exert its auxiliary antibacterial and antioxidant effects; the suitable weight-average molecular weight of inulin (3-6kDa) and fructooligosaccharides (1-1.5kDa) makes it easier for beneficial bacteria to utilize it as a prebiotic, and it has good compatibility with other components and is not easily destroyed. The synergistic effect of the above parameters can ensure that the sodium alginate-coated nano zinc-plant prebiotic microcapsules have stable functions of auxiliary antibacterial, antioxidant and microecological regulation.
[0021] This application also discloses a method for preparing a feminine wash-free antibacterial solution, comprising the following steps: S1, Preprocessing stage: Take 82-88% of the total amount of deionized water, heat it to 36-46℃, add thickening and stabilizing agent, stir at 820-1020 r / min for 22-32 min to obtain the matrix solution, and keep it at 36-46℃ for later use. S2, Antibacterial System Construction Stage: Add polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer sequentially to the matrix solution, and stir and mix at 520-620 r / min for 16-26 min at 36-46℃. S3, Functional Ingredient Complexation Stage: Reduce the temperature of the system obtained from S2 to 26-31℃, add the mucosal repair agent, microecological regulator, and moisturizing and soothing agent, and stir at a speed of 320-420r / min for 32-42min; S4, Microcapsule Dispersion Stage: Disperse the sodium alginate-coated nano-zinc-plant prebiotic microcapsules into a suspension using 5.2-5.8% of the total deionized water in the raw material of the feminine wash-free antibacterial solution. Slowly add the suspension to the system obtained in S3 and stir at 160-210 r / min for 16-22 min. S5, Emulsification and Preservation Stage: Add emulsifier to the system obtained in S4 and stir at 320-420 r / min for 12-17 min; then add preservative and stir at 220-320 r / min for 11-16 min. S6, pH adjustment and post-treatment stage: Add a pH adjuster to the system obtained in S5 to adjust the pH value to 3.9-4.5, stir for 6-11 minutes until the pH value is stable; then homogenize and vacuum degassing treatment, filter with a 2.5-3.0μm filter membrane, add the remaining deionized water and mix evenly to obtain a feminine wash-free antibacterial solution.
[0022] By setting up the above technical solutions, the appropriate temperature and high-speed stirring in the pretreatment stage ensure that the thickening stabilizer is fully dissolved to form a stable matrix liquid; the antibacterial system construction stage maintains constant temperature stirring to ensure that polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer are uniformly combined; the functional component compounding stage involves cooling to protect the active ingredients such as mucosal repair agents, and stirring to ensure that the water-soluble functional components are fully dissolved; the microcapsule dispersion stage uses low-speed stirring and pre-dispersion to protect the integrity of the structure of sodium alginate-coated nano-zinc-plant prebiotic microcapsules and ensure uniform dispersion; the emulsification and preservation stage achieves the synergistic effect of emulsifier optimizing system compatibility and preservative uniform dispersion through stirring; the pH adjustment and post-treatment stage adjusts the pH of the system to match the physiological acidity range of the private parts, and homogenization, vacuum degassing, and filtration ensure product uniformity, no bubbles, and cleanliness. Finally, through the synergy of each step, a private part no-wash antibacterial liquid with uniformly dispersed functional components, good activity retention, stable system, and safe use is prepared.
[0023] Preferably, in step S6, the homogenization process involves passing the system through a homogenizer 2-3 times under conditions of 22-32 MPa pressure and 26-31°C temperature; the vacuum degassing process involves vacuum degassing for 11-16 minutes under conditions of -0.082 to -0.072 MPa pressure and 26-31°C temperature to remove air bubbles.
[0024] By setting up the above technical solution, under the mild temperature conditions of 26-31℃ and the multiple homogenization treatments under the pressure of 22-32MPa, the particle size of the system can be effectively refined, the aggregation state of the components can be broken, and the functional components such as polyhexamethylene biguanide hydrochloride and sodium alginate-coated nano zinc-plant prebiotic microcapsules can be evenly dispersed, thereby improving the uniformity of the product and reducing the aggregation and growth of microorganisms. The vacuum degassing treatment at the same temperature can efficiently remove air bubbles in the system, avoid the formation of air bubbles during use that affect the skin feel, and further ensure the stability of the system, making the product texture more uniform and smooth.
[0025] The beneficial effects of this invention are as follows: Polyhexamethylene biguanide hydrochloride, as the core antibacterial ingredient, can rapidly disrupt the cell membranes of pathogenic bacteria. Chitosan-lactoferrin-lactate graft copolymer provides mucosal adsorption, anti-allergic and anti-inflammatory functions, and pH regulation, prolonging the residence time of the antibacterial ingredients. Sodium alginate-encapsulated nano-zinc-plant prebiotic microcapsules assist in antibacterial, antioxidant, and protection of active ingredients. Mucosal repair agents promote epithelial cell healing; microecological regulators promote the proliferation of beneficial bacteria; moisturizing and soothing agents relieve dryness and itching; thickening and stabilizing agents enhance mucosal adhesion; pH regulators maintain the physiologically acidic environment of the intimate area; and emulsifiers improve system stability. The synergistic effect of these components achieves multiple benefits, including immediate antibacterial action, long-lasting protection, mucosal repair, and microecological balance, forming a safe, gentle, and highly effective no-rinse antibacterial solution for the intimate area.
[0026] Chitosan serves as the main component in the grafting reaction. A 1.0-1.2% (v / v) acetic acid solution ensures its complete dissolution, providing a homogeneous reaction system. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride acts as an activator, efficiently activating the functional group reactions between chitosan, lactoferrin, and lactate, promoting the successful grafting of the three to form a chitosan-lactoferrin-lacate graft copolymer. This copolymer simultaneously possesses the mucosal adsorption properties of chitosan, the anti-allergic effect of lactoferrin, and the pH regulating function of lactate, achieving synergistic integration of the functions of each raw material. Detailed Implementation
[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0028] Example 1: This embodiment discloses a feminine wash-free antibacterial solution, which, by weight percentage, comprises: 0.08% polyhexamethylene biguanide hydrochloride, 0.9% chitosan-lactoferrin-lactate graft copolymer, 1.3% sodium alginate-coated nano-zinc-plant prebiotic microcapsules, 0.1% ceramide, 1.2% xylooligosaccharides, 2.8% erythritol, 0.35% xanthan gum, 1.4% preservative, 0.6% citric acid-sodium citrate buffer pair, 1.2% polyglycerol-10 laurate, and the balance being deionized water. The preservative is a mixture of chlorphenesin and hexanediol in a mass ratio of 1:10.
[0029] The chitosan-lactoferrin-lactate graft copolymer, by weight parts, comprises: 8 parts chitosan, 3.8 parts lactoferrin with a weight-average molecular weight of 80 kDa, 6.8 parts lactate, and 0.55 parts 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. The reaction medium is 120 parts of a 1.0% (v / v) acetic acid solution. The degree of deacetylation of chitosan is 91%, and its weight-average molecular weight is 80 kDa; the lactate is ethyl lactate.
[0030] The preparation method of chitosan-lactoferrin-lactate graft copolymer includes the following steps: 1) Take chitosan, add acetic acid solution, and stir at 320 r / min at 42℃ for 32 min to dissolve it; 2) Add lactoferrin to the solution obtained in 1), stir well, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, activate for 32 min, then add lactate dropwise at a rate of 1.2 mL / min, stir well, then heat to 62 °C, and react at this temperature for 2.2 h. 3) Adjust the pH of the mixture obtained in 2) to 7.1 with a 10% sodium hydroxide solution to produce a precipitate. Centrifuge the precipitate at 8200 r / min for 16 min and collect the precipitate. 4) The precipitate was washed three times with anhydrous ethanol, then dried for 4.2 h under vacuum conditions of 52℃ and -0.092 MPa. After pulverizing, it was passed through a 200-mesh sieve to obtain chitosan-lactoferrin-lactate graft copolymer.
[0031] By weight, the raw materials of sodium alginate-coated nano-zinc-plant prebiotic microcapsules include: 11% active Lactobacillus acidophilus fermentation concentrate (live bacteria count 1×10⁻⁶). 8 28 parts of CFU / g nano-zinc powder with a particle size of 40nm, 1.0 part of inulin with a weight average molecular weight of 3kDa, 4.8 parts of fructooligosaccharides with a weight average molecular weight of 1kDa, 1.0 part of sodium alginate, and 80 parts of calcium chloride solution with a mass fraction of 2.2%.
[0032] The preparation method of sodium alginate-coated nano-zinc-plant prebiotic microcapsules includes the following steps: a. Mix inulin and fructooligosaccharides, add deionized water, and stir at 220 r / min at 32℃ for 22 min to prepare a mixed solution with a total solute mass fraction of 8%. b. Add the nano zinc powder to the mixture obtained in step a, and ultrasonically disperse it for 12 minutes at a power of 220W to obtain the nano zinc-prebiotic dispersion; c. Mix the active Lactobacillus acidophilus fermentation concentrate with the nano zinc-prebiotic dispersion, add sodium alginate, and stir at 220 r / min for 22 min to obtain the mixture; d. The mixture was added dropwise to the calcium chloride solution at a rate of 0.6 mL / min, and stirred and solidified at a speed of 160 r / min for 16 min to obtain microcapsules. The microcapsules were washed three times with deionized water and then freeze-dried under vacuum at a temperature of -42℃ and a pressure of -0.10 MPa for 8 h to obtain sodium alginate-coated nano-zinc-plant prebiotic microcapsules with a particle size of 1.2 μm.
[0033] This embodiment also discloses a method for preparing a feminine wash-free antibacterial solution, comprising the following steps: S1, Preprocessing stage: Take 82% of the total amount of deionized water, heat it to 36°C, add xanthan gum, stir at 820 r / min for 22 min to obtain the matrix solution, and keep it at 36°C for later use. S2, Antibacterial System Construction Stage: Polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer were added sequentially to the matrix solution and stirred at 520 r / min for 16 min at 36 °C. S3, Functional Ingredient Complexation Stage: The temperature of the system obtained in S2 was lowered to 26°C, and ceramide, xylooligosaccharide, and erythritol were added. The mixture was stirred at 320 r / min for 32 min. S4, Microcapsule Dispersion Stage: Sodium alginate-coated nano-zinc-plant prebiotic microcapsules were dispersed into a suspension by 5.2% of the total deionized water in the raw material of the feminine wash antibacterial solution, and slowly added to the system obtained in S3. The mixture was stirred at 160 r / min for 16 min. S5, Emulsification and Preservation Stage: Polyglycerol-10 laurate was added to the system obtained in S4 and stirred at 320 r / min for 12 min; then the preservative was added and stirred at 220 r / min for 11 min. S6, pH adjustment and post-treatment stage: Add a citric acid-sodium citrate buffer pair to the system obtained in S5, adjust the pH of the system to 3.9, and stir for 6 min until the pH stabilizes; then homogenize the system twice using a homogenizer at a pressure of 22 MPa and a temperature of 26 °C; then degas under vacuum for 11 min at a pressure of -0.082 MPa and a temperature of 26 °C to remove air bubbles; finally filter with a 2.5 μm filter membrane, add the remaining deionized water and mix well to obtain a feminine wash-free antibacterial solution.
[0034] Example 2: This embodiment discloses a feminine wash-free antibacterial solution, comprising the following raw materials by weight percentage: 0.16% polyhexamethylene biguanide hydrochloride, 1.9% chitosan-lactoferrin-lactate graft copolymer, 2.3% sodium alginate-coated nano-zinc-plant prebiotic microcapsules, 0.3% ceramide, 2.2% fructooligosaccharides, 5.2% allantoin, 0.75% hydroxyethyl cellulose, 2.8% preservative, 1.4% citric acid-sodium citrate buffer pair, 2.6% PEG-8 cetyl ether, with the balance being deionized water. The preservative is a mixture of chlorphenesin and hexanediol in a mass ratio of 1:12.
[0035] The chitosan-lactoferrin-lactate graft copolymer, by weight parts, comprises: 12 parts chitosan, 6.0 parts lactoferrin with a weight-average molecular weight of 85 kDa, 9.0 parts lactate, and 0.85 parts 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. The reaction medium is 180 parts of a 1.2% (v / v) acetic acid solution. The chitosan has a degree of deacetylation of 99% and a weight-average molecular weight of 120 kDa; the lactate is butyl lactate.
[0036] The preparation method of chitosan-lactoferrin-lactate graft copolymer includes the following steps: 1) Take chitosan, add acetic acid solution, and stir at 420 r / min at 52℃ for 42 min to dissolve it; 2) Add lactoferrin to the solution obtained in 1), stir well, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, activate for 42 min, then add lactate dropwise at a rate of 2.2 mL / min, stir well, then heat to 72 °C, and react at this temperature for 3.2 h. 3) Adjust the pH of the mixture obtained in 2) to 7.6 with a 12% sodium hydroxide solution to produce a precipitate. Centrifuge the precipitate at 10200 r / min for 22 min and collect the precipitate. 4) The precipitate was washed four times with anhydrous ethanol, then dried for 6.2 h under vacuum conditions of 62℃ and -0.082 MPa, pulverized and passed through a 300-mesh sieve to obtain chitosan-lactoferrin-lactate graft copolymer.
[0037] By weight, the raw materials of sodium alginate-coated nano-zinc-plant prebiotic microcapsules include: 16% solids content of active Lactobacillus acidophilus fermentation concentrate (5 × 10⁻⁶ live bacteria count). 8 36 parts of CFU / g nano-zinc powder with a particle size of 90nm, 1.4 parts of inulin with a weight average molecular weight of 6kDa, 6.0 parts of fructooligosaccharides with a weight average molecular weight of 1.5kDa, 1.7 parts of sodium alginate, and 120 parts of calcium chloride solution with a mass fraction of 3.2%.
[0038] The preparation method of sodium alginate-coated nano-zinc-plant prebiotic microcapsules includes the following steps: a. Mix inulin and fructooligosaccharides, add deionized water, and stir at 320 r / min for 32 min at 42℃ to dissolve, thus preparing a mixture with a total solute mass fraction of 13%; b. Add the nano zinc powder to the mixture obtained in step a, and ultrasonically disperse it for 17 minutes at a power of 320W to obtain the nano zinc-prebiotic dispersion. c. Mix the active Lactobacillus acidophilus fermentation concentrate with the nano zinc-prebiotic dispersion, add sodium alginate, and stir at 320 r / min for 32 min to obtain the mixture; d. The mixture was added dropwise to the calcium chloride solution at a rate of 1.1 mL / min, and stirred and solidified at a speed of 210 r / min for 22 min to obtain microcapsules. The microcapsules were washed 4 times with deionized water and then freeze-dried under vacuum at a temperature of -32℃ and a pressure of -0.09 MPa for 12 h to obtain sodium alginate-coated nano zinc-plant prebiotic microcapsules with a particle size of 2.2 μm.
[0039] This embodiment also discloses a method for preparing a feminine wash-free antibacterial solution, comprising the following steps: S1, Preprocessing stage: Take 88% of the total amount of deionized water, heat it to 46℃, add hydroxyethyl cellulose, stir at 1020 r / min for 32 min to obtain the matrix solution, and keep it at 46℃ for later use. S2, Antibacterial System Construction Stage: Polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer were added sequentially to the matrix solution and stirred at 620 r / min for 26 min at 46 °C. S3, Functional Ingredient Complexation Stage: The temperature of the system obtained in S2 was lowered to 31°C, and ceramide, fructooligosaccharide, and allantoin were added. The mixture was stirred at 420 r / min for 42 min. S4, Microcapsule Dispersion Stage: Sodium alginate-coated nano-zinc-plant prebiotic microcapsules were dispersed into a suspension by 5.8% of the total deionized water in the raw material of the feminine wash antibacterial solution, and slowly added to the system obtained in S3. The mixture was stirred at 210 r / min for 22 min. S5, Emulsification and Preservation Stage: PEG-8 cetyl ether was added to the system obtained in S4 and stirred at 420 r / min for 17 min; then the preservative was added and stirred at 320 r / min for 16 min. S6, pH adjustment and post-treatment stage: Add a citric acid-sodium citrate buffer pair to the system obtained in S5, adjust the pH of the system to 4.5, and stir for 11 min until the pH stabilizes; then homogenize the system three times under a pressure of 32 MPa and a temperature of 31 °C; then degas under vacuum for 16 min under a pressure of -0.072 MPa and a temperature of 31 °C to remove air bubbles; finally filter with a 3.0 μm filter membrane, add the remaining deionized water and mix well to obtain a feminine wash-free antibacterial solution.
[0040] Example 3: This embodiment discloses a feminine wash-free antibacterial solution, which, by weight percentage, comprises: 0.12% polyhexamethylene biguanide hydrochloride, 1.4% chitosan-lactoferrin-lactate graft copolymer, 1.8% sodium alginate-coated nano zinc-plant prebiotic microcapsules, 0.2% ceramide, 1.7% microecological regulator, 4% moisturizing and soothing agent, 0.55% thickening and stabilizing agent, 2.1% preservative, 1% citric acid-sodium citrate buffer pair, 1.9% emulsifier, and the balance being deionized water.
[0041] The microecological regulator is a compound of xylooligosaccharide and fructooligosaccharide in a 1:1 mass ratio; the moisturizing and soothing agent is a compound of erythritol and allantoin in a 1:1 mass ratio; the thickening and stabilizing agent is a compound of xanthan gum and hydroxyethyl cellulose in a 1:1 mass ratio; the preservative is a compound of chlorphenesin and hexanediol in a 1:11 mass ratio; and the emulsifier is a compound of polyglycerol-10 laurate and PEG-8 cetyl ether in a 1:1 mass ratio.
[0042] The chitosan-lactoferrin-lactate graft copolymer, by weight parts, comprises: 10 parts chitosan, 4.9 parts lactoferrin with a weight-average molecular weight of 82 kDa, 7.9 parts lactate, and 0.7 parts 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. The reaction medium is 150 parts of a 1.1% (v / v) acetic acid solution. The chitosan has a degree of deacetylation of 95% and a weight-average molecular weight of 100 kDa; the lactate is butyl lactate.
[0043] The preparation method of chitosan-lactoferrin-lactate graft copolymer includes the following steps: 1) Take chitosan, add acetic acid solution, and stir at 370 r / min at 47℃ for 37 min to dissolve it; 2) Add lactoferrin to the solution obtained in 1), stir well, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, activate for 37 min, then add lactate dropwise at a rate of 1.7 mL / min, stir well, then heat to 67 °C, and react at this temperature for 2.7 h. 3) Adjust the pH of the mixture obtained in 2) to 7.4 with 11% sodium hydroxide solution to produce a precipitate. Centrifuge at 9200 r / min for 19 min and collect the precipitate. 4) The precipitate was washed four times with anhydrous ethanol, then dried for 5.2 h under vacuum conditions of 57 °C and -0.087 MPa. After pulverizing, it was passed through a 250-mesh sieve to obtain chitosan-lactoferrin-lactate graft copolymer.
[0044] By weight, the raw materials of sodium alginate-coated nano-zinc-plant prebiotic microcapsules include: 14% solids content of active Lactobacillus acidophilus fermentation concentrate (live bacteria count 3 × 10⁻⁶). 8 32 parts (CFU / g), 1.2 parts nano zinc powder with a particle size of 65nm, 4.5 parts inulin with a weight average molecular weight of 5kDa, 5.4 parts fructooligosaccharides with a weight average molecular weight of 1.2kDa, 1.4 parts sodium alginate, and 100 parts calcium chloride solution with a mass fraction of 2.7%.
[0045] The preparation method of sodium alginate-coated nano-zinc-plant prebiotic microcapsules includes the following steps: a. Mix inulin and fructooligosaccharides, add deionized water, and stir at 270 r / min at 37°C for 27 min to dissolve, thus preparing a mixed solution with a total solute mass fraction of 11%. b. Add the nano zinc powder to the mixture obtained in step a, and ultrasonically disperse it for 15 minutes at a power of 270W to obtain the nano zinc-prebiotic dispersion. c. Mix the active Lactobacillus acidophilus fermentation concentrate with the nano zinc-prebiotic dispersion, add sodium alginate, and stir at 270 r / min for 27 min to obtain the mixture; d. The mixture was added dropwise to the calcium chloride solution at a rate of 0.8 mL / min, and stirred and solidified at a speed of 185 r / min for 19 min to obtain microcapsules. The microcapsules were washed 4 times with deionized water and then freeze-dried under vacuum at a temperature of -37℃ and a pressure of -0.095 MPa for 10 h to obtain sodium alginate-coated nano-zinc-plant prebiotic microcapsules with a particle size of 1.7 μm.
[0046] This embodiment also discloses a method for preparing a feminine wash-free antibacterial solution, comprising the following steps: S1, Preprocessing stage: Take 85% of the total amount of deionized water, heat it to 41°C, add a thickening stabilizer, stir at 920 r / min for 27 min to obtain the matrix solution, and keep it at 41°C for later use. S2, Antibacterial System Construction Stage: Polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer were added sequentially to the matrix solution and stirred at 570 r / min for 21 min at 41 °C. S3, Functional Ingredient Complexation Stage: The temperature of the system obtained in S2 was lowered to 29°C, and ceramide, microecological regulator, and moisturizing and soothing agent were added. The mixture was stirred at 370 r / min for 37 min. S4, Microcapsule Dispersion Stage: Sodium alginate-coated nano-zinc-plant prebiotic microcapsules were dispersed into a suspension by 5.5% of the total deionized water in the raw material of the feminine wash antibacterial solution, and slowly added to the system obtained in S3. The mixture was stirred at 185 r / min for 19 min. S5, Emulsification and Preservation Stage: Add emulsifier to the system obtained in S4 and stir at 370 r / min for 15 min; then add preservative and stir at 270 r / min for 13 min. S6, pH adjustment and post-treatment stage: Add a citric acid-sodium citrate buffer pair to the system obtained in S5, adjust the pH of the system to 4.1, and stir for 8 minutes until the pH stabilizes; then homogenize the system three times under a pressure of 27 MPa and a temperature of 28 °C; then degas under vacuum for 13 minutes under a pressure of -0.077 MPa and a temperature of 28 °C to remove air bubbles; finally filter with a 3.0 μm filter membrane, add the remaining deionized water and mix well to obtain a feminine wash-free antibacterial solution.
[0047] Comparative Example 1: A feminine wash-free antibacterial solution and its preparation method are disclosed, which differ from Example 3 only in that: chitosan-lactoferrin-lactate graft copolymer is not added.
[0048] Comparative Example 2: A feminine wash-free antibacterial liquid and its preparation method are different from those in Example 3 only in that sodium alginate-coated nano-zinc-plant prebiotic microcapsules are not added.
[0049] Comparative Example 3: A feminine wash-free antibacterial solution and its preparation method are disclosed, which differ from Example 3 only in that polyhexamethylene biguanide hydrochloride is not added.
[0050] Comparative Example 4: A feminine wash-free antibacterial solution and its preparation method are disclosed, which differ from Example 3 only in that no ceramides are added.
[0051] Comparative Example 5: A feminine wash-free antibacterial liquid and its preparation method are different from those in Example 3 only in that the microecological regulator composed of xylooligosaccharides and fructooligosaccharides in a mass ratio of 1:1 is not added.
[0052] Comparative Example 6: A feminine wash-free antibacterial liquid and its preparation method are different from those in Example 3 only in that: no thickening and stabilizing agent composed of xanthan gum and hydroxyethyl cellulose in a mass ratio of 1:1 is added.
[0053] Comparative Example 7: A feminine wash-free antibacterial solution and its preparation method are different from those in Example 3 only in that the preservative composed of chlorphenesin and hexanediol in a mass ratio of 1:11 is not added.
[0054] Comparative Example 8: A feminine wash-free antibacterial liquid and its preparation method are different from those in Example 3 only in that the emulsifier, which is a compound of polyglycerol-10 laurate and PEG-8 cetyl ether in a mass ratio of 1:1, is not added.
[0055] Comparative Example 9: A feminine wash-free antibacterial liquid and its preparation method are disclosed, the only difference between this liquid and Example 3 is that chitosan-lactoferrin-lactate graft copolymer is replaced with pure chitosan in equal amounts.
[0056] Comparative Example 10: A feminine wash-free antibacterial liquid and its preparation method are disclosed. The only difference between this liquid and Example 3 is that the sodium alginate-coated nano-zinc-plant prebiotic microcapsules are replaced with an equal amount of uncoated plant prebiotics and nano-zinc mixture.
[0057] Comparative Example 11: A feminine wash-free antibacterial liquid and its preparation method are disclosed, the only difference between this liquid and Example 3 is that homogenization is not performed in the preparation process.
[0058] The antibacterial solutions obtained in Examples 1-3 and Comparative Examples 1-11 were tested for antibacterial rate, retention rate of active ingredients, skin irritation test, vaginal mucosal irritation test, skin allergic reaction test, microecological regulation effect, mucosal repair effect, and physicochemical indicators. The test methods and reference standards are as follows: 1. Antibacterial rate test: According to Appendix E.6.1 of GB 15979-2024 Hygienic Requirements for Disposable Sanitary Products, Escherichia coli (8099), Staphylococcus aureus, and Candida albicans were selected as test strains. The samples and bacterial suspensions were mixed at a volume ratio of 9:1 and allowed to act for 2 min and 24 h. The antibacterial rate was calculated by plate counting method. 2. Detection of the retention rate of effective ingredients: According to Item 2.2.1.2.12 of the "Disinfection Technical Specifications" (2002 edition), the content of polyhexamethylene biguanide hydrochloride after storage in a constant temperature incubator at 37℃ for 90 days was detected by high performance liquid chromatography, and the retention rate was calculated (retention rate = content after storage / initial content × 100%). 3. Skin irritation test: According to Appendix F of GB 15979-2024 Hygienic Requirements for Disposable Sanitary Products, three Japanese white rabbits were selected. After removing the hair on their backs, the original sample solution was applied once a day for 14 consecutive days. Skin erythema and edema reactions were observed, and the irritation index was calculated. 4. Vaginal mucosal irritation test: According to Appendix F of GB 15979-2024 Hygienic requirements for disposable sanitary products, 6 Japanese white rabbits were selected, and 2 mL of sample stock solution was injected into the vagina once a day for 5 consecutive days. The pathological changes of vaginal mucosa were observed 24 hours after the last exposure, and the irritation index was calculated. 5. Skin allergy test: According to Appendix F of GB 15979-2024 Hygienic requirements for disposable sanitary products, 32 Dunkin' Hartley guinea pigs were selected and divided into a test sample group and a negative control group (16 in each group). The skin reaction was observed at 24h and 48h through the induction-challenge test, and the sensitization rate was calculated. 6. Microecological regulation effect test: The plate count method was used to detect the change in the number of lactobacilli in the private parts after the use of the sample, and the growth rate was calculated (growth rate = (number after use - number before use) / number before use × 100%). 7. Mucosal repair effect detection: In vitro cell scratch assay was used to culture vaginal epithelial cells (VK2 / E6E7). After scratching, sample dilution solution (mass concentration 10%) was added. After culturing for 24 hours, the scratch healing rate was measured (healing rate = (initial scratch width - 24h scratch width) / initial scratch width × 100%). 8. Physicochemical index testing: pH value was determined using a pH meter (Mettler S210) according to item 2.2.1.4 of the "Disinfection Technical Specifications" (2002 edition); total bacterial count was determined using nutrient agar medium according to Appendix B of "GB 15979-2024 Hygienic Requirements for Disposable Sanitary Products"; viscosity was determined using a rotational viscometer (25℃, 60r / min) according to "GB / T 10247-2008 Viscosity Measurement Method".
[0059] The results are shown in Table 1.
[0060] Table 1 Performance parameters of the antibacterial solutions obtained in Examples 1-3 and Comparative Examples 1-11 Group Escherichia coli inhibition rate (2 min) (%) Staphylococcus aureus inhibition rate (2 min) (%) Candida albicans inhibition rate (2 min) (%) 24-hour inhibition rate (E. coli) (%) Polyhexamethylene biguanide hydrochloride retention (90d) (%) Skin irritation index Vaginal mucosal irritation index Sensitization rate (%) Lactobacillus count growth rate (%) Scratch healing rate (24h) (%) pH value Total bacterial count (CFU / mL) Viscosity (mPa·s) Example 1 99.93 99.91 99.92 95.5 95.8 0.16 0.31 0 86.5 79.2 4.1 <5 360 Example 2 99.96 99.94 99.95 97.8 98.1 0.11 0.26 0 93.8 86.5 4.4 <5 390 Example 3 99.99 99.98 99.97 99.3 99.2 0.09 0.21 0 99.5 93.6 4.1 <5 420 Comparative Example 1 98.60 98.40 98.50 89.2 90.5 0.46 0.66 0 73.8 66.5 4.8 <5 350 Comparative Example 2 98.30 98.10 98.20 87.1 91.8 0.36 0.56 0 47.2 71.5 4.3 <5 380 Comparative Example 3 66.50 63.80 61.90 46.5 - 0.13 0.23 0 69.8 76.8 4.5 13 370 Comparative Example 4 99.91 99.89 99.90 95.2 98.8 0.12 0.24 0 89.9 53.8 4.7 <5 410 Comparative Example 5 99.86 99.84 99.85 91.3 98.5 0.10 0.20 0 34.2 90.2 4.2 <5 400 Comparative Example 6 99.72 99.70 99.71 93.1 94.2 0.13 0.22 0 91.8 90.8 4.4 19 280 Comparative Example 7 99.88 99.86 99.87 94.5 97.2 0.14 0.25 0 92.3 88.6 4.3 45 400 Comparative Example 8 99.65 99.63 99.64 92.8 96.5 0.15 0.26 0 90.6 87.3 4.5 28 220 Comparative Example 9 97.50 97.30 97.40 84.3 89.2 0.51 0.71 0 66.8 64.2 5.0 <5 340 Comparative Example 10 98.10 97.90 98.00 86.2 83.5 0.33 0.51 0 60.5 74.8 4.1 <5 370 Comparative Example 11 99.52 99.50 99.51 94.1 97.9 0.13 0.25 0 92.6 85.5 4.4 35 390 In Comparative Example 3, the "Retention Rate of Polyhexamethylene Biguanide Hydrochloride (90d)" is marked with "-". Since there is no "Initial Content" of this component, the "Retention Rate" cannot be calculated, so it is represented by "-".
[0061] Using Example 3 as the control group, the performance differences and causes of Comparative Examples 1-11 are analyzed as follows: Comparative Example 1 (without chitosan-lactoferrin-lactate graft copolymer): The inhibition rate of *Escherichia coli* at 2 min decreased from 99.99% to 98.60%, a decrease of 1.39%; the inhibition rate of *Staphylococcus aureus* at 2 min decreased from 99.98% to 98.40%, a decrease of 1.58%; the inhibition rate of *Candida albicans* at 2 min decreased from 99.97% to 98.50%, a decrease of 1.47%; and the inhibition rate at 24 h decreased from 99.3% to 89.2%. The percentage decrease was 10.1%; the retention rate of polyhexamethylene biguanide hydrochloride decreased from 99.2% to 90.5%, a decrease of 8.77%; the skin irritation index increased from 0.09 to 0.46, an increase of 411.1%; the vaginal mucosa irritation index increased from 0.21 to 0.66, an increase of 214.3%; the growth rate of lactobacilli decreased from 99.5% to 73.8%, a decrease of 25.8%; and the scratch healing rate decreased from 93.6% to 66.5%, a decrease of 29.0%. The copolymer lacks mucosal adsorption function, resulting in a shorter residence time of polyhexamethylene biguanide hydrochloride on the mucosal surface. Furthermore, it lacks the anti-allergic effect of lactoferrin, and the pH-precise regulation function of the lactate ester segment disappears, leading to a decrease in antibacterial durability, stability, and mildness of polyhexamethylene biguanide hydrochloride. Consequently, the copolymer's auxiliary effect on mucosal repair is also lost.
[0062] Comparative Example 2 (without sodium alginate-coated nano-zinc-plant prebiotic microcapsules): The 2-minute inhibition rate of *E. coli* decreased from 99.99% to 98.30%, a decrease of 1.69%; the 2-minute inhibition rate of *Staphylococcus aureus* decreased from 99.98% to 98.10%, a decrease of 1.88%; the 2-minute inhibition rate of *Candida albicans* decreased from 99.97% to 98.20%, a decrease of 1.77%; and the 24-hour inhibition rate decreased from 99.3% to 87.1%. The percentage decrease was 12.3%; the retention rate of polyhexamethylene biguanide hydrochloride decreased from 99.2% to 91.8%, a decrease of 7.46%; the skin irritation index increased from 0.09 to 0.36, an increase of 300%; the vaginal mucosa irritation index increased from 0.21 to 0.56, an increase of 166.7%; the growth rate of lactobacilli decreased from 99.5% to 47.2%, a decrease of 52.6%; and the scratch healing rate decreased from 93.6% to 71.5%, a decrease of 23.6%. The lack of the auxiliary antibacterial and antioxidant effects of nano-zinc prevents the plant prebiotics from exerting their microecological regulatory function. Furthermore, the absence of sodium alginate coating to protect the active ingredients reduces the compatibility of polyhexamethylene biguanide hydrochloride with prebiotics, leading to a significant decline in antibacterial durability, stability, and microecological regulatory effects, while also weakening its mildness and repair-aiding effects.
[0063] Comparative Example 3 (without polyhexamethylene biguanide hydrochloride): The 2-minute inhibition rate of *E. coli* decreased from 99.99% to 66.50%, a reduction of 33.49%; the 2-minute inhibition rate of *Staphylococcus aureus* decreased from 99.98% to 63.80%, a reduction of 36.19%; the 2-minute inhibition rate of *Candida albicans* decreased from 99.97% to 61.90%, a reduction of 38.08%; the 24-hour inhibition rate decreased from 99.3% to 46.5%, a reduction of 53.17%; and the total bacterial count increased from <5 CFU / mL to 13 CFU / mL. Polyhexamethylene biguanide hydrochloride is the core antibacterial component. Its absence prevents the rapid disruption of pathogenic bacterial cell membranes, hindering immediate and efficient antibacterial action. Furthermore, the product itself lacks a core antibacterial barrier, allowing for easy microbial growth and rendering the core antibacterial function completely ineffective.
[0064] Comparative Example 4 (without ceramide): The scratch healing rate decreased from 93.6% to 53.8%, a reduction of 42.52%. Ceramide is a key component for mucosal repair. The absence of ceramide resulted in the inability to fill gaps in the mucosal barrier, significantly slowing down the healing speed of damaged mucosa and greatly weakening its repair function.
[0065] Comparative Example 5 (without microecological regulator): The growth rate of Lactobacillus decreased from 99.5% to 34.2%, a decrease of 65.63%; the 24-hour antibacterial rate decreased from 99.3% to 91.3%, a decrease of 8.06%. Without the addition of a microecological regulator composed of xylooligosaccharides and fructooligosaccharides in a 1:1 mass ratio, it was impossible to provide specific nutrition for beneficial bacteria such as Lactobacillus, and it was impossible to synergistically regulate the microecological balance with sodium alginate-coated nano-zinc-plant prebiotic microcapsules. The proliferation of beneficial bacteria was severely limited, and it was unable to competitively inhibit harmful bacteria, resulting in a weakened long-term antibacterial effect.
[0066] Comparative Example 6 (without thickener and stabilizer): The inhibition rate of Escherichia coli at 2 min decreased from 99.99% to 99.72%, a decrease of 0.27%; the inhibition rate of Staphylococcus aureus at 2 min decreased from 99.98% to 99.70%, a decrease of 0.28%; the inhibition rate of Candida albicans at 2 min decreased from 99.97% to 99.71%, a decrease of 0.26%; the inhibition rate at 24 h decreased from 99.3% to 93.1%, a decrease of 6.24%; the retention rate of polyhexamethylene biguanide hydrochloride decreased from 99.2% to 94.2%, a decrease of 5.04%; the total bacterial count increased from <5 CFU / mL to 19 CFU / mL; and the viscosity decreased from 420 mPa·s to 280 mPa·s, a decrease of 33.33%. Without the three-dimensional network structure formed by xanthan gum and hydroxyethyl cellulose, it is impossible to encapsulate the various functional components. Polyhexamethylene biguanide hydrochloride is easily degraded, and the system has insufficient stability, making it easy for microorganisms to grow. At the same time, the product's adhesion to the mucous membrane decreases, and the residence time of antibacterial components is shortened, resulting in abnormal viscosity, reduced antibacterial durability, and decreased cleanliness.
[0067] Comparative Example 7 (without preservatives): The total bacterial count increased from <5 CFU / mL to 45 CFU / mL. The lack of synergistic preservative effect between chlorphenesin and hexanediol prevented the inhibition of microbial growth within the product itself, leading to massive microbial proliferation during storage and severely impacting product safety and shelf life.
[0068] Comparative Example 8 (without emulsifier): The inhibition rate of Escherichia coli at 2 min decreased from 99.99% to 99.65%, a decrease of 0.34%; the inhibition rate of Staphylococcus aureus at 2 min decreased from 99.98% to 99.63%, a decrease of 0.35%; the inhibition rate of Candida albicans at 2 min decreased from 99.97% to 99.64%, a decrease of 0.33%; the inhibition rate at 24 h decreased from 99.3% to 92.8%, a decrease of 6.55%; the retention rate of polyhexamethylene biguanide hydrochloride decreased from 99.2% to 96.5%, a decrease of 2.72%; the total bacterial count increased from <5 CFU / mL to 28 CFU / mL; and the viscosity decreased from 420 mPa·s to 220 mPa·s, a decrease of 47.62%. Without emulsifiers to regulate the interfacial tension of the system, oil-soluble and water-soluble components are unevenly dispersed, and components such as polyhexamethylene biguanide hydrochloride are locally aggregated. Microorganisms are prone to grow in the aggregated areas. At the same time, the stability of the system decreases, resulting in abnormal viscosity, reduced antibacterial effect and stability of polyhexamethylene biguanide hydrochloride, and worse skin feel.
[0069] Comparative Example 9 (chitosan-lactoferrin-lactate graft copolymer replaced with pure chitosan): The 2-minute inhibition rate of *E. coli* decreased from 99.99% to 97.50%, a decrease of 2.49%; the 2-minute inhibition rate of *Staphylococcus aureus* decreased from 99.98% to 97.30%, a decrease of 2.68%; the 2-minute inhibition rate of *Candida albicans* decreased from 99.97% to 97.40%, a decrease of 2.57%; and the 24-hour inhibition rate decreased from 99.3% to 84.3%. The retention rate of polyhexamethylene biguanide hydrochloride decreased from 99.2% to 89.2%, a decrease of 10.08%; the skin irritation index increased from 0.09 to 0.51, an increase of 466.67%; the vaginal mucosa irritation index increased from 0.21 to 0.71, an increase of 238.10%; the growth rate of lactobacilli decreased from 99.5% to 66.8%, a decrease of 32.86%; and the scratch healing rate decreased from 93.6% to 64.2%, a decrease of 31.41%. Chitosan alone lacks the anti-allergic effect of lactoferrin, cannot inhibit the release of inflammatory factors, and lacks the precise pH regulation function of the lactate chain. The grafting synergistic effect is completely lost, and it cannot simultaneously achieve antibacterial durability, mildness, and mucosal repair auxiliary effects. The mucosal residence time of polyhexamethylene biguanide hydrochloride is also significantly shortened.
[0070] Comparative Example 10 (sodium alginate-coated nano-zinc-plant prebiotic microcapsules replaced with an uncoated mixture): The 2-minute inhibition rate of *E. coli* decreased from 99.99% to 98.10%, a decrease of 1.89%; the 2-minute inhibition rate of *Staphylococcus aureus* decreased from 99.98% to 97.90%, a decrease of 2.08%; the 2-minute inhibition rate of *Candida albicans* decreased from 99.97% to 98.00%, a decrease of 1.97%; and the 24-hour inhibition rate decreased from 99.3% to 86.2%. The percentage decrease was 13.19%; the retention rate of polyhexamethylene biguanide hydrochloride decreased from 99.2% to 83.5%, a decrease of 15.83%; the skin irritation index increased from 0.09 to 0.33, an increase of 266.67%; the vaginal mucosa irritation index increased from 0.21 to 0.51, an increase of 142.86%; the growth rate of lactobacilli decreased from 99.5% to 60.5%, a decrease of 39.19%; and the scratch healing rate decreased from 93.6% to 74.8%, a decrease of 20.09%. Unencapsulated plant prebiotics are easily degraded by polyhexamethylene biguanide hydrochloride, and nano-zinc tends to aggregate, leading to the failure of its auxiliary antibacterial and antioxidant effects. This prevents the formation of a synergistic effect of "active protection - auxiliary antibacterial action - microecological regulation," resulting in a comprehensive decline in all performance aspects.
[0071] Comparative Example 11 (unhomogenized): The inhibition rate of *E. coli* at 2 min decreased from 99.99% to 99.52%, a decrease of 0.47%; the inhibition rate of *Staphylococcus aureus* at 2 min decreased from 99.98% to 99.50%, a decrease of 0.48%; the inhibition rate of *Candida albicans* at 2 min decreased from 99.97% to 99.51%, a decrease of 0.46%; the inhibition rate at 24 h decreased from 99.3% to 94.1%, a decrease of 5.24%; and the total bacterial count increased from <5 CFU / mL to 35 CFU / mL. Without homogenization, the microbial aggregates in the system were not broken down, the components were unevenly dispersed, and polyhexamethylene biguanide hydrochloride could not act uniformly on the microorganisms, leading to an increase in the total bacterial count, a weakened antibacterial effect, and a decrease in product uniformity.
[0072] In summary, the chitosan-lactoferrin-lactate graft copolymer, in synergy with polyhexamethylene biguanide hydrochloride, prolongs the mucosal residence time of the antibacterial ingredients, enhancing their antibacterial durability and gentleness; sodium alginate-encapsulated nano-zinc-plant prebiotic microcapsules protect the active ingredients and assist in antibacterial action, improving the effect of microecological regulation; the mucosal repair agent (ceramide) accelerates the healing of damaged mucosa; the microecological regulator and microcapsules synergistically promote the proliferation of beneficial bacteria; and the thickener, stabilizer, and emulsifier ensure system stability and a pleasant user experience.
[0073] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A feminine wash with no washing required, characterized in that, By weight percentage, its constituent raw materials include: polyhexamethylene biguanide hydrochloride 0.08-0.16%, chitosan-lactoferrin-lactate graft copolymer 0.9-1.9%, sodium alginate-coated nano zinc-plant prebiotic microcapsules 1.3-2.3%, mucosal repair agent 0.1-0.3%, microecological regulator 1.2-2.2%, moisturizing and soothing agent 2.8-5.2%, thickening and stabilizing agent 0.35-0.75%, preservative 1.4-2.8%, pH adjuster 0.6-1.4%, emulsifier 1.2-2.6%, and the balance being deionized water.
2. The feminine wash-free antibacterial solution according to claim 1, characterized in that, The mucosal repair agent is ceramide; the microecological regulator is one or more of xylooligosaccharides and fructooligosaccharides; the moisturizing and soothing agent is one or more of erythritol or allantoin; the thickening and stabilizing agent is one or more of xanthan gum or hydroxyethyl cellulose; the preservative is a mixture of chlorphenesin and hexanediol in a mass ratio of 1:10-1:12; the pH adjuster is a citrate-sodium citrate buffer pair; and the emulsifier is one or more of polyglycerol-10 laurate or PEG-8 cetyl ether.
3. The feminine wash-free antibacterial solution according to claim 1, characterized in that, The raw materials comprising the chitosan-lactoferrin-lactate graft copolymer by weight are: 8-12 parts chitosan, 3.8-6.0 parts lactoferrin, 6.8-9.0 parts lactate, 0.55-0.85 parts 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 120-180 parts acetic acid solution with a volume fraction of 1.0-1.2%.
4. The feminine wash-free antibacterial solution according to claim 3, characterized in that, The preparation method of chitosan-lactoferrin-lactate graft copolymer includes the following steps: 1) Take chitosan, add acetic acid solution, and stir at 320-420 r / min at 42-52℃ for 32-42 min to dissolve it; 2) Add lactoferrin to the solution obtained in 1), stir well, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, activate for 32-42 min, then add lactate dropwise at a rate of 1.2-2.2 mL / min, stir well, then raise the temperature to 62-72℃ and react at this temperature for 2.2-3.2 h; 3) Adjust the pH of the mixture obtained in 2) to 7.1-7.6 with a 10-12% sodium hydroxide solution to produce a precipitate. Centrifuge the precipitate at 8200-10200 r / min for 16-22 min and collect the precipitate. 4) Wash the precipitate 3-4 times with anhydrous ethanol, then dry it under vacuum conditions of 52-62℃ and -0.092~-0.082MPa for 4.2-6.2h, pulverize it and pass it through a 200-300 mesh sieve to obtain chitosan-lactoferrin-lactate graft copolymer.
5. The feminine wash-free antibacterial solution according to claim 3, characterized in that, The degree of deacetylation of chitosan is 91-99%, and the weight-average molecular weight is 80-120 kDa; the weight-average molecular weight of lactoferrin is 80-85 kDa; the lactate is either ethyl lactate or butyl lactate.
6. The feminine wash-free antibacterial solution according to claim 1, characterized in that, By weight, the raw materials of sodium alginate-coated nano-zinc-plant prebiotic microcapsules include: 28-36 parts of active Lactobacillus acidophilus fermentation concentrate, 1.0-1.4 parts of nano-zinc powder, 4-5 parts of inulin, 4.8-6.0 parts of fructooligosaccharides, 1.0-1.7 parts of sodium alginate, and 80-120 parts of calcium chloride solution with a mass fraction of 2.2-3.2%.
7. The feminine wash-free antibacterial solution according to claim 6, characterized in that, The preparation method of sodium alginate-coated nano-zinc-plant prebiotic microcapsules includes the following steps: a. Mix inulin and fructooligosaccharides, add deionized water, and stir at 220-320 r / min at 32-42℃ for 22-32 min to prepare a mixed solution with a total solute mass fraction of 8-13%; b. Add the nano zinc powder to the mixture obtained in step a, and ultrasonically disperse it for 12-17 minutes at a power of 220-320W to obtain the nano zinc-prebiotic dispersion; c. Mix the active Lactobacillus acidophilus fermentation concentrate with the nano zinc-prebiotic dispersion, add sodium alginate, and stir at 220-320 r / min for 22-32 min to obtain the mixture; d. The mixture was added dropwise to the calcium chloride solution at a rate of 0.6-1.1 mL / min, and stirred and solidified at a speed of 160-210 r / min for 16-22 min to obtain microcapsules. The microcapsules were washed with deionized water 3-4 times and then freeze-dried under vacuum at a temperature of -42~-32℃ and a pressure of -0.10~-0.09 MPa for 8-12 h to obtain sodium alginate-coated nano zinc-plant prebiotic microcapsules with a particle size of 1.2-2.2 μm.
8. The feminine wash-free antibacterial solution according to claim 6, characterized in that, The solid content of the active Lactobacillus acidophilus fermentation concentrate is 11-16%, of which the viable bacteria count is 1×10⁻⁶. 8 -5×10 8 CFU / g; the particle size of the nano zinc powder is 40-90nm, the weight average molecular weight of inulin is 3-6kDa, and the weight average molecular weight of fructooligosaccharides is 1-1.5kDa.
9. A method for preparing a feminine wash-free antibacterial solution according to any one of claims 1-8, characterized in that, Includes the following steps: S1, Preprocessing stage: Take 82-88% of the total amount of deionized water, heat it to 36-46℃, add thickening and stabilizing agent, stir at 820-1020 r / min for 22-32 min to obtain the matrix solution, and keep it at 36-46℃ for later use. S2, Antibacterial System Construction Stage: Add polyhexamethylene biguanide hydrochloride and chitosan-lactoferrin-lactate graft copolymer sequentially to the matrix solution, and stir and mix at 520-620 r / min for 16-26 min at 36-46℃. S3, Functional Ingredient Complexation Stage: Reduce the temperature of the system obtained from S2 to 26-31℃, add the mucosal repair agent, microecological regulator, and moisturizing and soothing agent, and stir at a speed of 320-420r / min for 32-42min; S4, Microcapsule Dispersion Stage: Disperse the sodium alginate-coated nano-zinc-plant prebiotic microcapsules into a suspension using 5.2-5.8% of the total deionized water in the raw material of the feminine wash-free antibacterial solution. Slowly add the suspension to the system obtained in S3 and stir at 160-210 r / min for 16-22 min. S5, Emulsification and Preservation Stage: Add emulsifier to the system obtained in S4 and stir at 320-420 r / min for 12-17 min; then add preservative and stir at 220-320 r / min for 11-16 min. S6, pH adjustment and post-treatment stage: Add a pH adjuster to the system obtained in S5 to adjust the pH value to 3.9-4.5, stir for 6-11 minutes until the pH value is stable; then homogenize and vacuum degassing treatment, filter with a 2.5-3.0μm filter membrane, add the remaining deionized water and mix evenly to obtain a feminine wash-free antibacterial solution.
10. The method for preparing the feminine wash-free antibacterial solution according to claim 9, characterized in that, In step S6, the homogenization process is as follows: the system is homogenized 2-3 times under a pressure of 22-32 MPa and a temperature of 26-31℃ using a homogenizer; the vacuum degassing process is as follows: vacuum degassing is performed for 11-16 minutes under a pressure of -0.082~-0.072 MPa and a temperature of 26-31℃.