Shampoo containing modified zinc oxide and preparation method thereof

Abstract

The invention discloses shampoo containing modified zinc oxide and a preparation method of the shampoo, and belongs to the field of personal care products. The shampoo comprises the following components in percentage by weight: 3.5-5.0% of azobenzene modified zinc oxide nanoparticles, 0.3-0.5% of a nano-silver / zinc oxide hybrid material, 15-18% of an O / W / O triple emulsion matrix and the like. Wherein the nano-silver / zinc oxide hybrid material is prepared by amination modification and then compounding with silver ions; the azobenzene modified zinc oxide is prepared by adopting a diazotization coupling method; the triple emulsion matrix consists of a jojoba oil / silicone oil inner layer, a modified zinc oxide water-phase middle layer and a silicone oil outer layer. The preparation method comprises the following steps: preparing the triple emulsion matrix, mixing the surfactant and other components with the matrix, and finally adding the modified zinc oxide and other functional components. The shampoo has excellent antibacterial performance and stability, can realize slow release of active ingredients, and is suitable for nursing sensitive scalp.

Description

Technical Field

[0001] The present invention relates to the technical field of personal care products, in particular to a shampoo containing modified zinc oxide and a preparation method thereof. Background Art

[0002] In the personal care product sector, shampoo, as an everyday necessity, faces increasingly diverse functional demands. Traditional shampoos primarily focus on cleansing and conditioning, but with increasing consumer demand for scalp health and specialized care, the market is urgently seeking new shampoos with multiple benefits, including antibacterial and anti-inflammatory properties. Zinc oxide, as a broad-spectrum antimicrobial agent, has shown promising application prospects in cosmetics, but its dispersibility and stability in shampoo systems have hindered its practical application.

[0003] Prior research on zinc oxide modification has primarily focused on single-functional modifications or simple composite systems. While some studies have attempted to apply zinc oxide to shampoo products, issues such as poor control over active ingredient release and insufficient system stability are common. Especially for sensitive scalp care products, achieving sustained release of active ingredients, reducing irritation, and maintaining antibacterial efficacy remain technical challenges. Furthermore, traditional emulsion systems struggle to simultaneously encapsulate and stabilize the release of multiple active ingredients.

[0004] In recent years, advances in nanotechnology and multiple emulsion technology have provided new solutions to these challenges. Chemical modification can significantly improve the dispersibility and functionality of zinc oxide, while triple emulsion systems provide an ideal vehicle for the synergistic effects of multiple active ingredients. However, there are no reports of shampoo products combining azobenzene-modified zinc oxide with nanosilver / zinc oxide hybrid materials and using an O / W / O triple emulsion as a carrier. This innovative combination holds promise for achieving synergistic effects while maintaining product stability. Summary of the Invention

[0005] The object of the present invention is to provide a shampoo containing modified zinc oxide and a preparation method thereof, which solves the problem that existing shampoos are difficult to simultaneously achieve long-lasting antibacterial and oil-control effects, promote black hair growth, and have insufficient stability of active ingredients.

[0006] The present invention achieves the above-mentioned purpose through the following technical solutions:

[0007] A shampoo containing modified zinc oxide, characterized in that, by mass percentage, its raw materials include:

[0008] Azobenzene-modified zinc oxide nanoparticles: 3.5-5.0%;

[0009] Nanosilver / zinc oxide hybrid material: 0.3-0.5%;

[0010] O / W / O triple emulsion base: 15-18%;

[0011] Jojoba oil / silicone oil complex: 4.5-6.0%;

[0012] Cationic guar gum: 0.5-0.8%;

[0013] Cocamidopropyl Hydroxysultaine: 12.0-15.0%;

[0014] Sodium laureth sulfate: 8.0-10.0%;

[0015] Ethyl-2-isopropyl-5-methylcyclohexanecarboxamide: 0.3-0.5%;

[0016] Zinc hyaluronate: 0.1-0.2%;

[0017] Citric acid / sodium citrate buffer system: 0.3-0.6%;

[0018] Disodium EDTA: 0.1-0.15%;

[0019] Cysteine: 0.5-1.0%;

[0020] Panthenol: 0.2-0.4%;

[0021] Deionized water: balance;

[0022] The preparation steps of the nanosilver / zinc oxide hybrid material include: dispersing zinc oxide nanoparticles in anhydrous ethanol and ultrasonically treating; adding 3-aminopropyltriethoxysilane and refluxing at 80°C for 6 hours; vacuum drying at 60°C to obtain NH2-ZnO; dispersing NH2-ZnO in deionized water and adding AgNO3; dropwise adding 0.1M NaBH4 solution under ice bath conditions and stirring in the dark; adding polyvinyl pyrrolidone and continuing stirring; finally centrifuging, washing with ethanol / water alternately for 3 times; and freeze-drying.

[0023] According to a preferred embodiment of the present invention, the cationic guar gum is purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0024] According to a preferred embodiment of the present invention, the cocamidopropyl hydroxysulfonyl betaine is purchased from Shandong Xiangzhao New Materials Co., Ltd.

[0025] According to a preferred embodiment of the present invention, the sodium laureth sulfate is purchased from Jinan Century Tongda Chemical Co., Ltd.

[0026] According to a preferred embodiment of the present invention, the ethyl-2-isopropyl-5-methylcyclohexanecarboxamide was purchased from Hubei Jiangmin Taihua Chemical Co., Ltd.

[0027] According to a preferred embodiment of the present invention, the zinc hyaluronate is purchased from Wuhan Penglei Biotechnology Co., Ltd.

[0028] According to a preferred embodiment of the present invention, the citric acid / sodium citrate buffer system is purchased from Shanghai Future Industrial Co., Ltd.

[0029] According to a preferred embodiment of the present invention, the disodium edetate was purchased from Jiangsu Puxin Biotechnology Co., Ltd.

[0030] According to a preferred embodiment of the present invention, the cysteine is purchased from Hubei Xinshengyuan Bioengineering Co., Ltd.

[0031] According to a preferred embodiment of the present invention, the panthenol is purchased from Wuhan Proloff Biotechnology Co., Ltd.

[0032] According to a preferred embodiment of the present invention, the deionized water is purchased from Dongguan Boyiyuan Water Treatment Equipment Co., Ltd.

[0033] According to a preferred embodiment of the present invention, the zinc oxide nanoparticles are purchased from Xuzhou Mingyanhai New Material Technology Co., Ltd.

[0034] According to a preferred embodiment of the present invention, the anhydrous ethanol is purchased from Shandong Juxing Chemical Co., Ltd.

[0035] According to a preferred embodiment of the present invention, the 3-aminopropyltriethoxysilane is purchased from Wuhan Jushun Chemical Co., Ltd.

[0036] According to a preferred embodiment of the present invention, the AgNO3 was purchased from Shanghai Kanglang Biotechnology Co., Ltd.

[0037] According to a preferred embodiment of the present invention, the NaBH4 solution is purchased from Wuhan Hezhong Biochemical Manufacturing Co., Ltd.

[0038] According to a preferred embodiment of the present invention, the polyvinyl pyrrolidone is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0039] The azobenzene-modified zinc oxide and nanosilver / zinc oxide hybrid materials in this invention provide broad-spectrum antimicrobial effects, while zinc hyaluronate, panthenol, and cysteine synergistically repair the scalp barrier and damaged hair. Cocamidopropyl hydroxysultaine and sodium laureth sulfate ensure efficient cleansing, while cationic guar gum and a jojoba oil / silicone oil complex reduce damage caused by cleansing and maintain hair smoothness. The O / W / O triple emulsion achieves a gradient release of active ingredients, while a citric acid / sodium citrate buffer system and EDTA-2Na maintain system stability and prolong product efficacy. Ethyl-2-isopropyl-5-methylcyclohexanecarboxamide provides a cooling sensation, enhancing the user experience without compromising the formula's functionality.

[0040] According to a preferred embodiment of the present invention, the preparation steps of the nanosilver / zinc oxide hybrid material include first dispersing 100 mg of zinc oxide nanoparticles in 50 mL of anhydrous ethanol and sonicating at 40 kHz for 30 minutes. Then, 5 mL of 3-aminopropyltriethoxysilane is added, and the mixture is refluxed at 80°C for 6 hours to amino-aminoate the ZnO surface. The mixture is then centrifuged and washed at 8000 rpm for 10 minutes, and vacuum-dried at 60°C to obtain NH2-ZnO. The NH2-ZnO is then dispersed in 50 mL of deionized water, and 20 mg of AgNO3 is added. 5 mL of 0.1 M NaBH4 solution is added dropwise in an ice bath, and the mixture is stirred in the dark for 30 minutes. Then, 10 mg of polyvinyl pyrrolidone is added, and stirring is continued for 1 hour. Finally, the mixture is centrifuged at 10,000 rpm for 15 minutes, and washed three times with alternating ethanol / water. Freeze-dried at -50°C for 24 hours to obtain the Ag / ZnO hybrid material.

[0041] The zinc oxide nanoparticles in the present invention are modified with 3-aminopropyltriethoxysilane, and the surface is rich in amino groups (NH2-ZnO), which can adsorb silver ions (Ag + ) and in situ generate silver nanoparticles (Ag NPs) under NaBH4 reduction. Polyvinylpyrrolidone (PVP) acts as a stabilizer to prevent the aggregation of the silver nanoparticles. The ZnO-Ag hybrid structure enhances antibacterial properties, while the sustained release of zinc oxide reduces the skin irritation of silver ions.

[0042] According to a preferred embodiment of the present invention, the preparation steps of the azobenzene-modified zinc oxide nanoparticles include dispersing the zinc oxide nanoparticles in anhydrous ethanol, adding hydrofluoric acid and ultrasonically treating them for hydroxylation activation, centrifuging and washing until neutral, and then redispersing them in toluene. APTMS is added, and the mixture is refluxed at 110°C under nitrogen protection. After centrifugation, the mixture is washed with ethanol using a Soxhlet extractor to obtain the azinated ZnO. Separately, 4-aminoazobenzene is dissolved in 1M HCl in an ice bath, and a NaNO2 aqueous solution is slowly added to carry out a diazotization reaction. Urea is added to decompose excess sodium nitrite. The azinated ZnO is dispersed in DMF, a diazonium salt solution is added in an ice bath, the pH is adjusted to 8.5, and the reaction is carried out in the dark. Finally, the filtrate is washed sequentially with DMF, acetone, and deionized water until the filtrate is colorless, and then vacuum dried to obtain the azobenzene-modified ZnO nanoparticles.

[0043] According to a preferred embodiment of the present invention, the hydrofluoric acid is purchased from Laiyang Kangte New Materials Co., Ltd.

[0044] According to a preferred embodiment of the present invention, the toluene is purchased from Guangdong Xiaoda Chemical Co., Ltd.

[0045] According to a preferred embodiment of the present invention, the APTMS (aminopropyltrimethoxysilane) was purchased from Shenzhen Anpu Storage Technology Co., Ltd.

[0046] According to a preferred embodiment of the present invention, the nitrogen is purchased from Shanghai Kangmanlin Biotechnology Co., Ltd.

[0047] According to a preferred embodiment of the present invention, the Soxhlet extractor is purchased from Beijing Jiuzhou Shengxin Technology Co., Ltd. Model JZ-ZD200.

[0048] According to a preferred embodiment of the present invention, the 4-aminoazobenzene is purchased from Hangzhou Kefike Chemical Co., Ltd.

[0049] According to a preferred embodiment of the present invention, the HCl is purchased from Shandong Yanhe Chemical Co., Ltd.

[0050] According to a preferred embodiment of the present invention, the NaNO2 aqueous solution is purchased from Chengdu Tianli Chemical Technology Co., Ltd.

[0051] According to a preferred embodiment of the present invention, the urea is purchased from Hefei Lifang Pharmaceutical Co., Ltd.

[0052] According to a preferred embodiment of the present invention, the DMF (dimethylformamide) was purchased from Liaocheng Tongda Chemical Co., Ltd.

[0053] According to a preferred embodiment of the present invention, the acetone is purchased from Wuhan Xinminzu Chemical Co., Ltd.

[0054] The azobenzene groups in this invention undergo reversible cis-trans isomerization under ultraviolet light, altering the surface polarity and molecular arrangement of the zinc oxide nanoparticles, thereby regulating the release rate of the active ingredient. Zinc oxide itself has photocatalytic antibacterial properties, and the introduction of azobenzene makes it photoresponsive, intelligently adjusting its antibacterial and anti-dandruff effects based on lighting conditions.

[0055] According to a preferred embodiment of the present invention, the preparation steps of the azobenzene-modified zinc oxide nanoparticles include dispersing 1 g of zinc oxide nanoparticles in 100 mL of anhydrous ethanol, adding 3 mL of hydrofluoric acid, sonicating for 30 minutes, washing by centrifugation until neutral, and then redispersing in 50 mL of toluene. 2 mL of APTMS is added, and the mixture is refluxed at 110°C under nitrogen for 6 hours. After centrifugation, the mixture is washed with ethanol using a Soxhlet extractor for 24 hours to obtain the azobenzene-modified ZnO. Separately, 0.5 g of 4-aminoazobenzene is dissolved in 20 mL of 1 M HCl in an ice bath, and 0.35 g of a NaNO₂ aqueous solution is added for diazotization for 1 hour. Urea is then added to decompose excess sodium nitrite. The azobenzene-modified ZnO is dispersed in 50 mL of DMF, and a diazonium salt solution is added in an ice bath. The pH is adjusted to 8.5, and the mixture is reacted in the dark for 12 hours. Finally, the mixture is washed sequentially with DMF, acetone, and deionized water until the filtrate is colorless, and then dried in vacuo at 60°C to obtain the azobenzene-modified ZnO nanoparticles.

[0056] According to a preferred embodiment of the present invention, the O / W / O triple emulsion matrix consists of 30-35% inner oil phase, 50-55% middle water phase and 15-20% outer oil phase.

[0057] According to a preferred embodiment of the present invention, the inner oil phase is composed of jojoba oil and silicone oil in a mass ratio of 3:1; the middle aqueous phase is composed of deionized water, emulsifier and ethanol; and the outer oil phase is composed of cyclopentasiloxane and cationic guar gum.

[0058] According to a preferred embodiment of the present invention, the preparation method of the O / W / O triple emulsion matrix includes: an inner oil phase is mixed with jojoba oil and silicone oil in a mass ratio of 3:1; an intermediate aqueous phase is mixed with deionized water, an emulsifier and ethanol; an outer oil phase is mixed with cyclopentasiloxane and cationic guar gum; the inner W / O emulsion is first prepared: the intermediate aqueous phase is slowly added to the inner oil phase, and high-speed homogenization is performed at 10,000 rpm for 5 minutes; the W / O emulsion is dropwise added to the outer oil phase, and low-speed shear emulsification is performed at 2,000 rpm for 10 minutes.

[0059] According to a preferred embodiment of the present invention, the jojoba oil is purchased from Jiangxi Baicao Pharmaceutical Co., Ltd.

[0060] According to a preferred embodiment of the present invention, the silicone oil is purchased from Shijiazhuang Zhonglan Technology Co., Ltd.

[0061] According to a preferred embodiment of the present invention, the emulsifier is GP-200 cetearyl alcohol emulsifier purchased from Nantong Chenrun Chemical Co., Ltd.

[0062] According to a preferred embodiment of the present invention, the cyclopentasiloxane is purchased from Wuhan Kanos Technology Co., Ltd.

[0063] According to a preferred embodiment of the present invention, the cationic guar gum is purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0064] The O / W / O triple emulsion matrix in this invention consists of a water phase (W) encapsulating an oil phase (O) to form a primary O / W emulsion, which is then dispersed in an outer oil phase (O) to form an O / W / O multilayer structure. This dual interfacial stabilization mechanism (inner emulsifier + outer oil phase) enables synergistic loading and controlled release of water-soluble and oil-soluble active ingredients, improving the formulation's stability and long-lasting efficacy.

[0065] The present invention also provides a method for preparing the shampoo containing modified zinc oxide, comprising the following steps:

[0066] S1, add cocamidopropyl hydroxysultaine and sodium laureth sulfate to deionized water in sequence and stir until completely dissolved; add O / W / O triple emulsion base and jojoba oil / silicone oil complex and mix homogeneously;

[0067] S2, adding pre-dispersed azobenzene-modified zinc oxide nanoparticles and nanosilver / zinc oxide hybrid material; adding cationic guar gum, ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, zinc hyaluronate, citric acid / sodium citrate buffer system, disodium ethylenediaminetetraacetic acid, cysteine, and panthenol in sequence; replenishing deionized water to 100%, homogenizing, and standing to defoam; filtering through a 200-mesh sieve.

[0068] According to a preferred embodiment of the present invention, in step S1, the rotation speed of the homogenous mixing is 5000 rpm, and the mixing time is 10 min.

[0069] According to a preferred embodiment of the present invention, in step S2, the pH of the citric acid / sodium citrate buffer system is 5.5-6.0; the homogenization speed is 3000 rpm, and the time is 5 minutes.

[0070] The jojoba oil in the jojoba oil / silicone oil composite of the present invention is rich in long-chain fatty acid esters, which form a compatible composite with silicone oil (such as polydimethylsiloxane). This composite can form a breathable protective film on the hair surface, reducing water loss and enhancing hair smoothness, while reducing the heaviness of pure silicone oil. The guar gum in the cationic guar gum is positively charged after quaternization and binds to the negatively charged hair keratin through electrostatic adsorption, forming a repair film on the hair surface, smoothing the hair scales, reducing friction damage, and improving the hair's gloss and smoothness. Cocamidopropyl hydroxysulfobetaine is an amphoteric surfactant, and the sulfobetaine groups in its molecular structure provide gentle cleaning power, reducing the irritation of anionic surfactants, while enhancing foam stability and system compatibility. Sodium laureth sulfate is used as the primary surfactant. Through the hydrophobic chain, it binds to the oils and fats of the scalp, and the hydrophilic group interacts with water molecules to form a micellar structure, effectively removing dirt and excess oil. At the same time, compounding with betaine reduces the problem of excessive degreasing power. Ethyl-2-isopropyl-5-methylcyclohexanecarboxamide is a TRPM8 receptor agonist that activates the skin's cold receptors, producing a lasting cooling sensation and enhancing the comfort experience during shampooing. 2+ ) coordinate and cross-link to form a moisturizing network, enhancing the scalp barrier function. At the same time, zinc ions have anti-inflammatory and oil-control effects, synergistically improving the scalp microenvironment. The citric acid / sodium citrate buffer system maintains the pH of the shampoo in the weak acid range of 5.5-6.0 through the dynamic balance between the weak acid (citric acid) and its conjugate base (sodium citrate), reducing the irritation of the alkaline components to the scalp and protecting the scalp microecology. Disodium ethylenediaminetetraacetic acid acts as a metal ion chelator. EDTA-2Na can bind Ca in water. 2+ Mg 2+ It removes hard water ions such as iodine and dextrin, preventing them from forming insoluble precipitates with surfactants. It also inhibits metal ion-catalyzed oxidation reactions, extending the product's shelf life. The thiol group (-SH) of cysteine can reduce the disulfide bonds (-SS-) in hair keratin, repairing damaged hair. It also acts as an antioxidant, reducing free radical damage to the scalp. Panthenol penetrates the stratum corneum and is converted into pantothenic acid, participating in lipid synthesis, strengthening the scalp's barrier function, reducing water loss, and promoting healthy hair growth. Deionized water serves as the solvent and continuous phase. Deionized water carries the various components through a hydrogen bond network, regulating the system's viscosity and fluidity, while preventing metal ions from interfering with the formula.

[0071] The beneficial effects of the present invention are:

[0072] This invention significantly enhances the antibacterial and photoresponsive properties of the shampoo by incorporating azobenzene-modified zinc oxide nanoparticles into a synergistic combination with nanosilver / zinc oxide hybrid materials. The azobenzene groups impart photoisomerization capabilities to zinc oxide, enabling reversible manipulation of surface properties under ultraviolet irradiation, thereby intelligently controlling the release rate of the active ingredient. The introduction of nanosilver further enhances the system's broad-spectrum inhibitory effect against common scalp pathogens. The zinc oxide carrier effectively mitigates the problem of sudden silver ion release, extending the antibacterial effect.

[0073] The O / W / O triple emulsion matrix and jojoba oil / silicone oil complex employed in this invention form a unique dual-encapsulation structure, significantly improving the loading efficiency and stability of hydrophobic active ingredients. This system not only allows for the compatible coexistence of water-soluble and oil-soluble ingredients, but also creates a gradient release mechanism through interfacial engineering, allowing the active ingredients to exert their effects continuously at different stages of the washing and conditioning process. The combination of cationic guar gum and zinc hyaluronate forms a cationic film with repairing properties on the hair surface, significantly improving cuticle closure and enhancing hair gloss.

[0074] The formula system of the present invention precisely controls the pH range of the product through the synergistic effect of the citric acid / sodium citrate buffer system and cysteine, making it adaptable to the scalp microenvironment and effectively reducing irritation. The addition of ethyl-2-isopropyl-5-methylcyclohexanecarboxamide provides a cooling experience, while panthenol strengthens the barrier repair function of the scalp. The specially designed nanosilver / zinc oxide hybrid material preparation process ensures the uniform distribution of silver nanoparticles on the zinc oxide surface through the control of surface amination and in-situ reduction steps, thereby fully utilizing the synergistic antibacterial effect of the two inorganic materials. The overall formula achieves a multiple functional balance of anti-allergic, repair and comfortable experience while maintaining cleaning power. DETAILED DESCRIPTION

[0075] The following specific implementation methods are only used to further illustrate the present application and should not be understood as limiting the scope of protection of the present application. Technicians in this field may make some non-essential improvements and adjustments to the present application based on the above application content.

[0076] 1. Implementation

[0077] Example 1

[0078] This embodiment provides a shampoo containing modified zinc oxide, and its specific preparation method is as follows: first, a nanosilver / zinc oxide hybrid material is prepared, 100 mg of zinc oxide nanoparticles are dispersed in 50 mL of anhydrous ethanol, and ultrasonically treated at 40 kHz for 30 minutes; 5 mL of 3-aminopropyltriethoxysilane is added, and the mixture is refluxed at 80° C. for 6 hours; centrifugation is performed at 8000 rpm for 10 minutes, and vacuum drying is performed at 60° C. to obtain NH2-ZnO; NH2-ZnO is dispersed in 50 mL of deionized water, and 20 mg of AgNO3 is added; 5 mL of 0.1 M NaBH4 solution is dropwise added under ice bath conditions, and the mixture is stirred in the dark for 30 minutes; 10 mg of polyvinyl pyrrolidone is added, and stirring is continued for 1 hour; centrifugation is performed at 10000 rpm for 15 minutes, and the mixture is washed three times with ethanol / water alternately, and freeze-dried at -50° C. for 24 hours to obtain the Ag / ZnO hybrid material. Azobenzene-modified zinc oxide nanoparticles were then prepared: 1 g of zinc oxide nanoparticles was dispersed in 100 mL of anhydrous ethanol, 3 mL of hydrofluoric acid was added, and the mixture was ultrasonically treated for 30 min. The mixture was washed by centrifugation until neutral and then redispersed in 50 mL of toluene. 2 mL of APTMS was added, and the mixture was refluxed at 110°C under nitrogen protection for 6 h. After centrifugation, the mixture was washed with ethanol using a Soxhlet extractor for 24 h to obtain amino-modified ZnO. Separately, 0.5 g of 4-aminoazobenzene was dissolved in 20 mL of 1 M HCl in an ice bath, and 0.35 g of NaNO2 aqueous solution was added for diazotization reaction for 1 h. Urea was added to decompose excess sodium nitrite. The amino-modified ZnO was dispersed in 50 mL of DMF, and a diazonium salt solution was added in an ice bath to adjust the pH to 8.5. The mixture was reacted in the dark for 12 h. Finally, the filtrate was washed with DMF, acetone, and deionized water in sequence until it was colorless, and then dried in a vacuum at 60°C to obtain azobenzene-modified ZnO nanoparticles. Next, an O / W / O triple emulsion matrix was prepared: the inner oil phase was composed of 30 g of jojoba oil and 10 g of silicone oil in a mass ratio of 3:1; the middle aqueous phase was composed of 100 g of deionized water, 35 g of emulsifier, and 5 g of ethanol; and the outer oil phase was composed of 20 g of cyclopentasiloxane and 10 g of cationic guar gum. The middle aqueous phase was slowly added to the inner oil phase, and the W / O emulsion was prepared by high-speed homogenization at 10,000 rpm for 5 min. The W / O emulsion was then added dropwise to the outer oil phase, and low-speed shear emulsification was performed at 2,000 rpm for 10 min to obtain the O / W / O triple emulsion matrix.The final shampoo formula is: 42g azobenzene modified zinc oxide nanoparticles, 4g nanosilver / zinc oxide hybrid material, 165g O / W / O triple emulsion base, 52g jojoba oil / silicone oil complex (30g jojoba oil and 22g silicone oil), 6g cationic guar gum, 135g cocamidopropyl hydroxysulfobetaine, 90g sodium laureth sulfate, 4g ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, 1.5g zinc hyaluronate, 4.5g citric acid / sodium citrate buffer system (2g citric acid and 2.5g sodium citrate), 1.2g disodium edetate, 7g cysteine, 3g panthenol, and deionized water is added to 1000g. During the preparation, 135 g of cocamidopropyl hydroxysulfobetaine and 90 g of sodium laureth sulfate were first dissolved in 600 g of deionized water and stirred at 5000 rpm for 10 min until completely dissolved; 165 g of an O / W / O triple emulsion base and 52 g of a jojoba oil / silicone oil complex were added, and the mixture was homogenized at 5000 rpm for 10 min; 42 g of pre-dispersed azobenzene-modified zinc oxide nanoparticles and 4 g of a nanosilver / zinc oxide hybrid material were added; 6 g of cationic guar gum, 4 g of ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, 1.5 g of zinc hyaluronate, 4.5 g of a citric acid / sodium citrate buffer system (adjusted to pH 5.8), 1.2 g of disodium ethylenediaminetetraacetic acid, 7 g of cysteine, and 3 g of panthenol were sequentially added; the mixture was filled with deionized water to 1000 g, homogenized at 3000 rpm for 5 min, allowed to stand for defoaming, and filtered through a 200-mesh sieve to obtain a finished product.

[0079] Example 2

[0080] The difference between this embodiment and embodiment 1 is that the contents of some components are adjusted: 35 g of azobenzene-modified zinc oxide nanoparticles, 3 g of nanosilver / zinc oxide hybrid material, 150 g of O / W / O triple emulsion matrix (inner oil phase 27 g of jojoba oil and 9 g of silicone oil, middle water phase 90 g of deionized water and 31.5 g of emulsifier, outer oil phase 18 g of cyclopentasiloxane and 9 g of cationic guar gum), 45 g of jojoba oil / silicone oil complex (jojoba oil and silicone oil). Oil 27g and silicone oil 18g composite), cationic guar gum 5g, cocamidopropyl hydroxysultaine 120g, sodium laureth sulfate 80g, ethyl-2-isopropyl-5-methylcyclohexanecarboxamide 3g, zinc hyaluronate 1g, citric acid / sodium citrate buffer system 3g (citric acid 1.3g and sodium citrate 1.7g), disodium edetate 1g, cysteine 5g, panthenol 2g, deionized water is supplemented to 1000g.

[0081] Comparative Example 1

[0082] The difference between this embodiment and embodiment 1 is that the contents of some components are adjusted: 50 g of azobenzene-modified zinc oxide nanoparticles, 5 g of nanosilver / zinc oxide hybrid material, 180 g of O / W / O triple emulsion matrix (inner oil phase 36 g of jojoba oil and 12 g of silicone oil, middle water phase 108 g of deionized water and 37.8 g of emulsifier, outer oil phase 24 g of cyclopentasiloxane and 12 g of cationic guar gum), 60 g of jojoba oil / silicone oil complex (jojoba oil and silicone oil). Oil 36g and silicone oil 24g composite), cationic guar gum 8g, cocamidopropyl hydroxysultaine 150g, sodium laureth sulfate 100g, ethyl-2-isopropyl-5-methylcyclohexanecarboxamide 5g, zinc hyaluronate 2g, citric acid / sodium citrate buffer system 6g (citric acid 2.7g and sodium citrate 3.3g), disodium edetate 1.5g, cysteine 10g, panthenol 4g, deionized water is supplemented to 1000g.

[0083] Comparative Example 1

[0084] The difference between this comparative example and Example 1 is that the azobenzene-modified zinc oxide nanoparticles and the nanosilver / zinc oxide hybrid material are not contained, and the amount of deionized water is increased accordingly to make up 1000 g. The other components and amounts are exactly the same as those in Example 1.

[0085] Comparative Example 2

[0086] The difference between this comparative example and Example 1 is that 42 g of ordinary zinc oxide nanoparticles are used instead of azobenzene-modified zinc oxide nanoparticles, and no nanosilver / zinc oxide hybrid material is contained. The amount of deionized water is increased accordingly to make up 1000 g. The other components and amounts are exactly the same as in Example 1.

[0087] Comparative Example 3

[0088] The difference between this comparative example and Example 1 is that 165 g of a conventional O / W emulsion is used instead of the O / W / O triple emulsion base (composed of 135 g of deionized water and 30 g of an emulsifier). The remaining components and amounts are exactly the same as in Example 1. The emulsification step in the preparation process is adjusted accordingly: 52 g of the jojoba oil / silicone oil complex is directly added to the aqueous phase for emulsification.

[0089] 2. Performance Testing

[0090] The shampoos prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests according to the following method:

[0091] Antibacterial performance test

[0092] Using the method for evaluating the antimicrobial properties of textiles specified in GB / T 20944.3-2008, shampoo samples prepared in Examples 1-3 and Comparative Examples 1-3 were inoculated with Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 8739), respectively. After incubation at 37°C for 24 hours, the inhibition zone diameter and bacterial reduction rate were measured. For testing, 0.1 mL of bacterial suspension (1×106 CFU / mL) was mixed with 1 mL of sample solution and incubated at 37°C for 24 hours before plate counts were performed.

[0093] Photoresponsive release performance test

[0094] The drug release behavior of azobenzene-modified zinc oxide under alternating irradiation of 365 nm ultraviolet light and visible light was determined by UV-visible spectrophotometry. 50 mg of the sample was dispersed in 50 mL of PBS buffer (pH = 7.4) and exposed to UV light (365 nm, 10 mW / cm 2 ) and visible light (>420nm, 100mW / cm 2 ) was used to measure the concentration of active ingredient released within 0-24 hours under irradiation, and the cumulative release rate was calculated.

[0095] Emulsion stability test

[0096] The emulsion samples prepared in Examples 1-3 and Comparative Example 3 were placed in a 50°C thermostat for accelerated aging for 30 days. Delamination was observed and particle size changes were measured. The initial and aged emulsion particle size distributions were measured using a laser particle size analyzer, and the D50 change rate was calculated. A centrifugal stability test (3000 rpm, 30 min) and a freeze-thaw cycle test (-20°C to 25°C, 5 cycles) were also conducted.

[0097] Hair repair performance test

[0098] Bleached, damaged human hair tresses (15 cm long, 0.5 g in weight) were treated with the samples from Examples 1-3 and Comparative Examples 1-3 (5 mL each, 37°C for 5 minutes, rinsed, and blow-dried). The treatments were repeated 10 times before testing the hair properties. The hair scales were observed using a scanning electron microscope, the breaking strength was measured using a fiber strength tester, and the surface hydrophobicity was determined using a contact angle meter.

[0099] Scalp irritation test

[0100] Thirty healthy volunteers were recruited for a patch test. Skin reactions were observed 24 hours after the samples were applied to the inner forearm. Stratum corneum water content was measured using a Corneometer CM825, transepidermal water loss (TEWL) using a Tewameter TM300, and erythema index (EI) using a Mexameter MX18.

[0101] Performance test results:

[0102] Table 1: Performance test results of various embodiments and comparative examples

[0103]

[0104]

[0105] As can be seen from Table 1, the test data analysis of the present invention shows that the present invention successfully solves the technical problems that existing shampoos are difficult to achieve long-term antibacterial and oil control, promote black hair formation, and lack of stability of active ingredients. Examples 1-3 show antibacterial properties that are significantly better than the comparative examples. Among them, the antibacterial rates of Example 3 against Staphylococcus aureus and Escherichia coli reached 99.1% and 98.3%, respectively, which is more than 50 percentage points higher than that of Comparative Example 1 (not containing modified zinc oxide), verifying the synergistic antibacterial effect of azobenzene-modified zinc oxide and nanosilver / zinc oxide hybrid materials. The light response release test showed that the active ingredient release rate of the example group under ultraviolet light reached 78.5-85.6%, while that of Comparative Example 2 (ordinary zinc oxide) was only 15.2%, confirming the key role of azobenzene photoisomerization in controlled release. In terms of emulsion stability, the particle size change rate of the example group (7.5-9.7%) was significantly lower than that of Comparative Example 3 (35.6%), proving that the O / W / O triple emulsion matrix effectively improved the stability of the system. In hair repair testing, the breaking strength retention of the Example group (86.5-91.3%) increased by approximately 30 percentage points compared to Comparative Example 1. Combined SEM observations revealed significant hair scale repair, attributed to the synergistic repair effect of cysteine and cationic guar gum. In skin irritation testing, the erythema index change (1.9-2.3ΔEI) of the Example group was lower than that of Comparative Example 2 (3.5ΔEI), demonstrating that the modified zinc oxide significantly reduced the irritation of traditional antimicrobial agents. Comprehensive test data demonstrates that the present invention, through three core technologies: light-controlled release of azobenzene-modified zinc oxide, sustained-release antimicrobial effects of nanosilver / zinc oxide hybrid materials, and stable encapsulation of an O / W / O triple emulsion, achieves a synergistic improvement in both antimicrobial durability and system stability, successfully overcoming the technical bottleneck of traditional shampoo products, which suffer from limited efficacy and easily inactivated active ingredients.

[0106] The above-described embodiments merely illustrate several implementations of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, and all such variations and improvements fall within the scope of protection of the present invention.

Claims

1. A shampoo containing modified zinc oxide, characterized in that: In terms of mass percentage, the raw materials include: Azobenzene-modified zinc oxide nanoparticles: 3.5-5.0%; Nanosilver / zinc oxide hybrid material: 0.3-0.5%; O / W / O triple emulsion base: 15-18%; Jojoba oil / silicone oil complex: 4.5-6.0%; Cationic guar gum: 0.5-0.8%; Cocamidopropyl Hydroxysultaine: 12.0-15.0%; Sodium laureth sulfate: 8.0-10.0%; Ethyl-2-isopropyl-5-methylcyclohexanecarboxamide: 0.3-0.5%; Zinc hyaluronate: 0.1-0.2%; Citric acid / sodium citrate buffer system: 0.3-0.6%; Disodium EDTA: 0.1-0.15%; Cysteine: 0.5-1.0%; Panthenol: 0.2-0.4%; Deionized water: balance; The preparation steps of the nanosilver / zinc oxide hybrid material include: dispersing zinc oxide nanoparticles in anhydrous ethanol and ultrasonically treating; adding 3-aminopropyltriethoxysilane and refluxing at 80°C for 6 hours; vacuum drying at 60°C to obtain NH2-ZnO; dispersing NH2-ZnO in deionized water and adding AgNO3; dropwise adding 0.1M NaBH4 solution under ice bath conditions and stirring in the dark; adding polyvinyl pyrrolidone and continuing stirring; finally centrifuging, washing with ethanol / water alternately for 3 times; and freeze-drying.

2. The shampoo containing modified zinc oxide according to claim 1, characterized in that The preparation steps of the nanosilver / zinc oxide hybrid material include first dispersing 100 mg of zinc oxide nanoparticles in 50 mL of anhydrous ethanol and sonicating at 40 kHz for 30 minutes. Then, 5 mL of 3-aminopropyltriethoxysilane is added, and the mixture is refluxed at 80°C for 6 hours to amino-aminoate the ZnO surface. The mixture is then centrifuged and washed at 8000 rpm for 10 minutes, and vacuum-dried at 60°C to obtain NH2-ZnO. The NH2-ZnO is then dispersed in 50 mL of deionized water, and 20 mg of AgNO3 is added. 5 mL of 0.1 M NaBH4 solution is added dropwise in an ice bath, and the mixture is stirred in the dark for 30 minutes. Then, 10 mg of polyvinyl pyrrolidone is added, and stirring is continued for 1 hour. Finally, the mixture is centrifuged at 10,000 rpm for 15 minutes, and washed three times with alternating ethanol and water. The mixture is then freeze-dried at -50°C for 24 hours to obtain the Ag / ZnO hybrid material.

3. The shampoo containing modified zinc oxide according to claim 1, characterized in that The preparation steps of the azobenzene-modified zinc oxide nanoparticles include dispersing the zinc oxide nanoparticles in anhydrous ethanol, adding hydrofluoric acid for ultrasonic treatment to activate hydroxylation, centrifuging and washing until neutral, and then redispersing in toluene. APTMS is added, and the mixture is refluxed at 110°C under nitrogen protection. After centrifugation, the mixture is washed with ethanol using a Soxhlet extractor to obtain amino-modified ZnO. 4-Aminoazobenzene is dissolved in 1M HCl in an ice bath, and a NaNO2 aqueous solution is slowly added to perform a diazotization reaction. Urea is added to decompose excess sodium nitrite. The amino-modified ZnO is dispersed in DMF, a diazonium salt solution is added in an ice bath, the pH is adjusted to 8.5, and the reaction is carried out in the dark. Finally, the filtrate is washed with DMF, acetone, and deionized water in sequence until the filtrate is colorless, and then vacuum dried to obtain the azobenzene-modified ZnO nanoparticles.

4. The shampoo containing modified zinc oxide according to claim 3, characterized in that The preparation steps for azobenzene-modified zinc oxide nanoparticles include dispersing 1 g of zinc oxide nanoparticles in 100 mL of anhydrous ethanol, adding 3 mL of hydrofluoric acid, sonicating for 30 minutes, washing by centrifugation until neutral, and then redispersing in 50 mL of toluene. 2 mL of APTMS is added, and the mixture is refluxed at 110°C under nitrogen for 6 hours. After centrifugation, the mixture is washed with ethanol using a Soxhlet extractor for 24 hours to obtain azinated ZnO. Separately, 0.5 g of 4-aminoazobenzene is dissolved in 20 mL of 1 M HCl on ice, and 0.35 g of aqueous NaNO2 is added for diazotization for 1 hour. Urea is then added to decompose excess sodium nitrite. The azinated ZnO is dispersed in 50 mL of diazonium chloride (DMF), and a diazonium salt solution is added on ice to adjust the pH to 8.

5. The mixture is then reacted in the dark for 12 hours. Finally, the filtrate is washed sequentially with DMF, acetone, and deionized water until colorless, and then dried under vacuum at 60°C to obtain azobenzene-modified ZnO nanoparticles.

5. The shampoo containing modified zinc oxide according to claim 1, characterized in that The O / W / O triple emulsion matrix consists of 30-35% inner oil phase, 50-55% middle water phase and 15-20% outer oil phase.

6. The shampoo containing modified zinc oxide according to claim 5, characterized in that The inner oil phase consists of jojoba oil and silicone oil in a mass ratio of 3:1; the middle water phase consists of deionized water, emulsifier and ethanol; and the outer oil phase consists of cyclopentasiloxane and cationic guar gum.

7. The shampoo containing modified zinc oxide according to claim 1, characterized in that The preparation method of the O / W / O triple emulsion matrix includes: preparing an inner oil phase by mixing jojoba oil and silicone oil in a mass ratio of 3:1; mixing deionized water, an emulsifier, and ethanol in an intermediate aqueous phase; and mixing cyclopentasiloxane and cationic guar gum in an outer oil phase. The inner W / O emulsion is first prepared: the intermediate aqueous phase is slowly added to the inner oil phase, and homogenized at a high speed of 10,000 rpm for 5 minutes; and the W / O emulsion is dropwise added to the outer oil phase, and low-speed shear emulsification is performed at 2,000 rpm for 10 minutes.

8. A method for preparing a shampoo containing modified zinc oxide according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, add cocamidopropyl hydroxysultaine and sodium laureth sulfate to deionized water in sequence and stir until completely dissolved; add O / W / O triple emulsion base and jojoba oil / silicone oil complex and mix homogeneously; S2, adding pre-dispersed azobenzene-modified zinc oxide nanoparticles and nanosilver / zinc oxide hybrid material; adding cationic guar gum, ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, zinc hyaluronate, citric acid / sodium citrate buffer system, disodium ethylenediaminetetraacetic acid, cysteine, and panthenol in sequence; replenishing deionized water to 100%, homogenizing, and standing to defoam; filtering through a 200-mesh sieve.

9. The method for preparing a shampoo containing modified zinc oxide according to claim 6, wherein: In step S1, the rotation speed of the homogenous mixing is 5000 rpm and the mixing time is 10 min.

10. The method for preparing a shampoo containing modified zinc oxide according to claim 6, wherein: In step S2, the pH of the citric acid / sodium citrate buffer system is 5.5-6.0; the homogenization speed is 3000 rpm, and the time is 5 minutes.

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