A waterproof makeup composition and a method of preparing the same

Abstract

The application discloses a waterproof makeup composition in the field of cosmetics and a preparation method thereof. The composition comprises a self-repairing organic silicon polyurethane elastomer, double-hydrophobic modified nano silicon dioxide, cyclopentasiloxane, red iron oxide, hydroxyethyl cellulose, polyglyceryl isostearate, sodium hyaluronate, phenoxyethanol, vitamin E acetate and deionized water. The preparation process comprises the following steps: dissolving the self-repairing organic silicon polyurethane elastomer in cyclopentasiloxane to form an oil phase; dissolving hydroxyethyl cellulose in water and then adding other components to form an aqueous phase; mixing and emulsifying the two phases, adding double-hydrophobic modified nano silicon dioxide and other components for grinding, and finally adjusting the pH value. The composition has excellent waterproof performance, long-lasting makeup effect and self-repairing function, and has good skin compatibility.

Description

Technical Field

[0001] This invention relates to the field of cosmetic technology, specifically to a waterproof makeup composition and its preparation method. Background Technology

[0002] In today's cosmetics industry, consumers have increasingly higher demands for the performance of contouring products. They not only expect precise sculpting of facial contours for a three-dimensional effect, but also excellent staying power and practicality, with waterproof and sweat-resistant properties being particularly crucial. However, most waterproof contouring products currently available often suffer from fundamental contradictions in their technological approach. To achieve waterproofing, formulas typically rely heavily on traditional silicone oil derivatives and polymeric film-forming agents. These ingredients form a continuous film on the skin's surface to block moisture. However, while this dense film provides waterproofing, it also severely hinders the skin's normal breathing and perspiration. Prolonged wear can easily lead to stuffiness, stickiness, and other discomforts, significantly reducing comfort. Even worse, an overly thick film can make the makeup look stiff and unnatural, losing the softness and adherence that contouring products should have. Furthermore, with frequent facial expressions, the film is prone to developing micro-cracks due to insufficient elasticity, not only ruining the integrity of the makeup effect but also causing the claimed waterproof function to quickly fail. Therefore, how to ensure excellent waterproof performance while also taking into account the skin's breathability and the user's comfort has been a long-standing technical challenge in this field.

[0003] On the other hand, existing waterproof contouring products also face serious challenges in terms of the durability of their contouring effects. The core technological bottleneck lies in the fact that traditional film-forming agents generally lack self-adaptive and self-repairing capabilities. Once the film is damaged by external forces, such as accidental wiping or contact with sweat, its protective function will have a permanent gap, allowing moisture to easily penetrate, causing contouring pigments to dissolve, shift, or even the entire makeup to become patchy and flake off. This means that users may need to frequently touch up their makeup, which is extremely inconvenient. Furthermore, to achieve natural shadow and highlight effects, contouring products need to contain an appropriate amount of coloring pigments. However, in traditional formulas, these pigment particles are often not effectively fixed when exposed to water, lacking stability and easily washed away, directly resulting in decreased color saturation and weakened contouring effects. The market urgently needs a material with intelligent responsiveness that can autonomously repair its film structure to a certain extent after minor damage occurs during daily use, thereby maintaining the durability and stability of the makeup effect and ensuring that the coloring pigments are firmly locked in place.

[0004] Beyond functional limitations, existing technologies also need improvement in terms of biocompatibility and environmental friendliness in ingredient selection. Many highly effective waterproofing ingredients originate from petrochemical systems, and their inherent properties may not be suitable for sensitive skin, posing a potential risk of skin discomfort with long-term use. Simultaneously, some traditional waterproofing agents, such as those containing fluorine compounds, are difficult to degrade in nature, and their environmental footprint is receiving increasing attention. There is an urgent need within the industry to develop new waterproofing ingredients that combine high performance and high safety. In summary, the current technological development in the waterproof makeup product field is constrained by three major bottlenecks: the contradiction between waterproofing and breathability, the lack of intelligence in film-forming materials, and insufficient biocompatibility of ingredients. The industry yearns for an innovative technological solution that can break away from traditional formulation thinking, fundamentally solving the above problems through novel material design and sophisticated compounding processes, thereby providing an ideal product that integrates long-lasting waterproofing, natural makeup application, comfortable skin feel, and gentle safety. Summary of the Invention

[0005] The purpose of this invention is to provide a waterproof makeup composition and its preparation method, which solves the technical problems of existing waterproof makeup products that are difficult to balance waterproofness and breathability, are prone to cracking after film formation leading to short-lasting makeup effect, and have a sticky feel and insufficient comfort of conventional ingredients.

[0006] The present invention achieves the above objectives through the following technical solutions:

[0007] A method for preparing a waterproof makeup repair composition, comprising the following steps:

[0008] S1. At room temperature, add self-healing silicone polyurethane elastomer to cyclopentamethoxysiloxane and stir until completely dissolved to form an oil phase; then add hydroxyethyl cellulose to deionized water and heat in a water bath to 68-72℃ and stir until completely dissolved. Then add sodium hyaluronate, glycerin and phenoxyethanol and continue stirring to form an aqueous phase.

[0009] S2. Then, the aqueous phase is added to the oil phase and emulsified using a high-speed homogenizer to form an emulsion; the temperature is lowered to 44-46℃, and double hydrophobic modified nano silica, iron oxide red and vitamin E acetate are added and ground.

[0010] S3. Finally, adjust the pH to 6.0-6.5 with lactic acid, stir to room temperature, and degas.

[0011] In this invention, the preparation reaction mechanism of the waterproof makeup composition itself is a complex physicochemical and colloidal chemical process. The core lies in integrating the various functional components into a stable, homogeneous, and synergistically performing dispersion system through precise processes. This begins with the separate preparation and subsequent emulsification of the oil and aqueous phases. In the oil phase, the self-healing silicone polyurethane elastomer dissolves in cyclic silicone oil. The silicone oil acts as a solvent, allowing the elastomer molecular chains to fully extend; its volatility and spreadability also lay the foundation for subsequent film formation. In the aqueous phase, the hydrophilic polymer hydrates and dissolves in deionized water under heating and stirring, forming a viscous colloidal solution. This network structure effectively thickens and stabilizes the final system; subsequently added small-molecule moisturizers and preservatives are uniformly dispersed within this hydrated network. When the aqueous phase is added to the oil phase under shear force, the emulsifier, due to its amphiphilic structure, is rapidly adsorbed at the oil-water interface, significantly reducing interfacial tension. High-speed homogeneous shearing breaks one phase into fine droplets, dispersing them into the other phase, forming an oil-in-water or water-in-oil emulsion. This process forcibly integrates the originally incompatible oil and water phases into a macroscopically uniform dispersion. Subsequently, after appropriate cooling, the added double hydrophobic modified nano-silica and iron oxide red pigment, whose surface properties have been modified to have good compatibility with the emulsion system, are effectively dispersed, wetted, and stably suspended in the continuous emulsion phase under high-shear grinding. Some of the nano-silica particles are embedded in the elastomer network, while others are distributed at the interface, synergistically constructing a double hydrophobic barrier with the soon-to-be-formed elastic film; while the iron oxide red pigment is fully depolymerized and uniformly distributed, ensuring the uniformity and stability of the color tone. Finally, by adding organic acids to adjust the pH of the system to approximate the physiological values ​​of the skin, the product's gentleness is enhanced, and the charge state of certain components may also be affected, thereby further optimizing the emulsion's storage stability. The entire preparation process involves a series of meticulous operations, including sequential feeding, stepwise construction, shear emulsification, and grinding dispersion, ultimately achieving a perfect fusion and synergistic effect of the functions of each component.

[0012] According to a preferred embodiment of the present invention, in step S1, the stirring time at 68-72°C is 1-2 hours; the stirring time is continued for 30-40 minutes.

[0013] According to a preferred embodiment of the present invention, in step S2, the emulsification time using a high-speed homogenizer is 10-20 min.

[0014] According to a preferred embodiment of the present invention, the method for preparing the dual hydrophobic modified nano-silica includes:

[0015] A1. Disperse nano-silica in anhydrous toluene, sonicate to form a suspension, add (3-aminopropyl)triethoxysilane, and reflux at 78-82℃ to obtain an amino-modified nano-SiO2 intermediate.

[0016] A2. Then, lower the temperature to 24-26℃, add heptadecafluorodecyltrimethoxysilane first, react, then add triethoxysilylethylpolydimethylsiloxane, add deionized water, adjust the pH to 5-6 with acetic acid, and continue the reaction under nitrogen protection; after the reaction is completed, wash with acetone by centrifugation, and finally dry in a vacuum drying oven at 78-82℃.

[0017] In this invention, the core of the preparation reaction mechanism of the dual hydrophobic modified nano-silica lies in constructing a composite hydrophobic layer with low surface energy and microscopic roughness on nanoparticles through precise two-step surface engineering. The process begins with nano-silica dispersed in anhydrous toluene. The abundant silanol groups on its surface serve as reactive sites, undergoing a hydrolysis-condensation reaction with introduced aminosilanes. Toluene, as an inert solvent, effectively eliminates moisture interference, ensuring the formation of strong siloxane-silicon covalent bonds between the silanol groups of the reaction-directing silane and the silanol groups on the silica surface. This chemically grafts the long organic chain with terminal amino groups onto the nanoparticle surface, obtaining an amino-modified intermediate. This step is fundamental for the subsequent robust modification. Subsequently, a crucial dual hydrophobic modification is performed at mild room temperature: the first added fluoroalkylsilane, with its highly reactive methoxy group, rapidly reacts with the primary amino groups or remaining silanol groups on the intermediate surface. The fluorocarbon long chain, with its extremely low surface energy, first forms a dense inner hydrophobic film on the particle surface. Subsequently, branched alkyl silicones with a large spatial structure are added. Under weakly acidic conditions, their ethoxy groups hydrolyze to generate silanol groups, which then condense with the remaining active sites (such as unreacted silanol groups or amino groups) on the particle surface. Due to the large size of the branched silicone molecules, their grafting onto the particle surface and around the existing fluorocarbon chains not only provides additional hydrophobic effects, but more importantly, their three-dimensional structure constructs the necessary surface roughness at the nanoscale. This composite structure, achieved through stepwise modification and consisting of low surface energy fluorocarbon chains and a microscopically roughened branched silicone layer, synergistically amplifies the hydrophobic effect, ultimately giving the material excellent superhydrophobic properties.

[0018] According to a preferred embodiment of the present invention, in step A1, the reflux reaction time at 78-82°C is 12-14 hours.

[0019] According to a preferred embodiment of the present invention, in step A2, the reaction continues under nitrogen protection for 22-26 hours; the drying time in a vacuum drying oven at 78-82°C is 12-14 hours.

[0020] According to a preferred embodiment of the present invention, the method for preparing the self-healing silicone polyurethane elastomer includes:

[0021] B1. Under a dry nitrogen atmosphere, polydimethylsiloxane diol and isophorone diisocyanate were added to a three-necked flask, and dibutyltin dilaurate was added. The mixture was reacted at 84-86°C to obtain isocyanate-terminated polysiloxane prepolymer.

[0022] B2. Then, the temperature was lowered to 58-62℃, and 1-(2-aminoethyl)-2-amino-4-hydroxy-6-methylpyrimidine was added first to react. Then, 2,2'-dithiodiethylamine and triethylamine were added simultaneously, and the reaction was carried out under nitrogen protection. After the reaction was completed, the product was dissolved in tetrahydrofuran, purified by methanol precipitation, and finally dried in a vacuum drying oven at 48-52℃.

[0023] In this invention, the preparation mechanism of the self-healing silicone polyurethane elastomer is essentially based on the stepwise polymerization of isocyanate and active hydrogen compounds, and endows it with self-healing intelligence by introducing a dynamic reversible bonding system. The reaction first occurs under the action of a catalyst, where the hydroxyl groups at both ends of the flexible polydimethylsiloxane diol segment react with excess diisocyanate molecules to generate a prepolymer capped at both ends with highly reactive isocyanate groups. This step precisely controls the soft segment length and structure of the polymer backbone. Subsequently, the reaction enters the delicate stage of constructing self-healing functionality—chain elongation and functionalization. The system temperature is appropriately lowered to facilitate control of the reaction process, and two amine chain extenders with distinct functions are added stepwise. The first added is a diamine containing a ureidinium ketone structure. Its primary amine group preferentially reacts rapidly with the isocyanate groups at the end of the prepolymer, embedding the strong quadruple hydrogen bond donor-acceptor unit of the ureidinium ketone into the growing polymer hard segment in the form of a urea bond. After the reaction is essentially complete, a diamine containing disulfide bonds is added. Its primary amine groups react with the remaining isocyanate groups in the system, introducing dynamic disulfide bonds into the polymer backbone. The tertiary amine added during this process neutralizes any acids that may be generated during the reaction, preventing catalyst deactivation. The resulting block copolymer possesses a unique microphase separation structure: polysiloxane forms the soft segment phase region, providing flexibility, while hard segments composed of urea / urethane bonds, quadruple hydrogen bonds, and disulfide bonds aggregate to form physical crosslinking points. It is precisely these densely packed, reversibly fractured and reformed multiple hydrogen bonds and dynamic disulfide bonds within the hard segments that collectively endow the material with excellent self-healing capabilities under mild conditions.

[0024] According to a preferred embodiment of the present invention, in step B1, the reaction time is 3-4 hours at 84-86°C.

[0025] According to a preferred embodiment of the present invention, in step B2, the reaction time under nitrogen protection is 5-8 hours; the drying time in a vacuum drying oven at 48-52°C is 24-30 hours.

[0026] This invention also provides a waterproof makeup repair composition, which is prepared according to the method described above; wherein the waterproof makeup repair composition comprises the following raw materials in parts by weight: 8-15 parts of self-healing silicone polyurethane elastomer; 5-12 parts of bis-hydrophobic modified nano silica; 10-20 parts of cyclopentamethoxysiloxane; 3-8 parts of iron oxide red; 0.5-2 parts of hydroxyethyl cellulose; 2-5 parts of polyglycerol-4-isostearate; 0.5-2 parts of sodium hyaluronate; 0.05-0.1 parts of phenoxyethanol; 0.1-0.5 parts of vitamin E acetate; and 35-70 parts of deionized water.

[0027] The beneficial effects of this invention are as follows:

[0028] The waterproof makeup composition provided by this invention achieves a perfect balance between superior waterproof performance and a natural, long-lasting makeup effect based on its unique formula design and core functional components. Its technical effectiveness is primarily reflected in fundamentally resolving the core contradiction of traditional products that struggle to balance waterproofness and comfort. The self-healing silicone polyurethane elastomer introduced into the composition forms a continuous, flexible, and breathable three-dimensional network film on the skin surface. This film itself possesses extremely high hydrophobicity, effectively blocking external moisture intrusion; simultaneously, its special microphase separation structure provides channels for water vapor to pass through, allowing the skin to breathe naturally, thus avoiding the stuffiness and stickiness caused by traditional thick waterproof films. More importantly, the addition of double hydrophobic modified nano-silica produces a significant synergistic effect with the elastomer film. These precisely designed nanoparticles have a dual hydrophobic structure with both low surface energy and microscopic roughness. They are evenly embedded in and on the elastic film layer, like a strong "nano armor" for the skin. This greatly enhances the film layer's repellency to water droplets, causing water droplets to roll off quickly when they come into contact with water, making it difficult for them to soak into the makeup. This achieves excellent sweat and moisture resistance, ensuring that the makeup color can remain bright and vibrant even in humid environments.

[0029] Another breakthrough of this invention lies in its ability to endow the makeup composition with unprecedented durability and intelligent self-healing capabilities, significantly extending the duration of a perfect makeup effect. The self-healing silicone polyurethane elastomer serves as the film-forming matrix, incorporating a dynamically reversible network of hydrogen and disulfide bonds in its molecular structure. When applied to the face, daily facial expressions inevitably cause microscopic cracks in the film layer that are difficult to detect with the naked eye. At this time, in an environment close to skin temperature, these dynamic chemical bonds can spontaneously break and recombine, driving the material to flow to the cracks and re-bond, thereby effectively "healing" these damages, restoring the continuity and integrity of the film layer, and preventing further expansion of cracks that could lead to waterproofing failure and makeup peeling. This inherent self-healing mechanism allows the makeup to resist minor daily friction and touch, maintaining its perfect finish for several hours. At the same time, the double hydrophobic modified nano silica not only enhances waterproofness, but its nanoscale particles can also efficiently scatter light. It works synergistically with iron oxide red pigment to produce soft and natural shadows and skin tone adjustment effects, avoiding pigment aggregation and stiffness, making the contouring effect three-dimensional and vivid, and achieving an overall leap from "long-lasting waterproof" to "long-lasting makeup effect".

[0030] Finally, this invention, while achieving superior functionality, also fully considers product safety and user experience, demonstrating excellent overall product quality. The self-healing silicone polyurethane elastomer is derived from biocompatible polysiloxane raw materials, which are inherently mild, greatly reducing the risk of irritation to sensitive skin. The double hydrophobic modified nano-silica, with stable inorganic oxides as its core, has a safe and reliable surface modification layer, ensuring a worry-free experience when the final product comes into contact with the skin. The entire formulation system is carefully pH-adjusted to match the slightly acidic environment of healthy skin, further enhancing its affinity for use. In terms of skin feel, the combination of components such as cyclopentamethoxysiloxane gives the product a smooth and easy-to-apply texture, with a refreshing and non-greasy feel. The introduction of sodium hyaluronate provides continuous skin-friendly hydration, avoiding potential dryness and tightness caused by film formation. In summary, this waterproof makeup composition successfully combines superior waterproofing, long-lasting makeup effect, self-healing intelligence, excellent skin feel, and high safety, representing a significant advancement in this technological field. Detailed Implementation

[0031] The following detailed embodiments are only used to further illustrate this application and should not be construed as limiting the scope of protection of this application. Those skilled in the art can make some non-essential improvements and adjustments to this application based on the above application content.

[0032] The following is information on domestic suppliers of key related equipment and materials:

[0033] The cyclopentadimethylsiloxane was purchased from Bluestar Chemical New Materials Co., Ltd.

[0034] The hydroxyethyl cellulose was purchased from Heda Group Co., Ltd.

[0035] The sodium hyaluronate was purchased from Bloomage Biotechnology Co., Ltd.

[0036] The glycerin was purchased from COFCO Biotechnology Co., Ltd.

[0037] The phenoxyethanol was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0038] The iron oxide red was purchased from Shanghai Iron Oxide Pigment Factory Co., Ltd.

[0039] The vitamin E acetate was purchased from Zhejiang NHU Co., Ltd.

[0040] The nano-silica was purchased from Quecheng Silicon Chemical Co., Ltd.

[0041] The (3-aminopropyl)triethoxysilane was purchased from Wuhan Huaxiang Kecheng Biotechnology Co., Ltd.

[0042] The heptadecafluorodecyltrimethoxysilane was purchased from Zhonghao Chenguang Chemical Research Institute Co., Ltd.

[0043] The triethoxysilyl ethyl polydimethylsiloxane was purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.

[0044] The acetic acid was purchased from Jiangsu Suopu Group Co., Ltd.

[0045] The polydimethylsiloxane diol was purchased from Shandong Dongyue Organosilicon Materials Co., Ltd.

[0046] The isophorone diisocyanate was purchased from Wanhua Chemical Group Co., Ltd.

[0047] The dibutyltin dilaurate was purchased from Beijing Huawirui Chemical Co., Ltd.

[0048] The 1-(2-aminoethyl)-2-amino-4-hydroxy-6-methylpyrimidine was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0049] The 2,2'-dithiodiethylamine was purchased from Jiangsu Yongda Pharmaceutical Co., Ltd.

[0050] The triethylamine was purchased from Hualu Hengsheng Chemical Co., Ltd. Example 1

[0051] The preparation process of the double hydrophobic modified nano-silica is as follows: 10.00g of nano-silica was placed in a dry three-necked flask, and 90.00g of anhydrous toluene was added. The mixture was ultrasonically dispersed for 30min at 200W using an ultrasonic cell disruptor to form a uniform suspension. Subsequently, 0.50g of triaminopropyltriethoxysilane was slowly added dropwise through a constant pressure dropping funnel at a rate of 1 drop / second. A Dean-Stark water separator was installed, and the mixture was refluxed in an oil bath at 80℃ for 13h, with nitrogen continuously purging for protection. After the reaction, an amino-modified nano-silica intermediate was obtained. The reaction system was cooled to 25℃, and 0.80g of heptadecafluorodecyltrimethoxysilane was added using a precision syringe. The reaction was maintained at 25℃ for 5h, and then 1.20g of triethoxysilylethylpolydimethylsiloxane and 1.5g of deionized water were added. The pH was adjusted to 5.5 by adding acetic acid dropwise using a micropipette, and the reaction was continued for 24 hours under nitrogen protection. After the reaction was completed, the product was transferred to centrifuge tubes and washed three times with acetone at 10,000 rpm using a high-speed centrifuge for 10 minutes each time. Finally, the product was placed in a vacuum drying oven and dried at 80°C and -0.1 MPa for 13 hours to obtain bis-hydrophobic modified nano-silica.

[0052] The preparation process of self-healing silicone polyurethane elastomer is as follows: Under a dry nitrogen atmosphere, 10.00 g of polydimethylsiloxane diol and 4.50 g of isophorone diisocyanate were added to a three-necked flask that had undergone three vacuum-nitrogen purging treatments. 0.015 g of dibutyltin dilaurate was added, and the mixture was mechanically stirred in an oil bath at 85°C for 3.5 h at a stirring speed of 300 r / min to obtain isocyanate-terminated polysiloxane prepolymer. The reaction system was cooled to 60°C, and 2.00 g of 1-(2-aminoethyl)-2-amino-4-hydroxy-6-methylpyrimidine was weighed using a precision electronic balance and added to the reaction system in batches under nitrogen protection, with the addition time controlled at 10 min. After reacting for 1.5 h, 1.00 g of 2,2-dithiodiethylamine and 1.50 g of triethylamine were accurately weighed and added to the reaction system simultaneously. The reaction was continued at 60°C for another 6.5 h. After the reaction was completed, the product was dissolved in 80.00 g of tetrahydrofuran, and the insoluble matter was removed by filtration using a Buchner funnel. The filtrate was slowly added dropwise to 200.00 g of vigorously stirred methanol to precipitate. This purification process was repeated 3 times. Finally, the product was placed in a vacuum drying oven and dried at 50 °C and -0.1 MPa for 28 h to obtain a self-healing organosilicon polyurethane elastomer.

[0053] The preparation process of the waterproof makeup repair composition is as follows: At room temperature (25℃), 10.00g of self-healing silicone polyurethane elastomer was added to 15.00g of cyclopentamethoxydimethylsiloxane, and stirred at 500r / min for 30min using a mechanical stirrer until completely dissolved, forming a transparent oil phase. Separately, 48.50g of deionized water was added to 1.00g of hydroxyethyl cellulose, and the mixture was mechanically stirred at 800r / min for 1.5h in a 70℃ constant temperature water bath until completely dissolved. Then, 1.20g of sodium hyaluronate, 5.00g of glycerin, and 0.08g of phenoxyethanol were added sequentially, and stirring continued for 35min to form a homogeneous aqueous phase. The aqueous phase was slowly poured into the oil phase, and emulsified at 5000r / min for 15min using a high-speed homogenizer to form a stable emulsion. The emulsion temperature was lowered to 45°C, and 8.00g of double hydrophobic modified nano-silica, 5.00g of iron oxide red, and 0.30g of vitamin E acetate were accurately added. The emulsion was then ground three times using a three-roll mill with a roller gap of 0.01mm. Finally, the pH was adjusted to 6.2 with lactic acid, and the mixture was slowly stirred at 200r / min using an anchor stirrer until it reached room temperature of 25°C. The mixture was then degassed in a vacuum degassing machine at -0.08MPa for 20 minutes to obtain the final waterproof makeup repair composition. Example 2

[0054] The specific implementation method is the same as in Example 1, except that the preparation of the double hydrophobic modified nano silica is as follows: 10g of nano silica is dispersed in 90g of anhydrous toluene, and ultrasonically treated for 30min to form a suspension. 0.6g of triaminopropyltriethoxysilane is added, and the mixture is refluxed at 78℃ for 14h to obtain an amino-modified nano silica intermediate. Subsequently, the temperature is lowered to 24℃, and 1.0g of heptadecafluorodecyltrimethoxysilane is added first, and the mixture is reacted for 4h. Then, 1.5g of triethoxysilyl ethyl polydimethylsiloxane is added, along with 1.6g of deionized water. The pH is adjusted to 5.2 with acetic acid, and the reaction is continued for 22h under nitrogen protection. After the reaction is completed, the mixture is washed three times by centrifugation with acetone, and finally dried in a vacuum drying oven at 78℃ for 14h to obtain the double hydrophobic modified nano silica. Preparation of self-healing silicone polyurethane elastomer: Under a dry nitrogen atmosphere, 10g of polydimethylsiloxane diol and 4.2g of isophorone diisocyanate were added to a three-necked flask, followed by 0.014g of dibutyltin dilaurate. The mixture was reacted at 84℃ for 4h to obtain an isocyanate-terminated polysiloxane prepolymer. Subsequently, the temperature was lowered to 58℃, and 1.8g of 1-(2-aminoethyl)-2-amino-4-hydroxy-6-methylpyrimidine was added. The mixture was reacted for 2h, followed by 0.9g of 2,2-dithiodiethylamine and 1.3g of triethylamine. The mixture was reacted under nitrogen protection for 5h. After the reaction, the product was dissolved in 80g of tetrahydrofuran, purified three times by precipitation with 200g of methanol, and finally dried in a vacuum drying oven at 48℃ for 30h to obtain the self-healing silicone polyurethane elastomer. Preparation of the waterproof makeup repair composition: At room temperature, 8g of self-healing silicone polyurethane elastomer was added to 10g of cyclopentamethoxydimethylsiloxane and stirred at 500r / min until completely dissolved to form an oil phase; then 0.5g of hydroxyethyl cellulose was added to 55g of deionized water and heated in a water bath to 68℃ and stirred at 800r / min for 2h until completely dissolved. Then, 0.5g of sodium hyaluronate, 3g of glycerin and 0.05g of phenoxyethanol were added and stirred for another 30min to form an aqueous phase; subsequently, the aqueous phase was added to the oil phase and emulsified at 5000r / min for 10min using a high-speed homogenizer to form an emulsion; the temperature was lowered to 44℃, 5g of double hydrophobic modified nano silica, 3g of iron oxide red and 0.1g of vitamin E acetate were added, and the mixture was milled three times using a three-roll mill; finally, the pH was adjusted to 6.0 with lactic acid, and the mixture was stirred at 200r / min to room temperature to defoam and obtain the waterproof makeup repair composition. Example 3

[0055] The specific implementation method is the same as in Example 1, except that the preparation of the double hydrophobic modified nano silica is as follows: 10g of nano silica is dispersed in 90g of anhydrous toluene, and ultrasonically treated for 30min to form a suspension. 0.8g of triaminopropyltriethoxysilane is added, and the mixture is refluxed at 82℃ for 12h to obtain an amino-modified nano silica intermediate. Then, the temperature is lowered to 26℃, 1.2g of heptadecafluorodecyltrimethoxysilane is added, and the mixture is reacted for 6h. Then, 1.0g of triethoxysilylethylpolydimethylsiloxane is added, along with 1.7g of deionized water. The pH is adjusted to 5.8 with acetic acid, and the reaction is continued for 26h under nitrogen protection. After the reaction is completed, the mixture is washed three times by centrifugation with acetone, and finally dried in a vacuum drying oven at 82℃ for 12h to obtain the double hydrophobic modified nano silica. Preparation of self-healing silicone polyurethane elastomer: Under a dry nitrogen atmosphere, 10g of polydimethylsiloxane diol and 5g of isophorone diisocyanate were added to a three-necked flask, along with 0.015g of dibutyltin dilaurate. The mixture was reacted at 86℃ for 3h to obtain an isocyanate-terminated polysiloxane prepolymer. Subsequently, the temperature was lowered to 62℃, and 2.2g of 1-(2-aminoethyl)-2-amino-4-hydroxy-6-methylpyrimidine was added. The mixture was reacted for 1h, followed by the addition of 1.1g of 2,2-dithiodiethylamine and 1.6g of triethylamine. The mixture was reacted under nitrogen protection for 8h. After the reaction, the product was dissolved in 80g of tetrahydrofuran, purified three times by precipitation with 200g of methanol, and finally dried in a vacuum drying oven at 52℃ for 24h to obtain the self-healing silicone polyurethane elastomer. Preparation of the waterproof makeup repair composition: At room temperature, 12g of self-healing silicone polyurethane elastomer was added to 18g of cyclopentamethoxydimethylsiloxane and stirred at 500r / min until completely dissolved to form an oil phase; then, 1.5g of hydroxyethyl cellulose was added to 40g of deionized water and heated in a water bath to 72℃ and stirred at 800r / min for 1h until completely dissolved. Then, 1.5g of sodium hyaluronate, 4g of glycerin and 0.06g of phenoxyethanol were added and stirred for another 40min to form an aqueous phase; subsequently, the aqueous phase was added to the oil phase and emulsified at 5000r / min for 20min using a high-speed homogenizer to form an emulsion; the temperature was lowered to 46℃, and 10g of double hydrophobic modified nano silica, 6g of iron oxide red and 0.2g of vitamin E acetate were added and milled three times using a three-roll mill; finally, the pH was adjusted to 6.5 with lactic acid and stirred at 200r / min to room temperature to defoam and obtain the waterproof makeup repair composition.

[0056] Comparative Example 1

[0057] The specific implementation method is the same as in Example 1, except that the bis-hydrophobic modified nano-silica is not added, but is replaced with an equal amount of ordinary nano-silica. The remaining components and preparation process are exactly the same as in Example 1.

[0058] Comparative Example 2

[0059] The specific implementation method is the same as in Example 1, except that the self-healing silicone polyurethane elastomer is not added, but is replaced with an equal amount of ordinary polydimethylsiloxane. The remaining components and preparation process are exactly the same as in Example 1.

[0060] Comparative Example 3

[0061] The specific implementation method is the same as in Example 1, except that the double hydrophobic modified nano silica and the self-healing organosilicon polyurethane elastomer are not added. Instead, the double hydrophobic modified nano silica is replaced with an equal amount of ordinary nano silica, and the self-healing organosilicon polyurethane elastomer is replaced with an equal amount of ordinary polydimethylsiloxane. The remaining components and preparation process are exactly the same as in Example 1.

[0062] Comparative Example 4

[0063] The specific implementation method is the same as in Example 1, except that heptadecafluorodecyltrimethoxysilane is not added during the preparation of the bis-hydrophobic modified nano silica.

[0064] Comparative Example 5

[0065] The specific implementation method is the same as in Example 1, except that 2,2'-dithiodiethylamine is not added in the preparation process of the self-healing silicone polyurethane elastomer, while the remaining components and preparation process are exactly the same as in Example 1.

[0066] Performance testing

[0067] According to national and industry standard testing specifications, the waterproof makeup compositions prepared in Examples 1-3 and Comparative Examples 1-3 were tested according to the following performance testing methods: Breathability test: The sample was applied to the mouth of a breathability test cup filled with saturated potassium chloride solution to maintain 93% RH. The cup was placed in an environment of 25℃ and 50% RH, and the weight change was measured every hour to calculate the 24-hour water vapor transmission rate. Waterproof performance test: Using a water flow rinsing method, 30mg of makeup sample was evenly applied to a 3cm×3cm artificial skin plate and allowed to cure for 30 minutes at 25℃ and 50% humidity. A constant flow pump was used to vertically impact the sample surface with deionized water at a flow rate of 5L / min from a height of 15cm for 10 minutes. The color values ​​before and after rinsing were measured using a colorimeter, and the color retention rate was calculated. Durability test: The coated sample was placed in a constant temperature and humidity chamber at 40℃ and 80% RH. Samples were taken at 0h, 4h, and 8h, and the percentage of makeup integrity was calculated using image analysis software. Self-healing performance test: Standard scratches were created on the surface of the cured film using a nano-scratch instrument. The samples were placed in a 37℃ incubator, and the changes in scratch width were observed using a scanning electron microscope at 0h, 2h, 4h, and 6h, respectively, to calculate the repair efficiency. Stability test: The product was stored for 30 days under low temperature (-8℃), high temperature (45℃), and accelerated conditions (45℃ / 75%RH), respectively, and changes in properties were observed. Skin feel evaluation: 30 trained evaluators were recruited to rate the product's spreadability, stickiness, and refreshing feel on a 5-point scale. Routine index tests: The samples were tested for pH value, drop strength, and rubbing performance.

[0068] Performance test results:

[0069] Table 1: Performance test results of each embodiment and comparative example

[0070]

[0071] As shown in Table 1, the test results clearly demonstrate that Examples 1-3, through the synergistic effect of introducing self-healing silicone polyurethane elastomer and dual hydrophobic modified nano-silica, systematically solved the technical bottlenecks of traditional waterproof makeup products. Regarding waterproofness and breathability, the water vapor transmission rate of the examples reached 672-685 g / m²·24h, significantly higher than the comparative product (352-435 g / m²·24h), while achieving a color retention rate of over 97%. This proves that the constructed intelligent film layer effectively blocks liquid water intrusion while allowing water vapor to pass through, perfectly balancing the contradiction between waterproofness and breathability. In terms of durability, the examples maintained approximately 95% of the makeup effect integrity after 8 hours of testing and possessed a self-healing efficiency of over 95%. This is attributed to the dynamic bond network in the self-healing elastomer, which can repair micro-cracks in the film layer in real time, while the dual hydrophobic nanoparticles, by anchoring the colorant and enhancing surface hydrophobicity, jointly ensured the long-lasting stability of the makeup effect. In terms of skin comfort, the products in the examples achieved spreadability and stickiness scores of 4.3-4.6, far superior to the comparative products (2.8-3.8). This is attributed to the flexible film layer formed by the self-healing elastomer, which avoids the stiffness of traditional film-forming agents, and the unique slippery properties of the dual hydrophobic nanoparticles, which significantly reduce stickiness. Comparative Example 1 suffered a significant decrease in water resistance due to the lack of a dual hydrophobic structure, Comparative Example 2 showed obvious cracks due to the lack of self-healing function, and Comparative Example 3 performed the worst due to the simultaneous absence of two key components. This, in turn, verifies the synergistic mechanism achieved by the present invention through molecular design, fundamentally breaking through the technical barrier of traditional formulations where functionality and comfort are difficult to achieve simultaneously.

[0072] The embodiments described above are merely examples of several implementations of the present invention, and 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 those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a waterproof makeup composition, characterized in that the steps include... include: S1. At room temperature, add self-healing silicone polyurethane elastomer to cyclopentamethoxysilane and stir until completely dissolved to form an oil phase; then add hydroxyethyl cellulose to deionized water, heat in a water bath to 68-72℃ and stir until completely dissolved, then add sodium hyaluronate, glycerin and phenoxyethanol, and continue stirring to form an aqueous phase; S2. Then, the aqueous phase is added to the oil phase and emulsified using a high-speed homogenizer to form an emulsion; the temperature is lowered to 44-46℃, and double hydrophobic modified nano silica, iron oxide red and vitamin E acetate are added and ground. S3. Finally, adjust the pH to 6.0-6.5 with lactic acid, stir to room temperature, and degas. The preparation methods of double hydrophobic modified nano-silica include: A1. Disperse nano-silica in anhydrous toluene, sonicate to form a suspension, add (3-aminopropyl)triethoxysilane, and reflux at 78-82℃ to obtain an amino-modified nano-silica intermediate. A2. Then, lower the temperature to 24-26℃, add heptadecafluorodecyltrimethoxysilane first, react, then add triethoxysilylethylpolydimethylsiloxane, add deionized water, adjust the pH to 5-6 with acetic acid, and continue the reaction under nitrogen protection; after the reaction is completed, wash with acetone by centrifugation, and finally dry in a vacuum drying oven at 78-82℃. Methods for preparing self-healing silicone polyurethane elastomers include: B1. Under a dry nitrogen atmosphere, polydimethylsiloxane diol and isophorone diisocyanate were added to a three-necked flask, and dibutyltin dilaurate was added. The reaction was carried out at 84-86℃ to obtain isocyanate-terminated polysiloxane prepolymer. B2. Then, the temperature was lowered to 58-62℃, and 1-(2-aminoethyl)-2-amino-4-hydroxy-6-methylpyrimidine was added first to react. Then, 2,2'-dithiodiethylamine and triethylamine were added simultaneously, and the reaction was carried out under nitrogen protection. After the reaction was completed, the product was dissolved in tetrahydrofuran, purified by methanol precipitation, and finally dried in a vacuum drying oven at 48-52℃.

2. The method for preparing the waterproof makeup composition according to claim 1, characterized in that, In step S1, the stirring time at 68-72℃ is 1-2 hours; the stirring time is continued for 30-40 minutes.

3. The method for preparing the waterproof makeup composition according to claim 1, characterized in that, In step S2, the emulsification time using a high-speed homogenizer is 10-20 minutes.

4. The method for preparing the waterproof makeup composition according to claim 1, characterized in that, In step A1, the reflux reaction time at 78-82℃ is 12-14 hours.

5. The method for preparing the waterproof makeup composition according to claim 1, characterized in that, In step A2, the reaction continues under nitrogen protection for 22-26 hours; the drying time in a vacuum drying oven at 78-82℃ is 12-14 hours.

6. The method for preparing the waterproof makeup composition according to claim 1, characterized in that, In step B1, the reaction time is 3-4 hours at 84-86℃.

7. The method for preparing the waterproof makeup composition according to claim 1, characterized in that, In step B2, the reaction time under nitrogen protection is 5-8 hours; the drying time in a vacuum drying oven at 48-52℃ is 24-30 hours.

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