Temperature-sensitive anhydrous self-emulsifying egg yolk oil cleansing gel stick and preparation method thereof

Abstract

The invention discloses a temperature-sensitive anhydrous self-emulsifying egg yolk oil cleansing gel stick and a preparation method thereof. According to the makeup removing gel bar, egg yolk oil serves as a main oil phase, egg shell powder which is subjected to wet ball milling nanocrystallization and surface lipidation treatment serves as a particle gel framework, secondary fluid is introduced into the oil phase, particles are preferentially wetted by the secondary fluid, a pendulum capillary bridge network is formed, and therefore soft solid paste with the yield stress larger than or equal to 60 Pa at the temperature of 25 DEG C is obtained; the ointment is reversibly softened at the skin temperature (32-36 DEG C) and under the shearing action, and is self-emulsified to have the particle size Dlt within 60 seconds when encountering water; and the emulsion droplets of 10 microns are easy to wash away and low in residue. According to the formula, a PEG-free self-emulsifying system of lecithin and polyglycerol fatty acid ester is preferably selected, 12-hydroxystearic acid / beewax is preferably added to achieve temperature-sensitive regulation, the water content of the product is smaller than or equal to 1.0 wt%, the water activity aw is smaller than or equal to 0.6, a traditional water-phase preservative does not need to be added, and the product is suitable for sensitive skin.

Description

Technical Field

[0001] This invention belongs to the field of cosmetics, specifically relating to a temperature-sensitive anhydrous self-emulsifying egg yolk oil makeup remover gel stick and its preparation method. Background Technology

[0002] Cosmetic removal products are currently mainly in the form of cleansing oils, cleansing balms / creams, and water-oil dual-phase / microemulsions. Consumer usage scenarios are showing trends of high frequency, mobility, and an increasing proportion of people with sensitive skin, thus placing higher demands on portability, leak-proof properties, low irritation, and quick rinsing. At the same time, regulations and industry consensus are gradually strengthening risk control over preservatives, surfactant types and dosages, and fragrance allergens, prompting companies to continuously explore structured oil phases and gentle self-emulsifying technologies.

[0003] (1) Makeup remover oils typically consist of a fluid oil phase combined with nonionic surfactants to form a "water-emulsifying" system, possessing excellent dissolving / adsorption capabilities for hydrophobic makeup and sunscreen films. However, their low yield stress and low viscosity make them prone to leakage during transportation, carrying, and pouring, making it difficult to meet leakage prevention requirements in travel scenarios. To improve the "oil film feeling," it is often necessary to increase the proportion of surfactants or introduce ester-based light-feeling oils, but this may lead to side effects such as itching, barrier interference, or increased water consumption for rinsing. Some products are water-containing microemulsions or pre-emulsified systems, which require a robust preservative system and temperature-resistant design, and their compatibility with sensitive skin is uncertain.

[0004] (2) Makeup remover balms / creams often rely on a high proportion of waxes (beeswax, microcrystalline wax, etc.), saponification systems, or organic gelling agents to construct a three-dimensional structural network in order to achieve room temperature stability and leak-proof properties. However, excessively high wax content can lead to a heavy feel on the skin, difficulty in spreading, slow "phase inversion" upon contact with water, and high residue and water consumption during rinsing. Saponification or alkaline soap-based systems may cause irritation / tightness under certain conditions, and are prone to softening, collapse, or oil separation in the high temperatures of summer; in low-temperature cycling, crystal rearrangement may occur, leading to changes in texture and a narrow stability window.

[0005] (3) Water-oil biphase / microemulsion products are characterized by their thin appearance and clear visual appearance, and rely on the synergy of high HLB and low HLB surfactants to stabilize the interface. However, the aqueous phase requires corrosion protection and places higher demands on container sealing and aseptic / low-bacterial control during filling; during long-term storage, they are susceptible to changes in phase volume distribution or stratification due to temperature / vibration. Biphase bottles still pose a risk of leakage / splashing during personal transport and air transport.

[0006] In recent years, particle-induced capillary suspension gels have attracted attention as a structuring strategy. This approach introduces trace amounts of secondary fluid into a continuous fluid phase. When the secondary fluid preferentially wets the solid particles, capillary bridges can form between the particles, constructing a multi-scale three-dimensional network, thereby significantly improving the system's yield stress and static stability. Existing research has mostly focused on aqueous continuous phases or high-solids slurries; however, publicly available data on precisely controlling the wetting relationship and volume distribution of "particle-secondary fluid-oil phase" in oil-continuous, anhydrous systems to achieve both room-temperature rod formation, leak prevention, and rapid self-emulsification upon contact with water is relatively limited.

[0007] Mechanistically, the formation of capillary bridge networks is influenced by a combination of factors, including particle size and specific surface area, secondary fluid volume fraction, contact angle / wetting properties, interfacial tension, shear time, and addition sequence. Generally, nano- to submicron-scale particles can provide a higher contact interface for bridging; the secondary fluid should present a low contact angle on the particle surface to achieve pendular bridging, thus achieving considerable G′ / yield stress even at low addition levels. Insufficient addition results in poor network connectivity; excessive addition may lead to a semi-filled / filled state, causing agglomeration, exudation, or a rough feel. Furthermore, the droplet acceleration rate and shear rate determine the spatial distribution of the secondary fluid on the particle surface and the neck radius, thus affecting network connectivity and resilience. These parameters are particularly critical for consistency and reproducibility in industrial scale-up.

[0008] In cosmetic makeup removal applications, it is also necessary to simultaneously address the process compatibility issues of "structured oil phase" and "self-emulsification upon contact with water": on the one hand, rod-shaped products require penetration, compressibility, and yield stress to meet the thresholds for portability and durability; on the other hand, upon contact with water, they should be able to form fine droplets in a short time to reduce rinsing resistance and residue. Traditional structured solutions achieved through high wax content often contradict the goal of "rapid phase transition and minimal residue"; while capillary bridge gels promise to provide high yield and resilient structural support under low-wax / wax-free conditions. Furthermore, the introduction of mild self-emulsifying systems such as lecithin and polyglycerol fatty acid esters can rapidly spread at the interface and reduce interfacial tension upon contact with the aqueous phase, achieving "oil-to-emulsification" in conjunction with the dispersion process brought out by capillary network breakage. However, the coupling and trade-offs between the above two mechanisms within a system (such as the interference of surfactants on particle wetting, the competitive adsorption between secondary fluids and surfactants, and the influence of oil phase polarity on bridging stability) still lack publicly available system process windows and quantitative parameters.

[0009] Meanwhile, compatibility with sensitive skin presents additional constraints: the formulation should ideally be anhydrous or have very low water content to reduce adverse skin impact (AW), thereby reducing the pressure on the use of traditional preservatives; PEG-free low-irritant surfactants should be selected and the total amount used should be controlled to avoid itching and barrier interference; the control of oil phase oxidation stability, trace metal ions, and free fatty acids must also be taken into account. The rod-shaped form also has clear requirements for container matching (the tray of the rotary propulsion mechanism, the design of the baffle ring / sealing ring, and the top surface shrinkage allowance) and thermal history (filling temperature, cooling gradient, and rewind time) to avoid failure modes such as top surface collapse, sidewall oil seepage, softening in summer, or low-temperature crystal coarsening.

[0010] In summary, existing makeup remover products face a dilemma in achieving a balance between leak-proof portability, low irritation, rapid self-emulsification, and structural stability. While capillary bridge gels offer a potential pathway for oil-phase structuring, there is still a lack of publicly available and reproducible solutions for formulation composition, wetting parameters, addition order, and the synergistic window of shear-drop addition in oil-continuous, waterless makeup remover stick scenarios. This technological gap makes obtaining a stable stick with low secondary fluid usage and achieving skin-sensitive softening and efficient self-emulsification a key technical challenge that needs to be addressed. Summary of the Invention

[0011] Technical Problem to be Solved: To address the aforementioned problems, the present invention aims to provide a temperature-sensitive, anhydrous, self-emulsifying egg yolk oil makeup remover gel stick and its preparation method. The makeup remover gel stick is formed by using a small amount of secondary fluid in an anhydrous oil phase to trigger preferential wetting of nanoparticles and the formation of a pendulum capillary bridge network. This gel is a soft solid at room temperature, exhibiting significant yield stress to enhance leak-proofness and portability; it softens and spreads under skin temperature and abrasive shearing; it rapidly self-emulsifies upon contact with water and is easily rinsed off; it has low water content and low water activity, eliminating the need for traditional aqueous preservatives, making it suitable for sensitive skin.

[0012] Technical solution: A temperature-sensitive, anhydrous, self-emulsifying egg yolk yolk makeup remover stick, the ingredients of which, by weight percentage, include: a) Egg yolk oil and oil phase 70-90 wt% b) Surface-modified nano-eggshell powder 1-6 wt% c) Secondary fluid 0.3-2.0 wt% d) Self-emulsifying system 1-9 wt% e) Temperature-sensitive component 2-6 wt%.

[0013] Furthermore, it also contains 0.05-0.6 wt% of an antioxidant system; said antioxidant system includes one or more components selected from tocopherol, ascorbyl palmitate and rosemary extract.

[0014] Furthermore, the oil phase is selected from medium-chain triglycerides and / or squalane, with a content of 0-20 wt%.

[0015] Furthermore, the volume distribution of the surface-modified nano-eggshell powder satisfies D 50 =0.2-0.5 μm, D 90 ≤0.8μm.

[0016] Furthermore, the secondary fluid is one or more of glycerol and propylene glycol; the self-emulsifying system is a combination of lecithin and polyglycerol fatty acid ester; the temperature-sensitive component is 12-hydroxystearic acid and / or beeswax, with a mass ratio of (1:10) to (1:2); and the HLB of the polyglycerol fatty acid ester is 3-8.

[0017] The preparation method of the above-mentioned temperature-sensitive anhydrous self-emulsifying egg yolk oil makeup remover gel stick includes the following steps: (1) Pretreatment of nano eggshell powder particles: After removing the membrane, washing and drying the eggshell powder, wet ball milling is used to obtain nano eggshell powder slurry. Oleic acid and / or lecithin are added for surface esterification treatment, ultrasonic dispersion, and solvent removal under reduced pressure to make the residual alcohol ≤500ppm. The slurry is then passed through a 200-mesh sieve to obtain surface-modified nano eggshell powder. (2) Oil phase premix: Heat the egg yolk oil and oil phase until melted and stirred until clear, add the antioxidant system, and continue to stir evenly to obtain the oil phase premix liquid; (3) High shear dispersion of particles: The surface-modified nano eggshell powder is slowly added to the oil phase premix at 40-50 °C and dispersed at 9000-12000 r / min for 5-8 min to obtain a mixture; (4) Addition and homogenization of self-emulsifying system: Add lecithin and polyglycerol fatty acid ester to the mixture and homogenize at 6000 r / min for 2-5 min to obtain a homogeneous oil phase precursor; (5) Capillary bridge network induction: Under shear conditions of 3000-10000 r / min, the secondary fluid was added to the oil phase precursor at a controlled rate. After the addition was completed, the shearing was stopped, and the system was observed to thicken significantly and form a soft solid precursor. (6) Vacuum degassing: The soft solid precursor was vacuum degassed for 2-5 min under conditions of (-0.06)-(-0.09) MPa; (7) Filling and molding: Keep the degassed precursor in a flowable state at 45-60 ℃ and fill it into the matching rotary container from bottom to top. Control the filling height and leave a 1.0-2.0 mm top shrinkage allowance. After filling, scrape the top of the rod flat. (8) Cooling and setting and rewinding: After filling, the temperature is reduced from 55 ℃ to 25 ℃ in a gradient of 0.5-2.0 ℃·min⁻¹, and left to stand at room temperature for 12-24 h to complete the rewinding and setting, thus obtaining the temperature-sensitive anhydrous self-emulsifying egg yolk oil makeup remover stick.

[0018] Furthermore, the ball milling conditions in step (1) are as follows: the dispersion medium is ethanol, the ball milling medium is zirconium beads with a particle size of 0.3-0.5 mm, the rotation speed is 1500-2000 r / min, and the time is 1-2 h; oleic acid is 0.2-1.0 wt% and / or lecithin is 0.5-2.0 wt%.

[0019] Furthermore, the ultrasonic dispersion conditions in step (1) are: 400 W for 10-30 min.

[0020] Furthermore, in step (2), the heating and melting temperature is 40-60 ℃, and the stirring speed is 600-1000 r / min.

[0021] Furthermore, the controlled rate in step (5) is 0.05-0.30 g·min⁻¹·kg⁻¹.

[0022] The above-mentioned temperature-sensitive, anhydrous, self-emulsifying egg yolk oil makeup remover stick is used for cosmetic purposes to remove makeup, sunscreen, and sebum from keratin materials.

[0023] The above-mentioned temperature-sensitive, anhydrous, self-emulsifying egg yolk oil makeup remover stick is used for cleansing sensitive skin. Beneficial effects

[0024] 1. Low dosage triggers high-strength network: Only 0.3-2.0wt% of secondary fluid is needed in the oil continuous phase to form a pendulum capillary bridge network due to preferential wetting of nano-eggshell powder. This makes the system exhibit a yield stress ≥60 Pa, G′>G″ at 25 ℃ and has elasticity, which significantly improves the static anti-flow and transport anti-vibration performance. Compared with pastes that rely on high wax curing, it can reduce the heaviness and stickiness caused by the wax phase while maintaining structural strength.

[0025] 2. Synergistic effect of rapid self-emulsification and low irritation: Lecithin and polyglycerol fatty acid esters (PEG-free, HLB 3-8) rapidly spread and reduce interfacial tension upon contact with water, forming emulsion droplets D within 30-60 seconds. 50 <10 μm, reducing the amount of water needed for rinsing and the feeling of residue on the skin surface; the total amount of surfactant is controllable and does not contain ethoxylated surfactants, so the formula has little impact on the skin barrier and is more suitable for people with sensitive skin.

[0026] 3. Warm and skin-friendly, smooth application: Optional 12-HSA / beeswax micro-co-action to stabilize the softening point at 32-36℃; the stick's penetration and compression force fall within a comfortable window of 2.0-8.0 mm and 3-12 N when touching the skin and rubbing and shearing, without collapsing or dragging, improving the efficiency of facial diffusion and makeup coverage.

[0027] 4. Anhydrous, low aw content and safe storage: Water content ≤1.0 wt%, aw ≤0.6, no need to add aqueous preservatives, reducing irritation and formula complexity; no visible layering or oil separation after 4-8 weeks of accelerated storage at 45℃, egg yolk oil peroxide value can be controlled at ≤5 meq / kg, with better shelf-life stability and temperate / summer tolerance.

[0028] 5. Combining resource utilization and functionalization: Using eggshell-derived nano-eggshell powder as the skeleton material, the high-value utilization of by-product resources is realized; after its surface lipidization, its synergy with secondary fluids not only provides mechanical support, but also helps to reduce the risk of oil phase rancidity due to its weak alkalinity and interface effect, and further enhances the stability of the lipid phase in conjunction with the antioxidant system. Attached Figure Description

[0029] Figure 1 Photograph of the appearance of the anhydrous self-emulsifying egg yolk oil makeup remover gel prepared for Example 1; Figure 2 The anhydrous self-emulsifying egg yolk oil makeup remover stick prepared for Example 1 shows the removal effect on lipstick, eyebrow pencil and eyeshadow. Detailed Implementation

[0030] This invention proposes a temperature-sensitive, anhydrous, self-emulsifying egg yolk oil makeup remover gel stick and its preparation method. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following will provide a more detailed description of the invention with reference to specific embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0031] Example 1 (Basic Version) Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 80.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min at 10000 rpm using a rotor-stator high shear disperser; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Example 2 (Glycerin / Propylene Glycol Compound, Wax-Free Formulation)

[0032] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 82.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 5.0 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 2.5 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 3.0 wt% Secondary fluid: 0.2 wt% glycerol + 0.8 wt% propylene glycol 12-Hydroxystearic acid (12-HSA): 3.0wt% Beeswax: 0 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface lipoicated nano eggshell powder" was slowly sprinkled in at 50 ℃ and dispersed for 6 min at 10,000 rpm using a rotor-stator high shear disperser; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Example 3 (without squalane and MCT)

[0033] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 90.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt%. Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: Slowly sprinkle “surface esterified nano eggshell powder” at 45-50 ℃ and disperse for 6 min using a rotor-stator high shear disperser at 10000 rpm; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Example 4 (High Addition of Eggshell Powder)

[0034] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 80.00 wt% Medium-chain triglycerides (MCT): 5.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 6.00 wt%. Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface lipoicated nano eggshell powder" was slowly sprinkled in at 50 ℃ and dispersed for 6 min at 10000 rpm using a rotor-stator high shear disperser; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Example 5 (Low-dosage eggshell powder)

[0035] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 80.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 1.00 wt%. Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: Slowly sprinkle “surface esterified nano eggshell powder” at 50 ℃ and disperse for 6 min using a rotor-stator high shear disperser at 10000 rpm; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 1 (Nano-eggshell powder without surface modification)

[0036] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 80.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Nano eggshell powder (D) 50 =0.2-0.5 μm): 3.00 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min at 10000 rpm using a rotor-stator high shear disperser; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 2 (without secondary fluid)

[0037] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 81.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax, and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min using a rotor-stator high shear disperser at 10000 rpm; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (5) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 3 (using PEG-based surfactants instead of the self-emulsifying system)

[0038] Thermosensitive, anhydrous, self-emulsifying egg yolk oil makeup remover gel stick formula (wt%): Egg yolk oil: 80.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Polysorbate 80: 2.00 wt% PEG-40 hydrogenated castor oil: 1.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min using a rotor-stator high shear disperser at 10000 rpm; (3) Addition of self-emulsifying system: Polysorbate 80 and PEG-40 hydrogenated castor oil were added sequentially, and homogenized at 6000 rpm for 3 min to obtain oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 4 (without temperature-sensitive component)

[0039] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 82.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% glycerol Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min using a rotor-stator high shear disperser at 10000 rpm; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 5 (Excess Secondary Fluid)

[0040] Egg Yolk Oil Makeup Remover Gel Stick Formula (wt%): Egg yolk oil: 78.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: Glycerin 3.00 wt% 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min at 10000 rpm using a rotor-stator high shear disperser; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 6 (Traditional Wax-Based Cleansing Balm)

[0041] Thermosensitive, anhydrous, self-emulsifying egg yolk oil makeup remover gel stick formula (wt%): Egg yolk oil: 72.00 wt% Medium-chain triglycerides (MCT): 6.00 wt% Squalane: 0.50 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.00 wt% Microcrystalline wax: 6.00 wt% Beeswax: 12 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, microcrystalline wax, beeswax, and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (3) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill it into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (4) Cooling return network: at 1.0 ℃·min -1The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 7 (containing aqueous phase)

[0042] Thermosensitive, anhydrous, self-emulsifying egg yolk oil makeup remover gel stick formula (wt%): Egg yolk oil: 80.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Lecithin: 2.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 1.50 wt% Secondary fluid: 1.00 wt% deionized water 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min using a rotor-stator high shear disperser at 10000 rpm; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Under 5000 rpm shear, deionized water was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min), the machine was stopped and allowed to stand for 3 min, and the significant thickening into a soft solid precursor was observed. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min-1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Comparative Example 8 (insufficient amount of self-emulsifying system)

[0043] Thermosensitive, anhydrous, self-emulsifying egg yolk oil makeup remover gel stick formula (wt%): Egg yolk oil: 82.00 wt% Medium-chain triglycerides (MCT): 8.00 wt% Squalane: 2.00 wt% Surface-esterified nano-eggshell powder (D) 50 =0.2-0.5 μm; oleic acid 0.5% + lecithin 1.0% as surface treatment agent): 3.00 wt% Lecithin: 1.00 wt% Polyglycerol fatty acid esters (PGFE, PEG-free, HLB=4-6; e.g., polyglycerol-3 dioleate): 0.50 wt% Secondary fluid: 1.00 wt% glycerol 12-Hydroxystearic acid (12-HSA): 1.50 wt% Beeswax: 0.50 wt% Mixed tocopherols: 0.25 wt% Ascorbyl palmitate: 0.20 wt% Rosemary antioxidants: 0.05 wt% The preparation method includes the following steps: (1) Oil phase premixing: Add egg yolk oil, MCT, squalane, 12-HSA, beeswax and three antioxidants to a jacketed beaker and stir magnetically at 70 °C until clear and homogeneous (10 min). (2) Particle dispersion: "Surface esterified nano eggshell powder" was slowly added at 50 ℃ and dispersed for 6 min at 10000 rpm using a rotor-stator high shear disperser; (3) Addition to the self-emulsifying system: Lecithin and PGFE were added sequentially, and homogenized at 6000 rpm for 3 min to obtain the oil phase precursor; (4) Inducing capillary bridge network: Glycerol was added dropwise at a rate of 0.03 g·min⁻¹·kg⁻¹ (equivalent to 0.003 g·min⁻¹ for 100 g sample, i.e., 3 mg per min) under 5000 rpm shearing, and the machine was stopped and allowed to stand for 3 min. The precursor was observed to thicken significantly into a soft solid. (5) Degassing and molding: -0.08 MPa vacuum for 3 min, maintain the material flowability at 50 ℃, fill into the rotary rod tube from bottom to top, leave a 2 mm top gap and scrape it level; (6) Cooling return network: at 1.0 ℃·min -1 The temperature was lowered from 55 ℃ to 25 ℃, and the mixture was allowed to stand at room temperature for 16 hours to return to the wire mesh, thus obtaining the finished product. Performance testing:

[0044] (1) Determination of yield stress (τy) and shear thinning index n (rheological): A rotational rheometer (φ40 mm plate, 1 mm gap) was used at a constant temperature of 25 ℃. A flat surface of the top of the rod was cut off and the sample was lightly pressed. Strain scan (LVR): frequency 1 Hz, strain 0.01–10%; the region where G′ is basically constant with strain is taken as LVR. Frequency scan: within LVR, the strain is fixed, frequency 0.1–10 Hz, and G′ and G″ are recorded. Stress scan / yield: stress 0.1→500 Pa (logarithmic increase), the stress corresponding to the intersection of G′=G″ is taken as τy; if there is no intersection, Herschel–Bulkley fitting is used. Steady-state flow: shear rate γ̇ 0.01→100 s⁻¹, the shear stress τ and apparent viscosity η are recorded.

[0045] (2) Penetration (mm) determination: Use a penetration meter; probe Φ6 mm cylindrical end; load 100 g; hold for 5 s; 25 ℃. Fix the container, lightly touch the center of the top of the rod with the probe to zero; release the 100 g load and time for 5 s; record the displacement as the penetration. Repeat 3–5 times.

[0046] (3) Determination of 5 mm indentation force (F5, N): A texture analyzer was used with a P / 5 flat-head probe (φ5 mm) at 25 ℃. Pre-test velocity: 1.0 mm·s⁻¹; Test velocity: 1.0 mm·s⁻¹; Post-test velocity: 1.0 mm·s⁻¹; Triggering force: 0.02–0.05 N; Indentation displacement: 5.00 mm. The force was continuously indented to 5.00 mm, and then the instantaneous force (N) at 5 mm was recorded.

[0047] (4) DSC softening point (°C) determination: Differential scanning calorimetry (DSC) was used under nitrogen protection. 5–10 mg of sample was taken and sealed in an aluminum crucible. The sample was isothermated at 25°C for 2 min, and then the temperature was increased to 70°C at 1°C·min⁻¹.

[0048] (5) Self-emulsifying ability and droplet D 50 (μm) determination: Take 1.00 g of sample and add 10.0 g of pure water (25 ℃), gently shake or vortex for 30–60 s to form an emulsion, and measure the volume distribution D using a laser particle size analyzer. 50 .

[0049] (6) Water activity aw: aw was measured using a water activity meter at 25 ℃. Thin-layer sample was prepared and the value was taken after it stabilized (Δaw < 0.001 for 30 s). (7) Accelerated stabilization at 45 ℃ / oil separation and stratification determination: The sample was placed vertically in a constant temperature oven at 45±1 ℃ and stored in the dark for 8 weeks. The appearance (stratification / free oil / top surface shrinkage) and mass changes were recorded weekly. If necessary, the free oil was separated and weighed. The sample was considered qualified if there was "no visible stratification and oil separation" after 8 weeks.

[0050] (8) Determination of peroxide value (POV) (meq / kg): Iodometric method. The sample is dissolved in glacial acetic acid-chloroform (3:2, v / v) and then reacted with KI. The generated I2 is titrated with 0.01 mol·L⁻¹Na2S2O3 until colorless (starch indicator). POV is calculated as POV=[(V–V0)×N×1000] / m (V is the sample volume in mL, N is the titration concentration, and m is the sample in g).

[0051] Table 1 Performance Test Metrics Results Case Yield stress at 25℃ (Pa) n DSC softening point (°C) Penetration (mm) <![CDATA[F5(N)]]> <![CDATA[Milk droplet D 50 (μm)]]> aw 45℃ × 8 weeks stratification / oil separation POV (meq / kg) Remark Example 1 75 0.30 33 5.0 5.0 7.00 0.50 none 1.0 Example 2 70 0.43 34 5.2 4.8 5.00 0.45 none 1.5 Example 3 80 0.39 33 4.6 6.0 7.50 0.50 none 3.0 Example 4 95 0.35 33 3.8 7.5 6.50 0.45 none 1.4 Example 5 62 0.50 33 6.0 4.0 9.00 0.52 none 1.2 Comparative Example 1 / / / / / / / / / Non-oscillating capillary bridge network Comparative Example 2 / / / / / / / / / Non-oscillating capillary bridge network Comparative Example 3 75 0.40 33 4.7 5.8 0.55 0.50 none 1.0 Comparative Example 4 82 0.38 45 3.0 8.0 0.65 0.48 none 1.3 Comparative Example 5 45 0.60 33 7.5 3.0 0.90 0.55 have 1.5 Comparative Example 6 120 0.35 45 2.5 9.0 1.60 0.50 none 1.0 Comparative Example 7 / / / / / / / / / Non-oscillating capillary bridge network Comparative Example 8 80 0.40 33 5.0 6.0 1.30 0.50 none 1.1 The results in Table 1 show that the cosmetic gel stick prepared by this invention has suitable yield stress, softening point, penetration and stability.

[0052] (9) Patch Test: The makeup remover gel sticks obtained above were tested according to the human skin patch test in the "2022 Cosmetic Safety Technical Specifications". 20 mg of sample was placed in the patch tester chamber, and the control well served as a blank control (without any substance). The patch tester of the test substance was then applied to the flexor arm of the subject using special hypoallergenic tape, and the palm was used to gently press it to make it evenly adhered to the skin, and it was kept for 24 hours. Skin reactions were observed 30 minutes, 24 hours and 48 hours after the patch tester was removed, and the observation results are recorded as shown in Table 2.

[0053] Table 2 Patch Test Results Case 30 minutes 24 hours 48 hours Example 1 Level 0, 40 people Level 0, 40 people Level 0, 40 people Example 2 Level 0, 40 people Level 0, 40 people Level 0, 40 people Example 3 Level 0, 40 people Level 0, 40 people Level 0, 40 people Example 4 Level 0, 40 people Level 0, 40 people Level 0, 40 people Example 5 Level 0, 40 people Level 0, 40 people Level 0, 40 people Comparative Example 1 / / / Comparative Example 2 / / / Comparative Example 3 Level 0, 40 people Level 0, 40 people Level 0, 40 people Comparative Example 4 Level 0, 40 people Level 0, 40 people Level 0, 40 people Comparative Example 5 Level 0, 40 people Level 0, 40 people Level 0, 40 people Comparative Example 6 Level 0, 40 people Level 0, 40 people Level 0, 35 people; Level 1, 5 people. Comparative Example 7 / / / Comparative Example 8 Level 0, 40 people Level 0, 40 people Level 0, 40 people As shown in Table 2, no adverse skin reactions were observed 30 minutes, 24 hours and 48 hours after removing the spot tester. Therefore, the egg yolk gel makeup remover stick prepared by the present invention has no adverse reactions on the human body and has excellent safety.

[0054] (10) Sensory evaluation experiment: Forty subjects were recruited under conditions of 22–25 ℃ and RH 40–60%. The makeup remover stick of the present invention was compared by random half-face crossover / grouping. Makeup was uniformly applied (foundation / sunscreen / eyeliner), left to stand for 30 min, and then 0.30 g ± 0.02 g was applied and massaged in circles for 30 s → rinsed with running water for 15 s → patted dry with a tissue for 2 min before evaluation. Six items were evaluated on a scale of 0–10: makeup removal effect, refreshing feeling, gentleness (the lower the irritation, the higher the score), makeup dissolving speed, easy to rinse, and post-wash comfort (reverse scoring for "dryness / tightness"); the comprehensive score = the sum of the 6 items (maximum score 60). The mean ± SD of each item and the total score was reported.

[0055] Table 3 Sensory evaluation results Case Makeup removal effect Refreshing Mildness Makeup dissolving speed Easy to rinse Post-wash comfort Total Score Example 1 8.7 8.5 8.6 8.8 8.7 8.5 51.8 Example 2 9.0 8.8 8.6 9.2 9.0 8.7 53.3 Example 3 8.5 8.1 8.6 8.4 8.3 8.2 50.1 Example 4 8.6 8.3 8.5 8.6 8.6 8.4 51.0 Example 5 8.1 8.0 8.6 7.7 7.8 8.2 48.4 Comparative Example 1 / / / / / / / Comparative Example 2 / / / / / / / Comparative Example 3 8.0 7.9 6.8 8.1 8.1 7.6 46.5 Comparative Example 4 7.3 7.6 8.4 7.3 8.0 7.2 45.8 Comparative Example 5 7.7 7.1 8.3 7.0 6.8 7.0 43.9 Comparative Example 6 7.5 6.0 7.5 6.2 5.8 6.3 39.3 Comparative Example 7 / / / / / / / Comparative Example 8 7.8 7.3 8.5 6.4 6.5 7.2 43.7 As shown in Table 3, the makeup remover gel stick prepared by this invention has excellent makeup removal effect, refreshing feel, gentleness, makeup dissolving speed, post-wash comfort, and is easy to rinse.

[0056] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations to these embodiments without departing from the principles and spirit of the present invention still fall within the protection scope of the present invention.

Claims

1. A temperature-sensitive anhydrous self-emulsifying yolk oil make-up removal gel stick, characterized in that, The ingredients include, by mass percentage: a) egg yolk oil and oil phase 70-90 wt%; b) surface-modified nano eggshell powder 1-6 wt%; c) secondary fluid 0.3-2.0 wt%; d) self-emulsifying system 1-9 wt%; e) temperature-sensitive component 2-6 wt%.

2. A temperature sensitive water-free self-emulsifying yolk oil make-up removal gel stick according to claim 1, characterized in that, Also containing an antioxidant system 0.05-0.6 wt%; the antioxidant system includes one or more components selected from tocopherol, ascorbic acid palmitate and rosemary extract.

3. A temperature sensitive water-free self-emulsifying yolk oil make-up removal gel stick as claimed in claim 1, wherein, The oil phase is selected from medium-chain triglycerides and / or squalane, with a content of 0-20 wt%.

4. A temperature sensitive water-free self-emulsifying yolk oil make-up removal gel stick as claimed in claim 1, wherein, The volume distribution of the surface-modified nanoshell powder satisfies D 50 = 0.2 - 0.5 μm, D 90 ≤ 0.8 μm.

5. A temperature sensitive water-free self-emulsifying yolk oil make-up removal gel stick as claimed in claim 1, wherein, The secondary fluid is one or more of glycerol and propylene glycol; the self-emulsifying system is a combination of lecithin and polyglyceryl fatty acid ester; the temperature-sensitive component is 12-hydroxystearic acid and / or beeswax, with a mass ratio of (1:10) to (1:2).

6. A process for the preparation of a thermo-sensitive anhydrous self-emulsifying yolk oil make-up removal gel stick according to any one of claims 1 to 5, characterized in that, The steps include: (1) Nano eggshell powder particle pretreatment: after removing membranes, washing, drying and wet ball milling of eggshell powder, a nano eggshell powder slurry is obtained, and oleic acid and / or lecithin are added for surface lipidization treatment, ultrasonic dispersion, solvent removal under reduced pressure, and sieving through a 200-mesh screen to obtain surface-modified nano eggshell powder; (2) Oil phase premixing: egg yolk oil and the oil phase are heated, dissolved and stirred until clear, and an antioxidant system is added and stirred uniformly to obtain an oil phase premix; (3) Particle high-shear dispersion: the surface-modified nano eggshell powder is slowly added to the oil phase premix at 40-50 ℃, and dispersed at 9000-12000 r / min for 5-8 min to obtain a mixture; (4) Self-emulsifying system addition and homogenization: lecithin and polyglyceryl fatty acid ester are added to the mixture, and homogenized at 6000 r / min for 2-5 min to obtain a uniform oil phase precursor; (5) Capillary bridge network induction: the secondary fluid is added dropwise to the oil phase precursor at a controlled rate under shearing at 3000-10000 r / min, and after the addition is completed, the shearing is stopped, and the system is observed to appear significant thickening and form a soft solid precursor; (6) Vacuum degassing: the soft solid precursor is vacuum degassed at (-0.06) to (-0.09) MPa for 2-5 min; (7) Filling and shaping: the degassed precursor is kept in a flowable state at 45-60 ℃, filled into a matched rotary-twist container from bottom to top, the filling height is controlled and a 1.0-2.0 mm top shrinkage allowance is reserved, and the rod top is scraped flat after filling; (8) Cooling, setting and network recovery: after filling, the temperature is decreased from 55 ℃ to 25 ℃ at a gradient of 0.5-2.0 ℃·min⁻¹, and the network is recovered and set at room temperature for 12-24 h to obtain a temperature-sensitive anhydrous self-emulsifying egg yolk oil makeup gel rod.

7. The method of claim 6, wherein: In step (1), the ball milling conditions are: the dispersion medium is ethanol, the ball milling medium is zirconium beads with a particle size of 0.3-0.5 mm, the rotation speed is 1500-2000 r / min, and the time is 1-2 h; the oleic acid is 0.2-1.0 wt% and / or the lecithin is 0.5-2.0 wt%.

8. The method of claim 6, wherein: In step (5), the controlled rate is 0.05-0.30 g·min⁻¹·kg⁻¹.

9. The cosmetic use of a temperature-sensitive anhydrous self-emulsifying mayonnaise stick make-up removal gel according to any one of claims 1 to 5 for the removal of make-up, sunscreen and sebum dirt from keratin materials.

10. The cosmetic use of a temperature-sensitive anhydrous self-emulsifying mayonnaise stick make-up removal gel according to any one of claims 1 to 5 for the cleansing of sensitive skin.

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