Skin-care gel bead containing oil inner bead as well as preparation method and application of skin-care gel bead

Abstract

The invention discloses a skincare gel bead containing an oil inner bead, the skincare gel bead comprises a water-phase shell and an oil-phase inner bead, the water-phase shell material comprises one or two of agar and sodium alginate; and the oil-phase inner bead material is an oil-soluble functional active matter. The invention also provides a preparation method of the skin-care gel bead, a skin-care composition containing the skin-care gel bead, and an application of the skin-care gel bead in preparation of cosmetics. The skin-care gel bead disclosed by the invention adopts a zero-emulsifier formula, and is mild, non-irritant, high in transparency, uniform and consistent in appearance and good in stability.

Description

Technical Field

[0001] This invention belongs to the field of cosmetics, specifically relating to a skin care gel bead containing oil-containing inner beads, its preparation method, and its application. Background Technology

[0002] Traditional creams and ointments typically rely on emulsifiers, such as polysorbate-80 and sodium lauryl sulfate, to achieve a stable water-oil phase. These ingredients may damage the skin barrier and cause problems such as redness, swelling, and itching.

[0003] The advantages of encapsulation technology are: (1) reducing irritation by isolating the active ingredient from direct contact with the skin through a physical barrier, thus reducing the use of chemical penetration aids; (2) improving stability by protecting photosensitive and oxygen-sensitive ingredients from environmental degradation; and (3) achieving targeted release by extending the duration of action of the active ingredient through controlled-release design.

[0004] Existing technologies that encapsulate oil-phase inner beads within an aqueous shell have several limitations, such as irritation. Traditional microcapsules rely on emulsifiers to maintain their structure, and the use of lecithin wall materials containing free fatty acids may trigger lipid peroxidation with long-term use. Furthermore, existing water-in-oil inner beads suffer from insufficient stability; they are easily damaged at low temperatures, and after freezing and thawing, the shell layer is prone to cracking due to differences in thermal expansion coefficients. At high temperatures, delamination can occur, leading to increased particle size and decreased light transmittance. Additionally, opaque wall materials affect product aesthetics. A shell that is too soft is easily broken during transportation, while a shell that is too hard results in a grainy texture during application. Moreover, if the shell contains multiple inner beads, incompatibilities and mutual repulsion of active ingredients can easily occur. For example, when copper peptides and vitamin C coexist, the copper ions catalyze an oxidation reaction, generating free radicals that deactivate both. Current technologies cannot achieve compartmentalized isolation of multiple active ingredients, hindering formulation innovation.

[0005] It is evident that existing wall materials cannot simultaneously satisfy transparency, flexibility, and low-temperature stability. The product preparation process is highly complex, and the encapsulation of multiple active ingredients in compartments requires a multi-stage microfluidic system, which results in high equipment costs and low yield. The immature microfluidic technology can easily lead to a wide particle size distribution and uneven particle size. Furthermore, the low-temperature stability is poor; after storage at -15℃, the bead breakage rate is high, and the product turbidity increases. Summary of the Invention

[0006] One objective of this invention is to provide a skin care gel bead containing oil-containing inner beads to solve the problems of high irritation of active ingredients, incompatibilities, and poor stability in traditional skin care products.

[0007] Another object of the present invention is to provide a method for preparing the skin care gel beads.

[0008] Another object of the present invention is to provide the application of the skin care gel beads.

[0009] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0010] In a first aspect, the present invention provides a skin care gel bead containing oil-inner beads, comprising an aqueous outer shell and oil-inner beads.

[0011] The aqueous shell material includes one or both of agar and sodium alginate.

[0012] The oil-phase inner bead material is an oil-soluble active ingredient.

[0013] Preferably, the content of the oil-soluble active ingredient is 1-30% by weight; more preferably, the content of the oil-soluble active ingredient is 11-18.5%.

[0014] The aqueous shell comprises 0.8-1.5% agar and 0-0.8% sodium alginate.

[0015] More preferably, the weight ratio of agar to sodium alginate is 4:3 to 3:1. Most preferably, the weight ratio of agar to sodium alginate is 3:2.

[0016] More preferably, the aqueous shell comprises, by weight, 0.8-1.2% agar and 0.6-0.8% sodium alginate.

[0017] Preferably, the aqueous shell material further includes one or more of the following: gum arabic, carbomer, xanthan gum, guar gum, sodium polyacrylate, polyglycerol-3 polyricinoleate, polydimethylsiloxane copolyol, hydroxyethyl cellulose, magnesium aluminum silicate, methylcellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone, chitosan, whey protein, gelatin, hydroxypropyl methylcellulose, alginate, hydroxypropyl starch, polyol, sugars, hyaluronic acid, and p-hydroxyacetophenone. More preferably, the polyol is butanediol.

[0018] Preferably, the content of gum arabic is 0-0.5% by weight, more preferably 0.2-0.4%.

[0019] Agar provides a gel skeleton to enhance the flexibility of the shell, while sodium alginate forms a three-dimensional network structure through calcium ion cross-linking, thereby improving mechanical strength.

[0020] Preferably, by weight, the aqueous shell comprises 0.8-1.5% agar, 0-0.8% sodium alginate, 0-0.5% gum arabic, and the balance water.

[0021] More preferably, by weight, the aqueous shell comprises 0.8-1.2% agar, 0.6-0.8% sodium alginate, 0.2-0.4% gum arabic, and the balance being water.

[0022] Gum arabic accelerates solidification, shortening setting time to ≤10 seconds. Carbomer, through neutralization and thickening, is suitable for transparent gel textures. Xanthan gum and guar gum are natural polysaccharides that thicken and stabilize emulsions. Sodium polyacrylate (e.g., sodium polyacrylate): high thickening efficiency, but ionic stability must be considered. Polyglycerol-3 polyricinoleate: low HLB value, stabilizes O / W emulsions. Polydimethylsiloxane copolyol: thickens in oil-in-water systems, improving skin feel. Hydroxyethyl cellulose (HEC): thickens in the aqueous phase, compatibility with surfactants must be considered. Magnesium aluminum silicate (Veegum): a natural mineral colloid, stabilizes O / W systems. Methylcellulose: a water-soluble cellulose derivative, thickens and stabilizes emulsions, forms gels at low temperatures. Sodium carboxymethyl cellulose (CMC-Na): high water retention, enhances aqueous phase viscosity, suitable for transparent gel formulations. Polyvinylpyrrolidone (PVP): Strong film-forming properties, enhances shell mechanical strength, and is compatible with polar solvents. Chitosan: A natural cationic polysaccharide, antibacterial and biodegradable. Whey Protein: A biodegradable film-forming material that enhances barrier properties. Gelatin: A traditional film-forming agent that solidifies rapidly at low temperatures. Hydroxypropyl methylcellulose (HPMC): High transparency, high temperature resistance (≤80℃), suitable for heat-stable formulations. Alginate: Calcium ions crosslink to form a gel, allowing for controlled release of active ingredients. Hydroxypropyl Starch: A low-cost thickener that improves flowability.

[0023] Preferably, the oil-soluble active ingredients include one or more of the following: antioxidants, anti-aging ingredients, moisturizers, soothing and repairing ingredients, oil-controlling and anti-acne ingredients, whitening and spot-fading ingredients, sunscreen ingredients, anti-blue light ingredients, and photodamage repair ingredients.

[0024] More preferably, the antioxidant includes one or more of the following: vitamin E, coenzyme Q10, astaxanthin, and oil-soluble vitamin C derivatives.

[0025] More preferably, the anti-aging ingredients include one or more of the following: retinol and its derivatives, phytosterols, psoralen, aesculin, and sea celery extract.

[0026] More preferably, the moisturizer includes one or more of the following: jojoba oil, ceramide, shea butter, olive oil squalene, and squalane.

[0027] More preferably, the soothing and repairing ingredients include one or more of the following: bisabolol, frankincense oil, centella asiatica oil, chamomile oil, gentian oil, gentian oil, milk thistle oil, sea buckthorn fruit oil, aloe vera oil, meadowfoam seed oil, and sunflower seed oil.

[0028] More preferably, the oil-controlling and anti-acne ingredients include one or more of the following: capryloyl salicylic acid, pyridoxine tri-hexyldecanoate, tea tree oil, and white willow oil.

[0029] More preferably, the whitening and spot-fading ingredients include one or more of the following: oil-soluble arbutin derivatives, 4-butylresorcinol, phenylethylresorcinol, glycyrrhizin, resveratrol, and oil-soluble vitamin C derivatives.

[0030] More preferably, the sunscreen ingredient includes one or more of the following: avobenzone, ethylhexyl methoxycinnamate, and hexyl diethylaminohydroxybenzoyl benzoate (UvinulA Plus).

[0031] More preferably, the anti-blue light ingredient includes one or more of the following: Moringa seed oil, Rhodiola rosea oil, and brown algae extract.

[0032] More preferably, the photodamage repairing component includes one or more of the following: lycopene (oil-soluble), rosehip oil, marula oil, and sea buckthorn oil.

[0033] Preferably, the skin care gel beads contain 1-10 inner beads; more preferably, the skin care gel beads contain 1-5 inner beads.

[0034] More preferably, the diameter of the skin care gel beads is 1-10cm; more preferably, the diameter of the skin care gel beads is 4-7cm.

[0035] Secondly, the present invention also provides a method for preparing the skin care gel beads, which includes the following steps:

[0036] S1. Pretreatment of the aqueous shell phase: Add the aqueous shell phase raw material into the shell phase tank according to the formula ratio and start stirring at 300-500 rpm; heat to 60-65℃ and stir at a constant temperature for 20-30 minutes to ensure uniform dissolution; keep warm at 60℃ until ready for use.

[0037] S2. Oil phase bead pretreatment: Different oil-soluble active ingredients are placed into separate core phase tanks and kept at 60℃ for later use.

[0038] S3. Preparation of condensed beads: Open the valves of the shell phase tank and the core phase tank at the same time. After the shell phase and core phase are mixed, they are dripped into the cooling pool. The coolant in the cooling pool is liquid paraffin. The droplets are cooled and solidified rapidly to form condensed beads. The flow rate of the shell phase is 100-1000 mL / min and the flow rate of the core phase is 20-600 mL / min. The size and number of beads in the oil phase are controlled by adjusting the flow rates of the two phases.

[0039] Thirdly, the present invention also provides a skin care composition, wherein the skin care composition contains the skin care gel beads described in the present invention.

[0040] Fourthly, the present invention also provides the application of the skin care gel beads in the preparation of cosmetics.

[0041] Compared with existing beads, the beads of the present invention have the following advantages:

[0042] (1) A new type of bead product is provided, which is a water-soluble material as the shell and an oil-soluble material as the core. The shell phase is water phase and encapsulates oil phase active ingredients. The oil phase active ingredients form inner beads. This product fills the market gap.

[0043] (2) The outer shell of the gel beads is a transparent or semi-transparent oil phase gel with a certain strength, and the core layer is an aqueous phase containing active skin care ingredients. The gel beads are stable and do not deform under normal temperature conditions.

[0044] (3) The shell phase oil-soluble material contains soothing ingredients and does not contain emulsifiers or surfactants, ensuring that the gel beads are non-irritating or low-irritating to the skin.

[0045] (4) The core phase is isolated from the air by the shell phase and is not easily oxidized and deactivated.

[0046] (5) It has a light and soft texture and will not deform due to external force; it is not hard, easy to apply, and has good skin permeability and absorbability.

[0047] (6) It has a beautiful appearance and provides a pleasant visual experience.

[0048] (7) Adding this gel beads to a water-based cosmetic formulation system can achieve oil-water separation and avoid the use of emulsifiers. Attached Figure Description

[0049] Figure 1 A schematic diagram of the preparation process of the skin care gel beads of the present invention is shown.

[0050] Figure 2 The following is a sample image of the water-in-oil skin care beads of the present invention (left: a single inner bead; right: four inner beads). Detailed Implementation

[0051] The present invention will be further described below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0052] Unless otherwise specified, the reagents and instruments used in the embodiments of the present invention are all commercially available products known in the art, which are known to those skilled in the art and can be obtained through commercial means.

[0053] A skin care gel containing oil-inner beads, the formulation (by weight percentage) is shown in Table 1 below.

[0054] Table 1. Bead Formulation

[0055]

[0056]

[0057] The preparation steps of the skin care gel beads containing inner beads in Examples 1-5 are as follows:

[0058] S1. Aqueous shell pretreatment: Add the aqueous shell material to the shell tank according to the formula ratio and start stirring (300-500 rpm). Heat to 60-65℃ and stir for 20-30 minutes to ensure uniform dissolution. Keep at 60℃ until ready for use.

[0059] S2. Oil phase bead pretreatment: Different oil-soluble active ingredients are placed into separate core phase tanks and kept at 60℃ for later use.

[0060] S3. Preparation of condensed beads: Open the valves of the shell phase tank and the core phase tank at the same time. After the shell phase and core phase are mixed, drip them into the cooling pool (the coolant in the cooling pool is liquid paraffin). The droplets are cooled and quickly solidify into condensed beads. The flow rate of the shell phase is 100-1000 mL / min and the flow rate of the core phase is 20-600 mL / min. The size and number of beads in the oil phase can be controlled by adjusting the flow rates of the two phases.

[0061] Example 1: The outlet flow rate of the shell phase tank was 200 mL / min, the outlet flow rates of core phase tanks 1 and 2 were both 40 mL / min, and the outlet flow rate of core phase tank 3 was 80 mL / min. The resulting skin care beads had four inner beads and a diameter of 3-5 cm. Example 2: The outlet flow rate of the shell phase tank was 200 mL / min, and the outlet flow rates of core phase tanks 1, 2, and 3 were all 30 mL / min. The resulting skin care beads had three inner beads and a diameter of 3.0-5.0 cm. Examples 3-5: The outlet flow rate of the shell phase tank was 400 mL / min, the outlet flow rate of core phase tank 1 was 400 mL / min, and core phase tanks 2 and 3 were not used. The resulting skin care beads had one inner bead and a diameter of 5.0-7.0 cm.

[0062] Process flow as follows Figure 1 The process diagram is shown in the image. The resulting skincare beads can contain one or more beads, such as... Figure 2 The two product images are shown (left: single inner bead; right: 4 inner beads).

[0063] The skincare gel bead preparation process of this invention utilizes an oil-phase inner bead compartmentalization technology to achieve the presence of one, two, three, or more inner beads, each inner bead forming a compartment. These beads are simultaneously injected using an independent 3-needle array, distributing them among different inner beads to avoid compatibility issues. Furthermore, this process optimizes microfluidic preparation techniques and parameters, employing a multi-channel microfluidic chip and a 3-needle array (needle inner diameter 100-200 μm). A suitable external phase flow rate helps control the shell thickness within the range of 50-150 μm, while a suitable internal phase flow rate ensures uniform inner bead particle size. A molding temperature of 25±2℃ maintains the material's rheological properties and prevents pre-solidification. A coolant temperature of 4-10℃ facilitates rapid shaping and avoids microbead deformation.

[0064] Comparative Example 1

[0065] A skincare gel, the formula of which is shown in Table 1. The preparation method is similar to that in Table 1, except that it has no core phase and only a shell phase.

[0066] The resulting agglomerates were colorless, transparent, and without any internal beads.

[0067] Comparative Example 2

[0068] A skincare essential oil, the formulation of which is shown in Table 1. Compared with Example 1, it has no shell phase.

[0069] The product obtained is essential oil, not gel beads.

[0070] Comparative Example 3

[0071] Single-component retinyl palmitate was used for stability testing.

[0072] Stability test

[0073] High temperature stability: The samples of each embodiment and comparative example were left to stand at 50°C for 30 days.

[0074] The results are shown in Table 2.

[0075] Table 2. High Temperature Stability

[0076]

[0077] Low temperature stability: The samples of each example and comparative example were placed at -15°C for 30 days.

[0078] The results are shown in Table 3.

[0079] Table 3. Low-temperature stability

[0080]

[0081] Compared to Examples 1-5, the oil-soluble active ingredient in Comparative Example 2 was not encapsulated, and its color and odor changed after being stored at 50°C and -15°C for 30 days. This demonstrates that unencapsulated oil-soluble active ingredients are easily oxidized and deteriorated upon contact with oxygen, while the oil-phase beads of the present invention are protected, resulting in better stability.

[0082] Stability test of active ingredients in inner beads:

[0083] Test conditions: 25℃, protected from light, 30 days.

[0084] Calculation formula:

[0085] Record the absorbance values ​​(A_Tn, A_Cn) of Example 4 (T) and Comparative Example 3 (C) at 325 nm at each time point.

[0086] Calculate the residual rate (stability):

[0087] Residual rate in the experimental group (T_n%) = (A_Tn / A_T0) * 100%

[0088] Residual rate of control group (C_n%) = (A_Cn / A_C0) * 100%

[0089] By comparing the residual rates of T and C at different time points, the stability of the active ingredient can be determined.

[0090] The results are shown in Table 4.

[0091] Table 4. Stability of Inner Bead Active Ingredients

[0092]

[0093] The results showed a significant encapsulation effect: In Example 4, the absorbance (A_Tn) decreased only slightly throughout the 30-day test period (from 1.250 to 1.246), and the remaining percentage remained above 99.7%. This indicates that the beads effectively encapsulated retinyl palmitate within the core, isolating it from the external environment and greatly slowing its degradation rate, resulting in excellent stability. In contrast, the absorbance (A_Cn) of the unencapsulated Comparative Example 3 decreased rapidly and significantly (from 1.245 to 0.400), with a remaining percentage of only 32.1% after 30 days. This clearly demonstrates that unencapsulated retinyl palmitate is highly unstable under the same storage conditions and is prone to degradation reactions such as oxidation.

[0094] Visual evidence: The changes in appearance of Comparative Example 3 (yellowing and darkening, producing an odor) are consistent with the result of decreased absorbance.

[0095] Example 4 shows that the appearance remains relatively good, indicating that the packaging system provides effective protection.

[0096] Conclusion: This water-in-oil bead encapsulation system effectively protects the encapsulated retinyl palmitate. After 30 days of storage at 25°C in the dark, the active ingredient retention rate reached 99%, demonstrating excellent stability. In contrast, the unencapsulated comparative example 3 showed severe degradation and poor stability.

[0097] Moisturizing efficacy experiment

[0098] Objective: To verify the sustained moisturizing ability of the gel containing ceramide inner beads (Example 5).

[0099] Method: Use CM825 measurement of stratum corneum moisture content (n=15, inner forearm)

[0100] The groups are as follows:

[0101] (1) Experimental group (Example 5): Apply gel containing ceramide beads

[0102] (2) Control group: blank gel matrix

[0103] (3) Commercially available products: Emulsions containing ceramides (containing emulsifiers, with the same ceramide content as in Example 5)

[0104] Time point Water content (au) of the experimental group Water content (au) in the control group Moisture content (au) of commercially available products 0h (Initial) 42.3±1.2 42.5±1.1 42.1±0.9 1 hour later 58.7±2.1 47.6±1.5 54.2±1.8 4 hours later 52.4±1.8 43.8±1.3 47.6±1.4 8 hours later 48.9±1.6 41.2±1.0 44.3±1.2

[0105] After 1 hour, the experimental group showed a 38.8% increase in hydration rate, significantly higher than the commercially available product group (28.7%). Furthermore, the advantage lies in the natural ingredients of the skincare beads, which do not contain traditional emulsifiers. After 8 hours, the experimental group's moisture content remained 15.6% higher than the initial value, demonstrating that the slow-release properties of the beads enhance long-lasting hydration.

Claims

1. A skin care gel bead containing oil-inner beads, comprising an aqueous outer shell and oil-inner beads, characterized in that, The aqueous shell material includes one or both of agar and sodium alginate. The oil-phase inner bead material is an oil-soluble active ingredient.

2. The skin care gel beads according to claim 1, characterized in that, By weight, the aqueous shell comprises 0.8-1.5% agar and 0-0.8% sodium alginate.

3. The skin care gel beads according to claim 1, characterized in that, The weight ratio of agar to sodium alginate is 4:3 to 3:

1.

4. The skin care gel beads according to claim 1, characterized in that, The aqueous shell material also includes one or more of the following: gum arabic, carbomer, xanthan gum, guar gum, sodium polyacrylate, polyglycerol-3 polyricinoleate, polydimethylsiloxane copolyol, hydroxyethyl cellulose, magnesium aluminum silicate, methylcellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone, chitosan, whey protein, gelatin, hydroxypropyl methylcellulose, alginate, hydroxypropyl starch, polyols, sugars, hyaluronic acid, and p-hydroxyacetophenone.

5. The skin care gel beads according to claim 4, characterized in that, The content of gum arabic is 0-0.5% by weight.

6. The skin care gel beads according to any one of claims 1 to 5, characterized in that, The skin care beads contain 1-10 inner beads.

7. The skin care gel beads according to any one of claims 1 to 5, characterized in that, The diameter of the skin care beads is 1-10cm.

8. A method for preparing skin care gel beads as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Pretreatment of the aqueous shell: Add the aqueous shell material into the shell tank according to the formula ratio and start stirring at 300-500 rpm; heat to 60-65℃ and stir for 20-30 minutes to ensure uniform dissolution; keep warm at 60℃ until ready for use. S2. Oil phase bead pretreatment: Different oil-soluble active ingredients are placed into separate core phase tanks and kept at 60℃ for later use. S3. Preparation of condensed beads: Open the valves of the shell phase tank and the core phase tank at the same time. After the shell phase and the core phase are mixed, they are dripped into the cooling pool. The coolant in the cooling pool is liquid paraffin. The droplets are cooled and quickly solidify into condensed beads. The flow rate of the shell phase is 100-1000 mL / min, and the flow rate of the core phase is 20-600 mL / min. The size and number of beads in the oil phase are controlled by adjusting the flow rates of the two phases.

9. A skincare composition, characterized in that, The skincare composition contains skincare gel beads as described in any one of claims 1 to 7.

10. The use of skin care gel beads as described in any one of claims 1 to 7 in the preparation of cosmetics.

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