CN110917071B

CN110917071B - Core-shell structure flexible bead, preparation method thereof and personal care product comprising core-shell structure flexible bead

Info

Publication number: CN110917071B
Application number: CN201911336531.7A
Authority: CN
Inventors: 陈家明; 张川; 贾海东
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-12-23
Filing date: 2019-12-23
Publication date: 2022-11-08
Anticipated expiration: 2039-12-23
Also published as: CN110917071A

Abstract

The invention provides a core-shell structure flexible bead, a preparation method thereof and a personal care product containing the flexible bead. The soft beads comprise hydrogel shells formed by glue solution compositions containing agar, gellan gum, sodium alginate, a thickening agent, an ultraviolet absorbent and water; and a core layer formed of a core material composition including a hydrophobic photosensitive material and a grease. The flexible bead with the core-shell structure has a good protection effect on the photosensitive material.

Description

Core-shell structure flexible bead, preparation method thereof and personal care product comprising core-shell structure flexible bead

Technical Field

The invention relates to the field of personal care, in particular to a core-shell structure flexible bead and a preparation method thereof. The flexible bead with the core-shell structure can be used for protecting photosensitive materials.

Background

In recent years, more and more actives have been added to personal care products to nourish the skin, resist aging, protect the skin from ultraviolet light, and the like. However, part of the active substance has poor stability, and the activity thereof is easily deteriorated by external stimulus. For example, some active ingredients are sensitive to light and are inactivated by exposure to light, such as vitamin E. Vitamin E is stable to acid and heat, can be damaged when exposed to ultraviolet rays, and has a very limited antioxidant effect when being directly added into cosmetics. In addition, vitamin E is an oil-soluble viscous liquid, which feels slimy to the skin.

How to improve the stability of the oil-soluble active substance and enable the oil-soluble active substance to be added into an aqueous product to improve the skin feel of the product is a very important research direction in the field of personal care. Emulsification techniques, self-assembly techniques, and the like can disperse the oil phase into the aqueous phase. These techniques have been widely used in some fields, such as emulsion preparation by emulsification techniques, and chinese patent publication CN107802512a discloses a method for preparing vitamin E nanoemulsion. Wherein the vitamin E, the oil phase, the main surfactant, the cosurfactant and the water are mixed to prepare the emulsion with the particle size of 30-60 nm. Although the method is simple and convenient to operate, the content of the vitamin E is low and is in a range of 3-9%, the protection capability of the vitamin E is poor, and the problem that the vitamin E is easy to oxidize cannot be solved. In addition, the conventional technology has some common defects, such as complex preparation process, residual emulsifier in the system, insufficient stability of the water-oil system and the like. In the cosmetic field, the skin feel of the product may be affected by the residual emulsifier, the quality of the product may be affected by insufficient stability, and the cost may be increased by a complicated preparation process.

Disclosure of Invention

The present inventors have developed a new technique for the above pain spots through a large number of experimental studies. The technology can simply and efficiently prepare the flexible bead with the oil-water two-phase core-shell structure. The core-shell structure flexible beads can be uniformly and stably dispersed in a water phase, and an emulsifier is not required to be additionally added in the dispersing process. Meanwhile, the soft beads prepared by the technology can be coated with a large amount of photosensitive materials, and the coating amount can exceed 60% of the weight of the soft beads. By ingenious design, the technology enables the powder ultraviolet absorbent to be uniformly and stably distributed on the shell layer of the flexible bead, so that the shell layer of the flexible bead hydrogel has a strong ultraviolet absorption function. Meanwhile, further research finds that the stability of the photosensitive material can be remarkably improved by adding the Bridgkin fruit oil into the core layer oil phase. Research results show that by constructing the core-shell structure flexible bead, the shell layer of the flexible bead can filter ultraviolet rays, and the oil phase of the core layer can improve the stability of the photosensitive material, so that the photosensitive material of the core layer can be well protected by the technology.

According to an aspect of the present invention, there is provided a core-shell structured flexible bead, including:

a hydrogel shell layer formed by a glue solution composition containing agar, gellan gum, sodium alginate, a thickening agent, an ultraviolet absorbent and water; and

a core layer formed from a core material composition comprising a hydrophobic photosensitive material and a grease.

Agar content of 0.1 to 10wt%, preferably 0.1 to 5wt%, based on 100wt% of the glue solution composition; the gellan gum content is 0.1wt% to 10wt%, preferably 0.1wt% to 5wt%; the content of sodium alginate is 0.1-10 wt%, preferably 0.1-5 wt%; the content of the thickener is 0.1 to 10 weight percent, preferably 0.1 to 5 weight percent; the content of the ultraviolet absorbent is 0.1 to 3 weight percent, preferably 0.1 to 1 weight percent; the water content is from 57 to 90% by weight, preferably from 60 to 85% by weight.

The content of the hydrophobic photosensitive material is 0.1 to 15wt%, preferably 0.1 to 10wt%, based on 100wt% of the core material composition; the content of the grease is 85wt% -99.9 wt%, preferably 90wt% -99.9 wt%.

Preferably, the glue solution composition further comprises 1wt% -20 wt% of a humectant and 1wt% -20 wt% of a bacteriostatic agent, wherein the sum of the weight of the components of the glue solution composition is 100wt%.

Preferably, the core material composition further comprises 0.1wt% to 15wt%, preferably 0.1wt% to 10wt% of a burley fruit oil, wherein the sum of the weight of the components of the core material composition is 100wt%.

Preferably, the weight ratio of the core layer to the shell layer is 1:5-3:2, preferably 1:4-6:5.

The hydrophobic photosensitive material is one or the combination of more than two of vitamins or derivatives thereof, photosensitive probes and sunscreens.

The vitamins are preferably selected from one or the combination of more than two of vitamin A, vitamin E, vitamin D and vitamin K; the vitamin derivative is a reaction product of the vitamin with other compounds, such as vitamin C ₁ ～C ₆ The carboxylic acid of (a) forms an ester, etc.

The photosensitive probe is preferably selected from one or the combination of more than two of a polarity sensitive probe and a voltage sensitive probe for marking amino acid;

the sunscreen agent is preferably selected from one or a combination of two or more of benzophenone-3, benzophenone-4, 4-butyl-4-methoxy-dibenzoylmethane, 4-methyl-4-ethoxybenzoyl methane, bisethylhexyloxyphenol, p-methoxyphenyltriazine, ethylhexyltriazone, diethylamino hydroxybenzoyl hexyl benzoate, cresotriazoletrisiloxane, phenyl, octyl methyl cinnamate, octyl methoxycinnamate, octyl salicylate, octyl N, N-dimethyl-p-aminobenzoate, 2-cyano-3,3 diphenyl acrylate, octyl cyanbisacryhenate, diethylamino hydroxybenzoyl hexyl benzoate, N-dimethyl-p-carbamate, menthyl anthranilate, menthyl salicylate, phenyl salicylate, benzyl salicylate, p-aminobenzoic acid, glyceryl p-aminobenzoate, and ethyl-4-bis (hydroxypropyl) aminobenzoate.

The oil is one or a combination of more than two of natural vegetable oil or synthetic silane oil, preferably, the oil is one or a combination of more than two of jojoba ester, caprylic/capric triglyceride, argania spinosa kernel oil, octyl dodecanol olive oleate, st.John's wort oil, polydimethylsiloxane, cyclopentadecyldimethylsiloxane, and polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer.

The agar has a temperature-sensitive physical crosslinking performance, so that the glue solution composition is physically crosslinked at a lower temperature to form a hydrogel shell, and the agar is preferably biological-grade purified agar.

Preferably, the gellan gum is a high acyl gellan gum, which is capable of forming a gel with better elasticity after dissolution and cooling.

The glucoside group in the sodium alginate can be broken when irradiated by ultraviolet light, and can absorb part of the ultraviolet light, and the sodium alginate can be crosslinked in a divalent cation aqueous solution, so that the stability of a shell layer can be further improved.

The thickening agent can adjust the viscosity of shell glue solution, which is very important for finally preparing core-shell structure flexible beads. The thickening agent is preferably a water-soluble polymer thickening agent, and is preferably acrylamide dimethyl ammonium taurate/vinyl pyrrolidone copolymer.

The humectant is used for regulating skin feeling of the product, and is preferably polyhydric alcohol, more preferably one or more selected from glycerol, propylene glycol, polyethylene glycol (e.g., PEG-200) and sorbitol

The bacteriostatic agent plays a role in antisepsis, and is preferably one or a combination of more than two of phenoxyethanol, caprylyl glycol and 1,3-butanediol.

The ultraviolet absorber is preferably an inorganic ultraviolet absorber, more preferably a nano-sized inorganic ultraviolet absorber, and even more preferably one or a combination of two or more selected from titanium dioxide, zinc oxide, kaolin, ferrous oxide, calcium titanate, and talc, for absorbing ultraviolet rays to prevent ultraviolet rays from entering the core layer.

The Bridgkin fruit oil can obviously improve the stability of the photosensitive material, and is preferably crude Bridgkin fruit oil which is initially pressed and cold pressed.

Preferably, the particle size of the flexible beads is controllable, and can be controlled by setting the preparation conditions, for example, the particle size can be 0.5mm to 8mm, preferably 1mm to 6mm.

Preferably, the glue composition further comprises other additives as long as the object of the present invention is not impaired, examples thereof include, but are not limited to, fragrances, pigments, etc.; the amount thereof is within a range not impairing the object of the present invention, and may be, for example, 1 to 3% by weight relative to the dope composition. Further preferably, the glue solution composition consists of agar, gellan gum, sodium alginate, a thickening agent, a humectant, a bacteriostatic agent, an ultraviolet absorbent and optionally other additives.

Preferably, the core material composition further comprises other additives as long as the object of the present invention is not impaired, and examples thereof include, but are not limited to, fragrances, pigments, and the like; as long as the amount is within a range not impairing the object of the present invention, for example, it may be 1 to 3wt% with respect to the core material composition. Further preferably, the core material composition consists of a hydrophobic light sensitive material, a brigade oil, a grease and optionally other additives.

According to another aspect of the present invention, there is provided a method for preparing the core-shell structured flexible bead, which includes the following steps:

1) Dispersing all components in the glue solution composition in hot water at a temperature higher than room temperature to prepare the glue solution composition;

2) Mixing the components in the core material composition to prepare the core material composition, and mixing the hydrophobic photosensitive material, the Bridgkin fruit oil and the grease with the content to obtain the core material composition;

3) And adding the glue solution composition into a glue solution tank of a pill dropping machine, adding the core material composition latex into an oil tank of the pill dropping machine, immersing a dripper of the pill dropping machine into circulating oil at the temperature lower than room temperature, and converging the glue solution composition and the core material composition into core-shell coaxial drippers to form the flexible beads.

Preferably, the preparation method further comprises the following steps:

4) Placing the flexible beads obtained in the step 3) into an aqueous solution containing divalent cations to crosslink the sodium alginate in the shell layer.

The divalent cation includes, but is not limited to calcium ion, magnesium ion, zinc ion, etc., and the concentration of the divalent cation is 0.005-0.1 mol/L.

Preferably, the dripper is composed of two coaxial core-shell layers, the inner diameter of the core-shell dripper is 0.5-2 cm, and the inner diameter of the shell-layer dripper is 1-3 cm.

Preferably, the circulating oil is liquid paraffin or dimethicone with viscosity of 5-50 cps, and the temperature of the circulating oil is 0-20 deg.C.

Preferably, the heating temperature of the glue solution tank is 50-100 ℃, and the heating temperature of the dripper is 50-100 ℃.

Preferably, the dripper is submerged to the oil surface to a depth of 0 to 5cm, and the receiving column is from 5 to 50cm in height.

Preferably, the dropping rate is 3 to 60 drops/second.

The temperature of the hot water is 80-100 ℃, preferably 85-98 ℃.

The pill dropping machine is a pill dropping machine generally used in the field. The working principle is that the dripper of the dripping pill machine is immersed into the circulating condensed oil, and the hot glue solution composition forms gel when meeting cold. The circulating oil flowing downwards generates pressure to the liquid drops at the dripper part, so that the liquid drops are separated from the dripper to form spherical gel. The deeper the dripper is embedded into the oil surface, the higher the pressure at the liquid drop is, the more quickly the liquid drop is separated from the dripper, and the spherical gel is formed when the liquid drop is not long enough to grow. Meanwhile, the height of the receiving column is adjusted to generate a height difference with the circulating oil at the dripper, and the circulating oil carries gel particles to rapidly flow downwards to the discharge hole under the action of gravity.

In the invention, the dripper of the pill dropping machine consists of two coaxial core-shell layers, wherein the glue solution composition is positioned at the shell layer, the core material composition is positioned at the core layer, and the glue solution composition wraps the core material composition. The dripping head of the pill dripping machine is immersed in the circulating oil, and the glue solution composition is cooled and changes from a solution state to a gel state. The flexible beads with different sizes can be prepared by adjusting the flow rate of the core-shell layer material, the depth of the dripper submerged into the oil surface and the height of the receiving column.

According to yet another aspect of the present invention, a personal care article comprising the flexible beads is provided. The personal care products include, but are not limited to, cosmetics.

The flexible bead with the core-shell structure has a good protection effect on the photosensitive material. This is a result of the synergistic effect of the core-shell layer of the flexible beads. The ultraviolet absorbent (such as titanium dioxide particles) is uniformly and stably distributed on the shell layer of the flexible bead, so that the hydrogel shell layer of the flexible bead has a strong ultraviolet absorption function. Because the shell of the soft bead can filter ultraviolet rays, and the glucoside group of the calcium alginate of the shell can be broken when being irradiated by the ultraviolet rays, the shell can absorb part of the ultraviolet rays and can also play a role in protecting the photosensitive material of the core layer. In addition, the inventor creatively finds that the stability of the photosensitive material can be obviously improved by adding the Bridgman fruit oil into the core layer. The invention also proves that the technology for cooperatively protecting the photosensitive material by the core and the shell has stronger technical efficacy of absorbing ultraviolet rays than that of the ultraviolet absorbent with a single shell, and has the effect that one plus one is more than two. Agar has a temperature-sensitive physical cross-linking property, and sodium alginate has a chemical cross-linking property by combining with calcium ions. Therefore, the shell layer of the flexible bead forms more stable hydrogel by a double crosslinking mode of physical crosslinking and chemical crosslinking, and the core-shell structure flexible bead shows good stability in a temperature range of-15 ℃ to 50 ℃. The soft bead has good application prospect in the field of personal care. In addition, the preparation method of the core-shell structure flexible bead is simple, efficient, safe and environment-friendly. By innovatively controlling the process parameters, the invention can prepare core-shell structure flexible beads coated with photosensitive materials with different sizes. In addition, the personal skin care product containing the core-shell structure flexible bead has the advantages of prominent visual effect, fresh skin feeling, excellent moistening effect and good application prospect.

Drawings

FIG. 1 is a schematic diagram of a method for preparing core-shell structured flexible beads according to the present invention.

Fig. 2 shows a graph of the residual rate of vitamin E acetate alone under the same intensity of uv light for 6 hours for core-shell structured flexible beads and vitamin E acetate without any protection prepared according to example 1.

Detailed Description

In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

Example 1

Preparing the core-shell structure soft bead wrapping vitamin E acetate with the particle size of 1-2 mm

Based on 100wt% of the glue solution composition, 0.1wt% of agar (purified high strength agar), 5wt% of gellan gum (high acyl gellan gum), 0.1wt% of sodium alginate, 5wt% of acrylamide dimethyl ammonium taurate/vinyl pyrrolidone copolymer, 1wt% of glycerin, 20wt% of butylene glycol, and 0.1wt% of titanium dioxide were dissolved in hot water at 90 ℃ to prepare a glue solution composition as a shell material. The core composition was prepared by mixing 10wt% of burley fruit oil, 80wt% of jojoba ester, and 10wt% of vitamin E acetate based on 100wt% of the core composition. Selecting a JW machine of the cigarette platform Baiyaotai, wherein the diameters of the inner layer and the outer layer of the dripper (namely the inner diameters of the core layer dripper and the shell layer dripper) are 0.5 cm and 1.0 cm respectively, setting technological parameters according to a machine operation manual, and setting the weight ratio of the glue solution composition to the core material composition to be 1:1. the prepared core-shell structure flexible bead with the particle size of 1-2 mm. The shell of the soft bead is formed by a layer of hydrogel capable of absorbing ultraviolet rays, and the core layer comprises Bridgkin fruit oil, jojoba ester and a photosensitive material vitamin E acetate.

Experimental example 1

The core-shell structure flexible beads coated with vitamin E acetate prepared in example 1 and pure vitamin E acetate were exposed to uv light of the same intensity for 6 hours, and then the stability of vitamin E acetate was measured, and the results are shown in fig. 2. As can be seen from fig. 2, the remaining amount of vitamin E acetate in the core-shell structured flexible beads was nearly 80% after 6 hours of exposure to uv light, while the remaining amount of vitamin E acetate without any protection was only 20%. Therefore, the flexible bead with the core-shell structure can obviously protect the activity of vitamin E acetate.

In addition, 80wt% of the burley fruit oil was mixed with 20wt% of the vitamin E acetate, and uv irradiation was performed for 6 hours under the same conditions as above, and then the remaining amount of the vitamin E acetate was measured, and the result showed that the remaining amount of the vitamin E acetate was more than 50wt%, and the remaining amount of the vitamin E acetate without any protection was only 20wt%.

Example 2

Preparing core-shell structure flexible beads with particle size of 3-4 mm

Based on 100wt% of the glue solution composition, 5wt% of agar (purified high strength agar), 0.1wt% of gellan gum (high acyl gellan gum), 5wt% of sodium alginate, 0.1wt% of acrylamide dimethyl ammonium taurate/vinyl pyrrolidone copolymer, 20wt% of glycerin, 1wt% of butanediol and 1wt% of titanium dioxide were dissolved in hot water at 90 ℃ to prepare a glue solution composition as a shell material. The core composition consisted of 0.1wt% of burley fruit oil, 99.8wt% of caprylic/capric triglyceride, 0.1wt% of vitamin E acetate, based on 100wt% of the core composition. Selecting a JW machine of the cigarette platform Baiyaotai, wherein the inner diameter and the outer diameter (namely the inner diameter of a nuclear layer dripper and a shell layer dripper) of the drippers are respectively 2cm and 3cm, setting process parameters according to a machine operation manual, and setting the weight ratio of a glue solution composition to a core material composition to be 5:4. the prepared core-shell structure flexible bead with the thickness of 3-4 mm. The shell of the soft bead is composed of a layer of hydrogel capable of absorbing ultraviolet rays, and the core layer is composed of Bridgkin fruit oil, caprylic/capric triglyceride and a photosensitive material vitamin E acetate. The soft bead is stored in an oven at 50 ℃ for one month, the appearance is not obviously changed, and the residual amount of the vitamin E acetate exceeds 90 percent.

Example 3

Preparing 1-2 mm core-shell structure flexible beads wrapping vitamin A

Based on 100wt% of the glue solution composition, 2wt% of agar (purified high strength agar), 1wt% of gellan gum (high acyl gellan gum), 1wt% of sodium alginate, 3wt% of acrylamide dimethyl taurinate/vinyl pyrrolidone copolymer, 5wt% of glycerol, 5wt% of butanediol, and 0.2wt% of titanium dioxide were dissolved in hot water at 90 ℃ to prepare a glue solution composition as a shell material. The core material composition consists of 2wt% of burley fruit oil, 96wt% of caprylic/capric triglyceride, 2wt% of vitamin a, based on 100wt% of the core material composition. Selecting a JW machine of the cigarette platform Baiyaotai, wherein inner and outer diameters (inner diameters of a nuclear layer dripper and a shell layer dripper) are respectively 1 cm and 2cm, setting corresponding process parameters according to a machine operation manual, and setting the weight ratio of a glue solution composition to a core material composition to be 1:1. the prepared core-shell structure flexible bead with the thickness of 1-2 mm. The shell of the soft bead is composed of a layer of hydrogel capable of absorbing ultraviolet rays, and the core layer is composed of Bridgkin fruit oil, caprylic/capric triglyceride and vitamin A. The soft beads are stored in an oven at 50 ℃ for one month, the appearance is not obviously changed, and the residual quantity of the vitamin A is over 90 percent.

Example 4

Preparation of emulsifier-free core-shell structure soft bead essence

Based on 100wt% of the aqueous phase, 5wt% of glycerin, 2wt% of butanediol, 2wt% of propylene glycol, 0.2wt% of triethanolamine, 0.2wt% of carbomer 20, 0.2wt% of sodium hyaluronate, 0.2wt% of phenoxyethanol and 0.1wt% of caprylyl glycol are dissolved in water to prepare the aqueous phase of essence. The soft beads with the core-shell structure of 1-2 mm prepared in example 1 are added into the aqueous phase of the essence according to the proportion of 10wt% of the aqueous phase. Stirring to uniformly disperse the soft beads into the water phase to obtain the core-shell structure soft bead essence without emulsifier. In the absence of an emulsifier, the core-shell structure flexible beads wrapping the grease can be uniformly dispersed into an aqueous phase system. The above essence has refreshing skin feeling and excellent stability, and has no apparent change in appearance after being stored in an oven at 50 deg.C for one month. The product is non-irritating to the skin as measured by skin sensitivity tests.

Claims

1. A core-shell structured flexible bead comprising:

a core layer formed of a core material composition comprising a hydrophobic photosensitive material, a fat and a Bridgkin's fruit oil,

wherein, based on 100wt% of the glue solution composition, the agar content is 0.1wt% -10 wt%; the gellan gum content is 0.1wt% -10 wt%; the content of sodium alginate is 0.1wt% -10 wt%; the content of the thickening agent is 0.1wt% -10 wt%; the content of the ultraviolet absorbent is 0.1 to 3 weight percent; the water content is 57wt% -90 wt%; and

in the core material composition, the hydrophobic photosensitive material is contained in an amount of 0.1 to 15wt% based on 100wt% of the core material composition; the content of the grease is 85-99.9 wt%; and the content of the Bridgkin fruit oil is 0.1-15 wt%, and the sum of the content of the components in the core material composition is 100wt%.

2. The flexible bead of claim 1,

the glue solution composition further comprises 1-20 wt% of humectant and 1-20 wt% of bacteriostatic agent.

3. The flexible bead of claim 2,

in the glue solution composition,

the gellan gum is high acyl gellan gum;

the thickening agent is a water-soluble polymer thickening agent;

the humectant is polyhydric alcohol;

the bacteriostatic agent is one or the combination of more than two of phenoxyethanol, caprylyl glycol and 1,3-butanediol;

the ultraviolet absorbent is an inorganic ultraviolet absorbent;

in the core material composition,

the hydrophobic photosensitive material is one or the combination of more than two of vitamins, photosensitive probes and sunscreens,

the grease is one or a combination of more than two of natural vegetable grease or synthetic silane grease.

4. The flexible bead of claim 3, wherein the thickener is an acrylamide dimethyl taurate/vinyl pyrrolidone copolymer.

5. The flexible bead of claim 3,

the polyalcohol is one or the combination of more than two of glycerol, propylene glycol, polyethylene glycol and sorbitol,

the inorganic ultraviolet absorbent is one or the combination of more than two of titanium dioxide, zinc oxide, kaolin, ferrous oxide, calcium titanate and talcum powder,

the vitamin is one or the combination of more than two of vitamin A, vitamin E, vitamin D and vitamin K,

the photosensitive probe is one or the combination of more than two of a polarity sensitive probe and a voltage sensitive probe which are used for marking amino acid,

the sunscreen agent is one or a combination of two or more selected from benzophenone-3, benzophenone-4, 4-butyl-4-methoxy-dibenzoylmethane, 4-methyl-4-ethoxybenzoyl methane, bisethylhexyloxyphenol, p-methoxyphenyltriazine, ethylhexyltriazone, diethylamino hydroxybenzoyl hexyl benzoate, cresotriazoletrisiloxane, phenyl, octyl methyl cinnamate, octyl methoxycinnamate, octyl salicylate, octyl N, N-dimethyl-p-aminobenzoate, 2-cyano-3,3 diphenyl octyl acrylate, octocrylene, diethylamino hydroxybenzoyl hexyl benzoate, N-dimethyl-p-amyl carbamate, menthyl anthranilate, menthyl salicylate, phenyl salicylate, benzyl salicylate, p-aminobenzoic acid, glyceryl p-aminobenzoate, and ethyl-4-bis (hydroxypropyl) aminobenzoate, and

the oil is selected from one or more of jojoba ester, caprylic/capric triglyceride, aralia mandshurica Kernel oil, octyl dodecanol olive oleate, st John's wort oil, polydimethylsiloxane, cyclopentadecylpolydimethylsiloxane, and polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer.

6. The flexible bead of any one of claims 1 to 5, wherein,

the weight ratio of the core layer to the shell layer is 1:5-3:2;

the particle size of the soft beads is 0.5-8 mm.

7. The flexible bead of claim 6,

the weight ratio of the core layer to the shell layer is 1:4-6:5; the particle size of the soft beads is 1 mm-6 mm.

8. A method of making the flexible bead of any one of claims 1-7, comprising the steps of:

2) Mixing the components of the core material composition to prepare a core material composition;

3) And adding the glue solution composition into a glue solution tank of a pill dropping machine, adding the glue solution of the core material composition into an oil tank of the pill dropping machine, immersing a dripper of the pill dropping machine into circulating oil at the temperature lower than room temperature, and converging the glue solution composition and the core material composition into drippers with coaxial core-shell to form the flexible bead.

9. The method of claim 8, further comprising the steps of:

10. The method according to claim 9, wherein the divalent cation is one or a combination of two or more selected from the group consisting of calcium ion, magnesium ion and zinc ion, and the concentration of the divalent cation is 0.005 to 0.1mol/L.

11. The method of claim 8, wherein,

the circulating oil is liquid paraffin or dimethyl silicone oil with the viscosity of 5-50 cps, and the temperature of the circulating oil is 0-20 ℃;

the heating temperature of the glue solution tank is 50-100 ℃, and the heating temperature of the dripper is 50-100 ℃;

the dripper consists of two coaxial core-shell layers, the inner diameter of the dripper of the core layer is 0.5-2 cm, the inner diameter of the dripper of the shell layer is 1-3 cm,

the depth of the dripper submerged into the oil surface is 0-5 cm, the height of the receiving column is 5-50 cm,

the dripping speed is 3-60 drops/s.

12. A personal care article comprising the flexible bead of any one of claims 1-7.

13. The personal care article of claim 12 wherein the personal care article is a cosmetic.