METHOD FOR PREPARING MULTILAYER SPHERICAL PARTICLES AND COSMETIC COMPOSITION COMPRISING MULTILAYER SPHERICAL PARTICLES PREPARED THEREBY

Abstract

The present invention relates to a method for preparing multilayer spherical particles and, more specifically, to a method for preparing multilayer spherical particles comprising the steps of: (i) preparing a core component comprising an active ingredient and a shell solution comprising a first polymer component; (ii) forming the core component and shell solution of step (i) into core-shell particles by electro-coextrusion; (iii) drying the core-shell particles obtained from step (ii); and (iv) capsulizing the dried core-shell particles of step (iii) by means of a second polymer. Further, the present invention relates to a cosmetic composition comprising multilayer spherical particles prepared by the method.

Claims

1. A method for preparing multilayered spherical particles comprising: i) preparing a core component comprising an active ingredient and a shell solution comprising a first polymer; ii) forming core-shell particles by electro-coextrusion of the core component and the shell solution of step (i); iii) drying the core-shell particles obtained in step (ii); and iv) encapsulating the dried core-shell particles of step (iii) with a second polymer.

2. The method for preparing multilayered spherical particles according to claim 1, wherein the active ingredient of step (i) is selected from the group consisting of oil, wax, hydrocarbon, higher fatty acid, higher alcohol, silicone, ester and a mixture thereof.

3. The method for preparing multilayered spherical particles according to claim 2, wherein the active ingredient of step (i) forms a complex with a covalent organic framework (COF).

4. The method for preparing multilayered spherical particles according to claim 1, wherein the first polymer of step (i) is selected from the group consisting of nanocellulose, cellulose, hydroxyethyl cellulose, microcrystalline cellulose, starch, polymethyl methacrylate (PMMA), xanthan gum, carbomer, acrylates/C10-30 alkyl acrylate crosspolymer, acacia gum, guar gum, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), gelatin, hyaluronic acid, collagen, pullulan, polyglycolide (PGA), agar, gum arabic, carrageenan gum, gellan gum, karaya gum, methylcellulose, locust bean gum, alginate, sodium alginate, glucomannan, succinyl chitosan, pullulan lactide, chitosan, polyethylene glycol (PEG)-polycaprolactone (PCL)-polyethylene glycol (PEG) triblock copolymer, poloxamer 407, acetyl hydroxypropyl cellulose and a mixture thereof.

5. The method for preparing multilayered spherical particles according to claim 1, wherein the first polymer in the shell solution of step (i) has a concentration of 1 to 50% by weight.

6. The method for preparing multilayered spherical particles according to claim 1, wherein the electro-coextrusion of the core component in step (ii) is carried out at a flow rate of 0.1 to 10 mL/min.

7. The method for preparing multilayered spherical particles according to claim 1, wherein the electro-coextrusion of the shell solution in step (ii) is carried out at a flow rate of 0.5 to 20 mL/min.

8. The method for preparing multilayered spherical particles according to claim 1, wherein the electro-coextrusion of step (ii) is carried out at 1,000 to 5,000 volts (V).

9. The method for preparing multilayered spherical particles according to claim 1, wherein a calcium chloride solution is used as a curing agent in the electro-coextrusion of step (ii).

10. The method for preparing multilayered spherical particles according to claim 1, wherein the drying of step (iii) is carried out at 60 to 90 C.

11. The method for preparing multilayered spherical particles according to claim 1, wherein the second polymer of step (iv) is selected from the group consisting of collagen, hyaluronic acid, pullulan, proteoglycan, beta-glucan, glucan, polyglutamic acid, chitosan and a mixture thereof.

12. The method for preparing multilayered spherical particles according to claim 1, wherein the prepared multilayered spherical particles have a diameter of 200 to 1,500 m.

13. A cosmetic composition comprising the multilayered spherical particles prepared by the method according to claim 1.

14. The cosmetic composition according to claim 13, which comprises 0.1 to 50% by weight of the multilayered spherical particles.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0045] FIG. 1 is a schematic diagram of electro-coextrusion apparatus.

[0046] FIG. 2 is an enlarged photograph of multilayered spherical particles prepared in Example 1.

[0047] FIG. 3 is a result of measuring the particle size of multilayered spherical particles prepared in Example 1.

MODE FOR THE INVENTION

[0048] Hereinafter, the present invention is explained in more detail with the following examples. However, it must be understood that the protection scope of the present invention is not limited to the examples.

Example 1: Preparation of Multilayered Spherical Particles Using Gelatin/Acacia Gum/Carbomer

[0049] A shell solution was prepared from Ingredient A according to the composition recited in Table 1, and a solution was prepared by dissolving a core component of Ingredient B and 1% calcium chloride as a curing agent in purified water. Then, electro-coextrusion was carried out with the above solutions by the use of Encapsulator B-390 (Buchi, Switzerland) under the following conditions to obtain core-shell particles. [0050] Nozzle: 150 m (core), 400 m (shell) [0051] Flow rate: 1.5 mL/min (core), 10 mL/min (shell) [0052] Frequency: 600 Hz [0053] Pressure: 0.5 bar [0054] Amplitude: 3 [0055] Charge: 2,300 V

[0056] After drying the obtained core-shell particles at 80 C. for 12 hours, the dried core-shell particles were put in a container, and Ingredient C was slowly added thereto. Then, encapsulation was carried out by mixing them with a winged disperser for 10 minutes to prepare multilayered spherical particles.

TABLE-US-00001 TABLE 1 Ingredient Content (parts by weight) A Gelatin 2.5 Acacia gum 1.5 Carbomer 0.3 Dipropylene glycol 15 Glycerin 6 Butylene glycol 12 Purified water 15 B Retinol/capric/caprylic triglyceride 90 C Chitosan (2% solution) 50

Example 2: Preparation of Multilayered Spherical Particles Using Alginate/Nanocellulose/Carbomer

[0057] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 2.

TABLE-US-00002 TABLE 2 Ingredient Content (parts by weight) A Alginate 2 Nanocellulose 12 Carbomer 0.3 Dipropylene glycol 12 Glycerin 8 Butylene glycol 15 Purified water 15 B Olive oil 35 C Collagen (10% solution) 40

Example 3: Preparation of Multilayered Spherical Particles Using Alginate/Acacia Gum/Carrageenan Gum

[0058] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 3.

TABLE-US-00003 TABLE 3 Ingredient Content (parts by weight) A Alginate 3 Acacia gum 0.8 Carrageenan gum 1 Dipropylene glycol 15 Glycerin 12 Butylene glycol 8 Purified water 15 B Candelilla wax 40 C Hyaluronic acid (1% solution) 50

Example 4: Preparation of Multilayered Spherical Particles Using Xanthan Gum/PVA/Carbomer

[0059] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 4.

TABLE-US-00004 TABLE 4 Ingredient Content (parts by weight) A Xanthan gum 3 Polyvinyl alcohol 4 Carbomer 0.5 Dipropylene glycol 12 Glycerin 8 Butylene glycol 10 Purified water 18 B Paraffin 38 C Pullulan (10% solution) 40

Example 5: Preparation of Multilayered Spherical Particles Using PVP/Guar Gum/Acrylate/C10-30 Alkyl Acrylate Crosspolymer

[0060] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 5.

TABLE-US-00005 TABLE 5 Ingredient Content (parts by weight) A Polyvinylpyrrolidone 1.5 Guar gum 3 Acrylates/C10-30 alkyl acrylate 0.8 crosspolymer Dipropylene glycol 12 Glycerin 10 Butylene glycol 12 Purified water 18 B Palmitic acid 40 C Proteoglycan (10% solution) 40

Example 6: Preparation of Multilayered Spherical Particles Using Gum Arabic/Gellan Gum/Locust Bean Gum

[0061] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 6.

TABLE-US-00006 TABLE 6 Ingredient Content (parts by weight) A Gum arabic 2 Gellan gum 1.5 Locust bean gum 0.3 Dipropylene glycol 15 Glycerin 6 Butylene glycol 12 Purified water 15 B Stearyl alcohol 35 C Glucan (10% solution) 40

Example 7: Preparation of Multilayered Spherical Particles Using Glucomannan/Gellan Gum/Carbomer

[0062] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 7.

TABLE-US-00007 TABLE 7 Ingredient Content (parts by weight) A Glucomannan 3 Gellan gum 1.2 Carbomer 0.2 Dipropylene glycol 15 Glycerin 6 Butylene glycol 12 Purified water 15 B Dimethicone 38 C Polyglutamic acid (10% solution) 40

Example 8: Preparation of Multilayered Spherical Particles Using Succinyl Chitosan/Pullulan Lactide/Carbomer

[0063] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 8.

TABLE-US-00008 TABLE 8 Ingredient Content (parts by weight) A Succinyl chitosan 3 Pullulan lactide 1.5 Carbomer 0.5 Dipropylene glycol 15 Glycerin 12 Butylene glycol 8 Purified water 20 B Cyclodextrin-COF/olive oil 60 C Polyglutamic acid (10% solution) 40

Example 9: Preparation of Multilayered Spherical Particles Using Succinyl Chitosan/PEG-PCL-PEG/Carbomer

[0064] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 9.

TABLE-US-00009 TABLE 9 Ingredient Content (parts by weight) A Succinyl chitosan 2 PEG-PCL-PEG triblock copolymer 1.5 Carbomer 0.4 Dipropylene glycol 12 Glycerin 8 Butylene glycol 12 Purified water 18 B Cyclodextrin-COF/retinol/soybean oil 40 C Polyglutamic acid (10% solution) 40

Example 10: Preparation of Multilayered Spherical Particles Using Succinyl Chitosan/Nanocellulose/Carbomer

[0065] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 10.

TABLE-US-00010 TABLE 10 Ingredient Content (parts by weight) A Succinyl chitosan 2 Nanocellulose 1.8 Carbomer 0.5 Dipropylene glycol 12 Glycerin 8 Butylene glycol 10 Purified water 18 B Cyclodextrin-COF/retinol/soybean oil 45 C Polyglutamic acid (10% solution) 40

Example 11: Preparation of Multilayered Spherical Particles Using Succinyl Chitosan/Acetyl Hydroxypropyl Cellulose/Carbomer

[0066] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 11.

TABLE-US-00011 TABLE 11 Content (parts Ingredient by weight) A Succinyl chitosan 3 Acetyl hydroxypropyl cellulose 2 Carbomer 0.3 Dipropylene glycol 12 Glycerin 6 Butylene glycol 12 Purified water 20 B Cyclodextrin-COF/cica powder/soybean oil 38 C Polyglutamic acid (10% solution) 40

Example 12: Preparation of Multilayered Spherical Particles Using Succinyl Chitosan/Poloxamer 407/Carbomer

[0067] Multilayered spherical particles were prepared by the same method as described in Example 1 with the constitutional composition of Table 12.

TABLE-US-00012 TABLE 12 Ingredient Content (parts by weight) A Succinyl chitosan 2 Poloxamer 407 1.5 Carbomer 0.3 Dipropylene glycol 15 Glycerin 6 Butylene glycol 12 Purified water 15 B Cyclodextrin-COF/oil-soluble 42 glycyrrhizic acid/soybean oil C Collagen (10% solution) 40

Example 13 and Comparative Example: Preparation of Lotions with and without Multilayered Spherical Particles

[0068] With the constitutional composition of Table 13, each ingredient was introduced into a container and dissolved at a temperature of 80 C., then mixed for 5 minutes using a homo-mixer, cooled and deaerated to obtain a lotion.

TABLE-US-00013 TABLE 13 Example 13 Comparative Example Ingredient (% by weight) (% by weight) Multilayered spherical particles 10 of Example 1 Retinol 2.5 Polyglyceryl-3 stearate/citrate 2 2 Cetearyl alcohol 0.5 0.5 Olive oil 5 5 Capric/caprylic triglyceride 4 4 Macadamia nut oil 6 6 Glycerin 5 5 Carbopol 0.2 0.2 Purified water 67.3 74.8 Total 100 100

Example 14: Preparation of Body Lotion Containing Multilayered Spherical Particles

[0069] With the constitutional composition of Table 14, each ingredient was introduced into a container and dissolved at a temperature of 80 C., then mixed for 5 minutes using a homo-mixer, cooled and deaerated to obtain a body lotion.

TABLE-US-00014 TABLE 14 Ingredient Content (% by weight) Multilayered spherical particles of Example 2 5 Polyglyceryl-3 methylglucose distearate 3 Phytosqualane 5 Capric/caprylic triglyceride 2 Sunflower oil 5 Olive oil 5 Glycerin 8 Purified water 69 Total 100

Example 15: Preparation of Cream Containing Multilayered Spherical Particles

[0070] With the constitutional composition of Table 15, each ingredient was introduced into a container and dissolved at a temperature of 80 C., then mixed for 5 minutes using a homo-mixer, cooled and deaerated to obtain a cream.

TABLE-US-00015 TABLE 15 Ingredient Content (% by weight) Multilayered spherical particles of Example 3 6 Sorbitan stearate/sucrose cocoate 5 Cetearyl alcohol 1.5 Phytosqualane 3 Olive oil 3 Soybean oil 2 Glycerin 8 Carbopol 0.36 Purified water 71.14 Total 100

Example 16: Preparation of Essence Containing Multilayered Spherical Particles

[0071] With the constitutional composition of Table 16, each ingredient was introduced into a container and dissolved at a temperature of 80 C., then mixed for 5 minutes using a homo-mixer, cooled and deaerated to obtain an essence.

TABLE-US-00016 TABLE 16 Ingredient Content (% by weight) Multilayered spherical particles of Example 4 20 Carbopol 0.4 Hyaluronic acid 1 Coenzyme Q10 0.1 Sodium EDTA 0.05 Calcium hydroxide 0.03 PEG-1500 3 Glycerin 7 Purified water 68.42 Total 100

Example 17: Preparation of Transparent Essence Containing Multilayered Spherical Particles

[0072] With the constitutional composition of Table 17, each ingredient was introduced into a container and dissolved at a temperature of 80 C., then mixed for 5 minutes using a homo-mixer, cooled and deaerated to obtain a transparent essence.

TABLE-US-00017 TABLE 17 Ingredient Content (% by weight) Multilayered spherical particles of Example 5 10 Carbopol 0.4 Lubrajel 20 Glutamic acid 5 Sodium EDTA 0.05 Calcium hydroxide 0.03 PEG-1500 3 Glycerin 7 Purified water 54.52 Total 100

Example 18: Preparation of BB Cream Containing Multilayered Spherical Particles

[0073] Ingredient A was prepared by three (3)-time treatment with a triple roller mill device. Ingredient B was put into the manufacturing section and heated to 75 to and then Ingredient A treated with a triple roller mill device was added thereto and dispersed. Ingredient C was dissolved in a separate container, heated to 80 to 85 C. while stirring with a homo-mixer. Ingredient C was added to the above prepared ingredients, and the mixture was emulsified for 10 minutes. After emulsification was completed, the obtained product was cooled to 45 C. while stirring using a stirrer, then cooled to 25 C. again, and then put in a container and matured.

TABLE-US-00018 TABLE 18 Ingredient Content (% by weight) A Phenyl trimethicone 12 Titanium dioxide 6.2 Mica 1 Dimethylpolysiloxane 0.3 Iron oxide 0.5 B Beeswax 2 Cetyl PEG/PPG-10/1 dimethicone 1.5 Capric/caprylic triglyceride 3 Preservative 0.01 C Multilayered spherical particles 5 of Example 7 Disodium EDTA 0.05 Butylene glycol 5 Glycerin 4 Purified water 59.44 Total 100

Experimental Example 1: Measurement of Particle Size of Multilayered Spherical Particles

[0074] The particle size of the multilayered spherical particles prepared in Example 1 was measured by the use of a particle size analyzer (Mastersizer 2000, MLAVERN, UK), and the result is represented in FIG. 3. From the result of the measurement, it can be known that the particle size is 438 to 1,092 m.

Experimental Example 2: Measurement of Changes in Retinol Content

[0075] The change in retinol content in the lotions of Example 13 and Comparative Example was quantitatively analyzed at 7-day intervals for one month while maintaining light-shielding conditions at 25 C. and light-exposure conditions at 40 C. As an equipment HPLC (Waters, USA) was used, and the analysis conditions were as follows. The analyzed results are represented in Table 19, and light-exposure conditions at 40 C. are described in parentheses. [0076] Detection: UV-Spectrophotometer (325 nm) [0077] Column: C18 (3.9150 mm) [0078] Flow rate: 1.0 mL/min [0079] Mobile phase: Methanol: H.sub.2O (90:10)

TABLE-US-00019 TABLE 19 Days 0 7 13 22 29 35 Example 13 100 (100) 98 (99) 97 (95) 94 (92) 92 (88) 90 (86) Comparative 100 (100) 90 (90) 85 (84) 65 (60) 60 (32) 45 (20) Example (Retinol Residual Content %)

Experimental Example 3: Test for Effect on Promoting Transdermal Absorption

[0080] The artificial skin, Neoderm (Tego Science, Korea) was mounted to a Franz-type diffusion cell (Lab Fine Instruments, Korea). 50 mM phosphate buffer (pH 7.4, 0.1 M NaCl) was added to a receptor cell (5 ml) of the Franz-type diffusion cell. A diffusion cell was then mixed and diffused at 600 rpm, 32 C., and 50 l of the lotions of Example 13 and Comparative Example, respectively, were added to donor cells. Absorption and diffusion were carried out according to the predetermined time, and the area of the skin where the absorption and diffusion were carried out was 0.64 cm.sup.2. After finishing the absorption and diffusion of the active ingredient, the residueswhich were not absorbed and remained on the skinwere cleaned with dried Kimwipes or 10 ml of ethanol. The skin in which the active ingredient was absorbed and diffused was homogenized by the use of a tip-type homogenizer, and retinol absorbed into the skin was then extracted with 4 ml of dichloromethane. The extract was then filtrated with a 0.45 m nylon membrane filter. The content of retinol was measured by high-performance liquid chromatography (HPLC) with the following conditions, and the results are represented in Table 20.

TABLE-US-00020 TABLE 20 Transdermal absorption (g) Rate of increase Lotion of Example 13 3.213 2-fold Lotion of Comparative Example 1.5121 A) Column: C18 (3.9 150 mm, 5 m) B) Mobile phase: methanol:water = 90:10 C) Flow rate: 0.8 mL/min D) Detector: UV 325 nm

[0081] As can be seen from Table 20, it was confirmed that the lotion according to the present invention has superior transdermal absorption compared to the general lotion.

Experimental Example 4: Measurement of Skin Moisturizing Ability

[0082] After applying the lotions of Example 13 and Comparative Example, the moisturizing ability was measured by Corneometer CM850 (Courage+Khazaka electronic GmbH, Germany), and the results are represented in Table 21. As can be seen from Table 21, it can be known that the lotion containing the multilayered spherical particles has superior moisturizing ability than the lotion without them.

TABLE-US-00021 TABLE 21 Days 0 3 7 14 29 Lotion of Example 13 65 100 97 95 90 Lotion of Comparative Example 65 95 90 85 75 Untreated 65 75 74 73 70 (Corneometer/a.u.)