CORE-SHELL PCM MICROCAPSULE HAVING AUTOMATIC TEMPERATURE CONTROL FUNCTION AND COOLING COSMETIC COMPOSITION FOR EXTERNAL SKIN INCLUDING THE SAME
20220249337 · 2022-08-11
Inventors
- Chan Jae SHIN (Daejeon, KR)
- Hye Jin NAM (Seongnam-si, KR)
- JAE SUK OH (Daejeon, KR)
- Sol Bin LIM (Daejeon, KR)
- JI HYUN SON (Daejeon, KR)
- Jung-Hyun Park (Daejeon, KR)
Cpc classification
Y02E60/14
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
A61Q17/04
HUMAN NECESSITIES
A61K2800/412
HUMAN NECESSITIES
F28D20/023
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
A61K8/496
HUMAN NECESSITIES
A61K2800/805
HUMAN NECESSITIES
B01J13/125
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
Provided are preparation of a PCM microcapsule in the form of a core-shell having an excellent heat absorption function by using a temperature-controllable phase change material (PCM) as a core material and a biodegradable polymer material as a shell material, and a cooling cosmetic composition for external skin capable of exhibiting a prevention effect of thermal aging using the same. The core-shell PCM microcapsule having an automatic temperature control function according to the present invention is prepared by dissolving a shell material and a single or mixed PCM in a solvent to produce an oil phase polymer solution, dissolving an aqueous polymer to produce an external continuous phase, emulsifying the oil phase polymer solution and the external continuous phase, and removing the external continuous phase and the solvent and carrying out drying.
Claims
1. A core-shell PCM microcapsule having an automatic temperature control function, comprising: an inner core of a PCM and an outer shell of a biodegradable polymer.
2. The core-shell PCM microcapsule having an automatic temperature control function of claim 1, wherein the PCM is included at 5 wt % to 80 wt % with respect to a total weight of the microcapsule composition.
3. The core-shell PCM microcapsule having an automatic temperature control function of claim 1, wherein as the PCM, n-octacosane, n-heptacosane, n-hexacosane, n-pentacosane, n-tetracosane, n-tricosane, n-docosane, n-heneicosane, n-eicosane, n-nonadecane, n-octadecane, n-heptadecane, hexadecane, n-pentadecane, n-tetradecane, n-tridecane, stearic acid, and derivatives or composites thereof are used alone or in combination to adjust a melting point of the PCM.
4. The core-shell PCM microcapsule having an automatic temperature control function of claim 3, wherein the PCM is n-octadecane and n-eicosane having a melting point of 28-35° C. for a cooling cosmetic, and n-octadecane and n-eicosane are used alone or n-docosane having a melting point of 44° C. is mixed with n-octadecane at a constant ratio.
5. The core-shell PCM microcapsule having an automatic temperature control function of claim 1, wherein as the biodegradable polymer, polycaprolactone, polylactic acid, water-insoluble cellulose, polyhydroxybutyrate, and aliphatic-based unsaturated polyester compounds are used alone or in combination.
6. The core-shell PCM microcapsule having an automatic temperature control function of claim 1, further comprising a functional substance at a weight ratio of 1 to 50 with respect to a weight of the PCM in the capsule.
7. The core-shell PCM microcapsule having an automatic temperature control function of claim 6, wherein the functional substance is any one of menthol, a natural oil, a synthetic oil, an essential oil, a fragrance, a vitamin, a ceramide, and an organic UV absorber.
8. The core-shell PCM microcapsule having an automatic temperature control function of claim 1, wherein the core-shell PCM microcapsule has an average particle size of 0.05 μm to 50 μm.
9. A method of preparing a core-shell PCM microcapsule having an automatic temperature control function, the method comprising: dissolving a shell material which is a biodegradable polymer and a PCM which is a core material in a solvent to produce an oil phase polymer solution, dissolving an aqueous polymer to produce an external continuous phase, emulsifying the oil phase polymer solution and the external continuous phase, and removing the external continuous phase and the solvent and carrying out drying.
10. The method of preparing a core-shell PCM microcapsule having an automatic temperature control function of claim 9, wherein the PCM is included at 5 wt % to 80 wt % with respect to a total weight of the microcapsule composition.
11. The method of preparing a core-shell PCM microcapsule having an automatic temperature control function of claim 9, wherein as the PCM, n-octacosane, n-heptacosane, n-hexacosane, n-pentacosane, n-tetracosane, n-tricosane, n-docosane, n-heneicosane, n-eicosane, n-nonadecane, n-octadecane, n-heptadecane, hexadecane, n-pentadecane, n-tetradecane, n-tridecane, stearic acid, and derivatives or composites thereof are used alone or in combination to adjust a melting point of the PCM.
12. The method of preparing a core-shell PCM microcapsule having an automatic temperature control function of claim 9, wherein as the biodegradable polymer, polycaprolactone, polylactic acid, water-insoluble cellulose, polyhydroxybutyrate, and aliphatic-based unsaturated polyester compounds are used alone or in combination.
13. The method of preparing a core-shell PCM microcapsule having an automatic temperature control function of claim 9, wherein the core-shell PCM microcapsule has an average particle size of 0.05 μm to 50 μm.
14. The method of preparing a core-shell PCM microcapsule having an automatic temperature control function of claim 9, wherein a functional substance is further included at a weight ratio of 1 to 50 with respect to a weight of the PCM in the capsule.
15. The method of preparing a core-shell PCM microcapsule having an automatic temperature control function of claim 9, wherein the functional substance is any one of menthol, a natural oil, a synthetic oil, an essential oil, a fragrance, a vitamin, a ceramide, and an organic UV absorber.
16. A cosmetic composition for external skin comprising 0.1 wt % to 30 wt % of the core-shell PCM microcapsule of claim 1 with respect to a total weight of the cosmetic composition.
Description
DESCRIPTION OF DRAWINGS
[0024] The above and other objects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which:
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BEST MODE
[0039] Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.
[0040] The core-shell PCM microcapsule having an automatic temperature control function of the present invention includes an inner core of a PPM and an outer shell of a biodegradable polymer material.
[0041] The method of preparing a core-shell PCM microcapsule having an automatic temperature control function is preferably a dry-in-liquid method including: dissolving a shell material which is a biodegradable polymer and a PCM in a solvent to produce an oil phase polymer solution, dissolving a large amount of a aqueous polymer to produce an external continuous phase, emulsifying the oil phase polymer solution and the external continuous phase, and removing the external continuous phase and the solvent and carrying out drying.
[0042] The core-shell PCM microcapsule preferably has an average particle site of 0.05 μm to 50 μm.
[0043] The PCM of the present invention may be preferably at 5 wt % to 90 wt % with respect to a total weight of the microcapsule composition. As the PCM, n-octacosane, n-heptacosane, n-hexacosane, n-pentacosane, n-tetracosane, n-tricosane, n-docosane, n-heneicosane, n-eicosane, n-nonadecane, n-octadecane, n-heptadecane, hexadecane, n-pentadecane, n-tetradecane, n-tridecane, and the like, and derivatives or composites thereof may be used alone or in combination, and materials which undergo phase transition at 45-70° C. such as stearic acid may be also used. In particular, an optimal PCM which is effective in lowering a skin temperature in the cooling cosmetic field is n-octadecane and n-eicosane having a melting point of 28-35° C., and it is characterized that these are used alone or n-docosane having a melting point of 44° C. is mixed with n-octadecane at a constant ratio to prepare and use paraffin having a melting point corresponding to a skin temperature change range.
[0044] As the shell material of the present invention, polycaprolactone, polylactic acid, water-insoluble cellulose, polyhydroxybutyrate, and aliphatic-based unsaturated polyester compounds which are biodegradable polymers may be used alone or in combination.
[0045] In addition, the core-shell PCM microcapsule of the present invention may contain a functional substance inside the capsule. Here, as the functional substance, menthol, a natural oil, a synthetic oil, an essential oil, a fragrance, a vitamin, a ceramide, an organic UV absorber, and the like may be used and may be applied at a weight ratio of 1 to 90 with respect to the weight of the PCM, but considering the cooling effect by the PCM, may be preferably applied at a weight ratio of 1 to 50 with respect to the weight of the PCM.
[0046] Meanwhile, the cosmetic composition for external skin according to the present invention is prepared by including 0.1 wt % to 30 wt % of the core-shell PCM microcapsule with respect to the total weight of the cosmetic composition.
[0047] Hereinafter, the Examples and the Comparative Examples of the present invention will be described in more detail, but the following Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto only.
PREPARATION EXAMPLE 1: PREPARATION OF MICROCAPSULE
Example 1
[0048] An oil phase polymer solution was prepared by completely dissolving 4 g of polylactic acid and 6 g of a PCM (n-octadecane) in 80 g of a dichloromethane solvent using an agitator, and an external continuous phase was prepared by dissolving 2 g of polyvinyl alcohol in 98 g of distilled water.
[0049] The thus-prepared oil phase polymer solution and external continuous phase were mixed and emulsified at 4000 rpm of a homomixer for 5 minutes, stirred at a speed of 500 rpm so that the dichloromethane solvent was completely removed, washed and filtered with distilled water, and dried in a vacuum dry oven to prepare a core-shell PCM microcapsule in the form of white powder.
Example 2
[0050] A core-shell PCM microcapsule was prepared in the same manner as in Example 1, except that the PCM and the polylactic acid were added and dissolved at a ratio of 5:5 in the oil phase polymer solution.
Example 3
[0051] A core-shell PCM microcapsule was prepared in the same manner as in Example 1, except that the PCM and the polylactic acid were added and dissolved at a ratio of 4:6 in the oil phase polymer solution.
Experimental Example 1
[0052] A schematic diagram representing a preparation process of the core-shell PCM microcapsule according to Example 1 is shown in
[0053] As shown in
[0054] In addition, as shown in
Experimental Example 2
[0055] In order to confirm a stable phase transition cycle of the microcapsule according to a temperature change of the core-shell PCM microcapsule of Example 1, measurement was performed with a differential scanning calorimeter (DSC), a cycle test in which a heating temperature was changed from −60° C. to 70° C..fwdarw.−60° C..fwdarw.70° C..fwdarw.−60° C. was performed, and the measurement results are shown in the graph of
[0056] As shown in
Experimental Example 3
[0057] The core-shell PCM microcapsules prepared according to Examples 1, Example 2, and Example 3 of the present invention were thermally analyzed using a differential scanning calorimeter and the measurement results are shown in Table 1.
TABLE-US-00001 TABLE 1 Melting onset Melting Melting end Melting PCM temperature temperature temperature enthalpy content in Classification (° C.) (° C.) (° C.) (Jg.sup.−1) (%) n-Octadecane 28.1 29.9 32.8 248.4 Polylactic acid 167.3 173.4 176.8 48.4 (PLA) Example 1 PCM 27.4 29.8 32.3 151.8 61.1 PLA 166.3 171.2 174.7 19.2 39.7 Example 2 PCM 27.7 30.5 34.2 133.5 53.7 PLA 165.9 171.0 175.2 23.9 49.4 Example 3 PCM 27.6 29.4 31.6 107.2 43.2 PLA 166.5 171.3 175.0 30.7 63.4
[0058] As shown in Table 1, it was confirmed that the content of the PCM core material in the PCM microcapsule in the form of a core-shell was 61.1% in Example 1 in which a ratio of PCM:polylactic acid was applied as 6:4, which shows that the PCM was present at a very high content in the microcapsule, and a supercooling phenomenon did not occur though a nucleator which is commonly added for preventing a supercooling phenomenon was not used.
[0059] In addition, as in Example 2, when a ratio of PCM:polylactic acid was lowered to 5:5, the content of the PCM in the microcapsule was found to be 53.7%, and when a ratio of PCM:polylactic acid was lowered to 4:6 as in Example 3, the content of the PCM in the microcapsule was found to be 43.2%, and thus, it was confirmed that the content of the PCM in the microcapsule was adjustable by adjusting the ratio of PCM:polylactic acid.
Example 4
[0060] A microcapsule was prepared in the same manner as in Example 1, except that as the PCM, n-octadecane and n-eicosane were mixed at a ratio of 3:7 and used in the oil phase polymer solution.
Example 5
[0061] A microcapsule was prepared in the same manner as in Example 1, except that as the PCM, n-eicosane was used alone in the oil phase polymer solution.
Experimental Example 4
[0062] An SEM image in which the forms of the core-shell PCM microcapsules prepared according to Example 4 and Example 5 may be confirmed is shown in
[0063] As shown in
Experimental Example 5
[0064] The core-shell PCM microcapsules prepared according to Example 4 and Example 5 of the present invention were thermally analyzed using a differential scanning calorimeter and the measurement results are shown in Table 2.
[0065] In addition, in order to confirm a stable phase transition cycle of the microcapsule according to a temperature change of the core-shell PCM microcapsule prepared according to Example 4, measurement was performed with a differential scanning calorimeter (DSC), a cycle test in which a heating temperature was changed from −60° C. to 200° C..fwdarw.−60° C..fwdarw.200° C..fwdarw.−60° C. was performed, and the measurement results are shown in the graph of
TABLE-US-00002 TABLE 2 PCM T.sub.om T.sub.pm T.sub.em H.sub.m content in Classification (° C.) (° C.) (° C.) (Jg.sup.−1) capsule (%) n-Octadecane 28.1 29.9 32.8 248.4 n-Eicosane 34.9 37.2 39.8 223.9 Polylactic acid 167.3 173.4 176.8 48.4 (PLA) Example 4 PCM 29.7 32.9 35.1 132.5 57.3 PLA 166.5 171.3 175.0 19.8 40.9 Example 5 PCM 27.7 30.5 34.2 133.5 57.7 PLA 166.5 171.8 175.8 18.9 39.0
[0066] As shown in Table 2, the contents of the PCM core material in the core-shell PCM microcapsules prepared using the mixed PCM according to Example 4 and Example 5 were 57.3% and 57.7%, and it was confirmed that the microcapsules were prepared so that the ratio of PCM:polylactic acid was close to 6:4 similarly to the case of Example 1 in which the microcapsule was prepared using a single PCM.
[0067] As shown in
[0068] In addition, as a result of preparing the microcapsule by mixing and using two types of PCM at a constant ratio, it was confirmed that core-shell PCM microcapsules having different melting temperature properties from the used two type of PCMs without a supercooling phenomenon which may cause loss of latent heat accumulation ability were prepared.
[0069] Therefore, it was confirmed that the core-shell PCM microcapsule which allows melting temperature control and has melting temperature properties appropriate for being applied to skin in summer or cooling functional clothing may be prepared by the preparation process.
Example 6
[0070] A microcapsule was prepared in the same manner as in Example 1, except that ethyl cellulose was used instead of polylactic acid as the wall material in the oil phase polymer solution.
Experimental Example 5
[0071] The SEM and TEM images of the PCM microcapsule prepared according to Example 6 were confirmed and are shown in
[0072] As shown in
Example 7
[0073] A microcapsule was prepared in the same manner as in Example 1, except that a citron essential oil as a functional substance was used at a ratio of 1:1 wt % together with the PCM as the core material and polylactic acid or ethyl cellulose was used as the shell material in the oil phase polymer solution.
Experimental Example 6
[0074] The SEM image of the citron essential oil-containing PCM microcapsule prepared according to Example 7 was confirmed and is shown in
[0075] As shown in
Example 8
[0076] A microcapsule was prepared in same manner as in Example 1, except that menthol which is used as a general purpose cooling agent in the cosmetic field was added at 10 wt % with respect to the wt % of the PCM together with the PCM as the core material and a ratio of menthol-containing PCM:polylactic acid=6:4 or 3:7 was applied in the oil phase polymer solution.
Experimental Example 7
[0077] The SEM image of the menthol-containing PCM microcapsule prepared according to Example 8 was confirmed and is shown in
[0078] As shown in
<PREPARATION EXAMPLE 2>PREPARATION OF COSMETIC COMPOSITION FOR EXTERNAL SKIN
Example 9: Preparation of BB Cream Formulation
[0079] The PCM microcapsule of Example 1 was mixed as the cooling agent and stirring was performed to prepare a BB cream formulation in the form of a cream formulation to be applied to skin. The specific components and contents of the BB cream formulation are shown in Table 3. The preparation process of each formulation proceeded in the following order:
[0080] (1) an oil phase mixture was stirred at a speed of 500-700 rpm for 5 minutes under a heating condition of 70-80° C. to be completely dissolved;
[0081] (2) a powder phase was mixed with the mixture obtained in the step (1) and stirring was performed at 600-800 rpm using a homomixer so that the mixture was uniformly dispersed;
[0082] (3) an aqueous phase mixture which was completely dissolved by stirring at a stirring speed of 2800-3500 rpm for 5 minutes at 70-80° C. using a homomixer was mixed with the mixture in which the powder phase was dispersed obtained in the step (2) and stirring was performed;
[0083] (4) the mixture obtained in the step (3) was cooled to 45° C., mixed with a fragrance, stirred at 2800-3500 rpm for 5 minutes, and cooled to 30° C.; and
[0084] (5) the PCM microcapsule was added portionwise to the mixture obtained in the step (4) and dispersed to prepare the liquid phase cosmetic composition.
TABLE-US-00003 TABLE 3 Comparative Example Example Components (unit, wt %) (unit, wt %) Cyclopentasiloxane, cyclohexylsiloxane 15.00 15.00 Neopentylglycol diethylhexanoate 4.00 4.00 Butyleneglycol dicaprylate/dicaprate 4.00 4.00 Pentyl triraethicone 8.00 8.00 Ethylhexyl methoxycinnamate 4.00 4.00 PEG-10 dimethicone 3.00 3.00 Cetyl PEG/PPG-10/1 dimethicone 1.00 1.00 Diisostearyl maleate 0.50 0.50 Tocopheryl acetate 1.00 1.00 Disteadimonium hectorite, propylene 3.00 3.00 carbonate, cyclopentasiloxane Titanium dioxide, disodiumstearoyl 12.68 12.68 glutamate, aluminum hydroxide Nylon-12 1.56 1.56 Iron oxide, triethoxycaprylsilane 1.35 1.35 Water 18.88 18.88 1,3-BG 10.00 10.00 1,2-hexanediol 0.50 0.50 Glycerin 6.00 6.00 Fragrance Appropriate Appropriate amount amount PCM microcapsule 3.00
Comparative Example 1
[0085] A BB cream formulation was prepared in the same manner as in Example 9, except that the PCM microcapsule was not contained in the BB cream formulation as the cooling agent.
Example 10: Preparation of Sunscreen Formulation
[0086] The PCM microcapsule of Example 1 was mixed as the cooling agent and stirring was performed to prepare a sunscreen formulation in the form of a cream formulation to be applied to skin. The specific components and contents of the sunscreen formulation are shown in Table 4. The preparation process of each formulation proceeded in the following order:
TABLE-US-00004 TABLE 4 Example Comparative (unit, Example Components wt %) (unit, wt %) Ethylhexyl methoxycinnamate 7.00 7.00 Butyleneglycol dicaprylate/dicaprate 4.00 4.00 C12-15 alkyl benzoate 3.00 3.00 Bis-ethylhexyloxyphenol 3.00 3.00 methoxyphenyl triazine Diethylaminohydroxylbenzoyl 2.50 2.50 hexyl benzoate Cetearyl alcohol, cetearyl glucoside 3.00 3.00 Cetearyl alcohol 1.00 1.00 Polysorbate 60 1.00 1.00 Ethylhexyl triazone 0.0 0.50 Tocopheryl acetate 0.10 0.10 Sorbitan isostearate 0.50 0.50 Water 49.82 49.32 Dipropylene glycol 6.00 6.00 1,2-hexanediol 1.50 1.50 Allantoin 0.10 0.10 Butyleneglycol 1.00 1.00 Glycerin 0.50 0.50 Titanium dioxide 6.00 6.00 PCM microcapsule 3.00
[0087] (1) as oil phase mixture was stirred at a speed of 500-700 rpm for 5 minutes under a heating condition of 70-80° C. to be completely dissolved;
[0088] (2) an aqueous phase mixture was stirred at a speed of 500-700 rpm for 5 minutes under a heating condition of 70-80° C. to be completely dissolved;
[0089] (3) the mixture obtained in the step (1) was mixed with the mixture obtained in the step (2) at 75° C. slowly at a stirring speed of 3000-3500 rpm and stirring was performed for 3 minutes;
[0090] (4) a C-phase mixture was added to the mixture obtained in the step (3) and stirring was performed at 75° C. at a stirring speed of 3000-3500 rpm for 3 minutes;
[0091] (5) a raw material D was added to the mixture of the step (4) and stirring was performed at 75° C. at a stirring speed of 3000-3500 rpm for 3 minutes; and
[0092] (6) the PCM microcapsule was added portionwise to the mixture obtained in the step (5) and dispersed to prepare the liquid phase cosmetic composition.
Comparative Example 2
[0093] A sunscreen formulation was prepared in the same manner as in Example 10, except that the PCM microcapsule was not contained in the sunscreen formulation as the cooling agent.
Comparative Example 3
[0094] A sunscreen formulation was prepared in the same manner as in Example 10, except that menthol which is a commonly used cooling component was used as the cooling agent instead of the PCM microcapsule in the sunscreen formulation.
Experimental Example 8: Skin Temperature Lowering Test When Applied to Skin
[0095] In order to measure the skin cooling functionality of the cosmetic composition for external skin prepared according to Example 9, Example 10, Comparative Example 1, Comparative Example 2, and Comparative Example 3, the cooling formulation was applied to skin after waiting for 20 minutes under an isothermal-isohumidity environment of 25° C. and 50%, a skin temperature decrease and duration were measured, and a skin temperature change before and after applying the cooling formulation to skin was measured using an infrared thermal imaging camera (SEEK THERMAL, USA).
Experimental Example 8-1
[0096] Each of the BB cream formulation containing the PCM microcapsule prepared according to Example 9 and the BB cream formulation containing no PCM microcapsule of Comparative Example 1 was applied to a forearm area, skin temperature lowering and duration were measured, and the results are shown in the graph of
[0097] As shown in
[0098] As such, it was confirmed that when the PCM microcapsule prepared in the Example of the present invention was applied to the BB cream formulation, the formulation may have an excellent skin cooling function and durability.
Experimental Example 8-2
[0099] Each of the sunscreen formulation containing the PCM microcapsule prepared according to Example 10 and the sunscreen formulation containing no PCM microcapsule of Comparative Example 2 was applied to a forearm area, skin temperature lowering and duration were measured, and the results are shown in the graph of
[0100] In addition, a skin temperature change before and after application to a forearm area was measured with a thermal imaging camera and is shown in
[0101] As shown in
[0102] As such, it was confirmed that when the PCM microcapsule prepared in the Example of the present invention was applied to the sunscreen formulation, the formulation may have an excellent skin cooling function and durability.
Experimental Example 8-3
[0103] Each of the sunscreen formulation containing the PCM microcapsule prepared according to Example 10 and the sunscreen formulation containing no PCM microcapsule of Comparative Example 2 was long-term stored in an oven at 50° C. for 5 weeks and then formulation stability was observed, and after applying the formulation to a forearm area for confirming the cooling functionality, skin temperature lowering and duration were measured and the results are shown in the graph of
[0104] As shown in
Experimental Example 8-4
[0105] Each of the sunscreen formulation containing menthol prepared according to Comparative Example 3 and the sunscreen formulation of Comparative Example 2 was applied to a forearm area, skin temperature lowering and duration were measured, and the results are shown in the graph of
[0106] As shown in
[0107] As such, it was confirmed that when the PCM microcapsule prepared in the Example of the present invention served to have excellent cooling feeling and durability in the sunscreen formulation.
[0108] As described above, although the present invention has been described with reference exemplary embodiments and the accompanying drawings, it would be appreciated by those skilled in the art that the present invention is not limited thereto but various modifications and alterations might be made without departing from the scope defined in the range of equivalents of the following claims.