KR100485337B1 - Retinol Liquid Crystal Composition, and Cosmetic Composition and Medicine Composition Comprising It - Google Patents

Abstract

The present invention relates to a retinol liquid crystal composition for stabilizing a retinol or a derivative thereof and a cosmetic composition comprising the same. The retinol liquid crystal composition according to the present invention comprises 0.1 to 50% by weight of a retinol or a derivative thereof to stabilize a retinol or a derivative thereof. , 0.1 to 50.0% by weight of crystal forming material, 0.1 to 20.0% by weight of lecithin and 0.01 to 10% by weight of antioxidant.

Using the retinol liquid crystal composition and the cosmetic composition comprising the same according to the present invention, not only improves skin permeability and stability of the liquid crystal, but also allows the antioxidant to directly contact skin useful substances such as retinol by interaction of the antioxidant and lecithin. It is possible to prevent the oxidation of useful skin material. This can improve the stability of cosmetics, pharmaceuticals, and similar medicines containing the skin-utilizing substance by preventing discoloration, malodor, and degeneration of the skin-utilizing substance. That is, various skin useful substances, such as retinol, tocopherol or arbutin, which are useful but have high oxidative properties, can be easily contained in the cosmetic composition in a stable state, thereby improving wrinkles of skin useful substances, inhibiting aging of the skin, and preventing damage caused by ultraviolet rays. The skin protection effect such as can be sufficiently exhibited.

Description

Retinol Liquid Crystal Composition, and Cosmetic Composition and Medicine Composition Comprising It}

The present invention relates to a retinol liquid crystal composition. More particularly, the present invention relates to liquid crystal compositions for imparting stability to substances such as retinol, which are useful for skin but unstable.

Retinoids have been widely used for improving acne, skin wrinkle improvement and prevention, blemishes, and freckles. Retinoids used in skin care cosmetics include retinol, retinic acid and retinal. Among them, retinol or retinyl short-chain esters are known to be more effective than retinic acid. Retinol is vitamin A, an endogenous compound that occurs naturally in the human body and is essential for the differentiation of normal subcutaneous cells. Retinyl short chain esters are hydrolyzed in the body to produce retinol. However, despite showing the above excellent effects, the retinol is easily oxidized in the air or in an aqueous solution, causing discoloration and odor, and lowering the titer. Thus, until now, retinol has been extremely limited in its use in cosmetics.

In addition to the retinol and its derivatives, skin useful substances such as tocopherol and its derivatives, vitamin F and its derivatives, unsaturated fatty acids and arbutin are also easily oxidized in the air or in aqueous solutions. Therefore, there is an urgent need for a method for stabilizing such useful skin substances.

On the other hand, the liquid crystal has a relatively less molecular mobility than the liquid phase due to the regular orientation between the molecules, and thus has a unique property such as light scattering and crystallinity properties. Due to such relatively low intermolecular molecular mobility, the liquid crystal exhibits a property of improving the stability of an unstable substance in the fields of cosmetics, medicines, and similar medicines.

Liquid crystals consisting of cetyl alcohol, stearyl alcohol, octyl dodecanol, and nonionic surfactants have been known for many years (MMRieger, "Surfactant in Cosmetics", Mercel Dekker, INC, New York, 1985). It has been used for a long time to improve. However, the liquid crystal having the composition described above was only used to improve the hardness of the product, and could not be expected to improve the functionality on the product.

However, recently, it has been known that liquid crystals are formed by ceramides, cetyl alcohols, stearyl alcohols, cholesterol, nonionic surfactants, and the like, and liquid crystals having such a composition form a structure similar to the constituent form of skin intercellular lipids. It has been found to form a moisturizing film similar to a protective film to effectively moisturize and protect the skin. In addition, these liquid crystals have been found to contribute to improving the stability of the product by improving the stability of the skin useful material. The effect of such liquid crystals is disclosed in Korean Patent No. 0040578.

However, in the case of the liquid crystal composed of ceramide, cetyl alcohol, stearyl alcohol, cholesterol, nonionic surfactant and the like and liquid crystal composed of cetyl alcohol, stearyl alcohol, octyl dodecanol, nonionic surfactant and the like, the oxidizing property is the same as that of retinol. When it contains this high skin useful substance, the ability to prevent oxidation of the substance is poor, so there are many problems in using it as a product.

Meanwhile, there have been attempts to use lecithin for increasing skin permeability of cosmetics or medicines. A description of the skin permeation enhancing effect of lecithin is disclosed in WO9523780 and Effect of Egg Yolk Lecithinsand Commercial Soybean Lecithins on In Vitro Skin Permeation of Drugs , Journal of Controlled Release, Vol. 14 (1990), pp.243-252. have. However, when lecithin was used as the base of the product, there was a problem in using the product due to the instability of the lecithin itself.

Meanwhile, to stabilize the retinol, ascorbic acid, sodium sulfite, sodium metasulfite, sodium hydrogen sulfite, sodium thiosulfite, sodium formaldehyde sulfoxylate, isocorbic acid, thioglycerol, thiosorbitol, thiourea, thioglycolic acid Attempts have been made to use cysteine hydrochloric acid, 1,4-diazobicyclo- (2,2,2) octane, DL-α-tocopherol and the like. Such attempts are disclosed in US Pat. Nos. 3,906,108, 4,247,547 and 4,720,353.

However, none of the above documents mentions liquid crystals containing antioxidants to further stabilize the liquid crystals and to increase the stability of unstable lecithins and skin useful substances at the same time.

The present invention is to solve the above problems, an object of the present invention is to improve the skin permeability of the cosmetic composition and the stability of the liquid crystal, and to make the antioxidant of the skin useful substances by direct contact with skin useful substances such as retinol To prevent it. It aims at improving the stability of cosmetics, pharmaceuticals, and similar pharmaceutical products containing this skin useful substance by preventing discoloration, smell, and degeneration of a skin useful substance by this. That is, it is possible to easily integrate various unstable skin useful substances such as retinol, tocopherol or arbutin into the cosmetic composition in a stable state due to its high oxidative property, thereby improving wrinkles of skin useful substances, inhibiting aging of the skin and damage by ultraviolet rays. It is an object of the present invention to sufficiently exhibit skin protective effects such as inhibition.

In order to achieve the above object, the retinol liquid crystal composition according to the present invention, in order to stabilize the retinol or its derivatives, 0.1 to 50% by weight of the retinol or its derivatives, 0.1 to 50.0% by weight of the crystal forming material, 0.1 to lecithin It is characterized in that it comprises a 20.0% by weight and 0.01 to 10% by weight antioxidant.

In the retinol liquid crystal composition according to the present invention, the crystal forming material is characterized in that it comprises 0.3 to 20.0 parts by weight ceramide, 0.1 to 10.0 parts by weight of cholesterol and 1.0 to 20.0 parts by weight of cetostearyl alcohol.

In addition, the cosmetic and pharmaceutical composition according to the present invention is characterized in that it comprises 0.1 to 99% by weight of the total retinol liquid crystal composition.

Hereinafter, the present invention will be described in more detail.

Liquid crystals, also called liquid crystals, refer to quasi-crystalline phases that exhibit the structural properties of liquids in one spatial direction and regular structural properties of solids in the other direction. The organic compound breaks the crystal structure with increasing temperature. The structure between the time when the crystal structure starts to break and the time when the crystal structure is completely destroyed, that is, the time when the structure transitions from the complete crystal structure to the completely amorphous structure, is called liquid crystal. The liquid crystal has a relatively less molecular mobility than the liquid phase due to the regular orientation between molecules, and thus has a unique property such as light scattering and crystal properties. Due to such relatively low intermolecular molecular mobility, the liquid crystal exhibits a property of improving the stability of an unstable substance in the fields of cosmetics, medicines, and similar medicines.

One of the most important components in the liquid crystal composition according to the present invention is a crystal forming material. Examples of the crystal forming substance include sterols such as cholesterol, fatty acids, mixtures of soaps and fatty acids, fatty alcohols, ethoxylated derivatives of fatty acids or fatty alcohols, and the like. Especially, it is especially preferable to contain 0.3-20.0 weight part ceramide, 0.1-10.0 weight part cholesterol, and 1.0-20.0 weight part cetostearyl alcohol. Such crystal forming material is preferably included in the total liquid crystal composition of 0.1 to 50% by weight, more preferably 0.1 to 40.0% by weight.

It is preferable that the liquid crystal composition by this invention further contains ceramide as a bond formation material. Ceramides of the present invention include ceramides and sphingolipid derivatives formed by binding fatty acids to phytosphingosine produced using ceramides or microbial fermentations extracted and purified from animals or plants. Most preferred ceramide is any one or more of ceramide I to ceramide VI having the structure of formulas (1) to (6).

Content of ceramide is 0.3-20.0 weight part in all the liquid crystal compositions. Ceramide and its metabolic intermediates help collagen synthesis by signaling to the external environment of epidermal cells of the skin, inhibit skin aging by enhancing skin immunity, leading to normal skin, and It is effective in preventing elasticity loss due to evaporation and destruction of collagen.

As antioxidants used in the liquid crystal composition according to the present invention, ascorbic acid (vitamin C) and salts thereof, tocopherol (vitamin E), tocopherol sulfate, other esters of tocopherol, butylated hydroxy benzoic acid and salts thereof, 6-hydro Roxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, gallic acid and alkyl esters thereof, in particular propyl gallate, uric acid and salts thereof and alkyl esters, sorbic acid and salts thereof, ascorbyl esters of fatty acids And antioxidants such as amines (eg, N, N-diethylhydroxylamine, amino-guanidine), sulfhydryl compounds (eg, glutathione), dihydroxy fumaric acid and salts thereof. In addition, antioxidants derived from natural products, such as licorice extract, wolfberry, cinnamon, Schisandra chinensis, Sukjihwang, Korean Cheonggung, longan meat, mulberry leaf, chrysanthemum leaf rosemary extract, can also be used. The content of the antioxidant according to the present invention is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight in the whole liquid crystal composition.

The lecithin used in the liquid crystal composition according to the present invention is preferably derived from soybeans, egg yolks and seeds having a phosphatidylcholine content of 28% or more, and those obtained by physicochemical treatment and saturated with lecithin in a purified form. Lecithin stabilizes the particle structure of the internal particles formed by emulsification, and serves to harden the interfacial film of the liquid crystal. The lecithin is preferably 0.1 to 20.0 wt%, most preferably 0.1 to 5.0 wt% in the total liquid crystal composition.

In order to overcome the instability of the lecithin introduced to increase the stability of the liquid crystal, the liquid crystal composition according to the present invention may contain an antioxidant along with the lecithin, thereby significantly improving the stability of the liquid crystal. Liquid crystal compositions containing only antioxidants without lecithin have a very low effect even when a large amount of antioxidants are used due to a lack of contact area with skin useful substances. However, as in the present invention, the liquid crystal composition containing both lecithin and antioxidant exhibits excellent antioxidant effect by direct contact between the skin useful substance and the antioxidant in the liquid crystal state and at the same time, the synergistic antioxidant effect between the substances by liquid crystal formation. You can get it.

It is preferable that the liquid crystal composition by this invention contains 2 to 60 weight% of oil. Examples of the oils used in the present invention include hydrocarbons, silicone oils, silicone derivatives, higher alcohols, higher fatty acid esters, fatty alcohols, fatty acid triglycerides, animal oils, vegetable oils, cholesterol fatty acid esters, and the like, and are not particularly limited. The oil may be a mixture of various oils to achieve the purpose of controlling the solvent, feeling of use and promoting absorption of the skin. The fatty acid preferably has 8 to 28 carbon atoms of animal and plant origin.

Skin useful substances that can be applied and stabilized in the liquid crystal composition of the present invention are substances included in cosmetics, pharmaceuticals and similar medicines for skin protection. In particular, retinol and its derivatives, tocopherol and its derivatives, unsaturated fatty acids, arbutin or other vitamins, etc. are mentioned. In addition, the liquid crystal composition of the present invention can be used to stabilize various skin-soluble substances having poor oxidation stability in air and in a solvent.

The present inventors conducted the following experiment to prove the effect of the liquid crystal composition and the cosmetic composition according to the present invention.

Example

<Comparative Examples 1 and 2>

After heating the water phase and the oil phase of the composition shown in Table 1 to 75 ° C, respectively, the mixture was heated at 3,000 rpm for 3 minutes while slowly adding the heated oil phase to the heated water phase. At the end of the emulsification, it was slowly cooled to 30 ° C. with paddle mixing at 30 rpm.

division Raw material name Content (100 wt%) Comparative Example 1 Comparative Example 2 Award Purified water To 100 To 100 Concentrated glycerin 5 5 1,3-butylene glycol 3 3 Imidazolidinylurea 0.2 0.2 Disodium ID 0.0 0.2 The upper part Glycerin Monostearate One 0.8 Sorbitol Monostearate 0.3 0.3 Paraoxybenzoic Acid Ester 0.2 0.2 Liquid paraffin 5 5 Polyoxyethylene (40) Monostearate 1.5 1.5 Octyldodecanol 2 1.8 Tocopherol Acetate 0.0 0.3 Stearic acid 0.6 0.5 Triethanolamine 0.3 0.3 Retinol 0.1 0.1 Cetostearyl alcohol 2.0 1.5

<Comparative Examples 3 and 4>

The water phase part and the oil phase part having the composition shown in Table 2 were each heated to 75 ° C., and then homomixed at 3,000 rpm for 3 minutes while slowly adding the heated oil phase part to the heated water phase part. At the end of the emulsification, it was slowly cooled to 30 ° C. with paddle mixing at 30 rpm.

division Raw material name Content (100 wt%) Comparative Example 3 Comparative Example 4 Award Purified water To 100 To 100 Concentrated glycerin 5 5 1,3-butylene glycol 3 3 Imidazolidinylurea 0.2 0.2 Disodium ID 0.0 0.1 The upper part Ceramide III One 0.8 cholesterol 0.5 0.5 Paraoxybenzoic acid ester 0.2 0.2 Liquid paraffin 5 5 Polyoxyethylene (40) Monostearate 0.5 0.5 Cetostearyl alcohol 2 2 Stearic acid 0.6 0.6 Retinol 0.1 0.1 Tocopherol acetate 0.1 0.3

<Examples 1 and 2>

The oil phase having the composition shown in Table 3 below was heated to 80 ° C. to confirm whether the oil phase was completely dissolved. Thereafter, the aqueous phase heated to 70 ° C. in advance was homomixed at 3,000 rpm for 3 minutes while gradually adding to the oil phase portion. The aqueous phase was added completely to the oil phase and then slowly cooled to 30 ° C. with paddle mixing at 20 rpm.

division Raw material name Content (100 wt%) Example 1 Example 2 Award Purified water To 100 To 100 Concentrated glycerin 5 5 1,3-butylene glycol 3 3 Imidazolidinylurea 0.2 0.2 The upper part Stearic acid 0.6 0.5 Lecithin 2 1.5 Squalane 2 2 Macadamia Nuts 3 3 Cetostearyl alcohol 2 2 Paraoxybenzoic acid ester 0.2 0.2 Tocopherol Acetate 0.0 0.3 Ceramide III 1.0 0.8 cholesterol 0.5 0.4 Retinol 0.1 0.1

The present inventors experimented as follows to measure the stability of each liquid crystal composition prepared in Comparative Examples 1 to 4, Examples 1 to 2.

Experimental Example 1

While storing each composition at room temperature, the stability of each liquid crystal immediately after each composition was produced, after 1 week, and after 4 weeks was generated using a Nikon Microphot-FXA polarized light microscope. Was observed. The results are shown in Table 4 below.

division LCD stability Immediately after creation 1 week later 4 weeks later Comparative Example 1 4 2 One Comparative Example 2 4 2 One Comparative Example 3 4 3 2 Comparative Example 4 4 3 2 Example 1 4 4 3 Example 2 4 4 4

(Very stable: 4, stability: 3, anxiety: 2, a liquid crystal is not seen: 1)

As shown in Table 4, it can be seen that the effect of Example 1 and Example 2 is excellent. Therefore, it was found that the liquid crystal composition according to the present invention has higher stability of the liquid crystal than the conventional liquid crystal composition. That is, it can be concluded that a liquid crystal composition containing both lecithin and an antioxidant has higher stability than a liquid crystal composition that is not.

In addition, the polarization micrograph of the liquid crystal composition prepared in Example 2 is shown in FIG. As shown in Figure 1, it was found that the liquid crystal composition according to the present invention is very stable.

The present inventors conducted the following experiment to prove the effect of the liquid crystal composition according to the present invention on the stability of the skin useful material.

Experimental Example 2

Stability was measured after 0.1 wt% of retinol was added to each of the liquid crystal compositions prepared in Comparative Examples 1 to 4 and Examples 1 and 2 above. The stability was measured for absorbance at 325 nm by retinol titer immediately after preparation and retinol titer after being left at 45 ° C. for 1 month. The results are shown in Table 5 below.

division Retinol titer Immediately after creation 4 weeks later Comparative Example 1 95.2% 60.2% Comparative Example 2 96.4% 69.3% Comparative Example 3 97.3% 72.1% Comparative Example 4 98% 77.3% Example 1 98% 85.2% Example 2 98.5% 88.7%

As shown in Table 5, when the retinol is contained in the existing liquid crystal base, the retinol titer drops considerably with time, but when retinol is added to the liquid crystal composition base according to the present invention, four weeks pass. Titers were found to be significantly conserved. Therefore, when lecithin is included, antioxidants have a greater effect on the stability of skin useful substances.

The present inventors conducted the following experiment to prove that the liquid crystal composition according to the present invention has an effect of restoring damage in actual skin.

Experimental Example 3

After measuring the evaporation of skin moisture on both the back of 8-12 week old hairless mice (initial value of about 10 ± 2), the skin moisture was repeated about 5 to 10 times by attaching and removing the scotch tape at the same position. It continued until the evaporation amount was about 40-50. After damage to the dorsal skin of the hairless mouse, the liquid crystal compositions prepared in Comparative Examples 1 to 4 and Examples 1 to 2 at 12 hour intervals, that is, immediately after injury, after 12 hours, after 24 hours, and After 36 hours, it was applied to the skin of one of the injured mice (experimental group). There was no treatment on the other back (control). For each of the experimental group and the control group, the amount of evaporation of water according to the passage of time (initial, immediately after injury, after 2 hours, after 6 hours, after 24 hours, and after 48 hours) was measured to restore the skin barrier ( % recovery) was calculated. The results are shown in Table 6 below.

0 hours 6 hours 24 hours 48 hours Comparative Example 1 0 38 71 83 Comparative Example 2 0 42 74 87 Comparative Example 3 0 43 82 94 Comparative Example 4 0 42 84 93 Example 1 0 47 88 96 Example 2 0 48 89 98

As shown in Table 6, it was found that the damaged skin restoration effect of the liquid crystal composition according to the present invention is superior to the conventional liquid crystal composition.

Using the retinol liquid crystal composition and the cosmetic composition comprising the same according to the present invention, not only improves skin permeability and stability of the liquid crystal, but also allows the antioxidant to directly contact skin useful substances such as retinol by interaction of the antioxidant and lecithin. It is possible to prevent the oxidation of useful skin material. This can improve the stability of cosmetics, pharmaceuticals, and similar medicines containing the skin-utilizing substance by preventing discoloration, malodor, and degeneration of the skin-utilizing substance. That is, various skin useful substances, such as retinol, tocopherol or arbutin, which are useful but have high oxidative properties, can be easily contained in the cosmetic composition in a stable state, thereby improving wrinkles of skin useful substances, inhibiting aging of the skin, and preventing damage caused by ultraviolet rays. The skin protection effect such as can be sufficiently exhibited.

1 is a polarized light micrograph of a liquid crystal composition according to the present invention.

Claims (11)

delete  In order to stabilize the retinol or derivatives thereof, 0.1 to 50% by weight of retinol or derivatives thereof is included, together with 0.1 to 50.0% by weight of crystal forming material, 0.1 to 20.0% by weight of lecithin and 0.01 to 10% by weight of antioxidant. The crystal forming material is 0.3 to 20.0 parts by weight of ceramide, 0.1 to 10.0 parts by weight of cholesterol and 1.0 to 20.0 parts by weight of cetostearyl alcohol, characterized in that the retinol liquid crystal composition. The retinol liquid crystal composition according to claim 2, wherein the lecithin is obtained by purifying or saturating lecithin derived from soybean, egg yolk and seed having a phosphatidylcholine content of 28% by weight or more. The method of claim 2, wherein the antioxidant is ascorbic acid and salts thereof, tocopherol, tocopherol sulfate, other esters of tocopherol, butylated hydroxy benzoic acid and salts thereof, 6-hydroxy-2,5,7,8- Tetramethylchroman-2-carboxylic acid, gallic acid and alkyl esters thereof, uric acid and salts thereof and alkyl esters, sorbic acid and salts thereof, ascorbyl esters of fatty acids, amines, sulfhydryl compounds, dihydroxy fumaric acid and salts thereof, Retinol liquid crystal composition, characterized in that at least one antioxidant selected from the group consisting of licorice extract, wolfberry, cinnamon, Schisandra chinensis, Sukjihwang, Korean Cheonggung, longan, mulberry leaf, chrysanthemum leaf and rosemary extract. The retinol liquid crystal of claim 2, wherein the ceramide is one or more ceramides selected from the group consisting of ceramides derived from animals or plants, ceramides and sphingolipid derivatives in which fatty acids are bound to phytosphingosine produced by microbial fermentation. Composition. The retinol liquid crystal composition according to claim 5, wherein the ceramide is ceramide having a structure of any one of Formulas 1 to 6. Formula 1 (Formula 2) (Formula 3) (Formula 4) (Formula 5) (Formula 6) delete delete delete Cosmetic composition, characterized in that it comprises 0.1 to 99% by weight per total weight of the retinol liquid crystal composition according to any one of claims 2 to 6. A pharmaceutical composition comprising 0.1 to 99% by weight per total weight of the retinol liquid crystal composition according to any one of claims 2 to 6.