KR20140067222A - Cosmetic composition of oil in water emulsion stabilized retinoids derivative - Google Patents

Abstract

The present invention relates to an oil-in-water type emulsion cosmetic composition stabilizing retinoid derivatives, and more specifically, to an oil-in-water type emulsion cosmetic composition comprising retinoid derivatives represented by formula 1 in an oil phase, octyldodecanol and dipropylene glycol.

Description

TECHNICAL FIELD [0001] The present invention relates to an underwater type emulsion cosmetic composition stabilizing a retinoid derivative,

The present invention relates to an underwater type emulsion cosmetic composition in which a retinoid derivative is stabilized in a formulation by a single emulsification process.

Retinoids are derivatives of vitamin A and include retinol, retinal, retinoic acid, retinyl acetate, retinyl propionate, retinoic acid, Retinyl linoleate, retinyl palmitate, and the like.

However, since retinoid compounds are very unstable in light, heat, oxygen and water, stabilization is necessary for practical use, and there is a problem of cytotoxicity due to in vivo stability and adverse effects due to Retinoic Acid Receptor (RAR) . Therefore, development of retinoid derivatives that are excellent in stability, non-toxic, non-irritating, and maintained the photoaging inhibition effect has been under way.

The present applicant has developed a novel retinoid derivative having excellent collagen synthesis enhancing effect, non-irritating, non-toxic, excellent chemical stability, and superior skin absorbability, and has been registered as Korean Patent Registration No. 10-1194337.

On the other hand, a lot of studies on the stabilization of retinoid derivatives have been made. In order to minimize the contact with air and water as much as possible, cosmetics stabilizing retinoids by forming large liquid crystals using surfactants having a high phase transition temperature (Korean Patent Publication No. 10-0258674), stabilized with liposome (Korean Patent Laid-Open Publication No. 1998-703668), or by using an amphiphilic polymer having a self-assembled structure prepared by bonding a hydrophobic polyester polymer with a hydrophilic polymer Physiological activity of solubility There is a stabilized preparation using nanoparticles (Korean Patent Laid-Open Publication No. 2004-0062379) capable of stably collecting an active ingredient in an aqueous phase. Polymers are mainly used as a material capable of collecting retinoids therein. Examples of methods for encapsulating an active ingredient using the polymer include interfacial polymerization, spray drying, coacervation, solvent evaporation, and the like.

However, such a stabilization method is disadvantageous in that it is low in efficiency, economical, and time-consuming because a secondary step of applying the first preparation to the product after manufacture is accompanied.

Korea Patent No. 10-1194337 Korean Patent Registration No. 10-0258674 Korean Patent Publication No. 1998-703668 Korean Patent Publication No. 2004-0062379

The present inventors have conducted studies to stabilize retinoid derivatives directly in formulations to solve the above problems. As a result, they have found that when oil is emulsified into an underwater type by selecting the mixing ratio with an appropriate solvent using the solubility properties of retinoid derivatives, And found the present invention to be completed.

Accordingly, it is an object of the present invention to provide an underwater type emulsion cosmetic composition in which a retinoid derivative is directly stabilized in a formulation by a single emulsification process.

In order to achieve the above object,

A retinoid derivative represented by the following formula (1)

An oil-in-water type emulsion cosmetic composition comprising octyldodecanol and dipropylene glycol is provided:

[Chemical Formula 1]

(Wherein,

R ₁ and R ₂ are the same or different and each is hydrogen or a straight or branched alkyl group having 1 to 6 carbon atoms.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an oil-in-water (O / W) emulsified cosmetic composition having a long-term high-temperature stability by emulsifying a retinoid derivative by applying a mixed solvent of octyldodecanol and dipropylene glycol to an oily portion.

FIG. 1 is a photograph of dissolving a retinoid derivative in four kinds of oils, storing the mixture at room temperature for 1 month, and observing the state thereof.
Fig. 2 is a photograph of dissolving a retinoid derivative in four kinds of polyhydric alcohols, storing the solution at room temperature for one month, and observing the state thereof.
3 is a photograph showing the dissolution state of a retinoid derivative according to a content ratio of octyldodecanol and dipropylene glycol.
FIG. 4 is a graph showing the high temperature stability of an underwater type emulsion cosmetic composition according to the type of solvent in the oil phase.
FIG. 5 is a graph showing high temperature stability when a retinoid derivative is emulsified in water, liposome, or encapsulated. FIG.

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

The present invention provides an underwater type emulsion cosmetic composition in which a retinoid derivative is directly stabilized in a formulation. In general, the retinoid derivative in the cosmetic composition is stabilized in the form of liposome or encapsulation, but has a disadvantage in that the efficiency is low and the stability is not easy.

Thus, in the present invention, a retinoid derivative is stabilized in a single emulsification step by selecting and applying a specific solvent to the oil phase.

The retinoid derivative contained as an active ingredient in the composition according to the present invention has a structure represented by the following formula (1).

[Chemical Formula 1]

(Wherein,

R ₁ and R ₂ are the same or different and each is hydrogen or a straight or branched alkyl group having 1 to 6 carbon atoms.

More preferably, the retinoid derivative is represented by Formula 1 wherein R ₁ is a methyl group and R ₂ is Bis-retinamido of hydrogen is 2-methylpentane.

The retinoid derivative of Formula 1 according to the present invention can be prepared by reacting a compound of Formula 2 with a compound of Formula 3:

(2)

(3)

(Wherein,

Y is hydroxy or halogen,

R ₁ and R ₂ are the same or different and each is hydrogen or a straight or branched alkyl group having 1 to 6 carbon atoms.

In the present invention, the oily phase portion is a component added to form an internal phase of an oil-in-water type emulsion composition, and the retinoid derivative is dissolved in a mixed solvent of octyldodecanol and dipropylene glycol and applied to the oil phase.

Preferably, octyldodecanol and dipropylene glycol are used in a weight ratio of 1: 1 to 1: 2. If the content of octyldodecanol is less than the above range, the retinoid derivative can not be effectively dissolved and the dispersion stability of the water-in-oil type emulsion composition deteriorates. On the contrary, if the content exceeds the above range, the dispersion stability of the water- Use properly within the above range.

The mixed solvent of octyldodecanol and dipropylene glycol is preferably contained in an amount of 20 to 30 parts by weight based on 1 part by weight of the retinoid derivative represented by the formula (1). If the content of the mixed solvent is less than the above range, the retinoid derivative dissolves non-uniformly. On the other hand, if the content exceeds the above range, the effect of solubility increase is insignificant and the stability of the water-in-oil type emulsion composition deteriorates.

Preferably, in the oil-in-water type emulsion composition according to the present invention, the oil portion satisfies 100 wt%

(I) 0.1 to 5% by weight of a retinoid derivative represented by the formula (1)

(Ii) from 35 to 60% by weight of octyldodecanol, and

(Iii) from 35 to 60% by weight of dipropylene glycol,

.

The content of the retinoid derivative is preferably at least the above-mentioned minimum value so as to achieve the minimum skin wrinkle-improving effect, and it is preferable that the content of the retinoid derivative is lower than the maximum value in consideration of the deterioration of use feeling due to the excessive addition and applicability to various formulations . At this time, it is preferable that the content of the retinoid derivative is appropriately adjusted within the above-described range according to the content of the components contained in the formulation or cosmetic composition.

If the content of octyldodecanol and dipropylene glycol is less than the above range, it is difficult to dissolve the retinoid derivative, and it tends to be difficult to give a proper sense of softness. In addition, when it is blended above the above range, it is difficult to obtain an emulsified cosmetic composition having improved stability, and it is disadvantageously excessively bundled when it is applied to skin.

The water phase part included in the cosmetic composition of the present invention is added to form an external phase of an underwater type emulsion cosmetic composition, and is added for improving the moisturizing power and improving the feeling of use, and a moisturizer other than water is usually used.

In addition, additives such as water-soluble / usable physiologically active ingredients, preservatives, pH adjusters, fatty acids, emulsifiers, surfactants, antioxidants, sunscreens, pigments, dyes, fragrances and stabilizers And the kind and content thereof can be appropriately selected by those skilled in the art.

Preferably, a water-soluble physiologically active ingredient and a moisturizing agent and an oil-soluble physiologically active ingredient are contained in the upper part of the water.

The water-soluble and oil-soluble physiologically active ingredients are not particularly limited in the present invention, and all known active ingredients may be used. For example, as a physiologically active ingredient having a whitening effect, an oil soluble ingredient including an oil soluble licorice, ethyl ascorbyl ether,? -Bisabolol and the like is possible. In addition, an active ingredient having a wrinkle-reducing effect may be an oil-soluble ingredient such as adenosine. These water-soluble or oil-soluble physiologically active ingredients are used in an amount of 0 to 10.0% by weight, preferably 0.001 to 10.0% by weight, in the whole composition.

Usable humectants include polyhydric alcohols such as glycerin, erythritol, xylitol, maltitol glycerin, propylene glycol, 1,3-butylene glycol, sorbitol, polyglycerin, polyethylene glycol, 1,2-pentanediol and isoprene glycol; Amino acid, sodium lactate, and sodium pyrrolidonecarboxylate, and other ingredients such as xyloglucan, corn seed, carrageenan, pectin, mannan, cardan, galactan, deltansulfuric acid, glycocon, keratan sulfate, chondroitin, But are not limited to, tin sulfate, kerato sulfate, chondroitin, mucoitin sulfate, kerato sulfate, locust bean gum, succinoglucan, calonym acid, hyaluronic acid, heparan sulfate, sodium hyaluronate, collagen, mucopolysaccharide, chondroitin A water-soluble polymeric substance which is sulfuric acid; Dimethyl polysiloxane, methylphenyl siloxane; Culture supernatant of lactic acid bacteria and bifidobacteria; And a combination of these. Such a humectant is used in an amount of from 0 to 15.0% by weight, preferably from 0.5 to 10.0% by weight, in the whole composition.

The underwater type emulsifying cosmetic composition of the present invention can be used for cosmetics such as softening longevity, astringent lotion, nutritional lotion, nutritional cream, massage cream, essence, eye cream, eye essence, cleansing cream, cleansing foam, cleansing water, pack, gel, powder, body lotion, Body cream, body oil, body essence, and the like.

The method for producing the water-in-oil type emulsion composition according to the present invention is not particularly limited, and a commonly used emulsification method may be used.

Specifically,

S1) mixing the emulsifier, the moisturizing agent and the purified water to prepare a water phase;

S2) mixing the retinoid derivative, octyldodecanol, and dipropylene glycol to produce an oily portion;

S3) adding an oil phase to the water and mixing the oil phase; And

S4) cooling step.

The mixing process of S1), S2), and S3) is performed in a vacuum emulsification tank capable of temperature control and stirring by a conventional method, and stirring and heating are performed as necessary.

For example, the water phase is heated to 50 to 80 캜, preferably 65 to 75 캜, and the oil phase is heated to 50 to 80 캜, preferably 65 to 75 캜 to sufficiently dissolve other components in the oil .

The stirring is carried out in a vacuum emulsification tank at a speed of 2000 to 4000 rpm, preferably 3000 rpm for 3 to 10 minutes using a homomixer.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention.

However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples.

Experimental Example  One: Retinoid  Evaluation of Solubility of Derivatives

1,5-bis-retinamido 0.5 g of 2-methylpentane was added to 10 g of each solvent, heated until uniformly dissolved, cooled, and stored at room temperature for 1 month. The results are shown in Fig. 1 and Fig.

FIG. 1 is a photograph of dissolving a retinoid derivative in four kinds of oils, storing them at room temperature for one month, and observing the state thereof.

1, caprylic / capric triglyceride, mineral oil, and cetyl ethylhexanoate differ in that the retinoid derivatives are unevenly dissolved or precipitated, whereas octyldodecanol is dissolved uniformly Precipitation phenomenon did not occur.

Fig. 2 is a photograph of dissolving a retinoid derivative in four kinds of polyhydric alcohols, storing the solution at room temperature for one month, and observing the state thereof.

2, in the case of glycerin, butylene glycol, and propylene glycol, the retinoid derivatives dissolve non-uniformly, whereas when dipropylene glycol was used, the dissolution was uniform and the precipitation occurred a little after one month .

Experimental Example  2: Octyldodecanol  Depending on the content Retinoid  Evaluation of solubility of derivatives

0.5 g of 1,5-bis-retinamido 2-methylpentane was dissolved in 5, 10 and 15 g of octyldodecanol, respectively, and stored at room temperature for 1 month.

As a result, when 5 g of octyldodecanol was used, the retinoid derivative was dissolved heterogeneously while 10 g and 15 g were uniformly dissolved.

Experimental Example  3: Octyldodecanol and Dipropylene glycol  According to the content ratio Retinoid  Evaluation of solubility of derivatives

0.5 g of 1,5-bis-retinamido 2-methylpentane was dissolved in a mixed solvent of 1: 3, 1: 1, and 3: 1 in the respective solvents (total solvent amount 10 g) And the results are shown in Fig.

3 is a photograph showing the dissolution state of a retinoid derivative according to a content ratio of octyldodecanol and dipropylene glycol.

As shown in FIG. 3, when the content ratio of octyldodecanol and dipropylene glycol was 1: 3, precipitation occurred after one month, and when the content ratio was 3: 1, the content was unevenly dissolved.

Experimental Example  4: Retinoid  Identification of high temperature stability of derivatives

An emulsified composition was prepared from the ingredients shown in the following Table 1 through the following emulsion composition preparation method.

[Method for producing emulsion composition]

1) The water phase and the oil phase were heated to 75 ° C respectively

2) The oil phase 2 was heated to 75 ° C and uniformly mixed with the heated oil phase 1 at the same temperature

3) Homogenizer Mixed for 5 minutes at 3000 rpm

4) Gradually, after the addition, mix for 3 minutes with a homogenizer under the same conditions

5) Slow cooling, defoaming

Phase separation ingredient Content (% by weight) Example 1 Comparative Example 1 Comparative Example 2 Awards Purified water to 100 to 100 to 100 glycerin 5 5 5 Propanediol 5 5 5 Clofenine Suitable amount Suitable amount Suitable amount Remuneration 1 Methylglucose sesquistearate 2 2 2 Cetearyl alcohol One One One Squalane 3 3 3 Caprylic / capric triglyceride 2 2 2 Remuneration 2 Octyldodecanol 2 4 - Dipropylene glycol 2 - 4 Bis-retinamidomethylpentane 0.2 0.2 0.2 Increment Acrylate / C10-30 alkyl acrylate
Cross polymer 0.1 0.1 0.1 Tromethamine 0.1 0.1 0.1 adding Rosemary leaf extract 0.1 0.1 0.1 Phenoxyethanol Suitable amount Suitable amount Suitable amount

The content of retinoid derivatives was determined by HPLC analysis on the composition prepared in Example 1 and Comparative Examples 1 and 2, and detailed analysis methods and results are as follows.

The HPLC used for bis-retinamidomethylpentane analysis was a Waters model 1525 gradient system consisting of 1525 Binary HPLC Pump, 2707 Autosampler and 2998 Photodiode Array Detector. The analysis was carried out on a Shiseido capcell pak C18 (4.6 mm * 250 mm, 5 μm) column with 100% methanol as mobile phase at a flow rate of 1.0 ml / min. The peak area of bis-retinamidomethylpentane in the test solution and the standard solution was analyzed using Empower 3 Personal Single System Software under the condition of measuring wavelength of 345 nm with 10 μl each of the test solution and standard solution.

The method for preparing the sample solution and standard solution used in the above HPLC method is as follows. At this time, the sample solution was prepared from the emulsion composition stored at 45 ° C for 1 month.

Approximately 1.0 g of the emulsified composition was precisely weighed and dispersed with 10 ml of a mixed solution of ethanol and dichloromethane (1: 1), and then methanol was added to make 100 ml. Ultrasonic extraction was performed and the solution was filtered through a 0.45 μm syringe filter. Approximately 0.0020 g of amodimethylpentane standard product was precisely weighed and dissolved in 10 ml of a mixed solution of ethanol and dichloromethane (1: 1), and methanol was added again to make 100 ml.

The peak area of bis-retinamidomethylpentane in the sample solution and the standard solution was analyzed using Empower 3 Personal Single System Software at a wavelength of 345 nm with 10 μl each of the sample solution and the standard solution.

The result of the titration of the retinoid derivative was expressed as a percentage of the average content analyzed three times by the above HPLC analysis in comparison with the content of the retinoid derivative added in the composition, and the result is shown in FIG.

FIG. 4 is a graph showing the high temperature stability of an underwater type emulsion cosmetic composition according to the type of solvent in the oil phase.

Referring to FIG. 4, the titer of the retinoid derivative was different depending on the type of solvent, and when the mixed solvent of octyldodecanol and dipropylene glycol was used in the oil phase, the retinoid derivative had the highest stability at high temperature.

Experimental Example  5: According to formulation Retinoid  Identification of high temperature stability of derivatives

5-1. Liposome  Formulation Manufacturing

The ingredients in Table 2 were added to a mixer, homogeneously mixed using a homogenizer, and a liposome composition containing a retinoid derivative was prepared at 1000 atm using a high-pressure microfluidizer (US Patent 4533254) Respectively.

ingredient Content (% by weight) Purified water 30 glycerin 50 Lecithin 5 Octyldodecanol 10 Bis-retinamidomethylpentane 5

5-2. Encapsulation  Formulation Manufacturing

With the contents shown in the following Table 3, retinoid derivatives and polymethyl methacrylate dissolved in octyldodecanol were homogeneously dissolved in 30 mL of ethanol in an organic solvent and then added to purified water. When the particles were formed, the organic solvent was removed through evaporation to prepare an encapsulation formulation containing the retinoid derivative.

ingredient Content (% by weight) Octyldodecanol 5 Bis-retinamidomethylpentane 5 Polymethyl methacrylate 60 Purified water 30

5-3. Liposome  Formulation Encapsulation  Preparation of emulsified composition using formulation

The emulsion composition Comparative Examples 3 and 4 were prepared using the liposome and the encapsulation formulation as shown in Table 4 below.

ingredient Content (% by weight) Comparative Example 3 Comparative Example 4 Purified water to 100 to 100 glycerin 5 5 Propanediol 5 5 Clofenine Suitable amount Suitable amount Methylglucose sesquistearate 2 2 Cetearyl alcohol One One Squalane 3 3 Caprylic / capric triglyceride 2 2 Octyldodecanol - - Dipropylene glycol - - Bis-retinamidomethylpentane - - Acrylate / C10-30 alkyl acrylate
Cross polymer 0.1 0.1 Tromethamine 0.1 0.1 Retinoid liposome 4 - Retinoid encapsulation - 4 Rosemary leaf extract 0.1 0.1 Phenoxyethanol Suitable amount Suitable amount

In order to apply the same amount of retinoid derivatives as in Example 1, the contents of liposome and encapsulation agent were determined and Comparative Examples 3 and 4 were prepared by adding in the addition process in order to reduce factors inhibiting stabilization in the process.

The composition prepared through Example 1 and Comparative Examples 3 and 4 was stored at 45 ° C for one month, and the content of the retinoid derivative was confirmed by HPLC analysis. The results of the analysis are shown in FIG.

FIG. 5 is a graph showing high temperature stability when a retinoid derivative is emulsified in water, liposome, or encapsulated. FIG.

Referring to FIG. 5, it can be confirmed that the activity of the rayonid derivative is higher than that of the liposome and encapsulation formulation when the underwater type emulsion is maintained at a high temperature, and that the emulsion type of the underwater type can improve the stability of the retinoid derivative.

Claims (6)

A retinoid derivative represented by the following formula (1)
An underwater type emulsion cosmetic composition comprising octyldodecanol and dipropylene glycol:
[Chemical Formula 1]

(Wherein,
R ₁ and R ₂ are the same or different and each is hydrogen or a straight or branched alkyl group having 1 to 6 carbon atoms. The method according to claim 1,
Wherein R ₁ is a methyl group and R ₂ is Wherein the water-in-oil type cosmetic composition is hydrogen. The underwater type emulsion cosmetic composition according to claim 1, wherein the octyldodecanol and dipropylene glycol are in a weight ratio of 1: 1 to 1: 2. The underwater cosmetic composition according to claim 1, wherein the octyldodecanol and dipropylene glycol are contained in an amount of 20 to 30 parts by weight based on 1 part by weight of the retinoid derivative represented by the formula (1). The method according to claim 1, wherein the oil phase portion satisfies 100 wt%
(I) 0.1 to 5% by weight of a retinoid derivative represented by the formula (1)
(Ii) from 35 to 60% by weight of octyldodecanol, and
(Iii) from 35 to 60% by weight of dipropylene glycol,
Wherein the water-in-oil type emulsion cosmetic composition comprises: The composition of claim 1, wherein the composition is selected from the group consisting of softening longevity,
Sheep Cream, Massage Cream, Essence, Eye Cream, Eye Essence, Cleansing Cream, Cleansing Foam, Cleanser
Wherein the composition is any one selected from the group consisting of water, gel, powder, body lotion, body cream, body oil, and body essence.

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