KR101541400B1 - UV light absorbing emulsifiers - Google Patents

Abstract

The present invention relates to a UV light-absorbing emulsifier prepared by covalently bonding an ultraviolet absorbing functional group to a surfactant, and the ultraviolet absorbing emulsifier of the present invention is characterized by having ultraviolet absorbing ability and emulsifying ability at the same time.

Description

UV light absorbing emulsifiers < RTI ID = 0.0 >

The present invention relates to an ultraviolet absorbing emulsifier, and more particularly, to a UV light-absorbing emulsifier having both an ultraviolet absorbing ability and an emulsifying ability.

When the sun's ultraviolet rays are irradiated on the skin, some of them are reflected or scattered by the stratum corneum, but ultraviolet rays that are not blocked here penetrate into the skin. The ultraviolet rays are divided into 240-280 nm as UVB, 280-320 nm as UVB, and 320-400 nm as UVA. UVC disappears while passing through the ozone layer and UVB penetrates to the epidermis, Edema and the like. UVA penetrates into the dermis of the skin, promoting skin cancer, wrinkles and melanin formation, and is known to cause skin aging and skin irritation.

On the other hand, in order to produce lotions and creams having an ultraviolet blocking effect, an emulsifier must be added in an emulsification step, and a UV protecting agent must be added to the emulsion independently. However, the conventional manufacturing method as described above is not only troublesome, but also has a problem that the composition is not well mixed. In addition, the ultraviolet shielding composition thus prepared has disadvantages in that the oil layer is separately used after a lapse of time.

On the other hand, cinnamic acid (CA) is one of aromatic unsaturated carboxylic acids, which is obtained from cinnamon, balsams and shea buffer, which are natural substances, and can also be chemically synthesized. Generally, Shinnam acid is used as a raw material for spices and pharmaceuticals, and Shinnam acid ester derivative is used for perfume [1. M. D. Hilton, W. J. Cain, Appl. Environ. Microbio. 1990, 56, 3623; 2. G. C. Yen, Y. L. Chen, F. M. Sun, Y. L. Chiang, S. H. Lu, C. J. Weng, Eur. J. Pharm. Sci. 2011, 44 (3), 281.].

Upon irradiation with ultraviolet rays, (2 + 2) cycloaddition occurs to form a cinnamic acid dimmer, and the formed dimmer can be photo-cleaved reversibly (J. He, Y. Zhao, Dyes and Pigments, 2011, 89 (3), 278.]. Several types of photoreactive drug delivery systems have been developed using these photochemical properties of Shin-Nam-san [H. J. Seo, J. C. Kim, J. Nanosci. Nanotechnol. 2011, 11, 10262.].

In addition, cinnamic acid and its derivatives are used as UV absorbers in cosmetics because they absorb a wide range of ultraviolet light, have a high extinction coefficient, and are less toxic to humans (T. Mitsui (Ed.), Shin-Keshouhin-Gaku (New Cosmetics Learning), second ed., Nanzando (Tokyo), 2001, p. 154.].

Accordingly, the inventors of the present invention have made intensive studies on an ultraviolet absorbing emulsifier having both an emulsifying ability and an ultraviolet absorbing ability by using an ultraviolet absorbing functional group including cinnamic acid. As a result, the present invention has been completed.

Korean Patent No. 10-0903596, entitled " Ultraviolet protective composition for protection against harmful ultraviolet rays for health and for strengthening natural skin protective film ", is a solid polymorphic crystalline or partially crystalline lipid particle, Average value of the main group) is in the range of 100 nm to 1000 nm, and the lipid particles are present as a solid internal phase (lipid phase) dispersed in an external liquid, and the lipid particles are measured by a calorimetry method (DSC- Wherein the lipid particles are selected from the group consisting of natural and synthetic mono-, di- and triglycerides, natural and synthetic waxes, fatty alcohols, fatty alcohols, Esters and ethers thereof, carnauba waxes, cetyl palmitate, glycerol monostearate, glycerol palmitoste Characterized in that it comprises at least one member selected from the group consisting of glycerol trioleate, glycerol trioleate, light fat, hydrophilic beeswax, microcrystalline triglyceride and stearyl alcohol. Discloses an ultraviolet protective composition comprising a solid polymorphic crystalline or partially crystalline lipid particle. However, there is no description about an ultraviolet absorbing emulsifier prepared by covalently bonding an ultraviolet absorbing functional group to a surfactant. Korean Patent Laid-Open No. 10-2001-0050896 (Title of the Invention: Process for the preparation of ultraviolet absorbing composition) includes (a) at least one UV radiation-absorbing agent; And (b) one or more multifunctional monomers having at least one functional group capable of vinyl copolymerization based on the total weight of the shell portion and at least one functional group capable of reacting with reactive molecules effective to form a post- 5 to 70%, based on the total weight of non-volatile material, of a latex polymer particle comprising a shell part made from polymerization incorporating 4 to 80% monomer units, and having a SPF Enhancement Retention value of at least 40; , There is no description about the ultraviolet absorbing emulsifier prepared by covalently bonding the ultraviolet absorbing functional group to the surfactant.

An object of the present invention is to provide an ultraviolet absorptive emulsifier prepared by covalently bonding an ultraviolet absorbing functional group to a surfactant.

It is another object of the present invention to provide an ultraviolet absorptive emulsifier having both an ultraviolet absorbing ability and an emulsifying ability by covalently bonding an ultraviolet absorbing functional group to a surfactant.

In order to achieve the above object, the present invention provides an ultraviolet absorbing emulsifier having both an ultraviolet absorbing ability and an emulsifying ability, which is prepared by covalently bonding an ultraviolet absorbing functional group to a surfactant.

In the present invention, the ultraviolet absorbing functional group may be at least one selected from the group consisting of cinnamic acid, coumarin, azobenzene, spiropyran, spirooxazine, diarylethene, And fulgide are preferable.

Also, in the present invention, the surfactant may be at least one selected from the group consisting of polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, such as polyethylene alkyl ether, polyethylene alkyl ester, cyclodextrin, poly vinyl alcohol, gelatin, Pluronic F127, and Pluronic F68 F68). ≪ / RTI >

In the present invention, the ultraviolet absorbing emulsifier preferably has a ratio of the ultraviolet absorbing functional group and the surfactant in a molar ratio of 1: 1.3. If the ratio is out of the above range, the ultraviolet absorbing ability and emulsifying ability are not excellent due to the unbalance.

On the other hand, the ultraviolet absorbing emulsifier of the present invention can be prepared, for example, as follows. Tween 20 solution was prepared by dissolving 2.457 g of Tween 20 in 40 ml of benzene. Then, 1.68 ml of triethylamine (TEA) and 2 g of cinnamoyl chloride were added and mixed for 24 hours at room temperature The reaction solution is filtered, and the filtered reaction solution is dialyzed in ethanol for 2 days. Thereafter, it can be prepared by dialyzing in distilled water for 3 days and lyophilizing the purified reaction solution.

On the other hand, the ultraviolet absorbing emulsifier prepared in the above example is a Tween 20-Shinnam acid conjugate, which can maintain the surfactant activity of the surfactant and emulsify the oil phase into the water phase. After the conjugation reaction, Because the group remains intact, it can absorb ultraviolet light.

As described above, when the ultraviolet screening composition is prepared using the ultraviolet absorbing emulsifier having both the ultraviolet absorbing ability and the emulsifying ability of the present invention, the emulsifying step and the ultraviolet ray protecting agent adding step can be reduced to one step and a more stable composition can be provided .

On the other hand, the present invention provides a cosmetic composition comprising the ultraviolet absorbing emulsifier.

The components included in the sunscreen composition of the present invention may contain, as an active ingredient, components commonly used in cosmetic compositions in addition to the ultraviolet absorptive emulsifier. For example, conventional auxiliaries such as antioxidants, stabilizers, solubilizers, vitamins, pigments and flavors, and carriers.

In addition, the sunscreen compositions of the present invention can be prepared in any formulation conventionally produced in the art. But are not limited to, solutions, suspensions, emulsions, pastes, gels, creams, lotions, powders, oils, powder foundations, emulsion foundations, wax foundations and sprays. More specifically, it can be manufactured into formulations of sunscreen, supple lotion, astringent lotion, nutritional lotion, nutritional cream, massage cream, essence, eye cream, pack, spray or powder.

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According to the present invention, it is possible to provide an ultraviolet absorptive emulsifier capable of effectively stabilizing the oil / water interface simultaneously with ultraviolet absorption.

Further, according to the present invention, it is possible to provide an ultraviolet absorptive emulsifier that absorbs a wide range of ultraviolet rays, has a high ultraviolet absorption coefficient, and is low in toxicity to human body.

In addition, when a cosmetic product is manufactured using the ultraviolet absorbing emulsifier of the present invention, the emulsifying agent addition step and the ultraviolet blocking agent addition step can be reduced to one step.

Figure 1 shows the results of measurement of the interfacial tension of Tween 20 solution and Tween 20-cinnamic acid solution in the concentration range of 0.0005% (w / v) to 0.01% (w / v).
FIG. 2 shows the results of measuring the degree of photo-dimerization of Shinanamic acid and Tween 20-Shinnam acid conjugate with UV (254 nm, 6W) irradiation time.
FIG. 3 is a diagram showing the ultraviolet absorption spectra of the cinnamic acid solution (A) and the Tween 20-cinnamic acid conjugate solution (B) at 0.0046 mM, 0.0091 mM, 0.0183 mM, 0.0365 mM and 0.073 mM.
FIG. 4 is an optical microscope photograph of the emulsion prepared using Tween 20 (A) and Tween 20-Shinan acid conjugate (B) immediately after preparation (a) and after 70 hours (b).
Figure 5 shows the results of measuring the emulsion size of the emulsion prepared using Tween 20 and Tween 20-cinnamic acid conjugate over time.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following embodiments, and includes modifications of equivalent technical ideas.

Example  One: Tween  20- Shinnam-san Conjugate  Produce

Tween 20 solution was prepared by dissolving 2.457 g of Tween 20 in 40 ml of benzene. 1.68 ml of triethylamine (TEA) and 2 g of cinnamoyl chloride were added thereto to prepare a reaction mixture having a molar ratio of Tween 20: cinnamoyl chloride: triethylamine of 1: 6: 6 . The reaction mixture was reacted while mixing at room temperature for 24 hours, filtered, filtered, and dialyzed against ethanol for 2 days. At this time, the dialysis fluid was changed 6 times. Thereafter, the reaction solution dialyzed from the ethanol was dialyzed in distilled water for 3 days. At this time, the dialysis solution was changed every 6 hours. Thereafter, dialyzed with distilled water and the purified reaction solution was lyophilized to prepare a Tween 20-Shinnam acid conjugate.

Experimental Example  One: Tween  20- Shinnam-san Conjugate ^One H NMR  Measure

In this Experimental Example, the Tween 20-Shinnam acid conjugate prepared in Example 1^One≪ 1 > H NMR.

After the Tween 20-Shinnam acid conjugate prepared in Example 1 was dissolved in DMSO, ¹ H NMR was measured using a Bruker Avance 400 spectrometer.

As a result, the signal of methyl group of fatty acid residue of Tween 20 was found near 0.8 ppm, the signal of methylene group of fatty acid residue of Tween 20 was found near 1.2 ppm, and the fatty acid residue (-O-CO- CH ₂ -) signals were found near 1.5 ppm and the ethylene oxide (- CH ₂ - CH ₂ --O -) signals of Tween 20 were found near 3.2 ppm.

The signal of cinnamic acid residue (= CH ₂ -O-) was found near 6.7 ppm, the signal of aromatic proton of cinnamic acid residue was found near 7.75 ppm, and the residue of cinnamic acid (-CH ₂ ═C-CO -) signal was found near 7.65 ppm.

In addition, the peak area of the methyl group of the fatty acid residue of Tween 20 was 2.5, and the peak area of the aromatic proton of the cinnamic acid residue was 5.484. Therefore, the molar ratio of Tween 20 to the synnamic acid of the conjugate was calculated as 1: 1.3.

Experimental Example  2: Tween  20- Shinnam-san Conjugate Surfactant force  Measure

In this Experimental Example, the surfactant force of the Tween 20-Shinnam acid conjugate prepared in Example 1 was measured.

The air / water interfacial tension of the Tween 20 solution and the Tween 20-cinnamic acid conjugate solution was determined by the ring method. The ring method is a method of obtaining the interfacial tension from the process of measuring the force required to separate the ring at the interface.

Tween 20 and Tween 20-Shinnam acid conjugate were dissolved in distilled water to a concentration of 0.0005% to 0.01% (w / v). The interfacial tension of the solution was measured using a surface tension analyzer (SEO, DST 60, South Korea).

As a result, the interfacial tension rapidly decreased from 52.0 dyne / cm to 35.9 dyne / cm when the concentration of Tween 20 solution increased from 0.0005% to 0.007%. Since the critical micelle concentration of Tween 20 was 0.0073%, the interfacial tension rapidly decreased at a concentration of 0.007% or less, and the decrease of the interfacial tension was gentle at concentrations above 0.007%.

On the other hand, the tendency of the interfacial tension change according to the concentration of the Tween 20-Shinnam acid conjugate solution is similar to the tendency of the interfacial tension change according to the concentration of the Tween 20 solution. However, the interfacial tension of the Tween 20-Shinnam acid conjugate solution was lower than the interfacial tension of the Tween 20 solution at the entire concentration range tested. The above results indicate that the surfactant of the Tween 20-Shinnam acid conjugate is higher than the surfactant of Tween 20 (FIG. 1).

Experimental Example  3: Tween  20- Shinnam-san Conjugate  ore Dimerization  Measure

In this experiment, the photodimerization of the Tween 20-Shinnam acid conjugate prepared in Example 1 was measured.

Shin-Nansan and Tween 20-Shinnam acid conjugate were dissolved in distilled water to a concentration of 0.073 mM. The solution was irradiated with ultraviolet light (? = 254 nm, 6 W) for 180 minutes, and the photo-dimmerization degree was calculated using the following equation (1). Jin, X. Liu, G. Liu, J. Ji, Polym. 2010, 51, 1311.]. Absorbance was measured at 280 nm.

A ₀ : absorbance before UV irradiation

A _t : absorbance after ultraviolet irradiation for a specific period

As a result, the degree of photo - dimerization of Shin - Nam - san increased with saturation curve according to UV irradiation time, and the degree of photo - dimerization during 180 minutes was about 70%. When irradiated with ultraviolet rays, cinnamic acid is photo - dimerized by (2 + 2) cycloaddition reaction. Because photoreaction is reversible, photo-dimerization occurs with photo-cleavage. The increase in the degree of photodimerization due to the saturation curve is due to the fact that the photoreaction reaches equilibrium over time.

The degree of dimerization of the Tween 20 - Shinnam acid conjugate also increased with the saturation curve, and the degree of dimerization was higher than that of Shin - Nam - san during the entire UV irradiation period. From the above results, it was confirmed that the conjugated cinnamic acid residue can be more easily photopolymerized than the free cinnamic acid (FIG. 2).

Experimental Example  4: Tween  20- Shinnam-san Conjugate Extinction coefficient  Measure

In this experiment, the extinction coefficient of the Tween 20-Shinnam acid conjugate prepared in Example 1 was measured.

In order to obtain the UV spectrum of the Tween 20-Shinnam acid conjugate according to the concentration change, ShinNam and Tween 20-Shinnam acid conjugates were dissolved in distilled water and their molar concentrations were 0.0046 mM, 0.0091 mM, 0.0183 mM, 0.0365 mM, 0.073 mM. UV spectra were then obtained using a UV / Vis spectrophotometer (spectrophotometer 6505, Jenway, UK). The extinction coefficient at 280 nm was then calculated at each concentration and then the average extinction coefficient was determined.

As a result, the extinction coefficient of cinnamic acid at 280 nm was 14556.2 M^-Onecm^-One(Fig. 3A), and the extinction coefficient of the Tween 20-Shinnam acid conjugate was 14391.8 M^-Onecm^-One(Fig. 3B). Therefore, the change of the extinction coefficient of cinnamic acid by the conjugation reaction was not large. From the above results, it was confirmed that the photochemical properties remained even after the cinnamic acid was covalently bonded to Tween 20.

Example  2: Tween  20- Shinnam-san Conjugate  Used emulsion  Produce

In the present embodiment, Tween 20-Shinnam acid conjugate was used to prepare an emulsion for ultraviolet absorption.

As an emulsifier, 0.04 g of Tween 20-Shinnam acid conjugate was dissolved in 4 ml of distilled water to prepare an aqueous phase. 1 ml of mineral oil was added to the aqueous phase and homogenized for 1 minute in a high-speed homogenizer (Scientific Industries, G-560, USA). The emulsion was then sonicated for 2 minutes on a bath type sonicator (Ultrasonic processor, GEX-750, Sonics & Materials, USA) to prepare an emulsion using Tween 20-Shinnam acid conjugate.

Comparative Example  One: Tween  20 emulsion  Produce

In this Example, Tween 20 was used to prepare an emulsion for absorbing ultraviolet rays.

0.04 g of Tween 20 as an emulsifier was dissolved in 4 ml of distilled water to prepare an aqueous phase. 1 ml of mineral oil was added to the aqueous phase and homogenized for 1 minute in a high-speed homogenizer (Scientific Industries, G-560, USA). The emulsion was then sonicated for 2 minutes in a bath-type sonicator (Ultrasonic processor, GEX-750, Sonics & Materials, USA) to prepare an emulsion using Tween 20.

Experimental Example  5: Emulsion  Optical Microscopy

In this experiment, the emulsion prepared in Example 2 and Comparative Example 1 was photographed with an optical microscope.

Immediately after the preparation of the emulsion, an optical microscope image of the emulsion was taken using an optical microscope (Olympus, CX31-P, Tokyo, Japan) for 70 hours and droplet sizes of the emulsion were compared.

As a result, the oil droplet size of the emulsion prepared using Tween 20 was much larger after 70 hours than immediately after production (FIG. 4A). In addition, the size of the oil droplet after 70 hours in the emulsion prepared using the Tween 20-Shinan acid conjugate was slightly larger than that of the oil droplet immediately after the production but was not significantly large (FIG. 4B).

Experimental Example  6: Emulsion  Paid Droplet  Measure size

In this experimental example, the emulsion sizes of the emulsion prepared in Example 2 and Comparative Example 1 were measured and compared.

The size of emulsion droplet size was measured using IMT iSolution Lite version 9.6 (IMT i-Solution Inc., Canada) according to the elapsed time from 0 to 70 hours.

As a result, the emulsion size of the emulsion prepared using Tween 20 was 0.093 ㎛ immediately after the preparation, and the size did not change with the lapse of time during the first 10 hours. However, as the time increased from 10 hours to 70 hours, the size increased markedly from 12.8 ㎛ to 162.2 ㎛

In addition, the size of the droplets of the emulsion prepared using the Tween 20-Shinnam acid conjugate was 13.3 ㎛ immediately after preparation, and the droplet size did not change much during the first 30 hours but slightly increased for the remaining 40 hours. After 70 hours, the droplet size was 20.9 탆. (Fig. 5).

From the above results, it was confirmed that the emulsion using the Tween 20-Shinnam acid conjugate of the present invention is more stable than the emulsion using Tween 20 in terms of droplet size change.

Claims (5)

Characterized in that the twin 20-cinnamic acid conjugate having both an ultraviolet absorbing ability and an emulsifying ability is added as an emulsifying agent, and the emulsifying step and ultraviolet ray protecting agent adding step are performed in one step.
delete delete The method according to claim 1,
Wherein the molar ratio of Tween 20 to Shinmin acid in the Twin 20-Shinnam acid conjugate is 1: 1.3. delete

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