JP2012031125A - Fine emulsion composition containing ultraviolet-absorbing agent, and cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a composition for a skin care preparation for external use that permits stable micronization of a sparingly soluble ultraviolet-absorbing agent and incorporation thereof as a stable nano-emulsion into a skin care preparation for external use.SOLUTION: Excellent stability and serviceability are attained, when an oily component (a liquid ultraviolet-absorbing agent solution containing a sparingly soluble ultraviolet-absorbing agent) is dispersed as a fine emulsion in an aqueous phase, by incorporating one or two or more surfactants as a constituent of the emulsion and further compounding one or two or more polyols in a specific ratio. The fine emulsion composition comprises the following components (A)-(D) as essential ingredients and has an average particle size of 350 nm or less: (A) an ultraviolet-absorbing agent, (B) a surfactant not containing a polyoxyethylene-type surfactant, (C) polyols, and (D) water.

Description

  The present invention relates to a fine emulsion composition having an average particle diameter of 350 nm or less that is stably blended without crystallizing a poorly soluble ultraviolet absorber, and a cosmetic that blends this fine emulsion composition.

  To date, many cosmetic compositions containing a UV absorber for the purpose of protecting the skin have been provided. As one of the UV absorbers, poorly soluble UV absorbers such as bisethylhexyloxyphenol methoxyphenyl triazine and t-butylmethoxydibenzoylmethane are known, and are widely used as raw materials for cosmetics due to their excellent UV absorbing effect. ing. However, the ultraviolet absorber has a narrow range of choice of dissolving solvent, and there is only a highly polar ester oil as an oil exhibiting good solubility. Therefore, when it is intended to provide a cosmetic composition by dissolving them stably, the composition needs to contain a large amount of highly polar oil. These cosmetic compositions not only have ester-specific usability, but also have a difficulty in narrowing the composition application range of the composition. Under such circumstances, it is desired to develop a water-based composition in which a poorly soluble ultraviolet absorber does not crystallize during formulation and is stably blended.

  To date, there has been no research on technology related to water-based compositions in which poorly soluble UV absorbers are stably blended, but as a study to improve the solubility in oily systems, for example, UV absorbers having a triazine skeleton are used. There exists the technique (refer patent document 1) etc. which mix | blend with a camphor derivative.

JP-A-10-87470

  The present invention has been made in view of the above circumstances, and an object thereof is an aqueous fine emulsion composition in which a poorly soluble ultraviolet absorber does not crystallize and is stably and easily formulated, and the fine emulsion composition. It is providing the cosmetics which mix | blended.

  As a result of diligent research to solve the above problems, the present inventor has found that a poorly soluble ultraviolet absorber such as ethylhexyltriazone and t-butylmethoxydibenzoylmethane is obtained from a specific surfactant, polyol and water. It has been found that the above-mentioned problems can be solved by including the composition in a composition, and the present invention has been completed.

The present invention is an O / W fine emulsion composition in which a hardly soluble ultraviolet absorbent having a high ultraviolet absorbing ability but difficult to be stably blended can be used for both W / O and O / W emulsion preparations. A stable preparation can be obtained even in a system using an oil agent such as silicone oil or hydrocarbon oil, which is poorly compatible with the ultraviolet absorber. The cosmetic prepared with the present fine emulsion composition is only the cosmetic prepared with the present fine emulsion composition, although the formulation components are the same as the cosmetic prepared with the conventional preparation method. Crystals of the ultraviolet absorber did not form over time.

  Examples of the component (A) UV absorber used in the present invention include paraaminobenzoic acid (PABA) derivatives, cinnamic acid derivatives, benzophenone derivatives, salicylic acid derivatives, and the like, preferably (A1) paramethoxycinnamic acid. 2-ethylhexyl, (A2) ethylhexyltriazone, and (A3) t-butylmethoxydibenzoylmethane. Specifically, these ultraviolet absorbers are (A1) 2-methoxyhexyl paramethoxycinnamate, UVINUL MC80 (manufactured by BASF), UVINUL MC80T (manufactured by BASF), PARSOL MCX (manufactured by DMS Nutrition), It is commercially available as ESCALOL557 (manufactured by ISP JAPAN), Neo Heliopan AV (manufactured by Simrise), and Nomcoat TAB (manufactured by Ajinomoto Co.). (A2) Ethylhexyltriazone is commercially available as UVINUL T150 (manufactured by BASF). (A3) t-butylmethoxydibenzoylmethane is commercially available as PARSOL1789 (manufactured by DSM Nutrition), Neo Heliopan 357 (manufactured by Simrise). In the present invention, UVINUL MC80T, PARSOL MCX, UVINUL T150, and PARSOL1789 are used, but the present invention is not limited by these uses.

  Surfactants that do not contain the polyoxyethylene surfactant (B) used in the present invention include nonionic surfactants such as sucrose fatty acid esters and glycerin fatty acid esters, sodium laurate, and palmitic acid. Fatty acid soaps such as sodium, sulfates such as sodium lauryl sulfate, acylated amino acid salts such as sodium lauroyl sarcosine, sodium cocoyl-N-methyltaurate, sodium lauryl glutamate, phosphate esters such as sodium monolauryl phosphate, etc. Anionic surfactants, cationic surfactants such as quaternary ammonium salts, etc., preferably fatty acid esters having 12 to 22 carbon atoms and polyglycerol fatty acid esters having an HLB of 10 or more, more preferably carbon number. 12 HLB fatty acid esters of 22 are 12 to 16 of the polyglycerol fatty acid ester. Specifically, hexaglyceryl monolaurate, decaglyceryl monolaurate, hexaglyceryl monomyristate, decaglyceryl monomyristate, decaglyceryl monopalmitate, decaglyceryl monostearate, decaglyceryl monoisostearate, decaglyceryl monooleate And decaglyceryl monolinoleate and the like, and one or more of these can be used in combination. Of these, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monostearate, decaglyceryl monooleate are particularly preferred.

  Furthermore, as the surfactant which does not contain the polyoxyethylene-type surfactant as the component (B) used in the present invention, it is preferably a cationic surfactant of monoallyltrimethyl salt of a fatty acid having 14 to 22 carbon atoms. . Specific examples include trimethylammonium myristate, trimethylammonium palmitate, trimethylammonium stearate, trimethylammonium behenate, and trimethylammonium stearate is particularly preferable.

  Further, as the surfactant which does not contain the polyoxyethylene type surfactant (B) used in the present invention, preferably an anionic surfactant comprising an acyl lactic acid having 14 to 22 carbon atoms and / or a salt thereof. And / or an anionic surfactant comprising acyl taurine of a fatty acid having 12 to 22 carbon atoms and / or a salt thereof. Specifically, myristoyl lactic acid and / or its salt, palmitoyl lactic acid and / or its salt, stearoyl lactic acid and / or its salt, cocoyl methyl taurine and / or its salt, lauroyl methyl taurine and / or its salt, myristoyl methyl taurine, palmitoyl methyl taurine and Or a salt thereof, stearoylmetholtaurine and / or a salt thereof, and the like, stearoyl lactic acid and / or a salt thereof, stearoylmetholtaurine and / or a salt thereof are particularly preferable.

  Furthermore, the component (B) used in the present invention is a combination of one or more of the polyglycerin fatty acid esters described above and / or monoalkyltrimethyl salts, acyl lactates, and acyl taurines. Can do.

  Examples of the polyol (C) used in the present invention include propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, sorbitol, and the like, and glycerin is particularly preferred.

  In the present invention, the ratio (mass ratio) of the components (A1) to (A3) in the component (A) is (A1) / (A2 + A3) = 90/10 to 70/30 and (A2) / (A3) = 99/1 to 1/99, particularly preferably (A1) / (A2 + A3) = 85/15 to 75/25 and (A2) / (A3) = 80/20 to 20/80.

  Further, the ratio (mass ratio) of the components (A) to (C) is (A) / (B) = 95/5 to 70/30 and [(A) + (B)] / (C) = 90 / 10 to 70/30, particularly preferably (A) / (B) = 95/5 to 85/15 and [(A) + (B)] / (C) = 85/15 to 75/25. .

  Within the above range, a fine emulsion composition containing a hardly soluble ultraviolet absorber can be prepared more stably.

  The fine emulsion composition of the present invention may be composed of only the components (A) to (D), or in a range not impairing the effects of the present invention, surfactants generally used in cosmetics, higher alcohols, Alkyl glyceryl ethers, fatty acids, oily raw materials, active ingredients, moisturizing ingredients, antibacterial ingredients, viscosity modifiers, stabilizers, dyes, fragrances and the like can also be used in combination.

  The fine emulsion composition of the present invention is prepared by melting and mixing the components (A) to (D) and other arbitrary raw materials in advance to form a uniform mixture, and cooling the mixture to room temperature while stirring it. Can be obtained as

  The fine emulsion composition of the present invention composed of the above components has an average particle size of 350 nm or less, preferably 200 to 350 nm. If it is in the range of 200 to 350 nm, the curvature of the interface where the emulsified particles are arranged is not too large and there is no stress. If it exceeds 350 nm, creaming may occur, and it is difficult to ensure sufficient stability over time.

  The fine emulsion composition of the present invention can measure average particles (mass average) using a submicron particle size distribution measuring device (Coulter N4 PLUS) manufactured by Beckman Coulter, Inc.

  The fine emulsion composition of the present invention can be easily and stably blended in an arbitrary cosmetic in the range of 1 to 40% by mass. The above cosmetic is a sunscreen preparation to be applied to the face, body or hair, and can be easily and stably formulated in any preparation such as lotion, milk lotion, gel lotion, gel cream, cream. Furthermore, as a dosage form, it can mix | blend suitably in all the preparations which want to provide UV protection ability, such as a sheet form, spray form, and stick form.

  By the way, the fine emulsion composition prepared using a monoalkylammonium salt as a surfactant that does not contain the polyoxyethylene surfactant as the component (B) is suitable for hair cosmetics because of its adsorption properties as a cation. Particularly suitable for blending.

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

(Example 1) Preparation and evaluation of a composition for external skin preparation (1) Preparation of a composition for external skin preparation A 2-liter glass emulsifier equipped with a temperature controller, a stirrer and a vacuum pump was mixed with a UV absorber and Each component shown in the table was charged to a total of 1 kg. The inside of the emulsifier was depressurized to 20 to 30 mmHg, and stirred and mixed at a temperature of 40 to 50 ° C. for 1 hour to obtain a uniform viscous liquid. After mixing, the compositions for skin external preparations of the present invention products 1 to 7 and comparative examples 1 to 5 were obtained by cooling. Their compositions are shown in Tables 1 and 2.
(2) Stability evaluation The product of the present invention was left in a cycle thermostat at 45 ° C, 5 ° C, and -5 to 45 ° C for 1 month, the appearance was visually observed, and the particle size was measured (multi-angle sub) Micron Particle Analyzer / N4Plus type). These results are shown in Table 2.
○: No change in appearance was observed. ×: Turbidity or separation / creaming was observed. The presence or absence of crystals was observed with a microscope.

(Example 2) External preparation for skin containing the product 1 of the present invention obtained in Example 1 (daytime essence)
1. Invention product 1 obtained in Example 1 10.0
2. Dipropylene glycol: 1.0
3. Sodium hyaluronate: 0.01
4). Acrylic acid / alkyl methacrylate copolymer: 0.15
5. Preservative: appropriate amount KOH: adjusted to pH 6.5 It is made 100.0 mass% with purified water.

Preparation method: 1 to 7 are stirred and mixed, and the preparation is completed when the mixture becomes uniform.
Stability: The preparation was stored for 1 month in a 45 ° C., 5 ° C. and −5 ° C. to 45 ° C. cycle thermostatic bath and then visually observed to find no change. Also, even when observed under a microscope, no crystals were observed and the sample was stable.

(Example 3) An external preparation for skin containing the product 2 of the present invention obtained in Example 1 (day cream)
A phytosterol 1.0% by mass
Decaglyceryl monolaurate 2.0
Hydrogenated soybean lecithin 0.7
Tri (caprylic / capric) glyceryl 5.0
Squalane 4.0
Triethylhexanoin 3.0
Cetyl alcohol 6.0
Cyclopentasiloxane 4.0
Dimethicone (6mm ² / s) 2.0
B Carbomer (2% aqueous solution) 10.0
1,3-butylene glycol 5.0
Glycerin 3.0
L-hydroxyproline 0.1
EDTA-2Na 0.05
Preservative appropriate amount Purified water Remainder C Arginine 0.2
Purified water 3.0
D Sodium hyaluronate (1% aqueous solution) 2.0
Purified water 2.0
E Invention product 1 obtained in Example 1 15.0

Preparation method: A and B are each heated to 80 ° C. to be uniform. While stirring B with a homomixer at 80 ° C., A is gradually added to emulsify. Thereafter, C is added, the mixture is cooled with stirring with a paddle, D and E are added at 40 ° C., and the preparation is completed at 30 ° C.
Stability: The preparation was stored for 1 month in a 45 ° C., 5 ° C. and −5 ° C. to 45 ° C. cycle thermostatic bath and then visually observed to find no change. Also, even when observed under a microscope, no crystals were observed and the sample was stable.

(Example 4) Hair cosmetic (hair care treatment) containing the product 3 of the present invention obtained in Example 1
1. Invention product 3 obtained in Example 1 10.0
2. Hydroxyethyl cellulose 0.3
3. Acrylic acid / alkyl methacrylate copolymer 0.3
4). Sodium hyaluronate 0.01
5.1,3-Butylene glycol 3.0
6). Pantothenol 0.2
7). EDTA2Na 0.05
8). Preservative appropriate amount 9. It is made 100.0 mass% with purified water.

Preparation method: 2 to 9 are stirred and mixed, 1 is added when the mixture becomes uniform, and further stirred, and the preparation is completed when the mixture becomes uniform.
Stability: The preparation was stored for 1 month in a 45 ° C., 5 ° C. and −5 ° C. to 45 ° C. cycle thermostatic bath and then visually observed to find no change. Also, even when observed under a microscope, no crystals were observed and the sample was stable.

(Example 5) Hair cosmetic (hair care essence) containing the product 4 of the present invention obtained in Example 1
1. Invention product 4 obtained in Example 1 8.0
2. Hydroxyethyl cellulose 0.3
3. Acrylic acid / alkyl methacrylate copolymer 0.3
4). Sorbitol fermentation polysaccharide fluid 0.01
5. Dipropylene glycol 3.0
6). Pantothenol 0.2
7). EDTA2Na 0.05
8). Preservative appropriate amount 9. It is made 100.0 mass% with purified water.

Preparation method: 2 to 9 are uniformly mixed, 1 is added when the mixture becomes uniform, and the mixture is further stirred, and the preparation is completed when the mixture becomes uniform.
Stability: The preparation was stored for 1 month in a 45 ° C., 5 ° C. and −5 ° C. to 45 ° C. cycle thermostatic bath and then visually observed to find no change. Also, even when observed under a microscope, no crystals were observed and the sample was stable.

(Example 6) An external preparation for skin containing the product 5 of the present invention obtained in Example 1 (milk for daytime)
1. Invention product 5 20.0 obtained in Example 1
2. Hydroxyethyl cellulose 0.3
3. Xanthan gum 0.2
4). Sodium hyaluronate 0.01
5.1,3-Butylene glycol 3.0
6). Glycerin 2.0
7). EDTA2Na 0.05
8). Preservative appropriate amount 9. It is made 100.0 mass% with purified water.

Preparation method: 2 to 9 are mixed, and when uniform, 1 is added and further stirred. When it becomes uniform, the preparation is finished.
Stability: The preparation was stored for 1 month in a 45 ° C., 5 ° C. and −5 ° C. to 45 ° C. cycle thermostatic bath and then visually observed to find no change. Also, even when observed under a microscope, no crystals were observed and the sample was stable.

(Example 7) External preparation for skin containing the product 6 of the present invention obtained in Example 1 (day cream)
1. Invention product 6 22.0 obtained in Example 1
2. Polyglyceryl-6 polyricinoleate-6 2.0
(NIKKOL HEXAGLYN PR-15)
3. Squalane 10.0
4). Sodium hyaluronate 0.01
5.1,3-Butylene glycol 3.0
6). Glycerin 2.0
7). EDTA2Na 0.05
8). Preservative appropriate amount 9. It is made 100.0 mass% with purified water.

Preparation method: 2 to 3 are mixed, and when uniform, 4 to 9 are added with stirring to obtain a water-in-oil base. While further stirring, 1 is gradually added. After the addition is completed, the mixture is further stirred.
Stability: The preparation was stored for 1 month in a 45 ° C., 5 ° C. and −5 ° C. to 45 ° C. cycle thermostatic bath and then visually observed to find no change. Also, even when observed under a microscope, no crystals were observed and the sample was stable.

Claims (8)

A fine emulsion composition having an average particle size of 350 nm or less, comprising the following components (A) to (D) as essential components.
(A) Ultraviolet absorber (B) Surfactant not containing polyoxyethylene type surfactant (C) Polyols (D) Water (A) The ultraviolet absorber contains (A1) 2-ethylhexyl paramethoxycinnamate, (A2) ethylhexyltriazone, and (A3) t-butylmethoxydibenzoylmethane, and the mass ratio thereof is (A1) / ( A2 + A3) = 90 / 10-70 / 30
And (A2) / (A3) = 99/1 to 1/99
2. The fine emulsion composition according to claim 1, wherein (B) The surfactant which does not contain a polyoxyethylene type surfactant is an ester of a fatty acid having 12 to 22 carbon atoms and a polyglycerol fatty acid ester having an HLB of 10 or more. A fine emulsion composition as described in 1. (B) The surfactant which does not contain a polyoxyethylene-type surfactant is a cationic surfactant of a monoalkyltrimethyl salt of a fatty acid having 14 to 22 carbon atoms, A fine emulsion composition. (B) A surfactant that does not contain a polyoxyethylene-type surfactant is an anionic surfactant that is an acyl lactic acid of a fatty acid having 14 to 22 carbon atoms or a salt thereof, or an acyl of a fatty acid having 12 to 22 carbon atoms The fine emulsion composition according to claim 1 or 2, which is an anionic surfactant which is taurine and / or a salt thereof. The ratio (mass ratio) of the components (A) to (C) described in claims 1 to 5 is:
(A) / (B) = 95 / 5-70 / 30
And [(A) + (B)] / (C) = 90 / 10-70 / 30
The fine emulsion composition according to any one of claims 1 to 5. The total amount of said (A)-(D) component is contained 95-100 mass%, The fine emulsion composition of any one of Claims 1-6 characterized by the above-mentioned. A cosmetic comprising 1 to 40% by mass of the fine emulsion composition according to any one of claims 1 to 7 and not containing a polyoxyethylene-type surfactant.