JP2013047206A - Fine emulsion composition containing ultraviolet absorber, and cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based fine emulsion composition which can stably and easily blend an insoluble ultraviolet absorber with a cosmetic without crystallization.SOLUTION: When an oil (a liquid ultraviolet absorber solution containing the insoluble ultraviolet absorber) is made to disperse as a fine emulsion in a water phase, one or more kinds of detergents are used, and further one or more kinds of polyols of a specific ratio are blended, so that excellent stability is obtained. Namely, the fine emulsion composition having an average particle diameter of ≤150 nm contains components (A)-(D) as essential components, and further component (E) that is a sorbitan fatty acid ester, wherein (A) is an ultraviolet absorber, (B) is a polyoxyethylene hardened castor oil, (C) is a polyol, (D) is water, and (E) is the sorbitan fatty acid ester.

Description

  The present invention relates to a fine emulsion composition having an average particle diameter of 150 nm or less that is stably blended without crystallizing a poorly soluble ultraviolet absorber, and a cosmetic that blends the 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 agent showing 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.

  As a research of the technique regarding the oil-based composition which mix | blended the poorly soluble ultraviolet absorber stably, there exists a technique (refer patent document 1) etc. which mix | blend the ultraviolet absorber which has a triazine skeleton with a camphor derivative, for example.

  In recent years, research on water-based compositions in which a poorly soluble UV absorber is stably blended has been conducted. For example, a technology for blending a UV absorber having a triazine skeleton with a specific surfactant, ethanol and water (patent) However, it is necessary to add a large amount of surfactant to the amount of UV absorber, and it is essential to use it in combination with ethanol. There was a problem that the dosage form was limited.

JP-A-10-87470 Japanese Patent No. 4226951

  An object of the present invention is to provide a water-based fine emulsion composition in which a poorly soluble ultraviolet absorber does not crystallize and the ultraviolet absorber is blended stably and simply, and a cosmetic blended with the same.

  In view of these circumstances, the present inventors have conducted extensive research, and as a result, a composition comprising a slightly soluble ultraviolet absorber such as ethylhexyltriazone and t-butylmethoxydibenzoylmethane, a specific surfactant, a polyol and water. It has been found that the above-mentioned problems can be solved by including the compound in a product, and the present invention has been completed.

  According to the present invention, a hardly soluble ultraviolet absorber that has a high ultraviolet absorbing ability but is difficult to be stably mixed is prepared in advance as a stable O / W fine emulsion composition by combining specific components. It is a fine emulsion composition that can be easily blended in preparations and the like in which blending of oily components is difficult. 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, (A3) t-butylmethoxydibenzoylmethane and / or hexyl diethylaminohydroxybenzoylbenzoate. Specifically, these ultraviolet absorbers are (A1) 2-ethylhexyl paramethoxycinnamate, UVINUL MC80 (manufactured by BASF), UVINUL MC80N (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 Nisshin Oilio). (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), and hexyl diethylaminohydroxybenzoylbenzoate is commercially available as UVINUL A Plus Granular (manufactured by BASF). Has been. Although UVINUL MC80, PARSOL MCX, UVINUL T150, PARSOL1789, and UVINUL A Plus Granular are used in the present invention, the present invention is not limited by these uses.

  The component (B) polyoxyethylene hydrogenated castor oil used in the present invention is characterized in that the average polyoxyethylene addition mole number is 20 to 60 moles, specifically, NIKKOL HCO-20, HCO- 30, HCO-40, HCO-50, HCO-60, HCO-50 (for pharmaceutical use), HCO-60 (for pharmaceutical use) (manufactured by Nikko Chemicals Co., Ltd.), etc., and a combination of one or more of these Can be used.

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

The sorbitan fatty acid ester of the component (E) used in the present invention can be arbitrarily selected and is preferably in a liquid form, sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan monooleate, sorbitan sesquioleate, Examples include sorbitan trioleate. Specific examples include NIKKOL SI-10RV, SI-15RV, SO-10V, SO-15V, SO-30V (manufactured by Nikko Chemicals Co., Ltd.), etc., and these may be used alone or in combination. it can. Further, the ratio (weight ratio) of the components (B) and (E) is (B) / (E) = 100/0 to 30/70, preferably 100/0 to 50/50.
In the case of (B) / (E) = 100/0, the molecular tension (solid gel phase) formed by (B) polyoxyethylene hydrogenated castor oil is passed to reduce the interfacial tension, and the average Although it is possible to obtain a fine emulsion having a particle size of 150 nm or less, by using (E) sorbitan fatty acid ester in combination, the critical packing parameter of the surfactant is changed, and packing of the molecular assembly by the surfactant is performed. By relaxing, the formation of a strong gel phase is suppressed and a fine emulsion having an average particle diameter of 150 nm or less is obtained, so that the emulsion can be prepared more efficiently.

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 40/60 and (A2) / (A3) = 90/10 to 10/90, particularly preferably (A1) / (A2 + A3) = 80/20 to 50/50 and (A2) / (A3) = 70/30 to 30/70.
The ratio (mass ratio) of the components (A) to (C) is (A) / (B) = 80/20 to 40/60 and [(A) + (B)] / (C) = 90 / 10/60/40, particularly preferably (A) / (B) = 70/30 to 50/50 and [(A) + (B)] / (C) = 80/20 to 70/30 .

  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, pigments, fragrances and the like can also be used in combination.

  In the fine emulsion composition of the present invention, the components (A) to (D), (E) and any other raw materials are previously melt-mixed to obtain a uniform mixture, and cooled to room temperature while stirring. And can be obtained as a translucent to white emulsion composition.

  The fine emulsion composition of the present invention composed of the above components has an average particle size of 150 nm or less, preferably 60 to 110 nm. If it is the range of 60-110 nm, since the curvature of the interface where the emulsified particles are arranged is not too large and there is no stress, coalescence or collapse does not occur and it is more preferable. If it exceeds 150 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 in any formulation which wants to provide UV protection ability, such as a sheet form, spray form, and stick form. In particular, it can be suitably blended in a spray-type lotion preparation in which it is difficult to blend oily components.

  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 fine emulsion composition

(1) Preparation of fine emulsion composition A 2 liter glass emulsifier equipped with a temperature controller, a stirrer and a vacuum pump is preliminarily heated and dissolved, and each component shown in the table is 1 kg in total. It was prepared as follows. The inside of the emulsifier was depressurized to 20-30 mmHg, and stirred and mixed for 1 hour to obtain a uniform viscous liquid. After mixing, the fine emulsion compositions of Invention Products 1-14 and Comparative Examples 1-4 were obtained by cooling. These compositions are shown in Tables 1-3.

(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 Tables 4-6.
○: No change in appearance was observed. ×: Turbidity or separation / creaming was observed. The presence or absence of crystals was visually and microscopically observed.

(Example 2) A skin external preparation containing the product 2 of the present invention obtained in Example 1 (daytime essence)
1. Invention product 2 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 6. Adjust to KOH 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) External preparation for skin containing the product 4 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 4 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 6 of the present invention obtained in Example 1
1. Invention product 6 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 5 of the present invention obtained in Example 1
1. Invention product 5 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 8 of the present invention obtained in Example 1 (milk for daytime)
1. Invention product 8 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) An external preparation for skin containing the product 9 of the present invention obtained in Example 1 (day cream)
1. Invention product 9 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.

(Example 8) Hair cosmetic (hair care lotion spray) containing the product 12 of the present invention obtained in Example 1
1. Invention product 12 obtained in Example 1 15.0
2. Perfume appropriate amount 3. Preservative appropriate amount 4. It is made 100.0 mass% with purified water.
Preparation method: 1-2 and 3-4 are each stirred and mixed. 3-4 are gradually added to the place where 1-2 is stirred, and after the addition is completed, 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 9) Hair cosmetic (hair care mist) containing the product 14 of the present invention obtained in Example 1
1. Invention product 14 obtained in Example 1 15.0
2. Ethanol 10.0
3. Perfume appropriate amount 4. Preservative appropriate amount 5. It is made 100.0 mass% with purified water.
Preparation method: 1 to 3 and 4 to 5 are mixed with stirring. 4 to 5 are gradually added to the place where 1 to 3 are being stirred, and after the addition is completed, 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.

Claims (8)

A fine emulsion composition having an average particle size of 150 nm or less, comprising the following components (A) to (D) as essential components.
(A) UV absorber (B) polyoxyethylene hydrogenated castor oil (C) polyol (D) water (A) UV absorbers include (A1) 2-ethylhexyl paramethoxycinnamate, (A2) ethylhexyltriazone, (A3) t-butylmethoxydibenzoylmethane and / or hexyl diethylaminohydroxybenzoylbenzoate, Mass ratio of (A1) / (A2 + A3) = 90 / 10-40 / 60
And (A2) / (A3) = 90/10 to 10/90
2. The fine emulsion composition according to claim 1, wherein (B) The fine emulsion composition according to claim 1 or 2, wherein the polyoxyethylene hydrogenated castor oil has an average polyoxyethylene addition mole number of 20 to 60 moles. The fine emulsion according to any one of claims 1 to 3, wherein the polyol (C) is composed of one or more selected from propylene glycol, 1,3-butylene glycol, dipropylene glycol, and pentylene glycol. Composition. The ratio (mass ratio) of the components (A) to (C) described in any one of claims 1 to 4,
(A) / (B) = 80 / 20-40 / 60
And [(A) + (B)] / (C) = 90 / 10-60 / 40
The fine emulsion composition according to any one of claims 1 to 4. The total amount of said (A)-(D) component is contained 90-100 mass%, The fine emulsion composition of any one of Claims 1-5 characterized by the above-mentioned. Furthermore, in addition to said (A)-(D) component, (E) sorbitan fatty acid ester is contained, 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.