TWI638665B - Emulsion and manufacturing method thereof - Google Patents

Abstract

The present invention provides an emulsion containing an oily component with a finely dispersed particle size and good stability over time. It is selected from polyhydric alcohols having a valence of 3 or more in a specific ratio and selected from polyglyceryl fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and mixtures thereof. Groups of fatty acid esters, fluorenylamino acids and / or salts thereof. Here, an oily component is added under stirring to obtain an O / A emulsion in which the oily component is dispersed in the polyol phase. The O / A emulsion is added to the aqueous medium with stirring to obtain an oil-in-water emulsion.

Description

Emulsion and manufacturing method thereof

The present invention relates to an emulsion in which an oily component is dispersed in a polyol-containing phase, the emulsion is dispersed in an aqueous medium to form an oil-in-water (O / W) emulsion, and a manufacturing method of these emulsions. The present invention is particularly related to an emulsion having a small dispersed particle size of an oily component and excellent stability over time even when placed in a low viscosity environment.

In water-based external skin compositions such as lotions, serums, and hair restorers, oil-in-water emulsions are widely used in order to incorporate oily active ingredients into the system. In consideration of the feeling and convenience during use, the water-based external skin composition may be designed to have a low viscosity. Generally, in oil-in-water emulsions of low-viscosity formulations, the phenomenon of emulsifiation due to the difference in specific gravity between oily components and aqueous components is prone to cause the problem of deterioration of stability over time. A technique for mixing the lecithin hydroxide and hydrogenated lecithin in a specific ratio and containing the emulsified composition is reported as a technique for maintaining the stability of a low-viscosity preparation emulsion (Patent Document 1).

On the other hand, reducing the particle size of the dispersed particles of the active ingredient in the composition for external use on the skin is desirable because it may increase the skin permeability of the active ingredient. of. Dispersing the oil phase under high pressure or using a water-soluble polymer has been reported as a method of obtaining an oil-in-water emulsion with a small particle diameter (Patent Document 2).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-6739

[Patent Document 2] Japanese Patent No. 4444149

From this, it can be seen that it is advantageous for a composition for skin external use to produce an oil-in-water emulsion having a fine dispersion particle size and excellent stability over time even in a low-viscosity system. An object of the present invention is to provide an emulsion containing an oily component having a finely dispersed particle size having excellent skin permeability and excellent stability over time.

After intensive research, the inventors of the group found the following: in a polyhydric alcohol having a valence of 3 or more, a fatty acid ester, amidinoamino acid, and / or a salt thereof were mixed in a specific ratio, and then added under stirring Oily ingredients can be obtained by dispersing the oily ingredients in the polyol phase without using special equipment such as a high-pressure homogenizer. The dispersed particle diameter of the oily components in this emulsion is small (average particle diameter is 1 μm or less), and the small particle diameter can be maintained even after long-term storage. It was further found that by dispersing this emulsion in an aqueous medium, Oil-in-water emulsion with small dispersion particle size and excellent stability over time. The present invention includes not only these findings but also the following items.

An emulsion comprising the following components: 50 to 97% by weight of a trivalent or higher polyol, selected from the group consisting of a polyglyceryl fatty acid ester, a sorbitan fatty acid ester, and a polyoxyethylene sorbitan fatty acid ester And 1 to 10% by weight of fatty acid esters, 0.01 to 3% by weight of fluorenyl amino acids and / or salts thereof, and 1 to 30% by weight of oily components, and the aforementioned oily components are dispersed in Among the phases of the aforementioned polyol.

2. The emulsion according to the above 1, wherein the polyol having a valence of 3 or more is 80 to 97% by weight, and the oily component is 1 to 18% by weight.

3. The emulsion according to the above 1 or 2, wherein the polyhydric alcohol having a valence of 3 or more is glycerin.

4. The emulsion according to any one of 1 to 3, wherein the fatty acid ester is a polyglyceryl fatty acid ester.

5. The emulsion according to any one of 1 to 4, wherein the fluorenylamino acid and / or its salt is 0.01 to 1% by weight.

6. The emulsion according to any one of 1 to 5 above, wherein the average particle diameter of the dispersed oily component is 1 μm or less.

7. An oil-in-water emulsion, which is obtained by dispersing any of the aforementioned emulsions 1 to 6 in an aqueous medium.

8. The oil-in-water emulsion according to 7 above, which contains 90 to 99.5% by weight of the aqueous medium.

9. The oil-in-water emulsion according to 7 or 8 above, which has a viscosity of 1000 mPa · s or less based on a B-type viscosity meter (25 ° C, No. 1 rotor, 12 rpm).

10. The oil-in-water emulsion according to any of 7 to 9 above, wherein the average particle diameter of the dispersed oily component is 1 μm or less.

11. A fragrance cosmetic comprising the oil-in-water emulsion according to any one of 8 to 10 above.

12. A composition for external use on skin, comprising the oil-in-water emulsion according to any one of 8 to 10 above.

13. A method for producing an emulsion, comprising the steps of mixing a polyglyceryl fatty acid ester, a sorbitan fatty acid ester, and a polyoxyethylene sorbitan in a liquid containing a polyvalent alcohol having a valence of 3 or more. Fatty acid esters of alcohol fatty acid esters and their mixtures, and fluorenyl amino acids and / or their salts, and then add an oily component to the aforementioned liquid containing a polyol under stirring to form an oily component An emulsion dispersed in the aforementioned liquid containing a polyol; and the aforementioned fluorenylamino acid and / or its salts, based on the amount of the aforementioned emulsion, is 0.01 to 3% by weight.

14. A method for producing an oil-in-water emulsion, comprising the steps of mixing a polyglyceryl fatty acid ester, a sorbitan fatty acid ester, and a polyoxyethylene in a liquid containing a polyhydric alcohol having a valence of 3 or more. Sorbitan fatty acid esters, and fatty acid esters grouped with these mixtures, and fluorenylamino acids and / or their salts, Then, the oily component is added to the aforementioned liquid containing the polyol under stirring to form an emulsion in which the oily component is dispersed in the liquid containing the polyol, Next, the formed emulsion is mixed with an aqueous medium to form an oil-in-water emulsion in which oily components are dispersed in the aqueous medium. In addition, the amidinoamino acid and / or a salt thereof is 0.01 to 3% by weight based on the amount of the emulsion in which the oily component is dispersed in a liquid containing a polyol.

By the present invention, an emulsion having a finely dispersed particle size of its oily component can be obtained. The emulsion of the present invention does not use a device for pulverizing particles under pressure like a high-pressure homogenizer, and can be manufactured with a normal mixer with a rotating blade. Even if the emulsion of the present invention is manufactured by using the ordinary mixer, a finely dispersed particle size with an average particle size of less than 1 μm can be obtained. In the present invention, first, an emulsion in which an oily component is dispersed in a polyvalent alcohol phase having a trivalent or more is prepared. Next, this emulsion is added to an aqueous medium with stirring to obtain an oil-in-water emulsion. The obtained oil-in-water emulsion maintains a finely dispersed particle size and has excellent dispersion stability even with low viscosity changes over time. And because it is gentle on the skin and has a good feeling of use, it is suitable for use as a cosmetic or external skin composition such as lotions and hair care products. In addition, since oily ingredients have high permeability to the skin, they are particularly suitable for use in applications where active ingredients penetrate into the skin, such as external skin compositions such as essences and hair restorers.

[Fig. 1] Fig. 1 shows a measurement result of an average particle diameter in a time-dependent stability test in Example 3. [Fig.

FIG. 2 shows the measurement results of skin permeability in Example 4. FIG.

[Fig. 3] Fig. 3 shows measurement results of pH and absorbance in Example 5. [Fig.

In the present invention, a polyhydric alcohol having a valence of 3 or more is firstly mixed in a specific ratio and selected from the group consisting of polyglyceryl fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and mixtures thereof The group of fatty acid esters are mixed with fluorenylamino acid and / or its salts, and an oily component is added under stirring to form an emulsion in which the oily component is dispersed in the polyol phase (in this specification, The emulsion obtained at this stage is called "O / A emulsion".). The obtained O / A type emulsion has a fine dispersed particle size of an oily component, and the average particle size can reach a minute size of less than 1 μm. Next, this O / A emulsion is added to an aqueous medium with stirring to obtain an oil-in-water emulsion. The obtained oil-in-water emulsion maintains the finely dispersed particle size of the O / A emulsion, and even at a low viscosity (for example, B-type viscosity, 25 ° C, No. 1 rotor, 12 rpm measured as 1000 mPa‧s or less), it can still be within one stage. Stable dispersion is maintained for a long period of time. The oil-in-water emulsion of the present invention can be applied to perfumery products such as lotions and hair restorers and compositions for external skin application.

(O / A emulsion)

Blend O / A type emulsion (emulsion with oily components dispersed in polyol phase) In this case, a trivalent or higher polyhydric alcohol of 50 to 97% by weight based on the final amount of the O / A emulsion is mixed with a polyglyceryl fatty acid ester, sorbitan fatty acid ester, or polyoxyethylene. Sorbitan fatty acid esters and fatty acid esters in groups of 1 to 10% by weight, and 0.01 to 3% by weight with fluorenylamino acids and / or salts thereof. Here, oiliness is added under stirring. Ingredients 1 ~ 30% by weight.

The O / A emulsion of the present invention uses a polyol having a trivalent or higher valence as a continuous phase. For example, once a glycol such as 1,3-butanediol is used, the oily components are separated and therefore not good. Examples of polyhydric alcohols with a trivalent or higher value include polyglycerols such as glycerol, diglycerol, triglycerin, and tetraglycerol; sugar alcohols such as neopentyl tetraol, erythritol, xylitol, and mannitol; . Among them, glycerin is preferred. There are various grades of glycerin, and any grade can be used. For example, a cosmetic thick glycerin with a glycerol content of 95.0% or more may be suitably used.

The amount of the trivalent or higher polyhydric alcohol is 50 to 97% by weight, and preferably 80 to 97% by weight, based on the amount of the O / A emulsion finally obtained. When the amount used is less than 50% by weight, the dispersion particle diameter of the oily component in the obtained emulsion becomes large, and it becomes a substance with poor dispersion stability.

Next, a polyhydric alcohol having a valence of three or more is mixed with a fatty acid grouped from a polyglyceryl fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and a mixture thereof. Esters, and amidoamino acids and / or their salts.

For the polyglyceryl fatty acid ester, it is better to form a polyglycerol having a polymerization degree of 4 to 10 and one or more kinds of fatty acids having a carbon number of 12 to 22. For example There are: hexaglyceryl monooleate, hexaglyceryl monopalmitate, hexaglyceryl monomyristate, hexaglyceryl monolaurate, decaglyceryl monooleate, decaglyceryl monohard Fatty acid esters, decaglyceryl monopalmitate, decaglyceryl monomyristate, decaglyceryl monolaurate, and the like. Among them, deca glyceryl fatty acid ester is preferable, and deca glyceryl monomyristate is preferable. The HLB of the polyglyceryl fatty acid ester is preferably about 10 to 16.

For example, sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, Sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, and the like. Among them, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate are preferred, and sorbitan sesquioleate is more preferred.

Examples of polyoxyethylene sorbitan fatty acid esters are: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monomyristate, polyoxyethylene sorbitan monopalmitate Ester, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan triisohardate Fatty acid esters, etc. Among them, the average number of Fumaroles of ethylene oxide is about 20, and the average number of Fumaroles of ethylene oxide is 20, and polyoxyethylene sorbitan monooleate is favorably used.

Among these fatty acid esters, polyglyceryl fatty acid esters are most preferred. Compared with the case of using sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester, the use of polyglyceryl fatty acid ester can form minute dispersed particles path.

These fatty acid esters are used in an amount of 1 to 10% by weight, preferably 1.5 to 8% by weight, and more preferably 2 to 7.5% by weight based on the amount of the O / A emulsion finally obtained. If the amount used is less than 1% by weight, sufficient dispersion stability cannot be obtained, and if the amount used exceeds 10% by weight, a sticky feeling is produced, which is not good because the use feeling becomes worse.

In addition to the aforementioned fatty acid esters, fluorenylamino acids and / or salts thereof are mixed with a trivalent or higher polyhydric alcohol. The present inventors have found that by using amidinoamino acid and / or a salt thereof, the dispersion particle diameter of the oily component of the emulsion can be made small. In the case of fluorenylamino acids and / or their salts, long-chain fluorenylglutamic acid and its salts, and fluorenylglycine and its salts are excellent in safety. In terms of the carbon number of the fatty acid, it is preferably about 12-20. Examples of fluorenylamino acids and / or their salts are not limited, but examples include potassium coconut fatty acid potassium glutamate, sodium coconut fatty acid glutamate, coconut fatty acid glutamate triethanolamine, Potassium lauryl glutamate, sodium lauryl glutamate, triethanolamine lauryl glutamate, potassium myristyl glutamate, sodium myristyl glutamate, stearyl glutamate Potassium, sodium stearyl glutamate, disodium stearyl glutamate, hardened tallow fatty acid sodium glutamate, coconut fatty acid‧hardened tallow fatty acid glutamate sodium, coconut fatty acid glycine Potassium acid, sodium coco fatty acid glycine, coco fatty acid glycine triethanolamine, potassium lauryl glycine, sodium lauryl glycine, sodium lauryl glycine triethanolamine, myristic acid Potassium Glycine, Sodium Myristyl Glycine, Potassium Stearyl Glycine, Sodium Stearyl Glycine, Disodium Stearyl Glycinate, Sodium Tallow Fatty Acid Glycinate , Coconut oil fatty acids Hardened tallow fatty acid sodium glutamate and so on.

The amount of fluorenylamino acid and / or its salts, based on the final amount of O / A emulsion, is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, and 0.1 to 1% by weight. Better. By using fluorenylamino acids and / or their salts in this range, the particle size of the dispersed particles of the oily component can be greatly reduced (for example, the average particle diameter can be reduced to about 70% or 20%) compared with the case where it is not used. about). When the amount is less than 0.01% by weight, the above-mentioned effect of miniaturization cannot be sufficiently obtained, and if it is used in excess of 3% by weight, the irritation to the skin becomes strong, which is not preferable.

When a trivalent or higher polyhydric alcohol is mixed with the fatty acid ester and amidinoamino acid and / or a salt thereof, it may be performed while stirring under heating. The temperature at this time is not particularly limited as long as these components can sufficiently dissolve in the polyol. Usually it is around 75 ~ 85 ℃. As for the stirring, an ordinary mixer can be used.

In this way, a phase containing a trivalent or higher polyhydric alcohol having a specific fatty acid ester and amidinoamino acid and / or a salt thereof is prepared. The remainder of this phase is preferably water. However, as long as the effect of the present invention is not impaired, an additional component may be contained in a trace amount. Such ingredients include, for example, ethanol and the like.

The concentration of these additional ingredients is preferably less than about 5% by weight.

An oily component was added to the polyol phase containing trivalent or higher valence obtained as described above, and an O / A emulsion was prepared. There are no particular restrictions on the type of oily ingredients, but oils that are liquid at normal temperature are preferred. For oily ingredients, for example: squalane, olive oil, macadamia Kernel oil, jojoba oil, coconut oil, soybean oil and other animal and vegetable fats, mineral oils such as hydrocarbons, flowing paraffin, cetyl isooctanoate, isopropyl myristate, and glyceryl trioctanoate , Silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, cyclic silicone oil, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol, oleyl alcohol and other higher alcohols, vitamin A, Oil-soluble compounds such as vitamin D, vitamin E, vitamin K, coenzyme Q10, α-lipoic acid, rutin, lutein, and derivatives thereof, carmine red pigment, capsaicin, beta-carotene, chlorophyll, Oil soluble pigments such as red tincture pigment and turmeric pigment. These can also be used in combination of plural types. For example, a tocopherol derivative (vitamin E derivative) has an effect of promoting blood circulation, an antioxidant effect, and an effect of softening the skin, and an effect of promoting hair growth can also be expected.

The amount of the oily component is based on the amount of the O / A emulsion, and is 1 to 30% by weight, preferably 1 to 18% by weight, and more preferably 1 to 5% by weight. When the amount of the oily component exceeds 30% by weight, an emulsion having a small dispersed particle diameter cannot be obtained.

When adding oily ingredients, it is better to add a small amount in small amounts while stirring. The temperature when adding oily ingredients under stirring is not particularly limited, but is about 75 to 85 ° C. For stirring, for example, it is preferable to use a general mixer such as a rotary blade. For example, a homomixer, a dispersion mixer, a paddle mixer, or the like can be used. In the present invention, when forming fine particles, it is not necessary to use a high-pressure homogenizer such as a microjet homogenizer and a nano-type homogenizer to pulverize and disperse the particles under high pressure. When stirring, it is preferable to use a vacuum emulsification mixer capable of stirring under vacuum. By stirring under vacuum, the effect of air bubbles can be removed and a stable emulsion can be formed.

In addition, when obtaining the O / A type emulsion of the present invention, it is important to add an oily component to the phase containing a polyol. Even if a phase containing a polyol is added to the oily component, the oily component is separated from the phase of the polyol, and the emulsion desired in the present invention cannot be obtained.

The O / A emulsion of the present invention (emulsions with an oily component dispersed in a polyol phase containing a trivalent or more valence) thus obtained, the average particle diameter of the dispersed particles of the oily component is 1 μm or less, preferably 800 nm or less, and 600 nm or less More preferably, below 300 nm, and below 200 nm. The lower limit value of the average particle diameter in the present invention is not limited, but is considered to be about 50 nm. The average particle diameter of the dispersed particles can be measured by a laser diffraction type particle size distribution measuring device, a dynamic light scattering type measuring device, a particle size measuring device applying the Coulter principle, and the like. In the present invention, a laser diffraction type particle size distribution measuring device is used for measurement.

In general, in the case of using a device such as a high-pressure homogenizer and a microjet homogenizer to miniaturize particles by impact under pressure, the particle size distribution of dispersed particles sometimes widens, and sometimes plural numbers appear There are several wave fronts, but the O / A emulsion obtained by the present invention under relatively gentle stirring has the advantage of being able to obtain a particle size distribution with a single wave front.

The O / A emulsion obtained by the present invention can maintain dispersibility for a long period of time. For example, it is also suitable for storage as a raw material for formulating fragrance and skin external compositions. The O / A emulsion obtained by the present invention can be cooled to, for example, room temperature or about 5-30 ° C before being stored.

(Oil-in-water emulsion)

By mixing the O / A emulsion obtained above with an aqueous medium, an oil-in-water emulsion can be formulated. In the case of aqueous media, as long as water is the main component, there are no special restrictions on other components. It can also contain, for example, ingredients used in ordinary lotions, such as water-soluble polymers, humectants, UV absorbers, preservatives, pH adjusters, antioxidants, pigments, fragrances, water-based medicinal ingredients, etc. Wait.

The mixing ratio of the O / A type emulsion and the aqueous medium is: when the weight of the obtained oil-in-water emulsion is 100, the weight of the aqueous medium (including the weight of water and the weight of the other components in the case of containing other components) is 90 ~ 99.5, when the weight of O / A emulsion is 0.5 ~ 10, the stability and the feeling of use when used as a skin external preparation are excellent, so it is good. The weight of O / A emulsion is preferably 1 to 5.

When an aqueous medium is mixed with an O / A type emulsion, it is performed by adding an O / A type emulsion to an aqueous medium. The mixer used at this time is not particularly limited, and an ordinary mixer with a rotating blade may be used. The temperature at the time of mixing is not particularly limited, and it can be determined according to the stability of the oily ingredients used and the like. Generally around 30 ~ 40 ℃ should be suitable.

The obtained oil-in-water emulsion had a finely dispersed particle size of an oily component. The present inventors have confirmed that the particle size distribution of the original O / A emulsion in the oil-in-water emulsion is substantially unchanged. Therefore, the average particle diameter of the dispersed particles of the oily components in the oil-in-water type is the same as that of the O / A emulsion, which is 1 μm or less, preferably 800 nm or less, more preferably 600 nm or less, 300 nm or less, and 200 nm or less. Because the size of ordinary pores is considered to be around 200nm, once the particle size of the oily ingredients is less than 200nm, the oily ingredients (Including, for example, a hair growth promoting ingredient), it becomes easy to penetrate into the pores, and is expected to improve the hair growth effect. The lower limit value of the average particle diameter in the present invention is not limited, but is considered to be about 50 nm. As mentioned in the previous O / A emulsion, the average particle diameter can be measured by laser diffraction particle size distribution measurement equipment, dynamic light scattering measurement equipment, particle size measurement equipment using Coulter's principle, and so on. In the present invention, a laser diffraction type particle size distribution measuring device is used for measurement.

The oil-in-water emulsion obtained by the present invention has a low viscosity, and the viscosity obtained by a B-type viscosity meter (25 ° C, 12 rpm, No. 1 rotor) is preferably 1,000 mPa · s or less, and more preferably 300 mPa · s or less. In the present invention, even with such a low viscosity, it is possible to form an oil-in-water emulsion having excellent temporal dispersion.

The oil-in-water emulsion of the present invention has a fine dispersed particle diameter and high skin permeability of oily components. In addition, it can be designed with low viscosity, good use feeling, and easy to apply on the skin. In particular, its low viscosity and high permeability are convenient for applying to hairy scalp. In addition, the oil-in-water emulsion of the present invention can maintain dispersibility for a long period of time even with a low viscosity. Therefore, although the oil-in-water emulsion of the present invention is not limited to this, it can be said that it is suitable to be applied to cosmetics and products for external skin composition. Examples of the composition for external skin application include cosmetics, quasi-drugs, and pharmaceuticals that are directly applied to the skin. Examples are: lotions, serums, hair restorers, and so on. The so-called perfumery products refer to those who apply, spread on the body, or use it in other similar ways for the purpose of cleaning the body, beautifying, increasing charm, changing the appearance, and maintaining the health of the skin or hair. Contains skincare products (lotions, serums, facial cleansers, Bath milk, etc.), hair care products (shampoo, conditioner, conditioner, hair conditioner, etc.), cosmetics such as makeup products, perfumes mixed with perfume, and so on.

Examples of the present invention are described below, but the present invention is not limited to these. In addition, the units of the numerical values related to the blending amounts of the components in the following tables are all weight%.

[Example] (Reference example 1) Effect of the type of polyol on emulsification

The ingredients of the "polyol phase" in each of the following formulae 1 were mixed with a dispersion stirrer at a temperature of 80 ° C. The POE dehydrosorbide monooleate in Table 1 uses RHEODOL TW-O120V (Fugamor number 20 of ethylene oxide) manufactured by Kao Corporation, and glycerin is used for cosmetic glycerin (glycerin content is 98.5% or more). Here, while stirring at 80 ° C. with a dispersing mixer (K. ROBOMICS (registered trademark) manufactured by Primix Corporation, rotation speed 3500 rpm), an oily component (glyceryl tris (ethylhexanoate)) was slowly added over 5 minutes while stirring. After the addition of the oily component, stirring was continued at 80 ° C for 30 minutes to prepare an O / A emulsion. 10 parts by weight of an O / A emulsion cooled to room temperature was mixed with 0.01 parts by weight of citric acid, 0.09 parts by weight of sodium citrate, 5 parts by weight of butanediol, 3 parts by weight of glycerol, and 0.1 part by weight of methyl paraben Parts, 81.8 parts by weight of pure water, and an aqueous medium composed of an oil-in-water emulsion. The average particle diameter of the obtained oil-in-water emulsion was measured using a laser diffraction particle size distribution meter (SALD-200 manufactured by Shimadzu Corporation). In addition, the measurement is moderate according to the usual method. Dilute with water. The results are shown in Table 1. When the polyhydric alcohol uses only binary 1,3-butanediol (formulations A and B), the O / A type emulsion is separated immediately after cooling after formulation, and an oil-in-water type emulsion cannot be formulated. The same is true for Formula F.

(Reference example 2) Effects of types of fatty acid esters on emulsification

The ingredients of the "polyol phase" in each of the following Table 2 were mixed with a dispersion stirrer at a temperature of 80 ° C. The POE dehydrosorbide monooleate in Table 2 uses RHEODOL TW-O120V (Fugamor number of ethylene oxide 20) manufactured by Kao Corporation; the dehydrosorbide sesquiol oil uses RHEODOL A-O15V manufactured by Kao Corporation ; Deca glyceryl monomyristate was used as NIKKOL Decaglyn 1-M manufactured by Nikko Chemicals Co., LTD .; POE hardened castor oil was used as NIKKOL HCO-40 (POE40) manufactured by Nikko Chemicals Co., LTD .; glycerin was used for cosmetics Use concentrated glycerin (glycerin content over 98.5%). Here, while stirring at 80 ° C. with a dispersing mixer (K.ROBOMICS (registered trademark) manufactured by Primix Corporation, 3000 rpm), the oily component (isopropyl myristate; Nikko Chemicals Co. , LTD.Manufactured NIKKOL IPM-100), formulated with O / A emulsion. Then, it cooled to room temperature, and measured the average particle diameter using the laser diffraction type particle size distribution meter (SALD-200 by Shimadzu Corporation). In addition, during the measurement, moderate dilution with water was performed according to a conventional method. The results are shown in Table 2. When POE hardened castor oil for fatty acid esters (formulation J) has a poor dispersion state, an emulsion having a desired particle diameter cannot be obtained.

(Example 1)

The ingredients of the "polyol phase" in each of the formulas in the following Table 3 were mixed with a disperser under heating at 80 ° C. The deca glyceryl monomyristate in Table 3 uses NIKKOL Decaglyn 1-M manufactured by Nikko Chemicals Co., LTD .; sorbitan sesqui oil uses RHEODOL A-O15V manufactured by Kao Corporation; POE sorbitan monomer The oleate is made of RHEODOL TW-O120V (Fugamor number 20 of ethylene oxide) made by Kao Corporation; the N-stearyl-L-glutamate is made by Ajinomoto AMISOFT (registered trademark) HS-11P; Glycerin is used for cosmetic concentrated glycerin (glycerin content over 98.5%). Here, while stirring at 80 ° C. with a dispersing mixer (K.ROBOMICS (registered trademark) manufactured by Primix Corporation, rotation speed 8000 rpm), slowly add an oily component (tocopherol mixture; Nissin Oleo Group Co., Ltd.) while taking 5 minutes TOCOPHEROL 100) manufactured by the company, formulated with O / A emulsion. Then, it cooled to room temperature, and measured the average particle diameter using the laser diffraction type particle size distribution meter (SALD-200 by Shimadzu Corporation). In addition, during the measurement, moderate dilution with water was performed according to a conventional method. The results are shown in Table 3. By adding a fluorenyl amino acid salt to the polyol phase, the average particle diameter of the oily component can be significantly reduced.

(Example 2)

The ingredients of the "polyol phase" in each of the following Table 4 were mixed with a dispersing mixer under heating at 80 ° C. Decaglyceryl monomyristate of Table 4 was used NIKKOL manufactured by Nikko Chemicals Co., LTD. Decaglyn 1-M; Decaglyceryl monooleate is made of NIKKOL Decaglyn 1-OV manufactured by Nikko Chemicals Co., LTD .; N-stearyl-L-glutamate is made of AMISOFT manufactured by Ajinomoto Corporation ( (Registered trademark) HS-11P; glycerin uses cosmetic glycerin (glycerin content over 98.5%). Here, while stirring at 80 ° C. with a dispersing mixer (K. ROBOMICS (registered trademark) manufactured by Primix Corporation, rotation speed 8000 rpm), the oily ingredients were slowly added for 5 minutes to prepare an O / A emulsion. Then, it cooled to room temperature, and measured the average particle diameter using the laser diffraction type particle size distribution meter (SALD-2200 by Shimadzu Corporation). When measuring, dilute with water according to the usual method. As shown in Table 4, an O / A type emulsion having a minute particle diameter can be produced by the present invention.

(Example 3)

The ingredients of the "polyol phase" in each of the following Table 5 formulations were mixed with a dispersing agitator at a temperature of 80 ° C. The deca glyceryl monomyristate in Table 5 uses NIKKOL Decaglyn 1-M manufactured by Nikko Chemicals Co., Ltd .; Trademark) HS-11P; Glycerin use makeup Concentrated glycerin (more than 98.5% of glycerin). Here, while stirring at 75 to 85 ° C. with a dispersing mixer (K.ROBOMICS (registered trademark) manufactured by Primix Corporation, rotation speed 8000 rpm), the oily component was slowly added for 5 minutes to prepare an O / A emulsion. Then, it cooled to room temperature, and measured the average particle diameter using the laser diffraction type particle size distribution meter (SALD-200 by Shimadzu Corporation). When measuring, dilute with water according to the usual method. The obtained emulsion was stored in an environment of 40 ° C. and 75% RH for a period of 6 months, and the average particle diameter was measured every month during the storage period. The change with time of the average particle diameter is shown in FIG. 1. In addition, the condition of "storing at 40 ° C and 75% RH for 6 months" corresponds to a period of storage at room temperature for 3 years. As shown in FIG. 1, even if the O / A emulsion of the product 13 of the present invention is stored for a long period of time, no significant change in the dispersed particle size is observed, and it has high dispersion stability over time.

(Example 4)

The skin permeability of the product 13 of the present invention in Example 3 is as follows As described above, permeability experiments were performed using a cultured skin model. A 12-well cell culture partition was added with 2 ml of phosphate buffered saline (PBS), and a three-dimensional culture epidermal model EpiSkin (registered trademark) Large Model was set. The product 12 of the present invention was applied to the stratum corneum side of a skin model, and culture was started at 37 ° C. Skin models were collected 24 hours after application. The obtained skin model was placed in a microcentrifuge tube containing 1 ml of ethanol and broken with a Tissue Lyser. 0.1 ml of the supernatant was taken as a sample for the determination of tocopherol acetate, and the tocopherol acetate penetrated into the skin was quantitatively measured by high performance liquid chromatography (HPLC). The results are shown in Fig. 2. As shown in Fig. 2, the transdermal permeability of tocopherol acetate contained in the product 13 of the present invention has been confirmed.

(Example 5)

Using the present invention products 1 and 2 of Example 1, an oil-in-water emulsion was prepared. Specifically, according to the formula of Table 6 below, the O / A emulsions of the products 1 and 2 of the present invention were added to the aqueous medium phase and mixed with a dispersing mixer at a temperature of 35 ° C. The pH value and absorbance (630 nm) of the obtained oil-in-water emulsions (Inventions 14 and 15) were measured. Next, for each of the oil-in-water emulsions (the present inventions 14 and 15), changes in pH and absorbance during storage during a storage period of 5 months at 5 ° C or 40 ° C were measured. In addition, in general, the absorbance of an emulsion is related to the dispersion particle size of the emulsion. It is considered that the smaller the absorbance, the smaller the dispersion particle size. The results are shown in Fig. 3. As shown in FIG. 3, no matter which type of oil-in-water emulsion has dispersion stability over a long period of time, in particular, the product 14 of the present invention using polyglycerol fatty acid ester as a fatty acid ester has excellent stability over time Sorbitan fatty acid ester Of this invention 15.

(Example 6)

Using the product 1 of the present invention in Example 1, an oil-in-water emulsion (hair growth agent) was prepared. Specifically, the O / A emulsion of the product 1 of the present invention was added to the aqueous medium phase according to the formula of Table 7 below, and mixed with a paddle mixer at a temperature of 30 ° C. The viscosity of the obtained hair restorer measured by a B-type viscosity meter (VISCOMETER (MODEL: BM) manufactured by Toki Sangyo Co., Ltd., 25 ° C, 12 rpm, No. 1 rotor) was 130 mPa · s. The obtained hair restorer has no sticky feeling and is a hair restorer with good use feeling.

(Example 7)

Using the product 1 of the present invention in Example 1, an oil-in-water emulsion (lotion) was prepared. Specifically, the O / A emulsion of the product 1 of the present invention was added to the aqueous medium phase according to the formulation of the following Table 8 and mixed with a paddle mixer at a temperature of 30 ° C.

Claims (13)

An emulsion comprising the following components: 80-97% by weight of a polyhydric alcohol having a valence of 3 or more, selected from the group consisting of polyglyceryl fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like 1 to 10% by weight of fatty acid esters, 0.01 to 3% by weight of fluorenylamino acids and / or salts thereof, and 1 to 18% by weight of oily ingredients, and the aforementioned oily ingredients are dispersed in Alcoholic phase. The emulsion according to claim 1, wherein the polyhydric alcohol having a valence of 3 or more is glycerin. The emulsion according to claim 1 or 2, wherein the fatty acid ester is a polyglyceryl fatty acid ester. The emulsion according to claim 1 or 2, wherein the amidinoamino acid and / or its salt is 0.01 to 1% by weight. The emulsion of claim 1 or 2, wherein the average particle diameter of the dispersed oily component is 1 μm or less. An oil-in-water emulsion, which is obtained by dispersing the emulsion of any one of claims 1 to 5 in an aqueous medium. The oil-in-water emulsion according to claim 6, which contains 90 to 99.5% by weight of an aqueous medium. For example, the oil-in-water emulsion of claim 6 or 7 has a viscosity of 1000 mPa · s or less based on a B-type viscosity meter (25 ° C, No. 1 rotor, 12 rpm). The oil-in-water emulsion according to claim 6 or 7, wherein the average particle diameter of the dispersed oily component is 1 μm or less. A fragrance cosmetic comprising the oil-in-water emulsion according to any one of claims 7 to 9. A composition for external skin application comprising the oil-in-water emulsion according to any one of claims 7 to 9. A method for producing an emulsion, comprising the steps of mixing a polyglyceryl fatty acid ester, a sorbitan fatty acid ester, and a polyoxyethylene sorbitan fat in a liquid containing a polyhydric alcohol having a valence of 3 or more. Esters and fatty acid esters of these mixtures, and fluorenylamino acids and / or their salts, and then add the oily component to the aforementioned liquid containing the polyol under stirring to form an oily component dispersed in The emulsion in the liquid containing a polyhydric alcohol; and the fluorenylamino acid and / or a salt thereof based on the amount of the emulsion, 0.01 to 3% by weight; The amount is based on the amount of 80 to 97% by weight, and the oily component is the amount of 1 to 18% by weight based on the amount of the emulsion. A method for manufacturing an oil-in-water emulsion, comprising the steps of mixing a polyglyceryl fatty acid ester, a sorbitan fatty acid ester, and a polyoxyethylene dewatering solution in a liquid containing a polyhydric alcohol having a valence of 3 or more. Fatty acid esters of sorbitol fatty acid esters and the mixtures thereof, and fluorenylamino acids and / or their salts, and then add an oily component to the aforementioned liquid containing a polyol under stirring to form an oily property An emulsion in which the components are dispersed in a liquid containing a polyhydric alcohol, and the formed emulsion is then mixed with an aqueous medium to form an oil-in-water emulsion in which oily components are dispersed in the aqueous medium, and the amidinoamino acid and / or its salts Based on the amount of the emulsion in which the oily component is dispersed in a liquid containing a polyol, it is 0.01 to 3% by weight. The polyol having a valence of 3 or more is an emulsion in which the oily component is dispersed in a liquid containing a polyol. The amount is based on an amount of 80 to 97% by weight. The oily component is an amount of 1 to 18% by weight based on the amount of the emulsion in which the oily component is dispersed in a liquid containing a polyol.