JP2012171892A - External preparation for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external preparation of skin, which inhibits the separation of an oil, is excellent in storage stability, gives fresh cool feeling and moisture-retaining feeling, and gives a good feeling of use.SOLUTION: The external preparation for the skin comprises the following ingredients (A) to (F): (A) 0.1 to 1 mass% of agar, (B) 0.1 to 2 mass% of an acrylic acid-based polymer, (C) 5 to 20 mass% of an oily ingredient, (D) 3 to 20 mass% of ethanol, (E) 0.05 to 10 mass% of a powdery material, and (F) 50 to 91.7 mass% of water; and is prepared by dispersing the approximately spherical gel-like particles of the ingredient (A) in an aqueous phase comprising the ingredients (B), (C), (D), (E) and (F).

Description

  The present invention relates to an external preparation for skin.

Conventionally, as an aqueous cosmetic containing an oil component for the purpose of moisturizing, moistening and protecting the skin, there are known dosage forms such as an emulsified type, a solubilized type and a two-layered type.
As a consumer trend in recent years, a fresh and light O / W type or a high water content W / O type external preparation for skin is preferred. There is a growing need for daily use that is light and good, and that has a fresh feel with reduced oil stickiness.

  Based on such a background, capsule-containing cosmetics that stably incorporate oil-based ingredients while taking advantage of the characteristics of solubilized water-based cosmetics (skin lotions), have both a moisturizing and protective effect and a sustained effect thereof. Various proposals have been made.

  For example, a cosmetic containing a capsule encapsulating an oil-in-water (hereinafter referred to as O / W) emulsion, wherein the capsule membrane is composed of 0.1 to 1.0% by weight of calcium alginate with respect to the total amount of the capsule. An emulsion-encapsulated capsule-containing cosmetic (Patent Document 1), a barium alginate capsule in which at least part of an alginate is present in the form of a polyvalent metal salt containing a barium salt as an essential component is a pH-adjusted carboxyvinyl polymer. Capsule cosmetics (Patent Document 2) existing in an external phase composed of an aqueous solution, soft capsules based on agar, and water-containing cosmetics containing spheroids (Patent Document 3) have been proposed.

  In particular, when agar is applied to cosmetics, not only the function of a mere thickener, but also a cool refreshingness utilizing the “high water content” of agar can be obtained. That is, the agar gel is easily crushed on the skin when applied, and can give a cool and refreshing refreshing feeling. In particular, a cool feel during application is preferred for summer cosmetics. However, when agar is directly blended with cosmetics, the entire cosmetics are hardened, and the texture and feeling of use deteriorate.

  The present inventors have focused on this point and have so far developed cosmetics in which hydrogel particles are dispersed (Patent Documents 4 and 5). In addition, the hydrogel particles contain ceramide, UV scatterers, and absorbents, and the stability is investigated by suppressing aggregation, and oily components are included in the agar to suppress stickiness. And we succeeded in realizing a fresher feeling of use.

  On the other hand, when agar is blended with cosmetics, stickiness and sliminess peculiar to polysaccharides become a problem. For this reason, the present inventors examined improving the feeling of use such as freshness and refreshing feeling by blending ethanol.

  However, when an acrylic acid polymer is used as a thickening / emulsifier, the emulsifying power is weak and the stability of the emulsified composition deteriorates as the amount of ethanol increases. I couldn't. Further, it was also found that oil separation occurs because hydrogel particles (agar) collide with oil droplets in the gel of the outer phase of the agar and promote the coalescence of the oil.

Japanese Patent Laid-Open No. 2-117610 JP 11-29433 A JP-A-1-193216 JP 2002-20227 A Japanese Patent Laid-Open No. 2002-20228

  An object of the present invention is to provide an external preparation for skin having excellent storage stability, freshness, and good usability.

  By dispersing the powder in an aqueous phase containing agar and an oily component, the present inventors have a fresh and moist feeling during use, and the separation of oil generated on the surface of the external preparation is suppressed. It was found that an external preparation for skin having excellent stability over time can be obtained.

The present invention includes the following components (A) to (F);
(A) Agar 0.1-1% by mass,
(B) Acrylic acid-based polymer 0.1-2% by mass,
(C) Oily component 5-20% by mass,
(D) 3 to 20% by mass of ethanol,
(E) powder 0.05-10 mass%,
(F) Water 50-91.7 mass%
A skin external preparation in which substantially spherical gel-like particles of component (A) are dispersed in an aqueous phase containing components (B), (C), (D), (E) and (F) Is to provide.

  The external preparation for skin of the present invention has a fresh refreshing sensation and a moist moisturizing feeling and is excellent in stability over time because separation of oily components generated on the surface of the external preparation is suppressed.

(A) Agar:
The agar used in the present invention is not particularly limited, but the jelly strength (Nichikansui method) of the agar is 147 kPa (1500 g / cm ² ) or less from the viewpoint of feel when used when applied to the skin. It is preferably 19.6 kPa (200 g / cm ² ) to 127 kPa (1300 g / cm ² ). For the jelly strength, a 1.5% by mass aqueous solution of agar was prepared, and the aqueous solution was allowed to stand at 20 ° C. for 15 hours to solidify. The maximum mass (g) per 1 cm ² of the surface area when the gel withstands the load for 20 seconds at 20 ° C. can be obtained.
As the agar of the component (A), for example, Ina Agar PS-84, Z-10, AX-30, AX-100, AX-200, T-1, S-5, M-7, UP-16, CS Commercial products such as -16A, CS-420, and CS-670 (above, manufactured by Ina Food Industry Co., Ltd.) can be used. Of these, AX-200, UP-16, and CS-16A are preferred.

  In the present invention, agar forms gel-like particles. The gel particles have a substantially spherical shape such as a spherical shape or an elliptical shape, and have a volume-based average particle size of 10 to 10,000 μm, particularly 30 to 3,000 μm, in terms of feeling in use, appearance, and productivity. To preferred. The volume-based average particle diameter of the gel-like particles can be measured by a laser diffraction scattering method for particles of 1000 μm or less, and by a sieving method for particles exceeding 1000 μm.

Although the manufacturing method of the agar gel-like particle | grains is not specifically limited, For example, it can manufacture with the following method.
First, agar is mixed with water and heated to a temperature equal to or higher than its melting temperature to be sufficiently dissolved. In the case where an oily component, powder or the like is contained in the gel particles, an aqueous solution containing the oily component or the like is separately prepared and added and mixed therewith. Gel particles can be obtained from these solutions (mixed solutions) by a general dropping method, spraying method, stirring method or the like.

  The dripping method uses the property that a liquid mixture is discharged from a hole and the discharged liquid mixture becomes droplets due to its surface tension or interfacial tension, and the liquid droplets are cooled in a gas phase or liquid phase such as air. It is a method of solidifying and manufacturing. In this method, from the viewpoint of producing agar gel particles having a uniform particle size, it is preferable to discharge the mixed solution from the holes while applying vibration. For example, Japanese Patent Application Laid-Open No. 2002-58990 discloses that a dispersion liquid in which an oily component is dispersed in an aqueous component solution in which a non-crosslinked hydrogel is dissolved is ejected from a hole while being vibrated. A process for producing hydrogel particles is described in which the droplets are cooled and solidified after the formation of.

The spraying method is a method of manufacturing by using a spray nozzle, spraying a liquid mixture from the spray nozzle into the gas phase, forming droplets by the surface tension, and cooling and solidifying the droplets in the gas phase. .
For example, a microcapsule having a multi-core structure including a natural carotenoid is produced by a spray cooling method. More specifically, the gelation temperature is set in a tower provided with an atmosphere below the gelation temperature of the O / W emulsion. Microcapsules can be obtained by spraying the above O / W emulsion so that the particles have an average particle diameter of 50 to 3000 μm, cooling and solidifying, and collecting (Japanese Patent Laid-Open No. 9-302379). ). Moreover, the droplet formed by spraying the dispersion liquid in which the oil component is dispersed in the aqueous solution of the aqueous component in which the gel agent of the non-crosslinked hydrogel having a gel point of 30 ° C. or higher is dissolved is cooled. When solidifying, hydrogel particles can be produced without necessarily requiring a cooling facility for cooling droplets generated by spraying (Japanese Patent Laid-Open No. 2007-160277).

In the stirring method, the mixed liquid is poured into a liquid that has a property that does not substantially mix with the mixed liquid and is adjusted to a temperature equal to or higher than the gelling temperature, and the mixed liquid is atomized by a shearing force by stirring. This is a method of manufacturing by using the property of forming droplets and cooling and solidifying the droplets in a liquid that does not substantially mix with the liquid mixture.
For example, an O / W emulsion is prepared from an inner oil phase and an aqueous phase containing a hydrophilic polymer gelling agent that is solidified by heating and cooling, and this O / W emulsion is further dispersed and emulsified in the outer oil phase to obtain an O A microcapsule can be produced by forming a / W / O emulsion and solidifying and encapsulating the aqueous phase (Japanese Patent Laid-Open No. 2001-97818). Further, shear gel can be used to enhance the trapping of the active substance of the gel particles and improve the dispersibility (Japanese Patent No. 3949580).

  In any of the dropping method, the spraying method, and the stirring method, the temperature of the mixed solution at the time of discharging, spraying, or charging is preferably set to a temperature of not less than the gelling temperature and not more than 100 ° C. Further, from the viewpoint that spherical particles having excellent aesthetics can be easily produced, the temperature of the mixed solution is preferably set to a gelling temperature + 10 ° C. or higher, more preferably set to a gelling temperature + 20 ° C. or higher. preferable. The upper limit of this temperature is 100 ° C., which is the boiling point of water.

  In addition to the above method, a spherical microgel can also be produced by dissolving a hydrophilic thickening compound in water and then cooling the gel to form a spherical microgel (Japanese Patent Laid-Open No. 2001-342125). JP, 2009-203200, A).

  It is preferable that the gel-like particles contain 0.1 to 10% by mass, and further 1 to 3% by mass of agar, from the viewpoint of suppressing water separation from the agar particles and feeling freshness at the time of use. Moreover, when it contains an oil-based component and powder, it is preferable to contain 0-80 mass% in total in gel-like particle | grains, Furthermore, 10-50 mass% is contained.

The gel particles may contain an oil component, powder, emulsifying dispersant, preservative, fragrance and the like.
The oil component contained in the gel particles is not particularly limited as long as it is usually used in cosmetics, and may be any of solid fat, semi-solid oil, liquid oil and the like. Examples include fats and oils, waxes, ceramides, hydrocarbon oils, silicone oils, higher fatty acids, higher alcohols, ester oils and the like. Moreover, a ultraviolet absorber etc. can be contained.
Further, the powder is not particularly limited as long as it is usually used in cosmetics, and examples thereof include inorganic powders such as zinc oxide, titanium oxide, and iron oxide, and organic powders.

  The agar gel particles thus obtained are dispersed in an aqueous phase containing the components (B), (C), (D), (E) and (F).

Agar is contained in the skin external preparation in an amount of 0.1 to 1% by mass, preferably 0.2 to 0.7% by mass. If it is in this range, separation of the oily component is suppressed, the stability of the entire external preparation for skin is excellent, and a fresh feeling of refreshing and moisturizing feeling can be obtained.
Further, it is preferable that the agar gel-like particles are contained in the external preparation for skin in an amount of 10 to 70% by mass for uniform dispersion in the external preparation for skin.

(B) Acrylic acid polymer:
The acrylic acid polymer used in the present invention plays a role of dispersing gel-like particles (agar) by thickening the aqueous phase.
An acrylic acid polymer has a function of emulsifying various oil components by its emulsifying ability to produce a unique texture.

The acrylic acid polymer is not particularly limited, and examples thereof include polyacrylic acid, acrylic acid / alkyl methacrylate copolymer, and methacrylic acid alkyl ether copolymer.
Examples of commercially available products include CARBOPOL 980, 981, 1342, ETD2020, PEMULEN TR-1, PEMULEN TR-2 (above, manufactured by Lubrizol Advanced Materials), and Accurin 22 (Aculyn). Rohm & Haas), Aristoflex AVC, HMB (Clariant Japan) etc. can be used.
Of these, acrylic acid / alkyl methacrylate copolymers are preferred.

  The acrylic acid polymer is used as an acrylic acid polymer salt by neutralization with a base. Examples of the base include alkali metal hydroxides such as sodium and potassium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and basic amino acids such as arginine and lysine.

  The acrylic acid-based polymer is contained in the skin external preparation in an amount of 0.1 to 2% by mass, preferably 0.2 to 1% by mass, and more preferably 0.3 to 0.4% by mass. If it is in this range, it is excellent in the stability of the whole external preparation for skin, and a fresh feeling of refreshing and moisturizing feeling can be obtained.

(C) Oil component:
The oily component used in the present invention is not particularly limited as long as it is usually used in cosmetics, and may be solid or liquid at room temperature, and any oily component can be blended. Examples of liquids include vegetable oils such as olive oil, hydrocarbon oils such as squalane and liquid paraffin, silicone oils such as dimethylpolysiloxane, and ester oils. Solids include oils and fats, waxes, Examples include alcohols, higher fatty acids, fatty acid esters, ceramides, cholesterol, cholesterol esters and the like.

Moreover, in this invention, the ultraviolet absorber normally used for cosmetics can be used suitably as an oil-based component. For example, benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives, urocanic acid, ethyl urocanate, 4-tert-butyl-4′-methoxydibenzoyltan, 2- (2′-hydroxy-5) '-Methylphenyl) benzotriazole, methyl anthranilate, rutin and derivatives thereof.
The oil component preferably contains such an ultraviolet absorber.

  As the oily component of component (C), one or more kinds can be used, and 5 to 20% by mass, preferably 5 to 15% by mass is contained in the external preparation for skin. If it is in this range, separation of the oily component is suppressed, the stability of the entire external preparation for skin is excellent, and a fresh feeling of refreshing and moisturizing feeling can be obtained.

  The mass ratio of the component (B) to the component (C) is (B) / (C) = 0.006 to 0.33, further 0.0133 to 0.2, particularly 0.02 to 0.08. It is preferable that oil separation is suppressed, the stability of the entire skin external preparation is excellent, and a fresh feeling of refreshing and moisturizing can be obtained.

(D) Ethanol:
The skin external preparation of the present invention can improve freshness and refreshing feeling by containing a relatively large amount of ethanol.
In a system containing a thickener such as ethanol and component (B), the shape may deteriorate depending on the type of the thickener, and the viscosity stability over time and the appearance and properties may be impaired. However, in the present invention, a combination of agar, powder, and oily component can provide a fresh refreshing feeling and a feeling of use with a moisturizing feeling, and can also provide a skin external preparation excellent in stability over time.

  Ethanol is contained in the skin external preparation in an amount of 3 to 20% by mass, preferably 6 to 10% by mass. Within this range, oil separation is suppressed, the overall stability of the external preparation for skin is excellent, and a fresh feeling of refreshing and moisturizing can be obtained.

The mass ratio of the component (B) to the component (D) is (B) / (D) = 0.006 to 0.55, further 0.02 to 0.17, particularly 0.03 to 0.067. Is preferred.
Within this range, separation of oil is suppressed, the overall stability of the external preparation for skin is excellent, and a fresh, refreshing and moisturizing feeling can be obtained, which is preferable.

(E) Powder:
The powder used in the present invention is not particularly limited as long as it is used in ordinary cosmetics, and may be either organic powder or inorganic powder, and may have any shape. Examples thereof include nylon powder, cellulose powder, polyethylene powder, polymer powder such as polyacrylic acid polymer resin and silicone resin, and inorganic powder such as silica and siloxane.

Moreover, as a commercial item, for example, lauryl methacrylate / ethylene glycol / methacrylic acid sodium / sodium methacrylate copolymer (manufactured by Kao Corporation), Tokiwa Matsumoto Microsphere M-100 (Matsumoto Yushi Seiyaku Co., Ltd.) is used as a polymer powder. ), Matsumoto Microsphere M-503B (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), Tospearl 145A (made by Momentive Performance Materials Japan) as a siloxane polymer, Toray nylon fine particles SP-500 (made by Momentive Performance Materials Japan) Toray Industries, Inc.), PF-5 nylon SP-500 (manufactured by Daito Kasei Kogyo Co., Ltd.), nylon HK-5000 (manufactured by Sumika Enviro Science), urethane powder, plastic powders D-400, D-800 (Tohoku) Color Pigment)), Silica as silica Black (manufactured by Nippon insulation Co.) capsule KB, such as Aerosil (AEROSIL) 200 and 300 (manufactured by Nippon Aerosil Co., Ltd.) can be used.
Among these, nylon powder, polyacrylic acid polymer resin, silicone resin, and silica are preferable, and polyacrylic acid polymer resin is more preferable.

  These powders preferably have an average particle diameter of 100 nm to 10 μm, and more preferably 1 to 10 μm, in order to realize a fresh and light and light feeling of use. In the present invention, the average particle diameter is measured by a laser diffraction / scattering method.

  One or more kinds of the powder of component (E) can be used, and 0.05 to 10% by mass, preferably 0.1 to 5% by mass, is contained in the external preparation for skin. If it exists in this range, isolation | separation of an oil-based component will be suppressed and it will be excellent in the stability of the whole skin external preparation.

  The mass ratio of the component (C) and the component (E) is (C) / (E) = 0.5 to 400, more preferably 1 to 300, and particularly 1.2 to 25. In addition to being excellent in stability of the entire external preparation for skin, it is possible to obtain a fresh, refreshing and moisturizing feeling, which is preferable.

  The component (F) water forms the remainder of each component, and is contained in the skin external preparation in an amount of 50 to 91.7% by mass, preferably 60 to 80% by mass.

The external preparation for skin of the present invention is prepared by mixing the components (B), (C), (D), (E) and (F) to prepare an aqueous phase. It can be produced by dispersing the particles.
That is, in the external preparation for skin of the present invention, the component (A) is mixed with water, heated to a temperature equal to or higher than the dissolution temperature of agar to dissolve the agar, then cooled, and the volume standard average particle size is 10 to 10. A substantially spherical gel-like particle having a thickness of 10,000 μm is formed, while an aqueous phase containing components (B), (C), (D), (E) and (F) is prepared. It can be produced by dispersing the agar gel-like particles of the component (A).
The viscosity of the external preparation for skin of the present invention is preferably 500 to 100,000 mPa · s at 25 ° C.

The skin external preparation of the present invention is not limited to general skin cosmetics, but also includes medicinal cosmetics.
When used as a cosmetic, in addition to the above ingredients, any combination of moisturizers, alcohols, chelating agents, pH adjusters, preservatives, thickeners, pigments, fragrances, etc. that are usually used as cosmetic ingredients can do.
As described above, these components can be contained in the gel-like particles, or can be blended in the aqueous phase (outer layer).

  Various uses and forms such as O / W type emulsified cosmetics, aqueous cosmetics, gel cosmetics, creams, emulsions, lotions, foundations, skin cleansers, hair arts, hairdressing agents, hair nourishing agents, hair growth agents It can be used as such.

Production Example 1 (Production of agar gel-like particles)
As solid fat, stearic acid monoglyceride (trade name: Leodol MS-60, manufactured by Kao Corporation), and as crystalline organic ultraviolet absorber, hexyl diethylaminohydroxybenzoyl benzoate (trade name: ubinal Aplus, manufactured by BASF Japan), As the liquid oil, a dispersed phase component liquid containing octyl paramethoxycinnamate (BASF Japan, trade name: ubinal MC80) was prepared. At this time, the content in the obtained hydrogel particles is 3.0 parts by mass of stearic acid monoglyceride, 4.5 parts by mass of hexyl diethylaminohydroxybenzoyl benzoate, and 10.5 parts by mass of octyl paramethoxycinnamate. The mixture was mixed and dissolved by heating at 80 ° C.

  Agar (Ina Food Industry Co., Ltd., trade name: AX-200), As an emulsifying dispersant, acrylic acid / alkyl methacrylate copolymer (Lubrizol Advanced Materials, trade name: PEMULEN TR-2) and polyvinyl alcohol (Japan) Synthetic Chemical Industry, trade name: Gohsenol EG-05), 1N NaOH aqueous solution (manufactured by Kishida Chemical Co., Ltd.) and ion-exchanged water were mixed by heating at 80 ° C. to prepare a continuous phase component liquid. At this time, the content in the obtained hydrogel particles is 1.5 parts by mass of agar, 0.1 parts by mass of acrylic acid / alkyl methacrylate copolymer, 0.5 parts by mass of polyvinyl alcohol, 0.75 mass of 1N NaOH aqueous solution. Part and ion-exchanged water 79.15 parts by mass.

  A total of 1000 g of the dispersed phase component liquid and the continuous phase component liquid were prepared so as to have a mass ratio of 18:82, and the dispersed phase component liquid was heated and dissolved at 80 ° C. and the continuous phase component liquid was heated at 90 ° C., respectively. Thereafter, the dispersed phase component liquid is added to the continuous phase component liquid, and the mixture is stirred for 1 minute at a rotational speed of 8000 rpm using a homomixer (trade name: TK Robotics, manufactured by Primics Co., Ltd.). A mold dispersion was prepared.

The temperature of the oil-in-water dispersion is maintained at 80 ° C., and the oil-in-water dispersion is applied at a flow rate of 12 kg / hr at a height of 3.4 m from the spray nozzle (Ikeuchi Co., Ltd., empty cone nozzle K-010). Agar gel particles were recovered by spraying into a gas phase at 25 ° C. in the tank and cooling and solidifying the droplets of the oil-in-water dispersion formed by spraying at the bottom of the tank. This was designated Production Example 1.
The particle size of the agar gel-like particles was measured by a laser diffraction / scattering method using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model number: LA-920). The obtained agar gel-like particles have a substantially spherical shape with a volume-based average particle size of 120 μm and contain 1.5% by mass of agar.

Production Example 2 (Production of agar gel particles)
Agar gel particles were produced in the same manner as in Production Example 1 except that the dispersed phase component liquid was replaced with water, and this was designated Production Example 2. Production Example 2 is agar gel-like particles that do not contain an oily component.
The obtained agar gel-like particles have a substantially spherical shape with a volume-based average particle diameter of 140 μm and contain 1.5% by mass of agar.

Examples 1 to 6 and Comparative Example 1
Gels having the compositions shown in Table 1 were produced, and stability over time and usability were evaluated. The results are also shown in Table 1.

(Manufacturing method)
Components (1) to (6) are added to component (10) and dissolved. To this, component (8) is added to neutralize, then stirred, component (9) is added, and finally component (7) is added to obtain a gel.

(1) Stability over time:
Each gel was filled into a glass container (capacity: 50 mL) by 50 g, sealed, and subjected to a temperature cycle test. This is to change the temperature change at 40 ° C. into one cycle in 6 hours. The first cycle starts at 0 ° C to 40 ° C, the second cycle is -1 ° C to 39 ° C, the third cycle is -2 ° C to 38 ° C, and so on. To do. After 168 hours, the lower limit temperature reaches −28 ° C., and the temperature rises by 1 ° C. so that the lower limit temperature goes to 0 ° C. Two weeks later (336 hours later), each sample was taken out, visually evaluated for the presence or absence of oil on the sample surface, and judged according to the following criteria.
A: There is no liberation of oil on the composition surface by visual confirmation.
B: There is some oil liberation on the composition surface by visual confirmation.
C: There is oil liberation on the composition surface by visual confirmation.

(2) Feeling of use:
For each gel, three professional panelists applied to the forearm and performed an actual use test on the freshness of the skin. The feeling of use (freshness) was evaluated in increments of 0.1, assuming that the score 5 was fresh, the score 3 was neither, and the score 1 was not fresh, and an average score was obtained from the evaluation of three people.

(3) Measurement of viscosity:
At 25 ° C., a B8L viscometer (manufactured by Toki Sangyo Co., Ltd.), rotor No. 4. Measured at 30 rpm.

All of the gels obtained in Examples 1 to 6 are stable with respect to the temperature cycle test, have no oil separation on the gel surface, and have a moisturizing sensation with a refreshing and refreshing feeling. It was a light feeling. The gels of Examples 2 and 5 containing a polyalkyl acrylate resin were particularly fresh, had a refreshing feeling, had an excellent moisturizing feeling, and had a good feel.
On the other hand, the gel of Comparative Example 1 showed poor oil release on the gel surface by the temperature cycle test, and was poor in stability.

Example 7 (gel)
A gel having the following composition was produced.
(component)
(1) Lauryl methacrylate / ethylene glycol methacrylate / sodium methacrylate copolymer (spherical particles having an average particle size of 2.2 μm) 2.0 (mass%)
(2) Ethanol 7.0
(3) Alkyl-1,3-dimethylbutyl ether 3.0
(4) Squalane 3.0
(5) Dimethicone 3.0
(6) Acrylic acid / alkyl methacrylate copolymer
(PEMULEN TR-1, Lubrizol Advanced Materials) 0.3
(7) Agar gel-like particles of Production Example 1 30.0
(8) Potassium hydroxide 0.1
(9) Perfume appropriate amount
(10) Balance of purified water <br/> Total 100

(Manufacturing method)
Components (1) to (6) are added to component (10) and dissolved. To this, component (8) is added and neutralized, then component (9) is added, and finally component (7) is added and stirred to obtain a gel.
The viscosity of the gel was measured using a B8L viscometer, rotor no. It is 10,000 mPa · s when measured at 4, 30 rpm and 25 ° C.

Example 8 (gel)
A gel having the following composition was produced.
(component)
(1) Lauryl methacrylate / ethylene glycol methacrylate / sodium methacrylate copolymer (spherical particles having an average particle size of 2.2 μm) 2.0 (mass%)
(2) Ethanol 10.0
(3) Ethylhexyl methoxycinnamate 5.5
(4) Diethylaminohydroxybenzoyl hexyl benzoate 2.0
(5) Dimethicone 3.0
(6) Acrylic acid / alkyl methacrylate copolymer
(PEMULEN TR-1, Lubrizol Advanced Materials) 0.35
(7) Agar gel-like particles of Production Example 1 30.0
(8) Potassium hydroxide 0.1
(9) Perfume appropriate amount
(10) Balance of purified water <br/> Total 100

(Manufacturing method)
Components (1) to (6) are added to component (10) and dissolved. To this, component (8) is added and neutralized, then component (9) is added, and finally component (7) is added and stirred to obtain a gel.
The viscosity of the gel was measured using a B8L viscometer, rotor no. It is 15,000 mPa · s when measured at 4, 30 rpm and 25 ° C.

Example 9 (gel)
A gel having the following composition was produced.
(component)
(1) Lauryl methacrylate / ethylene glycol methacrylate / sodium methacrylate copolymer (spherical particles having an average particle size of 2.2 μm) 2.0 (mass%)
(2) Ethanol 8.0
(3) Ethylhexyl methoxycinnamate 6.5
(4) (4- (3,4-Dimethoxyphenylmethylene)
-2,5-dioxo-1-imidazolidinepropionate 2-ethylhexyl) 0.7
(5) Dimethicone 1.0
(6) Acrylic acid / alkyl methacrylate copolymer
(PEMULEN TR-1, Lubrizol Advanced Materials) 0.36
(7) Agar gel-like particles of Production Example 1 30.0
(8) Potassium hydroxide 0.1
(9) Perfume appropriate amount
(10) Balance of purified water <br/> Total 100

(Manufacturing method)
Components (1) to (6) are added to component (10) and dissolved. To this, component (8) is added and neutralized, then component (9) is added, and finally component (7) is added and stirred to obtain a gel.
The viscosity of the gel was measured using a B8L viscometer, rotor no. It is 13,000 mPa · s as measured at 4, 30 rpm and 25 ° C.

Example 10 (gel)
A gel having the following composition was produced.
(component)
(1) Lauryl methacrylate / ethylene glycol methacrylate / sodium methacrylate copolymer (spherical particles having an average particle size of 2.2 μm) 2.0 (mass%)
(2) Ethanol 6.0
(3) Ethylhexyl methoxycinnamate 7.0
(4) (2,4-bis-[{4- (2-ethylhexoroxy)
-2-hydroxy} -phenyl] -6- (4-
Methoxyphenyl) -1,3,5-triazine) 1.5
(5) Dimethicone 2.0
(6) Acrylic acid / alkyl methacrylate copolymer
(PEMULEN TR-1, Lubrizol Advanced Materials) 0.38
(7) Agar gel-like particles of Production Example 1 30.0
(8) Potassium hydroxide 0.1
(9) Perfume appropriate amount
(10) Balance of purified water <br/> Total 100

(Manufacturing method)
Components (1) to (6) are added to component (10) and dissolved. To this, component (8) is added and neutralized, then component (9) is added, and finally component (7) is added and stirred to obtain a gel.
The viscosity of the gel was measured using a B8L viscometer, rotor no. It is 12,000 mPa · s when measured at 4, 30 rpm and 25 ° C.

Example 11 (gel)
A gel having the following composition was produced.
(component)
(1) Lauryl methacrylate / ethylene glycol methacrylate / sodium methacrylate copolymer (spherical particles having an average particle size of 2.2 μm) 2.0 (mass%)
(2) Ethanol 8.0
(3) Ethylhexyl methoxycinnamate 5.5
(4) Diethylaminohydroxybenzoyl hexyl benzoate 2.0
(5) Dimethicone 3.0
(6) Acrylic acid / alkyl methacrylate copolymer
(PEMULEN TR-1, Lubrizol Advanced Materials) 0.34
(7) Agar gel-like particles of Production Example 2 30.0
(8) Potassium hydroxide 0.1
(9) Perfume appropriate amount
(10) Balance of purified water <br/> Total 100

(Manufacturing method)
Components (1) to (6) are added to component (10) and dissolved. To this, component (8) is added and neutralized, then component (9) is added, and finally component (7) is added and stirred to obtain a gel.
The viscosity of the gel was measured using a B8L viscometer, rotor no. It is 14,000 mPa · s when measured at 4, 30 rpm and 25 ° C.

  The gels obtained in Examples 7 to 11 are all fresh, have a refreshing feeling, have a light feeling and a moisturizing feeling, and are excellent in stability over time.

Claims (10)

The following components (A) to (F);
(A) Agar 0.1-1% by mass,
(B) Acrylic acid-based polymer 0.1-2% by mass,
(C) Oily component 5-20% by mass,
(D) 3 to 20% by mass of ethanol,
(E) powder 0.05-10 mass%,
(F) Water 50-91.7 mass%
A skin external preparation in which substantially spherical gel-like particles of component (A) are dispersed in an aqueous phase containing components (B), (C), (D), (E) and (F) .   The skin external preparation according to claim 1, wherein the mass ratio of the component (B) and the component (C) is (B) / (C) = 0.006 to 0.33.   The skin external preparation according to claim 1 or 2, wherein the mass ratio of the component (C) and the component (E) is (C) / (E) = 0.5 to 400.   The skin external preparation according to any one of claims 1 to 3, wherein a mass ratio of the component (B) and the component (D) is (B) / (D) = 0.006 to 0.55.   The average particle diameter of the powder of a component (E) is 100 nm-10 micrometers, The skin external preparation of any one of Claims 1-4. The skin external preparation according to any one of claims 1 to 5, wherein the mass ratio of the component (B) and the component (C) is (B) / (C) = 0.0133 to 0.2.   The skin external preparation according to any one of claims 1 to 6, wherein the mass ratio of the component (C) and the component (E) is (C) / (E) = 1 to 300.   The skin external preparation according to any one of claims 1 to 3, wherein a mass ratio of the component (B) and the component (D) is (B) / (D) = 0.02 to 0.17.   The skin external preparation according to any one of claims 1 to 8, wherein the oily component of the component (C) contains an ultraviolet absorber. The following components (A) to (F);
(A) Agar 0.1-1% by mass,
(B) Acrylic acid-based polymer 0.1-2% by mass,
(C) Oily component 5-20% by mass,
(D) 3 to 20% by mass of ethanol,
(E) powder 0.05-10 mass%,
(F) Water 50-91.7 mass%
Containing
The component (A) is mixed with water, heated to a temperature equal to or higher than the dissolution temperature of the agar, dissolved in the agar, then cooled, and a substantially spherical gel having a volume-based average particle size of 10 to 10,000 μm. On the other hand, an aqueous phase containing components (B), (C), (D), (E) and (F) is prepared, and the agar gel-like particles of component (A) are prepared in this aqueous phase. For producing an external preparation for skin.