JP7075261B2 - O / W / O type emulsified cosmetics - Google Patents

Description

The present invention relates to an oil-in-oil oil-type (hereinafter referred to as O / W / O-type) emulsified cosmetic.

Diethylaminohydroxybenzoyl hexyl benzoate and bisethyl hexyl oxyphenol methoxyphenyl triazine are known as effective UV absorbers for preventing sunburn (see, for example, Patent Documents 1 and 2). However, hexyl diethylaminohydroxybenzoylbenzoate and methoxyphenyltriazine bisethylhexyloxyphenol are known to be sparingly soluble substances, and it is particularly difficult to stably blend them in the coexistence with silicone oil. In order to solve this problem, a silicone-based oil-containing composite emulsion containing an organically modified clay mineral (see, for example, Patent Document 3), an ester oil agent satisfying the solubility of a sparingly soluble substance (for example, see Patent Document 4), and the like. Has been proposed. On the other hand, as a technique for improving water resistance, which is a function required for a sunscreen preparation, a blending of an oil-based film-forming agent has been proposed (see, for example, Patent Document 5).

Japanese Unexamined Patent Publication No. 2000-319628 Japanese Unexamined Patent Publication No. 9-188666 Japanese Unexamined Patent Publication No. 10-288858 Japanese Unexamined Patent Publication No. 2005-206573 Japanese Unexamined Patent Publication No. 2018-8910

However, the technique using an organically modified clay mineral as in Patent Document 3 may have insufficient storage stability as a pharmaceutical product when it is made into a milky liquid for the purpose of improving elongation. Further, in the technique of using an ester oil agent that satisfies the solubility of a sparingly soluble substance as in Patent Document 4, it is difficult to add another oil agent that does not satisfy the solubility, and the feeling of use such as non-stickiness cannot be sufficiently satisfied. There was a case. In addition, since the amount of non-volatile content in the formulation increases, even if a film-forming agent is added to improve the water resistance, the effect cannot be sufficiently exerted. As a result, diethylaminohydroxybenzoyl benzoate hexyl and bisethylhexyloxyphenol There was no choice but to reduce the amount of methoxyphenyl triazine compounded. Therefore, hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyltriazine can be stably blended without crystal precipitation, have excellent emulsion stability, have high water resistance, and have excellent usability without stickiness. The development of cosmetics was desired.

As a result of diligent studies, the present inventors have found that in the oil phase of the O / W type emulsified composition emulsified with phospholipids, hexyl diethylaminohydroxybenzoyl benzoate and / or bisethylhexyloxyphenol methoxyphenyltriazine, and inulin fatty acid ester and / Alternatively, it has been found that by blending a dextrin fatty acid ester, hexyl diethylaminohydroxybenzoylbenzoate and / or bisethylhexyloxyphenol methoxyphenyltriazine can be stably blended without crystallizing. Furthermore, by blending an oil-soluble film-forming agent and a volatile oil agent in the outer oil phase and emulsifying with a silicone surfactant to make an O / W / O type emulsified cosmetic, it has excellent emulsification stability and high water resistance. The present invention has been completed by finding that it has excellent usability without stickiness.
That is, in order to solve the above problems, the present invention
The following components (A) to (H);
(A) Phosphoridipid (B) Liquid oil (C) Diethylaminohydroxybenzoyl One or two selected from hexyl benzoate and bisethylhexyloxyphenol methoxyphenyltriazine (D) One or two selected from inulin fatty acid ester and dextrin fatty acid ester Provided is an O / W / O type emulsified cosmetic containing a seed (E) water (F) silicone surfactant (G) oil-soluble film-forming agent (H) volatile oil agent.

According to the present invention, hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyltriazine can be stably blended without crystallizing, have excellent emulsion stability, high water resistance, and excellent usability without stickiness. O / W / O type emulsified cosmetics can be provided.

Hereinafter, the present invention will be described. In addition, the numerical range represented by using "-" in this specification means the range including the numerical values before and after "-" as the lower limit value and the upper limit value.
The O / W / O type emulsified cosmetic in the present invention is a cosmetic containing the following components (A) to (H). In the O / W / O type emulsified cosmetics, more specifically, the oil-in-water (O1 / W) type emulsified composition is dispersed in the outer oil phase (O2). In the O / W / O type emulsified cosmetic of the present invention, the oil phase in the oil-in-water (O1 / W) type emulsified composition is referred to as an internal oil phase (O1).
In the present invention, an ultraviolet absorber that is sparingly soluble in non-polar or low-polar oils, such as hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyltriazine, is stably blended into emulsified cosmetics and has high water resistance. Regarding technology that demonstrates polarity. Diethylaminohydroxybenzoyl hexyl benzoate and bisethyl hexyloxyphenol methoxyphenyl triazine are compounds having a plurality of double bonds in the molecule as well as being sparingly soluble, and are characterized by high polarity. Therefore, it is difficult to mix it in a non-polar or low-polarity oil such as silicone oil, and there is a problem that precipitation occurs over time. On the other hand, the film-forming agent forms an insoluble film with water by volatilizing a volatile oil such as cyclic silicone oil, and exhibits water resistance. Therefore, in order to fully exert the effect of the film-forming agent, it is necessary to increase the ratio of volatile components in the preparation, but diethylaminohydroxybenzoylbenzoate hexyl and bisethylhexyloxyphenol methoxyphenyltriazine are used for volatile oils. Due to its low solubility, it was necessary to add a non-volatile polar oil, and it was difficult to combine the combination of hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyltriazine with the improvement of water resistance. .. In the present invention, hexyl diethylaminohydroxybenzoylbenzoate and / or bisethylhexyloxyphenolmethoxyphenyltriazine and inulin fatty acid ester and / or dextrin fatty acid ester are added to the internal oil phase of an O / W type emulsified composition containing a phospholipid as an emulsifying agent. By further blending and further dispersing the O / W type emulsified composition in the outer oil phase containing the oil-soluble film-forming agent and the volatile oil agent, diethylaminohydroxybenzoyl hexyl benzoate and / or While stably blending bisethylhexyloxyphenol methoxyphenyltriazine in the internal oil phase, we provide emulsified cosmetics that are not only stable over time, but also have high water resistance and are not sticky and have an excellent usability. ..
Hereinafter, each component used in the production of the O / W / O type emulsified cosmetic of the present invention and a method for producing the same will be described in detail.

Component (A): Phospholipids Phospholipids can generally be classified into two types: glycerophospholipids having a glycerophospholipid as a skeleton and sphingosine lipids having a sphingosine as a skeleton. The component (A) phospholipid used in the present invention includes glycerophospholipid and sphingolipid. Examples of the glycerophospholipid include, but are not limited to, phosphatidylcholine (also referred to as lecithin), phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, phosphatidylglycerol, and diphosphatidylglycerol. Examples of the sphingolipid include, but are not limited to, sphingomyelin. In the present invention, one or more of these compounds may be used as the phospholipid. In the present invention, as the phospholipid, egg yolk phospholipid, soybean phospholipid, or a purified product thereof and / or a hydrogenated product thereof or a hydroxide may be used. Further, in the present invention, a lysophospholipid from which one of the fatty acids of the phospholipid has been removed may be included. Examples of commercially available products include Resinol S-10E (Nikko Chemicals Co., Ltd.), Basis LS-60HR, Basis LP-20 (Nisshin Oillio Group Co., Ltd.) and the like.

The O / W type emulsified composition may contain cholesterol / and or phytosterol in addition to phospholipid as an agent that contributes to the improvement of dispersibility in the aqueous phase. These agents contribute to the improvement of dispersibility, as well as the moisturizing effect and the firmness effect. Further, in the present invention, as the component (A) phospholipid, a commercially available product in which cholesterol or the like is previously compounded can also be used. Commercially available products of phospholipid / cholesterol complex include EXTRASOME MMC (Nippon Oil Co., Ltd.), PRESOME CS2-101 (Nippon Seika Co., Ltd.), Basis CL-20 (Nisshin Oillio Group Co., Ltd.); Examples of commercially available phytosterol complexes include PHYTOPRESOME (Nippon Seika Co., Ltd.) and PYTOCOMPO-PP (Nippon Seika Co., Ltd.).

The content of the component (A) phospholipid in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 0.1 to 6% by mass (hereinafter, simply abbreviated as%), and 1 to 4%. Is even more preferable. This range is preferable because it has excellent emulsion stability.
Further, the component (A) is preferably contained in the internal oil phase (O1) of the O / W / O type emulsified cosmetic.

Ingredients: (B) Liquid oil Ingredient (B) in the present invention The liquid oil has a liquid property at 25 ° C. and is not particularly limited as long as it is an oil used in ordinary cosmetics, but its polarity is high. It is preferably a polar oil that is high and can dissolve the component (C) diethylaminohydroxybenzoyl benzoate hexyl and bisethylhexyloxyphenol methoxyphenyltriazine. Examples of the highly polar liquid oil include ester oil. As the ester oil, any of a monoester body, a diester body, a triester body and the like can be used, and for example, octyldodecyl myristate (IOB = 0.09), cetyl 2-ethylhexanoate (IOB = 0. 13), Octyldodecyl neopentate (IOB = 0.13), Isostearyl neopentate (IOB = 0.14), Isotridecyl isononanoate (IOB = 0.15), Isopropyl isostearate (IOB = 0.15), Tri Trimethylol propane isostearate (IOB = 0.16), olive oil (IOB = 0.16), isopropyl palmitate (IOB = 0.16), hexyl laurate (IOB = 0.17), isopropyl myristate (IOB =) 0.18), Isodecyl isononanoate (IOB = 0.19), Alkyl benzoate (C12-15) (IOB = 0.19), Isononyl isononanoate (IOB = 0.20), Isodecyl neopentanoate (IOB = 0) .22), neopentyl glycol dicaprate (IOB = 0.25), propylene glycol dicaprate (IOB = 0.26), diisostearyl malate (IOB = 0.28), ethylhexyl methoxycinnamate (IOB value =) 0.28), neopentyl glycol diethylhexanoic acid (IOB = 0.32), diethylhexyl succinate (IOB = 0.32), propylene glycol dicaprylate (IOB = 0.32), di (capryl / capric acid) Propropylene glycol (IOB = 0.32), glyceryl tri2-ethylhexanoate (IOB = 0.35), pentaerythrityl tetraethylhexanoate (IOB = 0.35), polyglyceryl-2 diisostearate (IOB = 0.41) ), Himashi oil (IOB = 0.42), and the like. The IOB value refers to the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, "inorganic value (IV) / organic value (OV)". Among these polar oils, liquid oils having an IOB value of 0.15 to 0.35 are particularly preferable, and polar oils having an IOB value of 0.25 to 0.30 are particularly preferable from the viewpoint of the solubility of the component (C). More preferred.
Among them, ethylhexyl methoxycinnamate is particularly preferable from the viewpoint of improving the ultraviolet absorbing ability because it is a highly polar liquid oil and has a UV-B absorbing ability by itself. As the component (B) liquid oil, one kind or two or more kinds can be used as needed.

The content of the component (B) liquid oil in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 1 to 12%, more preferably 3 to 10%. Within this range, the crystal precipitation of the component (C) can be further suppressed, and the water resistance is also excellent, which is preferable.
Further, the component (B) is preferably contained in the internal oil phase (O1) of the O / W / O type emulsified cosmetic.

Component (C): Diethylaminohydroxybenzoyl hexyl benzoate, bisethylhexyloxyphenol methoxyphenyltriazine Ingredient (C) diethylaminohydroxybenzoyl hexyl benzoate and bisethylhexyloxyphenol methoxyphenyltriazine in the present invention mainly have an absorption wavelength in the UVA region. It is an ultraviolet absorber that is sparingly soluble and highly crystalline, and is a compound that has a plurality of double bonds in the molecule and is characterized by high polarity. As the component (C) used in the present invention, one or two kinds can be used from hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyl triazine, but from the viewpoint of suppressing crystal precipitation and non-stickiness, two It is preferable to use seeds together.

The content of the component (C) in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 1 to 12%, more preferably 3 to 10%. Within this range, the emulsion stability is excellent and the usability is also excellent, which is preferable. Further, from the viewpoint of solubility, it is preferable that the content mass ratio (C) / (B) of the component (C) and the component (B) is 1 or less.
Further, the component (C) is preferably contained in the internal oil phase (O1) of the O / W / O type emulsified cosmetic.

Component (D): Inulin fatty acid ester, dextrin fatty acid ester The inulin fatty acid ester and dextrin fatty acid ester of the component (D) in the present invention are components involved in the inhibition of crystal formation of the component (B). In addition, by gelling the oily component, the effect of improving water resistance by lowering the fluidity (diffusibility) can be expected. In addition, it has the effect of imparting viscosity in a wide range, and is a component that improves the stability over time and the durability of makeup. The inulin fatty acid ester is an ester of inulin and a fatty acid or a fatty acid derivative, preferably an ester of a linear or branched saturated or unsaturated fatty acid having 8 to 32 carbon atoms and inulin, and the average molecular weight of inulin is The range of 300 to 10,000 is preferable. The average molecular weight in the present invention can be measured by a conventional method such as gel permeation chromatography or gel filtration chromatography. Specific examples thereof include those described in JP-A-3-197409 and JP-A-2002-193732, and examples of commercially available products include Leopard ISK2 (manufactured by Chiba Flour Milling Co., Ltd.). The dextrin fatty acid ester is an ester of dextrin and a fatty acid or a fatty acid derivative, preferably an ester of a higher fatty acid having 8 to 22 carbon atoms, and the average sugar polymerization degree of dextrin is preferably 3 to 150, and glucose of dextrin. The degree of fatty acid substitution per unit is preferably 1.5 to 1.7. Specific examples thereof include dextrin octanate, dextrin laurate, dextrin palmitic acid, dextrin myristic acid, dextrin stearate, dextrin behenate, coconut oil fatty acid dextrin, and (palmitic acid / octanoic acid) dextrin. Examples of commercially available products of these dextrin fatty acid esters include Leopard KL2, Leopard MKL2, Leopard TT2, and Leopard TL2 (all manufactured by Chiba Flour Milling Co., Ltd.). Among these, inulin fatty acid ester is more preferable, and inulin stearate is most preferable from the viewpoint of the effect of preventing crystal precipitation of the component (C).
The content of the component (D) in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 0.5% or more from the viewpoint of improving the effect of preventing crystal precipitation, and is not sticky. Therefore, 4% or less is preferable.
Further, the component (D) is preferably contained in the internal oil phase (O1) of the O / W / O type emulsified cosmetic.

Component (E): Water The component (E) water used in the present invention includes so-called water such as deionized water, distilled water, purified water, hot spring water, and plant-derived steam distilled water such as rose water and lavender water. Can be mentioned. The content of the component (D) in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 40 to 90%.
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Component (F): Silicone Surfactant The component (F) silicone surfactant in the present invention is an amphoteric surfactant having a silicone chain, and is a polyether-modified silicone having a polyether chain as a hydrophilic group. Examples of the hydrophilic group include polyglycerin-modified silicone having a polyglycerin chain, alkyl-modified silicone and the like.
The component (F) is a copolymer having at least an organopolysiloxane group and a hydrophilic group, and even a graft copolymer having the organopolysiloxane group as a main chain and a hydrophilic group in a side chain may be used. The organopolysiloxane group and the hydrophilic group may be a linear block copolymer in which they are alternately bonded. The organopolysiloxane group may be linear or may have a branched structure, and the hydrophilic group is not particularly limited, but a polyoxyalkylene group or a polyglyceryl group can be used. Further, the component (F) may be a co-modified organic group such as an alkyl group, a polyoxyalkylene group or a fluorine-substituted alkyl group.
The component (F) in the present invention is not particularly limited, but a polyoxyalkylene-modified organon having a linear-structured organopolysiloxane group as a main chain and a polyoxyalkylene group as a side chain is specifically defined. Examples thereof include polysiloxane, polyoxyalkylene-alkyl co-modified organopolysiloxane, and examples of commercially available products include KF-6017 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 5200 Formation Aid (manufactured by Toray Dow Corning Co., Ltd.). .. Further, as a substance grafted with a polyoxyalkylene group having an organopolysiloxane group having a branched structure as a main chain (silicone branched polyether-modified silicone), specifically, PEG-9 polydimethylsiloxyethyl dimethicone and lauryl. Examples thereof include PEG-9 polydimethylsiloxyethyl dimethicone and cetyl PEG-9 polydimethylsiloxyethyl dimethicone, and examples of these commercially available products include KF-6028 and KF-6038 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Be done. Specific examples of the product grafted with a polyglycerin group having an organopolysiloxane group having a branched structure as a main chain (silicone branched polyglycerin-modified silicone) include laurylpolyglyceryl 3-polydimethylsiloxyethyl dimethicone. Examples of commercially available products include KF-6105 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Specific examples of the block copolymer type include polyoxyethylene / butylene / dimethylpolysiloxane copolymer, polyoxyethylene / polyoxypropylene / butylene / dimethylpolysiloxane copolymer, and the like, which are commercially available. Examples of the product include FZ-2250, FZ-2233 (all manufactured by Toray Dow Corning Co., Ltd.), SILWET 236-L manufactured by Nippon Unicar Co., Ltd., and the like. Specific examples of the alkyl-modified silicone include methylpolysiloxane, cetylmethylpolysiloxane, poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, and poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer. Examples thereof include a coalesced dimethylsiloxane / methylcetylsiloxane copolymer, and examples of commercially available products include ABIL-EM90, ABIL-EM97, and ABILWAX9840 (all manufactured by Goldschmidt). Among these, silicone-branched polyether-modified silicone or alkyl-modified silicone is preferable from the viewpoint of emulsion stability over time and the effect of improving usability, and PEG-9 polydimethylsiloxyethyl dimethicone and lauryl PEG-9 polydimethylsiloxyethyl. Dimethicone and dimethylsiloxane / methylcetylsiloxane copolymers are more preferred. Two or more kinds of silicone surfactants can be used in combination as needed.
The content of the component (F) in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 0.1 to 8%, more preferably 0.5 to 4%. Within this range, the emulsion stability is excellent and the usability is also excellent, which is preferable.
Further, the component (F) is preferably contained in the external oil phase (O2) in the O / W / O type emulsified cosmetics.

Component (G): Oil-soluble film-forming agent The component (G) oil-soluble film-forming agent in the present invention is soluble in oils such as volatile oils and forms a film, and is usually used in cosmetics. Anything can be used without any particular restrictions. Here, the film having no fluidity is, for example, a film obtained by applying a mixture of an oil-soluble film forming agent in volatile oil to a glass plate, volatilizing the volatile oil, and then tilting the glass plate. It is a film whose shape does not change. For example, a terpene resin, a silicone resin, a hydrocarbon resin, and a vinyl acetate resin can be mentioned. Specific examples thereof include trimethylsiloxysilicic acid, polymethylsilsesquioxane, and (acrylate / dimethicone) copolymer), and trimethylsiloxysilicic acid is more preferable from the viewpoint of improving water resistance and non-stickiness. Commercially available products include KF-7312J (solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9821 (solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), BY11. -018 (solid content 30%, solvent: cyclopentasiloxane, manufactured by Toray Dow Corning), KP541 (solid content 60%, solvent: isopropanol, manufactured by Shin-Etsu Chemical Co., Ltd.), SR-1000 (momentive performance materials)・ KP545 (solid content 30%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), KP575 (solid content 30%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), SILFORM FLEXIBLE RESIN (manufactured by Shin-Etsu Chemical Co., Ltd.) Momentive Performance Materials Japan Co., Ltd.), Opanol B-100 (manufactured by BASF Co., Ltd.) and the like can be mentioned.
Among these, trimethylsiloxysilicic acid is more preferable from the viewpoint of water resistance and the effect of improving usability. As the component (G), two or more kinds can be used in combination as needed.

The blending amount of the component (G) in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 0.5% or more, and preferably 4% or less from the viewpoint of improving usability. This range is preferable from the viewpoint of improving the water resistance effect.
Further, the component (G) is preferably contained in the external oil phase (O2) in the O / W / O type emulsified cosmetics.

Component: (H) Volatile oil component The component (H) volatile oil agent in the present invention refers to an oil agent that is volatile at room temperature and has a low boiling point (boiling point at normal pressure is 260 ° C. or less) and is carbonized from isoparaffin or the like. Hydrogen oil, cyclic silicone oil (cyclomethicone) and the like are preferably used. When the component (H) is applied on the skin, it volatilizes over time, so that the film formation of the component (G) is not hindered and the stickiness is less likely to be felt, and the feeling of use of the O / W / O type emulsified cosmetic is felt. improves.
Examples of the hydrocarbon oil such as low boiling point isoparaffin include isododecane and isohexadecane. Examples of commercially available products include IP Solvent 2028MU (manufactured by Idemitsu Kosan Co., Ltd.), Pearl Dream 4 (manufactured by NOF Corporation), and ISODODECANE (manufactured by INEOS). Specific examples of the cyclic silicone oil (cyclomethicone) include hexamethylcyclotrisiloxane, octamethyltetracyclosiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetradecamethylcycloheptasiloxane, which are commercially available. As products, for example, Execol D-5 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SH245, DC345 (all manufactured by Toray Dow Corning Silicone Co., Ltd.) as decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane as dodecamethylcyclohexasiloxane. DC246 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like can be mentioned. The component (H) of the present invention can be used alone or in combination of two or more.
Among these, isododecane and decamethylcyclopentasiloxane are more preferable from the viewpoint of water resistance and the effect of improving usability. As the component (H), two or more kinds can be used in combination as needed.
The content of the component (H) in the O / W / O type emulsified cosmetic of the present invention is not particularly limited, but is preferably 1 to 60%, more preferably 20 to 50%. This range is preferable from the viewpoint of improving the water resistance effect and usability.
Further, the component (H) is preferably contained in the external oil phase (O2) in the O / W / O type emulsified cosmetics.

The cosmetic of the present invention is an O / W / O type emulsified cosmetic containing the above components (A) to (H), and preferably contains the components (A) to (D) in the internal oil phase O1. , Preferably a cosmetic containing the components (F) to (H) in the outer oil phase O2. This embodiment is preferable because the crystal precipitation of the component (C) is further suppressed and the water resistance is further improved.

The method for producing the O / W / O type emulsified cosmetic of the present invention is not particularly limited, and a normal method for producing an O / W / O type emulsified cosmetic can be used. An example is as follows.
(Method for producing O / W type emulsified composition)
First, the components (A) to (D) are mixed and, if necessary, heated to dissolve the component (C) in the component (B). The obtained oily composition is added to water and stirred to obtain an O / W type emulsified composition. Further, it is preferable to carry out high-pressure treatment to make the particles finer. Fine particle formation is preferable because it can improve the dispersion stability of the O / W type emulsified composition in the outer oil phase. A high-pressure processing device such as a microfluidizer can be used for atomization. By high-pressure treatment, the average particle size of the O / W type emulsified composition is preferably 500 nm or less, more preferably 300 nm or less. The average particle size was measured using a Coulter counter (Submicron Particle Analyzer N5: manufactured by Beckman Coulter).

(Manufacturing method of O / W / O type emulsified cosmetics)
Dispersion of the O / W type emulsified composition in the external oil phase (O2) can be carried out according to a usual method. An example is as follows.
An oily composition is prepared in which the components (F) and (G) are dispersed and / or dissolved in the component (H). The O / W type emulsified composition is gradually added to the oily composition and stirred to disperse the O / W type emulsified composition in the oily composition, resulting in O / W / O type. Emulsified cosmetics can be obtained.

The O / W / O type emulsified cosmetic of the present invention may contain other components other than the above (A) to (H) as long as the effects of the present invention are not impaired. For example, it may contain an ultraviolet absorber other than the ultraviolet absorber of the component (C), and it is preferable to contain another ultraviolet absorber because the ultraviolet absorbing ability is further improved. Among them, dimethicodiethylbenzalmalonate can be stably blended in the O / W / O type emulsified cosmetic of the present invention. Specific examples of the dimethicodiethylbenzalmalonate include PARSOL SLX (manufactured by DSM) and the like. It is preferable that dimethicodiethylbenzalmalonate is contained in the external oil phase (O2) of the O / W / O type emulsified cosmetics.

In addition to the above-mentioned components, the O / W / O-type emulsified cosmetic of the present invention includes components generally used in cosmetics as optional components, such as water-soluble components, moisturizers, oils, surfactants, and thickeners. , Powders, dyes, film-based preparations, pH adjusters, anti-fading agents, antioxidants, antifoaming agents, beauty ingredients, preservatives, fragrances, and other ingredients used in ordinary cosmetics impair the effects of the present invention. It can be appropriately blended within a non-quantitative and qualitative range. The O / W / O type emulsified cosmetic of the present invention can be applied to sunscreen cosmetics, base cosmetics and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. It should be noted that these do not limit the present invention in any way.

Example 1: Products 1 to 8 of the present invention and Comparative products 1 to 7: O / W / O type emulsified cosmetics O / W / O type emulsified cosmetics having the compositions shown in Tables 1 and 2 were prepared according to the following production method. .. (The comparative product 1 is a water-in-oil type (hereinafter referred to as W / O type) emulsified cosmetic.) The obtained O / W / O type emulsified cosmetics are evaluated by the following evaluation method. "Stability over time (emulsification stability)", b. "Stability over time (crystal precipitation)", c. "Water resistance", d. We evaluated the "feeling of use (no stickiness)". The results are also shown in Tables 1 and 2.

(Manufacturing method) (Products 1 to 8 of the present invention and Comparative products 2 to 6)
A: Ingredients 1 to 10 are uniformly mixed and dissolved at a temperature of 80 ° C.
B: Ingredients 11 to 12 are uniformly mixed at a temperature of 70 ° C.
C: B is added to A and emulsified (O / W type emulsified composition is obtained).
D: C is cooled to room temperature.
E: High-pressure treatment (800 MPa x 2 times) using a microfluidizer (manufactured by Mizuho Kogyo).
F: Components 13 to 20 are uniformly mixed at a temperature of 35 ° C. or lower.
E was dispersed in G: F to obtain an O / W / O type emulsified cosmetic.

(Manufacturing method) (Comparative product 1)
A: Ingredients 2 to 10 and 13 to 21 are uniformly mixed and dissolved at a temperature of 80 ° C.
B: Ingredients 11 to 12 are uniformly mixed.
C: B was added to A and emulsified to obtain a W / O type emulsified cosmetic.

(Evaluation method: a. Stability over time (emulsification stability))
Regarding the evaluation of emulsification stability, the O / W / O type emulsified cosmetics of the present invention and the comparative product were observed stored in a constant temperature bath at 50 ° C. for 1 month. Based on the state immediately after preparation, the change in appearance and the observation of the emulsified particles after one month were carried out visually and by observing with an optical microscope at a magnification of 40 times, and the judgment was made using the following (a) four-step judgment criteria.

(Emulsion stability (high temperature: 50 ° C, 1 month) evaluation criteria)
(A) 4-step judgment criteria
(Judgment): (Judgment criteria)
◎: No change
◯: Increase and aggregation of emulsified particles are observed, but drainage is not confirmed. Δ: A slight transparent layer (water layer) is observed in the lower layer.
×: A transparent layer (water layer) is clearly seen in the lower layer.

(Evaluation method: b. Stability over time (crystal precipitation))
For the evaluation of the crystal precipitation suppressing effect, the O / W / O type emulsified cosmetics of the present invention and the comparative product were stored in a constant temperature bath at 5 ° C. for 1 month, placed on a glass plate and observed under a microscope. Approximately 0.2 g of a sample was applied onto the skin to confirm its usability, and the determination was made using the following (b) 4-step criterion. The crystal precipitation state was observed with a polarizing filter at a magnification of 40 times with an optical microscope.
(B) 4-step judgment criteria (judgment): (evaluation)
⊚: No crystal precipitation is observed.
◯: Precipitation of crystals is slightly observed, but it is soft and crushed by hand with a thickness of less than 100 μm.
Δ: Slight precipitation of crystals was observed, and some crystals hit the skin with a thickness of 100 μm or more.
X: Precipitation of crystals of 1 mm or more is clearly seen.

(Evaluation method: C. Water resistance evaluation)
Regarding the evaluation of water resistance, for the sample in which the O / W / O type emulsified cosmetics of the present invention and the comparative product were applied to a PMMA plate (HELIOPLATE HD6 manufactured by Labsphere) at 2 mg / cm ² and then allowed to stand for 20 minutes. SPF measurement was performed using an SPF analyzer (UV-2000S manufactured by Labsphere), and the SPF value before bathing was measured. Next, I took a water bath. The water bath conditions were such that the sample was attached to the side surface of the container in which 2 L of water was stored at 35 ° C., and the water in the container was stirred at 300 rpm for 5 minutes using a paddle mixer.
After the water bath was completed, the product was allowed to stand and dry for 20 minutes, and then the SPF value was measured after the water bath using the SPF analyzer. Based on the obtained SPF values before and after the water bath, the water resistance was evaluated and judged on a 4-point scale according to the following (c) evaluation criteria.
(C) 4-step evaluation criteria (evaluation): (judgment)
(SPF measured value after water bath) / (SPF measured value before water bath) = 0.9 or more: ◎
(SPF measured value after water bath) / (SPF measured value before water bath) = 0.7 or more: ○
(Measured value of SPF after bathing) / (Measured value of SPF before bathing) = 0.4 or more: △
(Measured value of SPF after bathing) / (Measured value of SPF before bathing) = Less than 0.4: ×

(Evaluation method: D. No stickiness)
Regarding the evaluation of non-stickiness, the non-stickiness of the O / W / O type emulsified cosmetics of the present invention product and the comparative product was evaluated on a 5-point scale by the 10 cosmetics evaluation panel using the following absolute evaluation criteria. Further, the average value of the scores of each sample was determined using (d) a 4-step criterion.
Absolute evaluation criteria (score): (evaluation)
5 points: No stickiness 4 points: Almost no stickiness 3 points: Somewhat sticky 2 points: Very sticky 1 points: Very sticky (d) 4-step judgment criteria (judgment): (Score Average score)
◎: Exceeding 4 points: Very good ○: Exceeding 3 points and 4 points or less: Good △: Exceeding 2 points and 3 points or less: Slightly defective ×: 2 points or less: Defect

As is clear from the results in Tables 1 and 2, the O / W / O type emulsified cosmetics of Example 1 are the W / O type emulsified cosmetics of Comparative Product 1 and the O / W / O of Comparative Products 2 to 7. Compared with the emulsified cosmetics, it was superior in all of the time-dependent stability (emulsification stability, crystal precipitation), water resistance, and usability (no stickiness).
On the other hand, in Comparative Product 1, which is a W / O emulsified cosmetic, crystals of the component (C) were precipitated. Comparative product 2 using polyoxyethylene (60) hardened castor oil instead of component (A), comparative product 4 containing no component (B), and sorbitan monooleate instead of component (F). In Comparative Product 5, emulsified cosmetics could not be prepared and evaluated due to poor emulsification. In Comparative Product 3 containing no component (D), crystals of the component (C) were precipitated, and the emulsion stability was also inferior. The comparative product 6 containing no component (G) was inferior in water resistance. The comparative product 7 containing no component (H) was inferior in water resistance and usability. Further, for each sample of Example 1, the O / W type emulsified composition having an average particle size of about 1 μm is dispersed in F without performing step E of the above-mentioned production method, and O / W / O emulsified. Each cosmetic was prepared and evaluated in the same manner as above.
As a result, all the samples had the same usability as the results in Table 1 above, but the samples of the products 1 and 3 to 6 and 8 of the present invention were evaluated as "stability over time (emulsification stability)". It changed from "◎" to "○". From this result, the stability of the obtained O / W / O type emulsified cosmetic is more stable when the O / W type emulsified composition is treated with high pressure to have an average particle size of 500 nm or less and then dispersed in the external oil phase. It can be understood that it will be improved.

[Example]
[Example 2: Cream]
(Ingredient) (%)
1. 1. Hydrogenated lecithin * 2 2.0
2. 2. Glycerin 3.0
3.1,3-butylene glycol 3.0
4. Methylparaben 0.1
5. Cholesterol 0.1
6. Diethylaminohydroxybenzoyl hexyl benzoate 2.0
7. Bisethylhexyloxyphenol methoxyphenyl triazine 3.0
8. Ethylhexyl methoxycinnamate 5.0
9. Propylene Glycol Dicaprate 2.0
10. Inulin stearate 1.0
11. Tocopherol 0.05
12. Astaxanthin 0.01
13. Remaining amount of purified water 14. Sodium chloride 0.5
15. PEG-9 Polydimethylsiloxyethyl Dimethicone 2.0
16. Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 1.0
17. Polysilicone-15 2.0
18. Trimethylsiloxysilicic acid 2.0
19. Decamethylcyclopentasiloxane 10.0
20. Isohexadecane 15.0
21. Didimethylpolysiloxane 5.0
22. Triethylhexanoin 3.0
23. Polymethylsilsesquioxane 2.0
24. Ethanol 5.0
25. Appropriate amount of fragrance * 2 PHYTOCOMPO-PP (complex of hydrogenated lecithin and phytosterol) (manufactured by Nippon Fine Chemical Co., Ltd.)

(Manufacturing method)
A. Ingredients 1 to 12 are uniformly mixed and dissolved at a temperature of 80 ° C.
B. Ingredients 13-14 are uniformly mixed at a temperature of 70 ° C.
C. B is added to A and emulsified (O / W type emulsified composition is obtained).
D. Cool C to room temperature.
E. High-pressure treatment (800 MPa x 2 times) using a microfluidizer (manufactured by Mizuho Kogyo).
F. Ingredients 15 to 25 are uniformly mixed at a temperature of 35 ° C. or lower.
G. E was dispersed in F to obtain a cream.

The cream of Example 2 was an O / W / O type emulsified cosmetic that was excellent in all of temporal stability (emulsification stability, crystal precipitation), water resistance, and usability (no stickiness).

[Example 3: Cream]
(Ingredient) (%)
1. 1. Hydrogenated lecithin * 3 2.0
2. 2. Dipropylene glycol 3.0
3.1,3-butylene glycol 3.0
4. Methylparaben 0.1
5. Cholesterol 0.1
6. Diethylaminohydroxybenzoyl hexyl benzoate 3.0
7. Bisethylhexyloxyphenol methoxyphenyl triazine 2.0
8. Ethylhexyl methoxycinnamate 5.0
9. Diethyl succinate 2.0
10. Inulin stearate 1.0
11. Phenoxyethanol 0.05
12. Tocotrienols 0.01
13. Remaining amount of purified water 14. Sodium chloride 0.5
15. PEG-9 Polydimethylsiloxyethyl Dimethicone 1.0
16. Isotridecyl isononanoate 5.0
17. Zinc oxide 8.0
18. PEG-9 Polydimethylsiloxyethyl Dimethicone 2.0
19. Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 1.0
20. Polysilicone-15 2.0
21. Trimethylsiloxysilicic acid 2.0
22. Decamethylcyclopentasiloxane 10.0
23. Isohexadecane 10.0
24. Polymethylsilsesquioxane 2.0
25. Ethanol 6.0
26. Appropriate amount of fragrance * 3 PRESOME CS2-101 (complex of hydrogenated lecithin and cholesterol) (manufactured by Nippon Fine Chemical Co., Ltd.)

(Manufacturing method)
A. Ingredients 1 to 12 are uniformly mixed and dissolved at a temperature of 80 ° C.
B. Ingredients 13-14 are uniformly mixed at a temperature of 70 ° C.
C. B is added to A and emulsified (O / W type emulsified composition is obtained).
D. Cool C to room temperature.
E. High-pressure treatment (800 MPa x 2 times) using a microfluidizer (manufactured by Mizuho Kogyo).
F. Ingredients 15 to 17 are uniformly mixed and dispersed with a roll mill.
G. Ingredients 18 to 26 are uniformly mixed at a temperature of 35 ° C. or lower.
H. E and F were dispersed in G to obtain a cream.

The cream of Example 3 was an O / W / O type emulsified cream excellent in all of temporal stability (emulsification stability, crystal precipitation), water resistance, and usability (no stickiness).

[Example 4: Base cosmetic]
(Ingredient) (%)
1. 1. Hydrogenated lecithin * 2 1.0
2. 2. Glycerin 4.0
3.1,3-butylene glycol 4.0
4. Methylparaben 0.1
5. Ceramide 3 0.2
6. Diethylaminohydroxybenzoyl hexyl benzoate 2.0
7. Bisethylhexyloxyphenol methoxyphenyl triazine 2.0
8. Ethylhexyl methoxycinnamate 4.0
9. Alkyl benzoate (C12-15) 1.0
10. Inulin stearate 1.0
11. Remaining amount of purified water 12. Sodium lactate 2.0
13. Methylenebisbenzotriazolyl tetramethylbutylphenol 2.0
14. Decyl glucoside 0.3
15. Xanthan gum 0.008
16. Propylene glycol 0.016
17. PEG-9 Polydimethylsiloxyethyl Dimethicone 2.0
18. Setil Dimethicone Polyol 1.0
19. Decamethylcyclopentasiloxane 15.0
20. Didimethylpolysiloxane 5.0
21. Isotridecyl isononanoate 2.0
22. Dextrin palmitate 0.5
23. Inulin stearate 0.5
24. Gisteardimonium Hectorite 1.0
25. Silicone treated titanium oxide 1.2
26. Silicone treated Bengala 0.03
27. Silicone treated iron oxide 0.15
28. Silicone treated black iron oxide 0.005
29. Silicone treated fine particles titanium oxide 0.3
30. Nylon powder 1.0
31. Appropriate amount of fragrance

(Manufacturing method)
A. Ingredients 1 to 10 are uniformly mixed and dissolved at a temperature of 80 ° C.
B. Ingredients 11 to 16 are uniformly mixed at a temperature of 70 ° C.
C. B is added to A and emulsified (O / W type emulsified composition is obtained).
D. Cool C to room temperature.
E. High-pressure treatment (800 MPa x 2 times) using a microfluidizer (manufactured by Mizuho Kogyo).
F. Ingredients 17 to 31 are uniformly mixed and dispersed with a roll mill.
G. E was dispersed in F to obtain a base cosmetic.

The base cosmetic of Example 4 was an O / W / O type emulsified base cosmetic having excellent aging stability (emulsification stability, crystal precipitation), water resistance, and usability (no stickiness). ..

Claims (3)

The following components (A) to ( E );
(A) Phosphoridipid (B) Liquid oil (C) Diethylaminohydroxybenzoyl One or two selected from hexyl benzoate and bisethylhexyloxyphenol methoxyphenyltriazine (D) One or two selected from inulin fatty acid ester and dextrin fatty acid ester Seed (E) water
The O / W type emulsified composition containing
(F) Silicone surfactant
By
(G) Oil-soluble film-forming agent (H) Volatile oil agent
An O / W / O type emulsified cosmetic that is emulsified in an external oil phase containing . The O / W / O type emulsified cosmetic according to claim 1, wherein the liquid oil of the component (B) is ethylhexyl methoxycinnamate. The O / W / O type emulsified cosmetic according to claim 1 or 2, wherein the oil-soluble film-forming agent of the component (G) is trimethylsiloxysilicic acid.