JP5608365B2 - Oil-in-water emulsified cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water emulsified cosmetic excellent in sunscreen effect.

  Sunscreen cosmetics having a protective effect against ultraviolet rays are blended with metal oxides such as titanium oxide and zinc oxide, and organic ultraviolet absorbers such as 2-ethylhexyl paramethoxycinnamate. In cosmetics containing these metal oxides and organic ultraviolet absorbers, makeup collapse due to sweating or the like is likely to occur, so volatile silicone is often used in combination.

  Cosmetics containing volatile silicone have good elongation when applied to the skin, and the volatile silicone volatilizes as it stretches, increasing the feeling of adhesion and being resistant to sweat. When blended, metal oxides and organic ultraviolet absorbers have poor compatibility with water and volatile silicones, so it was difficult to blend them in an oil-in-water emulsified cosmetic with good dispersibility.

  In recent years, oil-in-water emulsified cosmetics in which volatile silicones, metal oxides, and organic ultraviolet absorbers are stably emulsified in water have been proposed (see Patent Documents 1 to 3). These enhance the emulsification stability of the oil-in-water emulsion composition by blending an alkyl-substituted polysaccharide derivative or blending a water-soluble polymer and an alkylsilane-treated powder.

  On the other hand, since 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester has an excellent ultraviolet-absorbing effect in the UV-A region, its application to sunscreen cosmetics has been studied (Patent Document 4). ).

Japanese Patent Laid-Open No. 11-12119 JP-A-11-71262 JP 2004-196740 A JP 2008-162988 A

However, 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester has poor solubility in various oils and solvents due to its special chemical structure and physical properties, and particularly improves the feeling of use and makeup sustainability. A cosmetic with good stability over time and containing a large amount of volatile silicone has not been obtained.
Accordingly, an object of the present invention is to provide an oil-in-water emulsified cosmetic that is stable for a long period of time and contains excellent sensation of use containing 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester and volatile silicone. Is to provide a fee.

  Therefore, as a result of investigations to solve the above problems, the present inventor, in an oil-in-water emulsion cosmetic containing a large amount of volatile silicone, together with 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester Water-soluble alkyl-substituted polysaccharide derivative obtained by substituting a hydroxyl group of a polysaccharide with a long-chain alkyl glyceryl ether group and / or a long-chain alkenyl glyceryl ether group and a substituent containing sulfonic acid, and a hydrophobized zinc oxide powder Oil-in-water emulsified cosmetics that can stably contain 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester in an oil-in-water emulsified cosmetic for a long period of time and have excellent usability. The inventors found that a cosmetic can be obtained and completed the present invention.

That is, this invention relates to the oil-in-water type emulsion cosmetic characterized by containing the following component (A)-(D).
(A) Some or all of the hydroxyl groups of the polysaccharide or derivative thereof are substituted with the following (a) and (b), and the degree of substitution with the substituent (a) is 0.001 per constituent monosaccharide residue: A water-soluble alkyl-substituted polysaccharide derivative having a substitution degree of 0.01 to 2.5 per constituent monosaccharide residue (a) a linear or branched chain having 10 to 40 carbon atoms An alkyl glyceryl ether group having an alkyl group and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms,
(B) the hydroxyl group is substituted with an optionally substituted sulfoalkyl group having 1 to 5 carbon atoms or a salt thereof;
The degree of substitution by the substituent (a) is 0.001 to 1.0 per constituent monosaccharide residue, and the degree of substitution by the substituent (b) is 0.01 to 2.5 per constituent monosaccharide residue. Alkyl-substituted polysaccharide derivative (B) 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester (C) hydrophobized zinc oxide powder (D) volatile silicone 15-40% by mass

  The oil-in-water emulsified cosmetic of the present invention can stably contain volatile silicone and 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester for a long period of time. Therefore, there is no change in appearance such as separation even when stored for a long period of time, excellent stability over time, high UV protection effect, high transparency when applied, no squeaky feeling, stickiness, etc. Excellent feeling.

  Examples of the water-soluble alkyl-substituted polysaccharide derivative of component (A) used in the present invention include those described in Patent Document 1. That is, as the substituent (a) of the water-soluble alkyl-substituted polysaccharide derivative (A), specifically, a 2-hydroxy-3-alkoxypropyl group, a 2-alkoxy-1- (hydroxymethyl) ethyl group, 2- Examples include hydroxy-3-alkenyloxypropyl group and 2-alkenyloxy-1- (hydroxymethyl) ethyl group, which are substituted with hydrogen atom of hydroxyl group of hydroxyethyl group or hydroxypropyl group bonded to polysaccharide molecule. May be. The alkyl group or alkenyl group having 10 to 40 carbon atoms substituted on these glyceryl ether groups is preferably a linear or branched alkyl or alkenyl group having 12 to 36 carbon atoms, particularly 16 to 24 carbon atoms, and is stable. From this point, an alkyl group, particularly a linear alkyl group is preferred. In addition, when the substituent (a) has a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a) or (b).

  Specific examples of the substituent (b) include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group, 2-sulfo-1- (hydroxymethyl) ethyl group, and the like. All or part of them may be a salt with alkali metals such as Na and K, alkaline earth metals such as Ca and Mg, cationic groups such as amines, ammonium ions and the like. In addition, when the substituent (b) has a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a) or (b).

  The degree of substitution of the substituent (a) is preferably 0.001 to 1, particularly 0.002 to 0.5, more preferably 0.003 to 0.1 per constituent monosaccharide residue, and the substituent (b) The substitution degree is preferably 0.01 to 2.5, particularly 0.02 to 2, and more preferably 0.1 to 1.5 per constituent monosaccharide residue. The ratio of the number of substituents (a) to substituents (b) is preferably 1: 1000 to 100: 1, particularly 1: 500 to 10: 1, and more preferably 1: 300 to 10: 1. In the water-soluble alkyl-substituted polysaccharide derivative, the substituents (a) and (b) are not necessarily present in the same repeating unit of the polysaccharide or its derivative, and when viewed as a whole molecule. The substituents (a) and (b) may be introduced. The degree of substitution is preferably within the above range on average.

  In addition, the polysaccharide that is the basic skeleton of the water-soluble alkyl-substituted polysaccharide derivative of component (A) or a derivative thereof includes cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch , Ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methylcellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, etc. Among them, cellulose, hydroxyethyl cellulose, Chill cellulose, ethyl cellulose, hydroxypropyl cellulose are preferred. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group and the like of these polysaccharides may be substituted with a single substituent or may be substituted with a plurality of substituents. The substitution degree per constituent monosaccharide residue is preferably 0.1 to 10, particularly 0.5 to 5. The weight average molecular weight of these polysaccharides or derivatives thereof is in the range of 10,000 to 10,000,000, preferably 100,000 to 5,000,000, particularly preferably 300,000 to 2,000,000.

  The substituents (a) and (b) in the polysaccharide derivative (A) are not only the hydroxyl groups of the polysaccharide or its derivative used as a raw material, but also the hydroxyl groups of other substituents (a) and substituents (b). In some cases, substitution may be performed on a group, and such substitution may occur in a superimposed manner. That is, in addition to the compound in which only the hydrogen atom of the hydroxyl group of the polysaccharide or derivative thereof is substituted with the substituents (a) and (b), when the sulfonation is carried out after the hydrophobization, the substituent (a) is further substituted. The group (a) or (b) may be substituted, and the substituent (b) may be further substituted with the substituent (b). When the group is hydrophobized after sulfonation, the substituent (a ) May be further substituted with a substituent (a), and the substituent (b) may be further substituted with a substituent (b) or (a). May include those in which the substituent (a) is further substituted with the substituent (a) or (b), and the substituent (b) is further substituted with the substituent (a) or (b). Furthermore, there may be included those in which substitution with other substituents occurs in a superimposed manner. In the present invention, any of such polysaccharide derivatives can be used.

  Moreover, as a commercial item of the water-soluble alkyl-substituted polysaccharide derivative of the component (A) of the present invention, for example, Poise 310 (manufactured by Kao Corporation), Natrosol PLUS 330 and Natrosol PLUS CS (NATROSOL PLUS) D-67 Alkyl-modified hydroxyethyl cellulose (manufactured by Aqualon Company Ltd.) and the like, hydrophobically modified sulfonated polysaccharide derivatives and the like can be used.

  The content of the water-soluble alkyl-substituted polysaccharide derivative of the component (A) used in the present invention is preferably 0.01 to 5% by mass (hereinafter simply abbreviated as%), more preferably based on the total amount of the cosmetic. It is 0.1 to 5%, more preferably 0.1 to 3%. Within this range, good stability and usability can be obtained.

  Component (B) 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester used in the present invention is an ultraviolet absorber represented by the following structural formula, and is commercially available as ubinal plus (manufactured by BSAF). Has been. The ultraviolet absorption is in the range of 310 to 390 nm (UV-A region) with a maximum absorption wavelength of about 354 nm.

  The component (B) of the present invention is preferably 0.01 to 10%, more preferably 0.1 to 5%, still more preferably 0.1 to 2.5%, based on the total amount of the cosmetic. is there. If it is in the said range, while being able to acquire a favorable ultraviolet-ray protective effect, the effect excellent also in stability and a usability | use_condition will be acquired.

The (C) hydrophobized zinc oxide powder used in the oil-in-water emulsified cosmetic of the present invention is obtained by hydrophobizing the surface of the zinc oxide powder.
The zinc oxide powder preferably has an average particle diameter of 0.01 to 1 μm, more preferably 0.012 to 0.2 μm, and most preferably 0.015 to 0.1 μm. Within such a range, problems such as aggregation and easy formulation opacification do not occur. Moreover, although the shape of these zinc oxide powders includes a spherical shape, a rod shape, a spindle shape, a needle shape, an indefinite shape, and the like, any shape can be used as long as the average particle diameter is in the above range.

  Examples of these zinc oxide powders include FINEX-25, FINEX-50, FINEX-75 (manufactured by Sakai Chemical Co., Ltd.), MZ500 series, MZ700 series (manufactured by Teika), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), and the like. It is commercially available.

  Moreover, these can contain +2 or more trace elements, and metals, such as iron, zirconium, calcium, manganese, magnesium, and yttrium, are contained alone or in combination of two or more in the zinc oxide powder. be able to.

  As the hydrophobizing treatment of these zinc oxide powders, conventionally known hydrophobizing treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, Examples include N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, and mechanochemical treatment.

  For example, a treatment using a hydrophobizing agent for methylhydrogenpolysiloxane or the following methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer, or a treatment using a hydrophobizing agent for a silane compound or a silazane compound is preferable. . Particularly preferred is a surface treatment using a hydrophobizing agent of a silane compound or a silazane compound.

(L and m are integers, 1 ≦ l + m ≦ 60)

  As the silane compound or silazane compound, a silane compound or silazane compound having an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms and having reactivity with an inorganic oxide is preferable. Or a silazane compound represented by the general formula 2, which can be used alone or in combination.

(N is an integer of 0 or 1, R represents an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group (which may be linear or branched), and R ¹ has ¹ carbon atom. -6 represents an alkyl group, and X represents a halogen atom or an alkoxy group.)

(R ^{2 to} R ⁷ represent an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms (which may be linear or branched), and may be independent or the same.)

  Specific silane compounds include hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like. It is done. Of these, octyltriethoxysilane and octyltrimethoxysilane are particularly preferable. Preferable examples of the silazane compound include hexamethyldisilazane, octyldisilazane, etc. Among them, octyldisilazane is particularly preferable. The silane compound or silazane compound is characterized in that it can be uniformly treated, is easy to supply and is inexpensive in cost, and further dispersibility when zinc oxide powder surface-treated with these compounds is blended into cosmetics. Etc. are preferable because of excellent properties.

  As the treatment method with the silane compound or silazane compound, the silane compound or silazane compound and zinc oxide powder are mixed in an organic solvent such as n-hexane, cyclohexane, or lower alcohol, and optionally pulverized, and then the organic solvent. A method of chemically reacting a silane compound or a silazane compound with a reactive group on the surface of zinc oxide, such as a method of removing by heating or reduced pressure, and preferably a heat treatment at 80 to 250 ° C., is mentioned.

  Further, as described in JP-A-2007-326902, a method of surface-treating alkylalkoxysilane in water after coating a cosmetic pigment with a specific polysiloxane compound is also included.

  The coating amount of the hydrophobizing agent on the zinc oxide powder is preferably 3 to 15% by mass, more preferably 5 to 10% by mass, based on the total amount of zinc oxide powder used. Within this range, the surface of the powder is uniformly coated with the hydrophobizing agent, and the hydrophobizing agent does not aggregate or precipitate on the surface of the zinc oxide powder.

  (C) The hydrophobized zinc oxide powder is preferably contained in an amount of 5 to 25% by mass, more preferably 5 to 20% by mass, and even more preferably 5%, based on the total amount of the oil-in-water emulsified cosmetic. ~ 18% by weight. If it is in the said range, it is excellent in a usability | use_condition and temporal stability is favorable.

The volatile silicone (D) used in the present invention refers to a silicone oil that volatilizes at room temperature (25 ° C.) and normal pressure (1 atm. 9.8 × 10 4 Pa). Examples of volatile silicones include linear, branched or cyclic silicone oils. Specifically, for example, dimethylpolysiloxane having a linear silicone oil viscosity of 5.0 to 7.0 mm ² / S. Examples include siloxane. As a commercial item, KF-96A (2cs), KF-96A (5cs) (above, Shin-Etsu Chemical Co., Ltd. make) is mentioned, for example. Examples of the cyclic silicone include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Examples of commercially available products include KF-995 and KF-994 (manufactured by Shin-Etsu Chemical Co., Ltd.). Etc. Furthermore, as the branched silicone oil, tristrimethylsiloxysilane (M3T) and tetrakistrimethylsiloxysilane (M4Q) can be used, and as a commercial product, silicone TMF1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned. .

  Content of the component (D) used by this invention is 15 to 40%, 15 to 30% is more preferable, and 18 to 25% is still more preferable. When it mix | blends in this range, it will be excellent in the makeup collapse prevention effect (makeup lasting effect or color transfer prevention effect), and transparency.

The oil-in-water emulsified cosmetic of the present invention can contain a surfactant in order to further improve the stability.
The surfactant is not particularly limited, and includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, natural surfactants, polyether-modified silicones, siloxane derivatives, and the like. Any of a silicone-containing surfactant and a surfactant containing a perfluoroalkyl group can be used.

  Among these, nonionic surfactants are preferable, and specific examples include sorbitan monoisosotearate, dimethicone copolyol, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan monolaurate (20EO), and the like.

  One or more kinds of the above surfactants can be used, and the preferable content thereof is 0.01 to 10%, more preferably 0.1 to 5%, based on the total amount of the cosmetic.

  Furthermore, the oil-in-water emulsified cosmetic of the present invention can be blended with a powder having an ultraviolet protection effect to the extent that the effects of the present invention are not impaired. Specifically, metal oxides such as low-order titanium oxide, zinc oxide and cerium oxide, metal hydroxides such as iron hydroxide, metal flakes such as plate-like iron oxide and aluminum flakes, and ceramics such as silicon carbide Is mentioned. Especially, what is chosen from 1 or more types of the fine particle metal oxide or fine particle metal hydroxide which exists in the range of 5-100 nm as an average particle diameter is especially preferable. These powders include, for example, fluorine compound treatment (perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment, etc.), silicone treatment (methyl hydrogen poly Siloxane treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment, etc.), silicone resin treatment (trimethylsiloxysilicic acid treatment, etc.), pendant treatment (after vapor phase silicone treatment, etc.) Method), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkyl silane, alkylsilazane treatment, etc.), oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment (stearic acid) Like treatment with myristate), acrylic resin treatment, metal oxide treatment or the like, it is preferable to have done a known surface treatment, further, may be used by combining a plurality of the surface treatment. For example, the surface of fine particle titanium oxide is coated with a metal oxide powder such as silane or alumina and then surface-treated with alkylsilane.

  In the oil-in-water emulsified cosmetic of the present invention, an ultraviolet absorber other than the component (B) can be appropriately blended within a range not impairing the effects of the present invention. For example, it can be selected from known cosmetic raw materials having ultraviolet absorbing ability, and two or more kinds can be used in combination. Specifically, benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, paramethoxycinnamate Cinnamic acid-based UV absorbers such as isopropyl acid and diisopropyl cinnamate esters, hydroxymethoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid, sodium hydroxymethoxybenzophenonesulfonate, dihydroxymethoxybenzophenone, sodium dihydroxymethoxybenzophenonesulfonate, dihydroxybenzophenone, Benzophenone-based UV absorbers such as tetrahydroxybenzophenone, paraaminobenzoic acid, ethyl paraaminobenzoate, glycerized paraaminobenzoate Benzoic acid ester-based UV absorbers such as ethyl, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, ethyl 4- [N, N-di (2-hydroxypropyl) amino] benzoate, ethylene glycol salicylate, salicylic acid Salicylic acid UV absorbers such as phenyl, octyl salicylate, benzyl salicylate, salicylic acid-p-tert-butylphenyl, homomenthyl salicylate, 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1'-oxy) Triazine-based ultraviolet absorbers such as -1,3,5-triazine, 4-tert-butyl-4′-methoxybenzoylmethane, oxybenzone, menthyl anthranilate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, Dimethoxybenzylide Dioxoimidazolidin propionic acid 2-ethylhexyl, and 2-phenylbenzimidazole-5-sulfonic acid. Among them, it is preferable to use paramethoxycinnamic acid-2-ethylhexyl and 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester in combination because a particularly excellent ultraviolet protection effect is obtained.

  When using ultraviolet absorbers other than the said component (B), content with respect to the total amount of cosmetics of ultraviolet absorbers other than the said component (B) and component (B) shall be 0.01-20 mass%. Preferably, it is 0.05 to 10% by mass. If it is in the said range, it is excellent in an ultraviolet-ray protective effect and a usability | use_condition is also favorable.

  In addition to the above components, the oil-in-water emulsified cosmetic of the present invention includes water, higher alcohols, fatty acids, esters, sterols, as long as the effects of the present invention are not impaired depending on the purpose. Sterol fatty acid esters, hydrocarbons, oils and fats, silicone oils, moisturizers, water-soluble polymers other than the component (A) of the present invention, plant extracts, vitamins, antioxidants, antibacterial and antiseptics, anti-inflammatory agents, Insect repellents, physiologically active ingredients, salts, chelating agents, neutralizing agents, pH adjusters, fragrances and the like can be blended.

  The dosage form of the cosmetic of the present invention is not particularly limited, and is prepared, for example, as an oil-in-water emulsion, gel, spray or mousse.

  As the use of the cosmetic of the present invention, it can be used as a cosmetic without any particular limitation, but it can be used for hair cosmetics such as shampoos, rinses, conditioners, face wash, cleansing cosmetics, sunscreen cosmetics, packs, massage cosmetics, etc. It can be suitably used as a skin cosmetic. Among these, it is particularly preferable to apply to sunscreen cosmetics (skin lotion, cream, milky lotion, beauty serum, etc.), suntan, cosmetic base cosmetics, foundations having UV protection ability, and the like.

  Hereinafter, although an example and a comparative example explain the present invention in detail, the present invention is not limited to these. The zinc oxide powder used in the present application will be described below. The untreated zinc oxide powder is the same as that before treatment in Production Example 1 below.

Production Example 1 (Production of alkylalkoxysilane-treated zinc oxide powder)
9 parts by mass of octyltrimethoxysilane is sprayed on 91 parts by mass of finely divided zinc oxide powder (average particle size 0.02 μm), heated in a nitrogen atmosphere at 120 ° C. for 8 hours with gentle stirring, and then under air circulation And deodorized by heating at 100 ° C. for 5 hours to obtain octyltrimethoxysilane-treated zinc oxide powder.

Production Example 2 (Production of silicon-treated zinc oxide powder)
A slurry composed of 93 parts by mass of finely divided zinc oxide powder (average particle size 0.02 μm), 7 parts by mass of methyl hydrogen polysiloxane (KF-99P, manufactured by Shin-Etsu Chemical Co., Ltd.) and isopropyl alcohol was stirred well and pulverized. Thereafter, the solvent was distilled off by heating under reduced pressure, and heat treatment was performed in air at 150 ° C. for 4 hours to obtain a methylhydrogenpolysiloxane-treated zinc oxide powder.

Production Example 3 (Production of silicon-treated titanium oxide powder)
A methyl hydrogen polysiloxane-treated titanium oxide powder was obtained in the same manner as in Production Example 2, except that the fine zinc oxide powder was changed to a fine titanium oxide powder (average particle size 0.02 μm).

Examples 1-9, Comparative Examples 1-9
According to the formulations shown in Tables 1 and 2, oil-in-water emulsified cosmetics were prepared by a conventional method. Using these, the following (1) UVA protective effect test, (2) stability test, and (3) usability test were performed. The results are shown in Tables 1 and 2 together. In addition, the comparative example 9 will be in a water-in-oil type emulsified state, and is not evaluated.

(1) UVA protection effect The SPF value was measured using an SPF analyzer (Labsphere), and was shown according to the following criteria.
[UVA protective effect evaluation criteria]
○: T (UVA) is less than 25% Δ: T (UVA) is 25% or more and less than 30% ×: T (UVA) is 30% or more

  Here, T (UVA) is defined by the following equation.

(2) Stability test The appearance of the O / W type oil-in-water emulsified cosmetics shown in Tables 1 and 2 was visually evaluated for the state after 3 months when stored in a thermostatic bath at 45 ° C.
[Precipitation criteria]
○: No precipitation is observed ×: Precipitation is observed [viscosity change criterion]
○: No change or slight viscosity change Δ: Clear viscosity change is observed ×: Separated

(3) Usability test Ten oil-in-water emulsified cosmetics shown in Tables 1 and 2 were used by 10 professional panelists. As for the feeling of use at the time of application, evaluation and determination are made based on the following evaluation criteria and judgment criteria regarding `` transparency of the coating film '', `` no squeaking feeling at the time of application '', `` no stickiness after application ''. went.
(Evaluation criteria)
5: Very preferable 4: Somewhat preferable 3: Neither can be said 2: Somewhat unfavorable 1: Very not preferable (determination criteria)
◎: Average point is 4.0 or more ○: Average point is 3.0 or more and less than 4.0 △: Average point is 2.0 or more and less than 3.0 ×: Average point is less than 2.0

From the results of Tables 1 and 2, the cosmetic composition of the present invention can stably contain 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester and is excellent in usability as compared with the comparative example. It is clear that it is.
In particular, it contains a relatively large amount of volatile silicone, has a good makeup-breaking prevention effect (makeup retention effect or color transfer prevention effect), and maintains a transparent uniform coating film. The squeaky feeling is also suppressed.

  Examples of emulsified cosmetics according to the present invention will be given below. All of these cosmetics have an anti-ultraviolet effect and are excellent in stability over time and feeling of use.

(Production method)
A: Components 1-4, 6-9, and 18 are heated to 70 ° C. and dispersed uniformly.
B: A is cooled and component 11 is added to make it uniform.
C: Components 5, 10, 12 to 17 were uniformly dispersed, B was charged, and after emulsification with a homomixer, deaeration and cooling were performed to obtain an oil-in-water emulsion cosmetic.

Formulation example 1 (makeup base)
When an oil-in-water emulsified cosmetic composition (makeup base) having the following composition was prepared and evaluated, it was excellent in all points of UV protection effect, feeling of use, and storage stability.
1. Alkylsilane-treated zinc oxide powder (Production Example 1) 10.0 (%)
2. Silicon-treated zinc oxide powder (Production Example 2) 5.0
3. Diethylaminohydroxybenzoyl hexyl benzoate 1.0
4). 2-Ethylhexyl paramethoxycinnamate 5.0
5. Octyldodecyl myristate 2.0
6). Sorbitan stearate 0.3
7). Polyoxyethylene / methylpolysiloxane copolymer 1.0
(Silicone KF-6017, Shin-Etsu Chemical)
8). Dimethicone (6cs) 3.0
9. Decamethylcyclopentasiloxane 15.0
10. Squalane 3.0
11. Polymethylsilsesquioxane 5.0
(Average primary particle size 4.5μm)
12 Ethanol 10.0
13. Stearoxy PG hydroxyethyl cellulose sulfonate Na 0.5
(Poise 310, manufactured by Kao Corporation)
14 Edetate disodium 0.02
15. Glycerin 2.0
16.1,3-Butylene glycol 6.0
17. Acerola extract 1.0
(Product name: Acerola extract BG25 (Maruzen Pharmaceutical Co., Ltd.)
18. Prune extract 0.5
(Product name: Prune extract WC (manufactured by Maruzen Pharmaceutical Co., Ltd.))
19. Hyaluronic acid 0.5
20. Fragrance 0.1
21. Phenoxyethanol 0.3
22. Purified water balance

Formulation example 2 (sunscreen emulsion)
1, alkylsilane-treated zinc oxide powder (Production Example 1) 15.0 (%)
2, Diethylaminohydroxybenzoyl hexyl benzoate 1.0
3. 2-Ethylhexyl paramethoxycinnamate 4.0
4). Sorbitan stearate 0.5
5. Polyoxyethylene / methylpolysiloxane copolymer 1.0
(Silicone KF-6015, manufactured by Shin-Etsu Chemical Co., Ltd.)
6). Dimethicone (6CS) 2.0
7). Tristrimethylsiloxysilane 15.0
(Silicone TMF-1.5, manufactured by Shin-Etsu Chemical Co., Ltd.)
8). Phenylmethylpolysiloxane 3.0
9. Nylon powder 1.0
Ten. Ethanol 7.0
11． Stearoxy PG hydroxyethyl cellulose sulfonate Na0.3
(Poise 310, manufactured by Kao Corporation)
12.1,3-Butylene glycol 7.0
13. Hyaluronic acid 0.1
14. Purified water balance

  In addition, the composition of the fragrance | flavor used in said Example and prescription example is shown in Table 3.

  The oil-in-water emulsified cosmetic of the present invention is excellent in the temporal stability of 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester, so that a high UV protection effect is obtained, and the usability at the time of application is also high. Also excellent. Therefore, according to the present invention, it is possible to provide an oil-in-water emulsified cosmetic that is safe and easy to use, has an excellent UV protection effect, has good skin spreading when in use, and has excellent usability without a squeaky or sticky feeling. .

Claims (4)

An oil-in-water emulsified cosmetic comprising the following components (A) to (D):
(A) Some or all of the hydroxyl groups of the polysaccharide or derivative thereof are substituted with the following (a) and (b), and the degree of substitution with the substituent (a) is 0.001 per constituent monosaccharide residue: A water-soluble alkyl-substituted polysaccharide derivative having a substitution degree of 0.01 to 2.5 per constituent monosaccharide residue (a) a linear or branched chain having 10 to 40 carbon atoms An alkyl glyceryl ether group having an alkyl group and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms,
(B) the hydroxyl group is substituted with an optionally substituted sulfoalkyl group having 1 to 5 carbon atoms or a salt thereof;
The degree of substitution by the substituent (a) is 0.001 to 1.0 per constituent monosaccharide residue, and the degree of substitution by the substituent (b) is 0.01 to 2.5 per constituent monosaccharide residue. 10-mass% hydrophobized zinc oxide powder surface-treated with a functional alkyl-substituted polysaccharide derivative (B) 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester (C) silane compound
(D) Volatile silicone 15-40% by mass   The substituent (a) of the component (A) is selected from an alkyl glyceryl ether group having a linear or branched alkyl group having 16 to 24 carbon atoms and / or a linear or branched alkenyl glyceryl ether group having 16 to 24 carbon atoms. The cosmetic according to claim 1, wherein the cosmetic is one type or two or more types.   One type wherein the substituent (b) of the component (A) is selected from 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group and 2-sulfo-1- (hydroxymethyl) ethyl group Or it is 2 or more types, The oil-in-water type emulsified cosmetics of Claim 1 or 2.   The polysaccharide of component (A) or a derivative thereof is cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxy The propyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum and hydroxypropyl methyl starch are selected. The oil-in-water emulsified cosmetic described in 1.