CN117580562A

CN117580562A - W/O type composition comprising organic UV filter and spherical hydrophobic silica

Info

Publication number: CN117580562A
Application number: CN202280045961.7A
Authority: CN
Inventors: 菅友美
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2021-08-26
Filing date: 2022-08-09
Publication date: 2024-02-20
Also published as: JP2023032127A

Abstract

The present invention relates to a composition in the form of a W/O emulsion comprising: (a) at least one organic UV filter; (b) at least one spherical hydrophobic silica; and (c) water. The composition according to the invention can be easily spread on keratin materials such as the skin while providing strong UV protection.

Description

W/O type composition comprising organic UV filter and spherical hydrophobic silica

Technical Field

The present invention relates to a composition in the form of a W/O emulsion comprising one or more organic UV filters and one or more spherical hydrophobic silica.

Background

Typically, UV filters are used to provide protection against UV (ultraviolet) radiation. Heretofore, sup>A number of sunscreen compositions have been proposed which are intended to protect the skin from UV-A and/or UV-B.

These sunscreen compositions are typically in the form of oil-in-water or water-in-oil emulsions, gels, or non-aqueous products containing one or more insoluble and/or fat-soluble and/or water-soluble organic and/or inorganic UV filters in various concentrations, said UV filters being capable of selectively absorbing harmful UV radiation. These UV filters and their amounts are selected according to the desired Sun Protection Factor (SPF).

SPF mathematically represents the ratio of the UV radiation dose required to reach the erythema threshold in the presence of a UV screening agent to the UV radiation dose required to reach the erythema threshold in the absence of a UV screening agent.

There is a need for compositions with higher SPF, which can be expressed by higher UV absorbance of the composition.

DISCLOSURE OF THE INVENTION

On the other hand, the use of organic UV filters in compositions (such as sunscreen compositions) makes the compositions difficult to spread and feel heavy when the composition is used.

It is thus an object of the present invention to provide a composition in the form of a W/O emulsion comprising one or more organic UV filters but which can be easily spread while enhancing the UV absorbance of the composition.

The above object of the present invention can be achieved by a composition in the form of a W/O emulsion comprising:

(a) At least one organic UV filter;

(b) At least one spherical hydrophobic silica; and

(c) And (3) water.

(a) The organic UV filter may be selected from butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 1' - (1, 4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl ] phenyl ] -methanone, 4-methylbenzylideneacamphora, ethylhexyl triazinone, bis-ethylhexyl oxyphenoxyphenyl triazine, diethylhexyl butyrylaminotriazinone, 2,4, 6-tris (4 ' -aminobenzylidene) dineopentyl) -s-triazine, 2,4, 6-tris (4 ' -aminobenzylidene) malonic acid diisobutyl) -s-triazine, 2, 4-bis- (4 ' -aminobenzylidene malonic acid di-n-butyl) -6- [ (3- {1, 3-tetramethyl-1- [ (trimethylsilyloxy ] disiloxy) propyl ] -triazines, 2,4, 6-tris (4 ' -aminobenzylidene) malonic acid di-neopental) -s-triazine, 2,4, 6-tris (4 ' -aminobenzylidene) malonic acid diisobutyl) -s-triazine, 2,4, 6-tris (4 ' -aminobenzylidene) malonic acid di-n-butyl) -s-triazine, 2, 4' -aminobenzylidene-malonic acid di-n-butyl-s-triazine, 3, 4' -t-butyl-phenylmethane, 1, 1-dicarboxylic acid (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene, 2, 4-bis [5-1 (dimethylpropyl) benzooxazol-2-yl (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, camphorbenzammonium methyl sulfate, and mixtures thereof.

The amount of the (a) organic UV filter(s) in the composition according to the invention may be from 1% to 40% by weight, preferably from 5% to 35% by weight, and more preferably from 10% to 30% by weight, relative to the total weight of the composition.

(b) The spherical hydrophobic silica may have an average roundness as determined by image analysis of 0.8 or more, and preferably 0.82 or more.

(b) The spherical hydrophobic silica may have an oil absorption measured at the wet point of 2ml/g or more, preferably 3ml/g or more, more preferably 4ml/g or more, and most preferably 5ml/g or more.

(b) The spherical hydrophobic silica may have a particle size of 200m ² Per gram or higher, preferably 400m ² /g or higher, and more preferably 500m ² And/g or higher, as determined by BET method.

(b) The spherical hydrophobic silica may have a pore volume as determined by the BJH method of 1ml/g or more, preferably 2ml/g or more, and more preferably 3ml/g or more.

(b) The spherical hydrophobic silica may have a peak pore radius as measured by the BJH method of 5nm or more, preferably 10nm or more, and more preferably 12nm or more.

(b) The spherical hydrophobic silica may have an average particle size of 0.5 μm to 30 μm, preferably 1 μm to 20 μm, and more preferably 2 μm to 15 μm.

The amount of (b) the spherical hydrophobic silica(s) in the composition according to the invention may be from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, and more preferably from 1 to 5% by weight, relative to the total weight of the composition.

The weight ratio of the amount of (a) one or more UV filters to the amount of (b) one or more spherical hydrophobic silica in the composition according to the invention may be from 3 to 35, preferably from 5 to 30, and more preferably from 10 to 25.

The composition according to the invention may further comprise (d) at least one oil, which may preferably be selected from polar oils, non-polar oils and mixtures thereof, more preferably from hydrocarbon oils, silicone oils, ester oils and mixtures thereof, and even more preferably from isododecane, isohexadecane, polydimethylsiloxane, diisopropyl sebacate and mixtures thereof.

The composition according to the invention may be a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care or make-up cosmetic composition.

The invention also relates to a cosmetic method for keratin materials, such as the skin, comprising the application to the keratin materials of a composition according to the invention.

The invention also relates to the use of (b) at least one spherical hydrophobic silica in a composition in the form of a W/O emulsion comprising (a) at least one organic UV filter and (c) water, for increasing the UV absorbance of the composition and improving the spreadability of the composition.

Brief description of the drawings

FIG. 1 shows a graph of UV absorbance for each of the compositions according to examples 1 and 2 and comparative examples 1-3.

Best Mode for Carrying Out The Invention

After diligent research, the inventors have found that compositions in the form of W/O emulsions can be provided that contain one or more organic UV filters but can be easily spread while enhancing the UV absorbance of the composition.

Thus, the composition according to the invention is in the form of a W/O emulsion and comprises:

(a) At least one organic UV filter;

(b) At least one spherical hydrophobic silica; and

(c) And (3) water.

The compositions according to the present invention may provide improved or enhanced UV absorbance, reflecting improved or enhanced UV protection.

On the other hand, the composition according to the invention can be spread easily on keratin materials such as the skin, reflecting the improved or enhanced spreadability when the composition is used.

Thus, the composition according to the invention can be easily spread on keratin materials such as the skin, while providing strong UV protection.

Furthermore, the composition according to the invention may capture sebum. Thus, the composition according to the invention may reduce the gloss on keratin materials such as the skin and may make, for example, roughness on the skin such as pores and wrinkles less pronounced. Thus, the composition according to the invention may also provide an optical matte effect.

Hereinafter, the composition, method, etc. according to the present invention will be explained in more detail.

[ organic UV Filter ]

The composition according to the invention comprises (a) at least one organic UV filter. If two or more of the (a) organic UV filters are used, they may be the same or different.

(a) The organic UV filter may be hydrophobic or water insoluble. (a) organic UV filters may act as oily components. Thus, (a) the organic UV filter may constitute the continuous phase or the external phase of the W/O type composition.

(a) The organic UV filter may be active in the UV-Sup>A and/or UV-B region. (a) the organic UV filter may be lipophilic or oil soluble.

(a) The organic UV filter may be solid or liquid. The terms "solid" and "liquid" refer to solids and liquids, respectively, at 25 ℃ at 1 atm.

(a) The organic UV filter may be selected from anthranilic acid compounds; dibenzoylmethane compounds; cinnamic acid compounds; a salicylic acid compound; a camphor compound; benzophenone compoundA compound; a beta, beta-diphenylacrylate compound; a triazine compound; a benzotriazole compound; a benzylidene malonate compound; benzimidazole compounds; an imidazoline compound; bis-benzoxazole compounds (bis-benzozolyl); para aminobenzoic acid (PABA) compounds; methylene bis (hydroxyphenyl benzotriazole) compounds; benzo (E) benzo (E An azole compound; light-blocking (masking) polymers and light-blocking silicones; dimers derived from alpha-alkylstyrene; 4, 4-diaryl butadiene compounds; guaiac and derivatives thereof; rutin and its derivatives; and mixtures thereof.

As examples of (a) one or more organic UV filters, mention may be made of those indicated below under their INCI names and mixtures thereof.

-anthranilic acid compound: menthyl anthranilate sold under the trademark "NeoHeliopan MA" by Haarmann and Reimer.

Dibenzoylmethane compound: butyl methoxydibenzoylmethane, in particular sold by Hoffmann-La Roche under the trademark "Parsol 1789"; and isopropyl dibenzoylmethane.

Cinnamic acid compounds: ethylhexyl methoxycinnamate, in particular sold under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropyl methoxycinnamate; isoamyl methoxycinnamate sold under the trademark "Neo Heliopan E1000" by Haarmann and Reimer; cinnolsha ester (2-ethoxyethyl-4-methoxycinnamate); methoxy cinnamic acid DEA ester; diisopropyl methyl cinnamate; and glycerol ethylhexanoate dimethoxy cinnamate.

Salicylic acid compound: homosalate (salicylic acid Gao Mengzhi) sold by Rona/EM Industries under the trademark "Eusolex HMS"; ethylhexyl salicylate sold under the trademark "Neo Heliopan OS" by Haarmann and Reimer; ethylene glycol salicylate; butyl octyl salicylate; phenyl salicylate; dipropylene glycol salicylate sold under the trademark "dipal" by Scher; and TEA salicylate sold under the trademark "Neo Heliopan TS" by Haarmann and Reimer.

-camphor compounds, in particular benzylidene camphor derivatives: 3-benzylidene camphor manufactured by Chimex under the trademark "Mexoryl SD"; 4-methylbenzylidene camphor sold under the trademark "Eusolex 6300" by Merck; benzylidene camphorsulfonic acid manufactured by Chimex under the trademark "mexyl SL"; camphorbenzalkonium methyl sulfate manufactured by Chimex under the trademark "mexyl SO"; and polyacrylamide aminomethyl benzylidene camphor manufactured by Chimex under the trademark "Mexoryl SW".

Benzophenone compound: benzophenone-1 (2, 4-dihydroxybenzophenone) sold under the trademark "Uvinul 400" by BASF; benzophenone-2 (tetrahydroxybenzophenone) sold by BASF under the trademark "Uvinul D50"; benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone sold by BASF under the trademark "Uvinul M40"; benzophenone-4 (hydroxymethoxybenzophenone sulfonic acid) sold under the trademark "Uvinul MS40" by BASF; benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxydimethoxybenzophenone) sold by norquat under the trademark "HeliSorb 11"; benzophenone-8 sold under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (disodium dihydroxydimethoxy benzophenone disulfonate) sold under the trademark "Uvinul DS-49" by BASF; benzophenone-12 and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate (UVINIUL A+ from BASF).

-beta, beta-diphenylacrylate compound: octocrylene, particularly sold by BASF under the trademark "Uvinul N539"; and etoricline sold under the trademark "Uvinul N35", in particular, by BASF.

-triazine compounds: diethylhexyl butyrylaminotriazinone sold under the trademark "uvarorb HEB" by Sigma 3V; 2,4, 6-tris (4' -aminobenzylidene-malonic acid dipivalyl) -S-triazine, bis-ethylhexyloxyphenol methoxyphenyl triazine sold by CIBA GEIGY under the trademark "TINOSORB S", and ethylhexyl triazone sold by BASF under the trademark "UVINUL T150".

-benzotriazole compounds, in particular phenylbenzotriazole derivatives: branched and linear 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol; and those described in USP 5240975.

-benzylidene malonate compounds: dineopentylene 4' -methoxybenzylidene malonate and polyorganosiloxanes containing benzylidene malonate functionality, such as polysiloxane-15 sold under the trademark "Parsol SLX" by Hoffmann-LaRoche.

-benzimidazole compounds, in particular phenylbenzimidazole derivatives.

Imidazoline compounds: dimethoxybenzylidene dioxoimidazoline propionic acid ethylhexyl ester.

-bis-benzoxazole (benzozolyl) compounds: such as the derivatives described in EP-669,323 and U.S. Pat. No. 2,463,264.

-para aminobenzoic acid compound: PABA (para-aminobenzoic acid), ethyl para-aminobenzoate, ethyl dihydroxypropyl para-aminobenzoate, amyl dimethyl para-aminobenzoate, ethylhexyl dimethyl para-aminobenzoate, in particular glycerol para-aminobenzoate sold by ISP under the trademark "Escalol 507" and PEG-25PABA sold by BASF under the trademark "Uvinul P25".

-methylenebis- (hydroxyphenyl-benzotriazole) compounds, such as 2,2 '-methylenebis [6- (2H-benzotriazole-2-yl) -4-methyl-phenol sold under the trademark "Mixxim BB/200" by Fairmount Chemical in solid form, 2' -methylenebis [6- (2H-benzotriazole-2-yl) -4- (1, 3-tetramethylbutyl) -phenol sold under the trademark "Tinosorb M" by BASF or under the trademark "Mixxim BB/100" by Fairmount Chemical in micronized form in aqueous dispersion, and derivatives as described in U.S. Pat. Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-197,26,184 and EP-893,119, and

cresol trisiloxane sold under the trademark "Silatrizole" by Rhodia Chimie or under the trademark "Mexoryl XL" by L' Oreal, as shown below.

-a benzoxazole compound: 2, 4-bis [5-1 (dimethylpropyl) benzooxazol-2-yl (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine sold by Sigma 3V under the trademark uvarorb K2A.

Light-blocking polymers and light-blocking silicones: silicones described in WO 93/04665.

-dimers derived from alpha-alkylstyrene: dimers described in DE-19855649.

-4, 4-diaryl butadiene compound: 1, 1-dicarboxylic acid (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene.

(a) The one or more organic UV filters are preferably selected from: butyl methoxy dibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 1'- (1, 4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl ] phenyl ] -methanone 4-methylbenzylidene camphor, ethylhexyl triazinone, bis-ethylhexyl oxyphenol methoxyphenyltriazine, diethylhexyl butyrylamiyltrianone, 2,4, 6-tris (4' -aminobenzylidene malonate dineopentyl) -s-triazine, 2,4, 6-tris (4 '-aminobenzylidene malonate diisobutyl) -s-triazine, 2, 4-bis- (4' -aminobenzylidene malonate di-n-butyl) -6- [ (3- {1, 3-tetramethyl-1- [ (trimethylsilyloxy ] disiloxy) propyl) amino ] -s-triazine, 2, 6- (2, 6 '-dimethylbenzylidene) -triazine, 2, 4' -dimethylbenzylidene, 4-triazolyl-15, 4-trimethylidene malonate, tris (2, 4 '-dibenzylidene malonate) -s-triazine, 2,4, 6-tris (4' -aminobenzylidene malonate) s-triazine, 2' -dimethylpropyl) -4, 4-diphenylbutadiene, 2, 4-bis [5-1 (dimethylpropyl) benzooxazol-2-yl (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, camphorbenzammonium methylsulfate, and mixtures thereof.

The amount of the (a) one or more organic UV filters in the composition according to the invention may be 1 wt% or more, preferably 5 wt% or more, and more preferably 10 wt% or more, relative to the total weight of the composition.

The amount of the (a) one or more organic UV filters in the composition according to the invention may be 40 wt% or less, preferably 35 wt% or less, and more preferably 30 wt% or less, relative to the total weight of the composition.

The amount of the (a) organic UV filter(s) in the composition according to the invention may be from 1 to 40 wt%, preferably from 5 to 35 wt%, and more preferably from 10 to 30 wt%, relative to the total weight of the composition.

[ spherical hydrophobic silica ]

The composition according to the invention comprises (b) at least one spherical hydrophobic silica. If two or more of (b) spherical hydrophobic silica are used, they may be the same or different.

(b) The spherical hydrophobic silica is preferably porous. In other words, (b) the spherical hydrophobic silica is preferably an aerogel.

Aerogels are materials with high porosity. Herein, silica aerogel refers to solid silica having a porous structure, which is generally obtained by replacing a medium contained in wet silica gel with air by drying while maintaining a solid network structure of silica. Porosity represents the amount of air contained in the apparent volume of the material, expressed as a percentage of the volume. The (b) spherical hydrophobic silica in aerogel form may have a porosity of 60% or more, preferably 70% or more, and more preferably 80% or more.

(b) Spherical hydrophobic silica is in the form of particles. (b) Spherical hydrophobic silica is characterized in that each particle has a spherical shape. Due to the spherical shape, (b) spherical hydrophobic silica can provide good smoothness. (b) The sphericity of spherical hydrophobic silica can be determined by average roundness.

(b) The spherical hydrophobic silica may have an average roundness of 0.8 or more, and preferably 0.82 or more. (b) The spherical hydrophobic silica may have an average roundness of less than 1, preferably 0.99 or less, more preferably 0.98 or less, even more preferably 0.97 or less, still more preferably 0.96 or less, and most preferably 0.95 or less.

The "average roundness" can be determined by image analysis. In particular, the "average circularity" may be an arithmetic average of circularities obtained by image analysis of a Scanning Electron Microscope (SEM) image of not less than 2000 particles observed at a magnification of 1000 times by secondary electron detection using a Scanning Electron Microscope (SEM).

The "roundness" of each particle is a value determined by:

C＝4πS/L ²

where C represents roundness, S represents the area (projected area) of the particles in the image, and L represents the peripheral length (perimeter) of the particles in the image. As the average roundness approaches 1, the shape of each particle becomes more spherical.

For (b) spherical hydrophobic silica, the term "hydrophobic" means that the silica particles are difficult to disperse in water. More specifically, the term means that after 1 g of silica particles and 100 g of ion-exchanged water are added to the flask, the flask is stirred or agitated for ten seconds or more, and the silica particles phase is completely separated from the aqueous phase after the flask is left to stand. Thus, in a particular embodiment of the invention, (b) the spherical hydrophobic silica does not exhibit water absorption.

The (b) spherical hydrophobic silicas which can be used according to the invention preferably have the type of silylated silica (INCI name: silylated silica). Most preferably, (b) the spherical hydrophobic silica may be those described in JP-A-2014-088307, JP-A-2014-218433 or JP-A-2018-177620.

Hydrophobicity can be obtained by reacting a hydrophobizing agent with silanol groups represented by the following formula present on the silica surface:

≡Si-OH

wherein the symbol "≡" represents the remaining three valencies of the Si atom,

thereby converting the silanol group into a group represented by the formula:

(≡Si-O-) _(4-n) SiR _n

wherein n is an integer from 1 to 3; each R is independently a hydrocarbyl group; and two or more R's may be the same or different from each other, wherein n is 2 or more.

The hydrophobic agent may be a silylating agent. Thus, according to a preferred embodiment, in (b) spherical hydrophobic silica, the silica particles may be surface modified by silylation. As examples of the silylating agent, there may be mentioned a treating agent having one of the following formulas (1) to (3).

Formula (1):

R _n SiX _(4-n)

wherein n represents an integer of 1 to 3; r represents a hydrocarbon group; x represents a group that can leave the molecule (i.e., a leaving group) by bond cleavage with a Si atom in reaction with a compound having a hydroxyl group; each R may be different, wherein n is 2 or greater; and each X may be different, where n is 2 or less.

Formula (2):

wherein R is ¹ Represents an alkylene group; r is R ² And R is ³ Independently represents a hydrocarbon group; and R is ⁴ And R is ⁵ Independently represents a hydrogen atom or a hydrocarbon group.

Formula (3):

wherein R is ⁶ And R is ⁷ Independently represents a hydrocarbon group; m represents an integer of 3 to 6; when there are two or more R ⁶ When each R ⁶ May be different; and when there are two or more R ⁷ When each R ⁷ May be different.

In the above formula (1), R is a hydrocarbon group, preferably a hydrocarbon group having a carbon number of 1 to 10, more preferably a hydrocarbon group having a carbon number of 1 to 4, and particularly preferably a methyl group.

As examples of leaving groups represented by X, mention may be made of halogen atoms such as chlorine and bromine; alkoxy groups such as methoxy and ethoxy; -NH-SiR ₃ (wherein R is defined as followsR in formula (1) is the same).

Specific examples of the hydrophobizing agent represented by the above formula (1) include: chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, monomethyl trimethoxysilane, monomethyl triethoxysilane and hexamethyldisilazane.

From the standpoint of advantageous reactivity, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane and/or hexamethyldisilazane are most preferably used.

The number of bonds between the Si atom and the silanol group on the silica skeleton varies depending on the number of leaving groups X (4-n). For example, if n is 2, the following bonding will occur:

(≡Si-O-) ₂ SiR ₂ ，

if n is 3, the following bonding will occur:

≡Si-O-SiR ₃ 。

in this way, silanol groups can be silylated and thus hydrophobized.

In the above formula (2), R ¹ Can be an alkylene group, preferably an alkylene group having a carbon number of 2 to 8, and particularly preferably an alkylene group having a carbon number of 2 to 3.

In the above formula (2), R ² And R is ³ Independently, a hydrocarbon group, and the same preferable group as R in the above formula (1) can be mentioned. R is R ⁴ Represents a hydrogen atom or a hydrocarbon group, and when it is a hydrocarbon group, the same preferable group as R in the above formula (1) can be exemplified. When the gel of silica is treated with a compound represented by formula (2) (cyclic silazane), cleavage of the si—n bond occurs by reaction with silanol groups, and thus the following bonding will occur on the surface of the silica skeleton in the gel:

(≡Si-O-) ₂ SiR ² R ³ 。

In this way, the silanol groups can be silylated by the cyclic silazanes of formula (2) above and thus hydrophobization can be performed.

Specific examples of the cyclic silazane represented by the above formula (3) include hexamethyl cyclotrisilazane and octamethyl cyclotetrasilazane.

In the above formula (3), R ⁶ And R is ⁷ Independently, a hydrocarbon group, and the same preferable group as R in the above formula (2) can be mentioned. m represents an integer of 3 to 6. When the gel of silica is treated with the compound (cyclic siloxane) represented by formula (3), the following bonding will occur on the surface of the silica skeleton in the gel:

(≡Si-O-) ₂ SiR ⁶ R ⁷ 。

in this way, the silanol groups can be silylated by the cyclic siloxanes of the above formula (3) and thus hydrophobization can be carried out.

Specific examples of the cyclic siloxane represented by the above formula (3) include hexamethylcyclotrisiloxane, octamethyltetrasiloxane and decamethyl cyclopentasiloxane.

(b) Spherical hydrophobic silica can be prepared by: preparing a silica sol, converting the sol into a gel, aging the gel, washing the aged gel, replacing water in the washed gel with a solvent, treating the gel with a hydrophobizing agent, and drying the hydrophobized silica.

(b) The spherical hydrophobic silica may have a particle size of 200m ² Per gram or higher, preferably 400m ² /g or higher, and more preferably 500m ² Per g or higher, and/or may have a specific surface area of 1,200m as determined by BET method ² /g or less, preferably 1,000m ² /g or less, and more preferably 800m ² And/g or less, as determined by BET method.

In the present invention, "specific surface area measured by BET method" means a value measured by: drying the sample for measurement at 200 ℃ under reduced pressure of not more than 1kPa for not less than three hours; then measuring only the adsorption isotherm of the nitrogen adsorption side at the liquid nitrogen temperature; and adsorption isotherms were analyzed by BET method. The pressure used for analysis ranged from 0.1 to 0.25 relative pressure.

(b) The spherical hydrophobic silica may have a pore volume as determined by the BJH method of 1ml/g or more, preferably 2ml/g or more, and more preferably 3ml/g or more, and/or may have a pore volume as determined by the BJH method of 10ml/g or less, preferably 8ml/g or less, and more preferably 7ml/g or less.

(b) The spherical hydrophobic silica may have a peak pore radius as determined by the BJH method of 5nm or more, preferably 10nm or more, and more preferably 12nm or more, and/or may have a peak pore radius as determined by the BJH method of 50nm or less, preferably 40nm or less, and more preferably 30nm or less.

The "pore volume measured by the BJH method" refers to a pore volume obtained from a pore having a pore radius of 1nm to 100nm by analyzing an adsorption isotherm of a nitrogen adsorption side obtained in the same manner as explained above for the "specific surface area measured by BET method", by the BJH method (Barrett, e.p.; joyner, l.g.; halenda, P.P., J.Am.Chem.Soc.73, 373 (1951)). "peak pore radius as determined by the BJT method" refers to a pore radius value that gives a peak in a pore distribution curve (volume distribution curve) that is plotted as follows: the vertical axis takes the derivative of the cumulative pore volume versus the logarithm of pore radius (obtained by analyzing the adsorption isotherm of the nitrogen adsorption side obtained in the same manner as above by the BJH method), and the horizontal axis takes the pore radius.

(b) The spherical hydrophobic silica may have an average particle size of 0.5 μm or more, preferably 1 μm or more, and more preferably 2 μm or more, and/or may have an average particle size by an image analysis method of 30 μm or less, preferably 20 μm or less, and more preferably 15 μm or less. Thus, (b) the spherical hydrophobic silica may have an average particle size of 0.5 μm to 30 μm, preferably 1 μm to 20 μm, and more preferably 2 μm to 15 μm. In a preferred embodiment, (b) the spherical hydrophobic silica may have an average particle size of from 6 μm to 16 μm, preferably from 7 μm to 14 μm, and more preferably from 8 μm to 12 μm.

The "average particle size" may be measured herein by image analysis. Specifically, the value of "average particle size" is an arithmetic average value of equivalent circle diameters, which can be obtained by, for example, image analysis of a Scanning Electron Microscope (SEM) image of not less than 2000 particles observed at a magnification of 1000 times by secondary electron detection using a Scanning Electron Microscope (SEM). The "equivalent circle diameter" of each particle is the diameter of a circle having an area equal to the area of the particle in the image (projected area).

Preferably, (b) the spherical hydrophobic silica may have an oil absorption measured at the wet point of 2ml/g or more, preferably 3ml/g or more, more preferably 4ml/g or more, and most preferably 5ml/g or more, and/or may have an oil absorption measured at the wet point of 12ml/g or less, preferably 11ml/g or less, more preferably 10ml/g or less, and most preferably 8ml/g or less.

The oil absorption measured at the wet point, denoted Wp, corresponds to the amount of oil that needs to be added to 100 grams of particles to obtain a uniform paste. It can be measured according to the wet spot method described in standard NF T30-022 or the method of measuring the oil absorption of the powder. As described below, the oil absorption may correspond to the amount of oil that is adsorbed onto the usable surface of the powder and/or absorbed by the powder by measuring the wet point.

An amount of m=2 grams of powder was placed on a glass plate and then an oil (such as ester oil, oleic acid or silicone oil) was added dropwise. After adding 4 to 5 drops of oil to the powder, mixing is performed with a spatula and the addition of oil is continued until an aggregate of oil and powder is formed. At this point, the oil is added one drop at a time and the mixture is subsequently ground with a spatula. The addition of oil was stopped when a firm, smooth paste was obtained. Such a paste must be capable of spreading on a glass sheet without cracking or forming lumps. The volume Vs (in milliliters) of oil used was then recorded. The oil absorption corresponds to the ratio Vs/m.

Alternatively, the oil absorption may be measured according to JIS-K6217-4.

In a preferred embodiment of the present invention, (b) the spherical hydrophobic silica may be selected from those described in JP-A-2014-088307, JP-A-2014-218433 or JP-A-2018-177620.

The amount of the (b) one or more spherical hydrophobic silica in the composition according to the invention may be 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more, relative to the total weight of the composition.

The amount of the (b) one or more spherical hydrophobic silica in the composition according to the invention may be 15 wt% or less, preferably 10 wt% or less, and more preferably 5 wt% or less, relative to the total weight of the composition.

[ Water ]

The composition according to the invention comprises (c) water.

(c) The water may form the discontinuous or dispersed (internal) phase of the W/O composition. Thus, (c) water may form the discontinuous or dispersed (internal) phase of the composition according to the invention in the form of a W/O emulsion.

The amount of (c) water in the composition according to the invention may be 10% by weight or more, preferably 15% by weight or more, and more preferably 20% by weight or more, relative to the total weight of the composition.

The amount of (c) water in the composition according to the invention may be 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less, relative to the total weight of the composition.

The amount of (c) water in the composition according to the invention may be from 10 to 50% by weight, preferably from 15 to 40% by weight, and more preferably from 20 to 30% by weight, relative to the total weight of the composition.

[ oil ]

The composition according to the invention may comprise (d) at least one oil. If two or more oils are used, they may be the same or different.

(d) The oil is different from (a) the organic UV filter.

Herein, "oil" refers to a fatty compound or substance that is in liquid or paste (non-solid) form at room temperature (25 ℃) at atmospheric pressure (760 mmHg). As the oil, those commonly used in cosmetology may be used alone or in combination thereof. These oils may be volatile or non-volatile.

(d) The oil may be a non-polar oil such as hydrocarbon oil, silicone oil, and the like; polar oils such as vegetable or animal oils, and ester or ether oils; or a mixture thereof.

(d) The oil may be selected from oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

As examples of vegetable oils, mention may be made, for example, of linseed oil, camellia seed oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower seed oil, jojoba oil, sunflower seed oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil and mixtures thereof.

As examples of animal oils, squalene and squalane may be mentioned, for example.

As examples of synthetic oils, alkane oils such as isododecane and isohexadecane, ester oils, ether oils and artificial triglycerides may be mentioned.

The ester oil is preferably saturated or unsaturated, linear or branched C ₁ -C ₂₆ Aliphatic mono-or polyacids with saturated or unsaturated, straight-chain or branched C ₁ -C ₂₆ Liquid esters of aliphatic monohydric or polyhydric alcohols having a total number of carbon atoms greater than or equal to 10.

Preferably, for esters of monohydric alcohols, at least one of the alcohol and acid from which the esters of the present invention are derived is branched.

Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dioctyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl pivalate and isostearyl pivalate.

C can also be used ₄ -C ₂₂ Di-or tricarboxylic acids with C ₁ -C ₂₂ Esters of alcohols and mono-, di-or tricarboxylic acids with non-sugar C ₄ -C ₂₆ Dihydric alcohol, trihydric alcoholEsters of alcohols, tetrahydroxy alcohols or pentahydroxy alcohols.

Mention may be made in particular of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis (2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis (2-ethylhexyl) adipate; diisostearyl adipate; bis (2-ethylhexyl) maleate; triisopropanol citrate; triisocetyl citrate; triisostearyl citrate; glycerol trilactate; glyceryl trioctanoate; tri (octyldodecanol) citrate; triol citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As the ester oil, C can be used ₆ -C ₃₀ Fatty acids and preferably C ₁₂ -C ₂₂ Sugar esters and diesters of fatty acids. Recall that the term "sugar" refers to an oxygen-containing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and which contains at least 4 carbon atoms. These sugars may be mono-, oligo-or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or sucrose), glucose, galactose, ribose, trehalose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, in particular alkyl derivatives such as methyl derivatives, for example methyl glucose.

The sugar esters of fatty acids may in particular be selected from the group consisting of the sugars previously described with linear or branched, saturated or unsaturated C ₆ -C ₃₀ Fatty acids and preferably C ₁₂ -C ₂₂ Esters or ester mixtures of fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from the group consisting of monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates or mixtures thereof, in particular, mixed esters such as oil palmitates, oil stearates and palm stearates, and pentaerythritol tetraethylhexanoate.

More particularly mono-and diesters are used, and in particular sucrose, glucose or methyl glucose mono-or dioleates, stearates, behenates, oil palmitates, linoleates, linolenates and oil stearates.

One example which may be mentioned is the company Amerchol under the nameDO, which is methyl glucose dioleate.

As examples of preferred ester oils mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl caproate, ethyl laurate, cetyl caprylate, octyldodecyl caprylate, isodecyl pivalate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dioctyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, tris (2-ethylhexanoate), pentaerythritol tetrakis (2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate and mixtures thereof.

As examples of artificial triglycerides, for example, decanoyl caprylyl glyceride, trimyristate glyceride, tripalmitin glyceride, trilineous glyceride, trilaurin glyceride, tricaprin glyceride, tricaprylin glyceride, tri (capric/caprylic) glyceride and tri (capric/caprylic/linolenic) glyceride may be mentioned.

As examples of silicone oils, mention may be made, for example, of linear organopolysiloxanes such as polydimethylsiloxane, methylphenyl polysiloxane, methyl hydrogen polysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, and the like; and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, in particular liquid Polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.

These silicone oils may also be organically modified. The organomodified silicones that can be used according to the invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups linked via hydrocarbon-based groups.

Organopolysiloxane is defined in more detail in the Academic Press, chemistry and Technology of Silicones by Walter Noll (1968). They may be volatile or non-volatile.

When they are volatile, the silicones are more particularly selected from those having a boiling point of 60 ℃ to 260 ℃, and even more particularly selected from:

(i) Cyclic polydialkylsiloxanes comprising 3 to 7 and preferably 4 to 5 silicon atoms. These are for example given the name Volatile by Union Carbide7207 or by Rhodia under the name +.>70045V2 octamethyl cyclotetrasiloxane, sold under the name Volatile->7158. Under the name Rhodia70045V5, and dodecamethyl cyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclic copolymers (of the type such as dimethylsiloxane/methylalkylsiloxane), such as Silicone +.>FZ 3109 has the formula: />

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as mixtures of octamethyltetrasiloxane and tetrakis (trimethylsilyl) pentaerythritol (50/50), and mixtures of octamethyltetrasiloxane and oxo-1, 1' -bis (2, 2', 3' -hexatrimethylsilyloxy) neopentane; and

(ii) Containing 2 to 9 silicon atoms and having a silicon atom number of less than or equal to 5X 10 at 25 DEG C ^-6 m ² Linear volatile polydialkylsiloxane of viscosity/s. One example is decamethyltetrasiloxane sold under the name SH200, particularly by the company Toray Silicone. Silicones belonging to this class are also described in Cosmetics and Toiletries, volume 91, month 1 of 76, pages 27-32, todd&In articles published in Byers, volatile Silicone Fluids for Cosmetics. The viscosity of the silicone was measured at 25 ℃ according to ASTM standard 445 appendix C.

Nonvolatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, by way of non-limiting example, of the following commercial products:

-series 47 and 70047 sold by RhodiaOil or->Oils, such as oil 70047V 500000:

sold by the company RhodiaA series of oils;

-come from200 series of oils from Dow Corning, inc., e.g. having a viscosity of 60,000 mm ² DC200 of/s; and

-from General ElectricOils and certain oils from the SF series from General Electric (SF 96, SF 18).

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the 48 series of oils from Rhodia.

Among the aryl-containing silicones, mention may be made of polydiarylsiloxanes, in particular polydiphenylsiloxanes and polyalkylarylsiloxanes, such as phenyl silicone oils.

The phenyl silicone oil may be selected from phenyl silicones of the formula:

wherein the method comprises the steps of

R ₁ To R ₁₀ C-based on straight, cyclic or branched chains, independently of one another, saturated or unsaturated ₁ -C ₃₀ Hydrocarbon-based groups, preferably based on C ₁ -C ₁₂ Hydrocarbon groups, and more preferably C-based ₁ -C ₆ Hydrocarbon radicals, in particular methyl, ethyl, propyl or butyl radicals, and

m, n, p and q are each independently an integer from 0 to 900 inclusive, preferably an integer from 0 to 500 inclusive and more preferably an integer from 0 to 100 inclusive,

provided that the sum of n+m+q is not 0.

Examples that may be mentioned include products sold under the following names:

70641 series from RhodiaAn oil;

-from Rhodia70633 and 763 series of oils;

oil from Dow Corning 556Cosmetic GradeFluid;

silicones from the Bayer PK series, such as product PK20;

certain oils from the SF series of General Electric, such as SF 1023, SF1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (in the above formula, R ₁ To R ₁₀ Is methyl; p, q and n=0; m=1) is preferable.

The organically modified liquid silicone may contain, in particular, polyoxyethylene groups and/or polyoxypropylene groups. Mention may thus be made of the silicones KF-6017 proposed by Shin-Etsu and the oils from the company UnioncarbideL722 and L77.

The hydrocarbon oil may be selected from:

-linear or branched, optionally cyclic, C ₆ -C ₁₆ Lower alkanes. Examples which may be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane; and

linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petrolatum (petrolatum), polydecene and hydrogenated polyisobutene such asAnd squalane.

As preferable examples of the hydrocarbon oil, for example, straight-chain or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum (petrolatum), naphthalene, and the like; hydrogenated polyisobutene, isoeicosane and decene/butene copolymers; and mixtures thereof.

The term "fat" in fatty alcohols means a compound comprising a relatively large number of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are included in the range of fatty alcohols. The fatty alcohols may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohol may have the structure R-OH, wherein R is selected from saturated and unsaturated, straight and branched groups containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be selected from C ₁₂ -C ₂₀ Alkyl and C ₁₂ -C ₂₀ Alkenyl groups. R may or may not be substituted with at least one hydroxy group.

As examples of fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenol, myristyl alcohol, octyldodecanol, hexyldecyl alcohol, oleyl alcohol, linolenyl alcohol, palmitol alcohol, arachidonic alcohol, erucyl alcohol and mixtures thereof.

Preferably the fatty alcohol is a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from linear or branched, saturated or unsaturated C ₆ -C ₃₀ Alcohols, preferably linear or branched saturated C ₆ -C ₃₀ Alcohols, and more preferably straight or branched saturated C ₁₂ -C ₂₀ An alcohol.

The term "saturated fatty alcohol" herein refers to an alcohol having a long aliphatic saturated carbon chain. Preferably the saturated fatty alcohol is selected from any linear or branched saturated C ₆ -C ₃₀ Fatty alcohols. In straight-chain or branched saturated C ₆ -C ₃₀ In fatty alcohols, it is preferable to use saturated C which is linear or branched ₁₂ -C ₂₀ Fatty alcohols. Any straight or branched saturated C may be more preferably used ₁₆ -C ₂₀ Fatty alcohols. Branched C may be used even more preferably ₁₆ -C ₂₀ Fatty alcohols.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenol, myristyl alcohol, octyldodecanol, hexyldecanol and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (e.g., cetostearyl alcohol), and behenyl alcohol may be used as the saturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in the composition according to the invention is preferably chosen from cetyl alcohol, octyldodecanol, hexyldecanol and mixtures thereof.

(d) The oil may be selected from non-polar or polar oils, preferably hydrocarbon oils, silicone oils, ester oils and mixtures thereof, and even more preferably isododecane, isohexadecane, polydimethylsiloxane, diisopropyl sebacate and mixtures thereof.

The amount of the (d) one or more oils in the composition according to the invention may be 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight or more, relative to the total weight of the composition.

The amount of the (d) one or more oils in the composition according to the invention may be 30 wt% or less, preferably 25 wt% or less, and more preferably 20 wt% or less, relative to the total weight of the composition.

The amount of the (d) one or more oils in the composition according to the invention may be from 5 to 30% by weight, preferably from 10 to 25% by weight, and more preferably from 15 to 20% by weight, relative to the total weight of the composition.

[ DIC gel ]

The composition according to the invention may comprise at least one gel, preferably a hydrogel, which is dynamic and ionically crosslinked. The dynamic and ionically crosslinked gels are abbreviated hereinafter as DIC gels.

Dynamic and ionic crosslinking in DIC gels differs from permanent covalent bonding in that it is cleavable but reformable. Dynamic crosslinking and ionic crosslinking can be easily broken by, for example, cutting, but can be easily reformed by, for example, contacting each other, thereby exhibiting self-healing or self-repairing properties. For example, if the gel is cut into two pieces, the ionic interactions between the cationic polymer and the crosslinking agent break. However, if the two sheets are in contact with each other, they can reform the ionic bond between the cationic polymer and the crosslinking agent, and they can adhere to each other. Thus, even if cracks are formed on the gel, for example, they can disappear.

The composition according to the invention can be used to prepare gel films having self-healing or self-healing properties by applying the composition to a substrate, preferably a keratin substrate such as the skin, and drying the composition.

DIC gels can be formed with at least one cationic polysaccharide and at least one crosslinker having three or more acid groups or salts thereof.

(cationic polysaccharide)

The composition according to the invention may comprise at least one cationic polysaccharide. Two or more different types of cationic polysaccharides may be used in combination. Thus, a single type of cationic polysaccharide or a combination of different types of cationic polysaccharides may be used.

The cationic polysaccharide has a positive charge density. The cationic polysaccharide may have a charge density of 0.01 to 20meq/g, preferably 0.05 to 15meq/g, and more preferably 0.1 to 10meq/g.

The molecular weight of the cationic polysaccharide is preferably 500 or more, preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 5,000 or more.

Unless otherwise defined in the specification, "molecular weight" refers to number average molecular weight.

The cationic polysaccharide may have at least one positively chargeable and/or positively charged moiety selected from primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanidino groups, imidazole groups, imino groups and pyridine groups. The term (primary) "amino" refers herein to the group-NH ₂ . The cationic polysaccharide preferably has at least one quaternary ammonium group.

The cationic polysaccharide may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

The cationic polysaccharide may be selected from natural and synthetic cationic polysaccharides.

The cationic polysaccharide is preferably selected from cationic cellulose polymers. Non-limiting examples of cationic cellulose polymers are as follows.

(1) Cationic cellulose polymers, such as cellulose ether derivatives containing one or more quaternary ammonium groups, for example as described in french patent No. 1492597, such as the polymers sold under the name "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Dow Chemical company. These polymers are also defined in the CTFA dictionary as quaternary amines of hydroxyethyl cellulose that have been reacted with epoxides substituted with trimethylammonium groups.

(2) Cationic cellulose polymers, such as cellulose copolymers and cellulose derivatives grafted with at least one water-soluble monomer of quaternary ammonium and described in, for example, U.S. Pat. No. 4,131,576, such as hydroxyalkyl celluloses, e.g., hydroxymethyl-, hydroxyethyl-and hydroxypropyl celluloses, grafted with at least one selected from, for example, methacryloylethyl trimethylammonium, methacrylamidopropyl trimethylammonium, and dimethyldiallylammonium. Commercial products corresponding to these polymers include, for example, those sold under the name "by Akzo Novel corporation" L200 'and'>H100 "product sold.

(3) Cationic cellulose polymers having at least one quaternary ammonium group comprising at least one fatty chain, such as an alkyl, aralkyl or alkaryl group comprising at least 8 carbon atoms. The cationic cellulose polymer is preferably a quaternized hydroxyethyl cellulose modified with at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, aralkyl or alkaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl groups carried by the quaternary ammonium groups may preferably contain from 8 to 30 carbon atoms, especially from 10 to 30 carbon atoms. Aryl preferably represents phenyl, benzyl, naphthyl or anthracenyl. More preferably, the cationic cellulose polymer may comprise at least one quaternary ammonium group comprising at least one C ₈ -C ₃₀ A hydrocarbon group. Containing C _8-30 Quaternized alkyl hydroxy groups of fatty chainsExamples of ethylcellulose include the products Quattrisoft LM 200, quattrisoft LM-X529-18-A, quattrisoft LM-X529-18B (C) ₁₂ Alkyl) and Quattrisoft LM-X529-8 (C) ₁₈ Alkyl) or Softcat Polymer SL, softcat SX-1300X, softcat SX-1300H, softcat SL-5, softcat SL-30, softcat SL-60, softcat SK-MH, softcat SX-400X, softcat SX-400H, softCat SK-L, softcat SK-M and Softcat SK-H, and the products Crodacel QM, crodacel, QL (C) sold by Croda company ₁₂ Alkyl) and Crodacel QS (C ₁₈ Alkyl).

The cationic polysaccharide is preferably selected from the group consisting of polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, and mixtures thereof.

The amount of the one or more cationic polysaccharides in the composition according to the present invention may be 0.01 wt% or more, preferably 0.03 wt% or more, and more preferably 0.05 wt% or more, relative to the total weight of the composition.

The amount of the one or more cationic polysaccharides in the composition according to the present invention may be 1 wt% or less, preferably 0.5 wt% or less, and more preferably 0.1 wt% or less, relative to the total weight of the composition.

The amount of the one or more cationic polysaccharides in the composition according to the invention may be from 0.01 to 1% by weight, preferably from 0.03 to 0.5% by weight, and more preferably from 0.05 to 0.1% by weight, relative to the total weight of the composition.

(crosslinking agent)

The composition according to the invention may comprise at least one crosslinker having three or more acid groups or a salt thereof. Two or more different types of crosslinking agents or salts thereof may be used in combination. Thus, a single type of crosslinker or salt thereof or a combination of different types of crosslinkers or salts thereof may be used.

At least one acid group of the crosslinking agent having three or more acid groups may be in the form of a salt. All acid groups of the crosslinker may be in the form of salts.

The term "salt" in this specification refers to a salt formed by adding one or more suitable bases to a crosslinker having three or more acid groups, which can be obtained from the reaction of a crosslinker having three or more acid groups with one or more bases according to methods known to those skilled in the art. As the salt, there may be mentioned metal salts, for example, salts with alkali metals such as Na and K, and salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

The cross-linking agent is preferably selected from non-polymeric acids having three or more acid groups, more preferably non-polymeric organic acids having three or more acid groups.

The term "non-polymeric" as used herein means that the crosslinking agent is not obtained by polymerizing two or more monomers. Thus, a non-polymeric acid, in particular a non-polymeric organic acid, does not correspond to an acid obtained by polymerizing two or more monomers, such as a polycarboxylic acid.

The molecular weight of the non-polymeric acid having three or more acid groups, particularly the non-polymeric organic acid, is preferably 1000 or less, preferably 800 or less, and more preferably 600 or less.

The cross-linking agent having three or more acid groups or a salt thereof may be hydrophilic or water-soluble.

The crosslinking agent having three or more acid groups may have three or more acid groups selected from the group consisting of carboxyl groups, sulfuric acid groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, and mixtures thereof.

The cross-linking agent having three or more acid groups or a salt thereof may be selected from the group consisting of tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids, hexacarboxylic acids, salts thereof, and mixtures thereof.

The cross-linking agent having three or more acid groups or a salt thereof may be selected from the group consisting of citric acid, aconitic acid, phytic acid, EDTA, glycyrrhizin, inositol triphosphate, inositol pentaphosphate, tripolyphosphate, adenosine triphosphate, salts thereof, and mixtures thereof.

The cross-linking agent having three or more acid groups or a salt thereof is preferably selected from the group consisting of citric acid, phytic acid, a salt thereof, and a mixture thereof.

The amount of one or more crosslinking agents having three or more acid groups or salts thereof in the composition according to the present invention may be 0.001 wt% or more, preferably 0.005 wt% or more, and more preferably 0.01 wt% or more, relative to the total weight of the composition.

The amount of one or more crosslinking agents having three or more acid groups or salts thereof in the composition according to the present invention may be 1 wt% or less, preferably 0.5 wt% or less, and more preferably 0.1 wt% or less, relative to the total weight of the composition.

The amount of one or more crosslinking agents having three or more acid groups or salts thereof in the composition according to the present invention may be 0.001 to 1 wt%, preferably 0.005 to 0.5 wt%, and more preferably 0.01 to 0.1 wt%, relative to the total weight of the composition.

(anionic Polymer)

The DIC gel amount can be prepared by the above cationic polysaccharide and the above crosslinking agent.

However, in addition, the composition according to the invention may further comprise at least one anionic polymer. Two or more different types of anionic polymers may be used in combination. Thus, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

The anionic polymer has a negative charge density. If the anionic polymer is a synthetic anionic polymer, the anionic polymer may have a charge density of 0.1meq/g to 20meq/g, preferably 1 to 15meq/g, and more preferably 4 to 10meq/g, and if the anionic polymer is a natural anionic polymer, the anionic polymer may have an average degree of substitution of 0.1 to 3.0, preferably 0.2 to 2.7, and more preferably 0.3 to 2.5.

The molecular weight of the anionic polymer is preferably 1,000 or more, preferably 10,000 or more, more preferably 100,000 or more, and even more preferably 1,000,000 or more.

The anionic polymer may have at least one negatively chargeable and/or negatively charged moiety selected from the group consisting of sulfate, sulfonate, phosphate, phosphonate, carboxylate and carboxylate.

The anionic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

The anionic polymer may be selected from natural and synthetic anionic polymers.

The anionic polymer may comprise at least one hydrophobic chain.

Anionic polymers which may comprise at least one hydrophobic chain may be obtained by copolymerization of: monomers (a) selected from the group consisting of carboxylic acids (monomers a ') and 2-acrylamido-2-methylpropanesulfonic acid (monomers a'), containing alpha, beta-ethylenic unsaturation resulting from the reaction of acrylic monomers containing alpha, beta-monoethylenically unsaturated or isocyanate monomers containing monoethylenically unsaturated with a monoanionic amphiphilic component or with a primary or secondary fatty amine, and non-surface-active monomers (b) containing ethylenic unsaturation and/or with monomers (c) containing ethylenic unsaturation.

Thus, anionic polymers having at least one hydrophobic chain can be obtained by two synthetic routes:

by copolymerization of the monomers (a ') and (c), or (a '), (b) and (c), or (a '), (b) and (c),

or by modification (and in particular esterification or amidation) of the monomers (a ') or of the copolymers formed from the monomers (a ') and (b), or of (a ') and (b) by a monobasic nonionic amphiphilic compound or a primary or secondary aliphatic amine.

As 2-acrylamido-2-methylpropanesulfonic acid copolymers there may be mentioned in particular those disclosed in the articles "Micelle formation of random copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,2000, volume 33, 10-3694-3704 pages" and in the applications EP-A-0 750 899 and EP-A-1 069 172.

The carboxylic acid comprising an α, β -monoethylenically unsaturated group constituting the monomer (a') may be selected from a number of acids and in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. It is preferably acrylic acid or methacrylic acid.

The copolymer may comprise a monomer (b) comprising monoethylenically unsaturated monomers that do not have surfactant properties. Preferred monomers are those which, when they are homopolymerized, give rise to water-insoluble polymers. They may be selected from, for example, acrylic acid C ₁ -C ₄ Alkyl esters and methacrylic acid C ₁ -C ₄ Alkyl esters, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. More particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers which may be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile and vinylidene chloride. Non-reactive monomers are preferred, these monomers being those in which the single alkenyl group is the only group reactive under the polymerization conditions. However, monomers containing groups that react under the influence of heat, such as hydroxyethyl acrylate, may optionally be used.

The monomer (c) is obtained by reacting an acrylic monomer comprising an α, β -monoethylenically unsaturated, such as (a) or an isocyanate monomer comprising a monoethylenically unsaturated, with a mono-nonionic amphiphilic compound or a primary or secondary aliphatic amine.

The mono-nonionic amphiphilic compounds or primary or secondary fatty amines used for the manufacture of the nonionic monomers (c) are well known. The monobasic nonionic amphiphilic compound is typically an alkoxylated hydrophobic compound comprising alkylene oxides constituting the hydrophilic portion of the molecule. The hydrophobic compound is generally composed of an aliphatic alcohol or an alkylphenol, in which a carbonaceous chain containing at least 6 carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.

Preferred monobasic nonionic amphiphilic compounds are those having the formula (V):

R-(OCH ₂ CHR') _m -(OCH ₂ CH ₂ ) _n -OH (V)

wherein R is selected from alkyl or alkylene groups containing from 6 to 30 carbon atoms and alkylaryl groups having alkyl groups containing from 8 to 30 carbon atoms, R' is selected from alkyl groups containing from 1 to 4 carbon atoms, n is an average number from about 1 to 150 and m is an average number from about 0 to 50, provided that n is at least as large as m.

Preferably, in the compounds of formula (V), the R groups are selected from alkyl groups containing from 12 to 26 carbon atoms and wherein alkyl is C ₈ -C ₁₃ An alkylphenyl group of (a); the R' group is methyl; m=0 and n=1 to 25.

Preferred primary and secondary aliphatic amines are composed of one or two alkyl chains containing from 6 to 30 carbon atoms.

The monomers used to form the nonionic urethane monomer (c) may be selected from a very wide variety of compounds. Any compound comprising copolymerizable unsaturation, such as acrylic, methacrylic or allylic unsaturation, may be used. The monomers (c) are obtainable in particular from isocyanates comprising monoethylenically unsaturated groups, such as, in particular, α -dimethyl-m-isopropenyl benzyl isocyanate.

The monomers (C) may in particular be chosen from oxyethylenated (1 to 50 EO) C ₆ -C ₃₀ Acrylic, methacrylic or itaconic esters of fatty alcohols, e.g. steareth-20 methacrylate, oxyethylenated (25 EO) behenyl methacrylate, oxyethylenated (20 EO) monocetyl itaconate, oxyethylenated (20 EO) monostearyl itaconate or by polyoxyethylenation (25 EO) C ₁₂ -C ₂₄ Alcohol-modified acrylic esters and selected from oxyethylenated (1 to 50 EO) C ₆ -C ₃₀ Dimethyl-m-isopropenyl benzyl isocyanate of fatty alcohols, in particular, for example, dimethyl-m-isopropenyl benzyl isocyanate of oxyethylenated behenyl alcohol.

According to a particular embodiment of the invention, the anionic polymer is selected from the acrylic terpolymers obtained from: (a) an alpha, beta-ethylenically unsaturated carboxylic acid comprising, (b) a non-ethylenically unsaturated non-surface-active monomer comprising (a) and (c) a nonionic urethane monomer which is the reaction product of a mono-nonionic amphiphilic compound with an isocyanate comprising monoethylenically unsaturated isocyanate.

As anionic polymers comprising at least one hydrophobic chain, mention may be made in particular of acrylic acid/ethyl acrylate/alkyl acrylate terpolymers, such as those obtained by Rohm&The product sold by Haas under the name Acusol 823 as a 30% aqueous dispersion; acrylate/steareth-20 methacrylate copolymers, e.g. fromRohm&Haas sold under the name Aculyn 22; (meth) acrylic acid/ethyl acrylate/oxyethylenated (25 EO) behenyl alcohol methacrylate terpolymers, e.g. from Rohm&The product sold by Haas under the name Aculyn 28 as an aqueous emulsion; acrylic acid/oxyethylenated (20 EO) monocetyl itaconate copolymers, such as the product sold under the name Structure 3001 by National Starch as a 30% aqueous dispersion; acrylic acid/oxyethylenated (20 EO) monostearyl itaconate copolymers, such as the product sold under the name Structure 2001 by National Starch as a 30% aqueous dispersion; acrylic ester/via polyoxyethylenated (25 EO) C ₁₂ -C ₂₄ Alcohol modified acrylate copolymers such as 30-32% copolymer latex sold under the name Synthalen W2000 by 3V SA; or a dimethyl-m-isopropenyl benzyl isocyanate terpolymer of methacrylic acid/methyl acrylate/ethoxylated behenyl alcohol, such as the product disclosed in document EP-A-0 173 109 as a 24% aqueous dispersion and comprising 40 ethylene oxide groups.

The anionic polymer is preferably selected from polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (e.g. cellulose gum, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethylhydroxyethyl cellulose and carboxymethyl cellulose), anionic (co) polyaminoacids such as (co) polyglutamic acid, (co) poly (meth) acrylic acid, (co) polyamic acid, (co) polystyrene sulfonate, (co) poly (vinyl sulfate), dextran sulfate, chondroitin sulfate, (co) polymaleic acid, (co) polyfumaric acid, maleic anhydride (co) polymers, and salts thereof.

The maleic anhydride copolymer may comprise one or more maleic anhydride comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing 2 to 20 carbon atoms and styrene.

Thus, "maleic anhydride copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic anhydride comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctene, and styrene, the maleic anhydride comonomers optionally being partially or completely hydrolyzed. Preferably, a hydrophilic polymer will be used, i.e. a polymer having a solubility in water of greater than or equal to 2 g/l.

Copolymers obtained by copolymerization of one or more maleic anhydride units are preferably used, wherein the maleic anhydride units are in hydrolyzed form, and more preferably in the form of basic salts, for example in the form of ammonium, sodium, potassium or lithium salts.

In one advantageous aspect of the invention, the maleic anhydride copolymer may have a mole fraction of maleic anhydride units of from 0.1 to 1, more preferably from 0.4 to 0.9.

The weight average molar mass of the maleic anhydride copolymer may be 1,000 to 500,000, and preferably 1,000 to 50,000.

The maleic anhydride copolymer is preferably a styrene/maleic anhydride copolymer, and more preferably a sodium styrene/maleic anhydride copolymer.

It will be preferred to use a 50/50 ratio copolymer of styrene and maleic anhydride.

For example, those labeled by Cray Valley may be usedStyrene/maleic anhydride (50/50) copolymers in the form of the ammonium salts sold 30% in water or marked by Cray Valley +.>Styrene/maleic anhydride (50/50) copolymer in the form of 40% sodium salt in water is sold.

The amount of the one or more anionic polymers in the composition according to the present invention may be 0.01 wt% or more, preferably 0.03 wt% or more, and more preferably 0.05 wt% or more, relative to the total weight of the composition.

The amount of the one or more anionic polymers in the composition according to the present invention may be 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less, relative to the total weight of the composition.

The amount of the one or more anionic polymers in the composition according to the invention may be from 0.01% to 1% by weight, preferably from 0.03% to 0.5% by weight, and more preferably from 0.05% to 0.1% by weight, relative to the total weight of the composition.

[ Filler ]

The composition according to the invention may comprise at least one additional filler different from (b) the spherical hydrophobic silica. Two or more additional fillers may be used in combination. Thus, a single type of additional filler or a combination of different types of additional fillers may be used.

The term "filler" is understood to mean colorless or white, inorganic or synthetic particles which are insoluble in the possible liquid components of the composition according to the invention, irrespective of the temperature at which the composition is manufactured.

The one or more fillers may be inorganic or organic and may be spherical or oval, regardless of the crystalline form (e.g., platelet, cube, hexagonal, rhombohedral, etc.). Mention may be made, without limitation, of talc, mica, (hydrophilic) silica, kaolin, sericite, calcined talc, calcined mica, calcined sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium bicarbonate and hydroxyapatite, polyamide @) Powder formed, poly-beta-alanine powder and polyethylene powder, polyurethane powder, tetrafluoroethylene polymer (++>) Powders formed, lauroyl lysine, starch, hollow microspheres of polymers, such as those of poly (vinylidene chloride)/acrylonitrile, for example +.>(Nobel industries), or acrylic copolymers, silicone resin microspheres (e.g., from Toshiba +.>) Particles formed of polyorganosiloxane elastomers, precipitated calcium carbonate, magnesium carbonate, basic magnesium carbonate, hollow silica microspheres, glass or ceramic microcapsules, or metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, such as 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate.

Examples of fillers for the purposes of the present invention include metal oxides, preferably titanium oxide, zinc oxide and mixtures thereof.

The filler suitable for the present invention may be, for example, a filler whose average particle size is less than 100 μm, and in particular from 1 to 50 μm, for example from 4 to 20 μm.

[ other optional additives ]

In addition to the aforementioned components, the composition according to the present invention may contain components generally used in cosmetic products, in particular surfactants (particularly nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents, inorganic UV filters, silicones and silicone derivatives other than (d) oils, natural extracts derived from animals or vegetables, waxes, etc., within the range that does not impair the effects of the present invention.

The composition according to the invention may comprise one or more of the above optional additives in an amount of 0.01 to 50 wt%, preferably 0.05 to 30 wt%, and more preferably 0.1 to 10 wt%, relative to the total weight of the composition.

[ composition ]

The composition according to the invention may be intended for use as a cosmetic composition. Thus, the cosmetic composition according to the invention may be intended to be applied to keratin materials. Keratin materials herein means materials containing keratin as a main constituent, examples of which include skin, scalp, nails, lips, hair, and the like. Thus, the cosmetic composition according to the invention is preferably used in a cosmetic process for keratin materials, in particular the skin.

Thus, the cosmetic composition according to the invention may be a skin cosmetic composition, preferably a skin care composition or a skin make-up composition, and more preferably a skin care composition.

The composition according to the invention may be prepared by mixing the above-mentioned essential and optional ingredients according to any method known to the person skilled in the art.

The above basic components or optional components may be heated if desired. Thus, when the above basic components and optional components are mixed, heating may be performed.

Since the composition according to the invention comprises (a) an oily organic UV filter and (c) water, it may be in the form of an emulsion. The composition according to the invention is in the form of a W/O emulsion.

Cosmetic method and use

The invention may also relate to:

a cosmetic method for keratin materials such as the skin, comprising:

applying the composition according to the invention to keratin materials; and optionally drying the composition to form a film on the keratin materials, preferably a film of a cosmetic product,

and

use of the composition according to the invention for the preparation of a film, preferably a cosmetic film, on keratin materials such as the skin.

Cosmetic methods refer herein to non-therapeutic cosmetic methods for caring for and/or making up the surface of keratin materials such as the skin.

If the composition according to the invention comprises the DIC gel described above, the membrane prepared by the composition according to the invention is capable of self-healing or self-healing. In other words, even if the film is broken due to, for example, scratch or the like, the film provided by the composition according to the present invention can be automatically repaired, and thus, the long durability of the cosmetic effect provided by the film can be improved.

In addition, the above-described membranes can withstand water having a pH of 7 or less and can be removed with water having a pH of greater than 7, preferably 8 or more, and more preferably 9 or more. In other words, the above-mentioned membrane may be water-repellent under neutral or acidic conditions, such as pH of 7 or less, preferably in the range of 6 or more to 7 or less, and more preferably in the range of 5 or more to 7 or less, while the above-mentioned membrane may be removed under alkaline conditions, such as pH of more than 7, preferably 8 or more, and more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.

Thus, the above-mentioned film may be water-resistant, and thus may remain on keratin materials (such as skin) even if the surface of the keratin materials becomes wet due to, for example, sweat and rainwater. On the other hand, the above-mentioned film can be easily removed from keratin materials such as skin under alkaline conditions. Thus, the above-described film is difficult to remove with water, but can be easily removed with soap capable of providing alkaline conditions.

Since the film may contain organic UV filters originally present in the composition according to the invention, the film may protect keratin materials such as skin from UV rays, thereby limiting skin darkening, improving the color and uniformity of skin tone, and/or treating skin aging.

Furthermore, due to the nature of DIC gel in the film, the above film may have cosmetic effects, such as absorption or adsorption of malodors and/or protection of keratinous materials from, for example, dirt or pollutants, even if the film does not contain any cosmetically active ingredient.

In addition, the above-described films can instantaneously change or modify the appearance of skin by changing the light reflection on the skin, etc., even though the film does not include any cosmetically active ingredient. Thus, the above films can mask skin imperfections, such as pores or wrinkles. In addition, the above film can instantaneously change or modify the feel of the skin by changing the surface roughness on the skin, or the like. In addition, the above-described films can immediately protect the skin from environmental stresses (e.g., contaminants, impurities) and the like by covering the skin surface and shielding the skin as a barrier.

The cosmetic effect may be modulated or controlled by varying the chemical composition, thickness and/or surface roughness of the film.

If the film comprises at least one additional cosmetically active ingredient, the film may have a cosmetic effect provided by the additional cosmetically active ingredient or ingredients. For example, if the film comprises at least one cosmetically active ingredient selected from the group consisting of anti-aging agents, anti-sebum agents, deodorants, antiperspirants, whitening agents, and mixtures thereof, the film may treat skin aging, absorb sebum on the skin, control odors on the skin, control perspiration on the skin, and/or whiten the skin.

The cosmetic composition may also be applied to the film after the film has been applied to the skin.

Furthermore, the invention may also relate to (b) the use of at least one spherical hydrophobic silica in a composition in the form of a W/O emulsion for enhancing the UV absorbance of the composition and improving the spreadability of the composition, said composition comprising (a) at least one organic UV filter and (c) water. In other words, the addition of (b) at least one spherical hydrophobic silica to a composition in the form of a W/O emulsion comprising (a) at least one UV filter and (c) water can enhance the UV absorbance of the composition and improve the spreadability of the composition on keratinous materials such as skin.

As a result, the composition according to the invention in the form of a W/O emulsion comprising (a) at least one UV filter, (b) at least one spherical hydrophobic silica, and (c) water can be easily spread on keratin materials such as the skin while providing strong UV protection.

Examples

The present invention will be described in more detail by way of examples. However, they should not be construed as limiting the scope of the invention.

Examples 1 and 2 and comparative examples 1 to 3

[ preparation ]

Each of the compositions according to examples 1 and 2 and comparative examples 1-3 in the form of W/O emulsions was prepared by mixing the ingredients shown in table 1. The amounts of the ingredients in table 1 are all based on "% by weight" as active material.

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[ evaluation ]

(spreadability)

5 panelists evaluated "spreadability" using the same amount of each composition according to examples 1 and 2 and comparative examples 1-3.

Each panelist placed each composition in their hand and then applied it to their face to evaluate the "spreadability" of each composition as applied, and rated it from 1 (very poor) to 5 (very good) and then averaged.

The results are shown in table 1.

(UV absorbance)

Each of the compositions according to examples 1 and 2 and comparative examples 1-3 was shaken 10 times in a capped container to homogenize it. Each homogeneous composition was pipetted at 20mg/em with an adjustable pipette ² Is transferred to a plate (Helio plate HD 6, PMMA, roughness: 6 μm) and then spread evenly with the fingers. The coated plates were air dried at room temperature for 15 minutes. The obtained sample plate was placed in a Labsphere ultraviolet transmittance analyzer (model UV-2000, from Solar LightCompany, philiadelphia, pennsylvania). UV radiation was performed at 12 points on the sample plate. The UV absorbance of the sample plate was recorded over the wavelength range 290 to 420 nm.

The results are shown in fig. 1.

Further, UV absorbance at 310nm of the compositions according to examples 1 and 2 and comparative examples 1-3 is shown in Table 1.

As is clear from fig. 1, the compositions according to examples 1 and 2 have a more enhanced UV absorbance than the compositions according to comparative examples 1-3, in particular 290nm to 380nm. It is recognized that enhanced UV absorbance is caused by the use of spherical hydrophobic silica.

In view of the evaluation results shown in table 1 and fig. 1, it is evident that the compositions according to examples 1 and 2 have a good balance of high spreadability and enhanced UV absorbance. Thus, the compositions according to examples 1 and 2 may provide excellent texture and improved UV protection.

Claims

A composition in the form of a 1.W/O emulsion comprising:

(a) At least one organic UV filter;

(b) At least one spherical hydrophobic silica; and

(c) And (3) water.
2. The composition according to claim 1 wherein said (a) organic UV filter is selected from the group consisting of butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid n-hexyl ester, 1'- (1, 4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl ] phenyl ] -methanone 4-methylbenzylidene camphor, ethylhexyl triazinone, bis-ethylhexyl oxyphenoxyphenyl triazine, diethylhexyl butyrylaminotriazinone, 2,4, 6-tris (4' -aminobenzylidene malonic acid dineopentyl) -s-triazine, 2,4, 6-tris (4 '-aminobenzylidene malonic acid diisobutyl) -s-triazine, 2, 4-bis- (4' -aminobenzylidene malonic acid di-n-butyl) -6- [ (3- {1, 3-tetramethyl-1-trimethylsilyl ] phenyl ] -methanone 4-methylbenzotriazine, tris (4 '-aminobenzyl) phenyl ] -triazolo-s-triazinone, 2,4, 6-tris (4' -aminobenzylidene) malonic acid di-n-butyl) s-triazine, tris (4 '-aminobenzylidene) propane-s-triazine, tris (4, 4' -aminobenzylidene) propane-s-triazin) and tris (4-n-4-hydroxybenzyl) phenylmethane Polysiloxane-15, 4 '-methoxybenzylidene malonic acid dipivalyl ester, 1-dicarboxylic acid (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene, 2, 4-bis [5-1 (dimethylpropyl) benzooxazol-2-yl (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, camphorbenzammonium methyl sulfate, and mixtures thereof.
3. The composition according to claim 1 or 2, wherein the amount of (a) one or more organic UV filters in the composition is from 1 to 40 wt%, preferably from 5 to 35 wt%, and more preferably from 10 to 30 wt%, relative to the total weight of the composition.
4. A composition according to any one of claims 1 to 3, wherein the (b) spherical hydrophobic silica has an average roundness as determined by image analysis of 0.8 or more, and preferably 0.82 or more.
5. The composition according to any one of claims 1 to 4, wherein the (b) spherical hydrophobic silica has an oil absorption measured at the wet point of 2ml/g or more, preferably 3ml/g or more, more preferably 4ml/g or more, and most preferably 5ml/g or more.
6. The composition according to any one of claims 1 to 5, wherein the (b) spherical hydrophobic silica has a particle size of 200m ² Per gram or higher, preferably 400m ² /g or higher, and more preferably 500m ² And/g or higher, as determined by BET method.
7. A composition according to any one of claims 1 to 6, wherein the (b) spherical hydrophobic silica has a pore volume as determined by the BJH method of 1ml/g or more, preferably 2ml/g or more, and more preferably 3ml/g or more.
8. The composition according to any one of claims 1 to 7, wherein the (b) spherical hydrophobic silica has a peak pore radius as determined by the BJH method of 5nm or more, preferably 10nm or more, and more preferably 12nm or more.
9. The composition according to any one of claims 1 to 8, wherein the (b) spherical hydrophobic silica has an average particle size of 0.5 μm to 30 μm, preferably 1 μm to 20 μm, and more preferably 2 μm to 15 μm.
10. The composition according to any one of claims 1 to 9, wherein the amount of (b) one or more spherical hydrophobic silica in the composition is from 0.1 to 15 wt%, preferably from 0.5 to 10 wt%, and more preferably from 1 to 5 wt%, relative to the total weight of the composition.
11. The composition according to any one of claims 1 to 10, wherein the weight ratio of the amount of (a) the one or more UV filters to the amount of (b) the one or more spherical hydrophobic silica in the composition is from 3 to 35, preferably from 5 to 30, and more preferably from 10 to 25.
12. The composition according to any one of claims 1 to 11, wherein the composition further comprises (d) at least one oil, preferably selected from the group consisting of polar oils, non-polar oils and mixtures thereof, more preferably hydrocarbon oils, silicone oils, ester oils and mixtures thereof, and even more preferably selected from the group consisting of isododecane, isohexadecane, polydimethylsiloxane, diisopropyl sebacate and mixtures thereof.
13. A composition according to any one of claims 1 to 12, wherein the composition is a cosmetic composition, preferably a dermatological cosmetic composition, and more preferably a dermatological or cosmetic composition.
14. Cosmetic process for keratin materials such as the skin, comprising:

application of a composition according to any one of claims 1 to 13 to keratin materials.
15. (b) Use of at least one spherical hydrophobic silica in a composition in the form of a W/O emulsion, said composition comprising (a) at least one organic UV filter and (c) water, for enhancing the UV absorbance of said composition and improving the spreadability of said composition.