WO2023026893A1 - W/o type composition comprising organic uv filter and spherical hydrophobic silica - Google Patents

W/o type composition comprising organic uv filter and spherical hydrophobic silica Download PDF

Info

Publication number
WO2023026893A1
WO2023026893A1 PCT/JP2022/030919 JP2022030919W WO2023026893A1 WO 2023026893 A1 WO2023026893 A1 WO 2023026893A1 JP 2022030919 W JP2022030919 W JP 2022030919W WO 2023026893 A1 WO2023026893 A1 WO 2023026893A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
composition according
weight
hydrophobic silica
spherical hydrophobic
Prior art date
Application number
PCT/JP2022/030919
Other languages
French (fr)
Inventor
Tomomi Suga
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2021138057A external-priority patent/JP2023032127A/en
Priority claimed from FR2110395A external-priority patent/FR3127691A1/en
Application filed by L'oreal filed Critical L'oreal
Priority to KR1020237044679A priority Critical patent/KR20240012564A/en
Priority to CN202280045961.7A priority patent/CN117580562A/en
Publication of WO2023026893A1 publication Critical patent/WO2023026893A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/025—Explicitly spheroidal or spherical shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966—Triazines or their condensed derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns

Definitions

  • the present invention relates to a composition, in the form of a W/O emulsion, including organic UV filter(s) and spherical hydrophobic silica(s).
  • UV filters are utilized to provide protection from UV (ultraviolet) rays.
  • Numerous anti-sun compositions intended for protecting the skin from UV-A and/or UV-B have been proposed to date.
  • anti-sun compositions often take the form of oil-in-water or water-in-oil emulsions, of gels, or of non-aqueous products which contain, in various concentrations, one or more insoluble and/or fat-soluble and/or water-soluble, organic and/or inorganic UV filters that are capable of selectively absorbing the harmful UV radiation.
  • UV filters and their amounts are selected as a function of the desired sun protection factor (SPF).
  • the SPF mathematically expresses the ratio of the dose of UV radiation necessary to achieve the erythematogenic threshold with the UV screening agent to the dose of UV radiation necessary to achieve the erythematogenic threshold without the UV screening agent.
  • compositions having a higher SPF which can be represented by a higher UV absorbance of the composition have been a need for compositions having a higher SPF which can be represented by a higher UV absorbance of the composition.
  • an organic UV filter in a composition, such as an anti-sun composition, makes the composition difficult to spread, and a heavy sensation when using the composition.
  • an objective of the present invention is to provide a composition, in the form of a W/O emulsion, which includes organic UV filter(s) but can be easily spread, while enhancing the UV absorbance of the composition.
  • composition in the form of a W/O emulsion, comprising:
  • the (a) organic UV filter may be selected from the group consisting of butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino- 2-hydroxybenzoyl)benzoate, 1 , 1 '-(1 ,4-piperazinediyl)bis[l - [2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl] -methanone 4-methylbenzylidene camphor, ethylhexyl triazone, bisethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6- tris(dineopentyl 4
  • the amount of the (a) organic UV fdter(s) in the composition according to the present 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.
  • the (b) spherical hydrophobic silica may have an average circularity determined by an image analysis method of 0.8 or more, and preferably 0.82 or more.
  • the (b) spherical hydrophobic silica may have an oil-absorbing capacity, measured at the wet point, of 2 ml/g or more, preferably 3 ml/g or more, more preferably 4 ml/g or more, and most preferably from 5 ml/g or more.
  • the (b) spherical hydrophobic silica may have a specific surface area determined by BET method of 200 m 2 /g or more, preferably 400 m 2 /g or more, and more preferably 500 m 2 /g or more.
  • the (b) spherical hydrophobic silica may have a pore volume determined by BJH method of 1 ml/g or more, preferably 2 ml/g or more, and more preferably 3 ml/g or more.
  • the (b) spherical hydrophobic silica may have a peak pore radius determined by BJH method of 5 nm or more, preferably 10 nm or more, and more preferably 12 nm or more.
  • the (b) spherical hydrophobic silica may have an average particle size of from 0.5 pm to 30 pm, preferably from 1 pm to 20 pm, and more preferably from 2 pm to 15 pm.
  • the amount of the (b) spherical hydrophobic silica(s) in the composition according to the present 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 the (a) UV filter(s) to the amount of the (b) spherical hydrophobic silica(s) in the composition according to the present invention may be from 3 to 35, preferably from 5 to 30, and more preferably from 10 to 25.
  • composition according to the present invention may further comprise (d) at least one oil which may be selected preferably 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, dimethicone, diisopropyl sebacate and mixtures thereof.
  • the composition according to the present invention may be a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care or makeup cosmetic composition.
  • the present invention also relates to a cosmetic process for a keratin substance such as skin, comprising applying to the keratin substance the composition according to the present invention.
  • the present invention also relates to a 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, in order to enhance the UV absorbance of the composition and improve the spreadability of the composition.
  • Figure 1 shows a graph of UV absorbance of each of the compositions according to Examples 1 and 2 and Comparative Examples 1-3.
  • compositions in the form of a W/O emulsion, which includes organic UV filter(s) but can be easily spread, while enhancing the UV absorbance of the composition.
  • composition according to the present invention is in the form of a W/O emulsion and comprises:
  • composition according to the present invention can provide an improved or enhanced UV absorbance, which reflects improved or enhanced protection from UV rays.
  • the composition according to the present invention can be easily spread on a keratin substance such as skin, which reflects improved or enhanced spreadability when using the composition.
  • composition according to the present invention can be easily spread on a keratin substance such as skin, while providing strong UV protection.
  • composition according to the present invention can capture sebum. Therefore, the composition according to the present invention can reduce gloss on a keratin substance such as skin, and can make, for example, roughness on the skin such as pores and wrinkles less noticeable. Accordingly, the composition according to the present invention can also provide optical mattifying effects.
  • composition according to the present invention comprises (a) at least one organic UV filter. If two or more (a) organic UV filters are used, they may be the same or different.
  • the (a) organic UV filter may be hydrophobic or water-insoluble.
  • the (a) organic UV filter may function as an oily ingredient.
  • the (a) organic UV filter can constitute a continuous or outer phase of a W/O type composition.
  • the (a) organic UV filter may be active in the UV-A and/or UV-B region.
  • the (a) organic UV filter may be lipophilic or oil-soluble.
  • the (a) organic UV filter may be solid or liquid.
  • solid and liquid mean solid and liquid, respectively, at 25°C under 1 atm.
  • the (a) organic UV filter can be selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; p,P-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole compounds; imidazoline compounds; bis-benzoazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4-diarylbutadiene compounds; guaiazulene and derivatives thereof; rutin and derivatives thereof; and mixtures thereof.
  • Anthranilic compounds Menthyl anthranilate, marketed under the trademark "Neo Heliopan MA” by Haarmann and Reimer.
  • Cinnamic compounds Ethylhexyl methoxycinnamate, marketed in particular under the trademark "Parsol MCX” by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, marketed under the trademark "Neo Heliopan E 1000" by Haarmann and Reimer; cinoxate (2-ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethylhexanoate dimethoxycinnamate.
  • Neo Heliopan OS by Haarmann and Reimer
  • glycol salicylate butyloctyl salicylate
  • phenyl salicylate dipropyleneglycol salicylate
  • TEA salicylate marketed under the trademark "Neo Heliopan TS” by Haarmann and Reimer.
  • benzylidenecamphor derivatives 3-benzylidene camphor, manufactured under the trademark “Mexoryl SD” by Chimex; 4-methylbenzylidene camphor, marketed under the trademark “Eusolex 6300” by Merck; benzylidene camphor sulfonic acid, manufactured under the trademark “Mexoryl SL” by Chimex; camphor benzalkonium methosulfate, manufactured under the trademark "Mexoryl SO” by Chimex; and polyacrylamidomethyl benzylidene camphor, manufactured under the trademark "Mexoryl SW” by Chimex.
  • Benzophenone- 1 (2,4-dihydroxybenzophenone), marketed under the trademark "Uvinul 400" by BASF; benzophenone-2 (Tetrahydroxybenzophenone), marketed under the trademark “Uvinul D50” by BASF; Benzophenone-3 (2-hydroxy-4- methoxybenzophenone) or oxybenzone, marketed under the trademark "Uvinul M40” by BASF; benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid), marketed under the trademark "Uvinul MS40" by BASF; benzophenone-5 (Sodium hydroxymethoxy benzophenone Sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone); marketed under the trademark "Helisorb 11 " by Norquay; benzophenone-8, marketed under the trademark "Spectra-Sorb UV-24” by American Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy benzophenone), marketed under the trademark
  • Octocrylene marketed in particular under the trademark "Uvinul N539” by BASF
  • Etocrylene marketed in particular under the trademark "Uvinul N35” by BASF.
  • Triazine compounds Diethylhexyl butamido triazone, marketed under the trademark “Uvasorb HEB” by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bisethylhexyloxyphenol methoxyphenyl triazine marketed under the trademark «TINOSORB S » by CIBA GEIGY, and ethylhexyl triazone marketed under the trademark «UVINUL T150 » by BASF.
  • Benzotriazole compounds in particular, phenylbenzotriazole derivatives: 2-(2H- benzotriazole-2-yl)-6-dodecyl-4-methylpheno, branched and linear; and those described in USP 5240975.
  • Benzalmalonate compounds Dineopentyl 4'-methoxybenzalmalonate, and polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, marketed under the trademark "Parsol SLX” by Hoffmann-LaRoche.
  • Benzimidazole compounds in particular, phenylbenzimidazole derivatives.
  • PABA p-aminobenzoic acid
  • ethyl PABA Ethyl dihydroxypropyl PABA
  • pentyl dimethyl PABA ethylhexyl dimethyl PABA
  • glyceryl PABA glyceryl PABA
  • PEG-25 PABA marketed under the trademark "Uvinul P25” by BASF.
  • Drometrizole trisiloxane marketed under the trademark "Silatrizole” by Rhodia Chimie or “Mexoryl XL” by L’Oreal, as represented below.
  • - Benzoxazole compounds 2,4-bis[5-l(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6- (2-ethylhexyl)imino-l,3,5-triazine, marketed under the trademark Uvasorb K2A by Sigma 3V.
  • Dimers derived from a-alkylstyrene The dimers described in DE-19855649.
  • the (a) organic UV filter(s) be selected from the group consisting of: butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone- 5, n-hexyl 2-(4- diethylamino-2-hydroxybenzoyl)benzoate, l,T-(l,4-piperazinediyl)bis[l-[2-[4- (diethylamino)-2-hydroxybenzoyl]phenyl] -methanone 4-methylbenzylidene camphor, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6-tris(dineopent)
  • the amount of the (a) organic UV filter(s) in the composition according to the present invention may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the composition.
  • the amount of the (a) organic UV filter (s) in the composition according to the present invention may be 40% by weight or less, preferably 35% by weight or less, and more preferably 30% by weight 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 present 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.
  • composition according to the present invention comprises (b) at least one spherical hydrophobic silica. If two or more (b) spherical hydrophobic silicas are used, they may be the same or different.
  • the (b) spherical hydrophobic silica be porous. In other words, it is preferable that the (b) spherical hydrophobic silica be an aerogel.
  • Aerogels are materials with high porosity.
  • silica aerogels refer to a solid silica with a porous structure generally obtained by replacing a medium included in wet silica gels with air by drying them while a solid network structure of the silica is maintained.
  • the porosity represents the amount of air contained in the apparent volume of a material by volume percentage.
  • the (b) spherical hydrophobic silica which is in the form of an aerogel may have a porosity of 60% or more, preferably 70% or more, and more preferably 80% or more.
  • the (b) spherical hydrophobic silica is in the form of particles.
  • the (b) spherical hydrophobic silica is characterized in that the shape of each of the particles is spherical. Due to this spherical shape, the (b) spherical hydrophobic silica can provide good smoothness.
  • the spherical degree of the (b) spherical hydrophobic silica may be determined by an average circularity.
  • the (b) spherical hydrophobic silica may have an average circularity of 0.8 or more, and preferably 0.82 or more.
  • the (b) spherical hydrophobic silica may have an average circularity of less than 1, preferably 0.99 or less, more preferably 0.98 or less, even more preferably 0.97 or less, still even more preferably 0.96 or less, and most preferably 0.95 or less.
  • the “average circularity” may be determined by an image analysis method.
  • the “average circularity” may be an arithmetic mean of circularity obtained by image analysis of a scanning electron microscope (SEM) image of no less than 2000 particles observed at a magnification of 1000 by secondary electron detection using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • C 4KS / L 2
  • S represents the area (projected area) of the particle in the image
  • L represents the length of the periphery (perimeter) of the particle in the image.
  • the term "hydrophobic" means that the silica particles are difficult to disperse in water. More specifically, this term means that a silica particle phase and an aqueous phase are completely separated after 1 g of the silica particles and 100 g of ion-exchange water are added to a bottle, the bottle is agitated or stirred for ten or more seconds, and the bottle is left to stand. Therefore, in one particular embodiment of the present invention, the (b) spherical hydrophobic silica does not exhibit a water absorption property.
  • the (b) spherical hydrophobic silica that may be used according to the present invention is preferably of silylated silica type (INCI name: silica silylate). Most preferably, the (b) spherical hydrophobic silica may be those described in JP-A-2014-088307, JP-A-2014- 218433, or JP-A-2018- 177620.
  • the hydrophobicity may be obtained by reacting a hydrophobizing agent with a silanol group represented by the following formula existing on the surface of silica:
  • n is an integer of 1 to 3; each R is independently a hydrocarbyl group; and two or more R may be the same or different from each other where n is 2 or more.
  • the hydrophobizing agent may be a silylating agent. Therefore, according to one preferred embodiment, in the (b) spherical hydrophobic silica, the silica particles may be modified at the surface by silylation.
  • silylating agents mention may be made of a treating agent having one of the following formulae (1) to (3).
  • RnSiX(4-n) wherein n represents an integer of 1 to 3; R represents a hydrocarbyl group; X represents a group (i.e., a leaving group) which can leave a molecule by cleavage of the bond with the Si atom in a reaction with a compound having a hydroxyl group; each R may be different where n is 2 or more; and each X may be different where n is 2 or less.
  • R 1 represents an alkylene group
  • R 2 and R 3 independently represent a hydrocarbyl group
  • R 4 and R 5 independently represent a hydrogen atom or a hydrocarbyl group.
  • R 6 and R 7 independently represent a hydrocarbyl group; m represents an integer of 3 to 6; each R 6 may be different when there are two or more R 6 ; and each R 7 may be different when there are two or more R 7 .
  • R is a hydrocarbyl group, preferably a hydrocarbyl group having a carbon number of 1 to 10, more preferably a hydrocarbyl group having a carbon number of 1 to 4, and especially preferably a methyl group.
  • halogen atoms such as chlorine and bromine
  • alkoxy groups such as a methoxy group and ethoxy group
  • groups represented by -NH-SiRs wherein the definition of R is the same as that of R in formula (1).
  • hydrophobizing agent represented by the above formula (1) examples include: chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, and hexamethyldisilazane.
  • chlorotrimethylsilane dichlorodimethylsilane, trichloromethylsilane, and/or hexamethyldisilazane may be used from the viewpoint of favorable reactivity.
  • the number of the bond of the Si atom with the silanol group on the silica framework varies depending on the number (4-n) of the leaving group X. For example, if n is 2, the following bonding will occur:
  • the silanol groups may be silylated, and thereby hydrophobization may be carried out.
  • R 1 may be an alkylene group, preferably an alkylene group having a carbon number of 2 to 8, and especially preferably an alkylene group having a carbon number of 2 to 3.
  • R 2 and R 3 are independently a hydrocarbyl group, and the same preferable groups as those of R in the formula (1) can be given.
  • R 4 represents a hydrogen atom or a hydrocarbyl group, and when it is a hydrocarbyl group, the same preferable groups as those of R in the above formula (1) can be given.
  • the silanol group may be silylated by the cyclic silazanes of the above formula (2) as well, and thereby hydrophobization may be carried out.
  • cyclic silazanes represented by the above formula (3) include hexamethylcyclotrisilazane, and octamethylcyclotetrasilazane.
  • R 6 and R 7 are independently a hydrocarbyl group, and the same preferable groups as those of R in the above formula (2) can be given, m represents an integer of 3 to 6.
  • silanol groups may be silylated by the cyclic siloxanes of the above formula (3) as well, and thereby hydrophobization may be carried out.
  • cyclic siloxanes represented by the above formula (3) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.
  • the (b) spherical hydrophobic silica may be prepared by producing a sol of silica, turning 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 dying the hydrophobized silica.
  • the (b) spherical hydrophobic silica may have a specific surface area determined by BET method of 200 m 2 /g or more, preferably 400 m 2 /g or more, and more preferably 500 m 2 /g or more, and/or may have a specific surface area determined by BET method of 1,200 m 2 /g or less, preferably 1,000 m 2 /g or less, and more preferably 800 m 2 /g or less.
  • the "specific surface area determined by BET method” means a value determined by: drying a sample for measurement at 200°C for no less than three hours under a reduced pressure of no more than 1 kPa; thereafter measuring an adsorption isotherm of only the nitrogen adsorption side at liquid nitrogen temperature; and analyzing the adsorption isotherm by BET method.
  • the pressure range used for the analysis is a relative pressure of 0.1 to 0.25.
  • the (b) spherical hydrophobic silica may have a pore volume determined by BJH method of 1 ml/g or more, preferably 2 ml/g or more, and more preferably 3 ml/g or more, and/or may have a pore volume determined by BJH method of 10 ml/g or less, preferably 8 ml/g or less, and more preferably 7 ml/g or less.
  • the (b) spherical hydrophobic silica may have a peak pore radius determined by BJH method of 5 nm or more, preferably 10 nm or more, and more preferably 12 nm or more, and/or may have a peak pore radius determined by BJH method of 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less.
  • the "pore volume determined by BJH method” refers to a pore volume which derives from a pore having a pore radius of 1 nm to 100 nm obtained by analyzing, by BJH method (Barrett, E. P.; Joyner, L. G.; Halenda, P. P., J. Am. Chem. Soc. 73, 373 (1951)), the adsorption isotherm of the nitrogen adsorption side obtained in the same manner as explained in the above "specific surface area determined by BET method".
  • peak pore radius determined by B JT method refers to the value of a pore radius which gives a peak in a pore distribution curve (volume distribution curve) which is plotted taking on the vertical axis differentiation of the cumulative pore volume by the logarithm of the pore radius obtained by analyzing, by BJH method, the adsorption isotherm of the nitrogen adsorption side obtained in the same manner as above, and taking the pore radius on the horizontal axis.
  • the (b) spherical hydrophobic silica may have an average particle size of 0.5 pm or more, preferably 1 pm or more, and more preferably 2 pm or more, and/or may have an average particle size by image analysis method of 30 pm or less, preferably 20 pm or less, and more preferably 15 pm or less.
  • the (b) spherical hydrophobic silica may have an average particle size of from 0.5 pm to 30 pm, preferably from 1 pm to 20 pm, and more preferably from 2 pm to 15 pm.
  • the (b) spherical hydrophobic silica may have an average particle size of from 6 pm to 16 pm, preferably from 7 pm to 14 pm, and more preferably from 8 pm to 12 pm.
  • the “average particle size” here can be measured by image analysis method.
  • the value of "average particle size” is an arithmetic mean of equivalent circle diameters which can be obtained by image analysis of a scanning electron microscope (SEM) image of, for example, no less than 2000 particles observed at a magnification of 1000 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 (projected area) of the particle in the image.
  • the (b) spherical hydrophobic silica may have an oil-absorbing capacity, which can be measured at the wet point, of 2 ml/g or more, preferably 3 ml/g or more, more preferably 4 ml/g or more, and most preferably from 5 ml/g or more, and/or may have an oil-absorbing capacity, measured at the wet point, of 12 ml/g or less, preferably 11 ml/g or less, more preferably 10 ml/g or less, and most preferably 8 ml/g or less.
  • the oil-absorbing capacity measured at the wet point corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a homogeneous paste. It can be measured according to the wet point method or the method for determining the oil uptake of a powder described in standard NF T 30-022.
  • the oil uptake can correspond to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measuring the wet point, described below.
  • An amount of m 2 g of powder is placed on a glass plate, and an oil (such as ester oil, oleric acid, or silicone oil) is then added drop-wise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until a conglomerate of oil and powder has formed. At this point, the oil is added one drop at a time and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be spreadable on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.
  • an oil such as ester oil, oleric acid, or silicone oil
  • the oil-absorbing capacity can be measured in accordance with JIS-K6217-4.
  • the (b) 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) spherical hydrophobic silica(s) in the composition according to the present 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) spherical hydrophobic silica(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
  • the amount of the (b) spherical hydrophobic silica(s) in the composition according to the present 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 the (a) UV filter(s) to the amount of the (b) spherical hydrophobic silica(s) in the composition according to the present invention may be from 3 to 35, preferably from 5 to 30, and more preferably from 10 to 25.
  • composition according to the present invention comprises (c) water.
  • the (c) water can form the discontinuous or dispersed (inner) phases of a W/O type composition. Therefore, the (c) water can form the discontinuous or dispersed (inner) phases of the composition according to the present invention which is in the form of a W/O emulsion.
  • the amount of the (c) water in the composition according to the present 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 the (c) water in the composition according to the present 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 the (c) water in the composition according to the present 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.
  • composition according to the present invention may comprise (d) at least one oil. If two or more oils are used, they may be the same or different.
  • the (d) oil is different from the (a) organic UV filter.
  • oils means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg).
  • oils those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile.
  • the (d) oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof.
  • the (d) oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils, and fatty alcohols.
  • plant oils examples include, for example, linseed oil, camellia oil, macadamia nut oil, com oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.
  • animal oils mention may be made of, for example, squalene and squalane.
  • alkane oils such as isododecane and isohexadecane
  • ester oils such as isododecane and isohexadecane
  • ether oils such as triglycerides
  • the ester oils are preferably liquid esters of saturated or unsaturated, linear or branched Ci- C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci- C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
  • At least one from among the alcohol and the acid from which the esters of the present invention are derived is branched.
  • ethyl palmitate ethyl hexyl palmitate
  • isopropyl palmitate dicaprylyl carbonate
  • alkyl myristates such as isopropyl myristate or ethyl myristate
  • isocetyl stearate 2-ethylhexyl isononanoate
  • isononyl isononanoate isodecyl neopentanoate
  • isostearyl neopentanoate isostearyl neopentanoate.
  • Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols may also be used.
  • esters of monocarboxylic, dicarboxylic, or tricarboxylic acids and of non-sugar C4-C26 dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols may also be used.
  • sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids.
  • sucrose means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.
  • suitable sugars include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.
  • esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters, and polyesters, and mixtures thereof.
  • esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate, and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.
  • monoesters and diesters and especially sucrose, glucose, or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearates.
  • ester oils mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2- ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laur
  • artificial triglycerides mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate), and glyceryl tri(caprate/ caprylate/linolenate) .
  • silicone oils mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.
  • linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like
  • cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodeca
  • the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
  • PDMS liquid polydimethylsiloxanes
  • silicone oils may also be organomodified.
  • organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
  • Organopolysiloxanes are defined in greater detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile.
  • the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:
  • cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
  • cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
  • These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the type such as dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide, of formula:
  • organosilicon compounds such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclot
  • decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C.
  • Non-volatile 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.
  • polydialkylsiloxanes mention may be made, in a non-limiting manner, of the following commercial products: the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000; the oils of the Mirasil® series sold by the company Rhodia; the oils of the 200 series from the company Dow Coming, such as DC200 with a viscosity of 60 000 mm 2 /s; and the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF
  • CTFA dimethiconol
  • silicones containing aryl groups mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.
  • the phenyl silicone oil may be chosen from the phenyl silicones of the following formula: in which
  • Ri to Rio independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, preferably C1-C12 hydrocarbon-based radicals, and more preferably Ci-Co hydrocarbon-based radicals, in particular methyl, ethyl, propyl, or butyl radicals, and m, n, p, and q are, independently of each other, integers of 0 to 900 inclusive, preferably 0 to 500 inclusive, and more preferably 0 to 100 inclusive, with the proviso that the sum n+m+q is other than 0.
  • oils of the 70 641 series from Rhodia examples include the products sold under the following names: the Silbione® oils of the 70 641 series from Rhodia; the oils of the Rhodorsil® 70 633 and 763 series from Rhodia; the oil Dow Coming 556 Cosmetic Grade Fluid from Dow Coming; the silicones of the PK series from Bayer, such as the product PK20; certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250, and SF 1265.
  • the organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.
  • Hydrocarbon oils may be chosen from: linear or branched, optionally cyclic, Ce-Cie lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane, and isodecane; and linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.
  • hydrocarbon oils As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.
  • linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.
  • fatty in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols.
  • the fatty alcohol 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 chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms.
  • R may be chosen from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.
  • fatty alcohol examples include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.
  • the fatty alcohol be a saturated fatty alcohol.
  • the fatty alcohol may be selected from straight or branched, saturated or unsaturated Ce- C30 alcohols, preferably straight or branched, saturated C6-C30 alcohols, and more preferably straight or branched, saturated C12-C20 alcohols.
  • saturated fatty alcohol here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C6-C30 fatty alcohols.
  • linear or branched, saturated C12-C20 fatty alcohols may preferably be used.
  • Any linear or branched, saturated C16-C20 fatty alcohols may be more preferably used.
  • Branched C16-C20 fatty alcohols may be even more preferably used.
  • saturated fatty alcohols mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.
  • cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol can be used as a saturated fatty alcohol.
  • the fatty alcohol used in the composition according to the present invention is preferably chosen from cetyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.
  • the (d) oil may be chosen from non-polar or polar oils, preferably hydrocarbon oils, silicone oils, ester oils, and mixtures thereof and even more preferably isododecane, isohexadecane, dimethicone, diisopropyl sebacate and mixtures thereof.
  • the amount of the (d) oil(s) in the composition according to the present 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) oil(s) in the composition according to the present invention may be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the composition.
  • the amount of the (d) oil(s) in the composition according to the present 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.
  • composition according to the present invention may comprise at least one gel, preferably a hydrogel, which is dynamically and ionically crosslinked.
  • a hydrogel which is dynamically and ionically crosslinked.
  • the dynamically and ionically- crosslinked gel is hereinafter abbreviated as a DIC-gel.
  • the dynamic and ionic-crosslinking in the DIC-gel is different from permanent covalent bonding because it is breakable but reformable.
  • the dynamic and ionic-crosslinking can be easily broken by, for example, cutting and the like, 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 interaction between the cationic polymer and the crosslinker breaks. However, if the two pieces contact each other, they can reform ionic-bonding between the cationic polymer and the crosslinker, and they can adhere to each other. Therefore, even if cracks, for example, are formed on the gel, they can disappear.
  • the composition according to the present invention can be used to prepare a film of a gel which has self-healing or self-repairing properties by applying the composition onto a substrate, preferably a keratin substrate such as skin, and drying the composition.
  • the DIC gel can be formed with at least one cationic polysaccharide and at least one crosslinker having three or more acid groups or salt thereof.
  • composition according to the present invention may include at least one cationic polysaccharide.
  • Two or more different types of cationic polysaccharides may be used in combination.
  • 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 charge density of the cationic polysaccharide may be from 0.01 meq/g to 20 meq/g, preferably from 0.05 tol5 meq/g, and more preferably from 0.1 to 10 meq/g.
  • the molecular weight of the cationic polysaccharide be 500 or more, preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 5,000 or more.
  • molecular weight means a number average molecular weight.
  • the cationic polysaccharide may have at least one positively chargeable and/or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group, and a pyridyl group.
  • the cationic polysaccharide may be a homopolymer or a copolymer.
  • copolymer is understood to mean both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
  • the cationic polysaccharide may be selected from natural and synthetic cationic polysaccharides.
  • the cationic polysaccharide be selected from cationic cellulose polymers.
  • Non-limiting examples of the cationic cellulose polymers are as follows.
  • Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described, for example, in French Patent No. 1 492 597, such as the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR” (LR 400, LR 30M) by the company Dow Chemical. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxy ethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.
  • Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with at least one water-soluble monomer of quaternary ammonium, and described, for example, in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instance, hydroxymethyl-, hydroxyethyl-, and hydroxypropylcelluloses grafted, for example, with at least one chosen from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and dimethyldiallylammonium.
  • Commercial products corresponding to these polymers include, for example, the products sold under the names "Celquat® L 200" and "Celquat® H 100" by the company Akzo Novel.
  • Cationic cellulose polymers having at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms. It is preferable that the cationic cellulose polymers be quatemized hydroxyethyl celluloses modified with at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.
  • the alkyl radicals borne by the quaternary ammonium group may preferably contain from 8 to 30 carbon atoms, especially from 10 to 30 carbon atoms.
  • the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. More preferably, the cationic cellulose polymer may comprise at least one quaternary ammonium group including at least one C8-C30 hydrocarbon group.
  • Examples of quatemized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529- 18B (Cl 2 alkyl) and Quatrisoft LM-X 529-8 (C18 alkyl) or Softcat Polymer SL100, 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, sold by the company Dow Chemical, and the products Crodacel QM, Crodacel, QL (Cl 2 alkyl) and Crodacel QS (Cl 8 alkyl) sold by the company Croda.
  • Quatrisoft LM 200 Quatrisoft LM-
  • the cationic polysaccharide be selected from the group consisting of polyquatemium-4, polyquatemium-10, polyquaternium-24, polyquatemium-67, and a mixture thereof.
  • the amount of the cationic polysaccharide(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
  • the amount of the cationic polysaccharide(s) 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 cationic polysaccharide(s) in the composition according to the present 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.
  • the composition according to the present invention may include at least one crosslinker having three or more acid groups or salt thereof. Two or more different types of crosslinkers 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 of the acid groups of the crosslinker having three or more acid groups may be in the form of a salt. All the acid groups of the crosslinker may be in the form of salts.
  • salt in the present specification means a salt formed by addition of suitable base(s) to the crosslinker having three or more acid groups, which may be obtained from a reaction with the crosslinker having three or more acid groups with the base(s) according to methods known to those skilled in the art.
  • suitable base(s) for example salts with alkaline metal such as Na and K, and salts with alkaline earth metal such as Mg and Ca, and ammonium salts.
  • the crosslinker be selected from non-polymeric acids having three or more acid groups, more preferably from non-polymeric organic acids having three or more acid groups.
  • non-polymeric here means that the crosslinker is not obtained by polymerizing two or more monomers. Therefore, the non-polymeric acid, in particular the non-polymeric organic acid, does not correspond to an acid obtained by polymerizing two or more monomers such as polycarboxylic acid.
  • the molecular weight of the non-polymeric acid, in particular the non- polymeric organic acid, having three or more acid groups be 1000 or less, preferably 800 or less, and more preferably 600 or less.
  • the crosslinker having three or more acid groups, or salt thereof, may be hydrophilic or water-soluble.
  • the crosslinker having three or more acid groups may have three or more acid groups selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphonic group, phosphoric group, a phenolic hydroxyl group, and a mixture thereof.
  • the crosslinker having three or more acid groups or salt thereof may be selected from the group consisting of tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids, hexacarboxylic acids, salts thereof, and mixtures thereof.
  • the crosslinker having three or more acid groups or salt thereof may be selected from the group consisting of citric acid, aconitic acid, phytic acid, EDTA, glycyrrhizin, inositol triphosphate, inositol pentakisphosphate, tripolyphosphate, adenosine triphosphate, a salt thereof, and a mixture thereof.
  • the crosslinker having three or more acid groups or salt thereof be selected from the group consisting of citric acid, phytic acid, a salt thereof, and a mixture thereof.
  • the amount of the crosslinker(s) having three or more acid groups or salt(s) thereof in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
  • the amount of the crosslinker(s) having three or more acid groups or salt(s) thereof 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 crosslinker(s) having three or more acid groups or salt(s) thereof in the composition according to the present invention may be from 0.001% to 1% by weight, preferably from 0.005% to 0.5% by weight, and more preferably from 0.01% to 0.1% by weight, relative to the total weight of the composition.
  • the DIC gel can be prepared by the above cationic polysaccharide and the above crosslinker.
  • composition according to the present invention may further include at least one anionic polymer.
  • anionic polymer Two or more different types of anionic polymers may be used in combination.
  • a single type of anionic polymer or a combination of different types of anionic polymers may be used.
  • An anionic polymer has a negative charge density.
  • the charge density of the anionic polymer may be from 0.1 meq/g to 20 meq/g, preferably from 1 to 15 meq/g, and more preferably from 4 to 10 meq/g if the anionic polymer is a synthetic anionic polymer, and the average substitution degree of the anionic polymer may be from 0.1 to 3.0, preferably from 0.2 to 2.7, and more preferably from 0.3 to 2.5 if the anionic polymer is a natural anionic polymer.
  • the molecular weight of the anionic polymer be 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 a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a phosphoric group, a phosphate group, a phosphonic group, phosphoric group, a phosphonate group, a carboxylic group, and a carboxylate group.
  • the anionic polymer may be a homopolymer or a copolymer.
  • copolymer is understood to mean both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
  • the anionic polymer may be selected from natural and synthetic anionic polymers.
  • the anionic polymer may comprise at least one hydrophobic chain.
  • the anionic polymer which may comprise at least one hydrophobic chain may be obtained by copolymerization of a monomer (a) chosen from carboxylic acids comprising an a,
  • the anionic polymer with at least one hydrophobic chain may be obtained by two synthetic routes:
  • 2-acrylamido-2-methylpropanesulphonic acid copolymers of those disclosed in the article “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, Vol. 33, No. 10 - 3694-3704” and in applications EP-A-0 750 899 and EP-A-1 069 172.
  • the carboxylic acid comprising an a,P ⁇ monoethylenic unsaturation constituting the monomer (a’) can be chosen from numerous acids and in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. It is preferably acrylic or methacrylic acid.
  • the copolymer can comprise a monomer (b) comprising a monoethylenic unsaturation which does not have surfactant property.
  • the preferred monomers are those which give waterinsoluble polymers when they are homopolymerized. They can be chosen, for example, from C1-C4 alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. The more particularly preferred monomers are methyl acrylate and ethyl acrylate.
  • the other monomers which can be used are, for example, styrene, vinyltoluene, vinyl acetate, acrylonitrile and vinylidene chloride.
  • Unreactive monomers are preferred, these monomers being those in which the single ethylenic group is the only group which is reactive under the polymerization conditions.
  • monomers which comprise groups which react under the effect of heat, such as hydroxy ethyl acrylate, can optionally be used.
  • the monomer (c) is obtained by reaction of an acrylic monomer comprising an a, - monoethylenic unsaturation, such as (a), or of an isocyanate monomer comprising a monoethylenic unsaturation with a monohydric nonionic amphiphilic compound or a primary or secondary fatty amine.
  • the monohydric nonionic amphiphilic compounds or the primary or secondary fatty amines used to produce the nonionic monomer (c) are well known.
  • the monohydric nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds comprising an alkylene oxide forming the hydrophilic part of the molecule.
  • the hydrophobic compounds are generally composed of an aliphatic alcohol or an alkylphenol, in which compounds a carbonaceous chain comprising at least six carbon atoms constitutes the hydrophobic part of the amphiphilic compound.
  • the preferred monohydric nonionic amphiphilic compounds are compounds having the following formula (V):
  • the preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising from 6 to 30 carbon atoms.
  • the monomer used to form the nonionic urethane monomer (c) can be chosen from highly varied compounds. Use may be made of any compound comprising a copolymerizable unsaturation, such as an acrylic, methacrylic or allylic unsaturation.
  • the monomer (c) can be obtained in particular from an isocyanate comprising monoethylenic unsaturation, such as, in particular, a,a-dimethyl-m-isopropenylbenzyl isocyanate.
  • the monomer (c) can be chosen in particular from acrylates, methacrylates or itaconates of oxyethylenated (1 to 50 EO) C6-C30 fatty alcohol, such as steareth-20 methacrylate, oxyethylenated (25 EO) behenyl methacrylate, oxyethylenated (20 EO) monocetyl itaconate, oxyethylenated (20 EO) monostearyl itaconate or the acrylate modified by polyoxyethylenated (25 EO) C12-C24 alcohols and from dimethyl-m-isopropenylbenzyl isocyanates of oxyethylenated (1 to 50 EO) C6-C30 fatty alcohol, such as, in particular, the dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol.
  • the anionic polymer is chosen from acrylic terpolymers obtained from (a) a carboxylic acid comprising a,P-ethylenic unsaturation, (b) a non-surface-active monomer comprising ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer which is the reaction product of a monohydric nonionic amphiphilic compound with an isocyanate comprising a monoethylenic unsaturation.
  • anionic polymers comprising at least one hydrophobic chain, of the acrylic acid/ethyl acrylate/alkyl acrylate terpolymer, such as the product as a 30% aqueous dispersion sold under the name Acusol 823 by Rohm & Haas; the acrylates/steareth-20 methacrylate copolymer, such as the product sold under the name Aculyn 22 by Rohm & Haas; the (meth)acrylic acid/ethyl acrylate/oxyethylenated (25 EO) behenyl methacrylate terpolymer, such as the product as an aqueous emulsion sold under the name Aculyn 28 by Rohm & Haas; the acrylic acid/oxyethylenated (20 EO) monocetyl itaconate copolymer, such as the product as a 30% aqueous dispersion sold under the name Structure 3001 by National Starch; the acrylic acid/
  • the anionic polymer be selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid, and cellulose polymers (e.g., cellulose gum, hydroxy ethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, and carboxymethylcellulose), anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly( vinyl sulfates), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, maleic anhydride (co)polymers, and salts thereof.
  • polysaccharides such as alginic acid, hyaluronic acid, and cellulose polymers
  • the maleic anhydride copolymer may comprise one or more maleic anhydride comonomers, and one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, and styrene.
  • maleic anhydride copolymer is understood to mean any polymer obtained by copolymerization of one or more maleic anhydride comonomers and of one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic anhydride comonomers optionally being partially or completely hydrolysed.
  • hydrophilic polymers that is to say polymers having a solubility of water of greater than or equal to 2 g/1.
  • copolymers obtained by copolymerization of one or more maleic anhydride units of which the maleic anhydride units are in the hydrolysed form and more preferably in the form of alkaline salts, for example in the form of ammonium, sodium, potassium or lithium salts.
  • the maleic anhydride copolymer may have a molar fraction of maleic anhydride units of between 0.1 and 1, more preferably between 0.4 and 0.9.
  • the weight-average molar mass of the maleic anhydride copolymer may be between 1 ,000 and 500,000, and preferably between 1,000 and 50,000.
  • the maleic anhydride copolymer be a styrene/maleic anhydride copolymer, and more preferably sodium styrene/maleic anhydride copolymer.
  • Use will preferably be made of a copolymer of styrene and of maleic anhydride in a 50/50 ratio.
  • Use may be made, for example, of the styrene/maleic anhydride (50/50) copolymer, in the form of an ammonium salt at 30% in water, sold under the reference SMA1000H® by Cray Valley or the styrene/maleic anhydride (50/50) copolymer, in the form of a sodium salt at 40% in water, sold under the reference SMAlOOOHNa® by Cray Valley.
  • the amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
  • the amount of the anionic polymer(s) 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 anionic polymer(s) in the composition according to the present 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.
  • composition according to the present invention may comprise at least one additional filler which is different from the (b) spherical hydrophobic silica.
  • additional fillers may be used in combination.
  • a single type of additional filler or a combination of different types of additional fillers may be used.
  • filler should be understood as meaning a colorless or white, inorganic or synthetic particle which is insoluble in a possible liquid component in the composition according to the present invention, whatever the temperature at which the composition is manufactured.
  • the filler(s) may be inorganic or organic, and can be of spherical or oblong shape, whatever the crystallographic form (for example, sheet, cubic, hexagonal, orthorhombic, and the like).
  • talc mica, (hydrophilic) silica, kaolin, sericite, calcinated talc, calcinated mica, calcinated sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate and hydroxyapatite, powders formed of polyamide (Nylon®), of poly-[3-alanine and of polyethylene, powders formed of polyurethane, powders formed of tetrafluoroethylene polymers (Teflon®), lauryllysine, starch, polymeric hollow microspheres, such as those of poly( vinylidene chloride)/acrylonitrile, for example Expance
  • examples of the filler include metal oxides, preferably titanium oxide, zinc oxide and a mixture thereof.
  • a filler that is suitable for the present invention may be, for example, a filler whose mean particle size is less than 100 pm, and especially between 1 and 50 pm, for example between 4 to 20 pm.
  • composition according to the present invention may comprise, in addition to the aforementioned components, components typically employed in cosmetics, specifically, surfactants (in particular, nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents, inorganic UV filters, silicones and silicone derivatives other than the (d) oil, natural extracts derived from animals or vegetables, waxes, and the like, within a range which does not impair the effects of the present invention.
  • surfactants in particular, nonionic surfactants
  • emulsifiers hydrophilic or lipophilic thickeners
  • organic volatile or non-volatile solvents organic volatile or non-volatile solvents
  • inorganic UV filters silicones and silicone derivatives other than the (d) oil, natural extracts derived from animals or vegetables, waxes, and the like, within a range which does not impair the effects of the present invention.
  • composition according to the present invention may comprise the above optional additive(s) in an amount of from 0.01% to 50% by weight, preferably from 0.05% to 30% by weight, and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.
  • the intended use of the composition according to the present invention may be as a cosmetic composition.
  • the cosmetic composition according to the present invention may be intended for application onto a keratin substance.
  • Keratin substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, nails, lips, hair, and the like.
  • the cosmetic composition according to the present invention be used for a cosmetic process for the keratin substance, in particular skin.
  • the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin makeup composition, and more preferably a skin care composition.
  • composition according to the present invention can be prepared by mixing the above essential and optional ingredients in accordance with any of the processes which are well known to those skilled in the art.
  • the above essential or optional ingredients may be heated. Thus, heating may be performed when mixing the above essential and optional ingredients.
  • composition according to the present invention includes the (a) organic UV filter which is oily, and (c) water, it can be in the form of an emulsion.
  • the composition according to the present invention is in the form of a W/O emulsion.
  • the present invention can also relate to: a cosmetic process for a keratin substance such as skin, comprising: applying to the keratin substance the composition according to the present invention; and optionally drying the composition to form a film, preferably a cosmetic film, on the keratin substance, and a use of the composition according to the present invention for the preparation of a film, preferably a cosmetic film, on a keratin substance such as skin.
  • the cosmetic process here means a non-therapeutic cosmetic method for caring for and/or making up the surface of a keratin substance such as skin.
  • the film prepared by the composition according to the present invention is capable of self- healing or self-repairing.
  • the film provided by the composition according to the present invention can be automatically repaired even though the film is broken due to, for example, scratching and the like, and therefore, long lastingness of cosmetic effects provided by the film can be improved.
  • the above film may be resistant to water with a pH of 7 or less, and is removable with water with a pH of more than 7, preferably 8 or more, and more preferably 9 or more.
  • the above film can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably in a range of 6 or more and 7 or less, and more preferably in a range of 5 or more and 7 or less, while the above film can be removed under alkaline conditions such as a 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.
  • the above film can be water-resistant, and therefore, it can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, sweat and rain.
  • the above film can be easily removed from a keratin substance such as skin under alkaline conditions. Therefore, the above film is difficult to remove with water, while it can be easily removed with a soap which can provide alkaline conditions.
  • the above film can include the organic UV filter which is originally present in the composition according to the present invention, the above film can protect a keratin substance such as skin from UV rays, thereby limiting the darkening of the skin, improving the colour and uniformity of the complexion, and/or treating aging of the skin.
  • the above film may have cosmetic effects such as absorbing or adsorbing malodour and/or protecting the keratin substance from, for example, dirt or pollutants, due to the properties of the DIC-gel in the film, even if the film does not include any cosmetic active ingredient.
  • the above film may immediately change or modify the appearance of the skin by changing light reflection on the skin and the like, even if the film does not include any cosmetic active ingredient. Therefore, it may be possible for the above film to conceal skin defects such as pores or wrinkles. Further, the above film may immediately change or modify the feeling to the touch of the skin by changing the surface roughness on the skin and the like. Furthermore, the above film may immediately protect the skin by covering the surface of the skin and shielding the skin, as a barrier, from environmental stresses such as pollutants, contaminants and the like.
  • the above cosmetic effects can be adjusted or controlled by changing the chemical composition, the thickness and/or the surface roughness of the above film.
  • the film can have cosmetic effects provided by the additional cosmetic active ingredient(s).
  • the film can treat the aging of the skin, absorb sebum on the skin, control odors on the skin, control perspiration on the skin, and/or whiten of the skin.
  • the present invention can also relate to a use of (b) at least one spherical hydrophobic silica in a composition in the form of an W/O emulsion, comprising (a) at least one organic UV filter, and (c) water, in order to enhance the UV absorbance of the composition and improve the spreadability of the composition.
  • the addition of the (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 a keratin substance such as skin.
  • composition according to the present invention which is in the form of a W/O emulsion, comprising both (a) at least one UV filter, (b) at least one spherical hydrophobic silica, and (c) water can be easily spread on a keratin substance such as skin, while providing strong UV protection.
  • compositions according to Examples 1 and 2 and Comparative Examples 1-3 in the form of a W/O emulsion, was prepared by mixing the ingredients shown in Table 1.
  • the numerical values for the amounts of the ingredients in Table 1 are all based on “% by weight” as active materials.
  • compositions according to Examples 1 and 2 and Comparative Examples 1 -3 were shaken 10 times in a capped container to be homogeneous.
  • Each of the homogenous compositions was transferred onto a plate (Helio plate HD 6, PMMA, roughness: 6 pm) with an adjustable pipette in an amount of 20 mg/cm 2 and then uniformly spread by the fingers.
  • the coated plate was air dried for 15 minutes at room temperature.
  • the obtained sample plate was placed into a Labsphere Ultraviolet Transmittance Analyzer (Model UV-2000 from Solar Light Company, Philadelphia, Pennsylvania). Irradiation of UV rays took place at 12 points on the sample plate.
  • the UV absorbance by the sample plate in the wavelength range of from 290 to 420 nm was recorded.
  • compositions according to Examples 1 and 2 have more enhanced UV absorbance than the composition according to Comparative Examples 1-3, in particular from 290 nm to 380 nm. It can be recognized that the enhanced UV absorbance is caused by the use of spherical hydrophobic silica.
  • compositions according to Examples 1 and 2 have a good balance of high spreadability and enhanced UV absorbance.
  • the compositions according to Examples 1 and 2 can provide both excellent texture and improved UV protection.

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 present invention can be easily spread on a keratin substance such as skin, while providing strong UV protection.

Description

DESCRIPTION
TITLE OF INVENTION
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, including organic UV filter(s) and spherical hydrophobic silica(s).
BACKGROUND ART
Generally, UV filters are utilized to provide protection from UV (ultraviolet) rays. Numerous anti-sun compositions intended for protecting the skin from UV-A and/or UV-B have been proposed to date.
These anti-sun compositions often take the form of oil-in-water or water-in-oil emulsions, of gels, or of non-aqueous products which contain, in various concentrations, one or more insoluble and/or fat-soluble and/or water-soluble, organic and/or inorganic UV filters that are capable of selectively absorbing the harmful UV radiation. These UV filters and their amounts are selected as a function of the desired sun protection factor (SPF).
The SPF mathematically expresses the ratio of the dose of UV radiation necessary to achieve the erythematogenic threshold with the UV screening agent to the dose of UV radiation necessary to achieve the erythematogenic threshold without the UV screening agent.
There has been a need for compositions having a higher SPF which can be represented by a higher UV absorbance of the composition.
DISCLOSURE OF INVENTION
On the other hand, the use of an organic UV filter in a composition, such as an anti-sun composition, makes the composition difficult to spread, and a heavy sensation when using the composition.
Thus, an objective of the present invention is to provide a composition, in the form of a W/O emulsion, which includes organic UV filter(s) but can be easily spread, while enhancing the UV absorbance of the composition.
The above objective 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) water.
The (a) organic UV filter may be selected from the group consisting of butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino- 2-hydroxybenzoyl)benzoate, 1 , 1 '-(1 ,4-piperazinediyl)bis[l - [2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl] -methanone 4-methylbenzylidene camphor, ethylhexyl triazone, bisethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6- tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4'- aminobenzalmalonate)-s-triazine, 2,4-bis-(n-butyl 4’-aminobenzalmalonate)-6-[(3-{ 1 ,3,3,3- tetramethyl- 1 -[(trimethyl-'silyl-,oxy]~'disiloxanyl}propyl)amino]-s-triazine, 2,4,6-tris-(di- phenyl)-triazine, 2,4,6-tris-(ter-phenyl)-triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane, polysilicone-15, dineopentyl 4'- methoxybenzalmalonate, 1 , 1 -dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4- bis [5 - 1 (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino] -6-(2-ethylhexyl)imino- 1,3,5- triazine, camphor benzalkonium methosulfate and mixtures thereof.
The amount of the (a) organic UV fdter(s) in the composition according to the present 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.
The (b) spherical hydrophobic silica may have an average circularity determined by an image analysis method of 0.8 or more, and preferably 0.82 or more.
The (b) spherical hydrophobic silica may have an oil-absorbing capacity, measured at the wet point, of 2 ml/g or more, preferably 3 ml/g or more, more preferably 4 ml/g or more, and most preferably from 5 ml/g or more.
The (b) spherical hydrophobic silica may have a specific surface area determined by BET method of 200 m2/g or more, preferably 400 m2/g or more, and more preferably 500 m2/g or more.
The (b) spherical hydrophobic silica may have a pore volume determined by BJH method of 1 ml/g or more, preferably 2 ml/g or more, and more preferably 3 ml/g or more.
The (b) spherical hydrophobic silica may have a peak pore radius determined by BJH method of 5 nm or more, preferably 10 nm or more, and more preferably 12 nm or more.
The (b) spherical hydrophobic silica may have an average particle size of from 0.5 pm to 30 pm, preferably from 1 pm to 20 pm, and more preferably from 2 pm to 15 pm.
The amount of the (b) spherical hydrophobic silica(s) in the composition according to the present 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 the (a) UV filter(s) to the amount of the (b) spherical hydrophobic silica(s) in the composition according to the present invention may be from 3 to 35, preferably from 5 to 30, and more preferably from 10 to 25.
The composition according to the present invention may further comprise (d) at least one oil which may be selected preferably 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, dimethicone, diisopropyl sebacate and mixtures thereof. The composition according to the present invention may be a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care or makeup cosmetic composition.
The present invention also relates to a cosmetic process for a keratin substance such as skin, comprising applying to the keratin substance the composition according to the present invention.
The present invention also relates to a 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, in order to enhance the UV absorbance of the composition and improve the spreadability of the composition.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 shows a graph of UV absorbance of 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 discovered that it is possible to provide a composition, in the form of a W/O emulsion, which includes organic UV filter(s) but can be easily spread, while enhancing the UV absorbance of the composition.
Thus, the composition according to the present 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) water.
The composition according to the present invention can provide an improved or enhanced UV absorbance, which reflects improved or enhanced protection from UV rays.
On the other hand, the composition according to the present invention can be easily spread on a keratin substance such as skin, which reflects improved or enhanced spreadability when using the composition.
Thus, the composition according to the present invention can be easily spread on a keratin substance such as skin, while providing strong UV protection.
Furthermore, the composition according to the present invention can capture sebum. Therefore, the composition according to the present invention can reduce gloss on a keratin substance such as skin, and can make, for example, roughness on the skin such as pores and wrinkles less noticeable. Accordingly, the composition according to the present invention can also provide optical mattifying effects.
Hereinafter, the composition, process, and the like according to the present invention will be explained in a more detailed manner. [Organic UV Filter]
The composition according to the present invention comprises (a) at least one organic UV filter. If two or more (a) organic UV filters are used, they may be the same or different.
The (a) organic UV filter may be hydrophobic or water-insoluble. The (a) organic UV filter may function as an oily ingredient. Thus, the (a) organic UV filter can constitute a continuous or outer phase of a W/O type composition. The (a) organic UV filter may be active in the UV-A and/or UV-B region. The (a) organic UV filter may be lipophilic or oil-soluble.
The (a) organic UV filter may be solid or liquid. The terms “solid” and “liquid” mean solid and liquid, respectively, at 25°C under 1 atm.
The (a) organic UV filter can be selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; p,P-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole compounds; imidazoline compounds; bis-benzoazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4-diarylbutadiene compounds; guaiazulene and derivatives thereof; rutin and derivatives thereof; and mixtures thereof.
Mention may be made, as examples of the (a) organic UV filter(s), of those denoted below under their INCI names, and mixtures thereof.
- Anthranilic compounds: Menthyl anthranilate, marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer.
- Dibenzoylmethane compounds: Butyl methoxy dibenzoylmethane, marketed in particular under the trademark "Parsol 1789" by Hofftnann-La Roche; and isopropyl dibenzoylmethane.
- Cinnamic compounds: Ethylhexyl methoxycinnamate, marketed in particular under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, marketed under the trademark "Neo Heliopan E 1000" by Haarmann and Reimer; cinoxate (2-ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethylhexanoate dimethoxycinnamate.
- Salicylic compounds: Homosalate (homomenthyl salicylate), marketed under the trademark "Eusolex HMS" by Rona/EM Industries; ethylhexyl salicylate, marketed under the trademark
"Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, marketed under the trademark "Dipsal" by Scher; and TEA salicylate, marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer.
- Camphor compounds, in particular, benzylidenecamphor derivatives: 3-benzylidene camphor, manufactured under the trademark "Mexoryl SD" by Chimex; 4-methylbenzylidene camphor, marketed under the trademark "Eusolex 6300" by Merck; benzylidene camphor sulfonic acid, manufactured under the trademark "Mexoryl SL" by Chimex; camphor benzalkonium methosulfate, manufactured under the trademark "Mexoryl SO" by Chimex; and polyacrylamidomethyl benzylidene camphor, manufactured under the trademark "Mexoryl SW" by Chimex. - Benzophenone compounds: Benzophenone- 1 (2,4-dihydroxybenzophenone), marketed under the trademark "Uvinul 400" by BASF; benzophenone-2 (Tetrahydroxybenzophenone), marketed under the trademark "Uvinul D50" by BASF; Benzophenone-3 (2-hydroxy-4- methoxybenzophenone) or oxybenzone, marketed under the trademark "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid), marketed under the trademark "Uvinul MS40" by BASF; benzophenone-5 (Sodium hydroxymethoxy benzophenone Sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone); marketed under the trademark "Helisorb 11 " by Norquay; benzophenone-8, marketed under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate), marketed under the trademark "Uvinul DS- 49" by BASF; benzophenone- 12, and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate (UVINUL A+ by BASF).
- P,P-Diphenylacrylate compounds: Octocrylene, marketed in particular under the trademark "Uvinul N539" by BASF; and Etocrylene, marketed in particular under the trademark "Uvinul N35" by BASF.
- Triazine compounds: Diethylhexyl butamido triazone, marketed under the trademark "Uvasorb HEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bisethylhexyloxyphenol methoxyphenyl triazine marketed under the trademark «TINOSORB S » by CIBA GEIGY, and ethylhexyl triazone marketed under the trademark «UVINUL T150 » by BASF.
- Benzotriazole compounds, in particular, phenylbenzotriazole derivatives: 2-(2H- benzotriazole-2-yl)-6-dodecyl-4-methylpheno, branched and linear; and those described in USP 5240975.
- Benzalmalonate compounds: Dineopentyl 4'-methoxybenzalmalonate, and polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche.
- Benzimidazole compounds, in particular, phenylbenzimidazole derivatives.
- Imidazoline compounds: Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
- Bis-benzoazolyl compounds: The derivatives as described in EP-669,323 and U.S. Pat. No. 2,463,264.
- Para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid), ethyl PABA, Ethyl dihydroxypropyl PABA, pentyl dimethyl PABA, ethylhexyl dimethyl PABA, marketed in particular under the trademark "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA, marketed under the trademark "Uvinul P25" by BASF.
- Methylene bis-(hydroxyphenylbenzotriazol) compounds, such as 2,2’-methylenebis[6-(2H- benzotriazol-2-yl)-4-methyl-phenol] marketed in the solid form under the trademark "Mixxim BB/200" by Fairmount Chemical, 2,2’-methylenebis[6-(2H-benzotriazol-2-yl)-4-(l,l,3,3- tetramethylbutyl)phenol] marketed in the micronized form in aqueous dispersion under the trademark "Tinosorb M" by BASF, or under the trademark “Mixxim BB/100” by Fairmount Chemical, and the 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
Drometrizole trisiloxane, marketed under the trademark "Silatrizole" by Rhodia Chimie or “Mexoryl XL” by L’Oreal, as represented below.
Figure imgf000006_0001
- Benzoxazole compounds: 2,4-bis[5-l(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6- (2-ethylhexyl)imino-l,3,5-triazine, marketed under the trademark Uvasorb K2A by Sigma 3V.
- Screening polymers and screening silicones: The silicones described in WO 93/04665.
- Dimers derived from a-alkylstyrene: The dimers described in DE-19855649.
- 4,4-Diarylbutadiene compounds: l,l-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.
It is preferable that the (a) organic UV filter(s) be selected from the group consisting of: butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4, benzophenone- 5, n-hexyl 2-(4- diethylamino-2-hydroxybenzoyl)benzoate, l,T-(l,4-piperazinediyl)bis[l-[2-[4- (diethylamino)-2-hydroxybenzoyl]phenyl] -methanone 4-methylbenzylidene camphor, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4'- aminobenzalmalonate)-s-triazine, 2,4-bis-(n-butyl 4’-aminobenzalmalonate)-6-[(3-{ 1 ,3,3,3- tetramethyl-1 - [(trimethylsilyloxy] disiloxanyl}propyl)amino]-s-triazine, 2,4,6-tris-(di-phenyl)- triazine, 2,4,6-tris-(ter-phenyl)-triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane, polysilicone-15, dineopentyl 4'-methoxybenzalmalonate, 1,1- dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-l (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-l,3,5-triazine, camphor benzalkonium methosulfate and mixtures thereof.
The amount of the (a) organic UV filter(s) in the composition according to the present invention may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the composition.
The amount of the (a) organic UV filter (s) in the composition according to the present invention may be 40% by weight or less, preferably 35% by weight or less, and more preferably 30% by weight 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 present 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.
[Spherical Hydrophobic Silica]
The composition according to the present invention comprises (b) at least one spherical hydrophobic silica. If two or more (b) spherical hydrophobic silicas are used, they may be the same or different.
It is preferable that the (b) spherical hydrophobic silica be porous. In other words, it is preferable that the (b) spherical hydrophobic silica be an aerogel.
Aerogels are materials with high porosity. Herein, silica aerogels refer to a solid silica with a porous structure generally obtained by replacing a medium included in wet silica gels with air by drying them while a solid network structure of the silica is maintained. The porosity represents the amount of air contained in the apparent volume of a material by volume percentage. The (b) spherical hydrophobic silica which is in the form of an aerogel may have a porosity of 60% or more, preferably 70% or more, and more preferably 80% or more. The (b) spherical hydrophobic silica is in the form of particles. The (b) spherical hydrophobic silica is characterized in that the shape of each of the particles is spherical. Due to this spherical shape, the (b) spherical hydrophobic silica can provide good smoothness. The spherical degree of the (b) spherical hydrophobic silica may be determined by an average circularity.
The (b) spherical hydrophobic silica may have an average circularity of 0.8 or more, and preferably 0.82 or more. The (b) spherical hydrophobic silica may have an average circularity of less than 1, preferably 0.99 or less, more preferably 0.98 or less, even more preferably 0.97 or less, still even more preferably 0.96 or less, and most preferably 0.95 or less.
The "average circularity" may be determined by an image analysis method. In particular, the "average circularity" may be an arithmetic mean of circularity obtained by image analysis of a scanning electron microscope (SEM) image of no less than 2000 particles observed at a magnification of 1000 by secondary electron detection using a scanning electron microscope (SEM).
The "circularity" of each particle is a value determined by the following formula: C = 4KS / L2 wherein C represents the circularity, S represents the area (projected area) of the particle in the image, and L represents the length of the periphery (perimeter) of the particle in the image. When the average circularity approaches 1, the shape of each of the particles becomes more spherical.
For the (b) spherical hydrophobic silica, the term "hydrophobic" means that the silica particles are difficult to disperse in water. More specifically, this term means that a silica particle phase and an aqueous phase are completely separated after 1 g of the silica particles and 100 g of ion-exchange water are added to a bottle, the bottle is agitated or stirred for ten or more seconds, and the bottle is left to stand. Therefore, in one particular embodiment of the present invention, the (b) spherical hydrophobic silica does not exhibit a water absorption property.
The (b) spherical hydrophobic silica that may be used according to the present invention is preferably of silylated silica type (INCI name: silica silylate). Most preferably, the (b) spherical hydrophobic silica may be those described in JP-A-2014-088307, JP-A-2014- 218433, or JP-A-2018- 177620.
The hydrophobicity may be obtained by reacting a hydrophobizing agent with a silanol group represented by the following formula existing on the surface of silica:
=Si-OH wherein the symbol
Figure imgf000008_0001
represents the remaining three valences of the Si atom, thereby converting the silanol group into a group represented by the following formula:
(=Si-O-)(4-n)SiRn wherein n is an integer of 1 to 3; each R is independently a hydrocarbyl group; and two or more R may be the same or different from each other where n is 2 or more.
The hydrophobizing agent may be a silylating agent. Therefore, according to one preferred embodiment, in the (b) spherical hydrophobic silica, the silica particles may be modified at the surface by silylation. As examples of the silylating agents, mention may be made of a treating agent having one of the following formulae (1) to (3). Formula (1):
RnSiX(4-n) wherein n represents an integer of 1 to 3; R represents a hydrocarbyl group; X represents a group (i.e., a leaving group) which can leave a molecule by cleavage of the bond with the Si atom in a reaction with a compound having a hydroxyl group; each R may be different where n is 2 or more; and each X may be different where n is 2 or less.
Formula (2):
Figure imgf000009_0001
wherein R1 represents an alkylene group; R2 and R3 independently represent a hydrocarbyl group; and R4 and R5 independently represent a hydrogen atom or a hydrocarbyl group.
Formula (3):
Figure imgf000009_0002
wherein R6 and R7 independently represent a hydrocarbyl group; m represents an integer of 3 to 6; each R6 may be different when there are two or more R6; and each R7 may be different when there are two or more R7.
In the above formula (1), R is a hydrocarbyl group, preferably a hydrocarbyl group having a carbon number of 1 to 10, more preferably a hydrocarbyl group having a carbon number of 1 to 4, and especially preferably a methyl group.
As examples of the leaving group represented by X, mention may be made of halogen atoms such as chlorine and bromine; alkoxy groups such as a methoxy group and ethoxy group; groups represented by -NH-SiRs (wherein the definition of R is the same as that of R in formula (1)).
Specific examples of the hydrophobizing agent represented by the above formula (1) include: chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, and hexamethyldisilazane.
Most preferably, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, and/or hexamethyldisilazane may be used from the viewpoint of favorable reactivity.
The number of the bond of the Si atom with the silanol group on the silica framework varies depending on the number (4-n) of the leaving group X. For example, if n is 2, the following bonding will occur:
(=Si-O-)2SiR2.
If n is 3, the following bonding will occur:
Figure imgf000010_0001
In this manner, the silanol groups may be silylated, and thereby hydrophobization may be carried out.
In the above formula (2), R1 may be an alkylene group, preferably an alkylene group having a carbon number of 2 to 8, and especially preferably an alkylene group having a carbon number of 2 to 3.
In the above formula (2), R2 and R3 are independently a hydrocarbyl group, and the same preferable groups as those of R in the formula (1) can be given. R4 represents a hydrogen atom or a hydrocarbyl group, and when it is a hydrocarbyl group, the same preferable groups as those of R in the above formula (1) can be given. When a gel of silica is treated with the compound (cyclic silazane) represented by the formula (2), cleavage of Si-N bonds will occur by the reaction with silanol groups, and therefore the following bonding will occur on the surface of the silica framework in the gel:
Figure imgf000010_0002
In this way, the silanol group may be silylated by the cyclic silazanes of the above formula (2) as well, and thereby hydrophobization may be carried out.
Specific examples of the cyclic silazanes represented by the above formula (3) include hexamethylcyclotrisilazane, and octamethylcyclotetrasilazane.
In the above formula (3), R6 and R7 are independently a hydrocarbyl group, and the same preferable groups as those of R in the above formula (2) can be given, m represents an integer of 3 to 6. When a gel of silica is treated with the compound (cyclic siloxane) represented by the formula (3), the following bonding will occur on the surface of the silica framework in the gel:
Figure imgf000010_0003
In this way, silanol groups may be silylated by the cyclic siloxanes of the above formula (3) as well, and thereby hydrophobization may be carried out.
Specific examples of the cyclic siloxanes represented by the above formula (3) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.
The (b) spherical hydrophobic silica may be prepared by producing a sol of silica, turning 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 dying the hydrophobized silica.
The (b) spherical hydrophobic silica may have a specific surface area determined by BET method of 200 m2/g or more, preferably 400 m2/g or more, and more preferably 500 m2/g or more, and/or may have a specific surface area determined by BET method of 1,200 m2/g or less, preferably 1,000 m2/g or less, and more preferably 800 m2/g or less.
In the present invention, the "specific surface area determined by BET method" means a value determined by: drying a sample for measurement at 200°C for no less than three hours under a reduced pressure of no more than 1 kPa; thereafter measuring an adsorption isotherm of only the nitrogen adsorption side at liquid nitrogen temperature; and analyzing the adsorption isotherm by BET method. The pressure range used for the analysis is a relative pressure of 0.1 to 0.25.
The (b) spherical hydrophobic silica may have a pore volume determined by BJH method of 1 ml/g or more, preferably 2 ml/g or more, and more preferably 3 ml/g or more, and/or may have a pore volume determined by BJH method of 10 ml/g or less, preferably 8 ml/g or less, and more preferably 7 ml/g or less.
The (b) spherical hydrophobic silica may have a peak pore radius determined by BJH method of 5 nm or more, preferably 10 nm or more, and more preferably 12 nm or more, and/or may have a peak pore radius determined by BJH method of 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less.
The "pore volume determined by BJH method" refers to a pore volume which derives from a pore having a pore radius of 1 nm to 100 nm obtained by analyzing, by BJH method (Barrett, E. P.; Joyner, L. G.; Halenda, P. P., J. Am. Chem. Soc. 73, 373 (1951)), the adsorption isotherm of the nitrogen adsorption side obtained in the same manner as explained in the above "specific surface area determined by BET method". The "peak pore radius determined by B JT method" refers to the value of a pore radius which gives a peak in a pore distribution curve (volume distribution curve) which is plotted taking on the vertical axis differentiation of the cumulative pore volume by the logarithm of the pore radius obtained by analyzing, by BJH method, the adsorption isotherm of the nitrogen adsorption side obtained in the same manner as above, and taking the pore radius on the horizontal axis.
The (b) spherical hydrophobic silica may have an average particle size of 0.5 pm or more, preferably 1 pm or more, and more preferably 2 pm or more, and/or may have an average particle size by image analysis method of 30 pm or less, preferably 20 pm or less, and more preferably 15 pm or less. Thus, the (b) spherical hydrophobic silica may have an average particle size of from 0.5 pm to 30 pm, preferably from 1 pm to 20 pm, and more preferably from 2 pm to 15 pm. In a preferable embodiment, the (b) spherical hydrophobic silica may have an average particle size of from 6 pm to 16 pm, preferably from 7 pm to 14 pm, and more preferably from 8 pm to 12 pm.
The "average particle size" here can be measured by image analysis method. Specifically, the value of "average particle size" is an arithmetic mean of equivalent circle diameters which can be obtained by image analysis of a scanning electron microscope (SEM) image of, for example, no less than 2000 particles observed at a magnification of 1000 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 (projected area) of the particle in the image.
Preferably, the (b) spherical hydrophobic silica may have an oil-absorbing capacity, which can be measured at the wet point, of 2 ml/g or more, preferably 3 ml/g or more, more preferably 4 ml/g or more, and most preferably from 5 ml/g or more, and/or may have an oil-absorbing capacity, measured at the wet point, of 12 ml/g or less, preferably 11 ml/g or less, more preferably 10 ml/g or less, and most preferably 8 ml/g or less.
The oil-absorbing capacity measured at the wet point, noted Wp, corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a homogeneous paste. It can be measured according to the wet point method or the method for determining the oil uptake of a powder described in standard NF T 30-022. The oil uptake can correspond to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measuring the wet point, described below.
An amount of m = 2 g of powder is placed on a glass plate, and an oil (such as ester oil, oleric acid, or silicone oil) is then added drop-wise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until a conglomerate of oil and powder has formed. At this point, the oil is added one drop at a time and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be spreadable on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.
Alternatively, the oil-absorbing capacity can be measured in accordance with JIS-K6217-4.
In one preferred embodiment of the present invention, the (b) 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) spherical hydrophobic silica(s) in the composition according to the present 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) spherical hydrophobic silica(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.
The amount of the (b) spherical hydrophobic silica(s) in the composition according to the present 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 the (a) UV filter(s) to the amount of the (b) spherical hydrophobic silica(s) in the composition according to the present invention may be from 3 to 35, preferably from 5 to 30, and more preferably from 10 to 25.
[Water]
The composition according to the present invention comprises (c) water.
The (c) water can form the discontinuous or dispersed (inner) phases of a W/O type composition. Therefore, the (c) water can form the discontinuous or dispersed (inner) phases of the composition according to the present invention which is in the form of a W/O emulsion.
The amount of the (c) water in the composition according to the present 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 the (c) water in the composition according to the present 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 the (c) water in the composition according to the present 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 present invention may comprise (d) at least one oil. If two or more oils are used, they may be the same or different.
The (d) oil is different from the (a) organic UV filter.
Here, “oil” means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile.
The (d) oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof.
The (d) oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils, and fatty alcohols.
As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, com oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.
As examples of animal oils, mention may be made of, for example, squalene and squalane.
As examples of synthetic oils, mention may be made of alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.
The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched Ci- C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci- C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present invention are derived is branched.
Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate. Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols, and esters of monocarboxylic, dicarboxylic, or tricarboxylic acids and of non-sugar C4-C26 dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols may also be used.
Mention may especially be made 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; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.
As ester oils, one can use sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term “sugar” means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.
Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 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 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 such as, especially, oleopalmitate, oleostearate, and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.
More particularly, use is made of monoesters and diesters and especially sucrose, glucose, or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearates.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2- ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.
As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate), and glyceryl tri(caprate/ caprylate/linolenate) .
As examples of silicone oils, mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.
Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
These silicone oils may also be organomodified. The organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
Organopolysiloxanes are defined in greater detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile.
When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:
(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the type such as dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide, of formula:
Figure imgf000015_0001
Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1, 1’ -bis(2,2,2’, 2’ ,3,3’- hexatrimethylsilyloxy)neopentane; and (ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 x 1 O’6 m2/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C.
Non-volatile 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, in a non-limiting manner, of the following commercial products: the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000; the oils of the Mirasil® series sold by the company Rhodia; the oils of the 200 series from the company Dow Coming, such as DC200 with a viscosity of 60 000 mm2/s; and the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF
18) from General Electric.
Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.
Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.
The phenyl silicone oil may be chosen from the phenyl silicones of the following formula:
Figure imgf000016_0001
in which
Ri to Rio, independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, preferably C1-C12 hydrocarbon-based radicals, and more preferably Ci-Co hydrocarbon-based radicals, in particular methyl, ethyl, propyl, or butyl radicals, and m, n, p, and q are, independently of each other, integers of 0 to 900 inclusive, preferably 0 to 500 inclusive, and more preferably 0 to 100 inclusive, with the proviso that the sum n+m+q is other than 0. Examples that may be mentioned include the products sold under the following names: the Silbione® oils of the 70 641 series from Rhodia; the oils of the Rhodorsil® 70 633 and 763 series from Rhodia; the oil Dow Coming 556 Cosmetic Grade Fluid from Dow Coming; the silicones of the PK series from Bayer, such as the product PK20; certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250, and SF 1265.
As the phenyl silicone oil, phenyl trimethicone (Ri to Rio are methyl; p, q, and n = 0; m=l in the above formula) is preferable.
The organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.
Hydrocarbon oils may be chosen from: linear or branched, optionally cyclic, Ce-Cie lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane, and isodecane; and linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.
As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.
The term “fatty” in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols. The fatty alcohol 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 chosen from saturated and unsaturated, linear and branched radicals 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 chosen from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.
As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.
It is preferable that the fatty alcohol be a saturated fatty alcohol.
Thus, the fatty alcohol may be selected from straight or branched, saturated or unsaturated Ce- C30 alcohols, preferably straight or branched, saturated C6-C30 alcohols, and more preferably straight or branched, saturated C12-C20 alcohols. The term “saturated fatty alcohol” here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C6-C30 fatty alcohols. Among the linear or branched, saturated C6-C30 fatty alcohols, linear or branched, saturated C12-C20 fatty alcohols may preferably be used. Any linear or branched, saturated C16-C20 fatty alcohols may be more preferably used. Branched C16-C20 fatty alcohols may be even more preferably used.
As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as a saturated fatty alcohol.
According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from cetyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.
The (d) oil may be chosen from non-polar or polar oils, preferably hydrocarbon oils, silicone oils, ester oils, and mixtures thereof and even more preferably isododecane, isohexadecane, dimethicone, diisopropyl sebacate and mixtures thereof.
The amount of the (d) oil(s) in the composition according to the present 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) oil(s) in the composition according to the present invention may be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the composition.
The amount of the (d) oil(s) in the composition according to the present 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 present invention may comprise at least one gel, preferably a hydrogel, which is dynamically and ionically crosslinked. The dynamically and ionically- crosslinked gel is hereinafter abbreviated as a DIC-gel.
The dynamic and ionic-crosslinking in the DIC-gel is different from permanent covalent bonding because it is breakable but reformable. The dynamic and ionic-crosslinking can be easily broken by, for example, cutting and the like, 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 interaction between the cationic polymer and the crosslinker breaks. However, if the two pieces contact each other, they can reform ionic-bonding between the cationic polymer and the crosslinker, and they can adhere to each other. Therefore, even if cracks, for example, are formed on the gel, they can disappear. The composition according to the present invention can be used to prepare a film of a gel which has self-healing or self-repairing properties by applying the composition onto a substrate, preferably a keratin substrate such as skin, and drying the composition.
The DIC gel can be formed with at least one cationic polysaccharide and at least one crosslinker having three or more acid groups or salt thereof.
(Cationic Polysaccharide)
The composition according to the present invention may include 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 charge density of the cationic polysaccharide may be from 0.01 meq/g to 20 meq/g, preferably from 0.05 tol5 meq/g, and more preferably from 0.1 to 10 meq/g.
It is preferable that the molecular weight of the cationic polysaccharide be 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 description, “molecular weight” means a number average molecular weight.
The cationic polysaccharide may have at least one positively chargeable and/or positively charged moiety selected from the group consisting of a primary, secondary or tertiary amino group, a quaternary ammonium group, a guanidine group, a biguanide group, an imidazole group, an imino group, and a pyridyl group. The term (primary) “amino group” here means the group -NH2. It is preferable that the cationic polysaccharide have 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 kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
The cationic polysaccharide may be selected from natural and synthetic cationic polysaccharides.
It is preferable that the cationic polysaccharide be selected from cationic cellulose polymers. Non-limiting examples of the cationic cellulose polymers are as follows.
(1) Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described, for example, in French Patent No. 1 492 597, such as the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the company Dow Chemical. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxy ethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group. (2) Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with at least one water-soluble monomer of quaternary ammonium, and described, for example, in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instance, hydroxymethyl-, hydroxyethyl-, and hydroxypropylcelluloses grafted, for example, with at least one chosen from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and dimethyldiallylammonium. Commercial products corresponding to these polymers include, for example, the products sold under the names "Celquat® L 200" and "Celquat® H 100" by the company Akzo Novel.
(3) Cationic cellulose polymers having at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms. It is preferable that the cationic cellulose polymers be quatemized hydroxyethyl celluloses modified with at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the quaternary ammonium group may preferably contain from 8 to 30 carbon atoms, especially from 10 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. More preferably, the cationic cellulose polymer may comprise at least one quaternary ammonium group including at least one C8-C30 hydrocarbon group. Examples of quatemized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529- 18B (Cl 2 alkyl) and Quatrisoft LM-X 529-8 (C18 alkyl) or Softcat Polymer SL100, 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, sold by the company Dow Chemical, and the products Crodacel QM, Crodacel, QL (Cl 2 alkyl) and Crodacel QS (Cl 8 alkyl) sold by the company Croda.
It is preferable that the cationic polysaccharide be selected from the group consisting of polyquatemium-4, polyquatemium-10, polyquaternium-24, polyquatemium-67, and a mixture thereof.
The amount of the cationic polysaccharide(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
The amount of the cationic polysaccharide(s) 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 cationic polysaccharide(s) in the composition according to the present 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.
(Crosslinker)
The composition according to the present invention may include at least one crosslinker having three or more acid groups or salt thereof. Two or more different types of crosslinkers 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 of the acid groups of the crosslinker having three or more acid groups may be in the form of a salt. All the acid groups of the crosslinker may be in the form of salts.
The term "salt" in the present specification means a salt formed by addition of suitable base(s) to the crosslinker having three or more acid groups, which may be obtained from a reaction with the crosslinker having three or more acid groups with the base(s) according to methods known to those skilled in the art. As the salt, mention may be made of metal salts, for example salts with alkaline metal such as Na and K, and salts with alkaline earth metal such as Mg and Ca, and ammonium salts.
It is preferable that the crosslinker be selected from non-polymeric acids having three or more acid groups, more preferably from non-polymeric organic acids having three or more acid groups.
The term “non-polymeric” here means that the crosslinker is not obtained by polymerizing two or more monomers. Therefore, the non-polymeric acid, in particular the non-polymeric organic acid, does not correspond to an acid obtained by polymerizing two or more monomers such as polycarboxylic acid.
It is preferable that the molecular weight of the non-polymeric acid, in particular the non- polymeric organic acid, having three or more acid groups be 1000 or less, preferably 800 or less, and more preferably 600 or less.
The crosslinker having three or more acid groups, or salt thereof, may be hydrophilic or water-soluble.
The crosslinker having three or more acid groups may have three or more acid groups selected from the group consisting of a carboxylic group, a sulfuric group, a sulfonic group, a phosphonic group, phosphoric group, a phenolic hydroxyl group, and a mixture thereof.
The crosslinker having three or more acid groups or salt thereof may be selected from the group consisting of tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids, hexacarboxylic acids, salts thereof, and mixtures thereof.
The crosslinker having three or more acid groups or salt thereof may be selected from the group consisting of citric acid, aconitic acid, phytic acid, EDTA, glycyrrhizin, inositol triphosphate, inositol pentakisphosphate, tripolyphosphate, adenosine triphosphate, a salt thereof, and a mixture thereof.
It is preferable that the crosslinker having three or more acid groups or salt thereof be selected from the group consisting of citric acid, phytic acid, a salt thereof, and a mixture thereof.
The amount of the crosslinker(s) having three or more acid groups or salt(s) thereof in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, relative to the total weight of the composition.
The amount of the crosslinker(s) having three or more acid groups or salt(s) thereof 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 crosslinker(s) having three or more acid groups or salt(s) thereof in the composition according to the present invention may be from 0.001% to 1% by weight, preferably from 0.005% to 0.5% by weight, and more preferably from 0.01% to 0.1% by weight, relative to the total weight of the composition.
(Anionic Polymer)
The DIC gel can be prepared by the above cationic polysaccharide and the above crosslinker.
However, in addition, the composition according to the present invention may further include 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.
An anionic polymer has a negative charge density. The charge density of the anionic polymer may be from 0.1 meq/g to 20 meq/g, preferably from 1 to 15 meq/g, and more preferably from 4 to 10 meq/g if the anionic polymer is a synthetic anionic polymer, and the average substitution degree of the anionic polymer may be from 0.1 to 3.0, preferably from 0.2 to 2.7, and more preferably from 0.3 to 2.5 if the anionic polymer is a natural anionic polymer.
It is preferable that the molecular weight of the anionic polymer be 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 a sulfuric group, a sulfate group, a sulfonic group, a sulfonate group, a phosphoric group, a phosphate group, a phosphonic group, phosphoric group, a phosphonate group, a carboxylic group, and a carboxylate group.
The anionic polymer may be a homopolymer or a copolymer. The term “copolymer” is understood to mean both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers, such as terpolymers obtained from three kinds of monomers.
The anionic polymer may be selected from natural and synthetic anionic polymers.
The anionic polymer may comprise at least one hydrophobic chain.
The anionic polymer which may comprise at least one hydrophobic chain may be obtained by copolymerization of a monomer (a) chosen from carboxylic acids comprising an a,|3-ethylenic unsaturation (monomer a’) and 2-acrylamido-2-methylpropanesulphonic acid (monomer a”) with a non-surface-active monomer (b) comprising an ethylenic unsaturation other than (a) and/or a monomer (c) comprising an ethylenic unsaturation resulting from the reaction of an acrylic monomer comprising a a,P-monoethylenic unsaturation or of an isocyanate monomer comprising a monoethylenic unsaturation with a monohydric nonionic amphiphilic component or with a primary or secondary fatty amine. Thus, the anionic polymer with at least one hydrophobic chain may be obtained by two synthetic routes:
- either by copolymerization of the monomers (a’) and (c), or (a’), (b) and (c), or (a”) and (c), or (a”), (b) and (c),
- or by modification (and in particular esterification or amidation) of a copolymer formed from the monomers (a’) or from the monomers (a’) and (b), or (a”) and (b), by a monohydric nonionic amphiphilic compound or a primary or secondary fatty amine.
Mention may in particular be made, as 2-acrylamido-2-methylpropanesulphonic acid copolymers, of those disclosed in the article “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, Vol. 33, No. 10 - 3694-3704” and in applications EP-A-0 750 899 and EP-A-1 069 172.
The carboxylic acid comprising an a,P~monoethylenic unsaturation constituting the monomer (a’) can be chosen from numerous acids and in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. It is preferably acrylic or methacrylic acid.
The copolymer can comprise a monomer (b) comprising a monoethylenic unsaturation which does not have surfactant property. The preferred monomers are those which give waterinsoluble polymers when they are homopolymerized. They can be chosen, for example, from C1-C4 alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate or the corresponding methacrylates. The more particularly preferred monomers are methyl acrylate and ethyl acrylate. The other monomers which can be used are, for example, styrene, vinyltoluene, vinyl acetate, acrylonitrile and vinylidene chloride. Unreactive monomers are preferred, these monomers being those in which the single ethylenic group is the only group which is reactive under the polymerization conditions. However, monomers which comprise groups which react under the effect of heat, such as hydroxy ethyl acrylate, can optionally be used.
The monomer (c) is obtained by reaction of an acrylic monomer comprising an a, - monoethylenic unsaturation, such as (a), or of an isocyanate monomer comprising a monoethylenic unsaturation with a monohydric nonionic amphiphilic compound or a primary or secondary fatty amine.
The monohydric nonionic amphiphilic compounds or the primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. The monohydric nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds comprising an alkylene oxide forming the hydrophilic part of the molecule. The hydrophobic compounds are generally composed of an aliphatic alcohol or an alkylphenol, in which compounds a carbonaceous chain comprising at least six carbon atoms constitutes the hydrophobic part of the amphiphilic compound.
The preferred monohydric nonionic amphiphilic compounds are compounds having the following formula (V):
R-(OCH2CHR’)m-(OCH2CH2)n-OH (V) in which R is chosen from alkyl or alkylene groups comprising from 6 to 30 carbon atoms and alkylaryl groups having alkyl radicals comprising from 8 to 30 carbon atoms, R’ is chosen from alkyl groups comprising from 1 to 4 carbon atoms, n is a mean number ranging from approximately 1 to 150 and m is a mean number ranging from approximately 0 to 50, provided that n is at least as great as m.
Preferably, in the compounds of formula (V), the R group is chosen from alkyl groups comprising from 12 to 26 carbon atoms and alkylphenyl groups in which the alkyl group is C8-C13; the R’ group is the methyl group; m = 0 and n = 1 to 25.
The preferred primary and secondary fatty amines are composed of one or two alkyl chains comprising from 6 to 30 carbon atoms.
The monomer used to form the nonionic urethane monomer (c) can be chosen from highly varied compounds. Use may be made of any compound comprising a copolymerizable unsaturation, such as an acrylic, methacrylic or allylic unsaturation. The monomer (c) can be obtained in particular from an isocyanate comprising monoethylenic unsaturation, such as, in particular, a,a-dimethyl-m-isopropenylbenzyl isocyanate.
The monomer (c) can be chosen in particular from acrylates, methacrylates or itaconates of oxyethylenated (1 to 50 EO) C6-C30 fatty alcohol, such as steareth-20 methacrylate, oxyethylenated (25 EO) behenyl methacrylate, oxyethylenated (20 EO) monocetyl itaconate, oxyethylenated (20 EO) monostearyl itaconate or the acrylate modified by polyoxyethylenated (25 EO) C12-C24 alcohols and from dimethyl-m-isopropenylbenzyl isocyanates of oxyethylenated (1 to 50 EO) C6-C30 fatty alcohol, such as, in particular, the dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol.
According to a specific embodiment of the present invention, the anionic polymer is chosen from acrylic terpolymers obtained from (a) a carboxylic acid comprising a,P-ethylenic unsaturation, (b) a non-surface-active monomer comprising ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer which is the reaction product of a monohydric nonionic amphiphilic compound with an isocyanate comprising a monoethylenic unsaturation.
Mention may in particular be made, as anionic polymers comprising at least one hydrophobic chain, of the acrylic acid/ethyl acrylate/alkyl acrylate terpolymer, such as the product as a 30% aqueous dispersion sold under the name Acusol 823 by Rohm & Haas; the acrylates/steareth-20 methacrylate copolymer, such as the product sold under the name Aculyn 22 by Rohm & Haas; the (meth)acrylic acid/ethyl acrylate/oxyethylenated (25 EO) behenyl methacrylate terpolymer, such as the product as an aqueous emulsion sold under the name Aculyn 28 by Rohm & Haas; the acrylic acid/oxyethylenated (20 EO) monocetyl itaconate copolymer, such as the product as a 30% aqueous dispersion sold under the name Structure 3001 by National Starch; the acrylic acid/oxyethylenated (20 EO) monostearyl itaconate copolymer, such as the product as a 30% aqueous dispersion sold under the name Structure 2001 by National Starch; the acrylates/acrylate modified by polyoxyethylenated (25 EO) C12-C24 alcohols copolymer, such as the 30-32% copolymer latex sold under the name Synthalen W2000 by 3V SA; or the methacrylic acid/methyl acrylate/dimethyl-meta- isopropenylbenzyl isocyanate of ethoxylated behenyl alcohol terpolymer, such as the product as a 24% aqueous dispersion and comprising 40 ethylene oxide groups disclosed in the document EP -A-0 173 109.
It is preferable that the anionic polymer be selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid, and cellulose polymers (e.g., cellulose gum, hydroxy ethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, and carboxymethylcellulose), anionic (co)polyamino acids such as (co)polyglutamic acids, (co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly( vinyl sulfates), dextran sulfate, chondroitin sulfate, (co)polymaleic acids, (co)polyfumaric acids, maleic anhydride (co)polymers, and salts thereof.
The maleic anhydride copolymer may comprise one or more maleic anhydride comonomers, and one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, and styrene.
Thus, the "maleic anhydride copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic anhydride comonomers and of one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic anhydride comonomers optionally being partially or completely hydrolysed. Use will preferably be made of hydrophilic polymers, that is to say polymers having a solubility of water of greater than or equal to 2 g/1.
It is preferable to use copolymers obtained by copolymerization of one or more maleic anhydride units of which the maleic anhydride units are in the hydrolysed form, and more preferably in the form of alkaline salts, for example in the form of ammonium, sodium, potassium or lithium salts.
In an advantageous aspect of the present invention, the maleic anhydride copolymer may have a molar fraction of maleic anhydride units of between 0.1 and 1, more preferably between 0.4 and 0.9.
The weight-average molar mass of the maleic anhydride copolymer may be between 1 ,000 and 500,000, and preferably between 1,000 and 50,000.
It is preferable that the maleic anhydride copolymer be a styrene/maleic anhydride copolymer, and more preferably sodium styrene/maleic anhydride copolymer.
Use will preferably be made of a copolymer of styrene and of maleic anhydride in a 50/50 ratio.
Use may be made, for example, of the styrene/maleic anhydride (50/50) copolymer, in the form of an ammonium salt at 30% in water, sold under the reference SMA1000H® by Cray Valley or the styrene/maleic anhydride (50/50) copolymer, in the form of a sodium salt at 40% in water, sold under the reference SMAlOOOHNa® by Cray Valley.
The amount of the anionic polymer(s) in the composition according to the present invention may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more, relative to the total weight of the composition.
The amount of the anionic polymer(s) 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 anionic polymer(s) in the composition according to the present 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 present invention may comprise at least one additional filler which is different from the (b) 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" should be understood as meaning a colorless or white, inorganic or synthetic particle which is insoluble in a possible liquid component in the composition according to the present invention, whatever the temperature at which the composition is manufactured.
The filler(s) may be inorganic or organic, and can be of spherical or oblong shape, whatever the crystallographic form (for example, sheet, cubic, hexagonal, orthorhombic, and the like). Non-limiting mention may be made of talc, mica, (hydrophilic) silica, kaolin, sericite, calcinated talc, calcinated mica, calcinated sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate and hydroxyapatite, powders formed of polyamide (Nylon®), of poly-[3-alanine and of polyethylene, powders formed of polyurethane, powders formed of tetrafluoroethylene polymers (Teflon®), lauryllysine, starch, polymeric hollow microspheres, such as those of poly( vinylidene chloride)/acrylonitrile, for example Expancel® (Nobel Industrie), or of acrylic acid copolymers, silicone resin microbeads (Tospearls® from Toshiba, for example), 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 from 8 to 22 carbon atoms, such as from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate.
For the present invention, examples of the filler include metal oxides, preferably titanium oxide, zinc oxide and a mixture thereof.
A filler that is suitable for the present invention may be, for example, a filler whose mean particle size is less than 100 pm, and especially between 1 and 50 pm, for example between 4 to 20 pm.
[Other Optional Additives]
The composition according to the present invention may comprise, in addition to the aforementioned components, components typically employed in cosmetics, specifically, surfactants (in particular, nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or non-volatile solvents, inorganic UV filters, silicones and silicone derivatives other than the (d) oil, natural extracts derived from animals or vegetables, waxes, and the like, within a range which does not impair the effects of the present invention.
The composition according to the present invention may comprise the above optional additive(s) in an amount of from 0.01% to 50% by weight, preferably from 0.05% to 30% by weight, and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.
[Composition]
The intended use of the composition according to the present invention may be as a cosmetic composition. Thus, the cosmetic composition according to the present invention may be intended for application onto a keratin substance. Keratin substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, nails, lips, hair, and the like. Thus, it is preferable that the cosmetic composition according to the present invention be used for a cosmetic process for the keratin substance, in particular skin.
Thus, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin makeup composition, and more preferably a skin care composition.
The composition according to the present invention can be prepared by mixing the above essential and optional ingredients in accordance with any of the processes which are well known to those skilled in the art.
If necessary, the above essential or optional ingredients may be heated. Thus, heating may be performed when mixing the above essential and optional ingredients.
As the composition according to the present invention includes the (a) organic UV filter which is oily, and (c) water, it can be in the form of an emulsion. The composition according to the present invention is in the form of a W/O emulsion.
[Cosmetic Process and Use]
The present invention can also relate to: a cosmetic process for a keratin substance such as skin, comprising: applying to the keratin substance the composition according to the present invention; and optionally drying the composition to form a film, preferably a cosmetic film, on the keratin substance, and a use of the composition according to the present invention for the preparation of a film, preferably a cosmetic film, on a keratin substance such as skin.
The cosmetic process here means a non-therapeutic cosmetic method for caring for and/or making up the surface of a keratin substance such as skin.
If the composition according to the present invention includes the DIC-gel described above, the film prepared by the composition according to the present invention is capable of self- healing or self-repairing. In other words, the film provided by the composition according to the present invention can be automatically repaired even though the film is broken due to, for example, scratching and the like, and therefore, long lastingness of cosmetic effects provided by the film can be improved.
Also, the above film may be resistant to water with a pH of 7 or less, and is removable with water with a pH of more than 7, preferably 8 or more, and more preferably 9 or more. In other words, the above film can be water-resistant under neutral or acidic conditions such as a pH of 7 or less, preferably in a range of 6 or more and 7 or less, and more preferably in a range of 5 or more and 7 or less, while the above film can be removed under alkaline conditions such as a 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.
Accordingly, the above film can be water-resistant, and therefore, it can remain on a keratin substance such as skin even if the surface of the keratin substance is wet due to, for example, sweat and rain. On the other hand, the above film can be easily removed from a keratin substance such as skin under alkaline conditions. Therefore, the above film is difficult to remove with water, while it can be easily removed with a soap which can provide alkaline conditions.
As the above film can include the organic UV filter which is originally present in the composition according to the present invention, the above film can protect a keratin substance such as skin from UV rays, thereby limiting the darkening of the skin, improving the colour and uniformity of the complexion, and/or treating aging of the skin.
Furthermore, the above film may have cosmetic effects such as absorbing or adsorbing malodour and/or protecting the keratin substance from, for example, dirt or pollutants, due to the properties of the DIC-gel in the film, even if the film does not include any cosmetic active ingredient.
In addition, the above film may immediately change or modify the appearance of the skin by changing light reflection on the skin and the like, even if the film does not include any cosmetic active ingredient. Therefore, it may be possible for the above film to conceal skin defects such as pores or wrinkles. Further, the above film may immediately change or modify the feeling to the touch of the skin by changing the surface roughness on the skin and the like. Furthermore, the above film may immediately protect the skin by covering the surface of the skin and shielding the skin, as a barrier, from environmental stresses such as pollutants, contaminants and the like.
The above cosmetic effects can be adjusted or controlled by changing the chemical composition, the thickness and/or the surface roughness of the above film.
If the above film includes at least one additional cosmetic active ingredient, the film can have cosmetic effects provided by the additional cosmetic active ingredient(s). For example, if the film includes at least one cosmetic active ingredient selected from anti-aging agents, antisebum agents, deodorant agents, anti-perspirant agents, whitening agents and a mixture thereof, the film can treat the aging of the skin, absorb sebum on the skin, control odors on the skin, control perspiration on the skin, and/or whiten of the skin.
It is also possible to apply a makeup cosmetic composition onto the above film after it has been applied onto the skin.
Furthermore, the present invention can also relate to a use of (b) at least one spherical hydrophobic silica in a composition in the form of an W/O emulsion, comprising (a) at least one organic UV filter, and (c) water, in order to enhance the UV absorbance of the composition and improve the spreadability of the composition. In other words, the addition of the (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 a keratin substance such as skin.
As a result, the composition according to the present invention, which is in the form of a W/O emulsion, comprising both (a) at least one UV filter, (b) at least one spherical hydrophobic silica, and (c) water can be easily spread on a keratin substance such as skin, while providing strong UV protection.
EXAMPLES
The present invention will be described in a more detailed manner by way of examples. However, they should not be construed as limiting the scope of the present invention.
[Examples 1 and 2 and Comparative Examples 1-3]
[Preparation]
Each of the compositions according to Examples 1 and 2 and Comparative Examples 1-3, in the form of a W/O emulsion, was prepared by mixing the ingredients shown in Table 1. The numerical values for the amounts of the ingredients in Table 1 are all based on “% by weight” as active materials.
Figure imgf000030_0001
Figure imgf000031_0001
[Evaluations]
(Spreadability)
5 professional panelists evaluated “spreadability” with the use of the same amount of each of the compositions according to Examples 1 and 2 and Comparative Examples 1-3.
Each panelist took each composition in their hands, then applied it on their faces to evaluate “spreadability” when applying each composition, and rated it from 1 (very poor) to 5 (very good), which was 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 be homogeneous. Each of the homogenous compositions was transferred onto a plate (Helio plate HD 6, PMMA, roughness: 6 pm) with an adjustable pipette in an amount of 20 mg/cm2 and then uniformly spread by the fingers. The coated plate was air dried for 15 minutes at room temperature. The obtained sample plate was placed into a Labsphere Ultraviolet Transmittance Analyzer (Model UV-2000 from Solar Light Company, Philadelphia, Pennsylvania). Irradiation of UV rays took place at 12 points on the sample plate. The UV absorbance by the sample plate in the wavelength range of from 290 to 420 nm was recorded.
The results are shown in Figure 1.
In addition, the UV absorbance at 310 nm of the compositions according to Examples 1 and 2 and Comparative Examples 1-3 is shown in Table 1.
It is clear from Figure 1 that the compositions according to Examples 1 and 2 have more enhanced UV absorbance than the composition according to Comparative Examples 1-3, in particular from 290 nm to 380 nm. It can be recognized that the enhanced UV absorbance is caused by the use of spherical hydrophobic silica.
In view of the evaluation results shown in Table 1 and Figure 1, it is clear 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 can provide both excellent texture and improved UV protection.

Claims

1. 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.
2. The composition according to Claim 1, wherein the (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, n-hexyl 2-(4-diethylamino-2- hydroxybenzoyl)benzoate, 1 , l'-( 1 ,4-piperazinediyl)bis [ 1 - [2- [4-(diethylamino)-2- hydroxybenzoyl]phenyl] -methanone 4-methylbenzylidene camphor, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, 2,4,6- tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine, 2,4-bis-(n-butyl 4’- aminobenzalmalonate)-6- [(3 -{1,3 ,3 ,3 -tetramethyl- 1 - [(trimethyl“,silyl“'oxy]~'disiloxanyl}propyl)amino]-s-triazine, 2,4,6-tris-(di-phenyl)- triazine, 2,4,6-tris-(ter-phenyl)-triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane, polysilicone-15, dineopentyl 4'- methoxybenzalmalonate, 1 , 1 -dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-l (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2- ethylhexyl)imino-l,3,5-triazine, camphor benzalkonium methosulfate and mixtures thereof.
3. The composition according to Claim 1 or 2, wherein the amount of the (a) organic UV filter(s) in the composition is 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.
4. The composition according to any one of Claims 1 to 3, wherein the (b) spherical hydrophobic silica has an average circularity determined by an image analysis method 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-absorbing capacity, measured at the wet point, of 2 ml/g or more, preferably 3 ml/g or more, more preferably 4 ml/g or more, and most preferably from 5 ml/g or more.
6. The composition according to any one of Claims 1 to 5, wherein the (b) spherical hydrophobic silica has a specific surface area determined by BET method of 200 m2/g or more, preferably 400 m2/g or more, and more preferably 500 m2/g or more.
7. The composition according to any one of Claims 1 to 6, wherein the (b) spherical hydrophobic silica has a pore volume determined by BJH method of 1 ml/g or more, preferably 2 ml/g or more, and more preferably 3 ml/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 determined by BJH method of 5 nm or more, preferably 10 nm or more, and more preferably 12 nm 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 from 0.5 pm to 30 pm, preferably from 1 pm to 20 pm, and more preferably from 2 pm to 15 pm.
10. The composition according to any one of Claims 1 to 9, wherein the amount of the (b) spherical hydrophobic silica(s) in the composition is 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.
11. The composition according to any one of Claims 1 to 10, wherein the weight ratio of the amount of the (a) UV filter(s) to the amount of the (b) spherical hydrophobic silica(s) 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 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, dimethicone, diisopropyl sebacate and mixtures thereof.
13. The composition according to any one of Claims 1 to 12, wherein the composition is a cosmetic composition, preferably a skin cosmetic composition, and more preferably a skin care or makeup cosmetic composition.
14. A cosmetic process for a keratin substance such as skin, comprising applying to the keratin substance the composition according to any one of Claims 1 to 13.
15. A 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, in order to enhance the UV absorbance of the composition and improve the spreadability of the composition.
PCT/JP2022/030919 2021-08-26 2022-08-09 W/o type composition comprising organic uv filter and spherical hydrophobic silica WO2023026893A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020237044679A KR20240012564A (en) 2021-08-26 2022-08-09 W/O type composition comprising organic UV filter and spherical hydrophobic silica
CN202280045961.7A CN117580562A (en) 2021-08-26 2022-08-09 W/O type composition comprising organic UV filter and spherical hydrophobic silica

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021138057A JP2023032127A (en) 2021-08-26 2021-08-26 W/o composition containing organic uv filter and spherical hydrophobic silica
JP2021-138057 2021-08-26
FR2110395A FR3127691A1 (en) 2021-10-01 2021-10-01 W/O TYPE COMPOSITION COMPRISING ORGANIC UV FILTER AND SPHERICAL HYDROPHOBIC SILICA
FR2110395 2021-10-01

Publications (1)

Publication Number Publication Date
WO2023026893A1 true WO2023026893A1 (en) 2023-03-02

Family

ID=83193239

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/030919 WO2023026893A1 (en) 2021-08-26 2022-08-09 W/o type composition comprising organic uv filter and spherical hydrophobic silica

Country Status (2)

Country Link
KR (1) KR20240012564A (en)
WO (1) WO2023026893A1 (en)

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
FR1492597A (en) 1965-09-14 1967-08-18 Union Carbide Corp New cellulose ethers containing quaternary nitrogen
US4131576A (en) 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
EP0173109A2 (en) 1984-08-23 1986-03-05 DeSOTO, INC. Alkali soluble latex thickeners
US5166355A (en) 1991-02-04 1992-11-24 Fairmount Chemical Co., Inc. Process for preparing substituted 2,2'-methylene-bis-[6-(2H-benzotriazol-2-yl)-4-hydrocarbyl-phenols]
WO1993004665A1 (en) 1991-08-29 1993-03-18 L'oreal Filtering cosmetic composition containing a liposoluble filter polymer with hydrocarbonated structure and a filter silicone
US5237071A (en) 1991-01-22 1993-08-17 Fairmount Chemical Company, Inc. Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)
US5240975A (en) 1988-04-11 1993-08-31 Ciba-Geigy Corporation Liquid substituted 2H-benzotriazole mixtures, stabilized compositions
EP0669323A1 (en) 1994-02-24 1995-08-30 Haarmann & Reimer Gmbh Utilization of benzazols as UV-absorbers, new benzazoles and process for their preparation
EP0750899A2 (en) 1995-06-30 1997-01-02 Shiseido Company Limited An emulsifier or solubilizer which consists of a water soluble amphiphilic polyelectrolyte, and an emulsified composition or a solubilized composition and an emulsified cosmetic or a solubilized cosmetic containing it
GB2303549A (en) 1995-07-22 1997-02-26 Ciba Geigy Ag Micronising organic UV absorbers with alkyl polyglucosides
DE19726184A1 (en) 1997-06-20 1998-12-24 Beiersdorf Ag Oil-in-water or multiple emulsion with high concentration of suspended UVB filter
EP0893119A1 (en) 1997-07-26 1999-01-27 Ciba SC Holding AG UV-protection formulation
DE19855649A1 (en) 1998-12-03 2000-06-08 Basf Ag Dimeric alpha-alkyl-styrene derivatives as photostable UV filters in cosmetic and pharmaceutical preparations
EP1069172A2 (en) 1999-07-11 2001-01-17 Moaz Betzer Tsilevich Endothermic heat shield composition
US6335037B1 (en) * 1999-03-17 2002-01-01 Shin-Etsu Chemical Co., Ltd. Cosmetic comprising spherical hydrophobic fine silica particles
US20100202984A1 (en) * 2005-07-25 2010-08-12 Heinz Langhals Naphthalene amidine imides
US20110020250A1 (en) * 2009-03-20 2011-01-27 Laurie Ellen Breyfogle Personal-care composition comprising a hydrocarbon wax and a polar oil
JP2011088832A (en) * 2009-10-20 2011-05-06 Shin-Etsu Chemical Co Ltd Cosmetic
JP2014088307A (en) 2012-10-03 2014-05-15 Tokuyama Corp Spherical shape oxide powder, and production method thereof
JP2014218433A (en) 2013-04-11 2014-11-20 株式会社トクヤマ Porous spherical metal oxide
US20140370062A1 (en) * 2011-11-07 2014-12-18 L'oreal Composition with a continuous oil phase containing at least one lipophilic organic uv-screening agent and hydrophobic silica aerogel particles
JP2018177620A (en) 2017-04-21 2018-11-15 株式会社トクヤマ Silica aerogel powder and production method thereof
JP2018188498A (en) * 2017-04-28 2018-11-29 ロレアル Composition in form of dispersion, preferably, emulsion, and more preferably, pickering emulsion
WO2021132044A1 (en) * 2019-12-24 2021-07-01 L'oreal Cosmetic composition in the form of w/o emulsion comprising spherical hydrophobic silica aerogel and ester oil

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
FR1492597A (en) 1965-09-14 1967-08-18 Union Carbide Corp New cellulose ethers containing quaternary nitrogen
US4131576A (en) 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
EP0173109A2 (en) 1984-08-23 1986-03-05 DeSOTO, INC. Alkali soluble latex thickeners
US5240975A (en) 1988-04-11 1993-08-31 Ciba-Geigy Corporation Liquid substituted 2H-benzotriazole mixtures, stabilized compositions
US5237071A (en) 1991-01-22 1993-08-17 Fairmount Chemical Company, Inc. Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)
US5166355A (en) 1991-02-04 1992-11-24 Fairmount Chemical Co., Inc. Process for preparing substituted 2,2'-methylene-bis-[6-(2H-benzotriazol-2-yl)-4-hydrocarbyl-phenols]
WO1993004665A1 (en) 1991-08-29 1993-03-18 L'oreal Filtering cosmetic composition containing a liposoluble filter polymer with hydrocarbonated structure and a filter silicone
EP0669323A1 (en) 1994-02-24 1995-08-30 Haarmann & Reimer Gmbh Utilization of benzazols as UV-absorbers, new benzazoles and process for their preparation
EP0750899A2 (en) 1995-06-30 1997-01-02 Shiseido Company Limited An emulsifier or solubilizer which consists of a water soluble amphiphilic polyelectrolyte, and an emulsified composition or a solubilized composition and an emulsified cosmetic or a solubilized cosmetic containing it
GB2303549A (en) 1995-07-22 1997-02-26 Ciba Geigy Ag Micronising organic UV absorbers with alkyl polyglucosides
DE19726184A1 (en) 1997-06-20 1998-12-24 Beiersdorf Ag Oil-in-water or multiple emulsion with high concentration of suspended UVB filter
EP0893119A1 (en) 1997-07-26 1999-01-27 Ciba SC Holding AG UV-protection formulation
DE19855649A1 (en) 1998-12-03 2000-06-08 Basf Ag Dimeric alpha-alkyl-styrene derivatives as photostable UV filters in cosmetic and pharmaceutical preparations
US6335037B1 (en) * 1999-03-17 2002-01-01 Shin-Etsu Chemical Co., Ltd. Cosmetic comprising spherical hydrophobic fine silica particles
EP1069172A2 (en) 1999-07-11 2001-01-17 Moaz Betzer Tsilevich Endothermic heat shield composition
US20100202984A1 (en) * 2005-07-25 2010-08-12 Heinz Langhals Naphthalene amidine imides
US20110020250A1 (en) * 2009-03-20 2011-01-27 Laurie Ellen Breyfogle Personal-care composition comprising a hydrocarbon wax and a polar oil
JP2011088832A (en) * 2009-10-20 2011-05-06 Shin-Etsu Chemical Co Ltd Cosmetic
US20140370062A1 (en) * 2011-11-07 2014-12-18 L'oreal Composition with a continuous oil phase containing at least one lipophilic organic uv-screening agent and hydrophobic silica aerogel particles
JP2014088307A (en) 2012-10-03 2014-05-15 Tokuyama Corp Spherical shape oxide powder, and production method thereof
JP2014218433A (en) 2013-04-11 2014-11-20 株式会社トクヤマ Porous spherical metal oxide
JP2018177620A (en) 2017-04-21 2018-11-15 株式会社トクヤマ Silica aerogel powder and production method thereof
JP2018188498A (en) * 2017-04-28 2018-11-29 ロレアル Composition in form of dispersion, preferably, emulsion, and more preferably, pickering emulsion
WO2021132044A1 (en) * 2019-12-24 2021-07-01 L'oreal Cosmetic composition in the form of w/o emulsion comprising spherical hydrophobic silica aerogel and ester oil

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Cosmetics and Toiletries", vol. 91, TODD & BYERS, article "Volatile Silicone Fluids for Cosmetics", pages: 27 - 32
"Walter Noll's Chemistry and Technology of Silicones", 1968, ACADEMIC PRESS
BARRETT, E. P.JOYNER, L. G.HALENDA, P. P., J. AM. CHEM. SOC., vol. 73, 1951, pages 373
MACROMOLECULES, vol. 33, no. 10, 2000, pages 3694 - 3704

Also Published As

Publication number Publication date
KR20240012564A (en) 2024-01-29

Similar Documents

Publication Publication Date Title
WO2018230673A1 (en) Composition comprising polyion complex particle and oil
CN107787214B (en) Oil-in-water emulsion composition
WO2018012557A1 (en) W/o sun care composition including porous organic particle
EP4259067A1 (en) Composition comprising polyion complex particle and filler
JP2019529424A (en) How to protect keratin materials from pollutants
CN110678168A (en) Cosmetic preparation
CN109069366B (en) UV-screening composition having matte effect and excellent texture
WO2023026893A1 (en) W/o type composition comprising organic uv filter and spherical hydrophobic silica
JP6831737B2 (en) Underwater oil type cosmetics
US20230025603A1 (en) Sun care composition
JP2023032127A (en) W/o composition containing organic uv filter and spherical hydrophobic silica
US20120148645A1 (en) Cosmetic composition based on substantially hemispherical particles
FR3127691A1 (en) W/O TYPE COMPOSITION COMPRISING ORGANIC UV FILTER AND SPHERICAL HYDROPHOBIC SILICA
US11833234B2 (en) Emulsions with a high internal oil phase
JP7403978B2 (en) W/O composition containing polyion complex and organic UV filter
WO2022124385A1 (en) Oil-in-water emulsion composition
EP3843689A1 (en) Foaming composition comprising oil
WO2021132734A1 (en) Composition comprising spherical hydrophobic silica aerogel and silicone polymer
KR20210093309A (en) topical
EP3975980A1 (en) Water-resistant cosmetic composition comprising light green clay and a probiotic-derived active ingredient
BR112019025398B1 (en) COMPOSITION, PROCESS FOR PREPARING A FILM, COSMETIC PROCESS FOR A KERATIN SUBSTRATE AND USE OF THE COMPOSITION

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22765243

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20237044679

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020237044679

Country of ref document: KR

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112023027480

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112023027480

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20231226

WWE Wipo information: entry into national phase

Ref document number: 2022765243

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2022765243

Country of ref document: EP

Effective date: 20240326