WO2025040281A1 - Two-step process for fixing a care and/or makeup product for keratin materials; fixing composition - Google Patents

Abstract

The present invention relates to a process for fixing a care and/or makeup product for keratin materials such as the skin, comprising at least the following steps: 1) applying, to the surface of the keratin material, a first layer constituted of a care and/or makeup composition (B); 2) applying, to the first layer thus formed, a second fixing layer by spraying with an aerosol device containing a composition (A) comprising, in particular in a physiologically acceptable medium: (a) at least one anionic fixing polymer of crotonic acid copolymer type; (b) at least one amphoteric fixing polymer chosen from polymers comprising units deriving: i) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group, ii) from at least one acidic comonomer containing one or more reactive carboxylic groups, and iii) from at least one basic comonomer; (c) at least one C2-C4 monoalcohol; (d) at least one plasticizer; and (e) at least one propellant.

Description

Two-step process for fixing a care and/or makeup product for keratin materials; fixing composition

The present application relates to the field of coating keratin materials, in particular the skin.

Currently, on the market for caring for and making up keratin materials such as the skin, many products claim a wear property that lasts for the whole day and is resistant to external attacking factors such as water, sebum, mechanical friction, etc. (long-lasting foundation), no transfer of the product to substrates such as clothing, and comfort on application. Long-lasting products for the face, which can be used at home, are mainly based on synthetic film-forming polymers in the presence of organic solvents. For compositions for making up the face, compositions comprising a silicone resin as film-forming agent are known, such as the compound with the INCI name: Trimethylsiloxysilicate or a compound with the INCI name: Polypropylsilsesquioxane, or else a silicone acrylate copolymer such as the product having the INCI name: Acrylates/Polytrimethylsiloxymethacrylate Copolymer).

Besides these long-lasting products, the current trend is towards semi-permanent makeup. More specifically, in recent years, conventional makeup products have encountered market competition from semi-permanent makeup in professional salons. It is encountered in the complexion sector (freckles, moles or whole face, fresh-faced or healthy glow effect). This new trend is driving consumers towards seeking increasingly long wear properties for greater practicality (avoiding having to apply and remove makeup daily, fresh-faced effect immediately on waking up, etc.).

Aerosol products for caring for and/or making up the face, which make it possible to fix previously applied makeup, are known on the market. They generally contain, in an aqueous, aqueous-alcoholic or anhydrous alcoholic medium, a fixing polymer such as the vinylpyrrolidone/vinyl acetate copolymer with the INCI name: VP/VA Copolymer and at least one propellant: butane, propane, isopropane. Mention may for example be made of the products Schwarzkopf Clock Block Make-Up Fixing Spray® (Henkel), Diego Dalla Palma Make-Up Fixer® (AGGF Cosmetic Group, Italy) and Make-Up Fixing Spray Catrice Haute Couleur® (Cosnova). Mention may also be made of the aqueous fixing aerosol with the film-forming polymers VP/Eicosene Copolymer and Dimethicone Crosspolymer.

Makeup fixing atomizers are also known that contain, in an alcoholic medium, a fixing polymer such as the copolymer Acrylates/Octylacrylamide Copolymer, for instance the commercial product Make-Up Fixing Spray My Health Mood Care® (Aeroflex Indústria de Aerossol), or the aqueous-alcoholic product April Skin Fixing Make-Up Fixer® with the film-forming polymer Polyvinylpyrrolidone (PVP).

However, these compositions are not entirely satisfactory in terms of wear property, in particular in terms of resistance to external attacking factors such as water, sebum and mechanical friction, in terms of non-transfer and/or in terms of comfort on application, in particular by depositing a film which crumbles (friable) and/or the tautness of the skin due to the lack of flexibility and elasticity of the deposited film.

The objective of the present invention is to provide novel aerosol devices for fixing a care and/or makeup product for keratin materials such as the skin which offer an excellent wear property for the expected cosmetic effects, in particular the colour of the makeup, good transfer-resistance properties with respect to substrates such as clothing, and also comfort on application to keratin materials, resulting in particular in the deposition of a flexible, elastic and non-friable film.

The applicant has discovered, surprisingly, that this objective can be achieved with a process for fixing a care and/or makeup product for keratin materials such as the skin, comprising at least the following steps:

1) applying, to the surface of the keratin material, a first layer (Base Coat) constituted of a care and/or makeup composition (B);

2) applying, to the first layer thus formed, a second fixing layer (Top Coat) by spraying with an aerosol device containing a composition (A) comprising, in particular in a physiologically acceptable medium:

(a) at least one anionic fixing polymer of crotonic acid copolymer type; and

(b) at least one amphoteric fixing polymer chosen from polymers comprising units deriving:

i) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,

ii) from at least one acidic comonomer containing one or more reactive carboxylic groups, and

iii) from at least one basic comonomer; and

(c) at least one C2-C4 monoalcohol; and

(d) at least one plasticizer; and

(e) at least one propellant.

Said aerosol device is capable, by spraying the composition (A) onto the first layer constituted of the composition (B), of producing a uniform, high wear, transfer-resistant film that is comfortable on application, in particular resulting in the absence of tackiness and tautness on the skin.

This discovery forms the basis of the invention.

Subjects of the invention

Thus, a first subject of the present invention is a process for fixing a care and/or makeup product for keratin materials such as the skin, comprising at least the following steps:

1) applying, to the surface of the keratin material, a first layer (Base Coat) constituted of a care and/or makeup composition (B);

2) applying, to the first layer thus formed, a second fixing layer (Top Coat) by spraying with an aerosol device containing a composition (A) comprising, in particular in a physiologically acceptable medium:

(a) at least one anionic fixing polymer of crotonic acid copolymer type; and

(b) at least one amphoteric fixing polymer chosen from polymers comprising units deriving:

i) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,

ii) from at least one acidic comonomer containing one or more reactive carboxylic groups, and

iii) from at least one basic comonomer; and

(c) at least one C2-C4 monoalcohol; and

(d) at least one plasticizer; and

(e) at least one propellant.

A second subject of the present invention is a cosmetic assembly or kit with two separately packaged components, comprising:

1) the aerosol device containing composition (A) and

2) the care and/or makeup composition (B).

A third subject of the present invention is a composition (A) as defined above containing no silicone, hydrocarbon propellant or hydrofluorocarbon agent.

Definitions

In the context of the present invention, the term "keratin material" is understood in particular to mean the skin (body, face, area around the eyes, eyelids), the lips and/or skin appendages such as the eyelashes or the eyebrows, and more particularly the skin.

The term “physiologically acceptable” means compatible with the skin and/or its integuments, which has a pleasant colour, odour and feel, and which does not cause any unacceptable discomfort (stinging or tautness) liable to discourage the consumer from using this composition.

Within the meaning of the present invention, the term "polymer" is understood to mean any material obtained by the (co)polymerization of monomers. These monomers can be identical or different. Unless otherwise indicated, the term polymers thus encompasses both homopolymers and copolymers.

Unless otherwise indicated, when the compounds are mentioned in the present patent application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the salts thereof or the solvates thereof, alone or as a mixture. In particular, reference to crotonic acid polymers, acidic comonomers containing one or more reactive carboxylic groups, or basic comonomers is also understood to mean the corresponding salts thereof.

For the purposes of the invention, the term "fixing polymer" is understood to mean any polymer capable, after application to keratin materials, in particular the skin, of forming a high wear film, in particular having good adhesion and good resistance to external attacking factors such as water, sebum and mechanical friction and also good transfer-resistance properties.

The term “silicone” is intended to mean any compound formed of a silicon-oxygen chain -Si-O-Si-O-Si-O in which organic groups attach to the silicon atoms.

The term "hydrocarbon" is understood to mean any compound constituted solely of carbon atoms and hydrogen atoms.

The term "hydrofluorocarbon" is understood to mean any compound constituted solely of carbon atom(s), hydrogen atoms and fluorine atom(s).

The expression “composition containing no silicone” is understood to mean any composition containing less than 1.0% by weight of silicone compound, indeed even less than 0.5% by weight, indeed even less than 0.1% by weight, relative to the total weight of the composition, indeed even free of silicone compound.

The expression “composition containing no hydrocarbon propellant” is understood to mean any composition containing less than 1.0% by weight of hydrocarbon propellant, indeed even less than 0.5% by weight, indeed even less than 0.1% by weight, relative to the total weight of the composition, indeed even free of hydrocarbon propellant.

The expression “composition containing no hydrofluorocarbon propellant” is understood to mean any composition containing less than 1.0% by weight of hydrofluorocarbon propellant, indeed even less than 0.5% by weight, indeed even less than 0.1% by weight, relative to the total weight of the composition, indeed even free of hydrofluorocarbon propellant.

Composition (A) (Top Coat)

Composition (A) according to the invention packaged in an aerosol device comprises, notably in a physiologically acceptable medium:

(a) at least one anionic fixing polymer of crotonic acid copolymer type; and

(b) at least one amphoteric fixing polymer chosen from polymers comprising units deriving:

i) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,

ii) from at least one acidic comonomer containing one or more reactive carboxylic groups, and

iii) from at least one basic comonomer; and

(c) at least one C2-C4 monoalcohol; and

(d) at least one plasticizer; and

(e) at least one propellant.

Anionic fixing polymer of crotonic acid copolymer type (a)

Anionic fixing polymers (a) of crotonic acid copolymer type that can be used in composition (A) of the invention may be chosen from those including vinyl acetate or propionate units in their chain and optionally other monomers such as allyl esters or methallyl esters, vinyl ethers or vinyl esters of a linear or branched saturated carboxylic acid having a long hydrocarbon chain, such as those comprising at least 5 carbon atoms, it optionally being possible for these polymers to be grafted or crosslinked, or alternatively another monomer which is a vinyl, allyl or methallyl ester of an α- or β-cyclic carboxylic acid.

The anionic fixing polymers (a) of crotonic acid copolymer type can be from 0 to 100% neutralized with an inorganic base such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) or with an organic base such as amines and amino alcohols. Use will more particularly be made of 1,3-dihydroxy-2-methyl-2-propylamine, also referred to as aminomethylpropanediol or AMPD, or 2-amino-2-methyl-1-propanol, also referred to as aminomethylpropanol (AMP), preferably 2-amino-2-methyl-1-propanol, also referred to as aminomethylpropanol.

Such polymers are described, inter alia, in the French patents FR1222944, FR1580545, FR2265782, FR2265781, FR1564110 and FR2439798.

Commercial products falling within this class are the commercial products RESYN® 28-2930 and RESYN® 28-1310 sold by Akzo Nobel, respectively having the INCI names: VA/CROTONATES/VINYL NEODECANOATE COPOLYMER which is a vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer and VA /CROTONATES COPOLYMER which is a vinyl acetate/crotonic acid copolymer.

Mention may also be made of the commercial products LUVISET® CA 66 sold by BASF, ARISTOFLEX® A60 sold by CLARIANT having the INCI name VA/CROTONATES COPOLYMER, and also the commercial products MEXOMERE® PW or MEXOMERE® PAM sold by CHIMEX with the INCI name: VA/VINYL BUTYL BENZOATE/CROTONATES COPOLYMER which is a vinyl acetate/vinyl butyl benzoate/crotonic acid terpolymer.

According to a particularly preferred form, use will be made of a vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer with the INCI name: VA/CROTONATES/VINYL NEODECANOATE COPOLYMER such as the commercial product RESYN® 28-2930 sold by Akzo Nobel.

According to a particularly preferred form, the anionic fixing polymer(s) (a) of crotonic acid copolymer type is (are) present in a total content ranging from 0.1% to 15% by weight, more preferentially from 1% to 10% by weight and better still from 3% to 8% by weight relative to the total weight of composition (A).

Amphoteric fixing polymer (b)

The amphoteric fixing polymers (b) are polymers comprising units deriving:

i) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,

ii) from at least one acidic comonomer containing one or more reactive carboxylic groups, and

iii) from at least one basic comonomer.

The N-substituted acrylamides or methacrylamides i) that are more particularly preferred according to the invention are compounds in which the alkyl groups include from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers ii) containing one or more reactive carboxylic groups are more particularly chosen from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, containing 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides.

The basic comonomers iii) are preferably chosen from esters bearing primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. More particularly, they are chosen from aminoethyl, butylaminoethyl, N,N’-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

Use will more particularly be made of the copolymer with the INCI name OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER, such as the products sold under the names Amphomer®, Amphomer® LV71 or Balance® 47 by the company AkzoNobel.

According to a particularly preferred form, the amphoteric fixing polymer(s) (b) is (are) present in a total content ranging from 0.01% to 10% by weight, more preferentially from 0.1% to 5% by weight and better still from 0.2% to 2% by weight relative to the total weight of composition (A).

C2-C4 monoalcohol (c)

Composition (A) according to the invention comprises at least one C2-C4 monoalcohol, preferably chosen from ethanol, isopropanol, propanol or butanol, and mixtures thereof, and more particularly ethanol.

The C2-C4 monoalcohol(s) is (are) preferably then present in a total content ranging from 20% to 95% by weight, and more preferentially ranging from 30% to 80% by weight, and more particularly from 40% to 60% by weight relative to the total weight of the composition (A).

Plasticizer (d)

The term "plasticizer" is understood to mean an organic chemical compound, which is in the solid state or in the liquid state, at room temperature (25°C) and at atmospheric pressure (760 mmHg or 10⁵ Pa), and which is added to a composition comprising various types of polymerizable ingredients (monomers) to make the polymer more supple, more flexible, and/or to improve its mechanical strength. Plasticizers are known to those skilled in the art; mention may be made, for example, of “Plasticizers”, Encyclopedia of Polymer Science and Technology, Helmut Reinecke, Rodrigo Navarro, Mónica Pérez, https:/doi.org/10.1002/0471440264.pst245.pub215 September 2011.

For the purposes of the invention, the plasticizers preferably have a molecular weight of between 100 and 1000 g/mol, particularly between 200 and 700, preferably between 250 and 500.

The agents are also organic compounds consisting of carbon and hydrogen atoms and of one or more heteroatoms chosen from oxygen, sulfur and silicon atoms, in particular chosen from oxygen and silicon atoms, preferably at least 3 heteroatoms, even more preferentially between 4 and 10 heteroatoms, and which may contain one or more aryl groups such as benzyl. In particular, they comprise one or more groups chosen from esters, phthalate, benzoate, sulfonate, citrate and siloxane.

Preferably, the plasticizer(s) of the invention are chosen from those of the phthalate, ester, citrate, benzoate and siloxane families, and mixtures thereof.

According to a particular embodiment of the invention, the plasticizer(s) are chosen from the compounds of formula (I) or (II) below:

(I)

in which:

- R^h and Rⁱ, which may be identical or different, represent a group from among: (C1-C20)alkyl, aryl such as phenyl, aryl(C1-C4)alkyl such as benzyl, preferably (C1-C4)alkyl such as n-butyl;

- n is 1, 2 or 3, preferably 2; and

- L represents a group from among: (1) divalent, trivalent or tetravalent C1-C10 alkyl, preferably trivalent (C2-C8)alkyl, said divalent, trivalent or tetravalent alkyl possibly being optionally substituted with one or more hydroxyl groups, (2) divalent or trivalent cycloalkyl, or

divalent, trivalent or tetravalent aryl, preferably divalent or trivalent phenyl; preferably, L represents a group (1)

(II)

in which:

- R^j, which may be identical or different, preferably identical, represent a group from among:

(C1-C10)alkyl, aryl such as phenyl, aryl(C1-C4)alkyl such as benzyl, preferably aryl such as phenyl,

- R^k, which may be identical or different, preferably identical, represent a hydrogen atom or a hydroxyl, (C1-C6)alkyl or (C1-C6)alkoxy group,

- L' represents a group chosen from a) divalent C2-C10 alkyl, preferably divalent (C4-C8)alkyl, which may be optionally substituted with one or more hydroxyl groups, and/or interrupted with one or more oxygen atoms, and/or interrupted with one or more divalent groups -Si(R^j)(R^k)- with R^j and R^k as defined previously, b) divalent or trivalent cycloalkyl, c) divalent, trivalent or tetravalent aryl, and d) -Si(R^j)(R^k)-; preferably, L' represents a group d) -Si(R^j)(R^k)-.

According to one particular embodiment of the invention, the compounds of formula (I) are chosen from the compounds of formula (I'):

(I')

in which:

- R^h and Rⁱ, which may be identical or different, represent a group from among: (C1-C6)alkyl,

aryl(C1-C4)alkyl such as benzyl, preferably (C1-C4)alkyl such as n-butyl;

- n is 1 or 2, preferably 2; and

- L represents a group from among: a) divalent, trivalent or tetravalent C2-C6 alkyl, preferably trivalent (C2-C8)alkyl, said alkyl possibly being optionally substituted with one or more hydroxyl groups, preferably substituted with one hydroxyl group.

According to one particular embodiment of the invention, the compounds of formula (II) are chosen from the compounds of formula (II'):

(II')

in which:

- R^j, which may be identical or different, preferably identical, represent a group from among: aryl such as phenyl, aryl(C1-C4)alkyl such as benzyl, preferably aryl such as phenyl, and

- R^k, which may be identical or different, preferably identical, represent a (C1-C6)alkyl and preferably (C1-C4)alkyl group such as methyl.

In particular, the plasticizer(s) of the invention are chosen from:

di-n-hexyl phthalate (DnHP), diisoheptyl phthalate, (DIHP), diheptyl phthalate (DnHP), di(2-ethylhexyl) phthalate (DEHP), diheptylnonyl phthalate (DnHNP),

di-n-octyldecyl phthalate (DNODP), diheptylnonylundecyl phthalate (DnHNUP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), di-n-nonyl phthalate (DnNP) diisodecyl phthalate (DIDP), di-n-nonyldecylundecyl phthalate (DnNDUP), dinonylundecyl phthalate (DnNUP), diundecyl phthalate (DUP), diisoundecyldodecyl phthalate (UDP), ditridecyl phthalate (DTDP), di(2-ethylhexyl) teraphthalate (DOTP), butylbenzyl phthalate (BBP), diheptylnonyl adipate (DnHNA), di(2-ethylhexyl) adipate (DEHA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), triheptylnonyl trimellitate (TnHNTM), tri(2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), di(2-ethylhexyl) sebacate (DOS), di(2-ethylhexyl) azelate (DOZ), tributyl citrate, triethyl citrate and trimethylpentaphenyltrisiloxane.

Preferably, the plasticizer(s) of the invention are chosen from

tri(C1-C6)alkyl citrates such as tributyl citrate and triethyl citrate and more particularly triethyl citrate.

Preferably, the plasticizer(s) according to the invention do not comprise a silicon atom in their structure.

According to one particular embodiment of the invention, the plasticizer(s) is (are) in a total amount ranging from 1% to 30% by weight, more preferentially from 5% to 20% by weight and better still from 7% to 15% by weight relative to the total weight of the fixing polymers (a) and (b).

According to another particular embodiment of the invention, the plasticizer(s) is (are) in a total amount ranging from 0.01% to 10% by weight, more preferentially from 0.1% to 5% by weight 12, better still from 0.2% to 2% by weight relative to the total weight of the composition (A).

Propellant (e)

The aerosol device according to the invention comprises one or more propellant(s) (e).

The propellants (e) may be chosen from compressed gases or liquefied gases.

Mention may be made, as examples of compressed gases, of air, nitrogen, carbon dioxide and mixtures thereof. Preferably, the compressed gas is carbon dioxide.

As examples of liquefied gases, mention may be made of dimethyl ether, chlorinated and/or fluorinated hydrocarbons, such as trichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, 1,1,1,2-tetrafluoroethane, chloropentafluoroethane, 1-chloro-1,1-difluoroethane or 1,1-difluoroethane, or volatile hydrocarbons, notably such as C3-C5 alkanes, such as propane, isopropane, n-butane, isobutane or pentane, alone or as a mixture. Preferably, the hydrocarbons are chosen from propane, isopropane, n-butane or isobutane, alone or as a mixture.

According to a particular embodiment, the propellant preferably comprises one or more liquefied gases, preferably dimethyl ether.

According to the invention, the propellant(s) (e) is (are) present in a total amount ranging from 20% to 70% by weight, preferably from 25% to 60% by weight, more preferentially from 30% to 50% by weight, better still from 35% to 45% by weight relative to the total weight of composition (A).

According to one preferred embodiment, the composition comprises dimethyl ether, the content of dimethyl ether ranging from 20% to 70% by weight, preferably from 25% to 60% by weight, more preferentially from 30% to 50% by weight, better still from 35% to 45% by weight, relative to the total weight of composition (A).

Water (f)

According to a preferred embodiment, the composition according to the invention further comprises (f) water. More preferentially, the water content in composition (A) ranges from 0.1% to 20% by weight, more particularly from 1% to 15% by weight and better still from 2% to 10% by weight, relative to the total weight of composition (A).

The water may be a demineralized water, or else a floral water, such as cornflower water, and/or a mineral water, such as Vittel water, Lucas water or La Roche Posay water, and/or a thermal water.

The water can form an aqueous phase with any type of water-soluble or water-miscible ingredient (miscibility with water of greater than 50% by weight at 25°C), for instance the abovementioned lower monoalcohols containing from 2 to 4 carbon atoms, polyols containing from 3 to 8 carbon atoms such as propylene glycol, 1,3-butylene glycol, caprylyl glycol, pentylene glycol, glycerol, and dipropylene glycol; C3-C4 ketones and C2-C4 aldehydes.

The compositions (A) containing no silicone, hydrocarbon propellant or hydrofluorocarbon propellant are novel per se and constitute another subject of the invention.

Aerosol device

The aerosol device comprising composition (A) according to the present invention is constituted of a container containing said composition (A) and of a means for spraying said composition.

The propellant(s) may be packaged together with the other components of composition (A) or separately. The contents described above are understood to mean propellant(s) included, whether it is (they are) packaged together with or separately from the other components of composition (A).

Composition (A) according to the invention is advantageously packaged under pressure, in an aerosol device, for example a one-piece device, which comprises a spraying means and a container.

The spraying means is generally constituted of a dispensing valve controlled by a dispensing head, itself comprising a nozzle through which the composition of the invention is sprayed.

The container containing the pressurized composition may be opaque or transparent. It may be made of glass, polymer material or metal, and may optionally be coated with a protective varnish layer.

Care and/or makeup composition (B) (Base Coat)

The care and/or makeup compositions (B) according to the invention are preferably chosen from gels, creams, milks and lotions.

Preferably, the compositions (B) according to the invention may be anhydrous formulations or aqueous formulations. They may be liquid or solid, such as hot-cast products or loose or compact powders.

The term "anhydrous" means that the composition contains less than 5% by weight of water relative to the total weight of the composition, or even less than 1% by weight, or even is free of water, water not being added during the preparation of the composition, but corresponding to the residual water supplied by the ingredients in the form of a mixture.

The care and/or makeup compositions (B) according to the invention may be chosen from aqueous dispersions, oily compositions, or multiphase compositions such as emulsions, for instance oil-in-water emulsions, water-in-oil emulsions, or two- or three-phase compositions. Suitable compositions (B) according to the invention may contain one or more compounds which are well known to those skilled in the art and generally present in foundations.

The compositions (B) according to the invention may additionally comprise additives commonly used in care and/or makeup products such as:

- volatile organic solvents and/or non-volatile organic solvents;

- active agents, for instance moisturizers such as hydroxyethyl urea, vitamins, for example vitamins A, E, C and B3, adenosine, and hyaluronic acid and salts thereof;

- ceramides;

- UV screening agents;

- colorants such as pulverulent colorants, water-soluble dyes, fat-soluble dyes;

- hydrophilic gelling agents;

- lipophilic gelling agents;

- fillers;

- fragrances;

- preserving agents;

- and mixtures thereof.

Such compositions (B) are in particular prepared according to the general knowledge of a person skilled in the art.

According to a particular embodiment, composition (B) is a skincare product, in particular an anti-sun product, a product for oily skin, a product for dry skin or an anti-ageing product.

According to a particular embodiment, composition (B) is a makeup product for the face such as a foundation; a makeup product for the eyelids, such as an eyeshadow; a makeup product for the cheeks, such as a face powder; a makeup product for the lips, such as lipsticks; a makeup product for the eyelashes or the eyebrows, such as mascaras or eyeliners.

Obviously, those skilled in the art will adapt the nature of the compounds and the solids content of the composition by using their common general knowledge to prepare a composition which can be used in the context of the invention.

For the high-viscosity compositions (B), such as thick creams, the viscosity, measured at 25°C and under atmospheric pressure, is greater than or equal to 4.5 Pa.s at a shear rate of 200 s^-1 and less than or equal to 50 Pa.s (using a Brookfield Rheomat RM 180® viscometer equipped with a No. 4 spindle, the measurement being effected after 10 minutes of rotation of the spindle in order to stabilize the rotational speed and the viscosity).

For the more fluid compositions (B), the viscosity may be less than 4.5 Pa.s, for example between 1 mPa.s (or 1 cps) and 4.5 Pa.s at a shear rate of 200 s^-1 (using a Brookfield Rheomat RM 180® viscometer equipped with a No. 4 spindle, the measurement being effected after 10 minutes of rotation of the spindle in order to stabilize the rotational speed and the viscosity).

Water-in-oil emulsions

According to a particular embodiment, composition (B) of the invention is a water-in-oil (W/O) emulsion.

For the purposes of the present invention, the term “water-in-oil emulsion”, also referred to as inverse emulsion, is understood to denote any composition constituted of a continuous oily phase in which the aqueous phase is dispersed in the form of droplets, so as to observe a mixture which is macroscopically homogeneous to the naked eye.

Emulsifiers with an HLB ≤ 8.0

The compositions (B) according to the invention in the form of a water-in-oil emulsion generally comprise one or more emulsifying surfactants with an HLB of less than or equal to 8.0, which are preferably nonionic surfactants.

According to one particular embodiment, the emulsifying surfactant(s) with an HLB of less than or equal to 8.0 is (are) present in contents ranging from 0.5% to 10% by weight, preferably from 2% to 8% by weight relative to the total weight of composition (B).

Within the meaning of the present invention, the term "emulsifying surfactant" is understood to mean an amphiphilic surface-active compound, that is to say one exhibiting two parts of different polarities. Generally, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). Emulsifying surfactants are characterized by the value of their HLB (Hydrophilic Lipophilic Balance), the HLB being the ratio of the hydrophilic part to the lipophilic part in the molecule. The term “HLB” is well known to a person skilled in the art and is described, for example, in “The HLB System. A Time-Saving Guide to Emulsifier Selection” (published by ICI Americas Inc.; 1984). For emulsifying surfactants, the HLB is less than or equal to 8.0 for the preparation of W/O emulsions. The HLB of the surfactant(s) used according to the invention can be determined by the Griffin method or the Davies method.

As examples of W/O emulsifying surfactants, mention may be made of alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars; silicone surfactants, such as dimethicone copolyols, such as the product having the INCI name DIMETHICONE (and) PEG/PPG-18/18 DIMETHICONE sold under the brand name X-22-6711D® by the company Shin-Etsu, the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C® by the company Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyl dimethicone copolyol, such as cetyl PEG/PPG-10/1 dimethicone, such as the product sold under the name Abil EM 90® by the company Evonik Goldschmidt, and the mixture of cetyl dimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name Abil WE 09® by the company Goldschmidt. One or more coemulsifiers, which may be chosen advantageously from the group comprising polyol alkyl esters, may also be added thereto.

Mention may also be made of non-silicone emulsifying surfactants, in particular alkyl esters or ethers of sorbitan, glycerol, polyol or sugars. Polyol alkyl esters that may notably be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name CITHROL DPHS-SO-(MV)® by the company Croda.

Examples of glycerol and/or sorbitan esters that may be mentioned include polyglyceryl isostearate (INCI name: Polyglyceryl-4 Isostearate), such as the product sold under the name Isolan GI 34® by the company Evonik Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986® by the company ICI, the diester of a mixture of isostearic, polyhydroxystearic and sebacic acids with Polyglycerin-4 (INCI name: Polyglyceryl-4 Diisostearate/Polyhydroxystearate/Sebacate), such as the product sold under the name Isolan GPS ® by the company Evonik, and mixtures thereof.

According to a particular form of the invention, the emulsifying surfactant may be chosen from emulsifying silicone elastomers.

The term "silicone elastomer" is intended to mean a supple, deformable organopolysiloxane that has viscoelastic properties and in particular the consistency of a sponge or a supple sphere. Its modulus of elasticity is such that this material withstands deformation and has limited stretchability and contractibility. This material is capable of regaining its original shape after stretching.

The emulsifying silicone elastomer may be chosen from polyoxyalkylenated silicone elastomers and polyglycerolated silicone elastomers, and mixtures thereof.

As polyoxyalkylenated silicone elastomers, use may be made of those having the following INCI names:

Dimethicone /PEG-10/15-Crosspolymer,

PEG-15/Lauryl Dimethicone Crosspolymer,

PEG-10/Lauryl Dimethicone Crosspolymer,

PEG-12 Dimethicone Crosspolymer,

PEG-10 Dimethicone Crosspolymer,

PEG-10 Dimethicone/Vinyl Dimethicone Crosspolymer,

PEG-12 Dimethicone/PPG-20 Crosspolymer, and mixtures thereof.

They are especially sold under the KSG® names by the company Shin-Etsu:

KSG-210® (INCI name: Dimethicone and Dimethicone/PEG-10/15- Crosspolymer

KSG-310® INCI name: PEG-15/Lauryl Dimethicone Crosspolymer and Mineral Oil;

KSG-320® INCI name: PEG-15/Lauryl Dimethicone Crosspolymer and Isododecane;

KSG-330® INCI name: PEG-15/Lauryl Dimethicone Crosspolymer and Triethylhexanoin;

KSG-340® INCI name: Squalane and PEG-15/Lauryl Dimethicone Crosspolymer.

They are especially sold by the company Dow Corning under the name Dow Corning 9011 Silicone Elastomer Blend®; INCI name: Cyclopentasiloxane and PEG-12 Dimethicone Crosspolymer. Mention may also be made of the product sold under the name Dow Corning EL-7040 Hydro Elastomer Blend® by the company Dow Corning for the compound with the INCI name: PEG-12 Dimethicone/PPG-20 Crosspolymer.

Use may be made, as polyglycerolated silicone elastomers, of the following compounds having the INCI name:

Dimethicone/Polyglycerin-3 Crosspolymer,

Lauryl Dimethicone/Polyglycerin-3 Crosspolymer, and mixtures thereof.

They are especially sold by the company Shin-Etsu under the following names:

KSG-710®; INCI name: Dimethicone/Polyglycerin-3 Crosspolymer and Dimethicone;

KSG-810®; INCI name: Mineral Oil and Lauryl Dimethicone/Polyglycerin-3 Crosspolymer;

KSG-820®; INCI name: Isododecane and Lauryl Dimethicone/Polyglycerin-3 Crosspolymer;

KSG-830®; INCI name: Triethylhexanoin and Lauryl Dimethicone/Polyglycerin-3 Crosspolymer;

KSG-840®; INCI name: Squalane and Lauryl Dimethicone/Polyglycerin-3 Crosspolymer.

Aqueous phase

The aqueous phase of a composition (B) according to the invention in the form of a water-in-oil emulsion comprises water and optionally one or more ingredients which are soluble or miscible in said aqueous phase, such as water-soluble solvents.

In the present invention, the term "water-soluble solvent" denotes a compound which is liquid at room temperature and miscible with water (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).

The water-soluble solvents which may be used in the composition of the invention may also be volatile.

Among the water-soluble solvents that may be used in the composition according to the invention, mention may be made in particular of lower monoalcohols containing from 2 to 4 carbon atoms such as ethanol and isopropanol, glycols containing from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C₃ and C₄ ketones and C₂-C₄ aldehydes.

The aqueous phase (water and optionally the water-miscible solvent) may be present in a content ranging from 1% to 80%, better still from 5% to 60% by weight and preferably from 10% to 55% by weight relative to the total weight of said composition (B).

According to one particular form, the water is present in a concentration ranging from 5% to 95% by weight, and more particularly from 10% to 90% by weight, relative to the total weight of said composition (B).

Oily phase

The oily phase of a composition (B) according to the invention in the form of a water-in-oil emulsion comprises at least one oil and optionally compounds which are soluble or miscible in said oily phase.

The term “oil” means any fatty substance that is in liquid form at ambient temperature (20-25°C) and atmospheric pressure (760 mmHg).

An oily phase that is suitable for preparing the compositions (A) according to the invention may comprise hydrocarbon oils, silicone oils and mixtures thereof.

The oils may be volatile or non-volatile.

They may be of animal, plant, mineral or synthetic origin. According to one implementation variant, oils of plant origin are preferred.

For the purposes of the present invention, the term “non-volatile oil” is understood to mean an oil with a vapour pressure of less than 0.13 Pa.

For the purposes of the invention, the term “volatile oil” refers to any oil that is capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, liquid at ambient temperature, having in particular a non-zero vapour pressure, at ambient temperature and atmospheric pressure, in particular having a vapour pressure ranging from 2.66 Pa to 40 000 Pa, especially ranging from 2.66 Pa to 13 000 Pa and more particularly ranging from 2.66 Pa to 1300 Pa.

For the purposes of the present invention, the term "silicone oil" is understood to mean an oil formed of a silicon-oxygen chain -Si-O-Si-O-Si-O in which organic groups attach to the silicon atoms.

For the purposes of the present invention, the term "hydrocarbon oil" is understood to mean an oil comprising at least carbon atoms and hydrogen atoms and optionally, in addition, oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.

The oily phase may be present in composition (B) according to the invention in a total content ranging from 1% to 90% by weight, preferably from 5% to 80% by weight, more preferentially ranging from 10% to 70% by weight, and more preferentially still from 25% to 60% by weight, relative to the total weight of composition (B).

Volatile oils

The volatile hydrocarbon oils which can be used in the compositions (A) according to the invention can be chosen from branched C₈-C₁₆ alkanes.

Mention may in particular be made, as C₈-C₁₆ isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the Isopar® or Permethyl® trade names.

Mention may also be made of branched C₈-C₁₆esters such asisohexyl neopentanoate. Other volatile hydrocarbon oils, such as petroleum distillates, in particular those sold under the name Shell Solt® by Shell, can also be used.

The volatile hydrocarbon oils which can be used in the compositions according to the invention can be chosen from volatile linear alkanes comprising from 6 to 14 carbon atoms.

Mention may be made, by way of examples of linear alkanes suitable for the invention, of the alkanes described in the patent applications WO 2007/068371 and WO 2008/155059 of Cognis (mixtures of different alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel oil or palm oil.

Mention may be made, by way of examples of linear C₆-C₁₄ alkanes suitable for the invention, of n-hexane (C₆), n-heptane (C₇), n-octane (C₈), n-nonane (C₉), n-decane (C₁₀), n-undecane (C₁₁), n-dodecane (C₁₂), n-tridecane (C₁₃), n-tetradecane (C₁₄) and their mixtures.

Mention may in particular be made of n-dodecane (C₁₂) and n-tetradecane (C₁₄), sold by Sasol respectively under the references Parafol 12-97® and Parafol 14-97®, and also their mixtures.

According to another embodiment, a mixture of n-dodecane and of n-tetradecane is used. Use may in particular be made of the dodecane/tetradecane mixture in the 85/15 weight ratio sold by Biosynthis under the reference Vegelight 1214®.

According to yet another embodiment, use is made of a mixture of volatile linear C₉-C₁₂ alkanes with the INCI name: C9-12 Alkane, such as the product sold by the company Biosynthis under the reference Vegelight Silk®.

According to yet another embodiment, use is made of a mixture of n-undecane (C₁₁) and of n-tridecane (C₁₃), such as those obtained in Examples 1 and 2 of Application WO 2008/155059 from Cognis and such as that sold under the trade name Cetiol Ultimate® by BASF.

According to one particularly preferred embodiment, the volatile hydrocarbon-based oil is chosen from branched C₈-C₁₆ alkanes, and more particularly is isododecane.

Volatile silicone oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, in particular those with a viscosity £ 5 centistokes (5 mm²/s), and in particular containing from 2 to 10 silicon atoms and preferably from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. Mention may in particular be made, as volatile silicone oil which can be used in the invention, of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

Non-volatile oils

Non-volatile hydrocarbon oils that may notably be mentioned include:

- hydrocarbon oils of animal origin,

- hydrocarbon oils of plant origin such as triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C₄ to C₂₄, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else caprylic/capric acid triglycerides, for instance those sold by the company Stéarinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel,

- synthetic ethers containing from 10 to 40 carbon atoms,

- linear or branched hydrocarbons, of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as

Parleam ® and squalane, liquid paraffins, and mixtures thereof,

- synthetic esters such as oils of formula R1COOR2 in which R1 represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a notably branched hydrocarbon chain containing from 1 to 40 carbon atoms, on the condition that R1 + R2 ³ 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, isodecyl neopentanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alkyl or polyalkyl heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters,

- fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol,

- higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof;

The nonvolatile silicone oils that may be used in the composition according to the invention may be nonvolatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, and mixtures thereof.

Pulverulent colorants

According to a particular form of the invention, the composition (B) according to the invention additionally comprises at least one pulverulent colorant.

The pulverulent colorants may be chosen from mineral pigments, organic pigments, pearlescent agents and mixtures thereof.

The term “pigments” means white or coloured, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify composition (B) and/or the resulting deposit. These pigments may be white or coloured, and mineral and/or organic.

According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

The term “mineral pigment” means any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on inorganic pigments. Mention may be made, among the mineral pigments which are of use in the present invention, of zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide or metal powders, such as aluminium powder and copper powder. The following mineral pigments may also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, ZrO₂ as a mixture with TiO₂, ZrO₂, Nb₂O₅, CeO₂ or ZnS.

The size of the pigment of use in the context of the present invention is generally greater than 100 nm and can range up to 10 µm, preferably from 200 nm to

5 µm and more preferentially from 300 nm to 1 µm.

According to a particular form of the invention, the pigments exhibit a size characterized by a D[50] of greater than 100 nm and which can range up to 10 µm, preferably from 200 nm to 5 µm and more preferentially from 300 nm to 1 µm.

The sizes are measured by static light scattering using a commercial particle size analyser of MasterSizer 3000® type from Malvern, which makes it possible to determine the particle size distribution of all of the particles over a wide range which can extend from 0.01 µm to 1000 µm. The data are processed on the basis of the conventional Mie scattering theory. This theory is the most suitable for size distributions ranging from the submicronic to multimicronic; it makes it possible to determine an “effective” particle diameter. This theory is described in particular in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.

D[50] represents the maximum size exhibited by 50% by volume of the particles.

According to a particular form of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating; the latter is preferably present in the oily phase of the composition (B) according to the invention.

According to a particular embodiment of the invention, the pigments can be coated according to the invention with at least one compound chosen from metal soaps; N-acylamino acids or their salts; lecithin and its derivatives; isopropyl triisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and their mixtures.

According to a preferential embodiment, the pigments can be coated according to the invention with an N-acylamino acid or one of its salts which can comprise an acyl group having from 8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.

The amino acid can, for example, be lysine, glutamic acid or alanine. The salts of these compounds can be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. Thus, according to a particularly preferred embodiment, the pigments can be coated with an N-acylamino acid derivative which can in particular be a glutamic acid derivative and/or one of its salts, and more particularly a stearoyl glutamate, such as, for example, aluminium stearoyl glutamate. Mention may be made, as examples of pigments treated with aluminium stearoyl glutamate, of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the trade name Nai® by Miyoshi Kasei.

According to a preferential embodiment, the pigments can be coated according to the invention with isopropyl triisostearyl titanate. Mention may be made, as examples of pigments treated with isopropyl titanium triisostearate (ITT), of those sold under the trade names BWBO-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BWYO-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate) and BWRO-I2® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by the company Kobo.

The pigments which can be used according to the invention can also be organic pigments.

The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on organic pigments. The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal-complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

The organic pigment(s) can be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Colour Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Colour Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Colour Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Colour Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Colour Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenol derivatives as are described in Patent FR 2 679 771.

These pigments can also be in the form of composite pigments as are described in patent EP 1 184 426 B1. These composite pigments can be composed in particular of particles comprising an inorganic core at least partially covered with an organic pigment and at least one binder providing the fixing of the organic pigments to the core.

The pigment can also be a lake. The term “lake” is understood to mean insolubilized dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

Mention may be made, among the organic dyes, of cochineal carmine. Mention may also be made of the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053) or D&C Blue 1 (CI 42 090).

Mention may be made, by way of example of a lake, of the product known under the name D&C Red 7 (CI 15 850:1).

Preferably, the composition according to the invention comprises at least one pulverulent dyestuff of mineral pigment type, in particular chosen from metal oxides, and more particularly chosen from titanium dioxides or iron oxides, which are or are not coated, and mixtures thereof.

The pearlescent agents can be chosen from white pearlescent pigments, such as mica covered with titanium or with bismuth oxychloride, coloured pearlescent pigments, such as titanium oxide-coated mica with iron oxides, titanium oxide-coated mica in particular with ferric blue or chromium oxide, or titanium oxide-coated mica with an organic pigment of the abovementioned type, and also pearlescent pigments based on bismuth oxychloride.

Preferably, the pulverulent colorant(s) is (are) preferably present in a content ranging from 0.5% to 30% by weight, preferably from 1% to 25% by weight, more particularly from 3% to 20% by weight, relative to the total weight of composition (B).

Fillers

According to a particular embodiment of the invention, the composition (B) additionally comprises at least one filler.

The term “fillers” should be understood as meaning colourless or white, mineral or synthetic particles of any shape, which are insoluble in the medium of the composition, irrespective of the temperature at which the composition is manufactured.

The fillers may be mineral or organic and of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders, poly-β-alanine powders, polyethylene powders, polymethyl methacrylates, polyurethane powders such as the powder of hexamethylene diisocyanate/trimethylol hexyllactone copolymer sold under the names PLASTIC POWDER D-400 by the company TOSHIKI, tetrafluoroethylene polymer (Teflon®) powders, micronized wax particles, in particular carnauba microwaxes, such as those sold under the name MicroCare 350® by the company Micro Powders, microwaxes of synthetic wax, such as those sold under the name MicroEase 114S® by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and of polyethylene wax, such as those sold under the names MicroCare 300® and 310® by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and of synthetic wax, such as those sold under the name MicroCare 325® by the company Micro Powders, polyethylene microwaxes, such as those sold under the names MicroPoly 200®, 220®, 220L® and 250S® by the company Micro Powders; and those sold under the name Cerapure H5-C by the company Shamrock, or polypropylene microwaxes such as those sold under the name Mattewax by the company Micro Powders; lauroyllysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie), acrylic acid copolymer microspheres, silicone resin powders, in particular silsesquioxane powders (silicone resin powders described in particular in patent EP 293795; for example Tospearls® from Toshiba), polyorganosiloxane elastomer particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres, glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate or lithium stearate, zinc laurate and magnesium myristate; barium sulfate, and mixtures thereof.

The fillers may be present in a total content ranging from 0.1% to 30% by weight, preferably ranging from 0.5% to 20% by weight and preferentially ranging from 0.8% to 10% by weight relative to the total weight of the composition (B).

Process for fixing a care and/or makeup product of composition (B)

Another subject of the present invention is a process for fixing a care and/or makeup product for keratin materials such as the skin, comprising the following steps:

a) applying, to the surface of the keratin material, a first layer (Base Coat) constituted of a care and/or makeup composition (B);

b) applying, to the first layer thus formed, a second fixing layer (Top Coat), constituted of the composition (A) as defined above, by spraying using the aerosol device containing it.

The leave-on time of the care and/or makeup composition (B) will vary according to its galenic form.

The drying time of the composition (A) Top Coat will generally be a few seconds.

Preferentially, the composition (A) packaged in an aerosol device will be sprayed at a distance ranging from 10 to 15 cm from the zone of keratin material to be treated.

It is understood that, in the context of the present invention, the weight percentages given for a compound or a family of compounds are always expressed as weight relative to the total weight of the composition.

Throughout the application, the term "contains one" or "comprises one" should be understood as meaning "containing at least one" or "comprising at least one", unless otherwise specified.

It is understood that the following examples are for illustrative purposes only and do not in any way limit the scope of protection conferred by the present invention.

Examples (A1), (Aa), (Ab), (Ac), (Ad), (Ae) and (B)

[Corrected under Rule 26, 16.09.2024]
The following fixing Top Coat compositions were prepared.

Each of these compositions was introduced into an aerosol device comprising an aluminium container, a COSTER® valve (internal spray nozzle: 0.4/Internal restriction: 2.5), with a 4 mm stem, a BUTYL® internal seal and a MILANO ® diffuser with a V06.235 nozzle.

[Corrected under Rule 26, 16.09.2024]
The following foundation Base Coat composition (B) was prepared:

Preparation of composition (B)

The components of phase a1 were weighed and the mixture was stirred at 55°C in order to obtain a homogeneous phase, and then cooled to 30°C. The components of phase a2 were then weighed and introduced into phase a1.

The aqueous phase b was emulsified in phase a with stirring for 20 minutes at 2500 rpm.

To prepare phase c, the pigments and the pearlescent agents were milled in an air jet mill with 11.1%, relative to their weight, of synthetic fluorophlogopite. Then c was introduced into the emulsion a+b with stirring for 10 minutes at 1500 rpm.

Test of in vitro wear property of the product obtained after application of the foundation base coat (B) and of the Top Coat aerosol fixing composition (A)

The wear property of the makeup was evaluated on a Supplale® support and Martindale® hot plate after application of the Base Coat foundation (B) and spraying of each of the Top Coat aerosol fixing compositions (A1), (Ab), (Ac), (Ad) and (Ae).

MATERIALS USED

Substrates

- 150 cm x 25 cm white Supplale® strip (supplier: Soudotique);

- 38 mm diameter circle of white WypAll® (supplier: PLG-KIMBERLY CLARK).

Apparatus

- Eppendorf® electronic pipette;

- Hot plate - Martindale®;

- IMEC® hyperspectral HSI camera connected to a computer;

- HIROX® camera connected to a computer.

Preparation of each sample of product obtained by application of the foundation base coat (B) and of each Top Coat aerosol fixing composition (A1), (Ab), (Ac), (Ad) and (Ae)

The hot plate was switched on at 32°C.

The area of application of the deposit of foundation (8 cm × 2.5 cm corresponding to a deposit area of 20 cm²) was delimited at the centre of the white Supplale® strip with a pencil.

The Eppendorf® pipette was programmed for taking 50 μl samples.

Each sample of foundation (B) was taken using the pipette and 50 μl were deposited on one of the sides of the application area (8 cm × 2.5 cm).

Each sample of foundation (B) was applied on a Supplale® strip with a single finger over the application zone by carrying out 10 passes from left to right and then 10 additional passes from right to left, ensuring uniform distribution over the entire application area.

The deposit of each sample was left to dry for 3 hours on the hot plate at 32°C.

Each strip of Supplale® covered by the Base Coat foundation (B) was suspended vertically and the aerosol containing one of the Top Coat aerosol fixing compositions (A1), (Ab), (Ac), (Ad), (Ae) was applied from 20 cm away with 3 back and forth movements, from bottom to top. It was then left to dry for 30 minutes.

The variation in the spectral angle SA and the variation in the % transfer were measured for each product thus obtained as an average of two tests.

The in vitro wear property and transfer resistance on Supplale® of the foundation (B) covered with each of the aerosol fixing compositions (A) was given by the graphical representation of the variation of the spectral angle SA as a function of the variation of the % transfer. The smaller the variation of the spectral angle SA, the stronger the in vitro "wear property". The smaller the variation in % transfer, the better the transfer resistance effect.

[Corrected under Rule 26, 16.09.2024]
The results obtained are indicated in the following table:

It was observed that the Top Coat fixing composition (A1) of the invention comprising a total amount of polymer active material equal to 6.6% by weight, namely the combination of the anionic crotonic acid copolymer VA/CROTONATES/VINYL DECANOATE COPOLYMER (6%) and of the amphoteric polymer OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER (0.6%) and a triethyl citrate plasticizing agent resulted, after spraying over the Base Coat foundation layer (B), in a better wear property compared to

- the comparative example (Ab) comprising 6.6% by weight of anionic crotonic acid copolymer VA/CROTONATES/VINYL DECANOATE COPOLYMER alone;

- the comparative example (Ac) comprising 6.6% by weight of amphoteric polymer OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER alone;

- the comparative example (Ad) having an identical composition but not containing any water-insoluble plasticizing agent;

- the comparative example (Ae) comprising 6% by weight of another anionic fixing polymer ACRYLATES/t-BUTYLACRYLAMIDE COPOLYMER and 0.6% by weight of amphoteric polymer OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER.

It was observed that the Top Coat fixing composition (A1) of the invention resulted, after spraying over the Base Coat foundation layer (B), in a better transfer resistance effect compared to the compositions outside the invention (Ab) and (Ad).

II/ Sensory tests on films formed by aerosol fixing compositions

For each of the Top Coat aerosol fixing compositions (A1), (Ac) and (Ae), 8 g of product to be tested were deposited in a Teflon Petri dish and left to dry for 2 days in a controlled atmosphere (24 h at 20% humidity).

Flexibility, elasticity and friability criteria of the film obtained

The performance in terms of flexibility, elasticity and friability of the film formed by each of the Top Coat fixing compositions (A1), (Ac) and (Ae) was evaluated blindly by 13 experts.

1) Flexibility

[Corrected under Rule 26, 16.09.2024]
Gesture: each of the experts folded the film between the fingers and graded its flexibility from 0 to 5 with 5 = very flexible and 0 = rigid.

2) Elasticity/Elastic deformation

[Corrected under Rule 26, 16.09.2024]
Gesture: each of the experts pulled on the film and graded its return to its initial position on a scale from 0 to 5 with 5 = highly deformable and 0 = not deformable.

3) Friability

[Corrected under Rule 26, 16.09.2024]
Each of the experts observed whether or not the film crumbled easily by grading it on a scale from 0 to 5 with 5 = very friable and 0 = not friable.

It was observed that the Top Coat fixing composition (A1) of the invention comprising a total amount of polymer active material equal to 6.6% by weight, namely the combination of the anionic crotonic acid copolymer VA/CROTONATES/VINYL DECANOATE COPOLYMER (6%) and of the amphoteric polymer OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER (0.6%) and a triethyl citrate plasticizing agent produced a film having better elasticity and flexibility properties compared to

- the example (Ac) outside of the invention comprising 6.6% by weight of amphoteric polymer OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER alone;

- the example (Ae) comprising 6% by weight of another anionic fixing polymer ACRYLATES/t-BUTYLACRYLAMIDE COPOLYMER and 0.6% by weight of amphoteric polymer OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER.

It was also observed that the Top Coat fixing composition (A1) of the invention produced a non-friable film, unlike the composition outside the invention (Ac).

Claims (23)

1. Process for fixing a care and/or makeup product for keratin materials such as the skin, comprising at least the following steps:
   1) applying, to the surface of the keratin material, a first layer constituted of a care and/or makeup composition (B);
   2) applying, to the first layer thus formed, a second fixing layer by spraying with an aerosol device containing a composition (A) comprising, in particular in a physiologically acceptable medium:
   (a) at least one anionic fixing polymer of crotonic acid copolymer type; and
   (b) at least one amphoteric fixing polymer chosen from polymers comprising units deriving:
   i) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,
   ii) from at least one acidic comonomer containing one or more reactive carboxylic groups, and
   iii) from at least one basic comonomer; and
   (c) at least one C2-C4 monoalcohol; and
   (d) at least one plasticizer; and
   (e) at least one propellant.
2. Process according to Claim 1, wherein, in composition (A), the anionic fixing polymer(s) (a) of crotonic acid copolymer type is (are) chosen from those including vinyl acetate or propionate units in their chain and optionally other monomers such as allyl esters or methallyl esters, vinyl ethers or vinyl esters of a linear or branched saturated carboxylic acid having a long hydrocarbon chain, such as those comprising at least 5 carbon atoms, it optionally being possible for these polymers to be grafted or crosslinked, or alternatively another monomer which is a vinyl, allyl or methallyl ester of an α- or β-cyclic carboxylic acid.
3. Process according to Claim 1 or 2, wherein, in composition (A), the anionic fixing polymer (a) of crotonic acid copolymer type is
   - a vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer with the INCI name: VA/CROTONATES/VINYL NEODECANOATE COPOLYMER;
   - a vinyl acetate/crotonic acid copolymer with the INCI name: VA/CROTONATES; or
   - a vinyl acetate/vinyl butyl benzoate/crotonic acid terpolymer
   with the INCI name: VA/VINYL BUTYL BENZOATE/CROTONATES COPOLYMER, and more particularly a vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer with the INCI name: VA/Crotonates/Vinyl Neodecanoate Copolymer
4. Process according to any one of the preceding claims, wherein, in composition (A), the anionic fixing polymer(s) (a) of crotonic acid copolymer type is (are) present in a total content ranging from 0.1% to 15% by weight, more preferentially from 1% to 10% by weight and better still from 3% to 8% by weight relative to the total weight of composition (A).
5. Process according to any one of the preceding claims, wherein, in composition (A), the amphoteric fixing polymer (b) is the terpolymer with the INCI name: OCTYLACRYLAMIDE/ACRYLATES/BUTYLAMINOETHYL METHACRYLATE COPOLYMER.
6. Process according to any one of the preceding claims, wherein, in composition (A), the amphoteric fixing polymer(s) (b) is (are) present in a total content ranging from 0.01% to 10% by weight, more preferentially from 0.1% to 5% by weight and better still from 0.2% to 2% by weight relative to the total weight of composition (A).
7. Process according to any one of the preceding claims, wherein, in composition (A), the C2-C4 monoalcohol (c) is chosen from ethanol, isopropanol, propanol or butanol, and mixtures thereof, and more particularly ethanol.
8. Process according to any one of the preceding claims, wherein, in composition (A), the C2-C4 monoalcohol(s) (c) is (are) present in a total content ranging from 20% to 95% by weight, and more preferentially ranging from 30% to 80% by weight and more particularly from 40% to 60% by weight relative to the total weight of composition (A).
9. Process according to any one of the preceding claims, wherein, in composition (A), the plasticizer(s) (d) is (are) chosen from those of the phthalate, ester, citrate, benzoate and siloxane families, and mixtures thereof.
10. Process according to any one of the preceding claims, wherein, in composition (A), the plasticizer(s) (d) is (are) chosen from tri(C1-C6)alkyl citrates such as tributyl citrate and triethyl citrate, and more particularly triethyl citrate.
11. Process according to any one of the preceding claims, wherein, in composition (A), the plasticizer(s) (d) is (are) in a total amount ranging from 1% to 30% by weight, more preferentially from 5% to 20% by weight and better still from 7% to 15% by weight relative to the total weight of the fixing polymers (a) and (b).
12. Process according to any one of the preceding claims, wherein, in composition (A), the plasticizer(s) (d) is (are) in a total amount ranging from 0.01% to 10% by weight, more preferentially from 0.1% to 5% by weight, better still from 0.2% to 2% by weight relative to the total weight of the composition (A).
13. Process according to any one of the preceding claims, wherein the propellant (e) is dimethyl ether.
14. Process according to any one of the preceding claims, wherein the propellant(s) (e) is (are) present in a total amount ranging from 20% to 70% by weight, preferably from 25% to 60% by weight, more preferentially from 30% to 50% by weight, better still from 35% to 45% by weight relative to the total weight of composition (A).
15. Process according to any one of the preceding claims, wherein composition (A) further comprises (f) water, preferably in a content ranging from 0.1% to 20% by weight, more preferentially from 1% to 15% by weight, better still from 2% to 10% by weight relative to the total weight of composition (A).
16. Process according to any one of the preceding claims, wherein composition (B) comprises at least one additive chosen from:
    - volatile organic solvents and/or non-volatile organic solvents;
    - active agents, such as moisturizers, vitamins, for example vitamins A, E, C and B3, adenosine, and hyaluronic acid and salts thereof;
    - ceramides;
    - UV screening agents;
    - colorants such as pulverulent colorants, water-soluble dyes, fat-soluble dyes;
    - hydrophilic gelling agents;
    - lipophilic gelling agents;
    - fillers;
    - fragrances;
    - preserving agents;
    - and mixtures thereof.
17. Process according to any one of the preceding claims, wherein composition (B) is a skincare product, in particular an anti-sun product, a product for oily skin, a product for dry skin or an anti-ageing product.
18. Process according to any one of the preceding claims, wherein composition (B) is a makeup product for the face such as a foundation; a makeup product for the eyelids, such as an eyeshadow; a makeup product for the cheeks, such as a face powder; a makeup product for the lips, such as a lipstick; a makeup product for the eyelashes or the eyebrows, such as a mascara or an eyeliner.
19. Process according to any one of the preceding claims, wherein composition (B) is a water-in-oil (W/O) emulsion comprising a continuous oily phase and an aqueous phase dispersed in the oily phase.
20. Process according to Claim 19, wherein composition (B) in the form of a water-in-oil emulsion comprises one or more emulsifying surfactants, which are preferably nonionic, with an HLB of less than or equal to 8.0.
21. Process according to Claim 20, wherein the emulsifying surfactant(s) with an HLB of less than or equal to 8.0 is (are) present in contents ranging from 0.5% to 10% by weight, preferably from 2% to 8% by weight relative to the total weight of composition (B).
22. Cosmetic assembly or kit with two separately packaged components, comprising:
    1) the aerosol device containing composition (A) as defined in the process according to any one of Claims 1 to 15 and
    2) composition (B) as defined in the process according to any one of Claims 1 and 16 to 21.
23. Composition (A) as defined in the process according to any one of Claims 1 to 15, containing no silicone, hydrocarbon propellant or hydrofluorocarbon agent.