FR3134988A1 - Makeup process with the application of a composition comprising a polyphenol and a polyoxyalkylenated and/or polyglycerol compound, and a coloring material then application of an anhydrous composition - Google Patents

Abstract

Title: Makeup process with the application of a composition comprising a polyphenol and a polyoxyalkylenated and/or polyglycerol compound, and a coloring material then application of an anhydrous composition The subject of the invention is a makeup process for the skin and/or or lips, consisting of implementing the following steps: 1) a coating agent formed in situ or previously by interaction by hydrogen bonds of at least one polyphenol different phenols with at least one compound Y capable of forming at least two hydrogen bonds with said phenol groups of polyphenol this step taking place in the presence of at least one coloring material; 2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated.

Description

Makeup process with the application of a composition comprising a polyphenol and a polyoxyalkylenated and/or polyglycerol compound, and a coloring material then application of an anhydrous composition

The subject of the present invention is a process for making up the skin and/or lips, in several stages, in which a coating agent formed in situ or previously, by interaction by hydrogen bond(s) of at at least one polyphenol of the application of a composition in the form of an emulsion.

Today on the skin and/or lip care and/or makeup market, many products claim to last all day, resistant to external factors such as water, sebum, food, mechanical friction. etc… These “long-lasting” products for the lips, or for the face, which can be used at home, are mainly based on synthetic coating polymers in the presence of organic solvents, most of the time volatile oils. For example, compositions are known comprising as coating agent a silicone resin, such as for example resins of the trimethylsiloxysilicate type (INCI name) or polypropylsilsesquioxane (INCI name) or even comprising silicone polymers such as silicone acrylate dendrimer copolymers (acrylates/ polytrimethylsiloxy-methacrylate copolymer – INCI name).

Another known way to protect color is to implement two-step makeup processes. In particular, they consist of depositing a first composition providing color then depositing a second composition on the first, usually transparent, with the aim of protecting the first colored layer. However, superimposing the layers is delicate because the application of the surface layer (top coat) must not damage the first layer (base coat). Furthermore, the deposit resulting from this superposition is often considered too thick and therefore uncomfortable because it is too present on the skin and/or lips.

Furthermore, in recent years, we have observed an increase in consumer demands regarding the composition of their cosmetic products. Indeed, the latter seek to use products containing an increasingly high content of natural ingredients or of natural origin, ingredients whose environmental impact is minimized and/or ingredients which are compatible with numerous packagings.

However, the difficulty remains in reconciling these latest trends with the fact that consumers do not want to give up the very high performance to which they are accustomed with the products they already use.

The present invention aims to propose compositions allowing excellent retention of the expected cosmetic effects in particular the color of makeup on the skin, the lips, which are resistant to mechanical friction, meals, water, sweat and perspiration, sebum, oil, or even cleaning products, particularly makeup removers, such as certain micellar waters and makeup remover wipes, for example.

Furthermore, the present invention aims to propose compositions and application methods providing hold with expected cosmetic effects, in particular the color of makeup, associated with an acceptable level of comfort.

These objectives and others are achieved by implementing the makeup process for the skin and/or lips, preferably the lips, consisting of implementing the following steps
1) a coating agent formed in situ or previously by interaction by hydrogen bonds of at least one polyphenol at least two hydrogen bonds with said phenol groups of polyphenol this step taking place in the presence of at least one coloring material;
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated.

Other aspects and advantages of the present invention will appear more clearly on reading the description and examples which follow.

In the context of the present invention, it is indicated that the skin designates the skin of the face (cheeks, eyelids, eye contour), of the body, of the hands.

The makeup and/or skin and/or lip care compositions according to the invention are cosmetic compositions. This implies that they advantageously comprise a physiologically acceptable environment. By "physiologically acceptable", we mean compatible with the skin and/or lips, which has a pleasant color, odor and touch and which does not generate unacceptable discomfort (tingling, tightness), likely to distract the consumer from 'use this composition.

For the purposes of the invention, the term “hydrogen bond interaction” means an interaction involving a hydrogen atom of one of the two reactants and an electronegative heteroatom of the other reactant such as oxygen, nitrogen, sulfur. and fluorine. In the context of the invention, the hydrogen bond(s) are made between the hydroxyl function(s) (OH) of the reactive phenol group(s). ) of polyphenol X and the hydroxyl group(s) of compounds Y capable of reacting by hydrogen bond(s) with polyphenol X.

By “room temperature” we mean 25°C.

By “atmospheric pressure”, we mean 760 mm of Hg or 1.013.10 ⁵ Pascals.

POLYPHENOL

The polyphenols X which can be used according to the present invention contain in their structure at least two different phenol groups.

By “polyphenol” is meant any compound having in its chemical structure at least two benzene compounds, in free or condensed form, each benzene compound comprising at least one hydroxyl group (OH), preferably at least 2 hydroxyl groups, or even 3 groups. hydroxyls.

By “different phenol groups” we mean chemically different phenol groups.

The polyphenols X which can be used according to the invention can be synthetic or natural. They can be in an isolated state or contained in a mixture, particularly contained in a plant extract. Polyphenols are phenols comprising at least two differently substituted phenolic groups on the aromatic ring.

The two classes of polyphenols are flavonoids and non-flavonoids.

Examples of flavonoids include chalcones such as phloretin, phloridzin, aspalathin or neohesperidin; flavanols such as catechin, fisetin, kaempferol, myricetin, quercetin, rutin, procyanidins, proanthocyanidins, pyroanthocyanidins, theaflavins or thearubigins (or thearubrins); dihydroflavonols such as astilbin, dihydroquercetin (taxifoline), or silibinin; flavanones such as hesperidin, neohesperidin, hesperetin, naringenin, naringin; anthocyanins such as cyanidin, delphinidin, malvidin, peonidin or petunidin; catechistic tannins such as tannic acid; isoflavonoids such as daidzein, or genistein; neoflavanoids; lignans such as pyroresorcinol; and their mixtures.

Among the natural polyphenols X which can be used according to the invention, we can also cite lignins.

As examples of non-flavonoids, we can cite curcuminoids such as curcumin or tetrahydrocurcumin; stilbenoids such as astringin, resveratrol or rhaponticin; aurones such as aureusidine; and their mixtures.

As polyphenols X which can be used according to the invention, we can also cite chlorogenic acid, verbascoside; coumarins substituted by phenols.

According to a particular embodiment of the invention, the polyphenol will be chosen from catechic tannins such as gallotannins chosen from tannic acid; ellagitannins such as epigallocatechin, epigallocatechin gallate, castalagin, vescalagin, vescaline, castaline, casuarictin, castanopsins, excoecarianins, grandinin, gradinin, roburines, pterocarinin, acutissimin, tellimagrandins, sanguiin, potentillin, pedunculagin, geraniin, chebulagic acid, diffusisinic acid, ascorgeraniin, stachyurine, casuarinin, casuariin, punicacortein, coriariin, cameliatannin, isodehydrodigalloyl , dehydrodigalloyl, hellinoyl, punicalagin, rhoipteleanins.

According to a particular mode of the invention, the polyphenol commercial product sold under the name DERMOFEEL PHENON 90 M-C® sold by the company Evonik Nutrition & Care or the commercial product sold under the name TEA POLYPHENOLS GREEN TEA EXTRACT® by the company Tayo Green Power.

According to a particular mode of the invention, the polyphenol procyanidins relative to the total weight of said extract such as the commercial product sold under the name PYCNOGENOL® sold by the company BIOLANDES AROMES.

We will use more particularly as polyphenol X, tannic acid. This compound is notably marketed under the name Brewtan F by the company AJINOMOTO OMNICHEM Nv.

Y COMPOUNDS

The compound(s) Y capable of forming at least two hydrogen bonds with said phenol groups of polyphenol

According to a particular embodiment, the compound(s) Y, in the medium of the composition, do not contain an anionic group in their chemical structure, and in particular are non-ionic.

Preferably, the compound(s) Y is/are chosen from compounds whose molar mass is greater than 200 g/mol, more particularly greater than 350 g/mol.

They are more particularly chosen from linear, branched or crosslinked, polyoxyethylenated and/or polyoxypropylenated and/or polyglycerolated silicone compounds, polyoxyethylenated and/or polyoxypropylenated alcohols, alkyl glycols or glycerin. polyoxyethylenated and/or polyoxypropylenated, polyethylene glycols, Poloxamer, polyoxyethylenated and/or polyoxypropylenated and/or polyglycerolated esters, polyoxyethylenated sorbitol or sorbitan esters and Polysorbates, ester or ether derivatives of polyoxyethylenated sugars, (poly)amines polyoxyethylene, as well as their mixtures.

Polyoxyethylenated and/or polyoxypropylenated and/or polyglycerolated silicone compounds

Nonionic, linear, branched or crosslinked, polyoxyethylenated and/or polyoxypropylenated and/or polyglycerolated polydimethylsiloxanes comprising from 2 to 50 oxyethylenated units and/or comprising from 2 to 50 oxypropylenated units and/or comprising from 2 to 20 glycerolated units, optionally comprising a alkyl group comprising 6 to 22 carbon atoms; nonionic polydimethylsiloxanes with ester(s) functions, polyoxyethylenated, comprising from 2 to 50 oxyethylenated units; as well as their mixtures.

Preferably, the compound(s) Y is/are chosen from the following compounds designated by their INCI name: PEG-10 dimethicone, PEG-12 dimethicone, PEG-9 polydimethyl-siloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, dimethicone/PEG -10/15 crosspolymer, PEG/PPG-17/18 Dimethicone, PEG/PPG-18/18 Dimethicone, PEG/PPG-22/24 Dimethicone, bis-PEG-12 dimethicone candelillate, Bis-PEG-12 dimethicone beeswax, Dimethicone /polyglycerin-3 crosspolymer as well as their mixtures.

Polyoxyethylenated and/or polyoxypropylenated alcohols

Among compounds of this type we can cite, alone or in mixtures:

Polyoxyethylenated fatty alcohols of the R(O-CH ₂ -CH ₂ )o-OH type, R representing a C ₈ -C ₃₀ alkyl radical, o representing an average integer ranging from 2 to 50 in particular chosen from Ceteth- 2, Ceteth-10, Ceteth-20, Ceteth-25, Ceteth-40, Isoceteth-20, Laureth-2, Laureth-3, Laureth-4, Laureth-12, Laureth -23, Oleth-2, Oleth-5, Oleth-10, Oleth-20, Oleth-25, Deceth-3, Deceth-5, Beheneth-10, Steareth -2, Steareth-10, Steareth-20, Steareth-21, Steareth-100, Ceteareth-10, Ceteareth-12, Ceteareth-15, Ceteareth-20, Ceteareth-25, Ceteareth -30, Ceteareth-33, Coceth-7, Trideceth-12, and their mixtures.

Polyoxyethylenated and polyoxypropylenated alcohols of type: R-(OC(CH ₃ )H-CH ₂ )o-(O-CH ₂ -CH ₂ )p-OH; R representing a C ₄ -C ₃₀ alkyl radical, o and p, independently of each other, representing an average integer ranging from 1 to 50. In particular, these compounds are chosen from the compounds with the following INCI names : PPG-26-Buteth-26, PPG-5-Ceteth-20, PPG-6-Decyltetradeceth-30, and their mixtures.

Polyoxyethylenated and/or polyoxypropylenated alkyl glycols or glycerin

We can cite in particular, alone or in mixtures:

Polyoxyethylenated glycerins, in particular oxyethylenated glycerin 26 EO (Glycereth-26).

Polyoxyalkylenated alkanediols such as PEG-8 Caprylyl Glycol.

Compounds of the type: R-(O-CH ₂ -CH ₂ )oO-CH ₂ -CH(R')OH in particular Ceteareth-60 Myristyl Glycol.

Polyoxyethylenated and/or polyoxypropylenated alkyl glycol ethers such as PPG-1-PEG-9 Lauryl Glycol Ether.

Compounds of the type H(O-CR-CH ₂ )o-(CH ₂ -CH ₂ -O)p-(CH ₂ -C(R)HO)rH
in particular PEG-45/Dodecyl Glycol Copolymer.

Polyethylene glycols

With regard to these compounds, the latter can be chosen, alone or in mixtures, from polyethylene glycols of the H(O-CH ₂ -CH ₂ )n-OH type, in particular chosen from PEG-6, PEG-8 , PEG-14M, PEG-20, PEG-45M, PEG-90, PEG-90M, PEG-150, PEG-180, PEG-220, and mixtures thereof.

The Poloxamers

Suitable for carrying out the invention are Poloxamer (INCI name) which correspond in particular to the following formula: HO-(CH ₂ -CH ₂ -O)n-(CHCH ₃ -CH ₂ -O) _O- (CH ₂ -CH ₂ -O) _p -H, and for example chosen from Poloxamer 124, Poloxamer 184, Poloxamer 338, Poloxamer 124, Poloxamer 184, Poloxamer 184, Poloxamer 338, as well as their mixtures.

Polyoxyethylenated and/or polyoxypropylenated and/or polyglycerolated esters

Suitable for example:

Polyethylene glycol and acid esters of the type:
R-CO-(O-CH ₂ -CH ₂ )n-OH or
R-CO-(O-CH ₂ -CH ₂ )qO-CO-R or
R-CO-(O-CH ₂ -CH ₂ )qOR or
RO-(CH(CH ₃ )-(CH ₂ ))p-(O-CH ₂ -CH ₂ )qO-CO-R
In which R represent, identical or not, saturated or unsaturated hydrocarbon groups, C2-C20; n, p, q, average integers, identical or not, varying from 2 to 150.

They may in particular be chosen from PEG-6 Isostearate, PEG-6 Stearate, PEG-8 Stearate, PEG-8 Isostearate, PEG-20 Stearate, PEG-30 Stearate, PEG-32 Stearate, PEG-40 Stearate, PEG-75 Stearate, PEG-100 Stearate, PEG-8 Distearate, PEG-150 Distearate, Mereth-3 Myristate, PEG-4 Olivate, Propylene Glycol Ceteth-3 Acetate, PEG -30 Dipolyhydroxystearate, as well as mixtures thereof.

Esters of glycerol and carboxylic acid(s) or polymer(s) of carboxylic acid(s) optionally hydroxylated at C ₆ -C ₄₀ , more particularly at C ₈ -C ₃₀ , or derived from vegetable oils, said esters being polyoxyethylenated, comprising from 2 to 200 oxyethylenated units, more preferably from 2 to 100 oxyethylenated units, even more particularly between 2 and 80 oxyethylenated units. These compounds are found more particularly in the form of mono-, di- or tri-glycerides, alone or in mixtures. As examples of such esters, mention may be made of PEG-6 Caprylic/Capric Glycerides, PEG-60 Almond Glycerides, PEG-10 Olive Glycerides, PEG-45 Palm Kernel Glycerides, PEG-7 Glyceryl Cocoate, PEG-30 Glyceryl Cocoate, PEG-40 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, PEG-30 Glyceryl Stearate, PEG-200 Glyceryl Stearate, PEG-20 Glyceryl Triisostearate, PEG-70 Mango Glycerides , Hydrogenated Palm/Palm Kernel Oil PEG-6 Esters, PEG-200 Hydrogenated Glyceryl Palmate, PEG-7 Glyceryl Cocoate, the mixture of polyoxyethylenated palm glycerides (200 EO) and polyoxyethylenated copra (7 EO), as well as their mixtures.

Polyglycerol esters comprising 2 to 20 glycerol units and carboxylic acid(s) or polymer(s) of carboxylic acid(s), saturated or unsaturated, comprising 6 with 40 carbon atoms, preferably 8 to 30 carbon atoms, or polyglycerol esters comprising 2 to 20 glycerol units and derivatives of vegetable oils, as well as mixtures thereof. Preferably, the compounds Y are chosen from polyglycerol esters comprising 2 to 20 glycerol units and carboxylic acid(s), saturated or unsaturated, comprising 6 to 40 carbon atoms, preferably 8 to 30 carbon atoms, or derivatives of vegetable oils, and mixtures thereof. The carboxylic acids may, among other things, comprise 1 to 3 carboxylic groups, and preferably, are monocarboxylic acids. Polyglycerol compounds are more particularly mono-, di- or triesters. As examples, we can cite the following compounds, designated by their INCI name: Polyglyceryl-2 Stearate, Polyglyceryl-2 Isostearate , Polyglyceryl-2 Diisostearate, Polyglyceryl-3 Diisostearate, Polyglyceryl-3 Dicitrate/Stearate, Polyglyceryl-4 Diisostearate, Polyglyceryl-4 Caprate, Polyglyceryl-4 Laurate , Polyglyceryl-5 Laurate, Poylglyceryl-5 oleate, Polyglyceryl-6 Caprylate, Polyglyceryl-6 dicaprate, Polyglyceryl-6 Distearate, Polyglyceryl-6 Caprylate/Caprate, Polyglyceryl-6 Dioleate, Polyglyceryl-6 trilaurate, Polyglyceryl-10 Laurate, Polyglyceryl-10 Dioleate, polyglycerol apricot kernel oil (Apricot Kernel Oil) esters comprising 3 to 10 glycerol units, as well as their mixtures.

Polyoxyethylenated butters, in particular polyoxyethylenated shea butter.

Polyoxyethylene waxes, in particular chosen from polyoxyethylene ester waxes such as polyoxyethylene jojoba wax (120 EO) (INCI name: Jojoba Wax PEG-120 Esters), PEG-8 Beeswax, PEG-60 Lanolin, PEG-75 Lanolin , PPG-12-PEG-50 Lanolin, and mixtures thereof

Polyoxyethylenated dihydrocholesteryl esters, in particular Dihydrocholeth-30.

PEG-55 Propylene Glycol Oleate.

Polyoxyethylenated pentaerythritol esters, in particular chosen from PEG-150 Pentaerythrityl Tetrastearate.

Polyoxyethylenated glycerol esters such as Glycereth-25 PCA Isostearate,

Polyoxyethylenated lanolins such as Laneth-15,

Their mixtures.

Polyoxyethylenated sorbitol or sorbitan esters and Polysorbates

These compounds are more particularly chosen from esters of sorbitol or sorbitan (also called sorbitan) and carboxylic acid(s), saturated or not, in C ₆ -C ₄₀ , advantageously in C ₈ - C ₃₀ , and comprise 2 to 50 oxyethylenated units.

Among the Polysorbates (INCI name), we can particularly cite the compounds with the following INCI names: Polysorbate-20, Polysorbate-21, Polysorbate-60, Polysorbate-61, Polysorbate-80, Polysorbate-85, as well as their mixtures. Among the esters, we can cite for example PEG-40 Sorbitan Peroleate.

Ester or ether derivatives of polyoxyethylenated sugars

The sugar derivatives are more particularly glucose derivatives such as for example polyoxyethylenated polyoxyethylenated alkylglucoses such as the compounds defined by the following INCI names: Methyl-Gluceth-10, Methyl-Gluceth-20. Polyoxyethylenated sugar esters are also suitable, for example the following INCI name compounds: PEG-120 Methyl Glucose Dioleate, PEG-20 Methyl Glucose Sesquistearate, as well as their mixtures.

Polyoxyethylenated (poly)amines

Suitable for carrying out the invention are polyoxyethylenated alkylamines , more particularly of formula RN[(CH ₂ -CH ₂ -O)H] _q [(CH ₂ -CH ₂ -O)rH] with R representing a hydrocarbon group, saturated or not, in C8-C30, and q or r, identical or not, represent an average integer ranging from 1 to 50 and in particular PEG-2-Oleamine. Polyoxyethylenated polyamines may also be suitable, for example PEG-15 Cocopolyamine.

Preferably, compound Y is chosen from the following compounds:
- Nonionic, linear, branched or crosslinked, (poly)oxyethylenated and/or (poly)oxypropylenated polydimethylsiloxanes comprising from 2 to 50 oxyethylenated units and/or comprising from 2 to 50 oxypropylenated units, optionally comprising an alkyl group comprising from 6 to 22 carbon atoms; nonionic polydimethylsiloxanes with ester(s) functions, polyoxyethylenated, comprising from 2 to 50 oxyethylenated units; as well as their mixtures;
- Polyoxyethylenated fatty alcohols of type R(O-CH ₂ -CH ₂ )o-OH, R representing a C ₈ -C ₃₀ alkyl radical, o representing an average integer ranging from 2 to 50;
- Polyoxyethylenated and oxypropylenated alcohols of type: R-(OC(CH ₃ )H-CH ₂ )o-(O-CH ₂ -CH ₂ )p-OH; R representing a C ₄ -C ₃₀ alkyl radical, o and p, independently of one another, representing an average integer ranging from 1 to 50; as well as their mixtures;
- polyglycerol esters comprising 2 to 20 glycerol units and carboxylic acid(s) or polymer(s) of carboxylic acid(s), saturated or unsaturated, comprising 6 to 40 carbon atoms, or derivatives of vegetable oils;
- Esters of glycerol and carboxylic acid(s) or polymer of carboxylic acid(s), saturated or unsaturated, in C ₆ -C ₄₀ , more particularly in C ₈ -C ₃₀ , or derivatives of vegetable oils, said esters being (poly)oxyethylenated, comprising from 1 to 200 oxyethylenated units; as well as their mixtures;
- Esters of sorbitan and carboxylic acid(s), saturated or not, C8-C30, polyoxyethylenated comprising from 2 to 50 oxyethylenated units; and particularly Polysorbates; as well as their mixtures;
- polyoxyethylenated alkylamines; the C8-C30 alkyl group, the number of oxyethylenated units between 1 and 50; as well as their mixtures;
- polyethylene glycols;
- their mixtures.

COMPOSITION (A) COMPRISING POLYPHENOL(S)

More particularly, composition (A) has a polyphenol(s) X content of at least 2% by weight, relative to the weight of composition (A). Preferably the content of polyphenol(s)

According to a first embodiment of the invention, composition (A) comprises water. It may for example be demineralized water, or even floral water such as cornflower water and/or mineral water such as VITTEL water, LUCAS water or water LA ROCHE POSAY and/or thermal water. More particularly, the water content is greater than or equal to 25% by weight, or even greater than 30% by weight, and more preferably ranging from 35 to 85% relative to the total weight of the composition (A).

Composition (A) may also comprise at least one C2-C8 mono alcohol, preferably C2-C5. As examples, we can cite ethanol, isopropanol, butanol, and preferably ethanol, isopropanol and even more preferably ethanol.

Preferably, the content of C2-C8 monoalcohol, preferably C2-C5, and more particularly ethanol, is greater than 25% by weight, or even greater than 30% by weight, and more preferably ranging from 35 to 85 % relative to the total weight of the composition (A).

The pH of composition (A) is preferably less than 8.0, more preferably less than 7.0, and more particularly varies from 2 to 6.

Composition (A) may optionally comprise other ingredients or solvents that are soluble or miscible in water (miscibility in water greater than 50% by weight at 25°C) such as polyols having 3 to 8 carbon atoms such as propylene glycol, 1,3-butylene glycol, caprylyl glycol, pentylene glycol, glycerin, dipropylene glycol; C ₃ -C ₄ ketones, C ₂ -C ₄ aldehydes.

According to another particular embodiment of the invention, composition (A) is anhydrous.

The term “anhydrous composition” means any composition comprising less than 5% by weight of water, or even less than 2% by weight, or even less than 1% by weight; relative to the total weight of the composition, or even free of water. Preferably, water is not deliberately added to the composition but may be present in small quantities, or even in trace amounts, in the various products used.

According to another particular embodiment of the invention, composition (A) comprises an oily phase.

The term “oil phase” means a liquid phase at room temperature and atmospheric pressure comprising at least one fatty substance, different from compounds Y, such as oils, waxes, pasty bodies as well as possibly all organic solvents and ingredients which are soluble or miscible in said phase.

Oils

The oil or oils may be chosen from volatile or non-volatile, polar or non-polar hydrocarbon oils, silicone oils, and mixtures thereof.

By “oil”, we mean a liquid fatty substance at room temperature (25°C) and atmospheric pressure (760mm Hg or 1,013.10 ⁵ Pa). The oil can be volatile or non-volatile.

For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si-O group, and more particularly an organopolysiloxane.

The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. These oils are therefore distinct from silicone oils.

By “volatile oil” is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13000 Pa, and more particularly ranging from 2.66 Pa to 1300 Pa.

By “non-volatile oil” is meant an oil remaining on the skin at room temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure less than 2.66 Pa, preferably less than 0.13 Pa. As for example, the vapor pressure can be measured using the static method or by the effusion method by isothermal thermogravimetry, depending on the vapor pressure (OECD standard 104).

Volatile hydrocarbon oils

Among the volatile hydrocarbon oils, mention may be made more particularly of those chosen from hydrocarbon oils of the hydrocarbon type (therefore non-polar hydrocarbon oils, consisting solely of carbon and hydrogen) as well as of the ester type. In particular, they can be chosen from volatile hydrocarbon oils having 8 to 16 carbon atoms and their mixtures, and in particular:
- branched C ₈ -C ₁₆ alkanes such as iso-alkanes (also called isoparaffins), isododecane, isodecane, isohexadecane, and their mixtures, and for example oils sold under the trade names of Isopars or Permetyls,
- linear alkanes, for example C ₁₁ -C ₁₅ , alone or in mixtures,
- branched C ₈ -C ₁₆ esters, for example iso-hexyl neopentanoate,
- their mixtures.

Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Solt by the company SHELL, can also be used; volatile linear alkanes such as those described in the patent application of the company Cognis DE10 2008 012 457.

Silicone volatile oils

Among the volatile silicone oils, mention may be made, among others, of linear, branched or cyclic silicone oils such as polydimethylsiloxanes (PDMS) having from 3 to 7 silicon atoms, preferably linear or branched polydimethylsiloxanes having from 3 to 7 silicon atoms. ; as well as their mixtures.

As an example of such oils, mention may be made of octyltrimethicone, hexyltrimethicone, methyl trimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethyltetrasiloxane, polydimethysiloxanes such as those marketed under the reference DC 200 (1 .5 cSt), DC 200 (3 cSt) by Dow Corning, or even KF 96 A from Shin Etsu; alone or in mixtures.

Polar non-volatile hydrocarbon oils

By “polar hydrocarbon oil” we mean an oil containing mainly hydrogen and carbon atoms and also comprising at least one oxygen atom. More particularly, such an oil comprises one or more functions chosen from hydroxyl, ester, ether, carboxylic, and preferably hydroxyl, ester, ether functions.

As an example of a non-volatile hydrocarbon oil which can be used in the invention, the following can be cited:
- triglycerides consisting of esters of fatty acids and glycerol, in particular the fatty acids of which may have chain lengths varying from C4 to C36, and in particular from C18 to C36, these oils being able to be linear or branched, saturated or unsaturated; these oils may in particular be heptanoic or octanoic triglycerides, wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soy, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, muscat rose; shea oil; or even caprylic/capric acid triglycerides such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
- linear aliphatic hydrocarbon esters of formula RCOOR' in which RCOO represents a carboxylic acid residue comprising from 2 to 40 carbon atoms, and R' represents a hydrocarbon chain containing from 1 to 40 carbon atoms, with at least such that cetostearyl octanoate, esters of isopropyl alcohol such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethyl-hexyl palmitate, stearate or isostearate isopropyl, isostearyl isostearate, octyl stearate, heptanoates, and in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate , tridecyl octanoate, 2-hexyl ethyl palmitate, alkyl benzoate, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, neopentanoate isostearyl, octyl-2-docecyl neopentanoate, esters of isononanoic acid such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, oleyl erucate; isocetyl stearate, isodecyl neopentanoate, isostearyl behenate;
- polyesters obtained by condensation of dimer and/or trimer of unsaturated fatty acid and diol such as those described in patent application FR 0 853 634, such as in particular dilinoleic acid and 1,4- butanediol. In particular, we can cite in this respect the polymer marketed by Biosynthis under the name Viscoplast 14436H® (INCI name: Dilinoleic Acid/Butane diol Copolymer), or even copolymers of polyols and diacid dimers, and their esters, such as Hailuscent ISDA ® ;
- esters and polyesters of linear fatty acids having a total carbon number ranging from 35 to 80 such as pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate;
- aromatic esters and polyesters such as tridecyl trimellitate, C12-C15 alcohol benzoate, 2-phenyl ethyl ester of benzoic acid, butyl octyl salicylate;
- esters and polyesters of dimer diol and mono-or dicarboxylic acid, such as esters of dimer diol and fatty acid and esters of dimer diol and dimer dicarboxylic acid, for example with INCI name: Dimer Dilinoleyl Dimer Dilinoleate, such as Lusplan DD-DA5® and Lusplan DD-DA7® marketed by the company NIPPON FINE CHEMICAL and described in application US 2004-175338, the content of which is incorporated into this application by reference;
- fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyl decanol, 2-undecyl pentadecanol, oleic alcohol;
- synthetic ethers having 10 to 40 carbon atoms such as dicaprylyl ether;
- di-alkyl carbonates, the two alkyl chains which may be identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC®, by Cognis;
- and their mixtures.

Non-polar non-volatile hydrocarbon oils

The oil can also be chosen from non-volatile apolar hydrocarbon oils, linear or branched, saturated or unsaturated, and preferably saturated.

The non-volatile non-polar hydrocarbon oil(s), linear or branched, are more particularly compounds comprising only carbon and hydrogen atoms (in other words, non-volatile oils of hydrocarbon type).

Said non-polar oils, linear or branched, can be of mineral or synthetic origin such as for example:
- paraffin oil,
- squalane,
- isoeicosane,
- mixtures of linear, saturated hydrocarbons, more particularly C ₁₅ -C ₂₈ , such as mixtures whose INCI names are for example the following: C15-19 Alkane (INCI name), C18-21 Alkane (INCI name) , C21-28 Alkane (INCI name), such as for example the products Gemseal 40, Gemseal 60, Gemseal 120 marketed by Total, Emogreen L19 marketed by SEPPIC,
- polybutenes, hydrogenated or not, such as for example products from the Indopol range marketed by the company INEOS Oligomers,
- polyisobutenes, hydrogenated or not, such as for example non-volatile compounds from the Parléam® range marketed by the company NIPPON OIL FATS,
- polydecenes, hydrogenated or not, such as for example non-volatile compounds from the PURESYN® range marketed by the company Exxonmobil),
- and their mixtures.

Non-volatile silicone oils

The non-volatile oil can also be chosen from phenyl or non-phenylated silicone non-volatile oils. More particularly, said silicone oils are devoid of (poly)alkoxylated groups, such as in particular (poly)ethoxylated or (poly)propoxylated groups, or (poly)glycerolated groups.

By “silicone oil”, within the meaning of the invention, is meant an oil comprising at least one silicon atom, and in particular at least one Si-O group.

More particularly, the non-volatile silicone oil, phenylated or non-phenylated, is chosen from dimethicones, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyltrimethicone, diphenylsiloxy phenyl trimethicone, as well as mixtures thereof. .

These products are notably marketed under the names PH-1555 HRI Cosmetic Fluid (Trimethyl Pentaphenyl Trisiloxane), Dow Corning 556 Cosmetic Grade Fluid (Phenyltrimethicone) by Dow Corning; Diphenyl Dimethicone such as the products KF-54, KF54HV, KF-50-300CS, KF-53 d, KF-50-100CS or Diphenylsiloxy Phenyl Trimethicone KF56 A marketed by Shin Etsu, marketed by Shin Etsu; the products Belsil PDM 1000, Belsil PDM 20 marketed by Wacker Chemie (Trimethylsiloxy Phenyl Dimethicone), alone or in mixtures. The values in parentheses represent the viscosities at 25°C (ASTM D-445 standard).

When composition (A) is anhydrous, preferably, the oily phase comprises at least one volatile hydrocarbon oil, more preferably chosen from C8-C16 isoalkanes of petroleum origin such as isodecane, isododecane, isohexadecane, and more particularly isododecane.

Raincoats

The composition may optionally comprise at least one wax.

By “wax” within the meaning of the present invention is meant a lipophilic compound, solid at 25°C, with a reversible solid/liquid state change, having a melting point greater than or equal to 40°C which can go up to 120°C.

For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in standard ISO 11357-3; 1999. The melting temperature of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "DSC Q2000" by the company TA Instruments.

The measurement protocol is as follows:
A wax sample of approximately 5 mg is placed in an airtight aluminum capsule crucible.
The sample is subjected to an initial rise in temperature ranging from -20°C to 120°C, at a heating rate of 10°C/minute, then is cooled from 120°C to -20°C at a rate of cooling of 10°C / minute and finally subjected to a second rise in temperature ranging from -20°C to 120°C at a heating rate of 5°C / minute. During the second rise in temperature, the melting temperature value of the solid fatty substance is measured which corresponds to the value of the top of the most endothermic peak of the observed melting curve, representing the variation in the difference in absorbed power as a function of temperature.

Waxes can be hydrocarbon-based, silicone-based, and of plant, mineral, animal and/or synthetic origin.

More particularly, the waxes are chosen from non-polar hydrocarbon waxes, polar hydrocarbon waxes, preferably esters, as well as mixtures thereof.

Among the nonpolar hydrocarbon waxes (that is to say comprising only carbon and hydrogen atoms in their structure), we can in particular cite polyethylene waxes, microcrystalline waxes, paraffin waxes, ozokerite , polymethylene waxes, waxes obtained by Fischer-Tropsch synthesis, microwaxes in particular of polyethylene, as well as their mixtures.

Among the polar hydrocarbon waxes (therefore comprising carbon, hydrogen and oxygen atoms), waxes advantageously comprising at least one alcohol, ester and/or ether group are suitable.

In particular, hydrocarbon waxes such as beeswax and lanolin wax can be used as wax; sunflower wax, rice wax, Carnauba wax, Candellila wax, Ouricury wax, Japanese wax, Berry wax, shellac wax and sumac wax; Montan wax, as well as their mixtures.

We can also cite waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, in C ₈ -C ₃₂ . Among these, we can notably cite hydrogenated jojoba oil, hydrogenated palm oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil. , di-(1,1,1-trimethylol propane) tetrastearate sold under the name "HEST 2T-4S®" by the company HETERENE, di-(1,1,1-trimethylol propane) tetrabehenate sold under the name name HEST 2T-4B® by the company HETERENE.

Also suitable are waxes of the (hydroxystearyloxy) C ₂₀ -C ₄₀ alkyl stearate type, alone or in a mixture, or a C ₂₀ -C ₄₀ alkyl stearate. Such waxes are sold in particular under the names “Kester Wax K 82 P®”, “Hydroxypolyester K 82 P®”, “Kester Wax K 80 P®”, or “KESTER WAX K82H” by the company KOSTER KEUNEN.

As an alcohol wax, we can cite mixtures of linear, saturated, C ₃₀ -C ₅₀ alcohols such as for example Performacol 550-L Alcohol wax from New Phase Technology, stearic alcohol and cetyl alcohol.

Paste compounds

By "pasty compound", within the meaning of the present invention, is meant a lipophilic fatty compound with a reversible solid/liquid state change, and comprising at a temperature of 20°C a liquid fraction and a solid fraction. Thus, a pasty compound may have a starting melting temperature lower than 20°C. Furthermore, the pasty compound can have an anisotropic crystalline organization in the solid state. The melting point of the pasty fatty substance is determined according to the same principle as that detailed previously for waxes.

In the case of a pasty compound, the measurement protocol is however as follows:
A sample of 5 mg of pasty fatty substance placed in a crucible is subjected to an initial rise in temperature ranging from -20°C to 100°C, at a heating rate of 10°C/minute, then is cooled by 100°C. C to -20°C at a cooling rate of 10°C/minute and finally subjected to a second rise in temperature ranging from -20°C to 100°C at a heating rate of 5°C/minute.
The melting point of the pasty fatty substance is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in absorbed power as a function of temperature.
It should be noted that the liquid fraction by weight of the pasty fatty substance at room temperature is equal to the ratio of the enthalpy of fusion consumed at room temperature to the enthalpy of fusion of the pasty fatty substance.
The enthalpy of fusion of the pasty fatty substance is the enthalpy consumed by the latter to go from the solid state to the liquid state. The pasty fatty substance is said to be in the solid state when its entire mass is in crystalline solid form. The pasty fatty substance is said to be in the liquid state when its entire mass is in liquid form.
The enthalpy of fusion of the pasty fat is the amount of energy required to change the pasty fat from the solid state to the liquid state. It is expressed in J/g. The enthalpy of fusion of the pasty fatty substance is equal to the area under the curve of the thermogram obtained.

Preferably, this or these pasty hydrocarbon compounds are chosen from:

- vegetable butters, such as for example mango butter, such as that marketed under the reference Lipex® 203 by the company AARHUSKARLSHAMN, shea butter, in particular that whose INCI name is Butyrospermum Parkii ButteR, such as that marketed under the Sheasoft® reference by the company AARHUSKARLSHAMN, cupuacu butter (Rain forest RF3410 from the company Beraca Sabara), murumuru butter (RAIN FOREST RF3710 from the company Beraca Sabara), cocoa butter, babassu butter such as that marketed under the name Cropure® Babassu by Croda, as well as orange wax such as, for example, that which is marketed under the reference Orange Peel Wax by the company Koster Keunen,

- partially hydrogenated vegetable oils, such as for example hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil, mixtures of hydrogenated vegetable oils such as the mixture of hydrogenated soya vegetable oil, copra, palm and rapeseed, for example the mixture marketed under the reference Akogel® by the company AARHUSKARLSHAMN (INCI name Hydrogenated Vegetable Oil), the partially hydrogenated trans isomerized jojoba oil manufactured or marketed by the company Desert Whale under the commercial reference Iso -Jojoba-50®, partially hydrogenated olive oil such as, for example, the compound marketed under the reference Beurrolive by the company Soliance,

- esters of hydrogenated castor oil and C16-C22 fatty acids, in particular isostearic acid such as the compound named INCI Hydrogenated Castor Oil Isostearate, for example SALACOS HCIS (V-L) sold by the company NISSHIN OIL ,

- triglycerides of fatty acids, saturated or unsaturated, linear or branched, optionally mono- or poly-hydroxylated, preferably C12-C18, optionally hydrogenated (totally or partially); such as for example glycerides of C12-C18 saturated fatty acids marketed under the name Softisan 100® by the company Cremer Oleo (INCI name: Hydrogenated Coco-Glycerides),

- polyesters resulting from the condensation of a linear or branched C6-C10 dicarboxylic acid and ester of diglycerol and monocarboxylic acids, optionally hydroxylated, linear or branched, in C6-C20, such as in particular the ester obtained by condensation of adipic acid and a mixture of diglycerol esters with a mixture of C6-C20 fatty acids such as caprylic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, and INCI name Bis-Diglyceryl Polyacyladipate-2. This type of compound is notably marketed under the reference Softisan® 649 by the company Cremer Oleo.

- polyesters obtained from an acid dimer, said acid being unsaturated and comprising from 16 to 24 carbon atoms, and at least one alcohol or polyol, such as for example:
* esters of dimer diol (for example of dilinoleic alcohol) and of dilinoleic acid whose hydroxyl groups are esterified with a mixture of phytosterols, behenyl alcohol and isostearyl alcohol, for example the ester sold under the name Plandool G by the company Nippon Fine Chemical (INCI name: Bis-Behenyl / Isostearyl / Phytosteryl Dimer Dilinoleyl Dimer Dilinoleate);
* esters of dilinoleic acid and a mixture of phytosterols, isostearyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol, for example the ester sold under the name Plandool H or Plandool S by the company Nippon Fine Chemical (INCI name: Phytosteryl/Isostearyl/Cetyl/Stearyl/Behenyl Dimer Dilinoleate);
* esters of hydrogenated castor oil and dilinoleic acid, such as those sold under the names RISOCAST-DA-L or RISOCASTDA-H by the company KOKYU ALCOHOL KOGYO (INCI name: Hydrogenated Castor Oil Dimer Dilinoleate).

Preferably, if the composition comprises them, the pasty hydrocarbon compound(s) are chosen from vegetable butters, partially hydrogenated vegetable oils, compounds with the INCI name Phytosteryl/Isostearyl/Cetyl/Stearyl/Behenyl Dimer Dilinoleate, Hydrogenated Coco-Glycerides, Bis-Diglyceryl Polyacyladipate-2 as well as their mixtures.

When composition (A) is anhydrous, the concentration in the oily phase of said composition is preferably greater than or equal to 5% by weight, more particularly greater than 10% by weight, and more particularly varies from 20 to 85% by weight per relative to the total weight of the composition relative to the total weight of the composition (A).

COMPOSITION (B) INCLUDING COMPOUNDS Y

The content of compound(s) Y in composition (B) advantageously represents at least 1% by weight, more particularly from 1 to 75% by weight, preferably from 2 to 50% by weight relative to the total weight of the composition. (B).

According to a first embodiment of the invention, the composition (B) comprising the compound(s) Y comprises at least water. It may for example be demineralized water, or even floral water such as cornflower water and/or mineral water such as VITTEL water, LUCAS water or water LA ROCHE POSAY and/or thermal water.

The quantity of water is preferably greater than or equal to 25% by weight, or even greater than 30% by weight, and more preferably ranging from 35 to 85% by weight, relative to the total weight of the composition (B).

Composition (B) may also comprise at least one C2-C8 mono alcohol, preferably C2-C5. As examples, mention may be made of ethanol, isopropanol, butanol, and preferably ethanol, isopropanol, preferably ethanol.

Preferably, the content of C2-C8 monoalcohol, preferably C2-C5, and more particularly ethanol, is greater than 25% by weight, or even greater than 30% by weight, and more preferably ranging from 35 to 85 % relative to the total weight of the composition (B).

The pH of composition (B) is preferably less than 8.0, more preferably less than 7.0, and more particularly varies from 2 to 6.

Composition (B) may optionally comprise other ingredients or solvents that are soluble or miscible in water (miscibility in water greater than 50% by weight at 25°C) such as polyols having 3 to 8 carbon atoms such as propylene glycol, 1,3-butylene glycol, caprylyl glycol, pentylene glycol, glycerin, dipropylene glycol; C3-C4 ketones, C2-C4 aldehydes.

According to another embodiment of the invention, composition (B) is anhydrous.

According to another embodiment, composition (B) may comprise at least one oily phase as defined above.

When composition (B) is anhydrous, preferably, the oily phase comprises at least one volatile hydrocarbon oil, more preferably chosen from C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isodecane, isohexadecane , isododecane and more particularly isododecane.

When composition (B) is anhydrous, the concentration in the oily phase of the composition of the invention is preferably greater than or equal to 5% by weight, more particularly greater than 10% by weight, and more particularly varies from 20 to 85 % by weight relative to the total weight of the composition (B).

Preferably, if composition (B) comprises an oily phase, this comprises at least one non-volatile polar hydrocarbon oil. It preferably does not contain silicone oil, volatile or non-volatile.

Of course, those skilled in the art will take care to choose the compositions (A) and (B) so that they are compatible and can be mixed and the quantities making it possible to obtain in the mixture obtained, the formation of a coating agent by hydrogen bond interaction of polyphenol X with compounds Y as defined.

COMPOSITION (C)

The present invention also relates to a composition (C) comprising, in particular in a physiologically acceptable medium, at least one coating agent previously formed by interaction by hydrogen bonds of at least one polyphenol .

Previously trained coating agent

The coating agent present in the compositions of the invention is obtained by reacting by interaction by hydrogen bonds, at room temperature and atmospheric pressure, at least one polyphenol X with at least one compound Y; these compounds being as described above.

Advantageously, the content of previously formed coating agent varies from 1 to 60% by weight, more preferably ranging from 2 to 40% by weight, preferably ranging from 10 to 40% by weight relative to the total weight of the composition. (VS).

Process for preparing coating agent

The reaction medium can be aqueous, hydrophilic or anhydrous. Ideally the solvent in which the coating agent is prepared is easily removable, in particular by evaporation. Thus, the coating agent can be advantageously synthesized in water or in a volatile oil such as those indicated above, preferably isododecane.

The polyphenol X and the compounds Y are preferably introduced into the reaction medium with a ratio of the mass of polyphenol and 3, preferably between 0.5 and 2.

The order of introduction does not matter. The contact time can be very quick or it can be left to incubate with stirring (a few hours).

The precipitate obtained corresponding to the coating agent is recovered either by filtration of the solvent or centrifugation or by evaporation of the solvent.

The precipitate is then washed several times in order to eliminate the initial reagents which were not involved in the constitution of the precipitate. The washing solvent is more particularly chosen from the solvents of polyphenol X and/or associated Y compounds. Ideally the washing solvent is water.

The number of washes can be determined by dosing the polyphenol X recovered in the wash water. When the rate is low we can consider that the excess reagents have been eliminated. The quantity of solvent present in the precipitate is more particularly less than 40% by weight relative to the weight of precipitate, or even less than 35% by weight relative to the weight of the precipitate.

Then the precipitate can be dried, in particular in the open air, under a heated atmosphere, under vacuum or freeze-dried.

According to a particular embodiment of the invention, the composition (C) comprises at least water. It may in particular be demineralized water, or even floral water such as cornflower water and/or mineral water such as VITTEL water, LUCAS water or water from LA ROCHE POSAY and/or thermal water.

Depending on the nature of the aqueous composition (C), the quantity of water is preferably greater than 30% by weight, or even greater than 40% by weight, and more preferably ranging from 30 to 75% by weight relative to the total weight. of the composition (C).

The composition comprises at least one coloring material which will be described later.

According to another particular embodiment, composition (C) may comprise at least one oily phase as defined above.

According to a particular embodiment of the invention, composition (C) is anhydrous.

According to another particular embodiment, the composition (C) can be presented in a multiphasic form, for example in the form of an oil-in-water emulsion (continuous aqueous phase in which an oily phase is dispersed in the form of droplets so as to obtain a macroscopically homogeneous mixture), in the form of a water-in-oil emulsion (continuous oily phase in which an aqueous phase is dispersed in the form of droplets so as to obtain a macroscopically homogeneous mixture).

When the composition (C) contains water, the pH of the aqueous phase is preferably less than 8.0, more preferably less than 7.0, and more particularly varies from 2 to 6.

When the composition (C) comprises an oily phase, this comprises at least one oil

When the composition (C) comprises an oily phase, the concentration in the oily phase is preferably greater than 10% by weight, or even greater than 20% by weight, and more preferably varies from 30 to 75% relative to the total weight of the composition (C).

Preferably, if composition (C) comprises an oily phase, this comprises at least one non-volatile polar hydrocarbon oil. It preferably does not contain silicone oil, volatile or non-volatile.

When composition (C) is an emulsion, it may comprise one or more emulsifying surfactants.

For the purposes of the present invention, the term “emulsifying surfactant” means an amphiphilic surfactant compound, that is to say having two parts of different polarity. In general, 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 (Hydrophile Lipophile balance or hydrophilic balance). -lipophilic), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule. The term HLB is well known to those skilled in the art and it 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 generally ranges from 3 to 8 for the preparation of water-in-oil (W/O) emulsions. The HLB is greater than 8 for the preparation of O/W emulsions. The HLB of the surfactant(s) used according to the invention can be determined by the GRIFFIN method or the DAVIES method.

According to a preferred form of the invention, when the composition (C) is anhydrous, the oily phase of the composition (C) comprises at least one volatile hydrocarbon oil, preferably chosen from hydrocarbon oils having 8 to 16 carbon atoms , and in particular C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane, isodecane, isohexadecane, and particularly isododecane.

The quantity of volatile hydrocarbon oil(s) can preferably range from 20% to 80% by weight, and even more preferably from 30% to 70% by weight, relative to the total weight of said composition. (VS).

According to a preferred embodiment of the invention, in order to improve the dispersibility of the coating agent homogeneously in the composition (C), a thickening system (polymers, waxes or pasty bodies), a suspending agent can be added. or an emulsifying system in particular of the lamellar phase type.

COMPOSITION (D)

Another object of the invention relates to a composition (D) comprising, in particular in a physiologically acceptable medium,
a) at least one polyphenol X as defined above,
b) at least two compounds Y as defined above, and
c) at least one mono-alcohol comprising from 2 to 8 carbon atoms, more particularly comprising from 2 to 5 carbon atoms, and preferably ethanol, isopropanol, even more preferably ethanol.

In this composition, the coating agent is in the latent state and only fully appears in situ, that is to say once composition (D) has been applied to the skin and/or lips. In other words, in composition (D), before its application, the conditions (ingredients, contents) are such that they do not favor the interaction of polyphenol(s) X and compound(s) Y between them. Preferably, these compounds do not precipitate in the composition before its application.

Preferably, the content of polyphenol of said composition.

Preferably, the content of compounds Y in composition (D) represents at least 1% by weight, more particularly at least 2% by weight, preferably from 2 to 40% by weight, relative to the total weight of said composition.

More particularly, the ratio of the mass of polyphenol X, expressed as active material, to the mass of compound(s) Y, expressed as active material, varies between 0.25 and 3, preferably between 0 ,5 and 2.

Advantageously, the content of C2-C8 mono-alcohol, more particularly C2-C5, in particular ethanol, is such that compounds X and Y do not react in composition (D) before its application. Said mono alcohol can thus be considered as an inhibitor of hydrogen bonds. By “hydrogen bond inhibitor agent” is meant any compound capable of preventing the interaction by hydrogen bonds between the polyphenol X and the compounds Y and/or of dissociating the complex formed by said interaction by breaking the hydrogen bonds. More particularly, the C2-C8 monoalcohol content is at least 25% by weight, in particular between 25 and 98% by weight, more particularly between 30 and 85% by weight and even more particularly between 35 and 80%. % by weight, relative to the total weight of said composition (D).

In accordance with a first embodiment of the invention, composition (D) comprises water. Here again, it can be demineralized water, or even floral water such as cornflower water and/or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and/or thermal water.

More particularly, the composition (D) comprises a water content less than or equal to less than or equal to 15% by weight, more particularly less than or equal to 10% by weight, relative to the total weight of the composition (D). In accordance with a particularly advantageous embodiment of the invention, the water content of composition (D) is between 0 and 5% by weight, limits included, relative to the total weight of said composition.

If the composition comprises water, then the pH of the aqueous phase is advantageously less than 8.0, more preferably less than 7.0, and more particularly varies from 2 to 6.

The composition may optionally comprise other ingredients or solvents that are soluble or miscible in water (miscibility in water greater than 50% by weight at 25°C) such as polyols having 3 to 8 carbon atoms such as propylene. glycol, 1,3-butylene glycol, caprylyl glycol, pentylene glycol, glycerin, dipropylene glycol; C ₃ -C ₄ ketones, C ₂ -C ₄ aldehydes.

According to a particular embodiment of the invention, composition (D) comprises an oily phase.

We can refer to the definition of the oily phase detailed previously during the description of composition (A).

More particularly, when composition (D) comprises it, the oily phase content is between 1 and 30% by weight, preferably between 1 and 25% by weight, relative to the total weight of said composition.

According to a first variant of the invention, if the oily phase is present in the composition, then it comprises at least one non-volatile oil.

According to another variant of the invention, the oily phase is present and comprises at least one volatile oil, preferably a siliconized volatile oil. Preferably, the content of volatile silicone oil is less than or equal to 10% by weight, relative to the total weight of the composition.

In accordance with another embodiment of the invention, the oily phase is present and comprises at least one volatile oil, preferably hydrocarbon-based. More particularly the content of volatile oil, preferably hydrocarbon, is less than or equal to 20% by weight, advantageously less than or equal to 10% by weight, more particularly less than or equal to 9% by weight, preferably less than or equal to 8 % by weight and even more precisely less than or equal to 5% by weight, relative to the total weight of the composition. Advantageously, composition (D) does not include volatile silicone oil.

Composition (D) is advantageously in liquid form.

Composition (D) may also comprise at least one wax. We can refer to the list indicated previously in the description of the composition (A). The content of wax(es), if composition (D) includes any, generally varies between 0.1 to 5% by weight, more particularly from 0.5 to 5% by weight, relative to the total weight of said composition. .

Composition (D) may optionally include at least one pasty compound, as described previously in the description of composition (A). If composition (D) comprises it, the content of pasty compound(s) is more particularly less than or equal to 20% by weight, preferably between 0.5 and 10% by weight, relative to the total weight of the composition .

Composition (D) can also be found in a monophasic or multiphasic form, in particular in the form of a biphasic composition. It should be noted that the phases may or may not be underdispersed into each other.

COLORING MATERIAL

According to a particular embodiment of the invention, the composition (A), (B), (C) and/or (D) comprises at least one coloring material, in particular chosen from synthetic, natural or natural coloring materials. .

More particularly, the content of coloring matter(s) of composition (A) and/or (B), of composition (C), of composition (D) is at least 0.01% in weight, more particularly between 0.05 and 30% by weight, in particular between 0.1 and 25% by weight, relative to the total weight of the composition concerned.

The coloring material can be chosen from coated or uncoated pigments, water-soluble dyes, fat-soluble dyes, and mixtures thereof.

Pigments

The term “pigments” means white or colored particles, mineral or organic, insoluble in the medium of the composition, intended to color and/or opacify the composition and/or the resulting deposit.

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

By “mineral pigment”, we mean any pigment which meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue. , chromium hydrate and ferric blue, titanium dioxide, metal powders such as aluminum powder and copper powder. The following mineral pigments can also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 mixed with TiO2, ZrO2, Nb2O5, CeO2, ZnS.

The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can go up to 10 μm, preferably from 200 nm to 5 μm, and more preferably from 300 nm to 1 μm.

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

The sizes are measured by static light scattering using a commercial particle size analyzer such as MasterSizer 3000® from Malvern, making it possible to understand the particle size distribution of all the particles over a wide range ranging from 0.01 µm. at 1000 µm. The data is processed based on classical Mie diffusion theory. This theory is most suitable for size distributions ranging from submicron to multi-micron, it makes it possible to determine an “effective” particle diameter. This theory is described in particular in the work of Van de Hulst, H.C., “Light Scattering by Small Particles”, Chapters 9 and 10, Wiley, New York, 1957.

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

In the context of the present invention, the mineral pigments are more particularly iron oxide and/or titanium dioxide. By way of example, we can cite more particularly titanium dioxides and iron oxide, coated with aluminum stearoyl glutamate, for example marketed under the reference NAI® by the company MIYOSHI KASEI.

As mineral pigments usable in the invention, we can also cite mother-of-pearl.

By “pearl”, we must understand colored particles of any shape, iridescent or not, in particular, produced by certain molluscs in their shell or synthesized and which present a color effect by optical interference.

The nacres can be chosen from pearlescent pigments, such as titanium mica coated with iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which at least two successive layers of metal oxides and/or organic coloring materials are superimposed.

We can also cite, as an example of mother-of-pearl, natural mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride.

Mother-of-pearl can more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or reflection.

Among the pigments which can be used according to the invention, we can also cite those with an optical effect different from a simple conventional tint effect, that is to say unified and stabilized as produced by conventional coloring materials, such as, for example , monochromatic pigments. For the purposes of the invention, “stabilized” means devoid of the effect of color variability with the angle of observation or in response to a change in temperature.

For example, this material can be chosen from particles with a metallic reflection, goniochromatic coloring agents, diffracting pigments, thermochromic agents, optical brightening agents, as well as fibers, in particular, interference fibers. Of course, these different materials can be combined in such a way as to provide the simultaneous manifestation of two effects, or even a new effect in accordance with the invention.

According to a particular embodiment, the composition ((A), (B), (C) and/or (D) according to the invention comprises at least one uncoated pigment.

According to another particular embodiment, the composition (A), (B), (C) and/or (D) according to the invention comprises at least one pigment coated with at least one lipophilic or hydrophobic compound.

This type of pigment is particularly advantageous. To the extent that they are treated with a hydrophobic compound, they show a predominant affinity for an oily phase which can then transport them.

The coating may also include at least one additional non-lipophilic compound.

For the purposes of the invention, “the coating” of a pigment according to the invention generally designates the total or partial surface treatment of the pigment with a surfactant, absorbed, adsorbed or grafted onto said pigment.

The surface-treated pigments can be prepared using chemical, electronic, mechano-chemical or mechanical surface treatment techniques well known to those skilled in the art. Commercial products can also be used.

The surfactant can be absorbed, adsorbed or grafted onto the pigments by solvent evaporation, chemical reaction and creation of a covalent bond.

According to one variant, the surface treatment consists of coating the pigments.

The coating can represent from 0.1% to 20% by weight, and in particular from 0.5% to 5% by weight, of the total weight of the coated pigment.

The coating can be carried out for example by adsorption of a liquid surfactant on the surface of the solid particles by simple mixing with stirring of the particles and said surfactant, possibly hot, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating can be carried out for example by chemical reaction of a surfactant with the surface of the solid pigment particles and creation of a covalent bond between the surfactant and the particles. This method is described in particular in US patent 4,578,266.

Chemical surface treatment may involve diluting the surfactant in a volatile solvent, dispersing the pigments in this mixture, and then slowly evaporating the volatile solvent, so that the surfactant is deposited on the surface pigments.

When the pigment comprises a lipophilic or hydrophobic coating, the latter is preferably present in the fatty phase of the composition 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 silicone surfactants; fluorinated surfactants; fluoro-silicone surfactants; metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and their mixtures.

According to a particular embodiment of the invention, the pigments can be coated with a hydrophilic compound.

According to another particular mode, the coloring material is an organic, synthetic, natural pigment or of natural origin.

By “organic pigment”, we mean any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment may in particular be chosen from the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

The organic pigment(s) may be chosen for example from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47 005, pigments green pigments coded in the Color Index under the references CI 61565, 61570, 74260, orange pigments coded in the Color Index under the references CI 11725, 15510, 45370, 71105, red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 5800 0, 73360, 73915, 75470, and the pigments obtained by oxidative polymerization of indolic and phenolic derivatives as described in the patent
FR 2 679 771.

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

The pigment can also be a lacquer. By lacquer we mean insolubilized dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

The inorganic substrates on which the dyes are adsorbed are for example alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

Among the organic dyes, we can cite cochineal carmine. We can also cite 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), D&C Blue 1 (CI 42 090).

As examples of lacquers, we can cite the product known under the name D&C Red 7 (CI 15 850:1).

The pigment(s) are preferably present in the composition ((A), (B), (C) and/or (D) at contents of at least 0.01% by weight, more particularly at least 1 % by weight, and even more particularly at least 2% by weight, relative to the weight of the composition concerned. More particularly, the coloring material content is less than 50% by weight, and more particularly between 0.05 and 30% by weight, and even better from 0.1 to 25% by weight relative to the total weight of the composition concerned (A), (B), (C) and/or (D).

Water-soluble or fat-soluble dyes

According to another particular embodiment of the invention, the coloring material is a water-soluble dye or a fat-soluble dye.

By “water-soluble coloring material”, within the meaning of the invention, is meant any generally organic compound, natural or synthetic, soluble in an aqueous phase or solvents miscible with water and capable of coloring.

By “fat-soluble coloring material”, within the meaning of the invention, is meant any generally organic compound, natural or synthetic, soluble in an oily phase or solvents miscible with the oily phase and capable of coloring.

As water-soluble dyes suitable for the invention, mention may in particular be made of synthetic or natural water-soluble dyes such as for example FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1.

Among the natural water-soluble dyes we can cite anthocyanins.

As fat-soluble dyes suitable for the invention, mention may in particular be made of fat-soluble dyes such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet. 2, DC Orange 5, Sudan Red, Sudan Brown.

As an illustration of natural fat-soluble dyes, we can particularly cite carotenes such as β-carotene, α-carotene, lycopene; quinole yellow; xanthophylls such as astaxanthin, antheraxanthin, citranaxanthin, cryptoxanthin, canthaxanthin, diatomoxanthin, flavoxanthin, fucoxanthin, lutein, rhodoxanthin, rubixanthin, siphonaxanthin, violaxanthin, zeaxanthin; annatto; curcumin; quinizarin (Ceres Green BB, D&C Green No. 6, CI 61565, 1,4-Di-p-Toluidinoanthraquinone, Green No. 202, Quinzaine Green SS) and chlorophylls.

The water-soluble or fat-soluble dye(s) are preferably present in the composition ((A), (B), (C) and/or (D) at contents of less than 4% by weight, or even less than 2% by weight, more preferably ranging from 0.01 to 2% by weight, and even better from 0.02 to 1.5% by weight relative to the total weight of the composition (A), (B), (C) or (D) .

COSMETIC ADDITIVES

The compositions (A), (B), (C) and/or (D) of the invention may contain usual additives in cosmetics. These include antioxidants, preservatives, neutralizers, gelling agents or thickeners, surfactants, cosmetic active ingredients such as emollients, moisturizers, vitamins, and mixtures thereof.

Antioxidants

In particular, the antioxidant agents are used to prevent the oxidation of polyphenol thiols especially cysteine. We can also mention carotenes and lycopenes which also play the role of fat-soluble dyes.

These additives may be present in compositions (A), (B), (C) and/or (D) in a content ranging from 0.01 to 15.0%, of the total weight of the composition.

Of course, those skilled in the art will take care to choose any additional additives and/or their quantity in such a way that the advantageous properties of the compositions (A), (B), (C) and/or (D) according to the invention are not, or substantially not, altered by the planned addition.

Compositions (A), (B), (C) and/or (D) can be manufactured by known processes, generally used in the cosmetic field.

COMPOSITION (M)

The process according to the invention is carried out in the presence of a composition (M) in the form of an emulsion.

It can be in the form of an oil-in-water emulsion (continuous aqueous phase in which an oily phase is dispersed in the form of droplets so as to obtain a macroscopically homogeneous mixture) or a water-in-oil emulsion (oil phase continuous in which an aqueous phase is dispersed in the form of droplets so as to obtain a macroscopically homogeneous mixture).

Aqueous phase

The water content of the composition (M) varies depending on the nature of the emulsion.

For example, the quantity of water can vary between 10 and 90% by weight, more particularly between 20 and 70% by weight, relative to the weight of the composition (M).

The aqueous phase of the emulsion may optionally comprise water-soluble solvents such as those indicated above.

In addition, the pH of the aqueous phase is preferably less than 8.0, more preferably less than 7.0, and more particularly varies from 2 to 6.

Lipophilic phase

The composition (M) comprises at least one lipophilic phase. The content of lipophilic phase of the composition (M) varies depending on the nature of the emulsion.

For example, the quantity of lipophilic phase can vary between 10 and 90% by weight, more particularly between 20 and 70% by weight, relative to the weight of the composition (M).

The term "lipophilic phase" means a phase immiscible with the aqueous phase and comprising at least one fatty substance such as oils, waxes, pasty bodies as well as possibly all organic solvents and ingredients which are soluble or miscible in said phase. It should be noted that if the lipophilic phase is liquid at room temperature and atmospheric pressure, the lipophilic phase is an oily phase.

With regard to oils, reference may be made to what has previously been indicated for the description of the oily phase of compositions (A) to (D).

Preferably, the composition (M) comprises at least one non-volatile silicone or hydrocarbon oil.

More particularly, the non-volatile silicone oil, phenylated or non-phenylated, is chosen from dimethicones, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyltrimethicone, diphenylsiloxy phenyl trimethicone, as well as mixtures thereof. .

With regard to non-volatile polar hydrocarbon oils, mention may particularly be made of ester oils, such as for example triglycerides of fatty acids (C4-C36) and glycerol, in particular capric/caprylic triglycerides, vegetable oils, fatty alcohols having from 12 to 26 carbon atoms such as octyldodecanol in particular, synthetic ethers having from 10 to 40 carbon atoms such as dicaprylyl ether; and their mixtures.

It may also comprise at least one volatile silicone or hydrocarbon oil such as for example volatile cyclic or linear silicones, C ₈ -C ₁₆ branched alkanes and more especially isododecane, as well as their mixtures.

More particularly, the oil content in the composition (M) varies from 10 to 90% by weight, preferably from 20 to 70% by weight, relative to the total weight of the composition.

The composition (M) may optionally comprise at least one wax. We can refer to the description a little above on this subject.

The wax content(s) varies depending on the galenic of the composition, if the composition contains any. For example, the content of wax(es), if this type of ingredient is present in the composition, varies from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight, from preferably between 0.5 and 20% by weight, relative to the weight of the composition.

The composition (M) may optionally comprise at least one pasty compound, preferably hydrocarbon-based, lists of which have been indicated previously.

If the composition comprises at least one pasty hydrocarbon compound, preferably their content varies from 0.5 to 50% by weight, preferably from 0.5 to 30% by weight, relative to the total weight of the composition.

Hydrophobic film-forming polymer

Very advantageously, the composition (M) comprises at least one hydrophobic film-forming polymer, in particular chosen from block hydrocarbon polymers; among silicone polymers such as silicone resins, silicone acrylate polymers with carbosiloxane dendrimer patterns, silicone acrylate copolymers; ethylcellulose, as well as their mixtures.

Silicone resins

More generally, the term “resin” means a compound whose structure is three-dimensional. Thus, for example, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin, within the meaning of the present invention.

The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known under the name "MDTQ", the resin being described according to the different siloxane monomeric units that it includes, each of the letters "MDTQ" characterizing a type of unit.

The letter “M” represents the Monofunctional unit of formula R1R2R3SiO _1/2 , the silicon atom being connected to a single oxygen atom in the polymer comprising this unit.

The letter “D” means a Difunctional unit R1R2SiO _2/2 in which the silicon atom is connected to two oxygen atoms

The letter “T” represents a trifunctional unit of formula R1SiO _3/2 .

Such resins are described for example in “Encyclopedia of Polymer Science and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or even US 5,082,706, US 5,319,040, US 5,302, 685 and US 4,935,484.

In the units M, D, T defined previously, Ri, namely R ₁ , R ₂ and R ₃ , identical or different, represent a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

Finally, the letter “Q” means a Tetrafunctional SiO _4/2 unit in which the silicon atom is linked to four oxygen atoms which are themselves linked to the rest of the polymer.

Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying depending on the type of monomers (or units), the nature and number of the radical(s) Ri, the length of the polymer chain, the degree of branching and the size of the pendant chains.

As silicone resins which can be used in the compositions according to the invention, it is possible to use, for example, silicone resins of the MQ type, of the T type or of the MQT type.

MQ resins

As an example of MQ type silicone resins, mention may be made of alkylsiloxysilicates of formula [(R1) ₃ SiO _1/2 ] _x (SiO _4/2 ) _y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R1 represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group,

As examples of solid silicone resins of the MQ type of trimethylsiloxysilicate type, we can cite those marketed under the reference SR1000 by the company Momentive Performances Materials, under the reference MQ 1600 by Dow Corning, under the reference Belsil TMS 803 by the company Wacker.

As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by the company Momentive Performance Materials). The preparation of such resins is described in particular in patent US5817302.

Resins T

As examples of type T silicone resins, mention may be made of polysilsesquioxanes of formula (RSiO _3/2 ) _x (T units) in which x is greater than 100 and such that the R group is an alkyl group having 1 with 10 carbon atoms, said polysilsesquioxanes being able to further comprise terminal Si-OH groups.

We can also cite polymethylsilsesquioxanes which are polysilsesquioxanes in which none of the methyl radicals are substituted by another group. Such polymethylsilsesquioxanes are described for example in document US 5,246,694.

Preferably, polymethylsilsesquioxane resins can be used in which R represents a methyl group, such as for example those marketed:
- by the company Wacker under the reference Resin MK such as Belsil PMS MK: polymer comprising repeating CH ₃ SiO _3/2 units (T units), which may also include up to 1% by weight of units (CH ₃ ) ₂ SiO _2/2 (D units) and having an average molecular weight of approximately 10,000 g/mol, or
- by the company SHIN-ETSU under the references KR-220L which are composed of T units of formula CH ₃ SiO _3/2 and have terminal groups Si-OH (silanol), under the reference KR-242A which comprise 98% of T units and 2% of dimethyl D units and have Si-OH end groups or under the reference KR-251 comprising 88% of T units and 12% of dimethyl D units and have Si- end groups OH,
- by the company Dow Corning under the references Dow Corning 670 Fluid, Dow Corning 680 Fluid, mixed in cyclopentasiloxane and in isododecane respectively.

MQT resins

As a resin comprising MQT patterns, we know in particular those cited in document US 5,110,890.

A preferred form of MQT type resins are MQT-propyl resins (also called MQTPr). Such resins which can be used in the compositions according to the invention are in particular those described and prepared in application WO 2005/075542, the content of which is incorporated here by reference.

The MQ-T-propyl resin preferably comprises the units: (i) (R1 ₃ SiO _1/2 ) _a ; (ii) (R2 ₂ SiO _2/2 ) _b ; (iii) (R3SiO _3/2 ) _c and (iv) (SiO _4/2 ) _d ; with R1, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms. carbon or a phenyl group; a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0, 6, a + b + c + d = 1, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

Preferably the siloxane resin comprises the units (i) (R1 ₃ SiO _1/2 ) _a ; (iii) (R3SiO _3/2 ) _c and (iv) (SiO _4/2 ) _d with R ₁ and R ₃ independently representing an alkyl group having from 1 to 8 carbon atoms, R ₁ preferably being a methyl group and R ₃ preferably being a propyl group, a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55, a + b + c + d = 1, and a, b, c and d being molar fractions, provided that more than 40% by mole of the R ₃ groups of the siloxane resin are propyl groups.

The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of:
A) an MQ resin comprising at least 80% by mole of units (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d R1 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than zero, the a/d ratio being between 0.5 and 1.5; and of
B) a propyl resin T comprising at least 80% by mole of (R3SiO _3/2 ) _c units, R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group , c being greater than zero, provided that at least 40 mol% of the R3 groups are propyl groups, where the mass ratio A/B is between 95:5 and 15:85, preferably the mass ratio A/ B is 30:70.

Advantageously, the mass ratio A/B is between 95:5 and 15:85. Preferably, the A/B ratio is less than or equal to 70:30. These preferred ratios have proven to allow comfortable deposits.

Preferably, the composition according to the invention comprises, as silicone resin, at least one MQ type, T type resin, and even more preferably at least one MQ type resin, as described above. In particular, the silicone resin is a siloxysilicate resin, preferably a trimethylsiloxysilicate resin.

Ethylene Block Copolymer

According to another embodiment of the invention, the hydrophobic film-forming polymer is an ethylenic block copolymer, containing at least one first block having a glass transition temperature (T _g ) greater than or equal to 40°C and being derived entirely or in part of one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least a second sequence having a glass transition temperature lower or equal to 20°C and being derived entirely or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20°C, said first sequence and said second sequence being linked together by a statistical intermediate segment comprising at least one of said first constituent monomers of the first sequence and at least one of said second constituent monomers of the second sequence, and said block copolymer having a polydispersity index I greater than 2.

Polymers of this type suitable for the invention are described in document EP 1 411 069.

As an example of such polymers, we can more particularly cite the copolymers with the name INCI acrylic acid/isobutyl acrylate/isobornyl acrylate copolymer marketed for example under the name MEXOMERE PAS® by Chimex (mixed at 50% in isododecane) .

Vinyl polymer comprising at least one carbosiloxane dendrimer unit

According to another particular embodiment, the composition (M) may comprise at least one vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer.

This type of vinyl polymer has in particular a skeleton and at least one side chain, which comprises a unit derived from a carbosiloxane dendrimer having a carbosiloxane dendrimer structure.

In particular, vinyl polymers comprising at least one carbosiloxane dendrimer unit may be used as described in applications WO03/045337 and EP 963 751 from the company Dow Corning.

The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure having branched groups having high molecular masses, said structure having high regularity in the radial direction starting from the bond to the backbone. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Japanese patent application Kokai 9-171,154.

A vinyl polymer having at least one unit derived from a carbosiloxane dendrimer has a side molecular chain containing a carbosiloxane dendrimer structure, and can be obtained from the polymerization:
(A) 0 to 99.9 parts by weight of a vinyl monomer; And
(B) 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing a radically polymerizable organic group represented by the general formula
[Chem 1]

in which Y represents an organic group polymerizable with radicals, R ¹ represents an aryl group or an alkyl group having 1 to 10 carbon atoms, and X ⁱ represents a silylalkyl group which, when i = 1, is represented by the formula:
[Chem 2]

in which R ¹ is as defined above, R ² represents an alkylene group having 2 to 10 carbon atoms, R ³ represents an alkyl group having 1 ^to 10 carbon atoms, hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a ⁱ is an integer from 0 to 3;
where said radical-polymerizable organic group contained in component (A) is chosen from
*organic groups containing a methacrylic group or an acrylic group and which are represented by the formulas: CH ₂ =C-(R ⁴ )-COO-R ⁵ - and CH ₂ =C(R ⁴ )-CO-NH-R ⁵ - ; in which R ⁴ represents a hydrogen atom or an alkyl group, R ⁵ represents an alkylene group having 1 to 10 carbon atoms; And
*organic groups containing a styryl group and which are represented by the formula:
[Chem 3]

in which R ⁶ represents a hydrogen atom or an alkyl group, R ⁷ represents an alkyl group having 1 to 10 carbon atoms, R ⁸ represents an alkylene group having 1 to 10 carbon atoms, b is an integer from 0 to 4, and c is 0 or 1, so that if c is 0, -(R ⁸ ) _c - represents a bond.

The vinyl-type monomer which is component (A) in the vinyl polymer is a vinyl-type monomer which contains a radical-polymerizable vinyl group.

There is no particular limitation regarding such a monomer.

The following are examples of this vinyl-type monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or an analogous lower alkyl methacrylate; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a higher analog methacrylate; vinyl acetate, vinyl propionate, or a lower analog fatty acid vinyl ester; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher analog fatty acid ester; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, or similar vinyl aromatic monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, N,Ndimethylmethacrylamide, or similar vinyl-type monomers which contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or similar vinyl-type monomers which contain hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or similar vinyl-type monomers which contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol-monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2- ether ethylhexyl and vinyl, or an analogous vinyl-type monomer with ether bonds; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or a similar silicone compound having unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid ; a radically polymerizable unsaturated monomer having a sulfonic acid group such as a sulfonic acid styrene group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and a methacrylic acid ester of an alcohol having a tertiary amine group such as a methacrylic acid ester of diethylamine.

Multifunctional vinyl-type monomers can also be used.

The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-dimethacrylate hexanediol, neopentylglycol dimethacrylate, trimethylolpropanetrioxyethylmethacrylate, neopentylglycol dimethacrylate,
tris-(2-hydroxyethyl)isocyanurate, tris-(2-hydroxyethyl)isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on both ends, or analogous silicone compounds having unsaturated groups.

To facilitate the mixture preparation of the raw material of cosmetic products, the number average molecular weight of the vinyl polymer which contains a carbosiloxane dendrimer, can be chosen in the range between 3,000 g/mol and 2,000,000 g/mol, from preferably between 5,000 g/mol and 800,000 g/mol. It can be a liquid, a gum, a paste, a solid, a powder, or any other form. The preferred forms are solutions formed by dilution in solvents such as a silicone oil or an organic oil, a dispersion, or a powder.

According to a preferred embodiment, a vinyl polymer suitable for the invention may be one of the polymers described in the examples of application EP 0 963 751.

According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer can result from the polymerization:
(A) from 0.1 to 99 parts by weight of one or more acrylate or methacrylate monomer(s); And
B) from 100 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy]silylpropyl carbosiloxane dendrimer.

According to one embodiment, a vinyl polymer having at least one unit derived from a carbosiloxane dendrimer may comprise a unit derived from a tri[tri(trimethylsiloxy)silylethyl dimethylsiloxy]silylpropyl carbosiloxane dendrimer corresponding to one of the formulas:
[Chem 4]

Or
[Chem 5]

According to a preferred embodiment, a vinyl polymer having at least one unit derived from carbosiloxane dendrimer used in the invention comprises at least one butyl acrylate monomer.

According to one embodiment, a vinyl polymer may also comprise at least one fluorinated organic group. A fluorovinyl polymer may be one of the polymers described in the examples of application WO 03/045337.

According to a preferred embodiment, a grafted vinyl polymer within the meaning of the present invention can be conveyed in an oil or a mixture of oil(s), preferably volatile in particular, chosen from oils of silicones and hydrocarbon oils and their mixtures.

According to a particular embodiment, a silicone oil suitable for the invention may be cyclopentasiloxane.

According to another particular embodiment, a hydrocarbon oil suitable for the invention may be isododecane.

The vinyl polymers grafted with at least one unit derived from carbosiloxane dendrimer which may be particularly suitable for the present invention are the polymers sold under the names TIB 4-100, TIB 4-101, TIB 4-120, TIB 4-130, TIB 4- 200, FA 4002 ID (TIB 4-202), TIB 4-220, FA 4001 CM (TIB 4-230) by the company Dow Corning. Preferably, the polymers sold under the names FA 4002 ID (TIB 4-202) and FA 4001 CM (TIB 4-230) by the company Dow Corning will be used.

Preferably, the vinyl polymer grafted with at least one unit derived from carbosiloxane dendrimer usable in a composition of the invention is a copolymer with the name INCI Acrylates/Polytrimethylsiloxymethacrylate Copolymer, in particular that marketed in isododecane under the name Dow Corning FA 4002 ID silicone acrylate by the company Dow Corning.

Silicone acrylate copolymers

According to another particular embodiment, the composition (M) comprises at least one copolymer comprising carboxylate groups and polydimethylsiloxane groups.

By “ copolymer comprising carboxylate groups and polydimethylsiloxane groups ” is meant in the present application, a copolymer obtained from (a) one or more carboxylic monomers (acid or ester), and (b) one or more polydimethylsiloxane chains ( PDMS).

In the present application, the term “ carboxylic monomer ” means both carboxylic acid monomers and carboxylic acid ester monomers. Thus, the monomer (a) can be chosen for example from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, their esters and mixtures of these monomers. As esters, the following monomers can be cited: acrylate, methacrylate, maleate, fumarate, itaconoate and/or crotonoate. According to a preferred embodiment of the invention, the monomers in the form of esters are more particularly chosen from linear or branched alkyl acrylates and methacrylates, preferably C ₁ -C ₂₄ and better still C ₁ -C ₂₂ , the alkyl radical being preferably chosen from the methyl, ethyl, stearyl, butyl, 2-ethylhexyl radicals, and their mixtures.

Thus, according to a particular embodiment of the invention, the copolymer comprises as carboxylate groups, at least one group chosen from acrylic acid, methacrylic acid, methyl, ethyl, stearyl acrylates or methacrylates, butyl, ethyl-2-hexyl, and mixtures thereof.

In the present application, the term "polydimethylsiloxanes" (also called organopolysiloxanes or, in abbreviation, PDMS) is intended to be designated, in accordance with general acceptance, any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and /or polycondensation of suitably functionalized silanes, and essentially constituted by a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond ºSi-O-Siº), comprising trimethyl radicals directly linked via a carbon atom to said silicon atoms. The PDMS chains which can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, that is to say the PDMS can have for example a polymerizable radical group on both ends of the chain or having a polymerizable radical group on one end of the chain and a terminal trimethylsilyl group on the other end of the chain. The polymerizable radical group may in particular be an acrylic or methacrylic group, in particular a group
CH ₂ = CR ₁ – CO – O - R ₂ , where R ₁ represents hydrogen or a methyl group, and R ₂ represents -CH ₂ -, -(CH ₂ ) _n - with n = 3, 5, 8 or 10 , -CH ₂ –CH(CH ₃ )–CH ₂ - , -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ -CH ₂ -CH ₂ –.

The copolymers used in the composition of the invention are generally obtained according to the usual polymerization and grafting methods, for example by radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one of the ends of the chain or on both) and (B) of at least one carboxylic monomer, as described for example in documents US-A-5,061,481 and US-A-5,219,560.

The copolymers obtained generally have a molecular weight ranging from approximately 3,000 g/mol to 200,000 g/mol and preferably from approximately 5,000 g/mol to 100,000 g/mol.

The copolymer used in the composition of the invention can be presented as such or in dispersed form in a solvent such as lower alcohols containing from 2 to 8 carbon atoms, such as isopropyl alcohol, or oils such as silicone oils. volatiles (e.g. cyclopentasiloxane).

As copolymers which can be used in the composition of the invention, mention may be made, for example, of copolymers of acrylic acid and of stearyl acrylate with polydimethylsiloxane grafts, copolymers of stearyl methacrylate with polydimethylsiloxane grafts, copolymers of acrylic acid and of stearyl methacrylate with polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Mention may be made in particular as copolymers usable in the composition of the invention, the copolymers marketed by the company SHIN-ETSU under the names KP-561 (CTFA name: acrylates/dimethicone), KP-541 where the copolymer is dispersed at 60 % by weight in isopropyl alcohol (CTFA name: acrylates/dimethicone and Isopropyl alcohol), KP-545 where the copolymer is dispersed at
30% in cyclopentasiloxane (CTFA name: acrylates/dimethicone and Cyclopentasiloxane). According to a preferred embodiment of the invention, KP561 is preferably used; this copolymer is not dispersed in a solvent, but is in waxy form, its melting point being approximately 30°C.

We can also cite the grafted copolymer of polyacrylic and dimethylpolysiloxane dissolved in isododecane marketed by the company Shin Etsu under the name KP-550.

Alkylcellulose

According to another particular embodiment, the composition (M) comprises at least alkylcellulose whose alkyl residue comprises between 2 and 6 carbon atoms, in particular between 2 and 3 carbon atoms, and preferably ethylcellulose.

Alkyl cellulose is an alkyl ether of cellulose comprising a chain consisting of β-anhydroglucose units linked together by acetal bonds. Each anhydroglucose unit has three replaceable hydroxyl groups, all or part of these hydroxyl groups can react according to the following reaction:
RONa + R’Cl to ROR’ + NaCl, where R represents a cellulose radical and R’ represents a C alkyl radical₂-VS₆.

Advantageously, the alkylcellulose can be chosen from ethylcellulose and propylcellulose, and preferably ethylcellulose.

The total substitution of the three hydroxyl groups would lead for each anhydroglucose unit to a degree of substitution of 3, in other words to an alkoxy group content of 54.88%.

The ethylcellulose polymers used in a cosmetic composition according to the invention are preferably polymers having a degree of substitution of ethoxy groups ranging from 2.5 to 2.6 per anhydroglucose unit, in other words comprising a content of ethoxy groups ranging from 44 at 50%.

The alkylcellulose used in the composition according to the invention is found more particularly in powder form.

It is for example marketed under the trade names “ETHOCEL Standard” from Dow Chemicals, including “ETHOCEL Standard 7 FP Premium” and “ETHOCEL standard 100 FP Premium”. Other commercially available products, such as those marketed by Ashland, Inc., under the names Aqualon Ethylcellulose type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable to the realization of the invention.

Preferably, the composition (M) comprises at least one film-forming polymer chosen from the following INCI name compounds: trimethylsiloxysilicate, polypropylsilsesquioxane, polymethylsilsesquioxane, acrylates/polytrimethylsiloxymethacrylate copolymer, acrylates/dimethicone, acrylic acid/isobutyl acrylate/isobornyl acrylate copolymer ethylcellulose, as well as than their mixtures. Preferably the composition comprises at least one silicone film-forming polymer.

If the composition (M) comprises it, the content of film-forming polymer(s) advantageously varies between 0.1 and 50% by weight, more particularly from 1 to 30% by weight, relative to the total weight of the composition. (M).

The composition (M) comprises at least one oil and optionally at least one coloring material chosen from those defined above.

The composition (M) may also contain one or more ingredients commonly used in this type of product such as organic solvents; hydrophilic and lipophilic thickening agents; charges ; additional moisturizing agents (also called humectants); salts (magnesium sulfate, sodium chloride); cosmetic active ingredients such as vitamins, UV sun filters, moisturizing agents, antioxidant agents.

The composition (M) in accordance with the invention can be a product, in particular makeup, care, or even a hybrid product (in other words with makeup and care action).

Composition (M) is more particularly a product intended to be applied to the lips, in particular a lipstick, lip gloss (gloss) and lip balm.

The compositions (M) for the lips can advantageously be presented in a fluid (gloss) or solid (stick) form.

By “fluid” (or liquid) we mean in particular a composition which is not solid at 25°C, and whose viscosity can be measured.

By “solid” we mean in particular a composition whose hardness can be measured using the so-called “butter-cutting wire” method at 20°C.

Between these two extremes, there are intermediate textures whose viscosity and hardness cannot be measured using the methods detailed below. Such compositions are then described as pasty.

Preferably the composition (M) is not in the form of a stick. It is advantageously in fluid or pasty form, and preferably in fluid form.

Protocol for measuring viscosity

The viscosity measurement is generally carried out at 25°C, using a RHEOMAT RM 180 viscometer equipped with a mobile no. 2, no. 3 or a mobile no. 4, according to the recommendations of use, the measurement being carried out after 10 minutes of rotation of the mobile within the composition at a speed of 200 rpm.

For example, the composition may have a viscosity of between 0.1 and 25 Pa.s at 25°C,

Hardness measurement protocol

The composition in stick form is stored at 20°C for 24 hours before measuring the hardness.

The measurement is carried out at 20°C and consists of cutting transversely a stick of product, preferably cylindrical of revolution, using a rigid tungsten wire with a diameter of 250 µm by moving the wire relative to the stick at a speed of 100mm/min.

The hardness of the samples of compositions of the invention, expressed in Nm-1, is measured using a DFGS2 dynamometer marketed by the company INDELCO-CHATILLON.

The measurement is reproduced three times then averaged. The average of the three values read using the dynamometer mentioned above, denoted Y, is given in grams. This average is converted into Newtons then divided by L which represents the highest dimension crossed by the wire. In the case of a cylindrical stick, L is equal to the diameter (in meters).

Hardness is converted to Nm ^-1 by the equation: (Y x 10 ^-3 x 9.8)/L

For example, the composition may have a hardness of between 20 and 200 Nm ^-1 .

MAKEUP AND/OR CARE PROCESSES

From compositions (A) and (B)

According to a particular mode, the invention relates to a method of making up the skin and/or the lips, preferably the lips, consisting of implementing the following steps:
1) a) at least one composition (A) comprising, in particular in a physiologically acceptable medium, at least one polyphenol X as defined above is applied to the skin and/or the lips, preferably to the lips; And
1) b) at least one composition (B) comprising, in particular in a physiologically acceptable medium, at least one compound Y as defined above;
said compositions (A) and (B) being applied to the skin and/or lips,
i) simultaneously; or ii) in the form of an extemporaneous mixture at the time of use; or iii) successively, regardless of the order of application;
one and/or the other of compositions (A) and (B) comprising at least one coloring material, preferably composition (A);
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated.

Advantageously, the composition (M) is applied to the composition obtained at the end of the first step, without mixing. It is also preferably applied after at least partial drying of the composition deposited during the first step. As an indication, the second step is carried out a few minutes after the first.

First stage

The first step can be carried out by applying composition (A) first, then composition (B).

According to another variant, composition (B) is applied first, then composition (A) on top of the first.

More particularly, the ratio of the mass of polyphenol 5 and 2.

This operation preferably takes place without mixing the two layers together, more particularly the second layer is applied to the first, once the latter has dried.

Both compositions (A) and (B) can be aqueous or anhydrous.

According to another possibility, one of the two compositions is aqueous, while the other is anhydrous.

According to a characteristic of the process according to the invention, this first step is carried out in the presence of at least one coloring material, as defined above.

The coloring material(s) may be found in composition (A), in composition (B), or even in both compositions at the same time.

Preferably, the coloring material(s) is(are) in the first composition which is applied.

In accordance with a particularly advantageous embodiment of the invention, compositions (A) and (B) are applied successively, preferably, by applying composition (B) before composition (A). Preferably, the second composition is applied to the first, without mixing. Advantageously, the second composition is applied to the first once it has dried.

According to a particularly preferred method, the following is applied successively to the skin and/or lips:
a) a first layer of makeup (base coat) with an anhydrous composition (B) as defined above comprising at least one coloring material, preferably a pigment, then
b) on the skin and/or lips thus colored, a second post-treatment layer (top coat) with an aqueous composition (A) as defined above.

From the composition (C)

Another cosmetic process for making up the skin and/or lips, preferably the lips, according to the invention, consists of implementing the following steps:
1) at least one composition (C) is applied to the skin and/or lips, preferably to the lips, comprising, in particular in a physiologically acceptable medium, at least one coating agent previously formed by interaction by hydrogen bonds of at least one at least one polyphenol X with at least one compound Y as defined above; the composition (C) comprising at least one coloring material;
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated.

Advantageously, the composition (M) is applied to the composition obtained at the end of the first step, without mixing. It is also preferably applied after at least partial drying of the composition deposited during the first step. As an indication, the second step is carried out a few minutes after the first.

From the composition (D)

Another cosmetic process for making up the skin and/or lips, preferably the lips, according to the invention, consists of implementing the following steps:
1) at least one composition (D) comprising, in particular in a physiologically acceptable medium, is applied to the skin and/or the lips, preferably to the lips,
a) at least one polyphenol
b) at least one compound Y as defined previously,
c) at least one mono-alcohol containing 2 to 8 carbon atoms, and more particularly ethanol and
d) at least one coloring matter,
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated.

Advantageously, the composition (M) is applied to the composition obtained at the end of the first step, without mixing. It is also preferably applied after at least partial drying of the composition deposited during the first step. As an indication, the second step is carried out a few minutes after the first.

PACKAGING AND APPLICATORS

The compositions (A), (B) (C), (D) and/or (M) according to the invention can each be packaged in a container delimiting at least one compartment which comprises said composition, said container being closed by an element closing.

The container can be in any suitable form. It can be in particular in the form of a bottle, a tube, a pot, a case.

The closure element can be in the form of a removable cap, a lid, a cover, in particular of the type comprising a body fixed to the container and a cap hinged to the body. It can also be in the form of an element ensuring the selective closure of the container, in particular a pump, a valve, or a valve.

The container can be associated with an applicator, for example in the form of a brush (as described for example in patent FR 2 722 380), in the form of an element, deformable or not, made of foam or elastomer, flocked or not. The applicator can also be free (sponge) or integral with a rod carried by the closure element, as described for example in US patent 5,492,426. The applicator can be integral with the container, as described by example in patent FR 2 761 959.

The product can be contained directly in the container, or indirectly.

The closure element can be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is done otherwise than by screwing, in particular via a bayonet mechanism, by snap-fastening, or by tightening. By “latching” we mean in particular any system involving the crossing of a bead or a cord of material by elastic deformation of a portion, in particular of the closing element, then by returning to the non-elastically constrained position of said portion after crossing the bead or cord.

The container may be at least partly made of thermoplastic material. As examples of thermoplastic materials, we can cite polypropylene or polyethylene.

The container may have rigid walls or deformable walls, in particular in the form of a tube or a tube bottle.

The container may include means intended to cause or facilitate distribution of the composition. For example, the container may have deformable walls so as to cause the composition to escape in response to an excess pressure inside the container, which excess pressure is caused by elastic (or non-elastic) crushing of the container walls. .

The container can be equipped with a wiper placed near the opening of the container. Such a wiper allows you to wipe the applicator and possibly the rod to which it can be attached. Such a wiper is described for example in patent FR 2 792 618.

Throughout the description, including the claims, the expression “comprising one” should be understood as being synonymous with “comprising at least one”, unless the contrary is specified.

The expressions “between… and…” and “ranging from… to…” must be understood inclusive, unless otherwise specified.

In addition, the sum of the quantities of the ingredients of the composition represents 100% by weight of the composition.

The invention is illustrated in more detail by the examples presented below.

Unless otherwise indicated, the quantities indicated are expressed as a mass percentage.

The examples which follow are presented by way of illustration and not limitation of the invention.

Examples

The following compositions (D) were prepared:

Ingredients (INCI name) (D1) (D2) Tannic acid
(Brewtan F - Ajinomoto Omnichem Nv) 5 5 PPG-5-CETETH-20
(Procetyl AWS-LQ-(AP) – Croda) 5 PEG-10 olive glyceride
(Olive Oil W - Lipoid Kosmetik) - 10 Red 7
(Unipure Red LC 3079 OR – Sensient) 10 5 Ethanol Qsp100 Qsp100

Preparation process
With Rayneri stirring, dissolve the tannic acid (compound X) in the solvent at room temperature.
Once the tannic acid has dissolved, add compound Y while maintaining stirring.
Once the mixture is homogenized, add the coloring material(s).
Leave to stir until the resulting mixture is well combined.
Condition.

Compositions (M)

Composition (M1)

The following composition (M1) was prepared

Ingredients (INCI name) Quantity
% in weight phase PEG-10 dimethicone ((KF-6017 - Shin Etsu) 2 HAS Cetyl PEG/PPG-10/1 dimethicone 1 Dodecamethylpentasiloxane, (DM-FLUID-2CS - Shin Etsu) Qsp 100 Trimethylsiloxyphenyl Dimethicone (Belsil PDM 1000 – Wacker Chemie) 4 Trimethyl pentaphenyl trisiloxane 5 2-Octyldodecanol 10 Acrylates/polytrimethylsiloxy methacrylate copolymer (Dow Corning FA 4002 ID silicone acrylate - Dow Corning, 40% wt in isododecane) 10 Water 34.5 B 1,3-Butylene glycol 6 Magnesium sulfate.7 H2O 0.7 Ethanol 5

Method of preparation
With Moritz stirring, mix directly all the compounds of phase A.
Prepare phase B under Rayneri at room temperature
Leave stirring until the mixtures of phase A and B are well homogeneous.
Add phase B to phase A and continue stirring until the mixture obtained is homogenized.
Condition

Composition (M2)

The following composition (M2) was prepared

Ingredients (INCI name) Quantity
% in weight Phase Octyldodecanol 31.3 HAS Ethylcellulose (Aquacoat ECD-30 - FMC Biopolymer – 26% ethylcellulose in water, with sodium lauryl sulfate and cetyl alcohol) 9 Conservative 0.7 B Water Qsp 100 Sorbitan stearate (and) Sucrose cocoate (Arlatone 2121U -Croda) 3.8 Hydroxypropyl guar 0.2 Trimethylsiloxyphenyl dimethicone (Belsil PDM 1000 - Wacker) 21.8 VS Ethanol 3

Method of preparation
With Rayneri stirring, mix phase A at 95°C until a homogeneous mixture is obtained.
Prepare B with Rayneri stirring and add phase B to phase A
Leave to stir until the mixture is well blended.
Add phase C and allow to cool to room temperature.
Condition.

Composition (M3)

The following composition (M3) was prepared

Ingredients (INCI name) Quantity
% in weight Phase Sucrose palmitate (SURFHOPE SE COSME C-1616 – Mitsubishi Kagaku Foods) 1.6 HAS Magnesium sulfate Qs Water 11.6 Glycerin 10.8 Capryloyl glycine 0.5 Citric acid Qs Sucrose laurate (SURFHOPE SE COSME C-1216 - Mitsubishi Kagaku Foods) 1.6 Propanediol 3.3 Dicaprylyl ether (Cetiol OE – BASF) Qsp100 B Perlite (OPTIMAT 2550 OR – Imerys) 1.1 Ethylcellulose (Aqualon EC N7 Pharm – Ashland) 9.3

Method of preparation
With stirring, mix all the compounds of phase A directly at 85°C.
Prepare phase B under Rayneri at 85°C.
Leave stirring until each mixture (phase A, phase B) is completely homogeneous.
Add phase B to phase A while stirring and continue stirring until the resulting mixture is homogenized.
Condition.

Application of compositions

One of the compositions (D) to (D3) is first applied so as to obtain a homogeneous deposit on the support (base coat).

Then, once the first composition has dried, a composition (M1), (M2) or (M3) (top coat) is applied on top without mixing, according to the combinations below:

Essay Trial 1 Test 2 Test3 Base coat (D1) (D2) (D1) Top coat (M1) (M2) (M3)

For makeup on the lips, compositions (D1) and (D2) are applied very easily with a dipping applicator, allowing you to obtain a very thin film on the lips, with an intense, homogeneous color.

Once the composition has dried, composition (M1) (M2) or (M3) is applied on top according to the combinations in the previous table.

Each time we obtain a non-sticky, very comfortable deposit.

The whole does not transfer (for example kiss test on a cup).

The resulting deposit was evaluated in a resistance test to mechanical and chemical attacks: dry friction, water and oil, according to the following protocol.

Performance evaluation protocol

1. Preparing for the test:

Support: Supplale beige (2.5 x 5 cm) (marketed by Soudotique).

Spread the composition (D) over the entire surface 3 times in a row to have a homogeneous deposit. Repeat the operation on two other strips.
Leave the deposit to dry on a plate heated to 34°C for 30 minutes.
Apply over composition (D), composition (M) over the entire surface 3 times in a row to have a homogeneous deposit. Do the same on the other two strips.
Allow the deposit to dry again on a plate heated to 34°C for 30 minutes.
If necessary, take a photo of each support with the deposit (made up) before solicitation.

2. Requests:

Preparing a tissue for each request:
Fold each tissue twice on the long edge then twice in the other direction to form a square.

Dry resistance:

Rub once with the handkerchief folded lengthwise one of the three made-up supports; the force applied is that normally exerted when removing makeup from the skin or lips.
Observe the condition of the rubbed support as well as the used surface of the tissue, in particular the remaining coloring, the transferred coloring.
Possibly take a photo.

In the event that several passes are carried out, they would then be carried out with the same force and always in the same direction (i.e.: after each pass, the tissue is lifted to be repositioned at the "beginning" of the strip in order to be reapplied to the deposit in the same way as in the previous passage). Possibly take a photo between each step or only at the end of the evaluation. This type of process can be implemented to evaluate the overall resistance of the deposit.

Water resistance :

Insert the second made-up support without bending it into a centrifuge tube.
Add 10 grams of demineralized water.
Centrifuge for 10 minutes at 450g.
Possibly take a photo of the support after mixing, immediately after the operation.
Rub once with a tissue along the length of the support, without waiting, with the same force as that applied for dry resistance.
Observe the condition of the rubbed support as well as the used surface of the tissue, in particular the remaining coloring, the transferred coloring.
Possibly take a photo.

The protocol for several passes is the same as that detailed previously for dry resistance.

Oil resistance:

Implement the same protocol as for water resistance, on the third stained support, replacing the water with the same quantity of olive oil (Refined Olive Oil – Aarhuskarlshamn).

Rating:

For each request, note the result according to the table below:

Note Deposit status Surface of the fabric in contact with the deposit - -
Total or partial elimination of the deposit on the rubbed area; the surface of the support appears in places Very intense coloring – very significant transfer to total color -
Partial elimination leading to significantly and visibly less intense coloring of the deposit. Intense coloring – significant color transfer +
Reduction in the intensity of the color of the deposit which is perceptible but does not reveal the support Medium coloring – medium color transfer ++
No substantial variation in the color of the deposit Light coloring – little color transfer +++
No variation in the color of the deposit No staining or barely visible staining – no to very little color transfer

It should be noted that to facilitate the evaluation of the resistance of the deposit, it includes at least one coloring material whose coloring is sufficiently intense (for example a red coloring material, such as Red 7 in particular).

When comparing several compositions, they have the same color (same quantity and same coloring matter).

It should be noted that the resistance of the deposit, as well as other properties (homogeneity, comfort, etc.) can also be evaluated by a Sensory Panel (group of trained experts making it possible to obtain a description of technical characteristics - ISO standards 8586, ISO 11132, ISO 13299).

Results  :

Essay Resistance to dry friction Resistance to water friction Resistance to oil friction Trial 1 +++ +++ ++ Test 2 +++ +++ +++ Test 3 +++ +++ +++

Claims (32)

Process for making up the skin and/or the lips, preferably the lips, consisting of carrying out the following steps:
1) a coating agent formed in situ is applied to the skin and/or lips or previously by interaction by hydrogen bonds of at least one polyphenol or polyoxypropylenated and/or polyglycerol; the first step taking place in the presence of at least one coloring matter
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated. Process according to claim 1, characterized in that the polyphenol X is chosen from catechic tannins, in particular chosen from gallotannins and ellagitannins. Process according to any one of claims 1 or 2, characterized in that the polyphenol X is epigallocatechin, in particular a green tea extract, in particular comprising at least 45% by weight of epigallocatechin relative to the weight of said extract. Process according to claim 1, characterized in that the polyphenol . Process according to any one of claims 1 or 2, characterized in that the polyphenol X is tannic acid. Process according to any one of the preceding claims, characterized in that the compounds Y have a molar mass greater than 200 g/mol, more particularly greater than 350 g/mol. Process according to any one of the preceding claims, characterized in that compound Y is chosen from linear, branched or crosslinked, polyoxyethylenated and/or polyoxypropylenated and/or polyglycerolated silicone compounds, polyoxyethylenated and/or polyoxypropylenated alcohols, alkyl glycols or polyoxyethylenated and/or polyoxypropylenated glycerin, polyethylene glycols, Poloxamer, polyoxyethylenated and/or polyoxypropylenated and/or (poly)glycerolated esters, polyoxyethylenated sorbitol or sorbitan esters and Polysorbate, ester or ether derivatives of polyoxyethylenated sugars, polyoxyethylenated (poly)amines, as well as mixtures thereof. Process according to any one of the preceding claims, characterized in that compound Y is chosen from:
- non-ionic, linear, branched or crosslinked, polyoxyethylenated and/or polyoxypropylenated polydimethylsiloxanes comprising from 2 to 50 oxyethylenated units and/or comprising from 2 to 50 oxypropylenated units, optionally comprising an alkyl group comprising from 6 to 22 carbon atoms; nonionic polydimethylsiloxanes with ester(s) functions, polyoxyethylenated, comprising from 2 to 50 oxyethylenated units; as well as their mixtures;
- Polyoxyethylenated fatty alcohols of type R(O-CH2-CH2)o-OH, R representing a C8-C30 alkyl radical, or representing an average integer ranging from 2 to 50
- Polyoxyethylenated and polyoxypropylenated alcohols of type: R-(OC(CH ₃ )H-CH ₂ )o-(O-CH ₂ -CH ₂ )p-OH; R representing a C ₄ -C ₃₀ alkyl radical, o and p, independently of one another, representing an average integer ranging from 1 to 50;
- Esters of glycerol and carboxylic acid(s) or polymer(s) of carboxylic acid(s) optionally hydroxylated at C ₆ -C ₄₀ , more particularly at C ₈ -C ₃₀ , or derivatives vegetable oils, said esters being polyoxyethylenated, comprising from 2 to 200 oxyethylenated units, more preferably from 2 to 100 oxyethylenated units, even more particularly between 2 and 80 oxyethylenated units;
- polyglycerol esters comprising 2 to 20 glycerol units and saturated or unsaturated carboxylic acid, comprising 6 to 40 carbon atoms, optionally substituted by at least one hydroxyl group, or polyglycerol esters comprising 2 to 20 glycerol units and derivatives of 'vegetal oils; as well as their mixtures
- esters of sorbitol or sorbitan and carboxylic acid(s), saturated or not, in C ₆ -C ₄₀ , advantageously in C ₈ -C ₃₀ , and comprise 2 to 50 oxyethylenated units, and preferably Polysorbate;
- polyoxyethylenated alkylamines; the C8-C30 alkyl group, the number of oxyethylenated units between 1 and 50;
- polyethylene glycols;
- their mixtures. Method of making up the skin and/or the lips, preferably the lips, according to any one of claims 1 to 8, consisting of implementing the following steps:
1)a) at least one composition (A) comprising, in particular in a physiologically acceptable medium, at least one polyphenol claims 1 to 5; And
1)b) at least one composition (B) comprising, in particular in a physiologically acceptable medium, at least one compound Y as defined according to any one of claims 1 or 6 to 8;
said compositions (A) and (B) being applied to the skin and/or lips,
i) simultaneously; or ii) in the form of an extemporaneous mixture at the time of use; or iii) successively, regardless of the order of application;
one and/or the other of compositions (A) and (B) comprising at least one coloring material, preferably composition (A);
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated. Process according to the preceding claim, in which compositions (A) and (B) are applied successively, preferably by applying composition (B) before composition (A). Process according to any one of claims 9 or 10, characterized in that the polyphenol content represents at least 2% by weight, more particularly from 2 to 50% by weight, preferably from 5 to 30% by weight relative to the total weight of the composition (A). Process according to any one of claims 9 or 11, characterized in that the content of compound Y represents at least 1% by weight, more particularly from 1 to 75% by weight, preferably from 2 to 50% by weight relative to the total weight of the composition (B). Process according to any one of Claims 9 to 12, characterized in that the composition (A) and/or the composition (B) comprises water, more particularly at a content greater than or equal to 25% by weight, or even greater than or equal to 25% by weight. equal to 30% by weight, and more preferably ranging from 35 to 85% relative to the total weight of composition (A) or (B). Process according to any one of claims 9 to 13, characterized in that the composition (A) and/or the composition (B) comprises at least one C2-C8 monoalcohol, more particularly C2-C5, preferably ethanol, more particularly at a content greater than or equal to 25% by weight, or even greater than or equal to 30% by weight, and more preferably ranging from 35 to 85% relative to the total weight of composition (A) or (B ). Process according to any one of Claims 9 to 14, characterized in that the composition (A) and/or (B) comprises at least one oily phase, more particularly at a content greater than or equal to 5% by weight, or even greater than or equal to 5% by weight. equal to 10% by weight, and more preferably ranging from 20 to 85% by weight, relative to the total weight of composition (A) or (B). Method of making up the skin and/or the lips, preferably the lips, according to any one of claims 1 to 8, consisting of implementing the following steps:
1) at least one composition (C) is applied to the skin and/or lips, preferably to the lips, comprising, in particular in a physiologically acceptable medium, at least one coating agent previously formed by interaction by hydrogen bonds of at least one at least one polyphenol X as defined according to any one of claims 1 to 5 with at least one compound Y as defined according to any one of claims 1 or 6 to 8; the composition (C) comprising at least one coloring material;
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated. Method according to claim 16, characterized in that the content of previously formed coating agent varies from 1 to 60% by weight, more preferably ranging from 2 to 40% by weight, preferably ranging from 10 to 40% by weight relative to to the total weight of said composition. Method of making up the skin and/or the lips, preferably the lips, according to any one of claims 1 to 8, consisting of implementing the following steps:
1) at least one composition (D) comprising, in particular in a physiologically acceptable medium, is applied to the skin and/or the lips, preferably to the lips,
a) at least one polyphenol X as defined according to any one of claims 1 to 5 and
b) at least one compound Y as defined according to any one of claims 1, 6 to 8 and
c) at least one mono-alcohol comprising from 2 to 8 carbon atoms, more particularly comprising from 2 to 5 carbon atoms, and more particularly ethanol,
d) at least one coloring matter;
2) a composition (M) in the form of an emulsion is applied to the skin and/or lips thus treated. Process according to claim 18, characterized in that the content of polyphenol total weight of the composition (D). Process according to any one of claims 18 or 19, characterized in that the content of compound Y represents at least 1% by weight, more particularly at least 2% by weight, preferably from 5 to 40% by weight, relative to to the total weight of the composition (D). Method according to any one of claims 18 or 20, characterized in that the ratio of the mass of polyphenol X, expressed as active material, to the mass of compound(s) Y, expressed as active material, varies between 0.25 and 3, preferably between 0.5 and 2. Process according to any one of claims 18 to 21, characterized in that the content of C2-C8 monoalcohol is greater than or equal to 25% by weight, more particularly ranging from 25 to 98% by weight, and even more particularly ranging from 30 to 90% by weight, and preferably ranging from 35 to 85% by weight, relative to the total weight of the composition (D). Process according to any one of claims 18 to 22, characterized in that the composition (D) comprises at least water, more particularly in a content less than or equal to less than or equal to 15% by weight, more particularly less or equal to 10% by weight, less than or equal to 5% by weight, relative to the total weight of the composition (D). Process according to any one of claims 18 to 23, characterized in that the composition (D) comprises an oily phase, more particularly at a content of between 1 and 30% by weight, preferably between 1 and 20% by weight, relative to the total weight of said composition (D). Method according to any one of claims 18 to 24, characterized in that the composition (D) comprises an oily phase comprising at least one volatile silicone oil. Process according to any one of claims 18 to 25, characterized in that the composition (D) comprises an oily phase comprising at least one volatile hydrocarbon oil, at a content less than or equal to 20% by weight, more particularly less than or equal at 10% by weight, preferably less than or equal to 8% by weight and even more precisely less than or equal to 5% by weight, relative to the total weight of the composition (D). Method according to any one of the preceding claims, characterized in that the coloring material comprises at least one synthetic, natural or natural coloring material; in particular chosen from coated or uncoated pigments, water-soluble dyes, fat-soluble dyes, and mixtures thereof. Process according to any one of the preceding claims, characterized in that the content of coloring matter(s) of the composition (A) and/or (B), of the composition (C), of the composition (D ) is at least 0.01% by weight, more particularly between 0.05 and 30% by weight, in particular between 0.1 and 25% by weight, relative to the total weight of the composition concerned. Method according to any one of the preceding claims, characterized in that the composition (M) is in the form of a water-in-oil emulsion. Method according to any one of the preceding claims, characterized in that the composition (M) comprises at least one oil, volatile or non-volatile, hydrocarbon or silicone. Method according to any one of the preceding claims, characterized in that the composition (M) comprises at least one wax or at least one pasty compound, as well as their mixtures. Method according to any one of the preceding claims, characterized in that the composition (M) comprises at least one film-forming polymer, for example chosen from silicone resins, silicone acrylate type copolymers, ethylenic block polymers, ethylcellulose, as well as their mixtures; and in particular chosen from the following INCI name compounds: trimethylsiloxysilicate, polypropylsilsesquioxane, polymethylsilsesquioxane, acrylates/polytrimethylsiloxy-methacrylate copolymer, acrylates/dimethicone, acrylic acid/isobutyl acrylate/isobornyl acrylate copolymer ethylcellulose, as well as their mixtures.