WO2013093803A1

WO2013093803A1 - Composition comprising a fatty phase, a structuring agent and a hydrophilic compound and/or active agent

Info

Publication number: WO2013093803A1
Application number: PCT/IB2012/057484
Authority: WO
Inventors: Amélie HEURTEMATTE; Frédéric Auguste
Original assignee: L'oreal
Priority date: 2011-12-20
Filing date: 2012-12-19
Publication date: 2013-06-27
Also published as: FR2984140A1; FR2984140B1

Abstract

The present invention relates to a transparent composition comprising: - at least 90% by weight, relative to the total weight of said composition, of a fatty phase, said fatty phase being free of polyhydroxylated polar oil(s), - at least one agent for structuring the fatty phase, - preferably at least one coloring agent chosen from water-soluble or liposoluble dyes, pigments and nacres, and mixtures thereof, -at least one hydrophilic compound and/or hydrophilic active agent, in a content of between 0.5% and 8% by weight relative to the total weight of the composition, -said composition being free of water and of C₁ -C₄ alcohols.

Description

COMPOSITION COMPRISING A FATTY PHASE, A STRUCTURING AGENT AND A HYDROPHILIC COMPOUND AND/OR ACTIVE AGENT The present invention relates to the field of caring for and/or making up the skin and/or the lips, in particular the lips.

Compositions for caring for and/or making up the skin and/or the lips generally contain one or more fatty substances structured with a "structuring" or "gelling" agent, conventionally a wax or a polymer, to improve the stiffness of the compositions and especially to obtain solid compositions which remain stable in this state and in particular which do not exude, especially at room temperature.

Moreover, it may be desirable to introduce hydrophilic compounds therein, in particular when it is desired to favor the "care" properties of these compositions; it may be necessary to introduce therein hydrophilic active agents that are immiscible with the fatty phase.

However, when care and/or makeup compositions contain a large amount of fatty phase, it is difficult to introduce hydrophilic compounds therein without risk of destabilizing this phase.

The underlying problem of the present invention was that of obtaining a composition for caring for and/or making up the skin and/or the lips, containing a predominant fatty phase and containing, in appreciable amount, at least one hydrophilic compound that is immiscible with the fatty phase and that is liable to destabilize said fatty phase.

Moreover, the inventors wished said composition to be optionally endowed with particular visual properties.

The inventors have solved this problem by means of the composition according to the present invention.

Thus, according to a first aspect, a subject of the present invention is a transparent composition comprising:

- at least 90% by weight, relative to the total weight of said composition, of a fatty phase, said fatty phase being free of polyhydroxylated polar oil(s), - at least one agent for structuring the fatty phase,

- preferably at least one coloring agent chosen from water-soluble or liposoluble dyes, pigments and nacres, and mixtures thereof, - at least one hydrophilic compound and/or at least one hydrophilic active agent, in a content of between 0.5% and 8% by weight relative to the total weight of the composition,

- said composition being free of water and of C1 -C4 alcohols.

According to a second aspect, a subject of the present invention is a process for caring for and/or making up the skin and/or the lips, in which the composition according to the invention is applied to the skin and/or the lips.

According to a third aspect, a subject of the present invention is the use of the composition according to the invention for caring for and/or making up the skin and/or the lips and in particular for improving the comfort and/or moisturization of keratin materials, especially a use as a lipstick.

The compositions according to the invention have the advantage of being stable even when they comprise a large amount of hydrophilic compound(s), i.e. compounds that are immiscible with the fatty phase. Specifically, they may contain up to 8% by weight of hydrophilic compounds relative to the total weight of the composition; a person skilled in the art will preferably adjust this content as a function of the desired transparency.

The compositions according to the invention are stable and easy to apply, they especially have good properties in terms of glidance on application, and/or of the amount applied and/or of homogeneity deposit, the deposit is comfortable and moisturizing, and the gloss is preferably satisfactory.

Advantageously, the composition according to the invention is in solid form, for example in the form of a stick, which is sufficiently solid and stable, in particular so as not to break during the application of the composition.

These compositions are visually very satisfactory: they are formed from a transparent base, which is preferably colorless, containing a hydrophilic phase in the form of inclusions, which are preferably colored, of immiscible hydrophilic compounds.

The base, which is preferably transparent, comprises and is preferably formed from the fatty phase, the structuring agent(s) for said fatty phase and optionally the liposoluble dyestuff(s). HYDROPHILIC PHASE

The composition according to the invention comprises at least one hydrophilic compound chosen from: sorbitol, poly hydrogen alcohols and mixtures thereof, the poly hydrogen alcohols preferably being of C₂-Cs and more preferably of C3-C6, preferably such as glycerol, propylene glycol, 1,3-butylene glycol, dipropylene glycol or diglycerol, and mixtures thereof.

According to one particular mode, the hydrophilic compound is glycerol.

The hydrophilic compound is preferably present in the fatty phase in a total content of between 0.5% and 8% by weight relative to the total weight of the composition.

The hydrophilic phase forms inclusions, i.e. droplets uniformly distributed in said base.

The presence of said hydrophilic compounds also affords the keratin materials comfort and/or moisturization. Furthermore, these hydrophilic compounds may convey other additional compounds such as hydrophilic active agents that provide other care properties: antiaging, softening, tensioning, moisturizing, etc. properties.

Advantageously, the composition according to the invention comprises at least one hydrophilic active agent.

The term "active agent" means a compound that has a cosmetic and/or dermato logical effect especially on the lips. The hydrophilic active agent is preferably chosen from moisturizers, cicatrizing agents and antiaging agents, and mixtures thereof.

Preferably, the hydrophilic active agent is chosen from hyaluronic acid, AHAs, BHAs, serine, collagen, C-glycoside derivatives and in particular proxylane, i.e. C-β-ϋ- xylopyranoside-2-hydroxypropane especially in the form of a solution at 30% by weight of active material in a water/propylene glycol mixture (60%/40% by weight), also known as Hydro xypropyltetrahydropyrantriol sold under the name Mexoryl SBB by the company Chimex, collagen and chondroitin sulfate spheres of marine origin (Ateocollagen), hyaluronic acid spheres, ceramides preferably such as ceramide V, and sugars such as glucose, rhamnose, xylose, mannose and fructose, and mixtures thereof.

According to another particular mode, the hydrophilic active agent is C-β-ϋ- xylopyranoside-2-hydroxypropane in the form of a solution at 30% by weight of active material in a water/propylene glycol mixture (60%/40% by weight). The hydrophilic active agent is preferably present in the fatty phase in a total content of between 0.5% and 8% by weight relative to the total weight of the composition.

The total amount of hydrophilic compound(s) and/or of hydrophilic active agent(s) ranges from 0.5% to 8% and preferably from 1% to 5% by weight relative to the total weight of the composition.

The composition according to the invention is also free of water and of C1-C4 alcohols such as ethanol.

More generally, it is preferably free of polar protic solvents.

A polar protic solvent is a solvent that is capable of forming hydrogen bonds.

For the purposes of the invention, the expression "free of water and of C1-C4 alcohols" or more generally "free of polar protic solvents" means a composition containing less than 2% and preferably less than 0.5% by weight of water and of C1-C4 alcohols or more generally of polar protic solvents, relative to the total weight of the composition.

The expression "free of water and of C1-C4 alcohols" or more generally "free of polar protic solvents" especially means that these compounds may be present in trace amount, which may in particular be provided by ingredients of the composition that contain them in residual amount, but are not deliberately introduced into the composition according to the invention.

Consequently, the present composition is anhydrous.

For the purposes of the invention, the term "anhydrous composition" means a composition containing less than 2% and preferably less than 0.5% by weight of water relative to the total weight of the composition. Where appropriate, such small amounts of water may be provided by ingredients of the composition that contain it in residual amount, but are not deliberately provided.

For the purposes of the present invention, a polar protic solvent and the fatty phase are not in the form of a single-phase mixture, which is homogeneous at room temperature and at atmospheric pressure.

The term "polar protic solvent" does not cover the hydrophilic compounds under consideration according to the present patent application. In addition, the term "polar protic solvent" does not cover the water-soluble dyestuffs or the "hydrophilic active agents" as defined according to the invention.

The composition according to the invention comprises at least one inclusion and preferably a plurality of inclusions. The composition may thus comprise several types of inclusion of identical or different nature.

Such inclusions are uniformly or non-uniformly distributed depending on the intended effect in said fatty phase.

The inclusions are substances dispersed in the fatty phase, these substances more particularly being formed from one or more particular hydrophilic compounds that are immiscible with the fatty phase.

The inclusions are visible to the naked eye due to the presence of at least one dyestuff The dyestuffs give a very esthetic speckled effect.

These inclusions may also comprise liquid substances, liquid substances encapsulated in a solid envelope, and mixtures thereof.

The substances are said to be liquid or solid at a temperature of 25°C and at atmospheric pressure. The liquid substances may by extension comprise solid compounds dissolved in the hydrophilic compound.

In addition, the fatty phase may comprise several types of inclusion that will lead to inclusions of differing visual aspect: size, color, etc.

The compositions according to the invention comprising inclusions of hydrophilic compounds are distinguished from dispersions/emulsions in that they do not contain any dispersing emulsifier. They are obtained by mixing the fatty phase and the hydrophilic phase that will form the inclusions with mechanical stirring.

The inclusions are generally of spherical or ovoidal shape, and have a size of greater than or equal to 1 μιη to 100 000 μιη, better still between 10 and 50 000 μιη, in particular between 10 and 1000 μιη and better still from 10 to 650 μιη.

Other subjects, aspects, properties and advantages of the present invention are presented in the rest of the present description.

For the purposes of the invention, the term "transparent composition" means a composition which transmits at least 40% of light at a wavelength of 750 nm without scattering it, i.e. a composition in which the scattering angle of the light is less than 5° and is better still about 0°.

The transparent composition may transmit at least 50%, especially at least 60% and especially at least 70% of light at a wavelength of 750 nm.

The transmission measurement is made with a Cary 300 Scan UV-visible spectrophotometer from the company Varian, according to the following protocol:

- the composition is poured into a square-sided spectrophotometer cuvette with a side length of 10 mm;

- the sample of the composition is then maintained in a thermostatically- regulated chamber at 20°C for 24 hours;

- the light transmitted through the sample of the composition is then measured on the spectrophotometer by scanning wavelengths ranging from 700 nm to 800 nm, the measurement being made in transmission mode;

- the percentage of light transmitted through the sample of the composition at a wavelength of 750 nm is then determined.

The transparent compositions, when they are placed 0.01 m in front of a black line 2 mm thick in diameter drawn on a sheet of white paper, allows this line to be seen; in contrast, an opaque composition, i.e. a non-transparent composition, does not allow the line to be seen.

Preferably, the transparent base is a colorless composition.

For the purposes of the invention, the term "colorless composition" means that the composition absorbs light outside the visible range, i.e. outside the range of wavelengths between 400 and 700 nm and advantageously between 380 and 780 nm.

According to another variant, the transparent base is a colored composition. In this case, the base comprises at least one liposoluble dyestuff chosen from nacres and dyes. The base may also comprise one or more liposoluble pigments, and in this case the content of liposoluble pigments will be less than 1% by weight relative to the total weight of the total composition. BASE

FATTY PHASE

The fatty phase represents at least 90% by weight and more preferably 95% by weight relative to the total weight of said composition.

The fatty phase of the composition according to the invention comprises at least one polar nonvolatile oil.

The term "oil" means a water-immiscible nonaqueous compound that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg).

The term "nonvolatile oil" means an oil that remains on keratin materials, at room temperature and atmospheric pressure, for at least several hours and that especially has a vapor pressure of less than 10^~3 mmHg (0.13 Pa). A nonvolatile oil may also be defined as having an evaporation rate such that, under the conditions defined previously, the amount evaporated after 30 minutes is less than 0.07 mg/cm².

Hydrocarbon-based apolar oils

According to a first embodiment, the composition according to the invention also comprises at least one apolar hydrocarbon-based oil, preferably at least one nonvolatile apolar hydrocarbon-based oil.

These oils may be of vegetable, mineral or synthetic origin.

For the purposes of the present invention, the term "apolar oil" means an oil whose solubility parameter at 25°C, 6_a, is equal to 0 (J/cm³)^½.

The definition and calculation of the solubility parameters in the Hansen three- dimensional solubility space are described in the article by CM. Hansen: "The three dimensional solubility parameters", J. Paint Technol. 39, 105 (1967).

According to this Hansen space:

- 6D characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts;

- δ_ρ characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles;

- 6_h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.); and

- 5_a is determined by the equation: δ_α= (δ_ρ ² + 6_h ²)^½.

The parameters δ_ρ, 6_h, 6o and 6_a are expressed in (J/cm³)^½. The term "hydrocarbon-based oil" means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The term "hydrocarbon-based ester oil" means a hydrocarbon-based oil comprising at least one ester group.

Preferably, the nonvolatile apolar hydrocarbon-based oil is free of oxygen atoms.

Preferably, the nonvolatile apolar hydrocarbon-based oil may be chosen from linear or branched hydrocarbons of mineral or synthetic origin, such as:

- liquid paraffin or derivatives thereof,

- squalane,

- isoeicosane,

- liquid petroleum jelly,

- naphthalene oil,

- polybutylenes such as Indopol H-100 (molar mass or MW = 965 g/mol), Indopol H-300 (MW = 1340 g/mol) and Indopol H-1500 (MW = 2160 g/mol) sold or manufactured by the company Amoco,

- hydrogenated polyisobutylenes such as Parleam® sold by the company Nippon Oil Fats, Panalane H-300 E sold or manufactured by the company Amoco (MW =

1340 g/mol), Viseal 20000 sold or manufactured by the company Synteal (MW = 6000 g/mol) and Rewopal PIB 1000 sold or manufactured by the company Witco (MW = 1000 g/mol),

- decene/butene copolymers, polybutene/polyisobutene copolymers, especially Indopol L- 14,

- polydecenes and hydrogenated polydecenes such as: Puresyn 10 (MW = 723 g/mol) and Puresyn 150 (MW = 9200 g/mol) sold or manufactured by the company Mobil Chemicals,

- and mixtures thereof.

Preferably, the content of apolar nonvolatile oil in the composition according to the invention ranges from 0 to 25%, advantageously from 1% to 20% and in particular from 2% to 18% by weight relative to the total weight of the composition. Polar oils

The composition according to the invention comprises at least one polar nonvolatile oil, preferably chosen from hydrocarbon-based oils and fluoro oils.

The fatty phase is advantageously free of polyhydroxylated oils; specifically, these oils, especially on account of their high polarity, would risk compromising the transparent appearance of the composition in accordance with the invention.

The term "silicone oil" means an oil containing at least one silicon atom, and especially containing Si-0 groups.

The term "fluoro oil" means an oil containing at least one fluorine atom.

According to a first preferred embodiment, said nonvolatile polar oil is a hydrocarbon-based oil.

For the purposes of the present invention, the term "polar oil" means an oil whose solubility parameter at 25°C, 6_a, is other than 0 (J/cm³)^½.

These oils may be of vegetable, mineral or synthetic origin.

Nonvolatile hydrocarbon-based oil

In particular, the nonvolatile polar hydrocarbon oil may be chosen from the list of oils below, and mixtures thereof:

- hydrocarbon-based plant oils such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance heptanoic or octanoic acid triglycerides or jojoba oil;

- hydrocarbon-based esters of formula RCOOR' in which RCOO represents a carboxylic acid residue containing from 2 to 30 carbon atoms, and R' represents a hydrocarbon-based chain containing from 1 to 30 carbon atoms, such as isononyl isononanoate, oleyl erucate or 2-octyldodecyl neopentanoate; isopropyl myristate;

- polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diol, such as those described in patent application FR 0 853 634, in particular such as dilinoleic acid and 1 ,4-butanediol. Mention may especially be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H (INCI name: Dilinoleic Acid/Butanediol Copolymer), or copolymers of polyols and of diacid dimers, and esters thereof, such as Hailuscent ISDA, - fatty monoalcohol or monohydroxylated alcohol oils containing from 12 to 26 carbon atoms, which are preferably branched, for instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol and isostearyl alcohol; the alcohol oil is preferably isostearyl alcohol;

- higher C12-C22 fatty acids, such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof;

- oils of plant origin, such as sesame oil (820.6 g/mol);

- fatty acids containing from 12 to 26 carbon atoms, for instance oleic acid;

- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC^® by Cognis; and

- nonvolatile oils of high molecular mass, for example between 650 and 10 000 g/mol, for instance:

i) vinylpyrrolidone copolymers such as the vinylpyrrolidone/l-hexadecene copolymer, Antaron V-216 sold or manufactured by the company ISP (MW = 7300 g/mol), ii) ester oils such as:

a) linear fatty acid esters with a total carbon number ranging from 35 to 70, for instance pentaerythrityl tetrapelargonate (MW = 697.05 g/mol),

b) hydroxylated esters such as polyglycerol-2 triisostearate (MW = 965.58 g/mol);

c) aromatic esters such as tridecyl trimellitate (MW = 757.19 g/mol), d) esters of C24-C28 branched fatty acids or fatty alcohols such as those described in patent application EP-A-0 955 039, and especially triisoarachidyl citrate (MW = 1033.76 g/mol), pentaerythrityl tetraisononanoate (MW = 697.05 g/mol), glyceryl triisostearate (MW = 891.51 g/mol), glyceryl tris(2-decyl)tetradecanoate (MW = 1143.98 g/mol), pentaerythrityl tetraisostearate (MW = 1202.02 g/mol), polyglyceryl-2 tetraisostearate (MW = 1232.04 g/mol) or else pentaerythrityl tetrakis(2- decyl)tetradecanoate (MW = 1538.66 g/mol),

e) esters and polyesters of a diol dimer and of a monocarboxylic or dicarboxylic acid, such as esters of a diol dimer and of a fatty acid and esters of a diol dimer and of a dicarboxylic acid dimer; mention may be made especially of the esters of dilinoleic diacids and of dilinoleyl diol dimers sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5^® and DD-DA7^®, - and mixtures thereof.

The esters of a diol dimer and of a monocarboxylic acid may be obtained from a monocarboxylic acid containing from 4 to 34 carbon atoms and especially from 10 to 32 carbon atoms, which acids are linear or branched, and saturated or unsaturated.

As illustrative examples of monocarboxylic acids that are suitable for use in the invention, mention may be made especially of fatty acids.

The esters of a diol dimer and of a dicarboxylic acid may be obtained from a dicarboxylic acid dimer derived in particular from the dimerization of an unsaturated fatty acid especially of Cs to C34, especially C₁₂ to C22, in particular C₁₆ to C20 and more particularly C₁₈.

According to one particular variant, it is more particularly the dicarboxylic acid dimer from which the diol dimer to be esterified is also derived.

The esters of a diol dimer and of a carboxylic acid may be obtained from a diol dimer produced by catalytic hydrogenation of a dicarboxylic acid dimer as described previously, for example hydrogenated dilinoleic diacid.

As illustrations of diol dimer esters, mention may be made especially of esters of dilinoleic diacids and of dilinoleyl diol dimers sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5® and DD-DA7®.

Preferably, the composition according to the invention comprises at least one nonvolatile oil chosen from hydrocarbon-based polar oils, preferably chosen from ester oils and monohydroxylated alcohol oils, and mixtures thereof.

Preferably, the composition according to the invention comprises at least one nonvolatile ester oil, preferably with a molecular weight of greater than 650 g/mol, preferably chosen from aromatic esters such as tridecyl trimellitate.

Preferably, the ester oils are chosen from isononyl isononanoate, isotridecyl isononanoate, tridecyl trimellitate and diisostearyl malate.

Preferably, the alcohol oils are chosen from octyldodecanol and isostearyl alcohol.

Preferably, the hydrocarbon-based nonvolatile polar oil is present in a total content of between 1% and 60%, preferably between 3% and 50% by weight, preferably between 5% and 40%, more preferably between 7% and 20% and even more preferably between 10% and 15% by weight relative to the weight of the composition. Preferably, the hydrocarbon-based nonvolatile polar oil is chosen from fatty monoalcohol or monohydroxylated alcohol oils containing from 12 to 26 carbon atoms.

Preferably, octyldodecanol and/or isostearyl alcohol are present in a total content of between 3% and 50% by weight, preferably between 5% and 40%> and more preferably between 7% and 20% by weight relative to the weight of the composition. Even more preferably, octyldodecanol and/or isostearyl alcohol are present in a total content of between 8% and 15% by weight relative to the weight of the composition. Preferably, isostearyl alcohol is present in a total content of between 3% and

50%) by weight, preferably between 5% and 40%> and more preferably between 7% and 20% by weight relative to the weight of the composition. Even more preferably, isostearyl alcohol is present in a total content of between 8% and 15% by weight relative to the weight of the composition.

Nonvolatile fluoro oil

According to a second embodiment, the second nonvolatile oil is a fluoro oil.

The term "fluoro oil" means an oil containing at least one fluorine atom.

The fluoro oils that may be used according to the invention may be chosen from fluorosilicone oils, fluoro polyethers and fluorosilicones as described in document EP-A-847 752, and perfluoro compounds.

According to the invention, the term "perfluoro compounds" means compounds in which all the hydrogen atoms have been replaced with fluorine atoms.

According to one particularly preferred embodiment, the fluoro oil according to the invention is chosen from perfluoro oils.

As examples of perfluoro oils that may be used in the invention, mention may be made of perfluorodecalins and perfluoroperhydrophenanthrenes.

According to one particularly preferred embodiment, the fluoro oil is chosen from perfluoroperhydrophenanthrenes, and especially the Fiflow® products sold by the company Creations Couleurs. In particular, use may be made of the fluoro oil for which the INCI name is Perfluoroperhydrophenanthrene, sold under the reference Fiflow 220 by the company F2 Chemicals. Preferably, the composition according to the invention advantageously contains from 1% to 90% by weight, in particular from 2% to 70% by weight and better still from 2% to 60% by weight of polar nonvolatile oil, relative to the total weight of the composition.

Preferably, the composition according to the invention is free of additional volatile oil.

The term "volatile oil" means an oil (or nonaqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a nonzero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10^~3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.1 to 10 mmHg).

Advantageously, the fatty phase comprises less than 0.5%> and better still less than 0.1% of wax, and even better still is free of wax. The reason for this is that such waxes would risk compromising the transparent appearance that is advantageously sought for a composition in accordance with the invention.

The wax under consideration is in general a lipophilic compound that is solid at room temperature (25°C), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and in particular up to 120°C.

In particular, the waxes that are suitable for use in the invention may have a melting point of greater than or equal to 45°C and in particular greater than or equal to 55°C.

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

Preferably, the waxes have a heat of fusion AHf of greater than or equal to 70

J/g. Preferably, the waxes comprise at least one crystallizable part, which is visible by X-ray observation.

The measuring protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from -20°C to 120°C, at a heating rate of 10°C/minute, is then cooled from 120°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 120°C at a heating rate of 5°C/minute. During the second temperature rise, the following parameters are measured:

- the melting point (T_f) of the wax, as mentioned previously corresponding to the temperature of the most endothermic peak of the melting curve observed, representing the variation of the difference in power absorbed as a function of the temperature,

- AHf: the heat of fusion of the wax, corresponding to the integral entire melting curve obtained. This heat of fusion of the wax is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.

The composition according to the invention may also contain at least one pasty fatty substance.

The term "pasty fatty substance" (also called "pasty compound") refers to a lipophilic fatty compound with a reversible solid/liquid change of state and comprising, at a temperature of 23°C, a liquid fraction and a solid fraction.

In other words, the starting melting point of the pasty compound can be less than 23°C. The liquid fraction of the pasty compound measured at 23°C can represent 9% to 97% by weight of the compound. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.

Preferably, the pasty fatty substances have an end melting point of less than 60°C.

Preferably, the pasty fatty substances have a hardness of less than or equal to 6

MPa.

Preferably, the pasty fatty substances have, in the solid state, an anisotropic crystal organization, which is visible by X-ray observation.

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

As regards the measurement of the melting point and the determination of the end melting point, the sample preparation and measurement protocols are as follows:

A sample of 5 mg of pasty fatty substance, preheated to 80°C and withdrawn with magnetic stirring using a spatula that is also heated, is placed in a hermetic aluminum capsule, or a crucible. Two tests are performed to ensure the reproducibility of the results.

The measurements are performed on the abovementioned calorimeter. The oven is flushed with nitrogen. Cooling is performed by an RCS 90 heat exchanger. The sample is then subjected to the following protocol: it is first placed at a temperature of 20°C, and then subjected to a first temperature rise passing from 20°C to 80°C, at a heating rate of 5°C/minute, then is cooled from 80°C to -80°C at a cooling rate of 5°C/minute and finally subjected to a second temperature rise passing from -80°C to 80°C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference between the power absorbed by the empty crucible and the crucible containing the sample of paste or wax as a function of the temperature is measured. The melting point of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The end melting point corresponds to the temperature at which 95% of the sample has melted.

The liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty compound.

The enthalpy of fusion of the pasty compound is the heat consumed by the compound in order to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when all of its mass is in crystalline solid form. The pasty compound is said to be in the liquid state when all of its mass is in liquid form.

The heat of fusion of the pasty compound is equal to the integral of the entire melting curve obtained using the abovementioned colorimeter, with a temperature rise of 5 or 10°C/minute, according to standard ISO 11357-3: 1999. The heat of fusion of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g. The heat of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23°C, constituted of a liquid fraction and a solid fraction.

The liquid fraction of the pasty compound measured at 32°C preferably represents from 30% to 100% by weight of the compound, preferably from 50%> to 100%, more preferably from 60% to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32°C is equal to 100%), the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.

The liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound. The heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.

As regards the measurement of the hardness, the sample preparation and measurement protocols are as follows:

The pasty fatty substance is placed in a mold 75 mm in diameter, which is filled to about 75% of its height. In order to overcome the thermal history and to control the crystallization, the mold is placed in a Votsch VC0018 programmable oven, where it is first placed at a temperature of 80°C for 60 minutes, then cooled from 80°C to 0°C at a cooling rate of 5°C/minute, and then left at the stabilized temperature of 0°C for 60 minutes, and then subjected to a temperature rise ranging from 0°C to 20°C, at a heating rate of 5°C/minute, and then left at the stabilized temperature of 20°C for 180 minutes.

The compression force measurement is taken using a ΤΑ/ΤΧ2Ϊ texturometer from Swantech. The spindle used is chosen according to the texture:

- cylindrical steel spindle 2 mm in diameter for very rigid starting materials; - cylindrical steel spindle 12mm in diameter for sparingly rigid starting materials.

The measurement comprises three steps: a first step after automatic detection of the surface of the sample, where the spindle moves at a measuring speed of 0.1 mm/s, and penetrates into the pasty fatty substance to a penetration depth of 0.3 mm, the software notes the maximum force value reached; a second "relaxation" step where the spindle remains at this position for one second and the force is noted after 1 second of relaxation; finally, a third "withdrawal" step in which the spindle returns to its initial position at a speed of 1 mm/s, and the probe withdrawal energy (negative force) is noted.

The hardness value measured during the first step corresponds to the maximum compression force measured in newtons divided by the area of the texturometer cylinder expressed in mm² in contact with the pasty fatty substance. The hardness value obtained is expressed in megapascals or MPa.

AGENT FOR STRUCTURING THE FATTY PHASE

The structuring agent is chosen from structuring polymers and lipophilic gelling agents, i.e. oil-gelling agents, also known as "organogelling agents", and mixtures thereof.

The fatty phase may also comprise several structuring agents chosen from structuring polymers and lipophilic gelling agents; this will then be referred to as a "structuring system".

ORGANOGELLING AGENT

The composition according to the invention may contain one or more particular organogelling agents.

According to the invention, an "organogelling agent" is defined as comprising an organic compound whose molecules may be capable of establishing, between themselves, at least one physical interaction leading to self-aggregation of the molecules with formation of a three-dimensional macromolecular network that may be responsible for the gelation of the liquid fatty phase. The network may result from the formation of a network of fibrils (caused by the stacking or aggregation of organogelling molecules), which immobilizes the molecules of the liquid fatty phase. Depending on the nature of the organogelling agent, the interconnected fibrils have variable sizes that may range from a few nanometers up to 1 μιη or even several micrometers. These fibrils may occasionally combine to form strips or columns.

The term "gelation" means structuring or, more generally, thickening of the medium, which may lead according to the invention to a fluid to pasty or even solid consistency. The ability to form this network of fibrils, and thus to gel the composition, depends on the nature (or chemical class) of the organogelling agent, on the nature of the substituents borne by its molecules for a given chemical class, and on the nature of the liquid fatty phase.

For example, this gelation is reversible under the action of an external stimulus such as the temperature.

The physical interactions are of diverse nature but may include co- crystallization. These physical interactions are, for example, interactions chosen from self- complementary hydrogen interactions, π interactions between unsaturated nuclei, dipolar interactions, and coordination bonds with organometallic derivatives. The establishment of these interactions may often be promoted by the architecture of the molecule, for example by nuclei, unsaturations and the presence of asymmetric carbon. In general, each molecule of an organogelling agent can establish several types of physical interaction with a neighboring molecule. Thus, in one embodiment, the molecules of the organic gelling agent according to the invention may comprise at least one group that is capable of establishing hydrogen bonds, for example at least two groups that are capable of establishing hydrogen bonds; at least one aromatic nucleus, for example at least two aromatic nuclei; at least one bond with ethylenic unsaturation; and/or at least one asymmetric carbon. The groups that are capable of forming a hydrogen bond may be chosen, for example, from hydroxyl, carbonyl, amine, carboxylic acid, amide, benzyl, sulfonamide, carbamate, thiocarbamate, urea, thiourea, oxamido, guanidino and biguanidino groups.

The organogelling agents of the invention may be solid or liquid at room temperature (20°C) and at atmospheric pressure.

Among the lipophilic gelling agents that may be mentioned are combinations of at least one low molecular weight dialkyl N-acylglutamide, chosen especially from (C₂- C₆)dialkyl N-acylglutamides in which the acyl group comprises a linear Cs to C₂₂ alkyl chain such as lauroylglutamic acid dibutylamide (or dibutyl lauroyl glutamide), with at least one low molecular weight dialkyl N-acylglutamide containing a branched alkyl chain, chosen especially from (C₂-C6)dialkyl N-acylglutamides in which the acyl group comprises a branched Cs to C₂₂ alkyl chain such as N-2-ethylhexanoyl glutamic acid dibutylamide (or dibutyl ethylhexanoyl glutamide) and preferably with a solvent that is capable of forming hydrogen bonds with these two low molecular weight lipophilic gelling agents.

Preferably, the dialkyl N-acylglutamide with a linear alkyl chain is used in a content ranging from 0.1% to 10%, preferably 0.5% to 5% and more preferably 1.0% to 3.0% by weight relative to the total weight of the fatty phase.

Preferably, the dialkyl N-acylglutamide with a branched alkyl chain is used in an amount ranging from 0.1% to 10%, preferably 0.5% to 5% and more preferably 1.0% to 3.0% by weight relative to the total weight of the fatty phase.

More preferably, the total amount of the lipophilic gelling agents of low molecular weight N-acylglutamic acid diamide type is preferably less than or equal to 7% by weight relative to the total weight of the fatty phase.

Lauroylglutamic acid dibutylamide is sold by the company Ajinomoto under the name GP-1, of INCI name: Dibutyl Lauroyl Glutamide, and N-2- ethylhexanoylglutamic acid dibutylamide is sold or manufactured by the company Ajinomoto under the name EB-21 , of INCI name: Dibutyl Ethylhexanoyl Glutamide. Such a compound is described in patent application JP2005-298635.

According to a preferred variant, the ratio of the low molecular weight linear-chain N- acylglutamic acid diamides/low molecular weight branched-chain N-acylglutamic acid diamide is between 1/1 and 5/1, preferably between 1.5/1 and 3/1 and preferably between 1.7/1 and 2/1.

The solvent that is capable of forming hydrogen bonds with the lipophilic gelling agents is a protic solvent preferentially chosen, for example, from alcohols, especially monoalcohols comprising more than 8 carbon atoms, dialcohols, acids and esters.

Preferably, the solvent that is capable of forming hydrogen bonds between the lipophilic gelling agents is chosen from C2-C5 glycols such as propylene glycol, butylene glycols and pentene glycols. This solvent may also be chosen from octyldodecanol and isostearyl alcohol. The amount of solvents capable of forming hydrogen bonds ranges from 3%) to 50%) by weight, preferably between 5% and 40%> and more preferably from 7% to 20% by weight relative to the total weight of the base. Preferentially, the solvent is a fatty alcohol, particularly chosen from fatty alcohols with a fatty chain length of between 12 and 28 carbon atoms, preferentially between 14 and 22 and better still between 16 and 20 carbon atoms.

Even more particularly, the solvent is a branched fatty-chain alcohol.

Among the lipophilic gelling agents that may be mentioned are fatty acid esters of dextrin such as dextrin palmitates, especially those sold under the names Rheopearl TL^® or Rheopearl KL^® by the company Chiba Flour; hydroxylated fatty acids, such as hydroxystearic acid, glyceryl esters such as glyceryl behenate/isostearate/eicosadioate.

STRUCTURING POLYMERS

Among the structuring polymers that may be mentioned are hydrocarbon-based polyamides, silicone polyamides, block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene, hydrocarbon-based indene resins, and polyurethanes of INCI name Dilinoleyl dimer diol-based polyurethane, or mixtures thereof.

Among the block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene or a mixture thereof, mention may be made especially of:

styrene-ethylene/propylene copolymers, styrene-ethylene/butadiene copolymers and styrene-ethylene/butylene copolymers. These diblock polymers are especially sold under the name Kraton® G 170 IE by the company Kraton Polymers;

- styrene-ethylene/propylene-styrene copolymers, styrene-ethylene/butadiene- styrene copolymers, styrene-ethylene/butylene-styrene copolymers, styrene-isoprene- styrene copolymers and styrene-butadiene-styrene copolymers. These triblock polymers are especially sold under the names Kraton® G1650, Kraton® G1652, Kraton® D1101, Kraton® Dl 102 and Kraton® Dl 160 by the company Kraton Polymers. The structuring polymer may also be chosen from indene hydrocarbon-based resins, preferably such as resins derived from the polymerization in major proportion of indene monomer and in minor proportion of a monomer chosen from styrene, methylindene and methylstyrene, and mixtures thereof. These resins may optionally be hydrogenated. These resins may have a molecular weight ranging from 290 to 1150 g/mol.

Examples of indene resins that may be mentioned include those sold under the reference Escorez 7105 by the company Exxon Chem., Nevchem 100 and Nevex 100 by the company Neville Chem., Norsolene SI 05 by the company Sartomer, Picco 6100 by the company Hercules and Resinall by the company Resinall Corp., or the hydrogenated indene/methylstyrene/styrene copolymers sold under the name "Regalite" by the company Eastman Chemical, in particular Regalite R1100, Regalite R1090, Regalite R-7100, Regalite R1010 Hydrocarbon Resin and Regalite Rl 125 Hydrocarbon Resin.

POLYAMIDES

For the purposes of the invention, the term "polymer" means a compound containing at least two repeating units, preferably at least three repeating units and better still ten repeating units.

For the purposes of the invention, the term "polyamide" means a compound containing at least two repeating amide units, preferably at least three repeating amide units and better still ten repeating amide units.

Hydrocarbon-based polyamide

The term "hydrocarbon-based polyamide" means a polyamide formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

For the purposes of the invention, the term "functionalized chains" means an alkyl chain comprising one or more functional groups or reagents chosen especially from hydroxyl, ether, ester, oxyalkylene and polyoxyalkylene groups.

Advantageously, this polyamide of the composition according to the invention has a weight-average molecular mass of less than 100 000 g/mol (especially ranging from 1000 to 100 000 g/mol), in particular less than 50 000 g/mol (especially ranging from 1000 to 50 000 g/mol) and more particularly ranging from 1000 to 30 000 g/mol, preferably from 2000 to 20 000 g/mol and better still from 2000 to 10 000 g/mol.

This polyamide is insoluble in water, especially at 25°C. According to a first embodiment of the invention, the polyamide used is a polyamide of formula (I):

in which X represents a group -N(Ri)₂ or a group -ORi in which Ri is a linear or branched C8 to C₂₂ alkyl radical which may be identical or different, R₂ is a C -C₄₂ diacid dimer residue, R₃ is an ethylenediamine radical and n is between 2 and 5;

and mixtures thereof.

According to a particular mode, the polyamide used is an amide-terminated polyamide of formula (la)

in which X represents a group -N(Ri)₂ in which Ri is a linear or branched Cs to C₂₂ alkyl radical which may be identical or different, R₂ is a C₂s-C₄₂ diacid dimer residue, R₃ is an ethylenediamine radical and n is between 2 and 5;

and mixtures thereof.

The composition may also comprise, additionally in this case, at least one additional polyamide of formula (lb)

X- -C— R^C— NH-R^NH- -C— R₉— C-X

O O O O (lb)

in which X represents a group -ORi in which Ri is a linear or branched Cs to C₂₂ and preferably C₁₆ to C₂₂ alkyl radical which may be identical or different, R₂ is a C -C₄₂ diacid dimer residue, R₃ is an ethylenediamine radical and n is between 2 and 5.

As polyamide compounds of formula (lb)

X- -C— R^C— NH-R^NH- -C— R₉— C-X

O O O O (lb) in which X represents a group -ORi in which Ri is a linear or branched Cs to C₂₂ and preferably C₁₆ to C₂₂ alkyl radical which may be identical or different, R₂ is a C28-C42 diacid dimer residue, R₃ is an ethylenediamine radical and n is between 2 and 5, mention may be made of the commercial products sold by the company Arizona Chemical under the names Uniclear 80 and Uniclear 100 or Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG, the INCI name of which is Ethylenediamine/stearyl dimer dilinoleate copolymer. They are sold, respectively, in the form of a gel containing 80% active material in a mineral oil and at 100% active material. They have a softening point of from 88 to 94°C. These commercial products are a mixture of copolymers of a C₃₆ diacid coupled with ethylenediamine, having a weight-average molecular mass of about 6000 g/mol. The terminal ester groups result from the esterification of the remaining acid end groups with cetyl alcohol, stearyl alcohol or mixtures thereof (also known as cetylstearyl alcohol).

As amide-terminated polyamide compounds such as those described in patent application US 2009/0 280 076, and in particular an amide-terminated polyamide of formula (la)

X- -C I I— R ^^C I I— NH-R^NH- -R„— C-X

I I I I I I

O O O O (la)

in which X represents a group -N(Ri)₂ in which Ri is a linear or branched Cs to C22, preferably Cs to C20, preferably C₁₄ to C20 and more preferentially C₁₄ to C₁₈ and better still Ci8 alkyl radical, which may be identical or different, R₂ is a C28-C42 diacid dimer residue, preferably a dilinoleic acid dimer residue, R₃ is an ethylenediamine radical, and n is between 2 and 5 and preferably between 3 and 4; mention may be made of the compound of formula (la) whose INCI name is Bis-dioctadecylamide dimer dilinoleic acid/ethylenediamine copolymer.

As a specific example of an amide-terminated polyamide that may be used, mention may be made of the compound Haimalate PAM sold by the company Kokyu Alcohol Kogyo, which is in combination with diisostearyl malate and whose INCI name is Diisostearyl malate (and) bis-dioctadecylamide dimer dilinoleic acid/ethylenediamine copolymer. According to another embodiment of the invention, the polyamide is a silicone polyamide.

Silicone polyamide

The silicone polyamides of the composition are preferably solid at room temperature (25°C) and atmospheric pressure (760 mmHg).

The silicone polyamides may be more particularly polymers comprising at least one unit of formula (III) or (IV):

(m) or

(IV) in which:

• R⁴, R⁵, R⁶ and R⁷, which may be identical or different, represent a group chosen from:

- linear, branched or cyclic, saturated or unsaturated, C₁-C40 hydrocarbon- based groups, possibly containing in their chain one or more oxygen, sulfur and/or nitrogen atoms, and possibly being partially or totally substituted with fluorine atoms, - C₆ to Cio aryl groups, optionally substituted with one or more Ci to C₄ alkyl groups,

- polyorganosiloxane chains possibly containing one or more oxygen, sulfur and/or nitrogen atoms,

· the groups X, which may be identical or different, represent a linear or branched Ci to C₃o alkylenediyl group, possibly containing in its chain one or more oxygen and/or nitrogen atoms;

• Y is a saturated or unsaturated Ci to C50 linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene divalent group, which may comprise one or more oxygen, sulfur and/or nitrogen atoms, and/or may bear as substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C₃ to Cs cycloalkyl, Ci to C₄o alkyl, C₅ to Cio aryl, phenyl optionally substituted with one to three Ci to C₃ alkyl, Ci to C₃ hydroxyalkyl and Ci to C₆ aminoalkyl groups, or Y represents a group corresponding to the formula:

in which:

T represents a linear or branched, saturated or unsaturated, C₃ to C₂₄ trivalent or tetravalent hydrocarbon-based group optionally substituted with a polyorganosiloxane chain, and possibly containing one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and

R⁸ represents a linear or branched C₁-C50 alkyl group or a polyorganosiloxane chain, possibly comprising one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups, which may possibly be linked to another chain of the polymer;

• n is an integer ranging from 2 to 500 and preferably from 2 to 200, and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200.

According to the invention, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of the polymer are preferably chosen from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of the polymer are methyl groups. According to the invention, Y can represent various divalent groups, furthermore optionally comprising one or two free valencies to establish bonds with other units of the polymer or copolymer. Preferably, Y represents a group chosen from:

a) linear Ci to C20 and preferably Ci to C10 alkylene groups,

b) branched C30 to C50 alkylene groups possibly comprising rings and unconjugated unsaturations,

c) C5-C6 cycloalkylene groups,

d) phenylene groups optionally substituted with one or more Ci to C40 alkyl groups,

e) Ci to C20 alkylene groups comprising from 1 to 5 amide groups, f) Ci to C20 alkylene groups comprising one or more substituents chosen from hydroxyl, C₃ to Cs cycloalkane, Ci to C₃ hydroxyalkyl and Ci to C₆ aminoalkyl groups,

g) polyorganosiloxane chains of formula:

or

in which R⁴, R⁵, R⁶, R⁷, T and m are as defined above.

Such a unit may be obtained: either by a condensation reaction between a silicone containing α, co- carboxylic acid ends and one or more diamines, according to the following reaction scheme:

or by reaction of two molecules of a-unsaturated carboxylic acid with a diamine according to the following reaction scheme:

CH,=CH-X¹-COOH+H,N-Y-NH-

CH,=CH-X -CO-NH-Y-NH-CO-X -CH=CH- followed by the addition of a siloxane to the ethylenic unsaturations, according to the following scheme:

CH₂=CH-X¹-CO-NH-Y-NH-CO-X¹-CH=CH;

in which X¹-(CH₂)2- corresponds to X defined above and Y, R⁴, R⁵, R⁶, R⁷ and m are as defined above, or by reaction of a silicone containing α, co-NH₂ ends and a diacid of formula HOOC-Y-COOH according to the following reaction scheme:

In these silicone polyamides of formula (III) or (IV), m is in the range from 1 to 700, in particular from 15 to 500 and especially from 50 to 200, and n is in particular in the range from 1 to 500, preferably from 1 to 100 and better still from 4 to 25,

X is preferably a linear or branched alkylene chain containing from 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially from 5 to 15 carbon atoms and more particularly 10 carbon atoms, and

Y is preferably an alkylene chain that is linear or branched or that possibly comprises rings and/or unsaturations, containing from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms and better still from 2 to 6 carbon atoms, in particular 6 carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y can optionally contain in its alkylene portion at least one of the following components:

• 1 to 5 amide, urea, urethane or carbamate groups,

• a C₅ or C₆ cycloalkyl group, and

• a phenylene group optionally substituted with 1 to 3 identical or different Ci to C₃ alkyl groups.

In formulae (III) and (IV), the alkylene groups may also be substituted with at least one component chosen from the group consisting of:

a hydroxy 1 group,

a C₃ to Cs cycloalkyl group, one to three Ci to C40 alkyl groups,

a phenyl group optionally substituted with one to three Ci to C₃ alkyl groups,

a Ci to C₃ hydroxyalkyl group, and

a Ci to C₆ aminoalkyl group.

In these formulae (III) and IV), Y may also represent:

in which R represents a polyorganosiloxane chain and T represents a group of formula:

_(CH₂)_a C (CH₂)_b Or (CH2)_a N (CH₂)_b .

(CH2)_C (C¾)_c

in which a, b and c are, independently, integers ranging from 1 to 10, and R¹³ is a hydrogen atom or a group such as those defined for R⁴, R⁵, R⁶ and R⁷.

In formulae (III) and (IV), R⁴, R⁵, R⁶ and R⁷ preferably represent, independently, a linear or branched Ci to C40 alkyl group, preferably a CH₃, C2H5, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.

As has been seen previously, the polymer may comprise identical or different units of formula (III) or (IV).

Thus, the polymer may be a polyamide containing several units of formula (III) or (IV) of different lengths, i.e. a polyamide corresponding to formula (V):

(V)

in which X, Y, n and R⁴ to R⁷ have the meanings given above, mi and m₂, which are different, are chosen in the range from 1 to 1000, and p is an integer ranging from 2 to 300.

In this formula, the units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer. In this copolymer, the units may be not only of different lengths, but also of different chemical structures, for example containin different groups Y. In this case, the polymer may correspond to formula VI:

(VI)

in which R⁴ to R⁷, X, Y, m_{l s} m₂, n and p have the meanings given above and Y¹ is different than Y but chosen from the groups defined for Y. As previously, the various units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the silicone polyamide may also consist of a grafted copolymer. Thus, the polyamide containing silicone units may be grafted and optionally crosslinked with silicone chains containing amide groups. Such polymers may be synthesized with trifunctional amines.

In this case, the polymer may comprise at least one unit of formula (VII):

(VII) in which X¹ and X², which are identical or different, have the meaning given for X in formula (III), n is as defined in formula (III), Y and T are as defined in formula (III), R¹⁴ to R²¹ are groups chosen from the same group as R⁴ to R⁷, mi and m₂ are numbers in the range from 1 to 1000, and p is an integer ranging from 2 to 500.

In formula (VII), it is preferred that:

p is in the range from 1 to 25 and better still from 1 to 7,

R¹⁴ to R²¹ are methyl groups,

T corresponds to one of the following formulae:

,23 . Al ,24

,25 in which R²² is a hydrogen atom or a group chosen from the groups defined for R⁴ to R⁷,

23 24 25

and R , R^Z4 and R" are, independently, linear or branched alkylene groups, and more preferably correspond to the formula:

23

R 24

- .R

in particular with R , R and R representing -CH₂-CH₂-,

- mi and m₂ are in the range from 15 to 500 and better still from 15 to 45,

- Xi and X₂ represent -(CH₂)₁₀-, and

- Y represents -CH₂-.

As has been seen previously, the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendant chains. In the main chain, the siloxane units may be in the form of segments as described above. In the side or grafted chains, the siloxane units may appear individually or in segments.

According to one preferred embodiment variant of the invention, a copolymer comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units, may be used. In this case, the polyamide-silicone units may be located at the ends of the hydrocarbon-based polyamide.

According to a preferred embodiment, the silicone polyamide comprises units of formula III.

Preferably, according to this embodiment, the groups R⁴, R⁵, R⁶ and R⁷ represent methyl groups, one from among X and Y represents an alkylene group containing 6 carbon atoms and the other represents an alkylene group containing 11 carbon atoms.

n is an integer ranging from 2 to 500, and n represents the degree of polymerization DP of the polymer. As examples of such silicone polyamides, mention may be made of the compounds sold by the company Dow Corning under the names DC 2-8179 (DP 100) and DC 2-8178 (DP 15), the INCI name of which is Nylon-61 1/dimethicone copolymers, i.e. Nylon-61 1/dimethicone copolymers.

Advantageously, the composition used according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) with an m value of about 100.

The index "m" corresponds to the degree of polymerization of the silicone part of the polymer.

More preferably, the composition used according to the invention comprises at least one polymer comprising at least one unit of formula (III) in which m ranges from 50 to 200, in particular from 75 to 150 and is preferably about 100.

More preferably, R⁴, R⁵, R⁶ and R⁷ independently represent a linear or branched Ci to C₄o alkyl group, preferably a group CH₃, C₂H₅, n-C₃H₇ or isopropyl in formula (III).

As examples of silicone polymers that may be used, mention may be made of one of the silicone polyamides obtained in accordance with Examples 1 to 3 of document US-A-5 981 680.

According to a preferred mode, use is made of the silicone polyamide polymer sold by the company Dow Corning under the name DC 2-8179 (DP 100).

The silicone polymers and/or copolymers used in the composition of the invention advantageously have a temperature of transition from the solid state to the liquid state ranging from 45°C to 190°C. Preferably, they have a temperature of transition from the solid state to the liquid state ranging from 70 to 130°C and better still from 80°C to 105°C.

The silicone polymers and/or copolymers used in the composition of the invention advantageously have a temperature of transition from the solid state to the liquid state ranging from 45°C to 190°C. Preferably, they have a temperature of transition from the solid state to the liquid state ranging from 70 to 130°C and better still from 80°C to 105°C. Preferably, the total amount of structuring polymers as defined previously present in the compositions used according to the invention is between 0.1% and 40%> by weight, or between 0.2%> and 25% by weight, or better still between 0.2%> and 20%> by weight of active material relative to the total weight of the composition (limits inclusive).

Advantageously, the total amount of structuring polymers as defined previously (structuring polymers and organogelling agents) present in the compositions used according to the invention is between 0.1 % and 40%> by weight, or between 0.2%> and 25% by weight, or better still between 0.2% and 20% by weight of active material relative to the total weight of the composition (limits inclusive).

According to one particular mode, the composition according to the invention comprises a structuring polymer comprising at least one:

(i) polyamide of formula (lb)

X- -C— R^C— NH-R^NH- C— R₀— C-X

O O O O _(Ib)

in which X represents a group -ORj in which Ri is a linear or branched Cs to C₂₂ and preferably C₁₆ to C₂₂ alkyl radical which may be identical or different, R₂ is a C -C₄₂ diacid dimer residue, R₃ is an ethylenediamine radical and n is between 2 and 5, and optionally

(ii) a combination

- of a (C₂-C₆)dialkyl N-acylglutamide in which the acyl group comprises a linear Cs to C₂₂ alkyl chain, preferably N-lauroylglutamic acid dibutylamide, and

- of a (C₂-C₆)dialkyl N-acylglutamide in which the acyl group comprises a branched Cs to C₂₂ alkyl chain, preferably N-2-ethylhexanoylglutamic acid dibutylamide.

According to one preferred embodiment, the structuring system comprises an ester-terminated polyamide, preferably the compound whose INCI name is Ethylenediamine/stearyl dimer dilinoleate copolymer sold by the company Arizona Chemical under the name Uniclear 100 VG, and optionally a combination of N- lauroylglutamic acid dibutylamide and of N-2-ethylhexanoylglutamic acid dibutylamide. DYESTUFFS

The composition according to the invention contains a coloring agent chosen from water-soluble or liposoluble dyes, pigments and nacres, and mixtures thereof.

Preferably, the composition comprises at least one water-soluble dyestuff, i.e. a dyestuff that is miscible with and preferably solvated by the hydrophilic compound. Visually, the presence of these water-soluble dyestuffs makes it possible to color the droplets of hydrophilic compound.

For the purposes of the invention, the term "water-soluble dye" means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of coloring. In particular, the term "water- soluble" means the capacity of a compound to be dissolved in water, measured at 25°C, to a concentration at least equal to 0.1 g/1 (production of a macroscopically isotropic, transparent, colored or colorless solution). This solubility is in particular greater than or equal to 1 g/1.

The term "pigments" should be understood to mean white or colored, inorganic or organic particles which are insoluble in an aqueous solution and are intended for coloring and/or opacifying the resulting film.

The pigments and/or nacres may be present in a proportion of from 0.01% to 1% by weight relative to the total weight of the composition.

As inorganic pigments that may be used in the invention, mention may be made of titanium oxide, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate.

It may also be a pigment having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts.

The dyestuff may also comprise a pigment with a structure that may be, for example, of silica microsphere type containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL-100 P, this pigment being constituted of silica microspheres containing yellow iron oxide.

Among the organic pigments that may be used in the invention, mention may be made of carbon black, pigments of D&C type, lakes based on cochineal carmine or on barium, strontium, calcium or aluminum, or alternatively the diketopyrrolopyrroles (DPPs) described in documents EP-A-542 669, EP-A-787 730, EP-A-787 731 and WO-A- 96/08537.

The terms "nacres" should be understood as meaning colored particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell, or alternatively synthesized, and which have a color effect via optical interference.

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

Examples of nacres that may also be mentioned include natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.

Among the nacres available on the market, mention may be made of the nacres

Timica, Flamenco and Duochrome (based on mica) sold by the company Engelhard, the Timiron nacres sold by the company Merck, the Prestige mica-based nacres, sold by the company Eckart, and the Sunshine synthetic mica-based nacres, sold by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery color or glint.

As illustrations of nacres that may be used in the context of the present invention, mention may be made in particular of gold-colored nacres sold especially by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold especially by the company Merck under the names Fine bronze (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold especially by the company Engelhard under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the names Passion orange (Colorona) and Matte orange (17449) (Microna); the brown-tinted nacres sold especially by the company Engelhard under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper glint sold especially by the company Engelhard under the name Copper 340A (Timica); the nacres with a red glint sold especially by the company Merck under the name Fine sienna (17386) (Colorona); the nacres with a yellow glint sold especially by the company Engelhard under the name Yellow (4502) (Chromalite); the red-tinted nacres with a golden glint sold especially by the company Engelhard under the name Sunstone GO 12 (Gemtone); the pink nacres sold especially by the company Engelhard under the name Opal tan G005 (Gemtone); the black nacres with a golden glint sold especially by the company Engelhard under the name Nu antique bronze 240 AB (Timica); the blue nacres sold especially by the company Merck under the name Matte blue (17433) (Microna); the white nacres with a silvery glint sold especially by the company Merck under the name Xirona Silver; and the golden-green pinkish-orange nacres sold especially by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

The term "dyes" should be understood as meaning compounds that are generally organic, which are soluble in fatty substances such as oils or in an aqueous- alcoholic phase.

The liposoluble dyes may be chosen from Sudan red, DC Red 17, DC Green 6, β-carotene, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5 and quinoline yellow. The water-soluble dyes are, for example, beetroot juice or methylene blue.

The cosmetic composition according to the invention may also contain at least one material with a specific optical effect.

This effect is different from a simple conventional hue effect, i.e. a unified and stabilized effect as produced by standard colorants, for instance monochromatic pigments. For the purposes of the invention, the term "stabilized" means lacking an effect of variability of the color as a function of the angle of observation or alternatively in response to a temperature change.

For example, this material may be chosen from particles with a metallic tint, goniochromatic coloring agents, diffracting pigments, thermochromic agents, optical brighteners, and also fibers, especially interference fibers. Needless to say, these various materials may be combined so as to simultaneously afford two effects.

The particles with a metallic tint that may be used in the invention are in particular chosen from:

particles of at least one metal and/or of at least one metal derivative, particles comprising a mono-material or multi-material organic or mineral substrate, at least partially coated with at least one coat with a metallic tint comprising at least one metal and/or at least one metal derivative, and

mixtures of said particles.

Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof (for example bronzes and brasses) are preferred metals.

The term "metal derivatives" is intended to denote compounds derived from metals, especially oxides, fluorides, chlorides and sulfides.

Illustrations of these particles that may be mentioned include aluminum particles, such as those sold under the names Starbrite 1200 EAC^® by the company Siberline and Metalure^® by the company Eckart.

Mention may also be made of copper metal powders or alloy mixtures such as the reference 2844 sold by the company Radium Bronze, metallic pigments such as aluminum or bronze, such as those sold under the name Rotosafe 700 from the company Eckart, the silica-coated aluminum particles sold under the name Visionaire Bright Silver from the company Eckart and metal alloy particles, for instance the silica-coated bronze (alloy of copper and zinc) powders sold under the name Visionaire Bright Natural Gold from the company Eckart.

They may also be particles comprising a glass substrate, such as those sold by the company Nippon Sheet Glass under the name Microglass Metashine.

The goniochromatic coloring agent may be chosen, for example, from interference multilayer structures and liquid-crystal coloring agents.

Examples of symmetrical interference multilayer structures that may be used in compositions produced in accordance with the invention are, for example, the following structures: Al/Si0₂/Al/Si0₂/Al, pigments having this structure being sold by the company DuPont de Nemours; Cr/MgF₂/Al/MgF₂/Cr, pigments having this structure being sold under the name Chromaflair by the company Flex; MoS₂/Si0₂/Al/Si0₂/MoS₂; Fe₂0₃/Si0₂/Al/Si0₂/Fe₂0₃, and Fe₂0₃/Si0₂/Fe₂0₃/Si0₂/Fe₂0₃, pigments having these structures being sold under the name Sicopearl by the company BASF; MoS₂/Si0₂/mica- oxide/Si0₂/MoS₂; Fe₂0₃/Si0₂/mica-oxide/Si0₂/Fe₂0₃; Ti0₂/Si0₂/Ti0₂ and Ti02/Al₂03/Ti0₂; SnO/Ti0₂/Si0₂/Ti0₂/SnO; Fe₂0₃/Si0₂/Fe₂03;

SnO/mica/Ti0₂/Si0₂/Ti0₂/mica/SnO, pigments having these structures being sold under the name Xirona by the company Merck (Darmstadt). By way of example, these pigments may be the pigments of silica/titanium oxide/tin oxide structure sold under the name Xirona Magic by the company Merck, the pigments of silica/brown iron oxide structure sold under the name Xirona Indian Summer by the company Merck and the pigments of silica/titanium oxide/mica/tin oxide structure sold under the name Xirona Caribbean Blue by the company Merck. Mention may also be made of the Infinite Colors pigments from the company Shiseido. Different effects are obtained depending on the thickness and the nature of the various layers. Thus, with the Fe₂0₃/Si0₂/Al/Si0₂/Fe₂0₃ structure, the color changes from greenish gold to reddish gray for Si0₂ layers of 320 to 350 nm; from red to gold for Si0₂ layers of 380 to 400 nm; from violet to green for Si0₂ layers of 410 to 420 nm; from copper to red for Si0₂ layers of 430 to 440 nm.

Examples of pigments with a polymeric multilayer structure that may be mentioned include those sold by the company 3M under the name Color Glitter.

Examples of liquid-crystal gonio chromatic particles that may be used include those sold by the company Chenix and also the product sold under the name Helicone® HC by the company Wacker.

FORM OF THE COMPOSITION

The base of the composition according to the invention is solid, and the resulting composition is advantageously a cosmetic product, preferably a lipstick. This product may be in the form of a stick or cast in a dish, for example. According to one preferred embodiment, it is a lipstick or a lip balm in stick form.

Protocol for measuring the hardness:

The term "solid" composition means the form of the composition at 20°C, and in particular the term "solid" means a composition whose hardness at 20°C and at atmospheric pressure (760 mmHg) is greater than or equal to 30 Nm^"1 when it is measured according to the protocol described below. The hardness of a solid composition is measured according to the following protocol:

The composition whose hardness is to be determined is stored at 20°C for 24 hours before measuring the hardness.

The hardness may be measured at 20°C via the "cheese wire" method, which consists in transversely cutting a wand of product, which is preferably a circular cylinder, by means of a rigid tungsten wire 250 μιη in diameter, by moving the wire relative to the stick at a speed of 100 mm/minute.

The hardness of the samples of compositions of the invention, expressed in Nm^"1, is measured using a DFGS2 tensile testing machine from the company Indelco- Chatillon.

The measurement is repeated three times and then averaged. The average of the three values read using the tensile testing machine mentioned above, noted Y, is given in grams. This average is converted into newtons and then divided by L which represents the longest distance through which the wire passes. In the case of a cylindrical wand, L is equal to the diameter (in meters).

The hardness is converted into Nm^"1 by the equation below:

(Y x 10^"3 9.8)/L

For a measurement at a different temperature, the stick is stored for 24 hours at this new temperature before the measurement.

According to this measuring method, the composition according to the invention preferably has a hardness at 20°C and at atmospheric pressure of greater than or equal to 40 Nm^"1 and preferably greater than 50 Nm^"1.

Preferably, the composition according to the invention especially has a hardness at 20°C of less than 500 Nm^"1, especially less than 400 Nm^"1 and preferably less than 300 Nm^"1.

Auxiliary agents

Filler

Advantageously, the fatty phase comprises less than 0.5% and better still less than 0.1% of fillers, and even better still is free of fillers. The reason for this is that such fillers would risk compromising the transparent appearance that is advantageously sought for a composition in accordance with the invention.

The term "fillers" should be understood as meaning colorless or white, mineral or synthetic particles of any shape, which are insoluble in the medium of the composition, irrespective of the temperature at which the composition is manufactured. These fillers serve especially to modify the rheology or the texture of the composition.

The fillers may be mineral or organic and of any shape, platelet-shaped, spherical or oblong, irrespective of the crystallo graphic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powder (Orgasol® from Atochem), poly-P-alanine powder and polyethylene powder, powders of tetrafluoroethylene polymers (Teflon®), lauroyllysine, starch, boron nitride, expanded hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie) or of acrylic acid copolymers (Polytrap® from the company Dow Corning) and silicone resin microbeads (for example Tospearls® from Toshiba), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate or lithium stearate, zinc laurate or magnesium myristate.

Other additional cosmetic ingredients

The composition according to the invention may also comprise any additional cosmetic ingredient that may be chosen in particular from sunscreens and film-forming agents, and mixtures thereof.

Needless to say, a person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisioned addition.

The composition according to the invention may be advantageously used for making up the skin and/or the lips depending on the nature of the ingredients used. In particular, the composition used according to the invention may be in the form of a solid foundation, a lipstick or lip paste, a lip balm, a concealer product, an eye contour product, an eyeshadow, a body makeup product or a skin coloring product.

In particular, the composition according to the invention may be in the form of a colored lip makeup product such as a lipstick or a pencil, optionally having care or treating properties. It may be in the form of an anhydrous stick.

The composition according to the invention may be obtained via the process comprising the following steps:

- mixing of at least one structuring agent and of the constituents of the fatty phase, preferably at a temperature of about 100 to 125°C, preferably while checking to ensure that the mixture obtained is homogeneous,

- preparation of the phase comprising the hydrophilic compound(s) with the fatty phase,

- introduction of the phase comprising the hydrophilic compound(s) into the fatty phase with stirring, preferably by means of a mechanical or magnetic stirrer,

- casting of the obtained dispersion in a conditioning unit.

Preferably, the introduction of the phase comprising a hydrophilic compound into the fatty phase is performed at a temperature of between 95 and 100°C.

The composition obtained is hot-cast, preferably at a temperature of between 95°C and 115°C, into a conditioning unit that is preferably a metal mold capable of giving it the final shape (for example as a stick), and the whole may be left to cool to room temperature or to -20°C, for example for 20 minutes to 1 hour.

The use of the particular organogelling agents (at least one lipophilic gelling agent chosen from low molecular weight dialkyl N-acylglutamides with a linear alkyl chain, and at least one lipophilic gelling agent chosen from low molecular weight dialkyl N-acylglutamides with a branched alkyl chain) makes it possible to perform the process for preparing the composition at a relatively low temperature typically ranging from 100 to 125°C.

The composition used according to the invention is in particular a lipstick. The composition according to the invention may also be used as a core composition in a core-shell product. The present invention is also directed toward a core-shell product comprising a first composition according to the invention forming the shell and a second composition, different from the first composition, comprising the core.

The expression "a second composition, different from the first composition" means that the first composition comprises ingredients that are different from those of the second composition or that the first composition comprises the same ingredients as the second composition in different contents; however, advantageously, for each ingredient, the ratio of the content in the first composition relative to the content in the second composition ranges from 0.9/1 to 1.1/1.

In this case, the core composition of the core-shell product comprises at least one oil.

Volatile oil

The core composition may comprise at least one volatile oil.

The volatile oil may be a silicone oil, a hydrocarbon-based oil or a fluoro oil.

Nonvolatile oils

The core composition according to the invention may comprise at least one other nonvolatile oil chosen from nonvolatile hydrocarbon-based oils and/or silicone oils and/or fluoro oils, and preferably from hydrocarbon-based oils.

Besides the oils described previously, the core composition may also comprise at least one fatty substance that is not liquid at room temperature (25°C) and at atmospheric pressure, known as a solid fatty substance, chosen from waxes and pasty fatty substances.

Pasty compound

The pasty compound is preferably chosen from synthetic compounds and compounds of vegetable origin. A pasty compound may be obtained by synthesis from starting products of plant origin.

The pasty compound is advantageously chosen from:

lanolin and derivatives thereof;

petroleum jelly, in particular the product whose INCI name is Petrolatum and which is sold under the name Ultima White PET USP by the company Penreco, - polyol ethers chosen from ethers of pentaerythritol and of polyalkylene glycol, ethers of fatty alcohol and of sugar, and mixtures thereof, the ethers of pentaerythritol and of polyethylene glycol comprising 5 oxyethylene units (5 OE) (CTFA name: PEG-5 Pentaerythrityl Ether), polypropylene glycol pentaerythrityl ether comprising five oxypropylene (5 OP) units (CTFA name: PEG-5 Pentaerythrityl Ether) and mixtures thereof, and more especially the mixture PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, which is a mixture in which the constituents are in a 46/46/8 weight ratio: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and 8% soybean oil,

- polymeric or nonpolymeric silicone compounds,

- polymeric or nonpolymeric fluoro compounds,

vinyl polymers, in particular:

• olefin homopolymers and copolymers,

• hydrogenated diene homopolymers and copolymers,

• linear or branched oligomers which are homopolymers or copolymers of alkyl (meth)acrylates preferably containing a C8-C30 alkyl group,

• oligomers which are homopolymers and copolymers of vinyl esters containing C8-C30 alkyl groups,

• oligomers which are homopolymers and copolymers of vinyl ethers containing C8-C30 alkyl groups,

fat-soluble polyethers resulting from the polyetherification between one or more C2-C100 and preferably C2-C50 diols,

esters,

and/or mixtures thereof.

The pasty compound is preferably a polymer, especially a hydrocarbon-based polymer.

Among the liposoluble polyethers that are particularly preferred are copolymers of ethylene oxide and/or of propylene oxide with C6-C30 long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will be made especially of copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel.

Among the esters, the following are especially preferred:

- esters of a glycerol oligomer, especially diglycerol esters, in particular condensates of adipic acid and of glycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid, and 12-hydroxystearic acid, preferably such as bis-diglyceryl polyacyladipate-2 sold under the brand name Softisan 649 by the company Sasol,

- vinyl ester homopolymers containing C8-C30 alkyl groups, such as polyvinyl laurate (sold especially under the reference Mexomer PP by the company Chimex) and arachidyl propionate sold under the brand name Waxenol 801 by Alzo,

- phytosterol esters,

- fatty acid triglycerides and derivatives thereof, for instance triglycerides of fatty acids, which are especially C₁₀-C₁₈, and partially or totally hydrogenated such as those sold under the reference Softisan 100 by the company Sasol,

- pentaerythritol esters,

- noncrosslinked polyesters resulting from polycondensation between a linear or branched C4-C50 dicarboxylic acid or polycarboxylic acid and a C2-C50 diol or polyol,

- aliphatic esters of an ester, resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid. Preferably, the aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms. It is preferably chosen from hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid, octyldodecanoic acid, heneicosanoic acid and docosanoic acid, and mixtures thereof. The aliphatic carboxylic acid is preferably branched. The aliphatic hydroxycarboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid containing from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to 20 hydroxyl groups, preferably from 1 to 10 hydroxyl groups and better still from 1 to 6 hydroxyl groups. The aliphatic hydroxycarboxylic acid ester is chosen from: a) partial or total esters of saturated linear monohydroxylated aliphatic monocarboxylic acids;

b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids;

c) partial or total esters of saturated monohydroxylated aliphatic polycarboxylic acids;

d) partial or total esters of saturated polyhydroxylated aliphatic polycarboxylic acids;

e) partial or total esters of C₂ to C₁₆ aliphatic polyols that have reacted with a monohydroxylated or polyhydroxylated aliphatic monocarboxylic or polycarboxylic acid,

and mixtures thereof.

esters of a diol dimer and of a diacid dimer, where appropriate esterified on their free alcohol or acid functional group(s) with acid or alcohol radicals, especially dimer dilinoleate esters; such esters may be chosen especially from the esters having the following INCI nomenclature: Bis-Behenyl/Isostearyl/Phytosteryl Dimer Dilinoleyl Dimer Dilinoleate (Plandool G), Phytosteryl/Isostearyl/Cetyl/Stearyl/Behenyl Dimer Dilinoleate (Plandool H or Plandool S), and mixtures thereof,

- mango butter, such as the product sold under the reference Lipex 203 by the company AarhusKarlshamn,

hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rape seed oil, mixtures of hydrogenated plant oils such as the mixture of hydrogenated soybean, coconut, palm and rape seed plant oil, for example the mixture sold under the reference Akogel® by the company Aarhuskarlshamn (INCI name: Hydrogenated Vegetable Oil).

- shea butter, in particular the product whose INCI name is Butyrospermum

Parkii Butter, such as the product sold under the reference Sheasoft® by the company Aarhuskarlshamn,

and mixtures thereof.

Among the pasty compounds, bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl, bis(diglyceryl) poly(2-acyladipate), hydrogenated castor oil dimer dilinoleate, for example Risocast DA-L sold by Kokyu Alcohol Kogyo, and hydrogenated castor oil isostearate, for example Salacos HCIS (V-L) sold by Nisshin Oil, polyvinyl laurate, mango butter, shea butter, hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rape seed oil and vinylpyrrolidone/eicosene copolymers, or a mixture thereof, will preferably be chosen. Waxes

The waxes that may be used in the core composition are chosen from waxes that are solid at room temperature, of animal, plant, mineral or synthetic origin, and mixtures thereof.

As illustrations of waxes that are suitable for use in the core composition, mention may be made especially of hydrocarbon-based waxes, for instance beeswax, lanolin wax and Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, alfalfa wax, berry wax, shellac wax, Japan wax and sumach wax; montan wax, orange wax and lemon wax, microcrystalline waxes (such as the wax sold under the reference Microwax HW by the company Paramelt), paraffins and ozokerite; polyethylene waxes such as those sold under the name Performalene 500-L and Performalene 400 by the company New Phase Technologies, and the waxes obtained by Fisher-Tropsch synthesis.

Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains. Among these waxes that may especially be mentioned are isomerized jojoba oil such as the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and bis(l,l,l- trimethylolpropane) tetrastearate sold under the name Hest 2T-4S® by the company Heterene.

Mention may also be made of silicone waxes (C30-45 alkyl dimethicone) and fluoro waxes.

The waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, sold under the names Phytowax ricin 16L64® and 22L73® by the company Sophim, may also be used. Such waxes are described in patent application FR-A-2 792 190.

A wax that may be used is a C20-C40 alkyl (hydroxystearyloxy)stearate (the alkyl group containing from 20 to 40 carbon atoms), alone or as a mixture. Such a wax is especially sold under the names Kester Wax K 82 P®, Hydroxypoly ester K 82 P®, Kester Wax K 80 P® and Kester Wax K 82 H® by the company Koster Keunen.

Filler

Advantageously, the core composition comprises at least one filler, especially in a content ranging from 0.01% to 50% by weight and preferably ranging from 0.01% to 30% by weight relative to the total weight of the core composition.

Structuring/thickening agent

The core composition may comprise, besides the waxes that may be present, at least one structuring agent chosen from lipophilic gelling agents, and mixtures thereof.

Lipophilic gelling agents

According to one embodiment, the core composition may comprise at least one gelling agent. The gelling agents that may be used in the compositions according to the invention may be organic or mineral, polymeric or molecular lipophilic gelling agents.

Advantageously, the core comprises the same gelling system as the shell.

According to a first variant, the core comprises at least one compound chosen from pasty fatty substances, waxes and fillers, and mixtures thereof.

According to a second variant, the core comprises the same gelling system as the shell and at least one pasty fatty substance.

Preferably, the core comprises at least 0.01% by weight and better still 0.1% by weight of dyestuff relative to the total weight of the composition, for example a content ranging from 0.01% to 10% by weight and more preferentially from 0.1% to 5% by weight.

According to one particular mode, the second composition, i.e. the core composition, comprises a combination of at least one low molecular weight dialkyl N- acylglutamide containing a linear alkyl chain, chosen especially from (C₂-C₆)dialkyl N- acylglutamides in which the acyl group comprises a linear Cs to C₂₂ alkyl chain such as lauroylglutamic acid dibutylamide (or dibutyl lauroyl glutamide), with at least one low molecular weight dialkyl N-acylglutamide containing a branched alkyl chain, chosen especially from (C₂-Ce)dialkyl N-acylglutamides in which the acyl group comprises a branched Cs to C₂₂ alkyl chain such as N-2-ethylhexanoyl glutamic acid dibutylamide (or dibutyl ethylhexanoyl glutamide) and preferably with a solvent that is capable of forming hydrogen bonds with these two low molecular weight lipophilic gelling agents, and it comprises at least 0.01% of at least one dyestuff

The present invention is also directed toward a process for caring for and/or making up the skin and/or the lips, in which said composition according to the invention or said core-shell product is applied to the skin and/or the lips, and also to the use of said composition according to the invention or of said core-shell product for caring for and/or making up the skin and/or the lips and in particular for moisturizing the skin and/or the lips, especially as a lipstick.

The examples that follow are given as nonlimiting illustrations of the present invention. The percentages are weight percentages.

Examples

The compositions of Examples 1 , 2 and 3 were obtained according to the following protocol.

The constituents of the fatty phase (phase A) were mixed together in a first beaker.

This mixture was prepared at a temperature of between 95 and 115°C.

The constituents of the phase which will form the inclusions (phase B) were mixed together in another beaker. The phase which constitutes the inclusions was introduced into the fatty phase with magnetic stirring or Rayneri blending.

The compositions obtained were then cast in a mold in order to obtain a stick 11.6 mm in diameter in the case of Example 1 and 12.7 mm in diameter in the case of the other examples.

The percentages are expressed by weight of starting material. Example 1 : transparent stick with colored glycerol inclusions

The sticks obtained have colored inclusions containing glycerol. These inclusions are individualized and well differentiated. The desired visual effect is obtained. The composition thus obtained is in the form of a stable stick, which does not break on application. The application is comfortable (the product is glidant on application and deposits easily on the lips). The deposit obtained is uniform, comfortable and has satisfactory gloss. In addition, it has good lip moisturizing properties.

Example 2: transparent stick with colored inclusions containing a glucoside derivative

* Mexoryl SBB sold by the company Chimex

The sticks obtained have colored inclusions containing a glucoside derivative. These inclusions are individualized and well differentiated. The desired visual effect is obtained.

The composition thus obtained is in the form of a stable stick, which does not break on application. The application is comfortable (the product is glidant on application and deposits easily on the lips). The deposit obtained is uniform, comfortable and has satisfactory gloss. In addition, it has good lip moisturizing properties.

Example 3: transparent stick with colored glycerol inclusions

Example 4: core-shell stick with a transparent shell with colored glycerol inclusions and a colored core

The stick was prepared using the composition below as core composition and the composition of Example 3 as shell composition:

PHASE Raw materials Weight%

A Isoeicosane 18.65

A Tridecyl trimellitate 22.88

A Isononyl isononanoate qs

A Ethylenediamine/stearyl dimer dilinoleate copolymer 17

A Isostearyl alcohol 11.35

A Dibutyl ethylhexanoyl glutamide (EB 21) 1.27

A Dibutyl lauroyl glutamide (GP 1) 2.57

Pentaerythrityl tetrakis(di-t-

A butyl)hydroxyhydrocinnamate 0.35

B Yellow 5 lake 0.85

B Blue 1 lake 0.2

B Red 7 0.45

B Titanium dioxide 0.2

B Iron oxides 0.95 The sticks of Examples 3 and 4 obtained have colored inclusions containing glycerol. These inclusions are individualized and well differentiated. The desired visual effect is obtained.

The application of the products obtained via these examples is comfortable and gives a light coloration that gives the lips a healthy look.

Claims

1. A transparent composition comprising:

- preferably at least one coloring agent chosen from water-soluble or liposoluble dyes, pigments, nacres, and mixtures thereof,

- at least one hydrophilic compound and/or hydrophilic active agent, in a content of between 0.5% and 8% by weight relative to the total weight of the composition,

- said composition being free of water and of C1-C4 alcohols.

2. The composition as claimed in claim 1, characterized in that it comprises at least one water-soluble dyestuff.

3. The composition as claimed in claim 1 or 2, in which the structuring agent is chosen from structuring polymers and lipophilic gelling agents, and mixtures thereof.

4. The composition as claimed in claim 3, in which the structuring polymers are chosen from hydrocarbon-based polyamides, silicone polyamides, block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene isoprene, hydrocarbon-based indene resins, polyurethanes of INCI name Dilinoleyl dimer diol-based polyurethane, or mixtures thereof.

5. The composition as claimed in claim 3 or 4, in which the lipophilic gelling agents are chosen from combinations of at least one low molecular weight dialkyl N- acylglutamide with a linear alkyl chain, chosen especially from (C2-Ce)dialkyl N- acylglutamides in which the acyl group comprises a linear Cs to C22 alkyl chain with at least one low molecular weight dialkyl N-acylglutamide with a branched alkyl chain, chosen especially from (C2-C6)dialkyl N-acylglutamides in which the acyl group comprises a branched Cs to C22 alkyl chain and preferably with a solvent that is capable of forming hydrogen bonds with these two low molecular weight lipophilic gelling agents.

6. The composition as claimed in claim 5, in which the dialkyl N- acylglutamide with a linear alkyl chain is lauroylglutamic acid dibutylamide, and the dialkyl N-acylglutamide with a branched alkyl chain is N-2-ethylhexanoylglutamic acid dibutylamide.

7. The composition as claimed in any one of the preceding claims, in which the hydrophilic compound is chosen from: sorbitol, poly hydrogen alcohols and mixtures thereof, the poly hydrogen alcohols preferably being of C₂-Cs and more preferably of C₃- C₆, preferably such as glycerol, propylene glycol, 1,3-butylene glycol, dipropylene glycol or diglycerol, and mixtures thereof.

8. The composition as claimed in any one of the preceding claims, in which the lipophilic gelling agent is chosen from fatty acid esters and dextrin esters, hydroxylated fatty acids and glycerol esters such as glyceryl behenate/isostearate/eicosadioate.

9. The composition as claimed in any one of the preceding claims, in which the fatty phase comprises at least one:

(i) polyamide of formula (lb)

X- -C— R^C— NH-R^NH- -C— R₀— C-X

I I I I I I

O O O O (lb)

in which X represents a group -ORj in which Ri is a linear or branched Cs to C₂₂ and preferably C₁₆ to C₂₂ alkyl radical which may be identical or different from each other, R₂ is a C₂8-C₄₂ diacid dimer residue, R₃ is an ethylenediamine radical, n is between 2 and 5, and optionally

(ii) a combination

- of a (C₂-C₆)dialkyl N-acylglutamide in which the acyl group comprises a branched Cs to C₂₂ alkyl chain, preferably N-2- ethylhexanoylglutamic acid dibutylamide.

10. The composition as claimed in any one of the preceding claims, comprising a hydrophilic active agent preferably chosen from moisturizers, cicatrizing agents and antiaging agents.

11. The composition as claimed in the preceding claim, in which the hydrophilic active agent is chosen from hyaluronic acid, AHAs, BHAs, serine, collagen, C- glycoside derivatives and in particular C-P-D-xylopyranoside-2-hydroxypropane especially in the form of a solution at 30% by weight of active material in a water/propylene glycol mixture (60%/40% by weight), collagen and chondroitin sulfate spheres of marine origin (Ateocollagen), hyaluronic acid spheres, ceramides preferably such as ceramide V, sugars such as glucose, rhamnose, xylose, mannose and fructose, and mixtures thereof.

12. A core-shell product comprising a first composition according to any one of the preceding claims forming the shell and a second composition, which is different from the first composition, forming the core.

13. The product as claimed in the preceding claim, in which the second composition comprises:

- a combination of at least one low molecular weight dialkyl N-acylglutamide with a linear alkyl chain, chosen especially from (C₂-C₆)dialkyl N-acylglutamides in which the acyl group comprises a linear Cs to C₂₂ alkyl chain such as lauroylglutamic acid dibutylamide, with at least one low molecular weight dialkyl N-acylglutamide with a branched alkyl chain, chosen especially from (C₂-C₆)dialkyl N-acylglutamides in which the acyl group comprises a branched Cs to C₂₂ alkyl chain such as N-2-ethylhexanoyl glutamic acid dibutylamide and preferably with a solvent that is capable of forming hydrogen bonds with these two low molecular weight lipophilic gelling agents, and

- at least 0.01% of at least one dyestuff

14. A process for caring for and/or making up the skin and/or the lips, in which the composition as claimed in any one of claims 1 to 11 or the core-shell product as claimed in either of claims 12 and 13 is applied to the skin and/or the lips.

15. The use of the composition as claimed in any one of claims 1 to 11 or of the core-shell product as claimed in either of claims 12 and 13 for caring for and/or making up the skin and/or the lips, in particular for moisturizing the skin and/or the lips, especially as a lipstick.