(en)The present invention is directed towards a composition, especially a cosmetic composition, in particular for coating keratin fibres such as the eyelashes, comprising: —at least one aqueous phase gelled with at least one synthetic polymeric hydrophilic gelling agent; and —at least one oily phase gelled with at least one lipophilic gelling agent chosen from meltable compounds, said oily phase also comprising at least one volatile oil; said phases forming therein a macroscopically homogeneous mixture, said composition comprising less than 10% by weight of non-volatile oil(s), relative to the total weight of the composition, said composition comprising from 10% to 70% by weight of volatile oil(s), relative to the total weight of the composition, said composition comprising a water content at least equal to 15% by weight relative to the total weight of the composition.

1.ApplicationNumber: US-201515507366-A
1.PublishNumber: US-2017239166-A1
2.Date Publish: 20170824
3.Inventor: DAUBERSIES LAURE
ILEKTI PHILIPPE
LISON CHRISTEL

4.Inventor Harmonized: DAUBERSIES LAURE(FR)
ILEKTI PHILIPPE(FR)
LISON CHRISTEL(FR)

5.Country: US
6.Claims:
(en)The present invention is directed towards a composition, especially a cosmetic composition, in particular for coating keratin fibres such as the eyelashes, comprising: —at least one aqueous phase gelled with at least one synthetic polymeric hydrophilic gelling agent; and —at least one oily phase gelled with at least one lipophilic gelling agent chosen from meltable compounds, said oily phase also comprising at least one volatile oil; said phases forming therein a macroscopically homogeneous mixture, said composition comprising less than 10% by weight of non-volatile oil(s), relative to the total weight of the composition, said composition comprising from 10% to 70% by weight of volatile oil(s), relative to the total weight of the composition, said composition comprising a water content at least equal to 15% by weight relative to the total weight of the composition.

7.Description:
(en)The present invention is directed towards proposing compositions, especially cosmetic compositions, with improved staying power over time, in particular which have increased water resistance but are nevertheless easy to remove. The invention also relates more particularly to the field of caring for and/or making up keratin materials, especially the skin, the lips and/or keratin fibres.
The term “keratin materials” preferably means human keratin materials, especially the skin, the lips and/or keratin fibres.
The present invention proves to be most particularly advantageous for caring for and/or making up keratin fibres.
The term “keratin fibres” especially means the eyelashes, the eyebrows, bodily hair and/or head hair, in particular the eyelashes and/or the eyebrows, and preferably the eyelashes.
The mascara formulations, intended for caring for and/or making up keratin fibres and more particularly the eyelashes, which are the most used are “waterproof” formulations, i.e. which have good resistance to water to ensure good staying power on the eyelashes. They thus have a substantially reduced water content or even are advantageously anhydrous. Such a formulation is usually a dispersion, of at least one oily structuring agent which may be a wax, a polymer, in particular a semi-crystalline polymer or a lipophilic gelling agent in a non-aqueous solvent medium.
Unfortunately, these mascara formulations, which are appreciated for their staying power over time, prove on the other hand to be difficult to remove especially with common makeup removers which are mainly aqueous or water-soluble. Their removal thus generally requires the use of special makeup removers based on oils or organic solvents. However, these makeup removers may leave on the skin around the eyes (eyelids) an uncomfortable greasy residual film or else an unaesthetic black deposit.
There thus remains a need for cosmetic compositions that are suitable for making up and/or caring for keratin fibres and in particular the eyelashes, which have staying power properties at least equivalent to those shown by “waterproof” mascara formulations, but which, on the other hand, are compatible with easy removal.
Contrary to all expectation, the inventors have especially found that the choice of a particular architecture in terms of galenical formulation can precisely satisfy this expectation.
Thus, according to one of its aspects, the present invention relates to a composition, especially a cosmetic composition, in particular for coating keratin fibres such as the eyelashes, comprising:
at least one aqueous phase gelled with at least one synthetic polymeric hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent chosen from meltable compounds, said oily phase also comprising at least one volatile oil;

said phases forming therein a macroscopically homogeneous mixture,
said composition comprising less than 10% by weight of non-volatile oil(s), relative to the total weight of the composition,
said composition comprising from 10% to 70% by weight of volatile oil(s), relative to the total weight of the composition,
said composition comprising a water content at least equal to 15% by weight relative to the total weight of the composition.
Contrary to all expectation, and as emerges from the examples given below, a galenical architecture in the form of a macroscopically homogeneous mixture of a gelled aqueous phase and of a gelled oily phase as defined above gives access to a mascara formulation which has expected staying power properties with regard to its meltable material composition, but which is advantageously easy to remove by virtue of the gelled aqueous phase.
The compositions according to the invention may especially be makeup compositions intended for affording the desired makeup effect solely by their use on the eyelashes, but which may also be non-pigmented or coloured compositions intended to be either superposed on a makeup already deposited on the eyelashes or coated with an associated makeup film, in which case they are termed, respectively, top coat or base coat. They may also be compositions intended solely to afford care on the keratin fibres and in particular the eyelashes.
Certainly, “gel-gel” compositions have already been proposed in the cosmetics field. Formulations of this type combine a gelled aqueous phase with a gelled oily phase. Thus, gel/gel formulations are described in Almeida et al., Pharmaceutical Development and Technology, 2008, 13:487, tables 1 and 2, page 488; WO 99/65455; PI 0405758-9; WO 99/62497; JP 2005-112834 and WO 2008/081175. However, to the inventors' knowledge, this type of formulation has never been proposed for the purposes of affording cosmetic compositions that are especially intended for makeup and/or care, in particular for coating keratin fibres, and which combine the advantages of “waterproof” formulations, i.e. excellent staying power over time and in particular satisfactory water resistance by virtue especially of their solid fatty substance component, with easy removal.
According to another of its aspects, a subject of the invention is also a process, especially a cosmetic process, for making up and/or caring for keratin fibres, especially the eyelashes, comprising at least one step which consists in applying the said keratin fibres a composition in accordance with the invention.
According to yet another of its aspects, the present invention relates to a process, especially a cosmetic process, for making up and/or caring for keratin fibres, especially the eyelashes, comprising at least the application to said keratin fibres of a macroscopically homogeneous composition obtained by extemporaneous mixing, before application or at a time of application to said keratin fibres, of at least one aqueous phase gelled with at least one synthetic polymeric hydrophilic gelling agent, and at least one oily phase gelled with at least one lipophilic gelling agent chosen from meltable compounds, said oily phase also comprising at least one volatile oil,
preferably said composition comprising less than 10% by weight of non-volatile oil(s), relative to the total weight of the composition,
said composition comprising from 10% to 70% by weight of volatile oil(s), relative to the total weight of the composition,
said composition comprising a water content at least equal to 15% by weight relative to the total weight of the composition.
According to another of its aspects, a subject of the invention is also a process for preparing a composition, especially a cosmetic composition, in particular for coating keratin fibres, such as the eyelashes, comprising at least one step of mixing:
an aqueous phase gelled with at least one synthetic polymeric hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent chosen from meltable compounds, said oily phase also comprising at least one volatile oil;

under conditions suitable for obtaining a macroscopically homogeneous mixture,
said composition comprising less than 10% by weight of non-volatile oil(s), relative to the total weight of the composition
said composition comprising from 10% to 70% by weight of volatile oil(s), relative to the total weight of the composition,
said composition comprising a water content at least equal to 15% by weight relative to the total weight of the composition.
According to one embodiment variant, this process may advantageously comprise a step of mixing at least three or even more gelled phases.
For obvious reasons, the number of gelled aqueous phases and of gelled oily phases to be considered for forming a composition according to the invention may range for each of the two types of phase beyond two.
Advantageously, the mixing of the phases may be performed at room temperature.
However, the process of the invention may comprise, if necessary, a step of heating the mixture.
According to one embodiment variant, the final formulation may be manufactured without following a particular order of introduction of the various constituents and, in certain cases, a “one-pot” manufacture may be performed.
According to a particular embodiment, the representative gelled phases of the same type of architecture are gelled with a different gelling agent.
Multi-phase formulas may thus be developed.
Cosmetic Composition
To begin with, it is important to note that a composition according to the invention is different from an emulsion.
An emulsion generally consists of an oily liquid phase and an aqueous liquid phase. It is a dispersion of droplets of one of the two liquid phases in the other. The size of the droplets forming the dispersed phase of the emulsion is typically about a micrometre (0.1 to 100 μm). Furthermore, an emulsion requires the presence of a surfactant or of an emulsifier to ensure its stability over time.
In contrast, a composition according to the invention consists of a macroscopically homogeneous mixture of two immiscible gelled phases. These two phases both have a gel-type texture. This texture is especially reflected visually by a consistent and/or creamy appearance.
The term “macroscopically homogeneous mixture” means a mixture in which each of the gelled phases cannot be individualized by the naked eye. More precisely, in a composition according to the invention, the gelled aqueous phase and the gelled oily phase interpenetrate and thus form a stable, consistent product. This consistency is achieved by mixing interpenetrated macrodomains. Thus, by microscope, the composition according to the invention is very different from an emulsion. A composition according to the invention cannot be characterized either as having a “sense”, i.e. an O/W or W/O sense this means that a continuous phase and a dispersed phase cannot be defined.
Thus, a composition according to the invention has a consistency of gel type. The stability of the composition is long-lasting without surfactant. Consequently, a cosmetic composition according to the invention does not require any surfactant or silicone emulsifier to ensure its stability over time.
A composition according to the invention is distinguishable from an emulsion by mean of at least one of the following tests: test using a dyestuff, drop test and dilution test.
Test Using a Dyestuff
It is known practice from the prior art to observe the intrinsic nature of a mixture of aqueous and oily gels in a gel-type composition, for example, by introducing a dyestuff either into the aqueous gelled phase or into the lipophilic gelled phase, before the formation of the gel-type composition. During visual inspection, in a gel-type composition, the dyestuff appears uniformly dispersed, even if the dye is present solely in the gelled aqueous phase or in the gelled oily phase. Specifically, if two different dyes of different colours are introduced, respectively, into the oily phase and into the aqueous phase, before formation of the gel-type composition, the two colours may be observed as being uniformly dispersed throughout the gel-type composition. This is different from an emulsion in which, if a dye, which is soluble in water or soluble in oil, is introduced, respectively, into the aqueous and oily phases, before forming the emulsion, the colour of the dye present will only be observed in the outer phase (Remington: The Science and Practice of Pharmacy, 19th Edition (1995), Chapter 21, page 282).
Drop Test
It is also known practice to distinguish a gel-type composition from an emulsion by performing a “drop test”. This test consists in demonstrating the bi-continuous nature of a gel-type composition. Specifically, as mentioned previously, the consistency of a composition is obtained by means of the interpenetration of the aqueous and oily gelled domains. Consequently, the bi-continuous nature of a gel-type composition may be demonstrated by means of a simple test with, respectively, hydrophilic and hydrophobic solvents. This test consists in depositing, firstly, one drop of a hydrophilic solvent on a first sample of the test composition, and, secondly, one drop of a hydrophobic solvent on a second sample of the same test composition, and in analysing the behaviour of the two drops of solvents. In the case of an O/W emulsion, the drop of hydrophilic solvent diffuses into the sample and the drop of hydrophobic solvent remains at the surface of the sample. In the case of a W/O emulsion, the drop of hydrophilic solvent remains at the surface of the sample and the drop of hydrophobic solvent diffuses throughout the sample. Finally, in the case of a gel-type composition (bi-continuous system), the hydrophilic and hydrophobic drops diffuse throughout the sample.
Dilution Test
In the case of the present invention, the test that will be preferred for distinguishing a gel-type composition from an emulsion is a dilution test. Specifically, in a gel-type composition, the aqueous and oily gelled domains interpenetrate and form a consistent and stable composition, in which the behaviour in water and in oil is different from the behaviour of an emulsion. Consequently, the behaviour during dilution of a gel-type composition (bi-continuous system) may be compared to that of an emulsion, obviously the behaviour during dilution of a gel/gel-type composition and the one of a emulsion will be different.
More specifically, the dilution test consists in placing 40 g of product and 160 g of dilution solvent (water or oil) in a 500 mL plastic beaker. The dilution is performed with controlled stirring to avoid any emulsification. In particular, this is performed using a planetary mixer: Speed Mixer™ DAC400FVZ. The speed of the mixer is set at 1500 rpm for 4 minutes. Finally, observation of the resulting sample is performed using an optical microscope at a magnification of ×100 (×10×10). It may be noted that oils such as Parleam® and Xiameter PMX-200 Silicone Fluid 5CS® sold by Dow Corning are suitable as dilution solvent.
In the case of a gel-type composition (bi-continuous system), when it is diluted in oil or in water, a heterogeneous appearance is always observed. When a gel-type composition (bi-continuous system) is diluted in water, pieces of oily gel in suspension are observed, and when a gel-type composition (bi-continuous system) is diluted in oil, pieces of aqueous gel in suspension are observed.
In contrast, during dilution, emulsions have a different behaviour. When an O/W emulsion is diluted in an aqueous solvent, it gradually reduces without having a heterogeneous and lumpy appearance. This same O/W emulsion, on dilution with oil, has a heterogeneous appearance (pieces of O/W emulsion suspended in the oil). When a W/O emulsion is diluted with an aqueous solvent, it has a heterogeneous appearance (pieces of W/O emulsion suspended in the water). This same W/O emulsion, when diluted in oil, gradually reduces without having a heterogeneous and lumpy appearance. In a preferred embodiment, the composition comprises less than 5% surfactant, better still less than 2%, or even less than 1% and is even free from surfactant.
According to the present invention, the aqueous gelled phase and the oily gelled phase forming a composition according to the invention are present therein in a weight ratio ranging from 90/10 to 10/90. More preferentially, the aqueous phase and the oily phase are present in a weight ratio ranging from 30/70 to 70/30.
The ratio between the two gelled phases is adjusted according to the desired cosmetic properties.
Advantageously, a composition according to the invention may thus be in the form of a creamy gel with a minimum stress below which it does not flow unless it has been subjected to an external mechanical stress.
As emerges from the text hereinbelow, a composition according to the invention may have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa.
The composition according to the invention may have a maximum threshold stress of 10 000 Pa.
It also advantageously has a stiffness modulus G* at least equal to 400 Pa and preferably greater than 1000 Pa. The composition according to the invention may have a stiffness modulus G* preferably lower than 50 000 Pa.
The ratio of the hydrophilic phase viscosity/lipophilic phase viscosity (measured at 25° C. and 100 s −1 ) preferably ranges from 0.5 and 1.5.
According to an advantageous embodiment variant, the gelled phases under consideration to form a composition according to the invention have, respectively, a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
The gelled phases under consideration to form a composition according to the invention may have a threshold stress lower than 10 000 Pa.
Characterization of the threshold stresses is performed by oscillating rheology measurements. Methodology is proposed in the illustrative chapter of the present text.
In general, the corresponding measurements are taken at 25° C. using a Haake RS600 imposed-stress rheometer equipped with a plate-plate measuring body (60 mm diameter) fitted with an anti-evaporation device (bell jar). For each measurement, the sample is placed delicately in position and the measurements start 5 minutes after placing the sample in the jaws (2 mm). The test composition is then subjected to a stress ramp from 10 −2 to 10 3 Pa at a set frequency of 1 Hz.
A composition according to the invention may also have a certain consistency. This consistency may be characterized by a stiffness modulus G* which, under this minimum stress threshold, may be at least equal to 400 Pa and preferably greater than 1000 Pa. The value G* of a composition may be obtained by subjecting the composition under consideration to a stress ramp from 10 −2 to 10 3 Pa at a set frequency of 1 Hz.
A composition according to the invention has a viscosity preferentially ranging from 5 to 50 Pa·s, measured at room temperature of 25° C. using a Rheomat RM100® rheometer.
Dry Extract
The composition according to the invention advantageously comprises a solids content of greater than or equal to 25%, preferably 30%, better still 35%, in particular 40%, or even 42% and preferentially 45%.
The aqueous phase of the composition according to the invention advantageously comprises water in an amount ranging from 80 to 95% relative to the weight of the aqueous phase.
The composition according to the invention advantageously comprises water in an amount ranging from 30 to 70% relative to the weight of the composition.
The oily phase of the composition according to the invention advantageously comprises oil(s) in an amount ranging from 40 to 70% relative to the weight of the oily phase.
For the purposes of the present invention, the “solids content” denotes the content of non-volatile material.
The amount of dry extract (abbreviated as DE) of a composition according to the invention is measured using a commercial halogen desiccator (Halogen Moisture Analyzer HR 73) from Mettler Toledo. The measurement is performed on the basis of the weight loss of a sample dried by halogen heating and thus represents the percentage of residual material once the water and the volatile materials have evaporated off.
This technique is fully described in the machine documentation provided by Mettler Toledo.
The measuring protocol is as follows:
About 2 g of the composition, referred to hereinbelow as the sample, are spread out on a metal crucible, which is introduced into the halogen desiccator mentioned above. The sample is then subjected to a temperature of 105° C. until a constant weight is obtained. The wet mass of the sample, corresponding to its initial mass, and the dry mass of the sample, corresponding to its mass after halogen heating, are measured by means of a precision balance.
The experimental error associated with the measurement is of the order of ±2%.
The solids content is calculated in the following manner:
Solids content (expressed as weight %)=100×(dry mass/wet mass)

Hydrophilic Gelling Agent
For the purposes of the present invention, the term “hydrophilic gelling agent” means a compound that is capable of gelling the aqueous phase of the compositions according to the invention.
The hydrophilic gelling agent is thus present in the aqueous phase of the composition.
The gelling agent may be water-soluble or water-dispersible.
As stated above, the aqueous phase of a composition according to the invention is gelled with at least one hydrophilic gelling agent chosen from synthetic polymeric gelling agents.
For the purposes of the invention, the term “synthetic” means that the polymer is neither naturally existing nor a derivative of a polymer of natural origin.
The synthetic polymeric hydrophilic gelling agent under consideration according to the invention may or may not be particulate.
For the purposes of the invention, the term “particulate” means that the polymer is in the form of particles, preferably spherical particles.
As emerges from the text hereinbelow, the polymeric hydrophilic gelling agent is advantageously chosen from crosslinked acrylic homopolymers or copolymers; associative polymers, in particular associative polymers of polyurethane type; polyacrylamides and crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers; modified or unmodified carboxyvinyl polymers, and mixtures thereof, especially as defined below.
Synthetic polymeric gelling agents may be detailed under the following subfamilies:
1. Associative polymers,
2. Polyacrylamides and crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, and
3. Modified or unmodified carboxyvinyl polymers.
I. Associative Polymers
For the purposes of the present invention, the term “associative polymer” means any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers in accordance with the present invention may be anionic, cationic, nonionic or amphoteric.
Associative Anionic Polymers
Among the associative anionic polymers that may be mentioned are those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit is formed by an unsaturated ethylenic anionic monomer, more particularly by a vinylcarboxylic acid and most particularly by an acrylic acid or a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the monomer of formula (I) below:
CH 2 ═C(R′)CH 2 OB n R (I)

in which R′ denotes H or CH 3 , B denotes the ethylenoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon-based radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms, preferably from 10 to 24 and even more particularly from 12 to 18 carbon atoms.
Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP 0 216 479.
Among the associative anionic polymers that may also be mentioned are maleic anhydride/C 30 -C 38 -α-olefin/alkyl maleate terpolymers, such as the product maleic anhydride/C 30 -C 38 -α-olefin/isopropyl maleate copolymer sold under the name Performa V 1608 by the company New Phase Technologies.
Among the associative anionic polymers, mention may be made, according to a preferred embodiment, of copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.
Preferentially, these compounds also comprise as monomer an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a C 1 -C 4 alcohol.
Examples of compounds of this type that may be mentioned include Aculyn 22® sold by the company Röhm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate (comprising 20 EO units) terpolymer or Aculyn 28° (methacrylic acid/ethyl acrylate/oxyethylenated behenyl methacrylate (25 EO) terpolymer).
Associative anionic polymers that may also be mentioned include anionic polymers comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit exclusively of the type such as a (C 10 -C 30 ) alkyl ester of an unsaturated carboxylic acid. Examples that may be mentioned include the anionic polymers described and prepared according to U.S. Pat. No. 3,915,921 and U.S. Pat. No. 4,509,949.
Associative anionic polymers that may also be mentioned include anionic terpolymers.
The anionic terpolymer used according to the invention is a linear or branched and/or crosslinked terpolymer, of at least one monomer (1) bearing an acid function in free form, which is partially or totally salified with a nonionic monomer (2) chosen from N,N-dimethylacrylamide and 2-hydroxyethyl acrylate and at least one polyoxyethylenated alkyl acrylate monomer (3) of formula (I) below:









in which R1 represents a hydrogen atom, R represents a linear or branched C 2 -C 8 alkyl radical and n represents a number ranging from 1 to 10.
The term “branched polymer” denotes a non-linear polymer which bears pendent chains so as to obtain, when this polymer is dissolved in water, a high degree of entanglement leading to very high viscosities, at a low speed gradient.
The term “crosslinked polymer” denotes a non-linear polymer which is in the form of a three-dimensional network that is insoluble in water but swellable in water, leading to the production of a gel.
The acid function of the monomer (1) is especially a sulfonic acid or phosphonic acid function, said functions being in free or partially or totally salified form.
The monomer (1) may be chosen from styrenesulfonic acid, ethylsulfonic acid and 2-methyl-2-[(1-oxo-2-propenyl]amino]-1-propanesulfonic acid (also known as acryloyldimethyl taurate), in free or partially or totally salified form. It is present in the anionic terpolymer preferably in molar proportions of between 5 mol % and 95 mol % and more particularly between 10 mol % and 90 mol %. The monomer (1) will more particularly be 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid in free or partially or totally salified form.
The acid function in partially or totally salified form will preferably be an alkali metal salt such as a sodium or potassium salt, an ammonium salt, an amino alcohol salt such as a monoethanolamine salt, or an amino acid salt such as a lysine salt.
The monomer (2) is preferably present in the anionic terpolymer in molar proportions of between 4.9 mol % and 90 mol %, more particularly between 9.5 mol % and 85 mol % and even more particularly between 19.5 mol % and 75 mol %.
In formula (I), examples of linear C 8 -C 16 alkyl radicals that may be mentioned include octyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl.
In formula (I), examples of branched C 8 -C 16 alkyl radicals that may be mentioned include 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 4-methylpentyl, 5-methylhexyl, 6-methylheptyl, 15-methylpentadecyl, 16-methylheptadecyl and 2-hexyloctyl.
According to a particular form of the invention, in formula (I), R denotes a C 12 -C 16 alkyl radical.
According to a particular form of the invention, in formula (I), n ranges from 3 to 5.
Tetraethoxylated lauryl acrylate will more particularly be used as monomer of formula (I).
The monomer (3) of formula (I) is preferably present in the anionic terpolymer in molar proportions of between 0.1 mol % and 10 mol % and more particularly between 0.5 mol % and 5 mol %.
According to a particular mode of the invention, the anionic terpolymer is crosslinked and/or branched with a diethylenic or polyethylenic compound in the proportion expressed relative to the total amount of monomers used, from 0.005 mol % to 1 mol %, preferably from 0.01 mol % to 0.5 mol % and more particularly from 0.01 mol % to 0.25 mol %.
The crosslinking agent and/or branching agent is preferably chosen from ethylene glycol dimethacrylate, diallyloxyacetic acid or a salt thereof, such as sodium diallyloxyacetate, tetraallyloxyethane, ethylene glycol diacrylate, diallylurea, triallylamine, trimethylolpropane triacrylate and methylenebis(acrylamide), or mixtures thereof.
The anionic terpolymer may contain additives such as complexing agents, transfer agents or chain-limiting agents.
Use will be made more particularly of an anionic terpolymer of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid partially or totally salified in the form of the ammonium salt, N,N-dimethylacrylamide and tetraethoxylated lauryl acrylate crosslinked with trimethylolpropane triacrylate, of INCI name Polyacrylate Crosspolymer-6, such as the product sold under the trade name Sepimax Zen® by the company SEPPIC.
Cationic Associative Polymers
Cationic associative polymers that may be mentioned include polyacrylates bearing amine side groups.
The polyacrylates bearing quaternized or non-quaternized amino side groups contain, for example, hydrophobic groups of the type such as steareth-20 (polyoxyethylenated (20) stearyl alcohol).
Examples of polyacrylates bearing amino side chains that may be mentioned are the polymers 8781-121B or 9492-103 from the company National Starch.
Nonionic Associative Polymers
The nonionic associative polymers may be chosen from:
copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers; copolymers of C 1 -C 6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain; copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer; associative polyurethanes.

Associative polyurethanes are nonionic block copolymers comprising in the chain both hydrophilic blocks usually of polyoxyethylene nature (polyurethanes may also be referred to as polyurethane polyethers), and hydrophobic blocks that may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.
In particular, these polymers comprise at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
Associative polyurethanes may be block polymers, in triblock or multiblock form. The hydrophobic blocks may thus be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example: multiblock copolymer). These polymers may also be graft polymers or star polymers. Preferably, the associative polyurethanes are triblock copolymers in which the hydrophilic block is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups. In general, associative polyurethanes comprise a urethane bond between the hydrophilic blocks, whence arises the name.
According to one preferred embodiment, a nonionic associative polymer of polyurethane type is used as gelling agent.
As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, it is also possible to use Rheolate® FX 1100 (Steareth-100/PEG 136/HDI (hexamethyl diisocyanate) copolymer), Rheolate® 205 containing a urea function, sold by the company Elementis, or Rheolate® 208, 204 or 212, and also Acrysol® RM 184 or Acrysol® RM 2020.
Mention may also be made of the product Elfacos® T210 containing a C 12 -C 14 alkyl chain, and the product Elfacos® T212 containing a C 16-18 alkyl chain (PPG-14 Palmeth-60 Hexyl Dicarbamate), from Akzo.
The product DW 1206B® from Röhm & Haas containing a C 20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.
Use may also be made of solutions or dispersions thereof. Examples of such polymers that may be mentioned are Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Elementis. The products DW 1206F and DW 1206J sold by the company Röhm & Haas may also be used.
The associative polyurethanes that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen, Colloid Polym. Sci., 271, 380-389 (1993).
Even more particularly, according to the invention, use may also be made of an associative polyurethane that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
Such polyurethane polyethers are sold in particular by the company Röhm & Haas under the names Aculyn® 46 and Aculyn® 44. Aculyn® 46 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%), and Aculyn® 44 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%).
Use may also be made of solutions or dispersions of these polymers. Examples of such polymers that may be mentioned include SER AD FX1010, SER AD FX1035 and SER AD 1070 from the company Elementis. Use may also be made of the products Aculyn® 44, Aculyn® 46, DW 1206F and DW 1206J, and also Acrysol® RM 184 from the company Röhm & Haas, or alternatively Borchigel LW 44 from the company Borchers, and mixtures thereof.
The nonionic associative polymers are advantageously used in a proportion of from 0.5% to 15% by weight of solids and preferably between 1% and 10% by weight, relative to the total weight of the composition.
Amphoteric Associative Polymers
Among the associative amphoteric polymers of the invention, mention may be made of crosslinked or non-crosslinked, branched or unbranched amphoteric polymers, which may be obtained by copolymerization:
1) of at least one monomer of formula (IVa) or (IVb):









in which R 4 and R 5 , which may be identical or different, represent a hydrogen atom or a methyl radical,
R 6 , R 7 and R 8 , which may be identical or different, represent a linear or branched alkyl radical containing from 1 to 30 carbon atoms;
Z represents an NH group or an oxygen atom;
n is an integer from 2 to 5;
A − is an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide;
2) of at least one monomer of formula (V):









in which R 9 and R 10 , which may be identical or different, represent a hydrogen atom or a methyl radical;
Z 1 represents a group OH or a group NHC(CH 3 ) 2 CH 2 SO 3 H;
3) of at least one monomer of formula (VI):









in which R 9 and R 10 , which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R 11 denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms;
4) optionally at least one crosslinking or branching agent; at least one of the monomers of formula (IVa), (IVb) or (VI) comprising at least one fatty chain containing from 8 to 30 carbon atoms and said compounds of the monomers of formulae (IVa), (IVb), (V) and (VI) possibly being quaternized, for example with a C 1 -C 4 alkyl halide or a C 1 -C 4 dialkyl sulfate.
The monomers of formulae (IVa) and (IVb) of the present invention are preferably chosen from the group consisting of:
dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide,

which are optionally quaternized, for example with a C 1 -C 4 alkyl halide or a C 1 -C 4 dialkyl sulfate.
More particularly, the monomer of formula (IVa) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyl-trimethylammonium chloride.
The compounds of formula (V) of the present invention are preferably chosen from the group formed by acrylic acid, methacrylic acid, crotonic acid, 2-methylcrotonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamido-2-methylpropanesulfonic acid. More particularly, the monomer of formula (V) is acrylic acid.
The monomers of formula (VI) of the present invention are preferably chosen from the group formed by C 12 -C 22 and more particularly C 16 -C 18 alkyl acrylates or methacrylates.
The crosslinking or branching agent is preferably chosen from N,N′-methylenebisacrylamide, triallylmethylammonium chloride, allyl methacrylate, n-methylolacrylamide, polyethylene glycol dimethacrylates, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allyl sucrose.
The polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C 1 -C 4 alkyl acrylates or methacrylates.
The ratio of the number of cationic charges/anionic charges in these amphoteric polymers is preferably equal to about 1.
The weight-average molecular weights of the associative amphoteric polymers have a weight-average molecular mass of greater than 500 g/mol, preferably between 10 000 g/mol and 10 000 000 g/mol and even more preferentially between 100 000 g/mol and 8 000 000 g/mol.
Preferably, the associative amphoteric polymers of the invention contain from 1 mol % to 99 mol %, more preferentially from 20 mol % to 95 mol % and even more preferentially from 25 mol % to 75 mol % of compound(s) of formula (IVa) or (IVb). They also preferably contain from 1 mol % to 80 mol %, more preferentially from 5 mol % to 80 mol % and even more preferentially from 25 mol % to 75 mol % of compound(s) of formula (V). The content of compound(s) of formula (VI) is preferably between 0.1 mol % and 70 mol %, more preferentially between 1 mol % and 50 mol % and even more preferentially between 1 mol % and 10 mol %. The crosslinking or branching agent, when it is present, is preferably between 0.0001 mol % and 1 mol % and even more preferentially between 0.0001 mol % and 0.1 mol %.
Preferably, the mole ratio between the compound(s) of formula (IVa) or (IVb) and the compound(s) of formula (V) ranges from 20/80 to 95/5 and more preferentially from 25/75 to 75/25.
The associative amphoteric polymers according to the invention are described, for example, in patent application WO 98/44012.
The amphoteric polymers that are particularly preferred according to the invention are chosen from acrylic acid/acrylamidopropyltrimethylammonium chloride/stearyl methacrylate copolymers.
Such an associative polymer is advantageously used in a proportion of from 0.1% to 10% by weight of solids and preferably between 0.2% and 6% by weight, relative to the total weight of the composition.
II. Polyacrylamides and 2-Acrylamido-2-Methylpropanesulfonic Acid Polymers and Copolymers
The polymers used that are suitable as aqueous gelling agent for the invention may be crosslinked or non-crosslinked homopolymers or copolymers comprising at least the 2-acrylamido-2-methylpropanesulfonic acid (AMPS®) monomer, in a form partially or totally neutralized with a mineral base other than aqueous ammonia, such as sodium hydroxide or potassium hydroxide.
They are preferably totally or almost totally neutralized, i.e. at least 90% neutralized.
These AMPS® polymers according to the invention may be crosslinked or non-crosslinked.
When the polymers are crosslinked, the crosslinking agents may be chosen from the polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization.
Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allylic ethers of alcohols of the sugar series, or other allylic or vinyl ethers of polyfunctional alcohols, and also the allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
According to one preferred embodiment of the invention, the crosslinking agent is chosen from methylenebisacrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01 mol % to 10 mol % and more particularly from 0.2 mol % to 2 mol % relative to the polymer.
The AMPS® polymers that are suitable for use in the invention are water-soluble or water-dispersible. In this case, they are:
either “homopolymers” comprising only AMPS monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above;
or copolymers obtained from AMPS® and from one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above. When said copolymers comprise hydrophobic ethylenically unsaturated monomers, these monomers do not comprise a fatty chain and are preferably present in small amounts.
For the purpose of the present invention, the term “fatty chain” is intended to mean any hydrocarbon-based chain comprising at least 7 carbon atoms.
The term “water-soluble or water-dispersible” means polymers which, when introduced into an aqueous phase at 25° C., at a mass concentration equal to 1%, make it possible to obtain a macroscopically homogeneous and transparent solution, i.e. a solution with a maximum light transmittance value, at a wavelength equal to 500 nm, through a sample 1 cm thick, of at least 60% and preferably of at least 70%.
The “homopolymers” according to the invention are preferably crosslinked and neutralized, and they may be obtained according to the preparation process comprising the following steps:
(a) the monomer such as AMPS in free form is dispersed or dissolved in a solution of tert-butanol or of water and tert-butanol;
(b) the monomer solution or dispersion obtained in (a) is neutralized with one or more mineral or organic bases, preferably aqueous ammonia NH 3 , in an amount making it possible to obtain a degree of neutralization of the sulfonic acid functions of the polymer ranging from 90% to 100%;
(c) the crosslinking monomer(s) are added to the solution or dispersion obtained in (b);
(d) a standard free-radical polymerization is performed in the presence of free-radical initiators at a temperature ranging from 10° C. to 150° C.; the polymer precipitates from the tert-butanol-based solution or dispersion.
The water-soluble or water-dispersible AMPS® copolymers according to the invention contain water-soluble ethylenically unsaturated monomers, hydrophobic monomers, or mixtures thereof.
The water-soluble comonomers may be ionic or nonionic.
Among the ionic water-soluble comonomers, examples that may be mentioned include the following compounds, and salts thereof:
(meth)acrylic acid, styrenesulfonic acid, vinylsulfonic acid and (meth)allylsulfonic acid, vinylphosphonic acid, maleic acid, itaconic acid, crotonic acid, water-soluble vinyl monomers of formula (A) below:










in which:
R 1 is chosen from H, —CH 3 , —C 2 H 5 and —C 3 H 7 , X 1 is chosen from: alkyl oxides of type —OR 2 where R 2 is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbon atoms, substituted with at least one sulfonic (—SO 3 —) and/or sulfate (—SO 4 —) and/or phosphate (—PO 4 H 2 —) group.

Among the nonionic water-soluble comonomers, examples that may be mentioned include:
(meth)acrylamide, N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methyl-N-vinylformamide, maleic anhydride, vinylamine, N-vinyllactams comprising a cyclic alkyl group containing from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam, vinyl alcohol of formula CH 2 ═CHOH, water-soluble vinyl monomers of formula (B) below:










in which:
R 3 is chosen from H, —CH 3 , —C 2 H 5 and —C 3 H 7 , X 2 is chosen from alkyl oxides of the type —OR 4 where R 4 is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbon atoms, optionally substituted with a halogen (iodine, bromine, chlorine or fluorine) atom; a hydroxyl (—OH) group; ether.

Mention is made, for example, of glycidyl (meth)acrylate, hydroxyethyl methacrylate, and (meth)acrylates of ethylene glycol, of diethylene glycol or of polyalkylene glycol.
Among the hydrophobic co-monomers without a fatty chain, mention may be made, for example, of:
styrene and derivatives thereof, such as 4-butylstyrene, α-methylstyrene and vinyltoluene; vinyl acetate of formula CH 2 ═CH—OCOCH 3 ; vinyl ethers of formula CH 2 ═CHOR in which R is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbons; acrylonitrile; caprolactone; vinyl chloride and vinylidene chloride; silicone derivatives, which, after polymerization, result in silicone polymers such as methacryloxypropyltris(trimethylsiloxy)silane and silicone methacrylamides; hydrophobic vinyl monomers of formula (C) below:










in which:
R 4 is chosen from H, —CH 3 , —C 2 H 5 and —C 3 H 7 ; X 3 is chosen from: alkyl oxides of the type —OR 5 where R 5 is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbon atoms.

Mention is made, for example, of methyl methacrylate, ethyl methacrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl acrylate, isobornyl acrylate and 2-ethylhexyl acrylate.
The water-soluble or water-dispersible AMPS® polymers of the invention preferably have a molar mass ranging from 50 000 g/mol to 10 000 000 g/mol, preferably from 80 000 g/mol to 8 000 000 g/mol, and even more preferably from 100 000 g/mol to 7 000 000 g/mol.
As water-soluble or water-dispersible AMPS homopolymers suitable for use in the invention, mention may be made, for example, of crosslinked or non-crosslinked polymers of sodium acrylamido-2-methylpropanesulfonate, such as that used in the commercial product Simulgel 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked ammonium acrylamido-2-methylpropanesulfonate polymers (INCI name: Ammonium Polyacryldimethyltauramide) such as those described in patent EP 0 815 928 B1 and such as the product sold under the trade name Hostacerin AMPS® by the company Clariant.
As preferred water-soluble or water-dispersible AMPS homopolymers in accordance with the invention, mention may be made of ammonium 2-acrylamido-2-methylpropanesulfonic acid polymers.
As water-soluble or water-dispersible AMPS copolymers in accordance with the invention, examples that may be mentioned include:
crosslinked acrylamide/sodium acrylamido-2-methylpropanesulfonate copolymers, such as that used in the commercial product Sepigel 305® (CTFA name: Polyacrylamide/C 13 -C 14 Isoparaffin/Laureth-7) or that used in the commercial product sold under the name Simulgel 600 (CTFA name: Acrylamide/Sodium acryloyldimethyltaurate/Isohexadecane/Polysorbate-80) by the company SEPPIC; copolymers of AMPS® and of vinylpyrrolidone or vinylformamide, such as that used in the commercial product sold under the name Aristoflex AVC® by the company Clariant (CTFA name: Ammonium Acryloyldimethyltaurate/VP copolymer) but neutralized with sodium hydroxide or potassium hydroxide; copolymers of AMPS® and of sodium acrylate, for instance the AMPS/sodium acrylate copolymer, such as that used in the commercial product sold under the name Simulgel EG® by the company SEPPIC); copolymers of AMPS® and of hydroxyethyl acrylate, for instance the AMPS®/hydroxyethyl acrylate copolymer, such as that used in the commercial product sold under the name Simulgel NS® by the company SEPPIC (CTFA name: Hydroxyethyl acrylate/Sodium acryloyldimethyltaurate copolymer (and) Squalane (and) Polysorbate 60), or such as the product sold under the name Sodium acrylamido-2-methylpropanesulfonate/Hydroxyethyl acrylate copolymer, such as the commercial product Sepinov EMT 10 or under the trade name Sepinov EM (INCI name: Hydroxyethyl acrylate/Sodium acryloyldimethyltaurate copolymer).

As preferred water-soluble or water-dispersible AMPS copolymers in accordance with the invention, mention may be made of copolymers of AMPS® and of hydroxyethyl acrylate.
In general, a composition according to the invention may comprise from 0.1% to 10% by weight, preferably from 0.2% to 8% by weight and more preferentially from 0.2% to 6% by weight of solids of polyacrylamide(s) and/or of crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid polymer(s) and copolymer(s) relative to the total weight of the composition.
III. Modified or Unmodified Carboxyvinyl Polymers
The modified or unmodified carboxyvinyl polymers may be homopolymers or copolymers derived from the polymerization of at least one monomer chosen from α,β-ethylenically unsaturated carboxylic acids or esters thereof.
The term “copolymers” means both copolymers obtained from two types of monomer and those obtained from more than two types of monomer, such as terpolymers obtained from three types of monomer.
Their chemical structure more particularly comprises at least one hydrophilic unit and at least one hydrophobic unit. The term “hydrophobic group or unit” means a radical with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
Preferably, these copolymers are chosen from copolymers derived from the polymerization:
of at least one monomer of formula (1) below:









in which R 1 denotes H or CH 3 or C 2 H 5 , i.e. acrylic acid, methacrylic acid or ethacrylic acid monomers, and
of at least one monomer of unsaturated carboxylic acid (C 10 -C 30 )alkyl ester type corresponding to the monomer of formula (2) below:











in which R 2 denotes H or CH 3 or C 2 H 5 (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH 3 (methacrylate units), R 3 denoting a C 10 -C 30 and preferably C 12 -C 22 alkyl radical.




The unsaturated carboxylic acid (C 10 -C 30 )alkyl esters are preferably chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, such as lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate, and mixtures thereof.
According to a preferred embodiment, these polymers are crosslinked.
Among the copolymers of this type that will be used more particularly are polymers derived from the polymerization of a monomer mixture comprising:
essentially acrylic acid, an ester of formula (2) described above in which R 2 denotes H or CH 3 , R 3 denoting an alkyl radical containing from 12 to 22 carbon atoms, and a crosslinking agent, which is a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

Among the copolymers of this type, use will more particularly be made of those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those consisting of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.
Among the abovementioned polymers, the ones that are most particularly preferred according to the present invention are acrylate/C 10 -C 30 -alkyl acrylate copolymers (INCI name: Acrylates/C 10-30 Alkyl acrylate Crosspolymer) such as the products sold by the company Lubrizol under the trade names Pemulen TR-1, Pemulen TR-2, Carbopol 1382, Carbopol EDT 2020 and Carbopol Ultrez 20 Polymer, and even more preferentially Pemulen TR-2.
Among the modified or unmodified carboxyvinyl polymers, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia SP® containing 90% solids and 10% water, or Cosmedia SPL® as an inverse emulsion containing about 60% solids, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis.
Mention may also be made of partially neutralized sodium polyacrylates that are in the form of an inverse emulsion comprising at least one polar oil, for example the product sold under the name Luvigel® EM sold by the company BASF.
The modified or unmodified carboxyvinyl polymers may also be chosen from crosslinked (meth)acrylic acid homopolymers.
For the purposes of the present patent application, the term “(meth)acrylic” means “acrylic or methacrylic”.
Examples that may be mentioned include the products sold by Lubrizol under the names Carbopol 910, 934, 940, 941, 934 P, 980, 981, 2984, 5984 and Carbopol Ultrez 10 Polymer, or by 3V-Sigma under the name Synthalen® K, Synthalen® L or Synthalen® M.
Among the modified or unmodified carboxyvinyl polymers, mention may be made in particular of Carbopol (INCI name: carbomer) and Pemulen (CTFA name: Acrylates/C 10-30 alkyl acrylate crosspolymer) sold by the company Lubrizol.
The modified or unmodified carboxyvinyl polymers may be present in a proportion of from 0.1% to 5% by weight of solids relative to the weight of the composition, in particular from 0.2% to 4% by weight and preferably from 0.3% to 3% relative to the weight of the composition.
Advantageously, a composition according to the invention comprises, as synthetic polymeric hydrophilic gelling agent, at least one gelling agent chosen from associative polymers which are preferably nonionic; 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers; and mixtures thereof, in particular associative polymers which are preferably nonionic.
According to a preferred variant, the synthetic polymeric hydrophilic gelling agent is chosen from copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate; ammonium 2-acrylamido-2-methylpropanesulfonate polymers; nonionic associative polyurethanes, in particular fatty-chain nonionic polyurethane polyethers; and mixtures thereof.
Lipophilic Gelling Agent
For the purposes of the present invention, the term “lipophilic gelling agent” means a compound that is capable of gelling the oily phase of the compositions according to the invention.
The gelling agent is lipophilic and is thus present in the oily phase of the composition.
The gelling agent is liposoluble or lipodispersible.
As emerges from the foregoing, the gelled oily phase comprises at least one lipophilic gelling agent chosen from meltable compounds.
A composition according to the invention may also comprise at least one lipophilic gelling agent chosen from modified clays.
I. Meltable Compounds
For the purposes of the invention, a meltable compound may be chosen from waxes, semi-crystalline polymers, and mixtures thereof, especially as detailed below.
This type of compound is particularly advantageous since it gives the compositions according to the invention the desired staying power properties and in particular good water resistance.
For the purposes of the invention, the meltable compound(s) advantageously have a melting point of between 40° C. and 120° C.
A composition according to the invention may comprise from 3% to 40% by weight, preferably from 5% to 35% by weight and even more preferentially from 10% to 30% by weight of meltable compound(s), relative to the total weight of the composition.
1. Wax
According to an embodiment variant, a composition according to the invention may comprise as meltable compound at least one wax.
The term “wax” generally means 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 40° C., which may be up to 200° C. and in particular up to 120° C.
For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the 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 MDSC 2920 by the company TA Instruments.
The measuring protocol is as follows:
A 5 mg sample of wax placed in a crucible is subjected to a first temperature increase from −20° C. to 100° C., at a heating rate of 10° C./minute, and then is cooled from 100° C. to −20° C. at a cooling rate of 10° C./minute and is finally subjected to a second temperature rise from −20° C. to 100° C. at a heating rate of 5° C./minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature. The melting point of the compound is the temperature value 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 waxes that may be used in the compositions according to the invention are chosen from waxes that are solid at room temperature of animal, plant, mineral or synthetic origin, and mixtures thereof.
The waxes, for the purposes of the invention, may be those used generally in the cosmetic or dermatological fields. They may in particular be polar or apolar, and hydrocarbon-based, silicone and/or fluoro waxes, optionally comprising ester or hydroxyl functions.
a) Apolar Waxes
For the purposes of the present invention, the term “apolar wax” means a wax whose solubility parameter at 25° C. as defined below, δ a , is equal to 0 (J/cm 3 ) 1/2 .
The definition and calculation of the solubility parameters in the Hansen three-dimensional solubility space are described in the article by C. M. Hansen: The three - dimensional solubility parameters , J. Paint Technol. 39, 105 (1967).
According to this Hansen space:
δ D characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts; δ p characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles; δ h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.); and δ a is determined by the equation: δ a =(δ p 2 +δ h 2 ) 1/2 .

The parameters δ p , δ h , δ D and δ a are expressed in (J/cm 3 ) 1/2 .
The apolar waxes are in particular hydrocarbon-based waxes constituted solely of carbon and hydrogen atoms, and free of heteroatoms such as N, O, Si and P.
The apolar waxes are chosen from microcrystalline waxes, paraffin waxes, ozokerite and polyethylene waxes, and mixtures thereof.
An ozokerite that may be mentioned is Ozokerite Wax SP 1020 P.
As microcrystalline waxes that may be used, mention may be made of Multiwax W 445® sold by the company Sonneborn, and Microwax HW® and Base Wax 30540® sold by the company Paramelt, and Cerewax® No. 3 sold by the company Baerlocher.
As microwaxes that may be used in the compositions according to the invention as apolar wax, mention may be made in particular of polyethylene microwaxes such as those sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders.
Polyethylene waxes that may be mentioned include Performalene 500-L Polyethylene and Performalene 400 Polyethylene sold by New Phase Technologies, and Asensa® SC 211 sold by the company Honeywell.
b) Polar Wax
For the purposes of the present invention, the term “polar wax” means a wax whose solubility parameter at 25° C., δa, is other than 0 (J/cm 3 ) 1/2 .
In particular, the term “polar wax” means a wax whose chemical structure is formed essentially from, or even consists of, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.
The polar waxes may in particular be hydrocarbon-based, fluoro or silicone waxes.
Preferentially, the polar waxes may be hydrocarbon-based waxes.
The term “hydrocarbon-based wax” is intended to mean a wax formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and that does not contain any silicon or fluorine atoms. It may also contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
According to the invention, the term “ester wax” is intended to mean a wax comprising at least one ester function. According to the invention, the term “alcohol wax” is intended to mean a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.
Polar waxes that may especially be used include those chosen from:
i) waxes of formula R 1 COOR 2 in which R 1 and R 2 represent linear, branched or cyclic aliphatic chains in which the number of atoms ranges from 10 to 50, which may contain a heteroatom such as O, N or P and whose melting point ranges from 25 to 120° C.;
ii) bis(1,1,1-trimethylolpropane) tetrastearate, sold under the name Hest 2T-4S® by the company Heterene;
iii) diester waxes of a dicarboxylic acid of general formula R 3 —(—OCO—R 4 —COO—R 5 ), in which R 3 and R 5 are identical or different, preferably identical, and represent a C 4 -C 30 alkyl group (alkyl group comprising from 4 to 30 carbon atoms) and R 4 represents a linear or branched C 4 -C 30 aliphatic group (alkyl group comprising from 4 to 30 carbon atoms) which may or may not comprise one or more unsaturations and which is preferably linear and unsaturated;
iv) mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C 8 -C 32 fatty chains, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol;
v) beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylenated lanolin wax, rice bran wax, ouricury wax, esparto grass wax, cork fibre wax, sugar cane wax, Japan wax, sumac wax, montan wax, orange wax, laurel wax, hydrogenated jojoba wax, sunflower wax, lemon wax, olive wax or berry wax.
According to another embodiment, the polar wax may be an alcohol wax. Alcohol waxes that may be mentioned include for example the C 30-50 alcohol wax Performacol® 550 Alcohol sold by the company New Phase Technologies, stearyl alcohol and cetyl alcohol.
It is also possible to use silicone waxes, which may advantageously be substituted polysiloxanes, preferably of low melting point.
The term “silicone wax” is intended to mean an oil comprising at least one silicon atom, and in particular comprising Si—O groups.
Among the commercial silicone waxes of this type, mention may be made in particular of those sold under the names Abilwax 9800, 9801 or 9810 (Goldschmidt), KF910 and KF7002 (Shin-Etsu), or 176-1118-3 and 176-11481 (General Electric).
The silicone waxes that may be used may also be alkyl or alkoxy dimethicones, and also (C 20 -C 60 )alkyl dimethicones, in particular (C 30 -C 45 )alkyl dimethicones, such as the silicone wax sold under the name SF-1642 by the company GE-Bayer Silicones or C 30-45 alkyl dimethylsilyl polypropylsilsesquioxane under the name SW-8005® C30 Resin Wax sold by the company Dow Corning.
2. Semi-Crystalline Polymers
According to an embodiment variant, a composition according to the invention may comprise as meltable compound at least one semi-crystalline polymer.
Preferably, the semi-crystalline polymer has an organic structure, and a melting point of greater than or equal to 40° C.
For the purposes of the invention, the term “semi-crystalline polymer” is intended to mean polymers comprising a crystallizable portion and an amorphous portion and having a first-order reversible change of phase temperature, in particular of melting point (solid-liquid transition). The crystallizable part is either a side chain (or pendent chain) or a block in the backbone.
When the crystallizable portion of the semi-crystalline polymer is a block of the polymer backbone, this crystallizable block has a chemical nature different than that of the amorphous blocks; in this case, the semi-crystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type. When the crystallizable part is a chain that is pendent on the backbone, the semi-crystalline polymer may be a homopolymer or a copolymer.
The melting point of the semi-crystalline polymer is preferably less than 120° C.
The melting point of the semi-crystalline polymer is preferably greater than or equal to 40° C. and less than 85° C.
The semi-crystalline polymer(s) according to the invention are solid at room temperature (25° C.) and atmospheric pressure (760 mmHg), with a melting point of greater than or equal to 40° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the company Mettler, with a temperature rise of 5° C. or 10° C. per minute. The melting point under consideration is the point corresponding to the temperature of the most endothermic peak in the thermogram.
Besides the crystallizable chains or blocks, the blocks of the polymers are amorphous. For the purposes of the invention, the term “crystallizable chain or block” is intended to mean a chain or block which, if it were alone, would change from the amorphous state to the crystalline state reversibly, depending on whether the temperature is above or below the melting point. For the purposes of the invention, a chain is a group of atoms, which are pendent or lateral relative to the polymer backbone. A “block” is a group of atoms belonging to the backbone, this group constituting one of the repeating units of the polymer.
The crystallizable blocks or chains of the semi-crystalline polymers may represent at least 30% of the total weight of each polymer and better still at least 40%. The semi-crystalline polymers containing crystallizable side chains are homopolymers or copolymers. The semi-crystalline polymers of the invention containing crystallizable blocks are block or multiblock copolymers. They may be obtained via polymerization of a monomer containing reactive double bonds (or ethylenic bonds) or via polycondensation. When the polymers of the invention are polymers containing crystallizable side chains, these side chains are advantageously in random or statistical form.
The semi-crystalline polymers of the invention may be of synthetic origin.
In particular, the semi-crystalline polymer may be chosen from:
homopolymers and copolymers comprising units resulting from the polymerization of one or more monomers bearing crystallizable hydrophobic side chain(s), polymers bearing in the backbone at least one crystallizable block, polycondensates of aliphatic or aromatic or aliphatic/aromatic polyester type, copolymers of ethylene and propylene prepared via metallocene catalysis, and acrylate/silicone copolymers.

The semi-crystalline polymers that may be used in the invention may be chosen in particular from:
block copolymers of polyolefins of controlled crystallization, whose monomers are described in EP 0 951 897, polycondensates, in particular of aliphatic or aromatic or aliphatic/aromatic polyester type, copolymers of ethylene and propylene prepared via metallocene catalysis, homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing in the backbone at least one crystallizable block, such as those described in document U.S. Pat. No. 5,156,911, such as the (C 10 -C 30 )alkyl polyacrylates corresponding to the Intelimer® products from the company Landec described in the brochure Intelimer® Polymers , Landec IP22 (Rev. 4-97), for example the product Intelimer® IPA 13-1 from the company Landec, which is a polystearyl acrylate with a molecular weight of about 145 000 and a melting point of 49° C., homopolymers or copolymers bearing at least one crystallizable side chain, in particular containing fluoro group(s), as described in document WO 01/19333, acrylate/silicone copolymers, such as copolymers of acrylic acid and of stearyl acrylate bearing polydimethylsiloxane grafts, copolymers of stearyl methacrylate bearing polydimethylsiloxane grafts, copolymers of acrylic acid and of stearyl methacrylate bearing polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate bearing polydimethylsiloxane grafts. Mention may be made in particular of the copolymers sold by the company Shin-Etsu under the names KP-561 (CTFA name: acrylates/dimethicone), KP-541 (CTFA name: acrylates/dimethicone and isopropyl alcohol), KP-545 (CTFA name: acrylates/dimethicone and cyclopentasiloxane), and mixtures thereof.

In the context of the present invention, particularly advantageous semi-crystalline polymers that may be mentioned include poly(C 10 -C 30 )alkyl acrylates, for example the product sold under the name Intelimer IPA 13-1 NG by the company Air Products and Chemicals.
According to a preferred embodiment, a composition according to the invention comprises at least one wax as meltable compound.
Preferably, in the context of the present invention, the meltable compound(s) are chosen from a beeswax, a paraffin wax, a carnauba wax, a poly(C 10 -C 30 )alkyl acrylate, a vinyl acetate/allyl stearate copolymer, and mixtures thereof.
II. Modified Clays
As mentioned previously, besides the presence of at least one lipophilic gelling agent chosen from meltable compounds, a composition according to the invention may also comprise at least one lipophilic gelling agent chosen from modified clays.
The clays may be natural or synthetic, and they are made lipophilic by treatment with an alkylammonium salt such as a C 10 to C 22 ammonium chloride, for example distearyldimethylammonium chloride.
They may be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.
They are preferably chosen from hectorites.
Hectorites modified with a C 10 to C 22 ammonium chloride, such as hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name Bentone 38VCG® by the company Elementis or bentone gel in isododecane sold under the name Bentone Gel ISD V® (87% isododecane/10% disteardimonium hectorite/3% propylene carbonate) by the company Elementis, are preferably used as lipophilic clays.
Lipophilic clay may especially be present in a content ranging from 0.1% to 15% by weight, in particular from 0.2% to 10% and more particularly from 0.2% to 8% by weight relative to the total weight of the oily phase.
Advantageously, a composition according to the invention comprises as lipophilic gelling agent at least one modified clay preferably chosen from bentonites, in particular hectorites.
Thus, a composition according to the invention preferably comprises as lipophilic gelling agent at least one meltable compound, especially a wax, in combination with at least one modified clay preferably chosen from bentonites, in particular hectorites.
Hydrophilic Gelling Agent/Lipophilic Gelling Agent System
As preferred synthetic polymeric hydrophilic gelling agents, mention may be made more particularly of:
a) 2-acrylamido-2-methylpropanesulfonic acid polymers, for instance AMPS, such as the ammonium 2-acrylamido-2-methylpropanesulfonate polymer sold under the trade name Hostacerin AMPS® by the company Clariant, and 2-acrylamido-2-methylpropanesulfonic acid copolymers and in particular copolymers of AMPS® and of hydroxyethyl acrylate, for instance the AMPS®/hydroxyethyl acrylate copolymer such as that used in the commercial product sold under the name Simulgel NS® by the company SEPPIC (CTFA name: Hydroxyethyl acrylate/Sodium acryloyldimethyltaurate copolymer (and) Squalane (and) Polysorbate 60), or such as the product sold under the name Sodium acrylamido-2-methylpropanesulfonate/Hydroxyethyl acrylate copolymer, such as the commercial product Sepinov EMT 10 (INCI name: Hydroxyethyl acrylate/Sodium acryloyldimethyltaurate copolymer);
b) associative polymers, in particular nonionic associative polymers, especially of polyurethane type, for instance associative polyurethanes, in particular fatty-chain nonionic polyurethane polyethers such as the Steareth-100/PEG-136/HDI copolymer sold under the name Rheolate FX 1100 by Elementis.
As mentioned previously, a composition according to the invention comprises as lipophilic gelling agent at least one lipophilic gelling agent chosen from meltable compounds.
Preferred meltable compounds that may be mentioned include waxes, and especially beeswax, for example the product sold under the name White Beeswax SP-453P by the company Strahl & Pitsch.
A composition according to the invention also preferably comprises at least one modified clay as lipophilic gelling agent.
Preferred modified clays that may especially be mentioned include bentonites and preferably hectorites. Mention may be made especially in this respect of Bentone 38VCG and Bentone gel in isododecane under the name Bentone Gel ISD V® sold by the company Elementis.
Thus, a composition according to the invention advantageously comprises as lipophilic gelling agent at least one meltable compound, preferably a wax, in combination with a modified clay such as bentonites and more particularly hectorites.
As non-limiting illustrations of hydrophilic gelling agent/lipophilic gelling agent systems that are most particularly suitable for use in the invention, mention may be made especially of the polymer and/or or copolymer system of 2-acrylamido-2-methylpropanesulfonic acid/wax(es) and optionally modified clay(s), or the system of associative polymer(s) which are preferably nonionic/wax(es) and optionally modified clay(s).
Thus, a composition according to the invention may advantageously comprise as hydrophilic gelling agent/lipophilic gelling agent system a system chosen from:
copolymer(s) of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate/wax(es); polymer(s) of ammonium 2-acrylamido-2-methylpropanesulfonate/wax(es); and

nonionic associative polyurethane(s)/wax(es);
and preferably the nonionic associative polyurethane(s)/wax(es) system.
Preferably, a composition according to the invention may comprise as hydrophilic gelling agent/lipophilic gelling agent system a system chosen from:
copolymer(s) of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate/wax(es)-modified clay(s) preferably chosen from hectorites; polymer(s) of ammonium 2-acrylamido-2-methylpropanesulfonate/wax(es)-modified clay(s) preferably chosen from hectorites; and nonionic associative polyurethane(s)/wax(es)-modified clay(s) preferably chosen from hectorites;

and preferably, the system of nonionic associative polyurethane(s)/wax(es)-modified clay(s) preferably chosen from hectorites.
Hydrophobic Film-Forming Polymers
The gelled oily phase of the claimed compositions may comprise at least one hydrophobic film-forming polymer especially as detailed below.
This type of polymer is particularly advantageous in so far as it makes it possible to significantly increase the staying power of the deposit over time. As indicated previously, the performance of these polymers is advantageously increased by means of using them in a composition according to the invention.
For the purposes of the invention, the term “polymer” means a compound corresponding to the repetition of one or more units (these units being derived from compounds known as monomers). This or these unit(s) are repeated at least twice and preferably at least three times.
For the purposes of the present invention, the term “hydrophobic film-forming polymer” is intended to denote a film-forming polymer that has no affinity for water and, in this respect, does not lend itself to a formulation in the form of a solute in an aqueous medium. In particular, the term “hydrophobic polymer” means a polymer having a solubility in water at 25° C. of less than 1% by weight.
The term “film-forming polymer” means a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous deposit on a support, especially on keratin materials, and preferably a cohesive deposit, and better still a deposit whose cohesion and mechanical properties are such that said deposit may be isolable and manipulable in isolation, for example when said deposit is prepared by pouring onto a non-stick surface, for instance a Teflon-coated or silicone-coated surface.
In particular, the hydrophobic film-forming polymer is a polymer chosen from the group comprising:
film-forming polymers that are soluble in an organic solvent medium, in particular liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and forms a single homogeneous phase when it is incorporated into the medium; and film-forming polymers that are dispersible in an organic solvent medium, which means that the polymer forms an insoluble phase in the organic medium, the polymer remaining stable and/or compatible once incorporated into this medium. In particular, such polymers may be in the form of non-aqueous dispersions of polymer particles, preferably dispersions in silicone oils or hydrocarbon-based oils; in one embodiment, the non-aqueous polymer dispersions comprise polymer particles stabilized on their surface with at least one stabilizer; these non-aqueous dispersions are often referred to as NADs.

Hydrophobic film-forming polymers that may especially be mentioned include homopolymers and copolymers of a compound bearing an ethylenic unit, acrylic polymers and copolymers, polyurethanes, polyesters, silicone polymers such as polymers bearing a non-silicone organic backbone grafted with monomers containing a polysiloxane, and polyisoprenes.
A composition according to the invention may comprise from 1% to 30% by weight, preferably from 2% to 25% by weight and even more preferentially from 5% to 20% by weight of hydrophobic film-forming polymer(s) relative to the total weight of the composition.
As hydrophobic film-forming polymers that are most particularly suitable for use in the invention, mention may be made especially of lipodispersible film-forming polymers in the form of non-aqueous dispersions (NAD), of polymer particles block ethylenic copolymers, vinyl polymers comprising at least one carbosiloxane dendrimer-based unit, silicone acrylate copolymers and mixtures thereof.
I. Lipodispersible Film-Forming Polymers in the Form of Non-Aqueous Dispersions of Polymer Particles, Also Known as NADs
According to another embodiment variant, a composition according to the invention may comprise, as hydrophobic film-forming polymer, at least one polymer chosen from lipodispersible film-forming polymers in the form of non-aqueous dispersions of polymer particles, also known as NADs.
Non-aqueous dispersions of hydrophobic film-forming polymer that may be used include dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid oily phase for example, in the form of surface-stabilized particles dispersed in the liquid fatty phase.
The dispersion of surface-stabilized polymer particles may be manufactured as described in document WO 04/055081.
II. Block Ethylenic Copolymer
According to a first embodiment of the invention, the hydrophobic film-forming polymer is a block ethylenic copolymer, containing at least a first block with a glass transition temperature (T g ) of greater than or equal to 40° C. and being totally or partly derived from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C., and at least a second block with a glass transition temperature of less than or equal to 20° C. and being derived totally or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C., said first block and said second block being connected together via a statistical intermediate segment comprising at least one of said first constituent monomers of the first block and at least one of said second constituent monomers of the second block, and said block copolymer having a polydispersity index I of greater than 2.
Polymers of this type in accordance with the invention are described in the document EP 1 411 069.
As an example of such polymers, mention may be made more particularly of Mexomere Pas® (Acrylic acid copolymer/Isobutylacrylate/Isobornyl acrylate diluted to 50% in isododecane) sold by the company Chimex.
III. Vinyl Polymer Comprising at Least One Carbosiloxane Dendrimer-Based Unit
According to one particular embodiment, a composition used according to the invention may comprise, as hydrophobic film-forming polymer, at least one vinyl polymer comprising at least one carbosiloxane dendrimer-based unit.
The vinyl polymer used according to the invention especially has a backbone and at least one side chain, which comprises a carbosiloxane dendrimer-based unit having a carbosiloxane dendrimer structure.
Vinyl polymers comprising at least one carbosiloxane dendrimer unit as described in applications WO 03/045 337 and EP 963 751 by the company Dow Corning may be used in particular.
The term “carbosiloxane dendrimer structure” in the context of the present invention represents a molecular structure with branched groups of high molecular masses, said structure having high regularity in the radial direction starting from the bond to the backbone. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in the laid-open Japanese patent application Kokai 9-171 154.
A vinyl polymer bearing at least one carbosiloxane dendrimer-based unit has a molecular side chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization of:
(A) from 0 to 99.9 parts by weight of a vinyl monomer; and
(B) from 100 to 0.1 part by weight of a carbosiloxane dendrimer containing a radical-polymerizable organic group, represented by the general formula:









in which Y represents a radical-polymerizable organic group, R 1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms, and X i represents a silylalkyl group which, when i=1, is represented by the formula:









in which R 1 is as defined above, R 2 represents an alkylene group containing from 2 to 10 carbon atoms, R 3 represents an alkyl group containing from 1 to 10 carbon atoms, X i+1 represents a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i=i+1; i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a i is an integer from 0 to 3;
in which said radical-polymerizable organic group contained in the component (A) is chosen from:
organic groups containing a methacrylic group or an acrylic group and that are represented by the formulae:










in which R 4 represents a hydrogen atom or an alkyl group, R 5 represents an alkylene group containing from 1 to 10 carbon atoms; and
organic groups containing a styryl group and that are represented by the formula:












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




The monomer of vinyl type that is the component (A) in the vinyl polymer is a monomer of vinyl type that contains a radical-polymerizable vinyl group.
There is no particular limitation as regards such a monomer.
The following are examples of this monomer of vinyl type: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate or a methacrylate of an analogous lower alkyl; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate or a higher-analogue methacrylate; vinyl acetate, vinyl propionate or a vinyl ester of an analogous lower fatty acid; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate or an ester of an analogous higher fatty acid; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone or similar vinylaromatic monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethyl-methacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide or similar monomers of vinyl type containing amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate or similar monomers of vinyl type containing hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or similar monomers of vinyl type containing a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether or a similar monomer of vinyl type with ether bonds; methacryloxypropyltrimethoxysilane, polydimethylsiloxane containing a methacrylic group on one of its molecular ends, polydimethylsiloxane containing a styryl group on one of its molecular ends, or a similar silicone compound containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, of itaconic acid, of crotonic acid, of maleic acid or of fumaric acid; a radical-polymerizable unsaturated monomer containing a sulfonic acid group such as a styrenesulfonic acid group; a quaternary ammonium salt derived from methacrylic acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and a methacrylic acid ester of an alcohol containing a tertiary amine group, such as a methacrylic acid ester of diethylamine.
Multifunctional monomers of vinyl type may also be used.
The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythrityl trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethylmethacrylate, tris(2-hydroxyethyl) isocyanurate dimethacrylate, tris(2-hydroxyethyl) isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups bearing divinylbenzene groups on the two ends, or similar silicone compounds bearing unsaturated groups.
To facilitate the preparation of starting material mixture for cosmetic products, the number-average molecular mass of the vinyl polymer bearing a carbosiloxane dendrimer may be chosen within the range between 3000 g/mol and 2 000 000 g/mol and preferably between 5000 g/mol and 800 000 g/mol. It may be a liquid, a gum, a paste, a solid, a powder, or any other form. The preferred forms are solutions consisting of the dilution of a dispersion or of a powder in solvents such as a silicone oil or an organic oil.
A vinyl polymer contained in the dispersion or the solution may have a concentration in the range between 0.1% and 95% by weight and preferably between 5% and 70% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 60% by weight.
According to one preferred mode, a vinyl polymer that is suitable for use in the invention may be one of the polymers described in the examples of patent application EP 0 963 751.
According to one preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer may be the product of polymerization of:
(A) from 0.1 to 99 parts by weight of one or more acrylate or methacrylate monomers; and
(B) from 100 to 0.1 part by weight of an acrylate or methacrylate monomer of a tris[tri(trimethyl siloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer.
According to one embodiment, a vinyl polymer bearing at least one carbosilaxane dendrimer-based unit may comprise a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer-based unit corresponding to one of the formulae:









According to one preferred mode, a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit used in the invention comprises at least one butyl acrylate monomer.
According to one embodiment, a vinyl polymer may also comprise at least one fluoro organic group. A fluorinated vinyl polymer may be one of the polymers described in the examples of patent application WO 03/045 337.
According to one preferred embodiment, a vinyl polymer grafted in the sense of the present invention may be conveyed in an oil or a mixture of oils, which is/are preferably volatile, chosen in particular from silicone oils and hydrocarbon-based oils, and mixtures thereof.
According to one particular embodiment, a silicone oil that is suitable for use in the invention may be cyclopentasiloxane.
According to another particular embodiment, a hydrocarbon-based oil that is suitable for use in the invention may be isododecane.
Vinyl polymers grafted with at least one carbosiloxane dendrimer-based unit that may be particularly suitable for use in the present invention are the polymers sold under the names TIB 4-100, TIB 4-101, TIB 4-120, TIB 4-130, TIB 4-200, FA 4002 ID (TIB 4-202), TIB 4-220 and FA 4001 CM (TIB 4-230) by the company Dow Corning. The polymers sold under the names FA 4002 ID (TIB 4-202) and FA 4001 CM (TIB 4-230) by the company Dow Corning will preferably be used.
Preferably, the vinyl polymer grafted with at least one carbosiloxane dendrimer-based unit that may be used in a composition of the invention is an acrylate/polytrimethyl siloxymethacrylate copolymer, especially the product sold in isododecane under the name Dow Corning FA 4002 ID Silicone Acrylate by the company Dow Corning.
III. Silicone Acrylate Copolymers
According to one particular embodiment, a composition used according to the invention may comprise, as hydrophobic film-forming polymer, at least one copolymer comprising carboxylate groups and polydimethylsiloxane groups.
In the present application, the term “copolymer comprising carboxylate groups and polydimethylsiloxane groups” means a copolymer obtained from (a) one or more carboxylic (acid or ester) monomers, and (b) one or more polydimethylsiloxane (PDMS) chains.
In the present application, the term “carboxylic monomer” means both carboxylic acid monomers and carboxylic acid ester monomers. Thus, the monomer (a) may be chosen, for example, from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, esters thereof and mixtures of these monomers. Esters that may be mentioned include the following monomers: acrylate, methacrylate, maleate, fumarate, itaconate and/or crotonate. According to one preferred embodiment of the invention, the monomers in ester form are more particularly chosen from linear or branched, preferably C 1 -C 24 and better still C 1 -C 22 alkyl acrylates and methacrylates, the alkyl radical preferably being chosen from methyl, ethyl, stearyl, butyl and 2-ethylhexyl radicals, and mixtures thereof.
Thus, according to one particular embodiment of the invention, the copolymer comprises as carboxylate groups at least one group chosen from acrylic acid and methacrylic acid, and methyl, ethyl, stearyl, butyl or 2-ethylhexyl acrylate or methacrylate, and mixtures thereof.
In the present application, the term “polydimethylsiloxanes” (also known as organopolysiloxanes and abbreviated as PDMS) denotes, in accordance with what is generally accepted, any organosilicon polymer or oligomer of linear structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond comprising trimethyl radicals directly linked via a carbon atom to said silicon atoms. The PDMS chains that may be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, i.e. the PDMS may contain, for example, a polymerizable radical group on the two ends of the chain or one polymerizable radical group on one end of the chain and one trimethylsilyl end group on the other end of the chain. The polymerizable radical group may especially be an acrylic or methacrylic group, in particular a group CH 2 ═R 2 , in which R 1 represents a hydrogen or a methyl group and R 2 represents —CH 2 —, —(CH 2 ) n — with n=3, 5, 8 or 10, —CH 2 —CH(CH 3 )—CH 2 —, CH 2 —CH 2 —O—CH 2 —CH 2 —, —CH 2 —CH 2 —O—CH 2 —CH 2 —CH(CH 3 )—CH 2 —, —CH 2 —CH 2 —O—CH 2 CH 2 —O—CH 2 —CH 2 —CH 2 —.
The copolymers used in the composition of the invention are generally obtained according to the usual methods of polymerization and grafting, for example by free-radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one of the ends of the chain or on both ends) and (B) of at least one carboxylic monomer, as described, for example, in documents U.S. Pat. No. 5,061,481 and U.S. Pat. No. 5,219,560.
The copolymers obtained generally have a molecular weight ranging from about 3000 g/mol to 200 000 g/mol and preferably from about 5000 g/mol to 100 000 g/mol.
The copolymer used in the composition of the invention may be in its native form or in dispersed form in a solvent such as lower alcohols containing from 2 to 8 carbon atoms, for instance isopropyl alcohol, or oils, for instance volatile silicone oils (for example cyclopentasiloxane).
As copolymers that may be used in the composition of the invention, mention may be made, for example, of copolymers of acrylic acid and of stearyl acrylate containing polydimethylsiloxane grafts, copolymers of stearyl methacrylate containing polydimethylsiloxane grafts, copolymers of acrylic acid and of stearyl methacrylate containing polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate containing polydimethylsiloxane grafts. As copolymers that may be used in the composition of the invention, mention may be made in particular of the copolymers sold by the company Shin-Etsu under the names KP-561 (CTFA name: acrylates/dimethicone), KP-541 in which the copolymer is dispersed at 60% by weight in isopropyl alcohol (CTFA name: acrylates/dimethicone and isopropyl alcohol), and KP-545 in which the copolymer is dispersed at 30% in cyclopentasiloxane (CTFA name: acrylates/dimethicone and cyclopentasiloxane). According to one preferred embodiment of the invention, KP561 is preferably used; this copolymer is not dispersed in a solvent, but is in waxy form, its melting point being about 30° C.
Mention may also be made of the grafted copolymer of polyacrylic acid and dimethylpolysiloxane dissolved in isododecane, sold by the company Shin-Etsu under the name KP-550.
Aqueous Phase
The aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.
In the present invention, the term “water-soluble solvent” denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at 25° C. and atmospheric pressure).
The water-soluble solvents that may be used in the composition of the invention may also be volatile.
Among the water-soluble solvents that may be used in the composition in accordance with the invention, mention may be made especially of lower monoalcohols containing from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols containing from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C 3 and C 4 ketones and C 2 -C 4 aldehydes.
The aqueous phase may be present in the composition in a content ranging from 10% to 80% by weight, better still from 15% to 70% by weight and in particular from 20% to 50% by weight relative to the total weight of said composition.
In particular, a composition according to the invention advantageously comprises a water content at least equal to 15% by weight, preferably at least equal to 20% by weight and preferentially ranging from 20% to 70% by weight relative to the total weight of the composition.
According to another embodiment variant, the aqueous phase of a composition according to the invention may comprise at least one C 2 -C 32 polyol.
For the purposes of the present invention, the term “polyol” should be understood as meaning any organic molecule comprising at least two free hydroxyl groups.
Preferably, a polyol in accordance with the present invention is present in liquid form at room temperature.
Such polyols may be used in a proportion of from 0.2% to 10% by weight, preferably from 0.5% to 8% by weight and even more preferentially from 0.5% to 6% by weight of C 2 -C 32 polyol, relative to the total weight of the composition.
The polyols advantageously suitable for the formulation of a composition according to the present invention are those exhibiting especially from 2 to 32 carbon atoms, preferably from 3 to 16 carbon atoms and in particular from 3 to 7 carbon atoms.
Advantageously, the polyol may be chosen, for example, from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, polyglycerols such as glycerol oligomers, for instance diglycerol, and polyethylene glycols, and mixtures thereof, in particular pentylene glycol.
According to a preferred embodiment of the invention, said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, pentylene glycol, glycerol, polyglycerols, polyethylene glycols and mixtures thereof.
According to a particular mode, the composition of the invention may comprise at least pentylene glycol.
Oily Phase
The oily phase of a composition according to the invention comprises at least one volatile oil and may comprise one or more non-volatile oil(s).
The term “oil” means any fatty substance that is in liquid form at room temperature and atmospheric pressure.
For the purposes of the present invention, the term “non-volatile oil” means an oil with a vapour pressure of less than 0.13 Pa.
For the purposes of the invention, the term “volatile oil” means any oil that is capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, which is liquid at room temperature, especially having a nonzero vapour pressure, at room temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10 −3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
An oily phase that is suitable for preparing the cosmetic compositions according to the invention may comprise hydrocarbon-based oils, silicone oils, fluoro oils or non-fluoro oils, or mixtures thereof.
An oily phase that is suitable for preparing a composition according to the invention may comprise at least one volatile hydrocarbon-based oil.
For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si—O group.
The term “fluoro oil” means an oil comprising at least one fluorine atom.
The term “hydrocarbon-based oil” means an oil mainly containing hydrogen and carbon atoms.
The oils may optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.
The oils of the invention may be of animal, plant, mineral or synthetic origin. According to one embodiment variant, oils of plant origin are preferred.
Volatile Oils
The volatile oils may be hydrocarbon-based oils or silicone oils.
Among the volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, mention may be made especially of branched C 8 -C 16 alkanes, such as C 8 -C 16 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar or Permethyl, branched C 8 -C 16 esters, such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon-based oil is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isododecane.
Mention may also be made of volatile linear alkanes comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms and more particularly from 11 to 13 carbon atoms, for instance n-dodecane (C 12 ) and n-tetradecane (C 14 ) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C 11 ) and of n-tridecane (C 13 ) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis, and mixtures thereof.
Volatile silicone oils that may be mentioned include linear volatile silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane.
Volatile cyclic silicone oils that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
Preferably, a composition according to the invention comprises at least one hydrocarbon-based oil as volatile oil, in particular isododecane.
More particularly, the volatile oil according to the invention is isododecane.
A composition according to the invention may comprise from 10% to 70% by weight, better still from 15% to 55% by weight and preferably from 20% to 50% by weight of volatile oil(s) relative to the total weight of said composition.
Non-Volatile Oils
The non-volatile oils may be chosen especially from non-volatile hydrocarbon-based, fluoro and/or silicone oils.
Non-volatile hydrocarbon-based oils that may especially be mentioned include:
hydrocarbon-based oils of plant origin, synthetic ethers containing from 10 to 40 carbon atoms, such as dicapryl ether, synthetic esters, such as the oils of formula R 1 COOR 2 , in which R 1 represents a linear or branched fatty acid residue comprising from 1 to 40 carbon atoms and R 2 represents a hydrocarbon-based chain, which is especially branched, containing from 1 to 40 carbon atoms, on condition that R 1 +R 2 ≧10. The esters may be chosen especially from fatty acid alcohol esters, for instance cetostearyl octanoate, isopropyl alcohol esters such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate, hydroxylated esters, such as isostearyl lactate or octyl hydroxystearate, alkyl or polyalkyl ricinoleates, hexyl laurate, neopentanoic acid esters, such as isodecyl neopentanoate or isotridecyl neopentanoate, and isononanoic acid esters, such as isononyl isononanoate or isotridecyl isononanoate, polyol esters and pentaerythritol esters, such as dipentaerythrityl tetrahydroxy stearate/tetraisostearate, fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol and oleyl alcohol, C 12 -C 22 higher fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof, non-phenyl silicone oils, for instance caprylyl methicone, and phenyl silicone oils, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, dimethicones or phenyl trimethicone with a viscosity of less than or equal to 100 cSt, and trimethyl-pentaphenyl-trisiloxane, and mixtures thereof; and also mixtures of these various oils.

Preferably, the composition according to the invention comprises less than 10% by weight of non-volatile oil(s), in particular less than 5% by weight and more particularly comprises no non-volatile oil(s).
As mentioned above, the gelled oily phase according to the invention may have a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
This threshold stress value reflects a gel-type texture of this oily phase.
Dyestuffs
The compositions in accordance with the invention may comprise at least one dyestuff.
This (or these) dyestuff(s) are preferably chosen from pulverulent dyes, liposoluble dyes and water-soluble dyes, and mixtures thereof.
Preferably, the compositions according to the invention comprise at least one pulverulent dyestuff. The pulverulent dyestuffs may be chosen from pigments and nacres, and preferably from pigments.
The pigments may be white or coloured, mineral and/or organic, and coated or uncoated. Among the mineral pigments, mention may be made of metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxide, and also iron, titanium or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments that may be mentioned are carbon black, pigments of D & C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.
The nacres may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica with iron oxides, titanium mica especially with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
The liposoluble dyes are, for example, Sudan Red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan Brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow and annatto.
Preferably, the pigments contained in the compositions according to the invention are chosen from metal oxides.
These dyestuffs may be present in a content ranging from 0.01% to 30% by weight relative to the total weight of the composition, and in particular from 1% to 22% by weight relative to the total weight of the composition.
Preferably, the dyestuff(s) are chosen from one or more metal oxides that are present in a content of greater than or equal to 1% by weight relative to the total weight of the composition, and advantageously inclusively between 3% and 22% by weight relative to the total weight of the composition.
Fibres
A composition according to the invention may also comprise at least one fibre.
The term “fibre” should be understood as meaning an object of length L and of diameter D such that L is greater than D, and preferably very much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or aspect ratio) is chosen in the range from 3.5 to 2500, in particular from 5 to 500 and more particularly from 5 to 150.
The fibres that may be used in the composition of the invention may be mineral or organic fibres, of synthetic or natural origin. They may be short or long, individual or organized, for example braided, and hollow or solid. They may have any shape and may especially have a circular or polygonal (square, hexagonal or octagonal) cross section depending on the specific application envisaged. In particular, their ends are blunted and/or polished to prevent injury.
In particular, the fibres have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm. Their cross section may be included in a circle with a diameter ranging from 2 nm to 500 μm, preferably ranging from 100 nm to 100 μm and better still from 1 μm to 50 μm. The weight or yarn count of fibres is often given in denier or decitex and represents the weight in grams per 9 km of yarn. Preferably, the fibres according to the invention have a yarn count chosen within the range from 0.01 to 10 denier, preferably from 0.1 to 2 denier and better still from 0.3 to 0.7 denier.
The fibres that may be used in the compositions of the invention may be chosen from rigid or non-rigid fibres, and may be mineral or organic fibres, of synthetic or natural origin.
Moreover, the fibres may or may not be surface-treated, may be coated or uncoated, and may be coloured or uncoloured.
As fibres that may be used in the compositions according to the invention, mention may be made of non-rigid fibres such as polyamide (Nylon®) fibres or rigid fibres such as polyimideamide fibres, for instance those sold under the names Kermel® and Kermel Tech® by the company Rhodia or poly(p-phenyleneterephthalamide) (or aramid) fibres sold especially under the name Kevlar® by the company DuPont de Nemours.
The fibres may be present in a content ranging from 0.01% to 10% by weight, relative to the total weight of the composition, in particular from 0.1% to 5% by weight and more particularly from 0.3% to 3% by weight.
Fillers
The compositions in accordance with the invention may also comprise at least one filler.
The fillers may be chosen from those that are well known to persons skilled in the art and that are commonly used in cosmetic compositions. The fillers may be mineral or organic, and lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders, for instance the Nylon® sold under the name Orgasol® by the company Atochem, poly-β-alanine powders and polyethylene powders, powders of tetra-fluoroethylene polymers, for instance Teflon®, lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance the products sold under the name Expancel® by the company Nobel Industrie, acrylic powders such as those sold under the name Polytrap® by the company Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (for example Tospearls® from Toshiba), precipitated calcium carbonate, magnesium carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms and in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate and magnesium myristate.
The fillers may represent from 0.1% to 15% by weight and in particular from 0.5% to 10% by weight relative to the total weight of the composition.
According to one embodiment of the invention, a composition may comprise at least solid particles such as pigments and/or fillers.
It is a matter of routine operations for a person skilled in the art to adjust the nature and the amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.
According to a preferred embodiment, a composition of the invention is in the form of a product for the eyelashes, in particular a mascara.
According to another embodiment, a composition of the invention may advantageously be in the form of a product for the eyebrows, in particular an eyebrow pencil.
Preferably, a composition according to the invention is in the form of a composition for caring for and/or making up keratin fibres in particular the eyelashes, preferably in the form of a mascara.
Such compositions are especially prepared according to the general knowledge of a person skilled in the art.
Throughout the description, including the claims, the term “comprising a” should be understood as being synonymous with “comprising at least one”, unless otherwise specified.
The terms “between . . . and . . . ” and “ranging from . . . to . . . ” should be understood as being inclusive of the limits, unless otherwise specified.
The invention is illustrated in greater detail by the example presented below. Unless otherwise mentioned, the amounts indicated are expressed as mass percentages.
Methodology for the Oscillating Dynamic Rheology Measurements
These are harmonic-regime rheology measurements for measuring the elastic modulus.
The measurements are taken using a Haake RS600 rheometer on a product at rest, at 25° C. with a plate-plate rotor Ø 60 mm and a 2 mm gap.
The harmonic-regime measurements make it possible to characterize the viscoelastic properties of the products. The technique consists in subjecting a material to a stress which varies sinusoidally over time and in measuring the response of the material to this stress. In a range in which the behaviour is linear viscoelastic behaviour (zone in which the strain is proportional to the stress), the stress (τ) and the strain (γ) are two sinusoidal functions of time which are written in the following manner:
τ( t )=τ 0 sin(ω t )

γ( t )=γ 0 sin(ω t +δ)

in which:
τ 0 represents the maximum amplitude of the stress (Pa);
γ 0 represents the maximum amplitude of the strain (−);
ω=2ΠN represents the angular frequency (rad·s −1 ) with N representing the frequency (Hz); and
δ represents the phase shift of the stress relative to the strain (rad).
Thus, the two functions have the same angular frequency, but they are shifted by an angle δ. Depending on the phase shift δ between τ(t) and γ(t), the behaviour of the system may be apprehended:
if δ=0, the material is purely elastic; if δ=Π/2, the material is purely viscous (Newtonian fluid); and if 0<δ<Π/2, the material is viscoelastic.

In general, the stress and the strain are written in complex form:
τ*( t )=τ 0 e iωt

γ*( t )=γ 0 e (iωt+δ)

A complex stiffness modulus, representing the overall resistance of the material to the strain, whether it is of elastic or viscous origin, is then defined by:



G*=τ*/γ*=G′+iG″


in which:
G′ is the storage modulus or elastic modulus, which characterizes the energy stored and totally restituted during a cycle, G′=(τ 0 /γ 0 ) cos δ; and
G″ is the loss modulus or viscous modulus, which characterizes the energy dissipated by internal friction during a cycle, G″=(τ 0 /γ 0 ) sin δ.
The parameter retained is the mean stiffness modulus G* recorded at the plateau measured at a frequency of 1 Hz.


EXAMPLES
Mascara formulations in accordance or not in accordance with the invention are prepared as described below.
1) Preparation of the Aqueous Phases
The aqueous phases are prepared from the compounds that follow in the weight proportions specified in the tables below.
The percentages are on a weight basis relative to the total weight of the phase under consideration.
The hydrophilic gelling agent is added to part of the water with hot stirring at 70° C. The stirring is adjusted so as not to incorporate air into the mixture. The rest of the water, the phenoxyethanol, the pentylene glycol and the denatured alcohol are then added thereto.
The mixture is stirred moderately with a Rayneri blender for about 10 minutes at room temperature.
Phase A1:









Weight %

Compounds
Phase A1



Microbiologically clean deionized water
qs 100

Steareth-100/PEG 136/HDI (hexamethyl diisocyanate)
10.0%

copolymer (Rheolate ® FX 1100 sold by the company

Elementis)

Phenoxyethanol
0.5%

Pentylene glycol
3.0%

Denatured alcohol
3.0%























Phase A2:









Weight %

Compounds
Phase A2



Microbiologically clean deionized water
qs 100

Hydroxyethyl acrylate/sodium acryloyldimethyltaurate
2.0%

copolymer (Sepinov ® EMT

10 sold by the company SEPPIC)

Phenoxyethanol
0.5%

Pentylene glycol
3.0%

Denatured alcohol
3.0%























Phase A3:












Weight %


Compounds
Phase A3





Microbiologically clean deionized water
qs 100


Ammonium polyacryldimethyltauramide
1.0%


(Hostacerin AMPS ® sold by the company Clariant)


Phenoxyethanol
0.5%


Pentylene glycol
3.0%


Denatured alcohol
3.0%























Phase A4:












Weight %


Compounds
Phase A4





Microbiologically clean deionized water
qs 100


Xanthan gum (Rhodiacare XC ® sold
8.0%


by the company Solvay)


Phenoxyethanol
0.5%


Pentylene glycol
3.0%


Denatured alcohol
3.0%























Phase A5:









Weight %

Compounds
Phase A5



Microbiologically clean deionized water
qs 100

Pregelatinized hydroxypropyl corn distarch phosphate
14.0%

(Structure ® ZEA sold by the company Akzo Nobel)

Phenoxyethanol
0.5%

Pentylene glycol
3.0%

Denatured alcohol
3.0%






















Phase A6:









Weight %

Compounds
Phase A6



Microbiologically clean deionized water
qs 100

Hydroxyethylcellulose (Cellosize ® QP 4400 H sold by the
4.0%

company Dow Chemical)

Phenoxyethanol
0.5%

Pentylene glycol
3.0%

Denatured alcohol
3.0%






















2) Preparation of the Oily Phase
The oily phase B1 is prepared from the compounds that follow in the weight proportions specified in the table below.
The percentages are on a weight basis relative to the total weight of phase B1.
The meltable compound is melted at 90-95° C. Once molten, the isododecane, the gelling agent, the pigments and the propylene carbonate are added. The mixture is stirred for 20 minutes. At room temperature, the mixture is treated three times with a three-roll mill.
Phase B1:









Weight %

Compounds
Phase B1








White beeswax (White beeswax SP 453P sold by the company
20.0%

Strahl & Pitsch)

Black iron oxides
4.0%

Isododecane
68.3%

Hectorite modified with distearyldimethylammonium
5.8%

(Bentone 38VCG ® sold by the company Elementis)

Propylene carbonate
1.9%



























3) Preparation of the Mascara Formulations
These formulations are obtained by mixing several phases intended to form mascaras in accordance with the invention (formulations 1 to 9) or not in accordance with the invention (formulations 10 to 17), in the weight proportions described in the table below.
The percentages are on a weight basis relative to the total weight of the composition.
The aqueous and oily gels are weighed out and then mixed with a Rayneri blender.
The fatty phase/aqueous phase ratio is established as a function of the desired performance.















Weight %
Weight %
Weight %
Weight %
Weight %
Weight %
Weight %

Formulations
phase A1
phase A2
phase A3
phase A4
phase A5
phase A6
phase B1














Formulation 1
30.0





70.0

(according to

the invention)

Formulation 2
50.0





50.0

(according to

the invention)

Formulation 3
70





30

(according to

the invention)

Formulation 4

50.0




50.0

(according to

the invention)

Formulation 5

30.0




70.0

(according to

the invention)

Formulation 6

70.0




30.0

(according to

the invention)

Formulation 7


50.0



50.0

(according to

the invention)

Formulation 8


30.0



70.0

(according to

the invention)

Formulation 9


70.0



30.0

(according to

the invention)

Formulation



50.0


50.0

10 (outside the

invention)

Formulation



30.0


70.0

11 (outside

the invention)

Formulation



70.0


30.0

12 (outside

the invention)

Formulation




50.0

50.0

13 (outside the

invention)

Formulation




30.0

70.0

14 (outside the

invention)

Formulation




70.0

30.0

15 (outside the

invention)

Formulation





50.0
50.0

16 (outside the

invention)

Formulation





30.0
70.0

17 (outside the

invention)







































































Protocol for Evaluating the Technical Effect of the Compositions
The ease of removal and the water resistance of these various formulations were evaluated.
The water resistance and makeup-removal tests are performed on samples of false eyelashes (straight black Caucasian hair with a fringe length of 19 mm, mounted between two 30 mm by 30 mm plates).
The hairs are made up by performing three times 10 passages of the test composition at two-minute intervals using a mascara brush. The samples are left to dry for one hour at room temperature (25° C.).
The evaluation of the water resistance was assessed in the following manner: the samples were immersed in water for one-hour and rubbed 10 times on a blotting paper with a pendulum. The water resistance was then evaluated as a function of the intensity of the mascara marks left on the blotting paper, according to the following notation scale:
0: no marks
1: imperceptible marks
2: few light-grey marks
3: a few light-grey marks
4: light-grey marks
5: dark grey marks
6: very dark grey marks
7: a few dark black marks
8: dark black marks
9: very dark black marks
The evaluation of the makeup-removing efficacy consists in counting the number of cotton wool pads required to totally remove the makeup from the fringe of made-up hair. 2 mL of makeup remover are applied to a pad of cotton wool, with which the fringe of hair is pinched for 10 seconds, and then drawn.
The makeup remover used is a two-phase lotion known as Bifacil from Lancôme.
The water resistance and makeup-removing efficacy results are collated in the table below. This table also indicates the quality of the mascara deposit on the hair.












Number




of cotton


Intensity of the
wool pads



marks on the
required


blotting paper
for total


after immersion
makeup
Quality of the

Formulations
for 1 hour
removal
deposit










Formulation 1 (according to
0
5
satisfactory

the invention)

Formulation 2 (according to
2
3
satisfactory

the invention)

Formulation 3 (according to
2
2
satisfactory

the invention)

Formulation 4 (according to
0
3
satisfactory

the invention)

Formulation 5 (according to
0
3
satisfactory

the invention)

Formulation 6 (according to
2
3
satisfactory

the invention)

Formulation 7 (according to
0
3
satisfactory

the invention)

Formulation 8 (according to
0
3
satisfactory

the invention)

Formulation 9 (according to
1
3
satisfactory

the invention)

Formulation 10 (outside the
7
4
unsatisfactory

invention)

Formulation 11 (outside the
4
8
unsatisfactory

invention)

Formulation 12 (outside the
9
3
unsatisfactory

invention)

Formulation 13 (outside the
0
5
unsatisfactory

invention)

Formulation 14 (outside the
0
5
unsatisfactory

invention)

Formulation 15 (outside the
3
5
unsatisfactory

invention)

Formulation 16 (outside the
4
5
unsatisfactory

invention)

Formulation 17 (outside the
0
4
unsatisfactory

invention)



























































The formulations were evaluated according to three criteria: the composition must form a film on the eyelashes that is suitable for a mascara application, must have a result of less than or equal to 2 in the water resistance test and must require not more than 5 cotton wool pads for total makeup removal.
The tests performed show that the formulations according to the invention (formulations 1 to 9) form an acceptable mascara deposit with better water resistance and are easier to remove than the formulations outside the invention (formulations 10 to 17).
Specifically, none of the formulations 10 to 17 satisfies these three criteria.