EP3352619B1

EP3352619B1 - Assembly for packaging and applying a liquid cosmetic product

Info

Publication number: EP3352619B1
Application number: EP16767296.3A
Authority: EP
Inventors: Eric Caulier; Alain Berhault; Marcel Sanchez
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2015-09-25
Filing date: 2016-09-20
Publication date: 2020-12-23
Anticipated expiration: 2036-09-20
Also published as: JP2018531675A; KR20180053729A; ES2858751T3; WO2017050782A1; EP3352619A1; FR3041510A1; FR3041510B1; CN108024611A; US20190000213A1

Description

The present invention relates to an assembly for packaging and applying a liquid cosmetic product.
The expression "cosmetic product" is understood to mean any product as defined in Regulation (EC) No 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products.
The packaging and application assembly is intended more particularly for the application of a cosmetic product to a human keratin surface, such as the skin, the lips or the nails.
The development of formulations devoted to making up and/or caring for the skin and/or lips, having satisfactory properties in terms of application, of comfort, of wear property and of coverage, but also in terms of make-up effect, such as for example the sheen, is an ongoing objective.
Numerous packaging and application assemblies have been developed to enable a satisfactory and comfortable application of such fluid products.
Generally, an assembly for packaging and applying a cosmetic product comprises, on the one hand, a body forming a reservoir which is intended to contain the cosmetic product to be applied and, on the other hand, an applicator comprising an application member that defines an application surface intended to come into contact with a body surface of the user.
As an example of an applicator, mention may be made of document FR 2 872 999 which describes a packaging and application assembly comprising an applicator, in particular for the lips, referred to as a dip applicator.
An applicator is referred to as a dip applicator when the loading with cosmetic product takes place by dipping or immersing its application member in said cosmetic product.
The fact of dipping the applicator into the cosmetic product allows high loading of the applicator. It is then in general necessary to equip the reservoir with a wiping device that makes it possible to eliminate the excess product. It is however common to seek to increase the loading of the applicator, by providing for example a central orifice.
Other packaging and application assemblies are also known that aim to better control the loading of product on the applicator.
By way of example, mention may in particular be made of documents FR 2 832 297 , FR 2 814 651 and FR 2 962 890 .
Document FR 2 832 297 describes an assembly for packaging and applying a cosmetic product comprising a reservoir, mounted on which is a porous applicator member that is passed through by the cosmetic product. The assembly comprises a cap which, in the closed position, compresses the application member so as to create, on opening, an effect of pumping the cosmetic product that facilitates its diffusion through the application member.
Documents FR 2 814 651 and FR 2 962 890 show yet another way of loading a product on the application member. More specifically, documents FR 2 814 651 and FR 2 962 990 provide a body which forms a reservoir, said body having a housing capable of receiving the application member and of which a dividing wall with the reservoir has at least one through-orifice in direct fluid communication with said reservoir. By shaking or inverting the assembly, the cosmetic product passes through the openings and impregnates the application member directly on its application surface.
Document FR 2 814 651 targets an optimal and relatively large loading of the application member. In order to do this, document FR 2 814 651 provides a porous application member with open porosity, the orifices for dispensing the cosmetic product being arranged opposite a non-compressed application portion when said application member is in place in the housing. The dispensing orifices are distributed substantially over the entire application surface.
Document FR 2 962 890 itself aims not to overload the application member. In order to do this, document FR 2 962 890 provides the combination of precisely located orifices with an application surface formed by a membrane that is not permeable to the product.
Document FR 3 003 448 discloses an assembly according to the preamble of claim 1.
Despite the many types of packaging and application assemblies that have been developed, there is still a need for assemblies that make it possible to improve the application properties of certain cosmetic products.
The applicant has noticed in particular that certain cosmetic product formulas still require the development of specific applicators for optimizing their application to the user and their makeup result thereon.
The packaging and application assembly targeted by the present application is very particularly intended for the application of a cosmetic product of lip oil type.
Such a composition, intended more particularly for making up and/or caring for the lips is in a liquid form and comprises for example at least 70% by weight of non-volatile oils, in particular silicone oils, and coloured or colourless solid particles, for example pigments and/or nacres.
Formulas intended for making up and/or caring for the lips have been known for a very long time and are in varied forms, ranging from fluid formulas such as glosses, to optionally supported solid compositions in the form of a stick, or even compositions in the form of a pencil.
In order to further diversify the compositions provided to consumers, anhydrous or virtually anhydrous formulas, which are even more fluid than the glosses, and which comprise high contents of oils, that are very comfortable to wear, have emerged. However, these formulas are available only in versions that are not very coloured. This comes essentially from the fact that it is very difficult to maintain high contents of particles in suspension in this type of oily medium, without losing the attraction of such compositions, which is precisely their great fluidity.
Indeed, with large amounts of pigments, nacres or fillers, sedimentation of these particles is observed, resulting in the formation of a relatively unattractive cake which can comprise clumps of particles. The cake thus formed has the additional drawback of being very cohesive. Thus, it cannot be easily redispersed so as to again have a homogeneous composition. Consequently, once the particles have sedimented, the composition becomes virtually unusable and no longer makes it possible to obtain a homogeneous deposit on the lips, which is not acceptable.
Thus, in order to minimize the sedimentation problem, these compositions comprise relatively low contents of solid particles. But in this case, the number of shades that can be attained, and also the intensity thereof, is limited. The compositions can also comprise dyes, therefore species that are soluble in the medium in which they are used. However, the number of dyes that can be used in this field is relatively restricted, which does not allow a great deal of extension of the range of colours proposed or of their intensity, whether or not the dyes are combined with coloured solid particles.
Besides the formulation difficulties mentioned above, this type of cosmetic product that has a tendency to sediment also gives rise to application difficulties that the current packaging and application assemblies do not resolve in an optimal manner.
More specifically, taking into account the presence of solid particles, the packaging assembly must in particular allow the solid particles to be resuspended as a homogeneous suspension and ensure a good loading of the applicator for an easy and precise application with an optimal makeup effect.
Taking into account these constraints, the assemblies of internal feed type in which the product must diffuse through the application member are not suitable, since the diffusion does not take place homogeneously.
Dip applicators are not optimal either since resuspending the particles homogeneously in the cosmetic product is difficult. Furthermore, considering the high colouring power of the pigmented compositions and the high oil contents in the compositions of lip oil type, it is advisable to be able to control the loading of the applicator. In case of excessive loading, it is advantageous for the user to be able to tone down the skin or lip surface in question with a surface of the applicator that is not loaded or that is loaded relatively little.
A device as described in document FR 2 814 651 has not proved satisfactory either, although it allows a relatively easy resuspension by simple manual shaking of the bottle.
Although document FR 2 962 890 mentions compositions that may contain pigments, it has turned out that such an assembly does not give satisfactory results. One problem is in particular that such an applicator unloads the formula very rapidly.
The present invention aims to attain all or some of these objectives and for this purpose proposes an assembly for packaging and applying a liquid cosmetic product according to claim 1.
The presence of an application member defining a convex application surface having an apex or a tip, enables in particular a precise application of the product.
The orifices made in the wall of the housing for receiving the application member enable in particular the loading of the application member with cosmetic product, in particular during a shaking or an inverting of the reservoir.
The expression "orifice located only at at least one end wall of the housing" is understood to mean that the remainder of the dividing wall is solid, i.e. not perforated.
Thus, by combining a plurality of through-orifices in direct fluid communication that are positioned in a very localized manner with a porous application surface, the applicant surprisingly observed that the targeted packaging and application assembly enabled a precise, comfortable and homogeneous application of the cosmetic product contained in the reservoir, in particular for cosmetic products containing solid particles such as nacres and/or pigments.
As is known, the use of very localized orifices makes it possible to limit the passage of the product through the dividing wall and thus to obtain a precise dose of product without overloading the applicator.
Within the context of a use with a liquid cosmetic product that contains solid particles, and that has in particular a tendency to sediment or to phase separate, the applicant became aware that, contrary to what it believed, the presence of localized orifices opposite the application tip of the application member made it possible to collect an amount of formula that is much more homogeneous than if they were distributed opposite the entire application surface. Thus, even though they are localized as sieving medium and at the tip of the applicator, a loading of the porous applicator with homogeneous product is still obtained.
Without wishing to be tied to any one theory, the applicant believes that the use of an application surface made from an open-cell porous material greatly facilitates the retention of solid particles such as pigments and nacres whilst the excess solvent, and in particular oil, may diffuse more easily through the material. The difference in migration between the solvent phase and the solid particles thus appears to provide particularly advantageous makeup properties.
This results in a concentration of the pigment and nacre type particles around the application tip. This allows a precise application, which does not run, and that has great coverage.
The rest of the application surface, in particular a peripheral or lateral zone, may be used to tone down the product applied and refine the makeup.
The solvent phase, in particular the oil, having diffuse through the porous applicator, contributes to a great softness of application over the entire application surface.
Direct fluid communication is understood to mean that the orifice is not combined with any selective-opening dispensing means of pump or aerosol type that makes it possible to force the passage of the cosmetic product through said orifice. The loading of the application member takes place by simple shaking or inverting of the reservoir.
This does not prevent the use of a selective-closure mechanism that makes it possible in particular to ensure the leaktightness of the reservoir when it is not used, the passage of the product through the orifice remaining unforced.
By "vicinity of an apex of the application member" the present application targets an apex portion extending close to the point-shaped geometric apex. It is considered that the orifices are located in a zone around the geometric apex representing 10% of the total surface of the application surface.
Preferentially, the orifices are located at an end wall of the housing corresponding to an absolute apex of the application member, preferably only at said end wall.
According to the invention, the wall of the housing has a plurality of orifices.
The presence of a plurality of orifices makes it possible to retain orifices of relatively small size making it possible to ensure the passage of an amount of product that is as homogeneous as possible, while ensuring a total passage area that is sufficient for good loading of the application member, after for example only a few shaking movements. In addition, the size of the orifices is also determined as a function of the size of the solid particles so as to prevent or limit clogging phenomena.
In the case of several orifices, the latter are preferentially uniformly distributed around the centre of the end wall. This makes it possible to ensure an optimal loading of the application tip.
In an advantageously complementary manner, the wall of the housing has a central orifice, located at the centre of the end wall. The centre of the end wall is understood to mean the point opposite the geometric apex of the applicator.
According to one preferred embodiment, all or some of the orifices have a substantially circular cross section. Such a cross section of circular shape is very suitable for avoiding clogging phenomena. Where appropriate, depending on the particles used, other cross sections may be envisaged.
In an advantageously complementary manner, the reservoir comprises at least one mixing element, in particular at least one mixing bead. The characteristics of the mixing element, such as the weight or the size will be chosen as a function of the sedimentation properties of the cosmetic product.
Preferentially, the application member has an application surface that is at least partially flocked, preferably completely flocked. Besides the great softness of application, the flock fibres also help with the retaining of the particles and improve the diffusion thereof.
Advantageously, the applicator is configured to be fastened to the container when not in use, the application member being received in the housing. Thus the applicator makes it possible to close the reservoir.
Preferentially, the application surface has no surface, in particular no concavity, capable of forming a space with the wall of the housing when the application member is received in the housing. In particular, the application surface has no concavity opposite the orifices. Indeed, the presence of a concavity would be capable of leading to the formation of a cavity between the applicator and the dividing wall of the housing, inside which cavity product could settle, which is undesirable.
Preferably, the application member has a conical general shape, in particular with a rounded or hemispherical tip. Such a shape is particularly suitable for an application to the lips.
More preferably, the orifices are closed off by the application surface when the applicator is fastened to the container. This makes it possible to avoid any leak of product through the orifices when the applicator is in the closed position.
In an advantageously complementary manner, the application surface deforms at least partially against the wall of the housing when the applicator is fastened to the container, the application member being slightly compressed. Thus, it is possible, as a function of the characteristics of the cosmetic product, to place the application member slightly under compression in order to add a pump effect that makes it possible to facilitate the diffusion of the product and in particular the adsorption of the solvent phase or oil. This compression also improves the closing off of the orifices by the application member.
In particular, the cosmetic product comprises at least 70% by weight, relative to the weight of the composition, of at least one non-volatile oil or of a single-phase mixture of several non-volatile oils, the composition comprising at least one polar or non-polar non-volatile hydrocarbon-based oil, at least one mineral thickener and at least one nonionic silicone surfactant and at least coloured or colourless solid particles.
The present invention will be understood better from reading the following detailed description with regard to the appended drawing, in which:

Figure 1 is a schematic representation, in longitudinal cross section, of a packaging and application assembly according to the invention,
Figure 2 is a schematic representation, in longitudinal cross section, of an application member equipping the assembly from Figure 1,
Figure 3 is a schematic representation, in longitudinal cross section, of a ring forming a housing for the application member from Figure 2,
Figure 4 is a top-view schematic representation of the ring from Figure 3. Figure 1 shows an assembly 1 for packaging and applying a liquid cosmetic product P.

The assembly 1 comprises a body 2 forming a reservoir 3 containing a cosmetic product P to be applied and an applicator 4 comprising an application member 5 that defines a convex application surface 50 having at least one apex 51.
The body 2 has a free upper edge 21 delimiting an opening 22 of said reservoir 3. More specifically, the opening 22 is situated at a free upper end of a neck 24 of the body 2.
The body 2 has rotational symmetry. The opening 22 has a circular cross section. Obviously other shapes can be envisaged.
The body 2 has, at the opening 22, a housing 7 capable of receiving the application member 5, said housing 7 being at least partially delimited by a dividing wall 8 with the reservoir 3.
In accordance with the present application, the dividing wall 8 has a plurality of through-orifices 9 in direct fluid communication with the reservoir 3.
The dividing wall 8 may be added on to the reservoir 3, as illustrated, or be made from a single part by moulding with the body of the reservoir.
In this case, the dividing wall 8 is borne by a ring 60 surmounting the opening 22.
The ring 60 may be mounted on the body 2 by any means, in particular by clip-fastening or adhesive bonding. It may or may not be removable.
In this case, the ring 60 is capable of engaging with the neck 24.
In order to do this, the ring 60 comprises an outer peripheral wall 61 and an inner peripheral wall 62 together defining a mounting skirt.
The mounting skirt also provides leaktightness to the product.
Alternatively, a ring as represented in Figure 10J of document FR 2 962 890 can also be envisaged.
The applicator 4 comprises uppermost a gripping portion 41 onto which the application member 5 is mounted.
The gripping portion 41 forms a cap and is capable of engaging in a removable manner with an upper peripheral wall 63 of the ring 60 thus closing the reservoir 3 in a leaktight manner. More particularly, the peripheral wall 63 of the ring 60 bears an outer thread 64 capable of cooperating with a complementary inner threading 65 of the gripping portion.
When not in use, and when the gripping portion 41 is screwed onto the ring 60, the application member 5 is received in the housing 7 (Figure 1).
In accordance with the present application, the application member 5 is made from an open-cell porous material, for example from a foam.
In particular, the application member 5 is made from a polyurethane foam, in particular of S90 type (DIN 4102-9 standard).
The application member 5 is mounted on the gripping portion 41 by any known means, in particular by fitting, clip-fastening or snap-fastening.
In this case, the application member 5 has a substantially cylindrical foot 55 which is introduced inside a corresponding shaft 42 of the gripping portion. An end wall 43 of the shaft 42 increases the attachment area. The end wall 43 also ensures that translational movement is blocked.
On the opposite side from the foot 55, the application member 5 has a head 56 that defines the application surface 51. The head 56 has a conical general shape. The head 56 has a free end or rounded tip forming the apex 51. In this case, the apex 51 is consequently an absolute apex.
The head 56 has a base that has a diameter slightly larger than the diameter of the foot 55 and thus has a shoulder 57 capable of bearing against an edge of the shaft 42. This shoulder 57 makes it possible in particular to give the application member a better hold.
The housing 7 is shaped so as to have a shape that is substantially complementary to the head 56.
As can be seen in Figure 1, when the applicator 4 is fastened to the reservoir 3 and the application member 5 is in place in the housing, the apex 51 is slightly compressed.
It will also be noted that the application surface 51 is flocked. For the application of the flock, use will be made of a glue that is relatively rigid after drying. Thus, by drying, the glue helps to rigidify the application member 5.
As indicated above, the housing 7 is in communication with the inside of the reservoir 3 by means of the perforated dividing wall 8, which is perforated by the permanently open through-orifices 9.
In accordance with the present application, the through-orifices 9 are located only at at least one end wall of the housing opposite the vicinity of the apex 51 of the application member 5 when said application member 5 is in place in the housing 7 of the body 2 which forms a reservoir 3.
In this case, the wall 8 comprises three through-orifices 9. The through-orifices 9 are regularly distributed close to and around the centre of the end of the wall 8. The through-orifices have a substantially circular cross section. In this case, the diameter of the orifices is 1.5 mm.
The total area of the through-orifices is thus around 5.3 mm². Preferably, the total area of the openings is less than 5.5 mm². The total area of each opening is also sufficient to limit or even prevent clogging phenomena.
The centre of each through-orifice 9 is located at a distance of 4.5 mm from the centre of the end wall corresponding to the apex 51 of the application member. Preferably, the through-orifices are located at less than 5 mm from the centre of the end wall.
The application member 5 advantageously closes off all the through-orifices of the wall 8 when the applicator 4 is in place on the reservoir 3. This may be useful for preventing excess product from spilling into the housing when the applicator closes the latter.
Advantageously, the reservoir 3 comprises at least one mixing element, in particular at least one mixing bead (not represented). During the shaking or inverting, the bead makes it possible to facilitate the homogenization of the product or even the resuspension of the particles where appropriate.
According to the invention the reservoir comprises a liquid cosmetic product containing solid particles, in particular pigments and/or nacres.

PREFERENTIALLY COMBINED COSMETIC COMPOSITION

As indicated above, the cosmetic product (composition) is in the form of a liquid at ambient temperature (25°C) and atmospheric pressure (1.013×10⁵ Pa). More particularly, the viscosity of the composition varies between 0.2 and 0.8 Pa.s, preferably between 0.3 and 0.7 Pa.s. The viscosity measurement is generally carried out at 25°C using a Rheomat RM180 viscometer equipped with a No. 2 spindle, the measurement being carried out after rotating the spindle within the composition for 10 minutes (after which time stabilization of the viscosity and of the rotational speed of the spindle is observed), at 200 revolutions/min (rpm).

NON-VOLATILE OILS

The composition therefore comprises at least 70% by weight, relative to the weight of the composition, of at least one non-volatile oil or of a single-phase mixture of several non-volatile oils, at least one of which being chosen from polar or non-polar hydrocarbon-based oils.
The mixture is said to be single-phase when no phase separation is observed by eye or under a phase-contrast microscope, at ambient temperature (25°C) after homogenization at temperature and mixing on a Rayneri mixer (550 rpm, 10 minutes) and storage while left to stand in a closed receptacle at ambient temperature for 24 hours (and atmospheric pressure). Under these conditions, the term stable single-phase mixture is used.
More particularly, for the purposes of the invention, the word "oil" denotes non-aqueous compounds that are liquid at 25°C and atmospheric pressure (1.013 × 10⁵ Pa), and water-immiscible. The term "immiscible" is intended to mean that the mixing of the same amount of water and oil, after mixing (for example Rayneri 550 rpm; 10 minutes), does not result in a stable solution comprising just one phase, under normal temperature and pressure conditions.
The term "non-volatile oil" is intended to mean an oil of which the vapour pressure at 25°C and atmospheric pressure is non-zero and is less than 0.02 mmHg (2.66 Pa) and better still less than 10^-3 mmHg (0.13 Pa).
The term "hydrocarbon-based oil" is intended to mean an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms.
For the purposes of the present invention, the term "non-polar oil" is intended to mean an oil chosen from hydrocarbons, i.e. from compounds comprising only carbon and hydrogen atoms.

Non-polar non-volatile hydrocarbon-based oils

These oils may be of plant, mineral or synthetic origin.
More particularly, the non-polar non-volatile hydrocarbon-based oil(s) can be chosen from linear or branched hydrocarbons of mineral or synthetic origin.
For example, the following are suitable for carrying out the present invention:

liquid paraffins,
squalane,
isohexadecane,
isoeicosane,
naphthalene oil,
polybutenes, for instance Indopol H-100 (molar mass or MW = 965 g/mol), Indopol H-300 (MW = 1340 g/mol) and Indopol H-1500 (MW = 2160 g/mol) sold or manufactured by the company Amoco,
polyisobutenes, hydrogenated polyisobutenes, for instance Parleam® sold by the company Nippon Oil Fats, Panalane H-300 E sold or manufactured by the company Amoco (MW = 1340 g/mol), Viseal 20000 sold or manufactured by the company Synteal (MW = 6000 g/mol) and Rewopal PIB 1000 sold or manufactured by the company Witco (MW = 1000 g/mol), or alternatively Parleam Lite sold by NOF Corporation,
decene/butene copolymers and polybutene/polyisobutene copolymers, in particular Indopol L-14,
polydecenes and hydrogenated polydecenes, for instance: Puresyn 10 (MW = 723 g/mol) and Puresyn 150 (MW = 9200 g/mol) sold or manufactured by the company Mobil Chemicals, or alternatively Puresyn 6 sold by ExxonMobil Chemical,
and mixtures thereof.

Polar non-volatile hydrocarbon-based oils

These polar hydrocarbon-based oils are thus formed from carbon and hydrogen atoms, and comprise at least one or more oxygen or nitrogen atoms, but are free of silicon or fluorine atoms.
They consequently contain at least one group chosen from alcohol, ester, ether, carboxylic acid, amine and/or amide functions.
Preferably, the polar non-volatile hydrocarbon-based oils are, in addition to being free of silicon and fluorine, free of heteroatoms such as nitrogen and phosphorus.
In the present case, the polar non-volatile hydrocarbon-based oils therefore comprise one or more oxygen atoms as heteroatom.
In particular, the polar non-volatile hydrocarbon-based oil(s) comprise at least one alcohol function (it is then an "alcohol oil") or at least one ester function (it is then an "ester oil"). It should be noted that the ester oils may in particular be hydroxylated.
The composition may comprise one or more non-volatile hydrocarbon-based oils, in particular chosen from:

saturated or unsaturated, branched or non-branched C ₁₀ -C ₂₆ , in particular C₁₀-C₂₄ and preferably C₁₂-C₂₂ alcohols, more particularly monoalcohols.

Advantageously, the C₁₀-C₂₆ alcohols are fatty monoalcohols, which are preferably branched when they comprise at least 16 carbon atoms.
As examples of fatty alcohols that may be used, mention may be made of linear or branched fatty alcohols, of synthetic origin or alternatively of natural origin, for instance alcohols derived from plant material (coconut, palm kernel, palm, etc.) or animal material (tallow, etc.).
Needless to say, other long-chain alcohols may also be used, for instance ether alcohols or alternatively "Guerbet" alcohols.
Finally, use may also be made of certain fractions of alcohols of varying length of natural origin, for instance coconut (C₁₂ to C₁₆) or tallow (C₁₆ to C₁₈) or compounds of diol or cholesterol type.
As particular examples of fatty alcohols that may preferably be used, mention may be made in particular of lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol and octyldodecanol, and mixtures thereof.
According to an advantageous embodiment, the alcohol is octyldodecanol.

optionally hydroxylated monoesters, diesters or triesters of a C ₂ -C ₈ monocarboxylic or polycarboxylic acid and of a C ₂ -C ₈ alcohol.
In particular:
- * optionally hydroxylated monoesters of a C₂-C₈ carboxylic acid and of a C₂-C₈ alcohol,
- * optionally hydroxylated diesters of a C₂-C₈ dicarboxylic acid and of a C₂-C₈ alcohol, such as, for example, diisopropyl adipate, 2-diethylhexyl adipate, dibutyl adipate or 2-diethylhexyl succinate,
- * optionally hydroxylated triesters of a C₂-C₈ tricarboxylic acid and of a C₂-C₈ alcohol, such as, for example, citric acid esters, such as trioctyl citrate, triethyl citrate, acetyl tributyl citrate, tributyl citrate or acetyl tributyl citrate;
esters of a C ₂ -C ₈ polyol and of one or more C ₂ -C ₈ carboxylic acids, such as glycol diesters of monoacids, such as in particular neopentyl glycol diheptanoate, propylene glycol dioctanoate, or glycerol triesters of monoacids, such as triacetin;
ester oils, in particular containing at least 18 carbon atoms and even more particularly between 18 and 70 carbon atoms.

Examples that may be mentioned include monoesters, diesters or triesters.
The ester oils may be hydroxylated or non-hydroxylated.
Thus, the non-volatile ester oil may be chosen, for example, from:

* monoesters comprising at least 18 carbon atoms and even more particularly comprising between 18 and 40 carbon atoms in total, in particular the monoesters of formula R₁COOR₂ in which R₁ represents a saturated or unsaturated, linear or branched or aromatic fatty acid residue comprising from 4 to 35 carbon atoms and R₂ represents a hydrocarbon-based chain, which is in particular branched, containing from 4 to 35 carbon atoms, on condition that the sum of the carbon atoms of the radicals R₁ and R₂ is greater than or equal to 18, for instance Purcellin oil (cetostearyl octanoate), isononyl isononanoate, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, C₁₂-C₁₅ alkyl benzoates, such as 2-octyldodecyl benzoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate or 2-octyldodecyl myristate;
Preferably, they are esters of formula R₁COOR₂ in which R₁ represents a linear or branched fatty acid residue comprising from 4 to 35 carbon atoms and R₂ represents a hydrocarbon-based chain that is in particular branched, containing from 4 to 35 carbon atoms, R₁ and R₂ being such that the sum of the carbon atoms of the radicals R₁ and R₂ is greater than or equal to 18.
* monoesters, in particular containing at least 18 carbon atoms and even more particularly from 18 to 22 carbon atoms, of a fatty acid in particular such as lanolic acid, oleic acid, lauric acid or stearic acid, and of diols such as glycols, for instance propylene glycol monoisostearate;
* diesters, in particular containing at least 18 carbon atoms and even more particularly comprising between 18 and 60 carbon atoms in total and in particular between 18 and 50 carbon atoms in total. Use may be made in particular of diesters of a dicarboxylic acid and of monoalcohols comprising more than 8 carbon atoms, preferably such as diisostearyl malate, diisostearyl adipate; or glycol diesters of monocarboxylic acids, such as, for example, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; or polyglyceryl-2 diisostearate (in particular such as the compound sold under the commercial reference Dermol DGDIS by the company Akzo);
* hydroxylated monoesters and diesters, preferably with a total carbon number of at least 18 carbon atoms and even more particularly ranging from 18 to 70, such as in particular polyglyceryl-3 diisostearate, isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or glyceryl stearate;
* triesters, in particular containing at least 35 carbon atoms and even more particularly comprising between 35 and 70 carbon atoms in total, in particular such as triesters of a tricarboxylic acid, such as, for example, triisostearyl citrate, or tridecyl trimellitate, or glyceryl triesters of monocarboxylic acids such as polyglyceryl-2 triisostearate;
* tetraesters, in particular containing at least 35 carbon atoms and even more particularly with a total carbon number ranging from 35 to 70, such as, for example, pentaerythrityl or polyglyceryl tetraesters of a monocarboxylic acid, for instance pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, glyceryl tris(2-decyl)tetradecanoate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetrakis(2-decyl)tetradecanoate;
* polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diols such as those described in patent application FR 0 853 634 . In particular, the unsaturated fatty acid dimer may comprise from 28 to 44 carbon atoms, 2 carboxylic acid functions and 2 to 4 unsaturations; the unsaturated fatty acid trimer may comprise from 42 to 66 carbon atoms, 3 carboxylic acid functions and also 3 to 6 unsaturations. Preferably, use is made of an unsaturated fatty acid dimer, in particular containing 36 carbon atoms and 2 carboxylic acid functions. Mixtures of unsaturated fatty acid dimers and trimers and/or of unsaturated fatty acid (not polymerized, thus corresponding to a monomer) may also be used. Moreover, the diol comprises from 2 to 10 carbon atoms and two hydroxyl functions. In particular, mention may be made of esters of dilinoleic acid and of 1,4-butanediol or propanediol. Mention may in particular be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid/butanediol copolymer), or else copolymers of polyols and of diacid dimers, and esters thereof, such as Hailucent ISDA;
* esters and polyesters of diol dimer and of monocarboxylic or dicarboxylic acid, such as esters of diol dimer and of fatty acid and esters of diol dimer and of dicarboxylic acid dimer, in particular which may be obtained from a dicarboxylic acid dimer derived in particular from the dimerization of an unsaturated fatty acid in particular of C₈ to C₃₄, in particular of C₁₆ to C₂₀ and more particularly esters of dilinoleic diacids and of dilinoleic diol dimers, for example sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5® and DD-DA7®;
* polyesters resulting from the esterification of at least one triglyceride of hydroxylated carboxylic acid(s) with an aliphatic monocarboxylic acid and with an aliphatic dicarboxylic acid, which is optionally unsaturated, for instance the succinic acid and isostearic acid castor oil sold under the reference Zenigloss by Zenitech;
* triglyceride oils of natural or synthetic origin, for instance hydrocarbon-based plant oils such as, for example, jojoba oil; and unsaturated triglycerides such as castor oil, olive oil, ximenia oil or pracaxi oil; fatty acid triglycerides (which are liquid at ambient temperature and atmospheric pressure), in particular of fatty acids, which are saturated or unsaturated, containing at least 7 carbon atoms and even more particularly containing from 7 to 40 carbon atoms, such as heptanoic or octanoic acid triglycerides or saturated triglycerides such as caprylic/capric acid triglyceride and mixtures thereof, for example such as the product sold under the reference Myritol 318 from Cognis, glyceryl triheptanoate, glyceryl trioctanoate, and C_18-36 acid triglycerides such as those sold under the reference Dub TGI 24 by Stéarineries Dubois;
- vinylpyrrolidone/1-hexadecene copolymers, for instance the product sold under the name Antaron V-216 (also known as Ganex V216) by the company ISP;
- C ₁₂ -C ₂₆ fatty acids, preferably C₁₂-C₂₂ fatty acids, which are preferably unsaturated, such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof;
- dialkyl carbonates, the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC® by Cognis;
- and mixtures thereof.

Non-volatile phenyl silicone oils

The composition may optionally comprise at least one non-volatile phenyl silicone oil.
The expression "phenyl silicone oil" denotes a silicone oil bearing at least one phenyl substituent.
These non-volatile phenyl silicone oils may be chosen from those also bearing at least one dimethicone fragment, or from those not bearing any.
The term "dimethicone fragment" denotes a divalent siloxane group in which the silicon atom bears two methyl radicals, this group not being located at the ends of the molecule. It may be represented by the following formula: -(Si(CH₃)₂-O)-.
The non-volatile phenyl silicone oil may thus be chosen from:

a) phenyl silicone oils optionally having a dimethicone fragment corresponding to formula (I) below:

in which the groups R, which are monovalent or divalent, represent, independently of each other, a methyl, methylene, phenyl or phenylene, with the proviso that at least one group R represents a phenyl.
More particularly, the phenyl silicone oil of formula (I) comprises at least three, for example at least four, advantageously at least five or at least six, phenyl groups;

b) phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (II) below:

in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
Preferably, in this formula, the compound of formula (II) comprises at least three, for example at least four or at least five, phenyl groups.
Mixtures of different phenyl silicone compounds described previously may be used.
Among the compounds of formula (II), mention may particularly be made of phenyl silicone oils not bearing any dimethicone fragments with at least 4 or at least 5 radicals R representing a phenyl radical, the remaining radicals representing methyls.
Such non-volatile phenyl silicone oils are preferably trimethylpentaphenyltrisiloxane or tetramethyltetraphenyltrisiloxane, for example PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl pentaphenyltrisiloxane), and Dow Corning 554 Cosmetic Fluid by Dow Corning (INCI name: tetramethyl-tetraphenyl-trisiloxane), sold by the company Dow Corning.
They correspond in particular to the following formulae (III), (III'):
in which Me represents methyl, and Ph represents phenyl.

c) phenyl silicone oils bearing at least one dimethicone fragment corresponding to formula (IV) below:

in which Me represents methyl, y is between 1 and 1000 and X represents -CH₂-CH(CH₃)(Ph).

d) phenyl silicone oils corresponding to formula (V) below, and mixtures thereof:

in which:

R₁ to R₁₀, independently of each other, are saturated or unsaturated, linear, cyclic or branched C₁-C₃₀ hydrocarbon-based radicals,
m, n, p and q are, independently of each other, integers between 0 and 900, with the proviso that the sum m+n+q is other than 0.

Preferably, the sum m+n+q is between 1 and 100. Advantageously, the sum m+n+p+q is between 1 and 900 and preferably between 1 and 800.
Preferably, q is equal to 0.
More particularly, R₁ to R₁₀, independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched C₁-C₃₀ hydrocarbon-based radical, and in particular a preferably saturated C₁-C₂₀, in particular C₁-C₁₈, hydrocarbon-based radical, or a monocyclic or polycyclic C₆-C₁₄, and in particular C₁₀-C₁₃, aryl radical, or an aralkyl radical, the alkyl part of which is preferably C₁-C₃ alkyl.
Preferably, R₁ to R₁₀ may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical. R₁ to R₁₀ may in particular be identical, and in addition may be a methyl radical.
According to a first more particular embodiment of formula (V), mention may be made of:

i) phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to formula (VI) below, and mixtures thereof:

in which:

R₁ to R₆, independently of each other, are saturated or unsaturated, linear, cyclic or branched C₁-C₃₀ hydrocarbon-based radicals, a preferably C₆-C₁₄ aryl radical or an aralkyl radical, the alkyl part of which is C₁-C₃ alkyl,
m, n and p are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.

Preferably, R₁ to R₆, independently of each other, represent a C₁-C₂₀, in particular C₁-C₁₈, hydrocarbon-based, preferably alkyl, radical, or a C₆-C₁₄ aryl radical which is monocyclic (preferably C₆) or polycyclic and in particular C₁₀-C₁₃, or an aralkyl radical (preferably the aryl part is C₆ aryl; the alkyl part is C₁-C₃ alkyl).
Preferably, R₁ to R₆ may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
R₁ to R₆ may in particular be identical, and in addition may be a methyl radical. Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 may be applied, in formula (VI).
Preferably, use may be made of oils corresponding to compounds of formula (VI) in which:

A) m = 0 and n and p are, independently of each other, integers between 1 and 100.
Preferably, R₁ to R₆ are methyl radicals.
According to this embodiment, the silicone oil is preferably chosen from a diphenyl dimethicone such as KF-54 from Shin-Etsu (400 cSt), KF54HV from Shin-Etsu (5000 cSt), KF-50-300CS from Shin-Etsu (300 cSt), KF-53 from Shin-Etsu (175 cSt) or KF-50-100CS from Shin-Etsu (100 cSt).
B) p is between 1 and 100, the sum n+m is between 1 and 100, and n = 0.

These phenyl silicone oils optionally bearing at least one dimethicone fragment correspond more particularly to formula (VII) below:
in which Me is methyl and Ph is phenyl, OR' represents a group

OSiMe₃ and p is 0 or is between 1 and 1000, and m is between 1 and 1000. In particular, m and p are such that compound (VII) is a non-volatile oil.

According to a first embodiment of non-volatile phenyl silicone bearing at least one dimethicone fragment, p is between 1 and 1000. m is more particularly such that the compound (VII) is a non-volatile oil. Use may be made, for example, of trimethylsiloxyphenyl dimethicone, sold in particular under the reference Belsil PDM 1000 by the company Wacker.
According to a second embodiment of non-volatile phenyl silicone not bearing a dimethicone fragment, p is equal to 0. m is between 1 and 1000, and in particular is such that the compound (VII) is a non-volatile oil.
Phenyltrimethylsiloxytrisiloxane, sold in particular under the reference Dow Corning 556 Cosmetic Grade Fluid (DC556) by the company Dow Corning, may, for example, be used.

ii) non-volatile phenyl silicone oils not bearing a dimethicone fragment corresponding to formula (VIII) below, and mixtures thereof:

in which:

R, independently of each other, are saturated or unsaturated, linear, cyclic or branched C₁-C₃₀ hydrocarbon-based radicals, preferably R is a C₁-C₃₀ alkyl radical, preferably a C₆-C₁₄ aryl radical, or an aralkyl radical, the alkyl part of which is C₁-C₃ alkyl,
m and n are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.

Preferably, R, independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched C₁-C₃₀ hydrocarbon-based radical, and in particular a preferably saturated, C₁-C₂₀, in particular C₁-C₁₈ and more particularly C₄-C₁₀, hydrocarbon-based radical, a monocyclic or polycyclic C₆-C₁₄, and in particular C₁₀-C₁₃, aryl radical, or an aralkyl radical of which preferably the aryl part is C₆ aryl and the alkyl part is C₁-C₃ alkyl.
Preferably, the R may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
The radicals R may in particular be identical, and in addition may be a methyl radical.
Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 may be applied, in formula (VIII).
According to one preferred embodiment, n is an integer between 0 and 100 and m is an integer between 1 and 100, with the proviso that the sum n+m is between 1 and 100, in formula (VIII). Preferably, R is a methyl radical.
According to this embodiment, the non-volatile phenyl silicone oil is preferably chosen from phenyl trimethicones (when n=0) such as DC556 from Dow Corning, or else from diphenylsiloxyphenyl trimethicone oil (when m and n are between 1 and 100) such as KF56 A from Shin-Etsu, or the Silbione 70663V30 oil from Rhône-Poulenc.

e) phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to the following formula, and mixtures thereof:

in which:

R₁, R₂, R₅ and R₆, which may be identical or different, are an alkyl radical containing 1 to 6 carbon atoms,
R₃ and R₄, which may be identical or different, are an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical (preferably C₆-C₁₄), with the proviso that at least one of R₃ and R₄ is a phenyl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,
n and p are integers greater than or equal to 1, chosen so as to give the oil a weight-average molecular mass of less than 200 000 g/mol, preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol.

f) and a mixture thereof.

The composition therefore comprises at least 70% by weight, relative to the weight of the composition, of a non-volatile oil or of a single-phase mixture of several non-volatile oils, at least one of which is a polar or non-polar, non-volatile hydrocarbon-based oil. More particularly, the content of non-volatile oil(s) represents from 70% to 90% by weight, more specifically from 75% to 90% by weight and preferably from 75% to 85% by weight relative to the weight of the composition.
If the composition comprises at least one non-volatile phenyl silicone oil, then its content preferably does not exceed 20% by weight, more advantageously does not exceed 15% by weight, and even more preferentially does not exceed 10% by weight, relative to the weight of the composition.
According to one particular embodiment, the composition does not comprise any non-volatile phenyl silicone oil.
It should be noted that, if the composition comprises a mixture of non-volatile oil(s), then said mixture is preferably single-phase. More particularly, the mixture is said to be single-phase when no phase separation is observed by eye or under a phase-contrast microscope, at ambient temperature (25°C) after homogenization at temperature and mixing on a Rayneri mixer (550 rpm, 10 minutes) and storage while left to stand in a closed receptacle at ambient temperature (and atmospheric pressure) for 24 hours.
Preferably, the composition comprises at least one polar non-volatile hydrocarbon-based oil, more particularly chosen from ester oils, in particular hydroxylated or non-hydroxylated monoesters and diesters comprising at least 18 carbon atoms in total, triesters, in particular containing at least 35 carbon atoms, tetraesters, in particular containing at least 35 carbon atoms, and mixtures thereof.
The composition preferably comprises, moreover, at least one non-polar non-volatile hydrocarbon-based oil, more particularly chosen from hydrogenated or non-hydrogenated polybutenes, hydrogenated or non-hydrogenated polyisobutenes, hydrogenated or non-hydrogenated polydecenes, and mixtures thereof.
In accordance with one particularly advantageous embodiment, the composition comprises a mixture of polar and non-polar hydrocarbon-based oils.
Preferably, the weight proportion of polar non-volatile hydrocarbon-based oil(s) relative to the non-polar non-volatile hydrocarbon-based oil(s) is greater than or equal to 1, more advantageously greater than or equal to 2.

MINERAL THICKENER

The composition comprises at least one mineral thickener more particularly chosen from optionally modified organophilic clays, silicas, which are preferably hydrophobic, and mixtures thereof.
According to one particular embodiment, the composition comprises at least one preferably modified organophilic clay, chosen from montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. The clay is more advantageously a bentonite or a hectorite.
These clays are modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.
Mention may thus be made of hectorites modified with a quaternary amine, more specifically with a C₁₀ to C₂₂ fatty acid ammonium halide, such as a chloride, such as hectorite modified with distearyldimethylammonium chloride (CTFA name: Disteardimonium hectorite), for instance the product sold under the name Bentone 38V®, Bentone 38V CG or Bentone EW CE by the company Elementis, or stearalkonium hectorites, such as Bentone 27 V.
Mention may also be made of quaternium-18 bentonites, such as those sold under the names Bentone 34 by the company Elementis, Tixogel VP by the company United Catalyst and Claytone 40 by the company Southern Clay; stearalkonium bentonites, such as those sold under the names Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; or quaternium-18/benzalkonium bentonites, such as those sold under the name Claytone HT by the company Southern Clay.
According to one preferred embodiment, the thickener is chosen from optionally modified organophilic clays, in particular organophilic hectorites in particular modified with benzyldimethylammonium stearate chloride or with distearyldimethylammonium chloride.
The composition may also comprise, as mineral thickener, at least one preferably hydrophobic silica, chosen from fumed silicas, which are preferably hydrophobically treated, silica aerogels, and mixtures thereof.
Mention may be made, for example, of fumed silica preferably hydrophobically treated at the surface, the size of the particles of which is more particularly less than 1 µm. It is possible in particular to replace silanol groups with hydrophobic groups, such as in particular:

trimethylsiloxyl groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;
dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "Silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.

The hydrophobic fumed silica in particular has a particle size ranging, for example, from 5 to 200 nm.
Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.
The hydrophobic silica aerogel particles that can be used have a specific surface area per unit mass (S_M) ranging from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and better still from 600 to 800 m²/g, and a size expressed as the volume mean diameter (D[0.5]) ranging from 1 to 1500 µm, better still from 1 to 1000 µm, preferably from 1 to 100 µm, in particular from 1 to 30 µm, more preferably from 5 to 25 µm, better still from 5 to 20 µm and even better still from 5 to 15 µm.
According to one embodiment, the hydrophobic silica aerogel particles that are suitable have a size expressed as the volume mean diameter (D[0.5]) ranging from 1 to 30 µm, preferably from 5 to 25 µm, better still from 5 to 20 µm and even better still from 5 to 15 µm.
The specific surface area per unit mass may be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in The Journal of the American Chemical Society, vol. 60, page 309, February 1938 and corresponding to international standard ISO 5794/1 (annex D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.
The sizes of the silica aerogel particles can be measured by static light scattering using a commercial particle size analyser of MasterSizer 2000 type from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is in particular described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, .
According to an advantageous embodiment, the hydrophobic silica aerogel particles that can be used have a specific surface area per unit mass (S_M) ranging from 600 to 800 m²/g and a size expressed as the volume mean diameter (D[0.5]) ranging from 5 to 20 µm and even better still from 5 to 15 µm.
The aerogels used are aerogels of hydrophobic silica, preferably of silylated silica (INCI name: silica silylate).
"Hydrophobic silica" is intended to mean any silica, the surface of which is treated with silylating agents, for example with halogenated silanes, such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes, such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.
As regards the preparation of hydrophobic silica aerogel particles modified at the surface by silylation, reference may be made to the document US 7 470 725 .
Use will preferably be made of hydrophobic silica aerogel particles modified at the surface by trimethylsilyl groups.
Mention may be made, as hydrophobic silica aerogels which can be used in the invention, for example, of the aerogel VM-2260 sold by Dow Corning (INCI name: Silica silylate: mean size of around 1000 µm; specific surface area per unit mass: 600 to 800 m²/g); AEROGEL TLD 201, AEROGEL OGD 201, AEROGEL TLD 203, ENOVA® AEROGEL MT 1100, ENOVA AEROGEL MT 1200, sold by Cabot. Preferably, use is made of the aerogel VM-2270 sold by Dow Corning (INCI name: Silica silylate: mean size: 5-15 µm; specific surface area per unit mass: 600 to 800 m²/g).
Preferably, the mineral thickeners are chosen from organophilic clays, in particular modified hectorites.
In accordance with one particular embodiment, the content of mineral thickener, expressed as active material, ranges from 0.2% to 2% by weight, preferably from 0.3% to 1.5% by weight, relative to the weight of the composition.

C ₂ -C ₈ MONOALCOHOL

The composition may comprise at least one linear or branched, preferably saturated, monoalcohol comprising from 2 to 8 carbon atoms, especially from 2 to 6 carbon atoms, and in particular from 2 to 4 carbon atoms.
As monoalcohol, mention may be made of ethanol, isopropanol, propanol or butanol, and preferably ethanol.
When the composition contains it, the content of C₂-C₈ monoalcohol is less than or equal to 6% by weight, preferably less than or equal to 4% by weight, relative to the weight of the composition.
The composition may not comprise any abovementioned C₂-C₈ monoalcohol.

NON-IONIC SILICONE SURFACTANT

The composition comprises moreover at least one non-ionic silicone surfactant in particular chosen from oxyalkylenated and preferably oxyethylenated polydimethylsiloxanes, alkyl or alkoxy dimethicone copolyols, and mixtures thereof. The silicone surfactants are advantageously not silicone elastomers.
Preferably, the silicone surfactant comprises polyoxyalkylene chains, more particularly chains of polyoxyethylene or of polyoxypropylene or combinations thereof, on the main chain (side or pendent polyoxyethylene or polyoxypropylene chains).
The number of ethylene oxide units can range from 0 to 100, preferably from 2 to 50 and even more particularly from 5 to 20; the number being strictly positive when the compound contains only ethylene oxide units. The number of propylene oxide units can range from 0 to 80; preferably, the compound does not contain only propylene oxide units.
Such silicone surfactants are in particular those called PEG-10 dimethicone sold by Shin-Etsu under the name KF-6017.
Also suitable are alkyl or alkoxy dimethicone copolyols bearing an alkyl or alkoxy chain that is pendent or at the end of the silicone backbone, for example containing from 6 to 22 carbon atoms.
In particular, the surfactant may be a C₈-C₂₂ alkyl dimethicone copolyol, i.e. an oxypropylenated and/or oxyethylenated polymethyl(C₈-C₂₂)alkyldimethylmethylsiloxane.
By way of example, mention may be made of cetyl dimethicone copolyol (INCI name: Cetyl PEG/PPG-10/1 Dimethicone), such as the product sold under the name Abil EM -90 by the company Evonik Goldschmidt.
Preferably, the non-ionic silicone surfactant is chosen from oxyalkylenated and preferably oxyethylenated polydimethylsiloxanes.
According to a first embodiment, the content of non-ionic silicone surfactant(s) is at least 1% by weight, relative to the weight of the composition. Preferably, the content of non-ionic silicone surfactant ranges from 1% to 3% by weight, preferably from 1% to 2% by weight, relative to the weight of the composition.
According to this variant, the composition sediments when it is stored. Unlike the fluid compositions having a high content of oils and comprising coloured or colourless solid particles, the composition has the advantage of being able to be easily resuspended, by simple manual shaking of the container in which it is packaged.
The composition is said to sediment when it allows the appearance of a supernatant liquid after standing for 48 hours at 25°C, measured under the following conditions:
Use is made of a cylindrical polyethylene terephthalate receptacle, the height of which is 46.9 mm and the radius of which is 15 mm, comprising two steel balls 6.35 mm in diameter, and fitted with a stopper.
The composition is introduced such that the height in the bottle reaches 3.5 cm (which represents approximately 4.5 g of composition) and the bottle is stoppered.
Said bottle is left for 48 hours at a temperature of 25°C.
After the 48 hours, the height of supernatant liquid is measured.
It is considered that the composition sediments when the height of supernatant liquid represents at least 5% of the total height of the composition, preferably at least 15% of the total height of the composition.
According to a second embodiment, the composition comprises a content of non-ionic silicone surfactant(s) of less than 1% by weight, relative to the weight of the composition. Preferably, the content of non-ionic silicone surfactant ranges from 0.2% to less than 1% by weight, preferably from 0.2% to 0.9% by weight, relative to the weight of the composition.
According to this variant, the composition is stable and does not sediment under the conditions indicated previously.

SOLID PARTICLES

As indicated previously, the composition comprises at least coloured or non-coloured solid particles.
Preferably, the solid particles are chosen from pigments and fillers, which are preferably platelet-shaped, alone or as mixtures.

Pigments

More particularly, mineral, organic or composite pigments, and mixtures thereof, are referred to as pigments.
The term "pigments" should be understood as meaning white or coloured particles or particles which afford a colour effect, which are insoluble in the medium of the composition, and which are intended to colour and/or opacify the composition and/or the deposit produced with the composition.
The pigments may thus be chosen from monochromatic mineral pigments, organic lakes, nacres, and pigments with an optical effect, for instance reflective pigments and goniochromatic pigments.
The mineral pigments may be chosen from metal oxide pigments, chromium oxides, iron oxides, titanium dioxide, zinc oxides, cerium oxides, zirconium oxides, manganese violet, Prussian blue, ultramarine blue, ferric blue and chromium hydrate, and mixtures thereof.
They may also be pigments having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts, and has a contrast ratio in the region of 30.
Organic lakes are organic pigments formed from a dye attached to a substrate. They may be chosen, for example, from:

cochineal carmine;
organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluoran dyes. Among the organic pigments that may in particular be mentioned are those known under the following names: D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6;
insoluble sodium, potassium, calcium, barium, aluminium, zirconium, strontium or titanium salts of acid dyes such as azo, anthraquinone, indigoid, xanthene, pyrene, quinoline, triphenylmethane or fluoran dyes, these dyes possibly comprising at least one carboxylic or sulfonic acid group.

The organic lakes may also be supported on an organic support such as rosin or aluminium benzoate, for example.
Among the organic lakes that may be mentioned in particular are those known under the following names: D&C Red No. 2 Aluminium lake, D&C Red No. 3 Aluminium lake, D&C Red No. 4 Aluminium lake, D&C Red No. 6 Aluminium lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminium lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No. 9 Aluminium lake, D&C Red No. 9 Barium lake, D&C Red No. 9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C Red No. 10 Sodium lake, D&C Red No. 19 Aluminium lake, D&C Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C Red No. 21 Aluminium lake, D&C Red No. 21 Zirconium lake, D&C Red No. 22 Aluminium lake, D&C Red No. 27 Aluminium lake, D&C Red No. 27 Aluminium/Titanium/Zirconium lake, D&C Red No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red No. 27 Zirconium lake, D&C Red No. 28 Aluminium lake, D&C Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No. 33 Aluminium lake, D&C Red No. 34 Calcium lake, D&C Red No. 36 lake, D&C Red No. 40 Aluminium lake, D&C Blue No. 1 Aluminium lake, D&C Green No. 3 Aluminium lake, D&C Orange No. 4 Aluminium lake, D&C Orange No. 5 Aluminium lake, D&C Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminium lake, D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminium lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6 Aluminium lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow No. 10 Aluminium lake, FD&C Blue No. 1 Aluminium lake, FD&C Red No. 4 Aluminium lake, FD&C Red No. 40 Aluminium lake, FD&C Yellow No. 5 Aluminium lake, FD&C Yellow No. 6 Aluminium lake.
The chemical materials corresponding to each of the organic colourants mentioned previously are mentioned in the publication "International Cosmetic Ingredient Dictionary and Handbook", 1997 edition, pages 371 to 386 and 524 to 528, published by The Cosmetic, Toiletries and Fragrance Association, the content of which is incorporated into the present patent application by reference.
The pigments may also have been subjected to a hydrophobic treatment.
The hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.
The N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine.
The term "alkyl" mentioned in the compounds cited above in particular denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
Hydrophobic treated pigments are described in particular in patent application EP-A-1 086 683 .
The colourant may also comprise a pigment having a structure which may be, for example, of the type such as silica microspheres containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL-100 P, this pigment being constituted of silica microspheres containing yellow iron oxide.
For the purposes of the present patent invention, the nacres are more particularly coloured particles of any form, which may or may not be iridescent, in particular produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.
Examples of nacres that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye in particular of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. They can also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic colourants.
The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or glint.
As illustrations of nacres that may be introduced as interference pigments into the first composition, mention may be made of the gold-coloured nacres sold in particular by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold in particular by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold in particular by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper glint sold in particular by the company Engelhard under the name Copper 340A (Timica); the nacres with a red glint sold in particular by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow glint sold in particular by the company Engelhard under the name Yellow (4502) (Chromalite); the red nacres with a gold glint sold in particular by the company Engelhard under the name Sunstone G012 (Gemtone); the pink nacres sold in particular by the company Engelhard under the name Tan opale G005 (Gemtone); the black nacres with a gold glint sold in particular by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold in particular by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery glint sold in particular by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold in particular by the company Merck under the name Indian summer (Xirona), and mixtures thereof.
The composition may also contain, as coloured particles, at least one material with a specific optical effect.
This effect is different from a simple conventional hue effect, i.e. a unified and stabilized effect as produced by standard coloured particles, for instance monochromatic pigments. Within the meaning of the invention, the term "stabilized" means devoid of an effect of variability in the colour with the angle of observation or alternatively in response to a change in temperature.
For example, this material may be chosen from particles with a metallic glint, goniochromatic colouring agents, diffractive pigments, thermochromic agents, optical brighteners, and also fibres, in particular interference fibres. Needless to say, these various materials may be combined so as to afford the simultaneous manifestation of two effects, or even of a novel effect.
Advantageously, the content of coloured particles, in particular of pigments, of nacres alone or as mixtures, ranges from 0.001% to 10% by weight and preferably from 0.01% to 8% by weight relative to the weight of the composition.

Fillers

The fillers are more particularly organic, mineral or mixed, and may be present alone or as a mixture.
The term "fillers" should be understood as meaning colourless or white solid particles of any form, which are in an insoluble and dispersed form in the medium of the composition, and which are not intended to colour the composition, but at the very most to opacify it.
The fillers may be, for example, platelet-shaped, spherical, oblong or fibrous, or of any other form intermediate between these forms, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Preferably, the fillers used are platelet-shaped.
It should be noted that the fillers are different from the mineral thickener previously mentioned.
The fillers that can be used may or may not be surface-coated, and in particular they can be surface-treated with silicones, amino acids, fluoro derivatives or any other substance which promotes the dispersion and compatibility of the filler in the composition.
Examples of mineral fillers that may be mentioned include talc, mica, perlite, kaolin, hollow silica microspheres, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, boron nitride, glass or ceramic microcapsules, or composites of silica and of titanium dioxide, for instance the TSG series sold by Nippon Sheet Glass.
Examples of organic fillers that may be mentioned include polyamide powders (Nylon® Orgasol from Atochem), polyethylene powders, polymethyl methacrylate powders, polytetrafluoroethylene (Teflon) powders, acrylic acid copolymer powders (Polytrap from the company Dow Corning), lauroyl lysine, hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel (Nobel Industrie), hexamethylene diisocyanate/trimethylol hexyllactone copolymer powder (Plastic Powder from Toshiki), silicone resin microbeads (for example Tospearls from Toshiba), synthetic or natural micronized waxes, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate, Polypore® L 200 (Chemdal Corporation), polyurethane powders, in particular powders of crosslinked polyurethane comprising a copolymer, said copolymer comprising trimethylol hexyllactone. It may in particular be a hexamethylene diisocyanate/trimethylol hexyllactone polymer. Such particles are in particular commercially available, for example, under the name Plastic Powder D-400® or Plastic Powder D-800® from the company Toshiki, and mixtures thereof.
As organic filler, mention may also be made of powders of crosslinked organopolysiloxane coated with silicone resin, in particular with silsesquioxane resin, as described, for example, in patent US 5 538 793 .
Such elastomer powders are sold under the names KSP-100®, KSP-101®, KSP-102®, KSP-103®, KSP-104® and KSP-105® by the company Shin-Etsu; mention may also be made of crosslinked organopolysiloxane elastomer powders coated with silicone resin, such as powders of hybrid silicone functionalized with fluoroalkyl groups, sold in particular under the name KSP-200 by the company Shin-Etsu; or hybrid silicone powders functionalized with phenyl groups, sold in particular under the name KSP-300 by the company Shin-Etsu.
Preferably, use is made of mineral fillers, which are advantageously platelet-shaped, and even more preferentially mica.
According to one particular embodiment, the content of fillers ranges from 0.001% to 5% by weight, preferably from 0.05% to 3% by weight, relative to the weight of the composition.

WATER

The composition can optionally comprise water.
If it contains water, the water content does not exceed 1% by weight, more particularly does not exceed 0.5% by weight, and preferably does not exceed 0.4% by weight, relative to the weight of the composition.

VOLATILE OILS

The composition may also comprise at least one volatile oil, preferably, chosen from volatile hydrocarbon-based oils, which are preferably non-polar, and volatile silicone oils.
The volatile silicone oil(s) may be chosen in particular from silicone oils with a flash point ranging from 40°C to 102°C, preferably greater than 55°C and less than or equal to 95°C, and even more particularly from 65°C to 95°C.
As volatile silicone oils that can be used, mention may be made of linear or cyclic silicones containing especially from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils, mention may be made of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
The volatile hydrocarbon-based oil(s), which are preferably non-polar, are chosen from oils of which the flash point ranges from 40°C to 102°C, preferably from 40°C to 55°C, and even more particularly from 40°C to 50°C.
Among the volatile hydrocarbon-based oils that can be used, mention may in particular be made of hydrocarbons containing from 8 to 16 carbon atoms, and mixtures thereof, and in particular:

branched C₈-C₁₆ alkanes such as C₈-C₁₆ isoalkanes (also known as isoparaffins), isododecane, isodecane and isohexadecane, and, for example, the oils sold under the trade name Isopar or Permethyl,
linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture (Cetiol UT), the mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis, and mixtures thereof.

In accordance with one advantageous embodiment, the composition comprises at least one volatile hydrocarbon-based oil, which is more particularly non-polar, at least one volatile silicone oil, and preferably a mixture of these two types of volatile oils.
More particularly, the content of volatile hydrocarbon-based oil(s), volatile silicone oil(s) or mixtures thereof is less than or equal to 10% by weight, more particularly less than or equal to 8% by weight, advantageously between 1% and 8% by weight, relative to the weight of the composition.
If the composition comprises a mixture of non-volatile oil(s) and volatile oil(s), then said mixture is single-phase. More particularly, the mixture is said to be single-phase when no phase separation is observed by eye or under a phase-contrast microscope, at ambient temperature (25°C) after homogenization at temperature and mixing on a Rayneri mixer (550 rpm, 10 minutes) and storage while left to stand in a closed receptacle at ambient temperature (and atmospheric pressure) for 24 hours.

SILICONE POLYMER

The composition may optionally comprise at least one silicone polymer chosen from:

(i) silicone resins of MQ type;
(ii) silsesquioxane resins;
(iii) vinyl polymers grafted with a carbosiloxane dendrimer;
(iv) their mixtures.

The term "polymer" is understood here to mean a compound having one or more repeat unit(s) and preferably at least 2 repeat units.

Silicone resins of MQ type

More generally, the term "resin" is understood to mean a compound, the structure of which is three-dimensional.
"Silicone resins" are also known as "siloxane resins". Thus, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin.
The nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units that it comprises, each of the letters "MDTQ" characterizing a type of unit.
The letter "M" represents the Monofunctional unit of formula R¹R²R³SiO_1/2, the silicon atom being connected to only one oxygen atom in the polymer comprising this unit.
The letter "D" signifies a Difunctional unit R¹R²SiO_2/2 in which the silicon atom is connected to two oxygen atoms.
The letter "T" represents a Trifunctional unit of formula R¹SiO_3/2.
Finally, the letter "Q" signifies a tetrafunctional unit SiO_4/2 in which the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the remainder of the polymer.
In the M, D and T units defined above, R¹, R² and R³ represent a hydrocarbon radical (in particular an alkyl radical) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or else a hydroxyl group.
Such resins are described, for example, in the Encyclopedia of Polymer Science and Enginnering, vol. 15, John Wiley and Sons, New York, (1989), pp. 265-270, and US 2 676 182 , US 3 627 851 , US 3 772 247 , US 5 248 739 or else US 5 082 706 , US 5 319 040 , US 5 302 685 and US 4 935 484 .
Mention may be made, as examples of silicone resins of MQ type which can be used, of the alkylsiloxysilicates of formula [(R₁)₃SiO_1/2]_x(SiO_4/2)_y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the R₁ group represents a radical as defined above and is preferably an alkyl group having from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.
Mention may be made, as examples of solid silicone resins of MQ type of trimethylsiloxysilicate type, of those sold under the reference SR1000 by General Electric, under the reference TMS 803 by Wacker, under the name KF-7312J by Shin-Etsu or DC749 or DC593 by Dow Corning.
Mention may also be made, as silicone resins comprising MQ siloxysilicate units, of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by General Electric). The preparation of such resins is described in particular in patent US 5 817 302 .

Silsesquioxane resins

Among the silsesquioxane resins that can be used in the compositions in accordance with the invention, mention may be made of the alkyl silsesquioxane resins which are homopolymers and/or copolymers of silsesquioxane containing an average siloxane unit of formula R_1nSiO_(4-n)/2, in which each R₁ independently denotes a hydrogen atom or a C₁-C₁₀ alkyl group, where more than 80 mol% of the R₁ radicals represent a C₃-C₁₀ alkyl group, n is a number from 1.0 to 1.4, and more particularly, use will be made of a silsesquioxane copolymer in which more than 60 mol% comprises units R₁SiO_3/2 in which R₁ has the definition previously indicated.
Preferably, the silsesquioxane resin is chosen such that R₁ is a C₁-C₁₀ alkyl group, preferably a C₁-C₄ alkyl group, and more particularly a propyl group. Use will more particularly be made of a polypropylsilsesquioxane or t-propyl silsesquioxane resin (INCI name: Polypropylsilsesquioxane (and) Isododecane) such as the product sold under the trade name Dow Corning® 670 Fluid by the company Dow Corning.

Vinyl polymers grafted with a carbosiloxane dendrimer

Among the silicone polymers that are suitable, mention may be made of vinyl polymers comprising at least one unit derived from carbosiloxane dendrimer.
The vinyl polymer has a backbone and at least one side chain, which side chain comprises a unit derived from carbosiloxane dendrimer exhibiting a carbosiloxane dendrimer structure.
In the context of the present invention, the term "carbosiloxane dendrimer structure" represents a molecular structure possessing branched groups having high molecular weights, 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 laid-open Japanese patent application Kokai 9-171 154 .
A vinyl polymer according to the invention may contain units derived from carbosiloxane dendrimers that may be represented by the following general formula (I):
in which:

R¹ represents an aryl group having from 5 to 10 carbon atoms or an alkyl group having from 1 to 10 carbon atoms;
X' represents a silylalkyl group which, when i = 1, is represented by formula (II):
in which:
- R¹ is as defined above in the formula (I),
- R² represents an alkylene radical having from 2 to 10 carbon atoms,
- R³ represents an alkyl group having from 1 to 10 carbon atoms,
- Xⁱ⁺ⁱ is chosen from: a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, an aryl group having from 5 to 10 carbon atoms and a silylalkyl group defined above of formula (II) with i = i + 1,
- i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and
- a¹ is an integer from 0 to 3;
Y represents a radically polymerizable organic group chosen from:
- organic groups comprising a methacrylic group or an acrylic group, said organic groups being represented by the formulae:
  in which:
  - * R⁴ represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms; and
  - * R⁵ represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, methylene and propylene groups being preferred; and
- organic groups comprising a styryl group of formula:
  in which:
  - * R⁶ represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, the methyl group being preferred;
  - * R⁷ represents an alkyl group containing from 1 to 10 carbon atoms;
  - * R⁸ represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the ethylene group being preferred;
  - * b is an integer from 0 to 4; and
  - * c is 0 or 1, such that, if c is 0, -(R⁸)c- represents a bond.

According to one embodiment, R¹ can represent an aryl group possessing from 5 to 10 carbon atoms or an alkyl group possessing from 1 to 10 carbon atoms. The alkyl group can preferably be represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group. The aryl group can preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is most preferred.
According to one embodiment, R² represents an alkylene group possessing from 2 to 10 carbon atoms, in particular a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1-methylpentylene or 1,4-dimethylbutylene group.
The ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are most preferred.
According to one embodiment, R³ is chosen from methyl, ethyl, propyl, butyl and isopropyl groups.
In the formula (II), i indicates the number of generations and thus corresponds to the number of repetitions of the silylalkyl group.
For example, when the number of generations is equal to 1, the carbosiloxane dendrimer can be represented by the general formula shown below, in which Y, R¹, R² and R³ are as defined above, R¹² represents a hydrogen atom or is identical to R¹ and a¹ is identical to aⁱ. Preferably, the total average number of OR³ groups in a molecule is within the range from 0 to 7.
When the number of generations is equal to 2, the carbosiloxane dendrimer can be represented by the general formula below, in which Y, R¹, R², R³ and R¹² are the same as defined above, and a¹ and a² represent the aⁱ of the indicated generation. Preferably, the total average number of OR³ groups in a molecule is within the range from 0 to 25.
In the case where the number of generations is equal to 3, the carbosiloxane dendrimer is represented by the general formula below, in which Y, R¹, R², R³ and R¹² are the same as defined above, and a¹, a² and a³ represent the aⁱ of the indicated generation. Preferably, the total average number of OR³ groups in a molecule is within the range from 0 to 79.
A vinyl polymer having at least one unit derived from carbosiloxane dendrimer has a molecular side chain containing a carbosiloxane dendrimer structure and can result from the polymerization of:

(A) of 0 to 99.9 parts by weight of a vinyl monomer, and
(B) of 100 to 0.1 parts by weight of a carbosiloxane dendrimer comprising a radically polymerizable organic group, represented by the general formula (I) as defined above.

The monomer of vinyl type which is the component (A) in the vinyl polymer having at least one unit derived from carbosiloxane dendrimer is a monomer of vinyl type which comprises a radically 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 lower alkyl analogue; 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 methacrylate analogue; vinyl acetate, vinyl propionate or a vinyl ester of a lower fatty acid analogue; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate or a higher fatty acid ester analogue; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone or similar vinylaromatic monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, 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 can also be used.
The following represent 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, ethoxylated trimethylolpropane trimethacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups possessing divinylbenzene groups on both ends, or analogous silicone compounds containing unsaturated groups.
A carbosiloxane dendrimer, which is the component (B), can be represented by the formula (I) as defined above.
The following represent the preferred examples of Y group of the formula (I): an acryloyloxymethyl group, a 3-acryloyloxypropyl group, a methacryloyloxymethyl group, a 3-methacryloyloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
A carbosiloxane dendrimer according to the present invention may be represented by the formulae having the average structures below:
Thus, according to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:
in which:

Y, R¹, R² and R³ are as defined in the formulae (I) and (II) above;
a¹, a² and a³ correspond to the definition of aⁱ according to the formula (II); and
R¹² is H, an aryl group having from 5 to 10 carbon atoms or an alkyl group having from 1 to 10 carbon atoms.

According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulae:
The vinyl polymer comprising the carbosiloxane dendrimer that can be used may be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154 .
The vinyl polymer can be a dispersion of a polymer of vinyl type having a carbosiloxane dendrimer structure in its molecular side chain, in a liquid such as a silicone oil, an organic oil, an alcohol or water.
The silicone oil may be a dimethylpolysiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methyl-3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, or similar unreactive linear silicone oils, and also hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane or a similar cyclic compound. In addition to the unreactive silicone oils, modified polysiloxanes containing functional groups such as silanol groups, amino groups and polyether groups on the ends or within the molecular side chains may be used.
The organic oils can be isododecane, liquid paraffin, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil, camelia oil, squalane, castor oil, cottonseed oil, coconut oil, egg yolk oil, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or an analogous glycol ester oil; triglyceryl isostearate, the triglyceride of a fatty acid of coconut oil, or an analogous oil of a polyhydric alcohol ester; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether or an analogous polyoxyalkylene ether.
The alcohol may be any type that is suitable for use in combination with a cosmetic product starting material. For example, it can be methanol, ethanol, butanol, isopropanol or analogous lower alcohols.
The solutions and dispersions can be easily prepared by mixing a vinyl polymer having at least one unit derived from carbosiloxane dendrimer with a silicone oil, an organic oil, an alcohol or water. The liquids can be present in the polymerization stage. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric pressure or reduced pressure.
In the case of a dispersion, the dispersity of the polymer of vinyl type can be improved by adding a surfactant.
Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow-trimethylammonium hydroxide, coconut oil-trimethylammonium hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylene alkylphenol, a polyoxyalkylene alkyl ester, the sorbitol ester of polyoxyalkylene, polyethylene glycol, polypropylene glycol, an ethylene oxide additive of diethylene glycol trimethylnonanol, and non-ionic surfactants of polyester type, and also mixtures.
In the dispersion, a mean particle diameter of the polymer of vinyl type can be within a range of between 0.001 and 100 microns and preferably between 0.01 and 50 microns.
A vinyl polymer contained in the dispersion or the solution can have a concentration within a range of between 0.1% and 95% by weight and preferably between 5% and 85% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 75% by weight.
A vinyl polymer suitable for the invention can also be one of the polymers described in the examples of patent application EP 0 963 751 .
According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer can result from the polymerization:

of 0 to 99.9 parts by weight of one or more acrylate or methacrylate monomer(s); and
of 100 to 0.1 part by weight of an acrylate or methacrylate monomer of a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer.

The monomers (A1) and (B1) correspond respectively to specific monomers (A) and (B).
According to one embodiment, a vinyl polymer having at least one unit derived from carbosiloxane dendrimer can comprise a unit derived from tris[tri(trimethylsiloxy)silylethyldimethylsiloxy] silylpropyl carbosiloxane dendrimer corresponding to one of the formulae:
or
According to a preferred mode, a vinyl polymer having at least one unit derived from carbosiloxane dendrimer used in the invention comprises at least one butyl acrylate monomer.
According to one embodiment, a vinyl polymer can additionally comprise at least one fluorinated organic group.
Structures in which the polymerized vinyl units constitute the backbone and carbosiloxane dendritic structures and also fluorinated organic groups are attached to side chains are particularly preferred.
The fluorinated organic groups can be obtained by replacing with fluorine atoms all or some of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl groups and of other alkyl groups of 1 to 20 carbon atoms, and also alkyloxyalkylene groups of 6 to 22 carbon atoms.
The groups represented by the formula -(CH₂)_x-(CF₂)_y-R¹³ are suggested as examples of fluoroalkyl groups obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups. In the formula, the subscript "x" is 0, 1, 2 or 3, and "y" is an integer from 1 to 20. R¹³ is an atom or a group chosen from a hydrogen atom, a fluorine atom, -CH(CF₃)₂- or CF(CF₃)₂. Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulae presented below: -CF₃, -C₂F₅, -nC₃F₇, -CF(CF₃)₂, -nC₄F₉, CF₂CF(CF₃)₂, -nC₅F₁₁, -nC₆F₁₃, -nC₈F₁₇, CH₂CF₃, -(CH(CF₃)₂, CH₂CH(CF₃)₂-CH₂(CF₂)₂F, -CH₂(CF₂)₃F, -CH₂(CF₂)₄F, -CH₂(CF₂)₆F, -CH₂(CF₂)₈F, -CH₂CH₂CF₃, -CH₂CH₂(CF₂)₂F, -CH₂CH₂(CF₂)₃F, -CH₂CH₂(CF₂)₄F, -CH₂CH₂(CF₂)₆F, -CH₂CH₂(CF₂)₈F, -CH₂CH₂(CF₂)₁₀F, -CH₂CH₂(CF₂)₁₂F, -CH₂CH₂(CF₂)₁₄F, -CH₂CH₂(CF₂)₁₆F, -CH₂CH₂CH₂CF₃, -CH₂CH₂CH₂(CF₂)₂F, -CH₂CH₂CH₂(CF₂)₂H, -CH₂(CF₂)₄H and -CH₂CH₂(CF₂)₃H.
The groups represented by -CH₂CH₂-(CF₂)_m-CFR¹⁴-[OCF₂CF(CF₃)]_n-OC₃F₇ are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups. In the formula, the subscript "m" is 0 or 1, "n" is 0, 1, 2, 3, 4 or 5, and R¹⁴ is a fluorine atom or CF₃. Such fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxyfluoroalkylene groups represented by the formulae presented below: -CH₂CH₂CF(CF₃)-[OCF₂CF(CF₃)]_n-OC₃F₇, -CH₂CH₂CF₂CF₂-[OCF₂CF(CF₃)]_n-OC₃F₇.
The number-average molecular weight of the vinyl polymer used in the present invention may be between 3000 and 2 000 000 and more preferably between 5000 and 800 000.
A fluorinated vinyl polymer can be one of the polymers described in the examples of application WO 03/045337 .
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 are preferably volatile, chosen in particular from volatile silicone oils and volatile hydrocarbon-based oils, and mixtures thereof.
According to a specific embodiment, a silicone oil suitable for the invention can be cyclopentasiloxane.
According to another specific embodiment, a hydrocarbon-based oil suitable for the invention can be isododecane.
Vinyl polymers grafted with at least one unit derived from carbosiloxane dendrimer which can be particularly suitable for the present invention are the polymers sold under the names TIB 4-100, TIB 4-101, TIB 4-120, TIB 4-130, TIB 4-200, FA 4002 ID (TIB 4-202), TIB 4-220 and FA 4001 CM (TIB 4-230) by Dow Corning.
According to one particular form, the silicone polymer(s) are chosen from:

a silicone resin of MQ type of trimethylsiloxysilicate type;
a resin of MQ type of phenylalkylsiloxysilicate type;
a polypropylsilsesquioxane or t-propyl silsesquioxane resin (INCI name: Polypropylsilsesquioxane (and) Isododecane);
a vinyl polymer grafted with at least one unit derived from carbosiloxane dendrimer (INCI name: Acrylates / Polytrimethylsiloxy methacrylate).

According to one particular form of the invention, the silicone polymer is a polypropylsilsesquioxane or t-propyl silsesquioxane resin (INCI name: Polypropylsilsesquioxane (and) Isododecane).
Preferably, the composition according to the invention comprises at least one silicone polymer in a content, expressed as active material of polymer, of from 0.1% to 4% by weight, preferably from 0.2% to 3% by weight, relative to the weight of the composition.

ADDITIVES

The composition may also comprise additional cosmetic ingredients conventionally used in compositions intended for lip treatment. By way of examples, mention may particularly be made of active ingredients, for instance plant extracts which are preferably soluble in the composition, non-volatile, phenyl or non-phenyl silicone oils, which do not result in a single-phase mixture with the non-volatile oil or the mixture of non-volatile oils previously mentioned (conditions described in detail above), preservatives, antioxidants, sweeteners, fragrances, sunscreens, bactericides, liposoluble dyes, and also mixtures thereof.
Of course, a person skilled in the art will take care to choose the optional additional ingredients and/or the amount thereof so that the advantageous properties of the composition are not, or not substantially, detrimentally affected by the envisaged addition.
By way of illustration, the additive contents are those conventionally used in the field under consideration, and for example range from 0.01% to 5% by weight relative to the weight of the composition.
It should be noted that, if one of the additives is a non-volatile oil, or several of them, then the total content of non-volatile oils present in the composition advantageously remains within the ranges previously given in detail.
The packaging and application assembly 1 is used in the following way:
The assembly 1 being in closed configuration, the user shakes or inverts the assembly, in particular for the purpose of homogenizing the cosmetic product.
In doing so, product is projected through the through-orifices 9 of the dividing wall 8 and impregnates the application member 5 very locally at an apex 51 of its application surface.
After a few shaking movements, the user unscrews the applicator 4 and grasps said applicator 4 by the gripping portion 41 and separates it from the reservoir 3. In doing so, the application member 5 is extracted from the housing 7 and the application surface is accessible to the user who can then carry out the application.
In order to do this, the user brings the apex portion of the application member in contact with the application surface to be covered, for example a surface of the lips, in order to deposit a layer of cosmetic product thereon.
Where appropriate, the user can use a lateral portion of the application surface in order to tone down or spread the product.

Claims

Assembly (1) for packaging and applying a liquid cosmetic product comprising, on the one hand, a body (2) forming a reservoir (3) comprising a liquid cosmetic product (P) containing solid particles, in particular pigments and/or nacres and, on the other hand, an applicator (4) comprising an application member (5) that defines a convex application surface (50) having at least one apex (51); the body (2) which forms the reservoir (3) comprising a housing (7) capable of receiving the application member (5) and of which a dividing wall (8) with the reservoir has a plurality of through-orifices (9) in direct fluid communication with the reservoir (3), wherein the application member (5) is produced from an open-cell porous material,
characterized in that said through-orifices (9) are located only at at least one end wall of the housing (7) opposite a zone around the geometric apex (51) representing 10% of the total surface of the application surface of the application member (5), when said application member (5) is in place in the housing (7) of the body (2) which forms the reservoir.
Assembly according to Claim 1, characterized in that the orifices are located at an end wall of the housing corresponding to an absolute apex of the application member, preferably only at said end wall.
Assembly according to any one of claims 1 or 2, characterized in that the wall of the housing comprises a plurality of orifices uniformly distributed around the centre of the end wall.
Assembly according to any one of Claims 1 to 3, characterized in that the wall of the housing has a central orifice, located at the centre of the end wall.
Assembly according to any one of Claims 1 to 4, characterized in that all or some of the orifices have a substantially circular cross section.
Assembly according to any one of Claims 1 to 5, characterized in that the reservoir comprises at least one mixing element, in particular at least one mixing bead.
Assembly according to any one of Claims 1 to 6, characterized in that the application member has an application surface that is at least partially flocked, preferably completely flocked.
Assembly according to any one of Claims 1 to 7, characterized in that the applicator is configured to be fastened to the container when not in use, the application member being received in the housing.
Assembly according to any one of Claims 1 to 8, characterized in that the application surface has no surface capable of forming a space with the wall of the housing when the application member is received in the housing.
Assembly according to any one of Claims 1 to 9, characterized in that the application member has a conical general shape, in particular with a rounded or hemispherical tip.
Assembly according to any one of Claims 1 to 10, characterized in that the orifices are closed off by the application surface when the applicator is fastened to the container.
Assembly according to any one of Claims 1 to 11, characterized in that the application surface deforms at least partially against the wall of the housing when the applicator is fastened to the container, the application member being slightly compressed.
Assembly according to Claim 1 to 12, characterized in that the reservoir comprises a liquid cosmetic product which additionally comprises at least 70% by weight, relative to the weight of the composition, of at least one non-volatile oil or of a single-phase mixture of several non-volatile oils, the composition comprising at least one polar or non-polar non-volatile hydrocarbon-based oil; at least one mineral thickener; at least one nonionic silicone surfactant.