WO2025132142A1

WO2025132142A1 - Invert emulsion comprising pullulan, an apolar hydrocarbon-based oil, a silicone film-forming polymer and a dyestuff, and makeup process

Info

Publication number: WO2025132142A1
Application number: PCT/EP2024/086442
Authority: WO
Inventors: Sandrine FERNANDES; Sylvie Manet; Claire PRUDHON
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2023-12-20
Filing date: 2024-12-16
Publication date: 2025-06-26
Anticipated expiration: 2026-06-20
Also published as: FR3157183A1

Abstract

The present invention relates to a cosmetic composition for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, in the form of a water-in-oil emulsion comprising: - at least 3% by weight of pullulan; - at least 12% by weight of at least a first apolar hydrocarbon-based oil comprising from 8 to 16 carbon atoms; - at least one silicone film-forming polymer chosen from silicone resins, silicone acrylate copolymers, silicone acrylamide copolymers, and also mixtures thereof, - at least one dyestuff. The invention also relates to a makeup process in which this composition is applied to said keratin materials.

Description

INVERT EMULSION COMPRISING PULLULAN, AN APOLAR HYDROCARBON-BASED OIL, A SILICONE FILM-FORMING POLYMER AND A DYESTUFF, AND MAKEUP PROCESS

The present invention relates to a cosmetic makeup composition, notably for the skin and/or the lips, preferably the lips, in the form of an invert emulsion (i.e. a water-in-oil emulsion) comprising at least 3% by weight of pullulan, at least one particular hydrocarbon-based oil, at least one silicone film-forming polymer and at least one dyestuff. The invention also relates to a makeup process using such a composition.

Compositions intended for application to the skin or the lips, and which provide a matte finish after application, are well known in the cosmetics field and mostly have the feature of comprising high contents of volatile oils and/or fillers. The high content of volatile oil(s) makes it possible to further increase the content of solid particles in the deposit, such as fillers and pigments, once the composition has been applied and dried. As regards the fillers used in compositions providing a matte finish, organic particles are often found, notably polymeric particles such as nylon, polytetrafluoroethylene, polyethylene, silicone resins or elastomers, or else mineral particles such as kaolin or silica for example. These fillers enable, inter alia, part of the remaining oily compounds to be absorbed, whether they originate from the composition or from the support to which it is applied (sebum). With the high contents of volatile oils and of solid particles in compositions with a matte rendering, the content of nonvolatile oils is consequently greatly reduced in the deposit after application and drying of the composition. For this reason, matte compositions are generally considered by users to be sparingly or totally uncomfortable, once they have been applied, and also to cause a more or less pronounced sensation of dryness.

In addition to the color effect provided on the skin and/or the lips, it is also sought to improve the staying power and the transfer-resistance properties of the compositions. Specifically, poor staying power leads to visible premature removal of the deposit (for example, fading of the color), thus obliging the user to reapply makeup more often than desired in order to maintain appropriate coloring. It is also sought to limit the transfer of the composition onto another support (clothes, cups, etc.), which limits staining problems and contributes in the majority of cases toward maintaining good staying power of the deposit.

Improving the staying power of compositions is obtained by means of compositions which form a film after application. Such compositions generally contain volatile solvents which evaporate on contact with the skin or the lips, leaving behind a layer comprising waxes and/or film-forming polymers, pigments and fillers. Film-forming polymers are synthetic polymers, usually silicone or acrylic polymers. Thus, mention may be made of the use of silicone resins, for instance trimethyl siloxysilicate (INCI name) or polypropylsilsesquioxane (INCI name) resins, or resins which comprise silicone polymers such as silicone acrylate dendrimer copolymers (acrylates/polytrimethyl siloxymethacrylate copolymer - INCI name). Acrylic polymers such as acrylic acid/isobutyl acrylate/isobornyl acrylate copolymers are also used. However, these compositions are, themselves also, often considered less comfortable, or even uncomfortable, from a sensory point of view for consumers.

The search is therefore still on for makeup compositions that are more comfortable to wear, without any loss of staying power performance, and this being despite having amounts of silicone film-forming polymers that might be reduced relative to those found in the long-lasting makeup products on the market.

These and other problems are solved by the present invention, one subject of which is a cosmetic composition for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, in the form of a water-in-oil emulsion, comprising:
- at least 3% by weight of pullulan relative to the total weight of the composition;
- at least 12% by weight, relative to the total weight of the composition, of at least a first apolar hydrocarbon-based oil comprising from 8 to 16 carbon atoms;
- at least one silicone film-forming polymer chosen from silicone resins, silicone acrylate copolymers, silicone polyamides, and also mixtures thereof,
- at least one dyestuff.

The present invention also relates to a makeup process in which the abovementioned cosmetic composition is applied to human keratin materials, in particular the skin and/or the lips, preferably the lips.

The composition according to the invention has the advantage of being stable over time and of being easy to apply, without dewetting on application or on blotting. Moreover, the deposit obtained is precise, homogeneous, not runny and sparingly or not at all tacky.

The deposit does not migrate either into the wrinkles and fine lines, in particular around the lips.

Finally, the resulting deposit is matte to satiny, with good staying power. It is also comfortable, without leaving a feeling of dryness or tautness.

The composition according to the invention is thus in the form of a water-in-oil emulsion, or invert emulsion. In other words, the composition comprises an aqueous phase dispersed within the lipophilic phase, which constitutes the continuous phase of the emulsion.

The composition according to the invention is advantageously in the form of a liquid composition.

The term “liquid composition” means any composition which has one or more of the following features:

i) it flows under its own weight at room temperature (20°C) and at atmospheric pressure (1.013 x 10⁵ Pa);

ii) it is not solid at room temperature and at atmospheric pressure and a viscosity or consistency characterized by its hardness may be measured for same;

iii) it does not have any particular shape such as that which can be obtained by hot casting in a mold or container of a given shape.

Such compositions may thus be found notably in fluid, creamy, pasty or gel form.

Protocol for measuring the viscosity

The viscosity measurement is generally performed with a sample of composition at 25°C, at least 24 hours after its manufacture (storage at room temperature), using a Rheomat RM180 viscometer equipped with a No. 2, 3 or 4 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the composition (after which time stabilization of the viscosity and of the spin speed of the spindle are observed), at a shear rate of 200 rpm.

According to one embodiment, the composition according to the invention may have, at 25°C, a viscosity of between 2 and 20 Pa.s, preferably between 3 and 15 Pa.s.

PULLULAN

As indicated previously, the composition comprises pullulan.

Pullulan is a polysaccharide formed from maltotriose units, known under the name α(1,4)-α(1,6)-glucan. Three glucose units in maltotriose are connected via an α(1,4) glycoside bond, whereas the consecutive maltotriose units are connected to each other via an α(1,6) glycoside bond. It is produced from starch by the fungus Aureobasidium pullulans.

Pullulan is produced, for example, under the trade name Pullulan PF 20® by the Hayashibara Group in Japan, or under the trade name Aqua Beta® by the company Daiso, Co., Ltd, like the product sold under the name Pullulan Cosmetic Grade® by the company Hayashibara.

The composition according to the invention comprises at least 3% by weight of pullulan, expressed as active material, relative to the total weight of the composition. More particularly, the pullulan content is between 4% and 15% by weight, more particularly between 5% and 10% by weight, relative to the total weight of the composition.

FIRST HYDROCARBON-BASED OIL

The composition also comprises at least a first apolar hydrocarbon-based oil comprising from 8 to 16 carbon atoms.

The term “oil” means any water-immiscible compound that is in liquid form at room temperature and at atmospheric pressure.

The term “water-immiscible” means that the mixing of the same amount of water and oil, after stirring, does not result in a stable solution comprising only a single phase, at room temperature and atmospheric pressure. Observation is made by eye or using a phase-contrast microscope, if necessary, on 100 g of mixture obtained after sufficient stirring with a Rayneri blender to produce a vortex within the mixture (as a guide, 200 to 1000 rpm), the resulting mixture being left to stand, in a closed flask, for 24 hours at room temperature before observation.

The term “apolar hydrocarbon-based oil” means an oil chosen from hydrocarbons, that is to say from compounds comprising only carbon and hydrogen atoms.

The apolar hydrocarbon-based first oils that may be used in the context of the invention are more particularly chosen from linear or branched, preferably saturated, oils containing from 8 to 16 carbon atoms, and mixtures thereof.

Advantageously, these oils are volatile.

The term “volatile oil” means an oil with a nonzero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 2.66 Pa to 40 000 Pa, in particular ranging up to 13 000 Pa and more particularly ranging up to 1300 Pa (standard OCDE 104).

The apolar hydrocarbon-based oils may thus be chosen from linear alkanes comprising from 8 to 14 carbon atoms.

As examples of linear alkanes, in particular C8-C14 alkanes, mention may be made of n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12) and n-tridecane (C13), and mixtures thereof. Mention may notably be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97® and Parafol 14-97®, and also mixtures thereof. According to another embodiment, use may be made of a mixture of n-dodecane and n-tetradecane, and in particular the dodecane/tetradecane mixture sold by the company Biosynthis under the reference Vegelight 1214®. According to yet another embodiment, use may also be made of a mixture of volatile linear C9-C12 alkanes of INCI name: C9-12 Alkane, such as the product sold by the company Biosynthis under the reference Vegelight Silk®. According to yet another embodiment, use may be made of a mixture of n-undecane (C11) and of n-tridecane (C13) as obtained in Examples 1 and 2 of patent application WO 2008/155 059 (mixtures of different alkanes differing by at least one carbon) from the company Cognis and the product sold under the trade name Cetiol Ultimate® by the company BASF.

Mention may also be made of the alkanes described in the Cognis patent applications WO 2007/068 371. These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel oil or palm oil.

The hydrocarbon-based oils that may be used in the compositions according to the invention may be chosen from branched C8-C16 alkanes. Mention may notably be made of C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the Isopar® or Permethyl® trade names.

According to a particularly preferred embodiment, the first is chosen from isododecane, the mixture of linear C9-C12 alkanes (INCI name: C9-12 Alkane), and the mixture of n-undecane (C11) and n-tridecane (C13), and mixtures thereof.

Preferably, the content of apolar hydrocarbon-based first oil(s) represents from 12% to 40% by weight and preferably from 12% to 35% by weight relative to the total weight of the composition.

SILICONE FILM-FORMING POLYMER

As indicated previously, the composition according to the invention comprises at least one silicone film-forming polymer chosen from non-glycerolated silicone resins; glycerolated silicone resins; silicone vinyl copolymers, such as carbosiloxane dendrimer-grafted vinyl polymers, silicone acrylate copolymers; silicone polyamides; and also mixtures thereof.

Non-glycerolated silicone resin

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

The nomenclature of silicone resins (also known as siloxane resins) is known under the name “MDTQ”, the resin being described as a function of the various siloxane monomer units 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 bonded to just one oxygen atom in the polymer comprising this unit.
The letter "D" means a difunctional unit R1R2SiO_2/2 in which the silicon atom is bonded to two oxygen atoms.
The letter "T" represents a trifunctional unit of formula R1SiO_3/2.

In the units M, D and T defined previously, Ri, namely R1, R2 and R3, which may be identical or different, represent a hydrocarbon-based radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.
Lastly, the letter "Q" means a tetrafunctional unit SiO_4/2 in which the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.

Such resins are described, for example, in the Encyclopedia of Polymer Science and Engineering, 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.

Various silicone resins with different properties may be obtained from these different units, the properties of these polymers varying as a function of the type of monomer (or unit), the nature and number of the radical(s) Ri, the length of the polymer chain, the degree of branching and the size of the side chains.

As silicone resins that may be used in the compositions according to the invention, use may be made, for example, of silicone resins of MQ type, of T type or of MQT type.

MQ resins

As examples of silicone resins of MQ type, mention may be made of resins of siloxysilicate type, such as the alkylsiloxysilicates, arylsiloxysilicates or alkylarylsiloxysilicates, of formula [(R1)₃SiO_1/2]_x(SiO_4/2)_y (MQ units) in which x and y are integers ranging for example from 50 to 80, and such that the group R1 represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.

The silicone resin may be used alone or else in the form of a mixture in an oil, which may notably be chosen from the first and second oil(s) and also combinations thereof.

As examples of MQ-type silicone resins of Trimethylsiloxysilicate (INCI name) type, mention may be made of those sold under the reference SR1000 by the company General Electric, under the reference TMS 803 by the company Wacker, or else mixtures comprising same such as the products sold under the names KF-7312J (in cyclopentasiloxane) by the company Shin-Etsu, Silsoft 74 Fluid (in isododecane) by the company Momentive, Dowsil RSN-749 Resin (in cyclopentasiloxane), Dowsil 593 Fluid (in a dimethicone) by the company Dow Corning.

As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyl dimethylsiloxysilicate (INCI name: Silshine 151 sold by the company General Electric). The preparation of such resins is notably described in patent US 5 817 302.

T resins

As examples of silicone resins of type T, mention may be made of the polysilsesquioxanes comprising predominantly units of formula (RSiO_3/2)_x (T units) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes possibly also comprising Si-OH end groups. Thus, these resins comprise for example at least 80 mol% of T units.

Mention may be made of polymethylsilsesquioxanes, which are polysilsesquioxanes in which none of the methyl radicals is substituted with another group. Such polymethylsilsesquioxanes are described, for example, in US 5 246 694.

Preferably, use may be made of the Polymethylsilsesquioxane (INCI name) resins in which R represents a methyl group, for instance those sold by the company Wacker under the reference Resin MK, such as Belsil PMS MK, and by the company Shin-Etsu under the references KR-220L or else under the reference KR-251. Also suitable for use are polymethylsilsesquioxane resins as a mixture with solvents, for instance Granresin PMSQ-C9 (polymethylsilsesquioxane (and) C9-12 Alkane), and Granresin PMSQ-ID (polymethylsilsesquioxane (and) isododecane), from the company Grant Industries.

Among the silsesquioxane resins that may be used in the present invention, mention may also be made of those corresponding to silsesquioxane homopolymers and/or copolymers having a mean siloxane unit of general formula R1n SiO(4-n)/2, in which each R1 is a propyl group, in which more than 80 mol% of R1 represent a C3 to C10 alkyl group, n is a value from 1.0 to 1.4, and more than 60 mol% of the copolymer comprises R1SiO3/2 units. Since each R1 is a propyl group, these polymers are called polypropylsilsesquioxane resins (INCI name) or "t-propyl" silsesquioxane resins. These resins and the processes for producing them are described for example in US 8586013, US 2012/0301415 and US 2006/0292096.

Polypropylsilsesquioxane resins that are suitable for use in the present invention include those sold by Dow Corning under the names Dowsil 670 Fluid or Dowsil 680 ID Fluid, which are mixtures of polypropylsilsesquioxane with cyclopentasiloxane or isododecane respectively, or the product Dowsil MQ-1640 Flake Resin from Dow, comprising a mixture of trimethylsiloxysilicate and polypropylsilsesquioxane.

MQT resins

Resins comprising MQT units that are notably known are those mentioned in US 5 110 890.

A preferred form of resins of MQT type are MQT-propyl (also known as MQTPr) resins. Such resins that may be used in the compositions according to the invention are notably the resins described and prepared in patent application WO 2005/075 542.

The MQ-T-propyl resin preferably comprises the units:
(i) (R1₃SiO_1/2)_a
(ii) (R2₂SiO_2/2)_b
(iii) (R3SiO_3/2)_c and
(iv) (SiO_4/2)_d with
R1, R2 and R3 independently representing a hydrocarbon-based radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or alternatively a hydroxyl group, and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group; a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d = 1, with the proviso that more than 40 mol% of the groups R3 in the siloxane resin are propyl groups.

Preferably, the siloxane resin comprises the units:
(i) (R1₃SiO_1/2)_a
(iii) (R3SiO_3/2)_c and
(iv) (SiO_4/2)_dwith
R1 and R3 independently representing an alkyl group containing from 1 to 8 carbon atoms, R1 preferably being a methyl group and R3 preferably being a propyl group, a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55, a + b + c + d = 1, and a, b, c and d being mole fractions, with the proviso that more than 40 mol% of the groups R3 in the siloxane resin are propyl groups.

Glycerolated silicone resin

The composition according to the invention may also comprise at least one glycerolated silicone resin.

The glycerolated silicone resin comprises in its chemical structure one or more monoglycerol or polyglycerol groups.

In particular, the glycerolated silicone resin contains at least one organosiloxane unit of the type RR’R’’SiO_1/2 in which R, R’ and R’’, which may be identical or different, denote hydrocarbon-based radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group, and more particularly the glycerolated silicone resin contains at least one dimethylsiloxane unit R(CH₃)₂SiO_1/2,, comprising a hydrocarbon-based radical R containing a monoglycerol group.

The term “hydrocarbon-based radical” refers to a radical mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

The glycerolated silicone resin(s) according to the invention are preferably chosen from those of formula (1) below:
(R¹ ₃SiO_1/2)_a(R²(CH₃)₂SiO_1/2)_b(R³ ₃SiO_1/2)_c(R¹ ₂SiO_2/2)_d(R¹SiO_3/2)_e(SiO_4/2)_f (1)
in which:
- each R¹, which may be identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof;
- each R² is a mono- or poly-glycerol group of the general formula (2) below
-(CH₂)₂—C_lH_2l—O—(CH₂CH(OH)CH₂O)_iR⁴ (2), in which R⁴ is a substituted or unsubstituted monovalent hydrocarbon-based group or a hydrogen atom, and the indices l and i are integers satisfying the conditions 0 ≤ l ≤ 15 and
0 < i ≤ 5,
- each R³ is an identical or different group of general formula (3), (4), (5) or (6) below:
—(CH₂)₂—C_mH_2m—(SiOR¹ ₂)j—SiR¹ ₃ (3)
—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ ₃)_3−k1) (4)
—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ ₃)_3−k2)_3−k1 (5)
—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ _k3(OSiR¹ ₃)_3−k3)_3−k2)_3−k1 (6)
in which
- each R¹, which may be identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof;
- the indices m, j and k₁ to k₃ are integers that satisfy the following conditions: 0 ≤ m ≤ 5, 0 ≤ j ≤ 500, 0 ≤ k₁ ≤ 2, 0 ≤ k₂ ≤ 2 and 0 ≤ k₃ ≤ 2;
- the indices a, b, c, d, e and f are numbers that satisfy the following conditions: 0 ≤ a ≤ 400, 0 < b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0 < f ≤ 1000 and 0.5 ≤ (a+b+c)/f ≤ 1.5.

The glycerolated silicone resins according to the invention are described in patent application US 2020/0332065 from Shin-Etsu.

According to a particular embodiment, the glycerolated silicone resin(s) of formula (1) as defined above are chosen from those whose indices b and c satisfy the conditions 0 < b ≤ 30 and 0 ≤ c ≤ 30; and whose index i in the general formula (2) of the monoglycerol or polyglycerol group R² is an integer which satisfies the condition 0 < i ≤ 3.

According to a particular embodiment, the glycerolated silicone resin(s) of formula (1) are in solid form at 25°C when the index c satisfies the condition 0 < c ≤ 400 and R³ is a group of general formula (3) where the index j satisfies the condition 0 ≤ j ≤ 10.

According to a particular embodiment, the glycerolated silicone resin(s) have a weight-average molecular weight ranging from 1000 to 100 000.

The glycerolated silicone resin(s) are amphiphilic, i.e. they have two parts of different polarity. Generally, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by the value of their HLB (hydrophilic-lipophilic balance), the HLB being the ratio of the hydrophilic part to the lipophilic part in the molecule. The term “HLB” is well known to those skilled in the art and is described, for example, in “The HLB system. A Time-Saving Guide to Emulsifier Selection” (published by ICI Americas Inc.; 1984). The value of the HLB of the glycerolated silicone resins according to the invention preferably ranges from 0.1 to 15 according to the Griffin method.

The glycerolated silicone resin(s) may be obtained via a preparation process comprising the step of hydrosilylation
A) of a silicone resin containing a hydrosilyl group of formula (7) below.
(R¹ ₃SiO_1/2)_aH_nR¹ _3-nSiO_1/2)_b+c(R¹ ₂SiO_2/2)_d(R¹SiO_3/2)_e(SiO_4/2)_f (7)
in which:
- each R¹, which may be identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof;
- the indices a, b, c, d, e and f are integers that satisfy the conditions 0 ≤ a ≤ 400, 0 < b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0 < f ≤ 1000 and 0.5 ≤ (a+b+c)/f ≤ 1.5;
- n is an integer which satisfies the condition 1 ≤ n ≤ 3, with
B) one or more compounds which are chosen from the alkenyl-terminated compounds of general formulae (8), (9), (10), (11) and (12) below.
CH₂═CH-C_lH_2l-O-(CH₂CH(OH)CH₂O)iR⁴ (8)
CH₂═CH-C_mH_2m-(SiOR¹ ₂)_j-SiR¹ ₃ (9)
CH₂═CH—C_mH_2m—SiR¹ _k1—(OSiR¹ ₃)_3-k1 (10)
CH₂═CH—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹3)_3-k2)_3-k1 (11)
CH₂═CH—C_mH_2m—SiR¹k¹—(OSiR¹ _k2(OSiR¹ _k3(OSiR¹ ₃)_3-k3)_3-k2)3-k1(12)
in which
- R⁴ is a substituted or unsubstituted monovalent hydrocarbon-based group or a hydrogen atom,
- the indices l and i are integers satisfying the conditions 0 ≤ l ≤ 15, 0 < i ≤ 5;
- the indices m, j and k₁ to k₃ are integers which satisfy the conditions 0 ≤ m ≤ 5, 0 ≤ j ≤ 500, 0 ≤ k₁ ≤ 2, 0 ≤ k₂ ≤ 2 and 0 ≤ k₃ ≤ 2; said silicone resin containing a hydrosilyl group of formula (7) reacting with at least one compound of formula (8).

The hydrosilylation reaction is performed in the presence, for example, of a platinum or rhodium catalyst. The preferred ranges for b, c, d, e, f, R⁴, l, m, i, j and k₁ to k₃ are as defined above.

Silicone resin containing a hydrosilyl group used as starting material.

The silicone resin containing a hydrosilyl group of formula (7) may be in solid or liquid form at 25°C, preferably in solid form. In terms of implementation, the resin is preferably diluted with an organic solvent. The use of a solvent having a boiling point higher than the reflux temperature during the hydrolysis is preferred.

Among the examples of organic solvents used for the dilution, mention may be made of cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; organic solvents of ketone type such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. From the point of view of storage stability and absence of volatility, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

The silicone resin containing a hydrosilyl group of formula (7) is prepared by:
i) hydrolyzing, in the presence of an acid catalyst, a mixture of one or more compounds chosen from the organosilicon compounds of general formulae (13) and (14) below, one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16) below and one or more compounds chosen from the hydrolyzable silanes of general formula (17) below, the partial hydrolysis condensates of these hydrolyzable silanes and the metal salts of these hydrolyzable silanes:
R¹ ₃SiOSiR¹ ₃ (13)
R¹ ₃SiX¹ (14)
H_nR¹ _(3-n)SiOSiR¹ _(3-n)H_n (15)
H_nR¹ _(3-n)SiX² (16)
in which each R¹, which may be identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof; X¹ and X² are hydrolyzable functional groups; and n satisfies the condition 1 ≤ n ≤ 3;
SiX³ ₄ (17) in which X³ is a hydrolyzable functional group);
ii) neutralizing the reaction system by adding a basic catalyst in an amount greater than the molar equivalent of the acid catalyst, and
iii) subsequently performing condensation.

In the general formulae (13), (14), (15) and (16), the examples and the preferred range for R¹ are the same as those mentioned above.

In the general formula (14), X¹ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the point of view of availability and the rate of hydrolysis, a methoxy group, an ethoxy group or a chlorine atom is preferred.

In the general formula (16), X² is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the point of view of availability and the rate of hydrolysis, a methoxy group, an ethoxy group or a chlorine atom is preferred.

In the general formula (17), X³ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, an alkoxy group is preferred; from the point of view of availability and the rate of hydrolysis, a methoxy group or an ethoxy group is preferred. The hydrolyzable groups X³ on the molecule may be similar or different groups.

Examples of organosilicon compounds of general formula (13) include 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,3-hexaphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3,3-hexavinyldisiloxane, 1,1,1,3,3-pentavinylmethyldisiloxane, 1,1,1,3,3-n-octylpentamethyldisiloxane, 1,1,1,3,3-chloromethylpentamethyldiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane. Among these, 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane are preferred.

Examples of organosilicon compounds of general formula (14) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinylchlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane and triphenylethoxysilane. Among these, trimethylchlorosilane and trimethylethoxysilane are preferred.

Examples of organosilicon compounds containing a hydrosilyl group of general formula (15) include 1,1,3,3-tetramethyldisiloxane and 1,1,1,3,3-pentamethyldisiloxane. 1,1,3,3-Tetramethyldisiloxane is particularly preferred.

In addition, in general formulae (15) and (16), n satisfies the condition 1 ≤ n ≤ 3. In general formula (15), the “n” associated with the hydrogen atom and with the R¹ bonded to one silicon atom and the “n” associated with the hydrogen atom and with the R¹ bonded to the other silicon atom may be identical or different.

Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

Examples of hydrolyzable silanes of general formula (17) include tetrachlorosilane, tetramethoxysilane and tetraethoxysilane. Examples of partial hydrolysis condensates of the hydrolyzable silane include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of the hydrolyzable silane include water glass, sodium silicate, and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

In the present invention, to a mixture of one or more compounds chosen from the organosilicon compounds of general formulae (13) and (14), one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16) and one or more compounds chosen from the hydrolyzable silanes of general formula (17), condensates of partial hydrolysis of these hydrolyzable silanes and metal salts of these hydrolyzable silanes may be added prior to hydrolysis under an acid catalyst, or a mixture of one or more compounds chosen from the organosilicon compounds of general formula (18) or of general formula (19) may be added after such hydrolysis and prior to the subsequently described rehydrolysis:
R¹SiX⁴ ₃ (18); R¹ ₂SiX⁵ ₂ (19) where each R¹ is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof; X⁴ and X⁵ are hydrolyzable functional groups.

In the general formulae (18) and (19), the examples and the preferred ranges for R¹ are the same as those mentioned above.

In the general formula (18), X⁴ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the point of view of availability and the rate of hydrolysis, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X⁴ on the same molecule may be similar or different.

In the general formula (19), X⁵ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the point of view of availability and the rate of hydrolysis, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X⁵ on the same molecule may be similar or different.

Examples of silicon compounds of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, triopropyltrimethoxysilane and methyltrichlorosilane. Among these, methyltrimethoxysilane, methyltriethoxysilane and methyltrichlorosilane are preferred.

Examples of silicon compounds of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropropyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane and dimethyldichlorosilane. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldichlorosilane are preferred.

A specific example of a process for preparing the silicone resin containing a hydrosilyl group of that is used as raw material in the present invention is described. A solvent (in particular an organic solvent) and a hydrolysis raw material (a mixture of one or more compounds chosen from organosilicon compounds of general formulae (13) and (14), one or more compounds chosen from organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16), and one or more compounds chosen from the hydrolyzable silanes of general formula (17), the partial hydrolysis condensates of these hydrolyzable silanes and the metal salts of these hydrolyzable silanes) are loaded into a reactor, an acid is added as catalyst, and water is added dropwise with stirring. It is also possible in this case to add the organic solvent after the dropwise addition of the water has been completed. Since the hydrolysis is preferably performed under acidic conditions, the addition of an acid catalyst is essential.

The temperature during the dropwise addition of water is preferably between 0 and 80°C, and more preferentially between 0 and 50°C. By keeping the temperature within this range, the heat of reaction of the hydrolysis reaction on the hydrolysis starting material in the system can be kept low. The amount of water added dropwise, expressed as a mole ratio per mole of hydrolyzable functional groups (alkoxy groups, etc.) is between 0.6 and 2, and preferably between 1.0 and 1.8. By keeping the amount of water added within this range, the deactivation of the hydrosilyl groups can be further suppressed.

In order to suppress a decrease in the reaction rate due to the retention and increase of the viscosity of the uniform reaction system during the hydrolysis reaction, it is preferable to use an organic solvent as solvent in the hydrolysis reaction. It is also desirable to use a solvent having a boiling point higher than the reflux temperature during the hydrolysis.

As examples of organic solvents, mention may be made of cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; organic solvents of ketone type such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane.

In certain cases, an alcoholic solvent of 1 to 10 carbon atoms may be used concomitantly. Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. Since alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of a long-chain alcoholic solvent limits the rate of the hydrolysis reaction. Consequently, methanol, ethanol, 1-propanol and 2-propanol are particularly preferred.

The solvent used is included in an amount, relative to the overall reaction system, of from 1% to 80% (here and below, "%" refers to the percentage by weight), and in particular from 5% to 50%. Within this range, the reaction system remains uniform and the reaction takes place efficiently.

Examples of acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid and citric acid. The acid catalyst can be used in a small amount, an amount of the order of 0.001% to 10% of the overall reaction system being preferred.

After having added water dropwise as mentioned above, the hydrolysis reaction is performed by heating the system to a temperature of between 50 and 150°C, preferably between 80 and 120°C, for about 2 to 8 hours. During this time, by performing the reaction at a temperature below the boiling point of the organic compound containing hydrosilyl groups used, deactivation of the hydrosilyl groups may be further suppressed.

After the hydrolysis has been performed in this manner on the above hydrolysis starting material in the presence of an acid catalyst, the system is cooled to a temperature of between 10 and 100°C, preferably between 10 and 60°C, more preferably between 10 and 30°C, and even more preferably to 25°C.

After the above hydrolysis, the system is neutralized between 10°C and 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate or an alkali metal hydroxide. At this time, by using a strong basic catalyst and a weak basic catalyst together, the deactivation of the hydrosilyl group is suppressed and the condensation reaction of the organosilicon resin is further promoted. Among the examples of such highly basic catalysts, mention may be made of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate and sodium bicarbonate. With respect to combinations of a strong basic catalyst with a weak basic catalyst, from the point of view of the ease of obtaining a high molecular weight, a combination of sodium hydroxide and calcium carbonate is desirable. With this combination, the molecular weight increases sufficiently, which makes it possible to more reliably obtain a high molecular weight organosilicon resin containing hydrosilyl groups.

The basic catalyst must be used in an amount greater than the molar equivalent of the acid catalyst. The fact of performing the neutralization with an amount of basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, which results in an increase in the molecular weight and makes it possible to obtain a high molecular weight organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents of the acid catalyst. Adjusting the amount of addition within this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, which makes it possible to obtain a resin of target molecular weight.

After neutralization, the alcohols formed, the solvent and the excess water may be expelled by heating to between 95 and 120°C under normal or reduced pressure. Then, after confirmation that the alcohols formed, the solvent and the excess water have been expelled, the condensation reaction is performed by heating between 120 and 150°C for about 2 to 5 hours. An organosilicon resin containing a hydrosilyl group is thus obtained.

In the process described above for preparing a silicone resin containing a hydrosilyl group, the ratio of the combined molar amount of the compounds of general formulae (13), (14), (15) and (16) to the molar amount of SiO_4/2 units in the compound of general formula (17), expressed as the mole ratio ((13)+(14)+(15)+(16)):(19) is preferably from 0.3:1 to 2:1, and more preferably from 0.6:1 to 1.3:1.

In addition, the ratio of the combined molar amount of the compounds of general formulae (13) and (14) to the combined molar amount of the compounds of general formulae (15) and (16), expressed as the mole ratio ((13)+(14))/((15)+(16)), is preferably from 0.3:1.0 to 2.0:1.0, and more preferably from 0.6:1.0 to 1.3:1.0. By setting the values within these ranges, the amount of hydrosilyl groups included in the organosilicon resin containing hydrosilyl groups can be quantitatively varied more precisely. In the present invention, by thus varying the amounts in which the compounds of general formulae (15) and (16) are loaded, it is possible to vary quantitatively the amount of hydrosilyl groups included on the organosilicon resin.

In the process described above for preparing a silicone resin containing hydrosilyl groups, after having performed the hydrolysis, in the presence of an acid catalyst, a mixture of one or more compounds chosen from organosilicon compounds of general formulae (13) and (14) with one or more compounds chosen from the hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, it is also possible to add gradually, dropwise, one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group, of general formulae (15) and (16).

Next, a rehydrolysis is performed. At this stage, the rehydrolysis reaction is preferably performed by heating to a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example to a temperature preferably between 40°C and 150°C, and more preferably between 40°C and 120°C, for about 2 to 8 hours. When the reaction is performed in this temperature range, deactivation of the hydrosilyl groups can be further suppressed.

In the process for preparing the silicone resin containing hydrosilyl groups, the reaction of formula (20) below, in which some of the hydrosilyl groups become deactivated, may take place:
SiO_1/2H_n’R3-n’ (M units) + -Si-OH -> -Si-O-SiO_1/2H_n’-1R_3-n’ (D units) (20)
in which R is a monovalent hydrocarbon-based group of 1 to 10 carbon atoms, and n’ is an integer from 1 to 3.

However, by suitably setting the order in which the raw materials are added, that is to say by hydrolyzing a mixture of one or more compounds chosen from organosilicon compounds of general formulae (13) and (14) with one or more compounds chosen from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, and by then adding one or more compounds chosen from the organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16) and by performing a rehydrolysis, the above reaction (20) can be kept to a minimum. This reaction can be further suppressed by astutely modifying the amounts in which the raw materials are added and the type of catalyst used.

The amount of hydrosilyl groups included in the organosilicon resin containing hydrosilyl groups which is thus obtained is readily adjustable, and it is even possible to introduce a large amount of hydrosilyl groups by varying the amount of the organosilicon compound containing hydrosilyl groups which is loaded. Moreover, by varying the amount of hydrolysis starting materials used, the type and amount of acid catalyst added, the reaction temperature and time, the amount of solvent added and the method of addition, the molecular weight range, the shape and other features of the organosilicon resin can be adjusted, which makes it possible to prepare an organosilicon resin containing hydrosilyl groups for the intended application.

The silicone resin containing a hydrosilyl group obtained as described above has the mean formula (7) above and is composed of Q units (SiO_4/2) and M units ((R¹ ₃SiO_1/2) and (H_nR¹ _3-nSiO_1/2)) as essential constituents, and also D units (R¹ ₂SiO_2/2) and T units (R¹SiO_3/2) as optional constituents. It may be in the form of a solid or a liquid at 25°C, although from the point of view of the formability of the film, it is preferably a solid. Among the examples, mention may be made of MQ resins, MTQ resins, MDQ resins and MDTQ resins. The weight-average molecular mass is preferably between 2000 and 30 000, although the range from 3000 to 15 000 is more preferred from the point of view of performance and ease of performing operations such as filtration. The weight-average molecular mass can be determined as the weight-average molecular mass equivalent to polystyrene in gel permeation chromatography (GPC).

Process for preparing the glycerolated silicone resin

A specific example of a process for preparing the glycerolated silicone resin according to the invention is described below.

As mentioned above, the glycerolated silicone resin according to the invention may be obtained via the step of hydrosilylation:
(A) of a silicone resin containing a hydrosilyl group of mean formula (7) below:
(R¹ ₃SiO_1/2)_a(H_nR¹ _3-nSiO_1/2)_b+c(R¹ ₂SiO_2/2)_d(R₁SiO_3/2)e(SiO_4/2)_f (7)
in which:
- each R¹ is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof;
- the indices a, b, c, d, e and f are integers which satisfy the conditions 0 ≤ a ≤ 400, 0 < b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0 < f ≤ 1000 and 0.5 ≤ (a+b+c)/f ≤ 1.5;
- n is an integer which satisfies the condition 1 ≤ n ≤ 3, with
(B) one or more compounds which are chosen from the alkenyl-terminated compounds of general formulae (8), (9), (10), (11) and (12) below
CH₂=CH-C_lH_2l-O-(CH₂CH(OH)CH₂O)iR⁴ (8)
CH₂=CH-C_mH_2m-(SiOR¹ ₂)_j-SiR¹ ₃ (9)
CH₂=CH—C_mH_2m—SiR¹ _k1—(OSiR¹ ₃)_3-k1 (10)
CH₂=CH—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ ₃)_3-k2)3-k1 (11)
CH₂=CH—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ _k3(OSiR¹ ₃)_{3-k3)3-k2)3-k1} (12)
in which
- R⁴ is a substituted or unsubstituted monovalent hydrocarbon-based group or a hydrogen atom,
- the indices l and i are integers satisfying the conditions 0 ≤ l ≤ 15 and 0 < i ≤ 5;
- the indices m, j and k₁ to k₃ are integers which satisfy the conditions 0 ≤ m ≤ 5, 0 ≤ k₁ ≤ 2, 0 ≤ k₂ ≤ 2 and 0 ≤ k₃ ≤ 2; said silicone resin comprises a compound of general formula (8).

The organosilicon resin containing hydrosilyl groups of mean composition formula (7) and the compound having terminal alkenyl groups of general formula (8), (9), (10), (11) or (12) are mixed in a mole ratio, expressed as hydrosilyl groups/terminal unsaturated groups, which is preferably from 0.5 to 2.0, and more preferentially from 0.8 to 1.2.

The addition reaction is preferably performed in the presence of a platinum or rhodium catalyst. Specific examples include chloroplatinic acid, chloroplatinic acid modified with an alcohol, and chloroplatinic acid-vinylsiloxane complexes. When an excessive amount of catalyst is included, discoloration of the sample occurs, and thus the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

Moreover, if necessary, the addition reaction can be performed in the presence of an organic solvent. Among the examples of organic solvents, mention may be made of cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; solvents of ketone type such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. From the point of view of reactivity, ethanol, 1-propanol and 2-propanol are preferred.

The amount of solvent used is preferably from 1% to 80%, and more preferably from 5% to 50%, of the overall reaction system. In the above range, the reaction system is kept uniform and the reaction takes place efficiently.

The conditions for the addition reaction are not particularly limited, although reflux heating at a temperature of between 50 and 150°C, in particular between 80 and 120°C, for about 1 to 10 hours is preferred.

After the addition reaction, the step of removing the rhodium or platinum catalyst used with activated carbon can be included. The amount of activated carbon used is preferably from 0.001% to 5.0%, and notably from 0.01% to 1.0%, of the overall system. By setting the amount of activated carbon in this range, the discoloration of the sample can be better suppressed.

After the addition reaction, if necessary, the step of removing the remaining hydrosilyl groups can be included. In particular, in cases where use in applications such as cosmetic preparations is intended, there is a possibility that these hydrosilyl groups become deactivated over time due to dehydrogenation reactions, which poses a problem from the point of view of safety. It is therefore preferable to include a step of maintaining the hydrosilyl groups.

An example of a step for removing hydrosilyl groups is the process of hydrolyzing the unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate or an alkali metal hydroxide, followed by neutralization by the addition of an amount of acid catalyst equal to the molar equivalent of the basic catalyst. Specific examples of the basic catalyst include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide; and weak basic catalysts such as sodium carbonate, calcium carbonate, and sodium bicarbonate. From the point of view of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, sodium hydroxide being particularly preferred. Among the acid catalysts, mention may be made of hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid and citric acid. In general, instead of using the acid or base alone, it is preferable to use them with water and heat them to a temperature not greater than the boiling point of water.

After the addition reaction, if necessary, a deodorization step for reducing the odor can be included. When use in applications such as cosmetic preparations in particular is intended, because the product acquires an odor over time, it is preferable to include a deodorization step. The mechanism for deodorizing common polyether-modified silicones can be explained as follows. When an addition reaction between a polyether etherified with allyl groups and a hydrogenopolyorganosiloxane is performed in the presence of a platinum catalyst, the allyl groups rearrange internally in the form of side reactions, forming a polyether etherified with propenyl groups. This propenyl-etherified polyether has no reactivity with the hydrogenopolyorganosiloxane, and thus remains in the system as an impurity. It is believed that when water acts on this propenyl-etherified polyether, the propenyl ether hydrolyses, giving rise to propionaldehyde, which gives off an unpleasant odor. It is known that the above hydrolysis reaction is further promoted in the presence of an acid catalyst. Consequently, when the polyether-modified silicone is used in a water-based cosmetic preparation, due to oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the hydrolysis reaction described above and giving rise to the appearance of a bad odor.

Typical examples of the deodorization step include two approaches. The first is that in which, by adding an acid catalyst to the solution after the addition reaction, all the propenyl ether remaining in the system is hydrolyzed and the propionaldehyde which forms is removed by strip purification (JP No. 2137062).

Specific examples of the acid catalyst used in the first approach include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid and citric acid. These acids are used in combination with water. In cases where it is necessary to remove the acid which has been used, it is preferable to use an acid with a low boiling point, such as hydrochloric acid, formic acid, acetic acid or trifluoroacetic acid. Similarly, from the point of view of the effectiveness of the treatment, it is preferable to use a strong acid such as hydrochloric acid or trifluoroacetic acid.

The treatment temperature is preferably set at 80°C or less so as to avoid oxidation of the hydrophilic groups. The amount of acidic aqueous solution added is preferably set at from 0.1% to 100% relative to the organosilicon resin modified with organic groups. The use of 5% to 30% is more preferred.

From the point of view of productivity, the process consisting in adding an aqueous solution to the post-reaction solution so as to adjust the pH to 7 or less and in performing a strip purification after stirring with heating is preferred. The purification of the strip can be performed at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. In order to efficiently purify the strip under these temperature conditions, it is preferable to perform this operation under reduced pressure; when it is performed at normal pressure, the operation is preferably performed under a stream of an inert gas, such as nitrogen or argon.

The second approach is that in which, by adding hydrogen to the solution after the addition reaction, the unsaturated double bonds are alkylated (subjected to a hydrogenation reaction) and the formation of propionaldehyde over time is controlled in a stable manner (patent US 5 225 509; JP-A H07-330907).

The hydrogenation reactions comprise methods involving the use of hydrogen and methods involving the use of metal hydrides, and there are also homogeneous reactions and heterogeneous reactions. These methods can be used alone but it is also possible to use them in combination. However, given the advantage that there is no trace of catalyst used in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is preferred.

The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron and others, in the uncombined form or in the compound form. In this case, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support may be, for example, activated carbon, silica, silica-alumina, alumina or zeolite. These catalysts can be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. Moreover, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is performed with an acidic aqueous solution.

It is preferable to perform the hydrogenation reaction at a pressure generally between 1 and 100 MPa and between 50°C and 200°C. The hydrogenation reaction can be performed batchwise or continuously. In the case of a batch process, the reaction time depends, for example, on the amount of catalyst and on the temperature, but it is generally between 3 and 12 hours. The hydrogen pressure can be adjusted to an appropriate fixed pressure. The end point of the hydrogenation reaction is the point at which the hydrogen pressure has stopped changing, and it can therefore be determined by carefully monitoring a pressure gauge.

The amount of aldehyde included in the glycerolated silicone resin which has been purified by this acid treatment and this hydrogenation treatment can be set to 70 ppm or less, preferably to 20 ppm or less, and more preferably to 10 ppm or less.

It is also possible to combine the two types of deodorization steps mentioned above. In the approach which involves an acid treatment, decomposition and removal of the aldehyde compound is possible, but as there is a limit to the complete removal of the unsaturated double bonds, the formation of odorous aldehyde from this cannot be completely suppressed. In the approach which involves a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound which is formed as a result of this. However, the aldehyde condensate which is formed with the condensation of a portion of the aldehyde remains in the system even after such a treatment has been performed and the removal by strip purification is also difficult. Consequently, by alkylating the unsaturated double bonds that remain when the solution following the addition reaction is subjected to hydrogenation, and then decomposing the aldehyde condensate in the system by adding an acid catalyst, complete deodorization is possible (WO 2002/05588).

The weight-average molecular mass of the glycerolated silicone resin of mean formula (1) preferably ranges from 1000 to 100 000; from the point of view of performance and ease of operations such as filtration, the weight-average molecular mass preferentially ranges from 3000 to 50 000. Here and below, the weight-average molecular weight can be determined as the weight-average molecular weight equivalent to polystyrene in gel permeation chromatography (GPC).

The glycerolated silicone resin according to the invention is in a form at 25°C which may be solid or liquid; from the point of view of film formability, it is preferably solid.

In particular, the glycerolated silicone resin according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b ≤ 30 and 0 ≤ c ≤ 30, the index i in the general formula (2) is an integer which satisfies the condition 0 < i ≤ 3 and the index j in the general formula (3) satisfies the condition 0 ≤ j ≤ 10 is in the form of a solid at 25°C and preferably has a weight-average molecular mass which preferably ranges from 1000 to 100 000 and more preferentially from 3000 to 50 000.

The glycerolated silicone resins according to the invention have a hydrophilic-lipophilic balance (HLB), as determined by Griffin's formula, preferably ranging from 0.1 to 15, and more preferably from 1.0 to 8.0.

According to a preferred form, the composition of the invention comprises at least one glycerolated silicone resin of formula (1) of (3-glyceroxypropyl) dimethylsiloxy trimethylsiloxysilicate type corresponding to formula (21) below:

[(CH₃)₃SiO_1/2]_a [R(CH₃)₂SiO_1/2]_b(SiO_4/2)_f (21)
in which
- R denotes the 3-glyceroxypropyl group of structure -C₃H₆OCH₂-CH(OH)CH₂OH;
- the indices a, b and f are integers which satisfy the conditions 0 ≤ a ≤ 400, 0 < b ≤ 30, 0 < f ≤ 1000 and 0.5 ≤ (a+b)/f ≤ 1.5.

According to a particularly preferred form, the (3-glyceroxypropyl) dimethylsiloxy trimethylsiloxysilicate glycerolated silicone resin of formula (21) is in the form of a solution in at least one volatile oil, more particularly chosen from hydrocarbon-based oils, silicone oils and mixtures thereof.

Preferably, the composition according to the invention comprises, as silicone resin, at least one non-glycerolated silicone resin chosen from alkylsiloxysilicate, arylsiloxysilicate, alkylarylsiloxysilicate, polysilsesquioxane, and also mixtures thereof; more particularly from the non-glycerolated silicone resins having the following INCI names: Trimethyl siloxysilicate, Phenylpropyldimethyl siloxysilicate, Polymethylsilsesquioxane, Polypropylsilsesquioxane, and also mixtures thereof.

Vinylsilicone copolymers

The term “vinyl polymer” means any polymer comprising a main chain (or backbone) formed from at least one hydrocarbon-based monomer of the type R₁R₂C=CR₃R₄ comprising at least one ethylenic double bond, where R₁, R₂, R₃ and R₄, which may be identical or different, denote a hydrogen atom or a hydrocarbon-based group, notably at least one monomer chosen from acrylic acid, methacrylic acid and esters thereof.

The term “hydrocarbon-based monomer or group” means any molecule constituted of carbon and hydrogen atoms, and possibly of oxygen or nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

Preferentially, the film-forming vinylsilicone polymer(s) are chosen from carbosiloxane dendrimer-grafted vinyl polymers, copolymers including (meth)acrylic groups and polydimethylsiloxane groups, and mixtures thereof.

Carbosiloxane dendrimer-grafted vinyl polymers

A vinyl polymer that is suitable for preparing a composition according to the invention comprises at least one carbosiloxane dendrimer-based unit. The vinyl polymer has a vinyl backbone (which is thus hydrocarbon-based) and at least one side chain, which comprises a carbosiloxane dendrimer-based unit having a carbosiloxane dendrimer structure.

In the context of the present invention, the term “carbosiloxane dendrimer structure” represents a molecular structure containing branched groups of high molecular masses, said structure having high regularity in the radial direction starting from the bond to the backbone. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Japanese patent application JPH11001530.

A vinyl polymer according to the invention may contain carbosiloxane dendrimer-based units that may be represented by the following general formula (I):

(I)

in which:

- R¹ represents an aryl group containing from 5 to 10 carbon atoms or an alkyl group containing from 1 to 10 carbon atoms;

- Xⁱ represents a silylalkyl group which, when i = 1, is represented by formula (II):

(II)

in which:

. R¹ is as defined above in the formula (I),

. R² represents an alkylene radical of 2 to 10 carbon atoms,

. R³ represents an alkyl group of 1 to 10 carbon atoms,

. Xⁱ⁺¹ is chosen from: a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 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

. aⁱ is an integer from 0 to 3;

- Y represents a radically polymerizable organic group chosen from:

. organic groups containing 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 of 1 to 10 carbon atoms; and

- R⁵ represents an alkylene group of 1 to 10 carbon atoms, such as a methylene, ethylene, propylene or butylene group, the 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 of 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 of 1 to 10 carbon atoms;

- R⁸ represents an alkylene group of 1 to 10 carbon atoms, such as a methylene, ethylene, propylene or 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 containing from 5 to 10 carbon atoms or an alkyl group containing 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 containing from 2 to 10 carbon atoms, notably 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.

A vinyl polymer that is suitable for use in the present invention, containing at least one carbosiloxane dendrimer-based unit, has a molecular side chain containing a carbosiloxane dendrimer structure, and may be the product of polymerization of:

(A) from 0 to 99.9 parts by weight of a vinyl monomer; and

(B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing a radically polymerizable organic group, represented by general formula (I) as defined above.

The monomer of vinyl type which is the component (A) in the vinyl polymer having at least one carbosiloxane dendrimer-based unit 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 lower analog alkyl methacrylate; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate or a higher-analog methacrylate; vinyl acetate, vinyl propionate or a vinyl ester of a lower analog fatty acid; vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate or an ester of a higher analog fatty acid; 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 may 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, trimethylolpropanetrioxyethyl methacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups containing divinylbenzene groups on both ends, or similar silicone compounds containing unsaturated groups.

A carbosiloxane dendrimer, which is the component (B), can be represented by the formula (I) as defined above. Preferably, the group Y of formula (I) may be an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl 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.

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 formula (II); and

. R¹² is H, an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms.

According to one embodiment, a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit may comprise a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer-based unit corresponding to one of the formulae:

or

According to a preferred mode, a vinyl polymer bearing at least one carbosiloxane dendrimer-based unit used in the invention comprises at least one butyl acrylate monomer.

The vinyl polymer comprising the carbosiloxane dendrimer may be obtained via the process described for synthesizing a branched silalkylene siloxane described in Japanese patent application JPH111530, or else may correspond to one of the polymers described in the examples of patent application EP963751.

According to one embodiment, a vinyl polymer may also comprise at least one organofluorine group. Structures in which the polymerized vinyl units constitute the backbone and carbosiloxane dendritic structures and also organofluorine groups are attached to side chains are particularly preferred. The organofluorine groups may be obtained by replacing all or some of the hydrogen atoms of C1-C20 alkyl groups, and also of C6-C22 alkyloxyalkylene groups, with fluorine atoms.

A fluorinated vinyl polymer may be one of the polymers described in the examples of patent application WO 2003/045 337. The carbosiloxane dendrimers may be prepared using the process for preparing siloxane/silalkylene branched copolymers described in EP 1 055 674.

According to a preferred embodiment, a vinyl polymer grafted in the sense of the present invention may be conveyed in an oil or a mixture of oils, which is/are in particular preferably volatile, chosen from silicone oils and hydrocarbon-based oils, and mixtures thereof.

According to one particular embodiment, a silicone oil that is suitable for use in the invention may be cyclopentasiloxane.

According to another particular embodiment, a hydrocarbon-based oil that is suitable for use in the invention may be isododecane.

Preferably, the vinyl polymer grafted with at least one carbosiloxane dendrimer-based unit is a copolymer having the INCI name: Acrylates / Polytrimethylsiloxy-methacrylate Copolymer.

Such copolymers are sold, for example, under the names Dowsil FA 4002 ID® Silicone Acrylate, Dowsil FA 4012 ID® Silicone Acrylate Dowsil FA 4001 CM® Silicone Acrylate, Dowsil FA 4003 DM® Silicone Acrylate and Dowsil FA 4004 ID® Silicone Acrylate by the company Dow Corning.

Silicone acrylate copolymers

The vinylsilicone polymer may also be chosen from copolymers including (meth)acrylic groups and polydimethylsiloxane groups.

In the present patent application, the term “copolymer including (meth)acrylic groups and polydimethylsiloxane groups” means a copolymer obtained from (a) one or more (meth)acrylic acid or (meth)acrylic acid ester monomers and (b) one or more polydimethylsiloxane (PDMS) chains.

Thus, the monomer (a) may be chosen, for example, from acrylic acid, methacrylic acid, esters thereof and mixtures of these monomers. Esters that may be mentioned include the following monomers; acrylate, methacrylate. According to a preferred embodiment of the invention, the monomers in ester form are more particularly chosen from linear or branched, preferably C₁-C₂₄ and better still C₁-C₂₂ alkyl acrylates and methacrylates, the alkyl radical preferentially being chosen from methyl, ethyl, stearyl, butyl and 2-ethylhexyl radicals, and mixtures thereof.

Thus, according to a particular embodiment of the invention, the copolymer comprises at least one group chosen from acrylic acid and methacrylic acid, and methyl, ethyl, stearyl, butyl or 2-ethylhexyl acrylate or methacrylate, and mixtures thereof.

In the present patent application, the term “polydimethylsiloxanes” (also abbreviated as PDMSs) denotes, in accordance with what is generally accepted, any organosilicon polymer or oligomer of linear structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and constituted essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond ), including trimethyl radicals directly linked via a carbon atom to said silicon atoms. The PDMS chains that may be used to obtain the copolymer used according to the invention include at least one polymerizable radical group, preferably located on at least one of the ends of the chain, i.e. the PDMS may contain, for example, a polymerizable radical group on the two ends of the chain or a polymerizable radical group on one end of the chain and a trimethylsilyl end group on the other end of the chain. The polymerizable radical group may notably be an acrylic or methacrylic group, in particular a group CH₂=CR₁-CO-O-R₂, in which R₁ represents a hydrogen or a methyl group and R₂ represents –CH₂-, -(CH₂)_n- with n = 3, 5, 8 or 10, -CH₂-CH(CH₃)-CH₂-, CH₂-CH₂-O-CH₂-CH₂-, -CH₂-CH₂-O-CH₂-CH₂-CH(CH₃)-CH₂- or -CH₂-CH₂-O-CH₂ CH₂-O-CH₂-CH₂-CH₂-.

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

The copolymers obtained generally have a molecular weight ranging from about 3000 to 200 000 and preferably from about 5000 to 100 000 g/mol.

Said copolymer may be in its native form or in dispersed form in a solvent such as lower alcohols containing from 2 to 8 carbon atoms, for instance isopropyl alcohol, or oils, for instance volatile silicone oils (for example cyclopentasiloxane).

As copolymers that may be used, mention may be made, for example, of copolymers of acrylic acid and of stearyl acrylate bearing polydimethylsiloxane grafts, copolymers of stearyl methacrylate bearing polydimethylsiloxane grafts, copolymers of acrylic acid and of stearyl methacrylate bearing polydimethylsiloxane grafts, copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate bearing polydimethylsiloxane grafts. As copolymers that may be used in the composition of the invention, mention may be made in particular of the copolymers sold by the company Shin-Etsu under the names KP-561® (INCI name: Acrylates/Stearyl Acrylate/Dimethicone Methacrylate Copolymer), KP-541® in which the copolymer is dispersed at 60% by weight in isopropyl alcohol (INCI name: Acrylates/Dimethicone (and) Isopropyl Alcohol), KP-545® in which the copolymer is dispersed at 30% in cyclopentasiloxane (INCI name: Acrylates/Dimethicone (and) Cyclopentasiloxane).

Mention may also be made of a copolymer of polydimethylysiloxane and of one or more monomers chosen from acrylic acid, methacrylic acid and esters thereof and dissolved in isododecane, sold by the company Shin-Etsu under the name KP-550® and having the INCI name Acrylates/Dimethicone Copolymer (and) Isododecane.

Silicone polyamide

The silicone polyamides of the composition are preferably solid at 20°C and atmospheric pressure (1.013 × 10⁵ Pa).

The silicone polyamides that may be used may be polymers of the polyorganosiloxane type, for instance those described in US 5 874 069, US 5 919 441, US 6 051 216 and US 5 981 680.

According to the invention, the silicone polymers may belong to the following two families:
(1) polyorganosiloxanes including at least two amide groups, these two groups being located in the polymer chain, and/or
(2) polyorganosiloxanes including at least two amide groups, these two groups being located on grafts or branches.

A) According to a first variant, the silicone polymers are polyorganosiloxanes in which the amide units are located in the polymer chain.

The silicone polyamides may more particularly be polymers comprising at least one unit corresponding to the general formula (I):

1) in which: G’ represents C(O) when G represents –C(O)-NH-Y-NH-, and G’ represents –NH- when G represents -NH-C(O)-Y-C(O)-
2) R⁴, R⁵, R⁶ and R⁷, which may be identical or different, represent a group chosen from:
- saturated or unsaturated, linear, branched or cyclic C₁ to C₄₀ hydrocarbon-based groups, which may contain in their chain one or more oxygen, sulfur and/or nitrogen atoms, and which may be partially or totally substituted with fluorine atoms,
- C₆ to C₁₀ aryl groups, optionally substituted with one or more C₁ to C₄ alkyl groups,
- polyorganosiloxane chains possibly containing one or more oxygen, sulfur and/or nitrogen atoms,
3) the groups X, which may be identical or different, represent a linear or branched C₁ to C₃₀ alkylenediyl group, possibly containing in its chain one or more oxygen and/or nitrogen atoms,
4) Y is a saturated or unsaturated, linear or branched C₁ to C₅₀ alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene divalent group, which may include one or more oxygen, sulfur and/or nitrogen atoms, and/or may bear as substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C₃ to C₈ cycloalkyl, C₁ to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyl optionally substituted with one to three C₁ to C₃ alkyl, C₁ to C₃ hydroxyalkyl and C₁ to C₆ aminoalkyl groups, or
5) Y represents a group corresponding to the formula: R₈-T<; in which:
- T represents a linear or branched, saturated or unsaturated, C₃ to C₂₄ trivalent or tetravalent hydrocarbon-based group optionally substituted with a polyorganosiloxane chain, and possibly containing one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and
- R⁸ represents a linear or branched C₁-C₅₀ alkyl group or a polyorganosiloxane chain, possibly including one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups, which may possibly be linked to another chain of the polymer,
6) n is an integer ranging from 2 to 500 and preferably from 2 to 200, and m is an integer ranging from 50 to 1000, preferably from 50 to 700 and better still from 50 to 200.

It will be noted that "m" corresponds to the mean degree of polymerization of the silicone portion of the silicone polyamide.

According to one embodiment of the invention, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of the polymer are preferably chosen from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of the groups R⁴, R⁵, R⁶ and R⁷ of the polymer are methyl groups.

B) According to the second variant, the silicone polyamides may be polymers comprising at least one unit corresponding to the formula (II):

in which:
- R⁴ and R⁶, which may be identical or different, are as defined above for formula (I),
- R¹⁰ represents a group as defined above for R⁴ and R⁶, or represents a group of formula -X-G”-R¹² in which X are as defined above for formula (I) and R¹² represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated, C₁-C₅₀ hydrocarbon-based group optionally including in its chain one or more atoms chosen from O, S and N, optionally substituted with one or more fluorine atoms and/or one or more hydroxyl groups, or a phenyl group optionally substituted with one or more C₁-C₄ alkyl groups, and G’’ represents -C(O)NH- and –HN-C(O)-,
- R¹¹ represents a group of formula -X-G”-R¹² in which X, G” and R¹² are as defined above,
- m₁ is an integer ranging from 50 to 998, and
- m₂ is an integer ranging from 2 to 500.

It will be noted that "m₁" corresponds to the mean degree of polymerization of the silicone portion of the silicone polyamide.

According to the invention, the silicone polymer may be a homopolymer, i.e. a polymer including a plurality of identical units, in particular units of formula (I) or of formula (II).

According to the invention, it is also possible to use a polymer constituted of a copolymer including a plurality of different units of formula (I), i.e. a polymer in which at least one from among R⁴, R⁵, R⁶, R⁷, X, G, Y, m and n is different in one of the units. The copolymer may also be formed from a plurality of units of formula (II), in which at least one from among R⁴, R⁶, R¹⁰, R¹¹, m₁ and m₂ is different in at least one of the units.

It is also possible to use a polymer including at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) possibly being identical to or different from each other.

These copolymers may be block polymers, sequenced polymers or grafted polymers.

In formulae (I) and (II), R⁴, R⁵, R⁶ and R⁷ preferably represent, independently, a linear or branched C₁ to C₄₀ alkyl group, preferably a CH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.

According to a variant, the polymer may be a polyamide containing several units of formula (I) or (II) of different lengths, i.e. a polyamide corresponding to formula (III):

in which X, Y, n and R⁴ to R⁷ have the meanings given above, m₁ and m₂, which are different, are chosen in the range from 1 to 1000, and p is an integer ranging from 2 to 300.

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

in which R⁴ to R⁷, X, Y, m₁, m₂, n and p have the meanings given above and Y¹ is different from Y but chosen from the groups defined for Y. As previously, the various units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.

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

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

According to one embodiment variant of the invention, a copolymer of silicone polyamide and of hydrocarbon-based polyamide, or a copolymer including units of formula (I) or (II) and hydrocarbon-based polyamide units, may be used. In this case, the polyamide-silicone units may be arranged at the ends of the hydrocarbon-based polyamide.

Advantageously, the composition comprises at least one polyamide/polydimethylsiloxane polymer, notably a polymer of general formula (I) with an index m with a value of greater than 50, in particular greater than 75 and notably of about 100.

Advantageously, the silicone polyamide of formula (I) has a weight-average molecular mass ranging from 10 000 to 500 000 g/mol.

More preferably, X and Y independently represent a group chosen from linear C₁ to C₂₀, preferably C₁ to C₁₀, alkylene groups.

As examples of silicone polyamides, mention may be made of one of the silicone polyamides obtained in accordance with Examples 1 to 3 of US 5 981 680, and also the product sold under the reference DC 2-8179 by Dow Corning (INCI name: Nylon-611/Dimethicone Copolymer).

The composition according to the invention preferably comprises at least one silicone polyamide, when the composition comprises at least one glycerolated or non-glycerolated, preferably non-glycerolated, silicone resin.

More particularly, the content of silicone film-forming polymer represents from 2% to 25% by weight and preferably from 3% to 20% by weight relative to the total weight of the composition.

Preferably, the composition according to the invention comprises, as silicone film-forming polymer, at least one silicone resin, which is preferably non-glycerolated. Preferably, the silicone resin is chosen from the silicone resins having the following INCI names: Trimethyl siloxysilicate, Phenylpropyldimethyl siloxysilicate, Polymethylsilsesquioxane, Polypropylsilsesquioxane, and also mixtures thereof, and even more preferentially Trimethyl siloxysilicate, Polymethylsilsesquioxane, Polypropylsilsesquioxane, and also mixtures thereof.

LIPOPHILIC MINERAL THICKENER

The composition according to the invention comprises at least one lipophilic mineral thickener, in particular chosen from lipophilic clays.

The term “lipophilic clay” refers to any clay that is liposoluble or lipodispersible in the oily phase of the composition.

Clay denotes a material based on hydrated silicates and/or aluminosilicates, of lamellar structure.

The clays may be natural or synthetic, and they are made lipophilic by treatment with an alkylammonium salt such as a C10 to C22 ammonium chloride, in particular stearalkonium chloride or distearyldimethylammonium chloride.

They may be chosen from bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

They are preferably chosen from hectorites and bentonites.

For example, use may be made of a lipophilic clay chosen from hydrophobically modified bentonites and hydrophobically modified hectorites, notably modified with a C10 to C22 quaternary ammonium chloride, such as:
- a bentonite modified with stearalkonium chloride, such as the commercial products sold under the name Claytone AF®, Garamite VT®, Tixogel® LG-M, Tixogel® MP 250 Tixogel® VZ and Tixogel® VZ-V XR, by the company BYK Additives Inc; or the commercial products sold under the name Viscogel® B3, Viscogel® B4, Viscogel® B7, Viscogel® B8, Viscogel® ED, Viscogel® GM, Viscogel® S4 and Viscogel® SD by the company Bentec S.P.A;
- a bentonite modified with stearalkonium chloride in the presence of at least propylene carbonate and at least one oil, such as the commercial products Dub Velvet Gum® from the company Stéarinerie Dubois Fils, Miglyol Gel T® from the company Cremer Oleo, Tixogel® CGT 6030, Tixogel® DBA 6060, Tixogel® FTN, TIXOGEL® FTN 1564, Tixogel® IPM, Tixogel® LAN, Tixogel® LAN 1563 from the company BYK Additives Inc.;
- a hectorite modified with distearyldimethylammonium chloride (INCI name: Disteardimonium Hectorite), for instance the product sold under the name Bentone® 38VCG Rheological Additive by the company Elementis Specialties;
- a hectorite modified with distearyldimethylammonium chloride in the presence of at least propylene carbonate or triethyl citrate and of at least one oil, such as the commercial products sold under the name Bentone® Gel DOA V, Bentone® Gel EUG V, Bentone® Gel IHD V, Bentone® Gel ISD V, Bentone® Gel MIO V, Bentone® Gel PTM V, Bentone® SS-71 V, Bentone® VS-5 PC V or Bentone® VS-5 by the company Elementis Specialities; the commercial products sold under the name Creagel Bentone CPS/Hectone CPS or Creagel Bentone ID/Hectone ID by the company Créations Couleurs; the commercial products sold under the name NS Gel DM1®, NS Gel PTIS® or NS MGel 1152® by the company Next Step Laboratories Stop.

More particularly, if the composition comprises any, the content of lipophilic thickener represents from 0.2% to 4% by weight, preferably from 0.3% to 3% by weight, relative to the total weight of the composition.

SECOND OIL

The composition according to the invention may optionally comprise at least one second oil, different from the first oil(s), chosen from nonvolatile, polar or apolar hydrocarbon-based oils, from volatile or nonvolatile silicone oils, and also mixtures thereof.

The term “hydrocarbon-based oil” refers to an oil mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. These oils are thus different from silicone oils.

The term “polar hydrocarbon-based oil” means that said oils comprise, in addition to carbon and hydrogen atoms, at least one oxygen atom. Thus, said hydrocarbon-based oil comprises at least one hydroxyl, ester, ether and/or carboxylic function.

The term “silicone oil” refers to an oil comprising at least one silicon atom, and notably at least one Si-O group, and more particularly an organopolysiloxane.

The term “nonvolatile oil" means an oil whose vapor pressure at 20°C and atmospheric pressure is nonzero and is less than 2.66 Pa and preferably less than or equal to 0.13 Pa. By way of example, the vapor pressure may be measured according to the static method or via the effusion method by isothermal thermogravimetry, depending on the vapor pressure of the oil (standard OCDE 104).

Polar nonvolatile hydrocarbon-based oils

The composition according to the invention may thus comprise at least one nonvolatile polar hydrocarbon-based oil, more particularly chosen from:
* saturated or unsaturated, linear or branched, C₁₀-C₂₆ fatty alcohols, preferably monoalcohols, which are preferably branched when they comprise at least 16 carbon atoms. More particularly, the fatty alcohol comprises from 10 to 24 carbon atoms and more preferentially from 12 to 22 carbon atoms;
* ethers of formula ROR’ or carbonates of formula RO(CO)OR', in which formulae the groups R and R’, which may be identical or different, represent a saturated or unsaturated, branched or unbranched, hydrocarbon-based group comprising not more than 16 carbon atoms, preferably a C₃-C₁₆ group;
* hydroxylated or non-hydroxylated plant oils;
* ester oils comprising one or more ester functions, preferably one to four ester functions, and comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon-based group comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; the ester oil may optionally comprise one or more ether or hydroxyl functions;
* liquid polyesters derived from the reaction of a monounsaturated or polyunsaturated acid dimer; the fatty acid comprising from 16 to 22 carbon atoms;
* and mixtures thereof.

Preferably, the second oil is chosen from:
- lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol and octyldodecanol, and mixtures thereof; preferably octyldodecanol;
- dicaprylyl ether;
- dipropyl carbonate, diethylhexyl carbonate, dicaprylyl carbonate, and C₁₄-C₁₅ dialkyl carbonate;
- castor oil, olive oil, jojoba oil, ximenia oil, pracaxi oil, wheat germ oil, corn oil, sunflower oil, sweet almond oil, macadamia oil, apricot kernel oil, soybean oil, rapeseed oil, groundnut oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant oil, argan oil, evening primrose oil, millet oil, barley oil, linseed oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, musk rose oil, the liquid fraction of shea butter and the liquid fraction of cocoa butter, and mixtures thereof;
- 2-ethylhexyl palmitate, 2-octyldecyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, butyl stearate, 2-octyldodecyl erucate, C₁₂ to C₁₅ alkyl benzoates, 2-octyldodecyl benzoate, isocetyl isostearate, isostearyl isostearate, isononyl isononanoate, isopropyl palmitate, hexyl laurate, 2-hexyldecyl laurate, isopropyl myristate, 2-octyldodecyl myristate, diisostearyl malate, neopentyl glycol dicaprate, glyceryl tris(2-decyltetradecanoate), capric acid triglyceride, alone or as a mixture, such as capric/caprylic acid triglycerides, C_18-36 acid triglycerides, glyceryl triheptanoate, glyceryl trioctanoate, glyceryl tris(2-decyltetradecanoate), triisostearyl citrate, tridecyl stearate, tridecyl trimellitate, pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrakis(2-decyltetradecanoate); polyglycerol-2 tetraisostearate; Pentaerythrityl Isostearate / Caprate / Caprylate / Adipate (INCI name, for example the Supermol L products from the company Croda); isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate;

- the polyesters having the following INCI names: Dilinoleic Acid/Butanediol Copolymer, Dilinoleic Acid/Propanediol Copolymer, sold, for example, under the names: Viscoplast, by the company Biosynthis; Dimer Dilinoleyl Dilinoleate, notably sold under the name Lusplan by the company Nippon Fine Chemical;
- and also mixtures thereof.

Apolar nonvolatile hydrocarbon-based oils

The apolar, nonvolatile hydrocarbon-based oil may be chosen from linear or branched hydrocarbons of mineral, plant or synthetic origin, for instance:
- liquid paraffin,
- squalane, in particular of plant origin,
- isoeicosane,
- mixtures of saturated linear hydrocarbons, more particularly of C₁₅-C₂₈, such as the mixtures of which the INCI names are, for example, the following: C15-19 Alkane, C18-C21 Alkane, C21-C28 Alkane, for instance the products Gemseal 40, Gemseal 60 and Gemseal 120 sold by Total, and Emogreen L15 and L19 sold by SEPPIC,
- hydrogenated or non-hydrogenated polybutenes, for instance products of the Indopol range sold by the company Ineos Oligomers,
- hydrogenated or non-hydrogenated polyisobutenes, for instance the nonvolatile compounds of the Parleam® range sold by the company Nippon Oil & Fats,
- hydrogenated or non-hydrogenated polydecenes, for instance nonvolatile compounds of the Silkflo range sold by the company Ineos, and Dekanex by the company IMCD,
- and mixtures thereof;

Nonvolatile silicone oils

The composition according to the invention may comprise at least one nonvolatile phenyl silicone oil, optionally comprising at least one dimethicone fragment, or comprising at least one nonvolatile non-phenyl silicone oil, or mixtures thereof.

The term “phenyl(ated)” specifies that said oil includes, in its structure, at least one phenyl radical.

The term “dimethicone fragment” denotes a divalent siloxane group, the silicon atom of which bears two methyl radicals, this group not being located at one or both ends of the molecule. It may be represented by the following formula:
-(Si(CH₃)₂-O)-.

Preferably, the silicones do not contain a C₂-C₃ alkylene oxide group or a glycerolated group.

As nonvolatile phenylated oil comprising at least one dimethicone fragment, mention may be made of the oils having the following INCI names: Trimethylsiloxyphenyl Dimethicone, Diphenyl Dimethicone, Tetramethyl Tetraphenyl Trisiloxane and also mixtures thereof, preferably Trimethylsiloxyphenyl Dimethicone. The Diphenyl Dimethicones are notably sold by the company Shin-Etsu under the names KF-54, KF54HV, KF-50-300CS, KF-53 d and KF-50-100CS. The Trimethylsiloxy Phenyl Dimethicones are sold, for example, by the company Wacker Chemie under the names Belsil PDM 1000 and Belsil PDM 20.

Among the nonvolatile phenyl silicone oils not containing a dimethicone fragment, mention may be made of the compounds having the following INCI names: Phenyltrimethicone, Trimethyl Pentaphenyl Trisiloxanes, alone or as mixtures. As nonvolatile, non-phenyl silicone oils that are suitable for performing the invention, mention may be made of those sold by the company Wacker under the Belsil DM range, by the company Dow Corning with the Xiameter PMX 200 Silicone Fluid range, and by the company Shin-Etsu with the KF-96 A range.

Representative examples of the nonvolatile non-phenyl silicone oils include polydimethylsiloxanes and alkyl dimethicones. It should be noted that the term “dimethicone” (INCI name) corresponds to a polydimethylsiloxane (chemical name). Preferably, these nonvolatile, non-phenyl silicone oils are chosen from polydimethylsiloxanes and alkyl dimethicones comprising at least one C₂-C₂₄ alkyl group, and also mixtures thereof. Thus, these oils may be chosen from dimethicone, cetyl dimethicone and stearyl dimethicone, alone or as mixtures. As nonvolatile, non-phenyl silicone oils that are suitable for use, mention may be made of those sold by the company Wacker under the Belsil DM range, by the company Dow Corning with the Xiameter PMX 200 Silicone Fluid range, and by the company Shin-Etsu with the KF-96 A range. The alkyldimethicones may be sold, for example, under the trade names Abil Wax 9800 and Abil Wax 9801 from Evonik Goldschmidt, or Dowsil 2502 Cosmetic Fluid, Dowsil 2503 Cosmetic Wax, from Dow Corning; and mixtures thereof.

Volatile silicone oils

The volatile silicone oils may be chosen from linear, branched or cyclic silicone oils, such as polydimethylsiloxanes containing from 3 to 7 silicon atoms.

As examples of such oils, mention may be made of the oils having the following INCI names: Cyclopentasiloxane, Cyclotetrasiloxane, Cyclohexasiloxane, Caprylyl Methicone, Disiloxane, Trisiloxane, Dimethicones notably with a viscosity of less than 5 cSt, such as those sold under the reference Xiameter PMX-200 Silicone Fluid, sold by the company Dow Corning, with viscosities notably of 1 cSt, 1.5 cSt, 3 cSt, or also KF 96 L 2 cs from Shin-Etsu, alone or as mixtures.

Preferably, the second oil, if the composition according to the invention comprises one, is at least chosen from nonvolatile, preferably polar, hydrocarbon-based oils, alone or as mixtures.

Preferably, the second oil is chosen from polar nonvolatile hydrocarbon-based oils.

Preferably, the second oil(s) are chosen from ether oils and ester oils. In accordance with an even more preferred embodiment, if the composition comprises them, the second oil(s) are chosen from plant oils; optionally hydroxylated ester oils comprising 1 to 4 ester functions, comprising at least one linear or branched, saturated, unsaturated or aromatic group, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; ether oils of formula ROR’ where R and R’, which may be identical or different, represent a saturated or unsaturated, branched or unbranched hydrocarbon-based group comprising not more than 16 carbon atoms; and also mixtures thereof.

According to a preferred embodiment, the second oil is chosen from triglycerides of fatty acids containing from 8 to 24 carbon atoms, and more particularly a caprylic/capric acid triglyceride (INCI name: Caprylic/Capric Triglyceride), plant oils, dicaprylyl ether, and also mixtures thereof.

If the composition comprises any, the content of second oil(s) does not exceed 15% by weight, more particularly from 0.1% to 10% by weight, relative to the total weight of the composition.

Preferably, if the composition comprises at least one volatile or nonvolatile silicone oil, then their content does not exceed 5% by weight, more particularly does not exceed 3% by weight, even more preferentially does not exceed 1% by weight, relative to the total weight of the composition. Preferably, the composition according to the invention does not contain any.

WATER

The composition according to the invention also comprises water.

A water that is suitable for use in the invention may be a demineralized water, a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a spring water.

According to a particular embodiment of the invention, the water content is at least 20% by weight, preferably between 20% and 50% by weight and preferably between 20% and 40% by weight relative to the total weight of the composition.

C2-C6 MONOALCOHOL

The composition according to the invention may optionally comprise at least one saturated or unsaturated, preferably saturated, C2-C6 and more particularly C2-C4 monoalcohol. The monoalcohol(s) may be represented, for example, by the formula RaOH, in which Ra represents a linear or branched alkyl group comprising from 2 to 6 carbon atoms, preferably comprising from 2 to 4 carbon atoms. Monoalcohols that may be mentioned include include ethanol, isopropanol, tert-butanol or butanol, or mixtures thereof. Preferably, said monoalcohol comprises at least ethanol, and even more preferentially the monoalcohol is ethanol.

According to an advantageous embodiment of the invention, the monoalcohol content represents from 3% to 20% by weight, preferably from 5% to 15% by weight, relative to the total weight of the composition.

LIQUID POLYOL

The composition according to the invention may optionally comprise at least one saturated or unsaturated, linear or branched C2-C8 and preferably C3-C6 polyol that is liquid at room temperature, comprising from 2 to 6 hydroxyl groups. More particularly, the liquid polyol is chosen from glycerol, diglycerol, and linear or branched, saturated C3-C8 glycols or alkanediols. Propylene glycol, propanediol, butylene glycol, pentanediol, pentylene glycol, caprylyl glycol, dipropylene glycol and also mixtures thereof, and preferably glycerol, are notably suitable for use.

According to an advantageous embodiment of the invention, the content of liquid polyol ranges from 3% to 20% by weight, in particular from 4% to 15% by weight, relative to the total weight of the composition.

NONIONIC SURFACTANT

The composition according to the invention comprises at least one nonionic hydrocarbon-based or silicone surfactant with an HLB of less than or equal to 8.

For the purposes of the present invention, the term “surfactant” refers to an amphiphilic compound, i.e. a compound containing two parts of different polarities. Generally, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). Nonionic surfactants are characterized by the value of their HLB (Hydrophilic Lipophilic Balance), the HLB being the ratio of the hydrophilic part to the lipophilic part in the molecule. The term “HLB” is well known to those skilled in the art and is described, for example, in “The HLB System. A Time-Saving Guide to Emulsifier Selection” (published by ICI Americas Inc.; 1984). For the surfactants used in the context of the present invention, their HLB value is more particularly less than or equal to 8 and more particularly ranges from 3 to 8. The HLB value may be determined via the Griffin method or the Davies method.

More particularly, the nonionic surfactant(s) are chosen from optionally (poly)oxyethylenated, (poly)oxypropylenated or (poly)glycerolated compounds.

Nonionic hydrocarbon-based surfactant

Among the hydrocarbon-based nonionic surfactants that may be used in the context of the invention, mention may be made of (poly)oxyethylenated and/or (poly)oxypropylenated C₈-C₃₀ alcohols; (poly)oxyethylenated or (poly)oxypropylenated C₈-C₃₀ esters; preferably polyhydroxylated, polyoxyalkylenated C₁₂-C₂₀ fatty acid polyesters containing from 4 to 50 ethylene oxide units; (C₈-C₃₀)alkyl and (C₈-C₃₀)polyalkyl esters of sorbitan; (C₈-C₃₀)alkyl and (C₈-C₃₀)polyalkyl esters of (poly)glycerol; alone or as mixtures.

Examples of such surfactants that are notably suitable for use include:

(poly)oxyethylenated or (poly)oxypropylenated, preferably (poly)oxyethylenated, C₈-C₃₀ alcohols, more particularly comprising a number of ethylene oxide (EO) units ranging from 2 to 4. Examples that may notably be mentioned include laureth-2; steareth-2; oleth-2; oleth-3; ceteth-2 and ceteareth-3;
(poly)oxyethylenated or (poly)oxypropylenated, preferably (poly)oxyethylenated, (C₈-C₃₀)alkyl and (C₈-C₃₀)polyalkyl esters, more particularly comprising a number of ethylene oxide (EO) units ranging from 1 to 5, with for example glycol distearate, glycol stearate, PEG-2 oleate; PEG-3 oleate; PEG-4 dilaurate (HLB 6), propylene glycol isostearate; PEG-2.5 castor oil; PEG-3 castor oil;

3) polyoxyalkylenated C₁₂-C₂₀ fatty acid polyesters, which are preferably polyhydroxylated, containing from 4 to 50 ethylene oxide units. In particular, these polymers are block polymers, preferably of ABA structure, including poly(hydroxylated ester) blocks and polyethylene glycol blocks. The fatty acid of said surfactant polymer as defined above preferably contains from 14 to 18 carbon atoms. The esters may notably be chosen from oleates, palmitates or stearates. The polyethylene glycol blocks of said surfactant polymer as defined above preferably include from 20 to 40 ethylene oxide units. A polymeric surfactant that is particularly suitable for preparing the compositions of the invention is polyethylene glycol dipolyhydroxystearate containing 30 EO, sold under the trade name Arlacel P 135 by the company Croda.

4) (C₈-C₃₀)alkyl and (C₈-C₃₀)polyalkyl esters of sorbitan, for instance sorbitan trioleate, sorbitan sesquioleate, sorbitan oleate, sorbitan palmitate, sorbitan stearate, sorbitan isostearate, (Span 120 from the company Croda), sorbitan sesquiisostearate (Cosmol 182V from the company Nisshin Oillio), mixtures of sorbitan stearate and sucrose cocoate (Arlacel 2121 sold by the company Croda), sorbitan isostearate mixed with hydrogenated castor oil, stearic acid and white wax (Arlacel 986 sold by the company Croda), and mixtures thereof.

5) (C₈-C₃₀)alkyl and poly(C₈-C₃₀)alkyl esters of (poly)glycerol more particularly comprising a number of glycerol units ranging from 1 to 10.
Mention may be made, for example, of glyceryl isostearate, glyceryl stearate and glyceryl laurate, alone or as mixtures.
Among the polyglycerolated nonionic surfactants, mention may be made notably of:
- esters of isostearic acid and of polyglycerol containing from 2 to 10 mol of glycerol units, for instance Polyglyceryl-4 Isostearate sold under the name Isolan GI34® by the company Evonik Nutrition & Care GmbH, Polyglyceryl-2 sesquiisostearate sold under the name Hostacerin® DGI by the company Clariant, Polyglyceryl-3 Diisostearate sold under the name Lameform TGI® by the company Cognis; Polyglyceryl-2 Diisostearate sold under the name Emalex PGSA® by the company Nihon Emulsion; Polyglyceryl-10 Isostearate sold under the name Nikkol Decaglyn 1-IS® by the company Nihon Surfactant; Polyglyceyl-4 Diisostearate/Polyhydroxystearate Sebacate sold under the name ISOLAN GPS® by Evonik Nutrition & Care GmbH; Polyglyceryl-2 Triisostearate sold under the name Cithrol PG23IS® by Croda Europe, Ltd;
- stearic acid esters of polyglycerol containing from 2 to 3 mol of glycerol units, such as Polyglyceryl-2 Sesquistearate sold under the name Sunsoft Q-18B® by the company Taiyo Kagaku Company, Polyglyceryl-3 Distearate sold under the name Cremophor GS 32® by the company BASF, and Polyglyceryl-2 Stearate sold under the name Hostacerin DGMS® by Clariant International Ltd;
- oleic acid esters of polyglycerol containing 2 or 3 mol of glycerol units, such as Polyglyceryl-2 Oleate sold under the name Nikkol DGMO-CV® by Nikko Chemicals, Polyglyceryl-3 Oleate sold under the name Isolan GO 33® by Evonik Nutrition & Care GmbH, Polyglyceryl-2 Dioleate; Polyglyceryl-3 Dioleate sold under the name Plurol Oleique CC 497® by Gattefosse;
- polyglyceryl polyricinoleate(s) containing from 3 to 6 mol of glycerol units, such as Polyglyceryl-3 Polyricinoleate, notably sold by the company Karlshamns under the name Akoline PGPR® or by the company Stéarinerie Dubois Fils under the name DUB PGPR or by the company Dr. Straetmans under the name Dermofeel®, or by the company Croda under the name Crester PR® or else by the company Sasol under the name Imwitor 600®; Polygyceryl-5 Polyricinoleate sold by the company Taiyo Kagaku Co. Ltd under the name Sunsoft NO.818R®; Polyglyceryl-6 Polyricinoleate sold by the company Nikko Chemicals Co. Ltd under the name Hexaglyn PR-15® or by the company Sakamoto Yakuhin Kogyo Co. Ltd under the name SY-Glyster CRS-75®. According to one embodiment, mixtures of these compounds may be used.
More particularly, the nonionic polyglycerolated surfactant is chosen from polyglyceryl polyricinoleate(s) containing from 3 to 6 mol of glycerol units, and more particularly Polyglyceryl-6 Polyricinoleate sold by the company Nikko Chemicals Co. Ltd under the name Hexaglyn PR-15® or by the company Sakamoto Yakuhin Kogyo Co. Ltd under the name SY-Glyster CRS-75®.

Nonionic silicone surfactant

The nonionic surfactant may also be chosen from nonionic silicone surfactants, in particular linear oxyalkylenated (C3-C4) polydimethylmethylsiloxanes with an HLB of less than or equal to 8, preferably linear oxypropylenated and/or oxyethylenated, notably having the formula (I) below:
[Chem 12]
(I)
in which: R₁, R₂ and R₃, independently of each other, represent a C1-C6 alkyl radical or a radical -(CH2)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR₄, at least one radical R₁, R₂ or R₃ not being an alkyl radical; R₄ being a hydrogen atom, a C1-C3 alkyl radical or a C2-C4 acyl radical;
A is a mean integer ranging from 0 to 200;
B is a mean integer ranging from 0 to 50; on condition that A and B are not simultaneously equal to zero;
x is a mean integer ranging from 0 to 6;
y is a mean integer ranging from 1 to 30;
z is a mean integer ranging from 0 to 30.

According to a particular embodiment, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB ≤ 8 is chosen from those of formula (I) in which R₁ and R₃ denote methyl, R₂ is -(CH₂)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR₄ and R₄ is a hydrogen atom.

More particularly, among these compounds, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB ≤ 8 is chosen from those of formula (I) in which x is equal to 0.

More particularly, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB ≤ 8 is chosen from those of formula (I) in which R₁ and R₃ denote methyl, R₂ is
-(CH₂)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR₄, R₄ is a hydrogen atom and z is equal to 0.

According to a particular embodiment, the linear oxyalkylenated polydimethylmethylsiloxane surfactant of HLB ≤ 8 is chosen from those of formula (I) in which R₁ and R₃ denote -(CH₂)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR₄, R₂ is methyl and R₄ is a hydrogen atom.

As examples of silicone surfactants, mention may be made of the surfactants having the following INCI names: PEG/PPG-8/8 Dimethicone, Bis-PEG/PPG-14/14 Dimethicone, PEG/PPG-18/18 Dimethicone, PEG/PPG-19/19 Dimethicone, PEG-3 Dimethicone, PEG-10 Dimethicone, and also mixtures thereof.

The following products are notably suitable for use:
- PEG/PPG-8/8 dimethicone, such as the products sold under the trade names Silube J208-4I®, Silube J208-6I®, Silube J208-8I® and Silsurf J-1013-V-CG® by the company Siltech LLC; Andisil SP 1818® by the company AB Specialty Silicones; Jeesilc DMC 19® by the company Jeen International Corporation; Xiameter OFX-0190 Fluid® by the company Dow Chemical;
- the Bis-PEG/PPG-14/14 dimethicone (and) dimethicone mixture sold under the trade name Abil EM 97 S® by the company Evonik Goldschmidt;
- the cyclopentasiloxane and PEG/PPG-18/18 dimethicone mixture, such as the products sold under the trade names Dowsil 5225C Formulation Aid® by the company Dow Chemical; Emusil WO-5115® by the company Innospec Performance Chemicals; Gransurf 10C® by the company Grant Industries, Inc.; Jeesilc DMC522® by the company Jeen International Corporation; Silsurf 400R® by the company Siltech LLC;
- the cyclotetrasiloxane and cyclopentasiloxane and PEG/PPG-18/18 dimethicone mixture, such as the commercial products sold under the name Dowsil 3225C Formulation Aid® by Dow Chemical; Emulsil WO-3115® by Innospec Performance Chemicals; Jeesilc DMC252® and Jeesilc DMC322® by Jeen International Corporation;
- the dimethicone and PEG/PPG-18/18 dimethicone mixture, such as the commercial products Dowsil ES-5226 DM Formulation Aid® and Dowsil ES-5227 DM Formulations AID® from Dow Chemical; Gransurf 50C® and Gransurf 50C-HM® from Grant Industries, Inc. and X-22-6711D from Shin-Etsu.
- the PEG/PPG-19/19 dimethicone and C13-C16 isoparaffin and C10-C13 isoparaffin mixture, such as the commercial product Dow Corning® BY 25-337 from Dow Chemical;
- PEG-3 dimethicone, such as the commercial product KF-6015® from Shin-Etsu Chemical Co, Ltd;
- PEG-10 dimethicone, such as the commercial products KF-6017® from Shin-Etsu Chemical Co. Ltd; Serasol SC 86® and Serasol SC 86A® from KCC Corporation);
- mixtures thereof.

Preferably, the composition according to the invention comprises, as nonionic surfactant(s), at least one hydrocarbon-based surfactant with an HLB of less than or equal to 8 and even more preferably, at least one polyglycerolated hydrocarbon-based surfactant as described previously.

A composition of the invention preferably comprises from 2% to 10% by weight and in particular from 2% to 7% by weight of nonionic hydrocarbon-based or silicone surfactant(s) relative to the total weight of the composition.

DYESTUFF

The composition according to the invention comprises at least one dyestuff.

According to a particular form of the invention, the dyestuff may be chosen from pulverulent dyestuffs, liposoluble dyes, water-soluble dyes and mixtures thereof.

Pulverulent dyestuff

The pulverulent dyestuffs may be chosen from mineral pigments, organic pigments, nacres and mixtures thereof.

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

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

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

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

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

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

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

According to a particular form of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, said coating preferably being present in the oily phase of the composition according to the invention.

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

According to a preferential embodiment, the pigments may be coated according to the invention with an N-acylamino acid or a salt thereof, which 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 amino acid may be, for example, lysine, glutamic acid or alanine. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. Thus, according to a particularly preferred embodiment, the pigments may be coated with an N-acylamino acid derivative which may notably be a glutamic acid derivative and/or a salt thereof, and more particularly a stearoyl glutamate, for instance aluminum stearoyl glutamate. As examples of pigments treated with aluminum stearoyl glutamate, mention may be made of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the trade name NAI® by the company Miyoshi Kasei.

According to a preferential embodiment, the pigments may be coated according to the invention with isopropyl triisostearyl titanate. As examples of isopropyl titanium triisostearate (ITT)-treated pigments, mention may be made of titanium dioxide pigments and the black, red and yellow iron oxide pigments sold under the trade names BWBO-I2® (iron oxide CI77499 and isopropyl titanium triisostearate), BWYO-I2® (iron oxide CI77492 and isopropyl titanium triisostearate) and BWRO-I2® (iron oxide CI77491 and isopropyl titanium triisostearate) by the company Kobo.

The pigments that may be used according to the invention may also be organic pigments.

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

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

These pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including a mineral core at least partially covered with an organic pigment and at least one binder for fixing the organic pigments to the core.

The pigment may also be a lake. The term “lake” means insolubilized dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

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

Mention may be made, among the organic dyes, of cochineal carmine. Mention may also be made of the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 47 005), D&C Green 3 (CI 42 053), D&C Blue 10 (CI 42 090).

An example of a lake that may be mentioned is the product known under the name D&C Red 7 (CI 15 850:1).

Preferably, the composition according to the invention comprises at least one pulverulent dyestuff of mineral pigment type, in particular chosen from metal oxides, and more particularly chosen from coated or uncoated titanium dioxides or iron oxides and mixtures thereof.

The nacres may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica notably with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.

Preferably, the pulverulent dyestuff(s) are present in the composition in a content ranging from 3% to 25% by weight, preferably from 5% to 20% by weight, more particularly from 5% to 15% by weight, relative to the total weight of the composition.

Liposoluble or water-soluble dyestuff

A composition according to the invention may comprise at least one water-soluble or liposoluble dyestuff, preferably in a proportion of at least 0.01% by weight relative to the total weight of the composition.

For obvious reasons, this amount is liable to vary significantly with regard to the intensity of the desired color effect and of the color intensity afforded by the dyestuffs under consideration, and its adjustment clearly falls within the competence of a person skilled in the art.

The additional dyestuffs that are suitable for use in the invention may be liposoluble.

For the purposes of the invention, the term “liposoluble dyestuff” means any natural or synthetic, generally organic compound, which is soluble in an oily phase or in solvents that are miscible with a fatty substance, and which is capable of imparting color.

As liposoluble dyes that are suitable for use in the invention, mention may notably be made of synthetic or natural liposoluble dyes, for instance DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto and curcumin.

The additional dyestuffs that are suitable for use in the invention may be water-soluble.

For the purposes of the invention, the term “water-soluble dyestuff” means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of imparting color.

As water-soluble dyes that are suitable for use in the invention, mention may be made notably of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elder), caramel and riboflavin.

The water-soluble or liposoluble dye(s), if the composition comprises any, are preferably present in contents of less than 4% by weight, or even less than 2% by weight, more preferentially ranging from 0.01% to 2% by weight and better still from 0.02% to 1.5% by weight, relative to the total weight of the composition.

FILLER

The composition according to the invention preferably comprises at least one mineral filler, other than the mineral thickener described previously, or an organic filler, and also mixtures thereof.

The term “filler” denotes a particle of organic or mineral nature which is colorless or white, which is solid, which has any shape and which is insoluble in the medium of the composition at room temperature and atmospheric pressure. These fillers are advantageously dispersed in the composition.

Mineral filler

The term “mineral filler” refers to any compound in which the chemical structure does not comprise a carbon atom, independently of the presence of a coating of said filler.

The fillers are in the form of particles and are different from the dyestuffs described previously.

The fillers used in the compositions according to the present invention may be particles in lamellar, globular or spherical form, in the form of fibers or in any other form intermediate between these defined forms. The fillers may be spherical, i.e. they may comprise at least a rounded general portion, notably defining at least a sphere portion, preferably internally defining a concavity or a hollow (sphere, globules, bowls, horseshoe, and the like), or lamellar.

In accordance with a particular embodiment of the invention, the fillers more particularly have a mean particle size (expressed as volume-mean diameter - D[0.5]) of at least 1 µm, preferably of at least 2 µm, advantageously of between 2 and 15 µm. The size of the particles can be measured by laser diffraction using a commercial Mastersizer 3000 particle size analyzer from the company Malvern (see also the standard ISO 13320).

The fillers used in the composition according to the invention may or may not be surface coated, and in particular they may be coated with a hydrophobic treatment agent, in particular promoting the dispersion and compatibility of the filler in the composition. The hydrophobic treatment agent may be chosen from silicones, in particular silanes; fluorinated derivatives, fatty acids such as stearic acid; metal soaps such as aluminum dimyristate, the aluminum salt of hydrogenated tallow glutamate; 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 the aluminum, 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 previously notably denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.

Such fillers are advantageously chosen from:

- Silica (INCI name: Silica), such as the porous silica microspheres sold under the name Silica Beads SB-700 by the company Myoshi; Sunsphere H51, Sunsphere H33, SA Sunsphere H53, Sunsphere H121 by the company AGC SI-TECH; MSS-500/20N and Silica Shells by the company Kobo; Perluccia 14M by the company JGC Catalysts & Chemicals; hollow silica microspheres, for example BA4 silicas, by the company JGC Catalysts & Chemicals; amorphous silica microspheres coated with polydimethylsiloxane. Also suitable for use are the following products: Resifa FB-82 by the company AGC SI-TECH (INCI: Silica (and) Sodium Chloride); Aerova 5 Microns by the company JIOS Aerogel; Sunsil-Oleo 150H by the company Sunjin Beauty Science (INCI name: Silica (and) Cetyl Alcohol); Sensibeads SI 175 by the company Sensient; Miyofeel SXI-L by the company Myoshi (INCI name: Mica (and) Silica (and) Hydrogenated Lecithin (and) Calcium Chloride);

- Perlite such as those sold by the company World Minerals under the trade name Perlite P1430, Perlite P2550, Perlite P2040 or OpTiMatTM 1430 OR or 2550 OR. Europerl EMP-2 and Europerl 1 by the company Imerys; Perlite-MSZ12 by the company Myoshi;

- Zeolites such as the products sold by the company Zeochem under the names Zeoflair 300, Zeoflair 200, Zeoflair 100, X-Mol and X-Mol MT;

- Carbonate or hydrogen carbonate particles of alkaline-earth metals such as calcium or magnesium, or hydroxyapatite. Mention may be made, for example, of calcium magnesium carbonate particles such as those sold by the company Imerys under the name Calcidol. Also suitable for use is calcium carbonate, for example the products sold by the company Omya under the names Omyacare Extra 35-OG, Omyacare S 60-AV; by the company Sensient under the name Carbomat. Mention may also be made of magnesium carbonate and magnesium hydrogen carbonate particles.

- Kaolin and talc particles, for example sold under the Imercare, Imercare Pharma and Luzenac Pharma ranges by the company Imerys; Rose Talc by the company Nippon Talc, Hallopure Ultra by the company I-minerals (INCI name: Halloysite (and) Kaolin);

- Natural or synthetic mica, such as the product under the INCI name Synthetic Fluorphlogopite, sold under the names RonaFlair Silk Mica by the company Merck, Sericite PHN by the company Presperse, NHS-100 and NHS-150 by the company Myoshi Kasei, those sold under the names PDM-NSO or FNK-100 by the company Topy, Mearlmica DD by the company BASF.

- Boron nitride, for example the products Ronaflair Boroneige SQ-6 sold by the company Merck, Softouch Boron Nitride Powder CC6058 by the company Momentive Performances, Boron Nitride SHP 3 by the company Mizushima Ferroalloy; silica and titanium dioxide composites, such as the TSG® series sold by Nippon Sheet Glass; bismuth oxychloride;

- Glass or ceramic microcapsules; for instance borosilicate particles.

- Barium sulfates, for instance the products Flake Shaped Barium Sulfate H by the company Sakai Chemical, LLD-5 BASO4 (PL) by the company Daito Kasei (NCI name: Barium sulfate (and) lauroyl lysine);

- diatomaceous earths, for instance the Imercare references by the company Imerys;

- mixtures thereof.

Preferably, the composition according to the invention comprises, as mineral fillers, kaolin, mica, calcium carbonate and silica, and also mixtures thereof.

In accordance with a particularly advantageous embodiment of the invention, the content of mineral filler represents from 2% to 20% by weight, preferentially from 2% to 15% by weight, relative to the total weight of the composition.

Organic filler

For the purposes of the invention, the term "organic filler" refers to solid particles of at least one hydrocarbon-based or silicone compound, or combinations thereof, independently of their coating.

The fillers are in the form of particles which may or may not be surface-treated by means of compounds such as those described above in the context of the mineral fillers.

The fillers used in the compositions according to the present invention may be in lamellar, globular or spherical form, in the form of fibers or in any other intermediate form between these defined forms. The fillers may be spherical, i.e. they may comprise at least a rounded general portion, notably defining at least a sphere portion, preferably internally defining a concavity or a hollow (sphere, globules, bowls, horseshoe, and the like), or lamellar.

Among the suitable fillers, mention may be made of:

- Natural or synthetic micronized waxes.

- Metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

- Natural organic materials such as polysaccharide powders and in particular starch powders, notably crosslinked or non-crosslinked corn, wheat or rice starch powders, powders of starch crosslinked with octenylsuccinic anhydride sold under the name Dry-Flo® by the company National Starch or powders of waxy corn starch, such as those which are sold under the names C* Gel 04201 by the company Cargill, Corn Starch B by the company Roquette and Organic Corn Starch by the company Draco Natural Products, Amaze Nordic Barley by the company Nouryon, and Celus Bi Feel by the company Roelm;

- Cellulose, notably in the form of spherical particles, such as the products in the Cellulobeads range from Daito Kasei (for example Cellulobeads D-10, Cellulobeads D-5 and Cellulobeads USF). Tego Feel C10 cellulose by the company Evonik may also be used, or even microcrystalline celluloses, for example from the Vivapur range by the company Rettenmaier, or from the Avicel range by the company DuPont.

- N-(C8-C22 acyl)amino acids; the amino acid may be, for example, lysine, glutamic acid or alanine, preferably lysine. Mention may be made, for example, of lauroyl lysine notably sold under the names Amihope LL by the company Ajinomoto or Corum 5105 by the company Corum;

- Polyhdyroxyalkanoates, such as polyhydroxybutyrate particles (sold under the name Biosoft 915 by the company Micro Powders);

- Acrylic (co)polymers particles and derivatives thereof, in particular:
* polymethyl methacrylate (INCI name Methyl Methacrylate Crosspolymer), sold under the name Covabead LH85 by the company Sensient, or Polymethyl Methacrylate, under the names Sepimat P by the company SEPPIC, Microsphere M-100® by the company Matsumoto Yushi-Seiyaku;
* polymethyl methacrylate/ethylene glycol dimethacrylate (INCI name Methyl Methacrylate/Glycol Dimethacrylate Crosspolymer) sold under the name Dow Corning 5640 Microsponge Skin Oil Adsorber by the company Dow Corning;
* crosslinked acrylate (INCI name: Acrylates Crosspolymer) sold, for example, under the name Ganzpearl GMP-0820 by the company Ganz Chemical,
* the polyallyl methacrylate/ethylene glycol dimethacrylate powder sold under the name Poly-Pore L200 or Poly-Pore E200 by the company Amcol Health and Beauty Solutions Inc.;
* ethylene glycol dimethacrylate/lauryl methacrylate copolymer (INCI name: Lauryl Methacrylate/Glycol Dimethacrylate Crosspolymer) sold under the name Polytrap 6603 Adsorber by the company Amcol Health and Beauty Solutions Inc.;
* crosslinked acrylate/alkyl acrylate copolymer (INCI name: Acrylates/Ethylhexyl Acrylate Crosspolymer) sold under the name Techpolymer ACP-8C by the company Sekisui Plastics;
* ethylene/acrylate copolymer, such as the product sold under the name Flobeads® by the company Sumitomo Seika Chemicals;

* Acrylonitrile (co)polymer particles, in particular the expanded hollow particles sold under the name Expancel by the company AkzoNobel or the microspheres sold under the name Micropearl F 80 ED® by the company Matsumoto;

- Polyurethane particles, for example sold under the names D-400, D-800 (INCI name: HDI/Trimethylol Hexyllactone Crosspolymer (and) Silica), CS-400 (INCI name: HDI/PPG/Polycaprolactone Crosspolymer(and) Silica), by the company Toshiki;

- Silicone polymer particles,advantageously chosen from:
* silicone resin particles such as those sold under the INCI name Polymethylsilsesquioxane, notably sold under the name Tospearl, notably Tospearl 145 A, by the company Momentive Performance Materials,
* silicone elastomer powders coated with silicone resin, notably with silsesquioxane resin, such as the products sold under the name KSP-100, KSP-101, KSP-102, KSP-103, KSP-104 or KSP-105 (INCI name: Vinyl Dimethicone/Methicone Silsesquioxane Crosspolymer), or KSP-300 (INCI name: Diphenyl Dimethicone/Vinyl Diphenyl Dimethicone/Silsesquioxane Crosspolymer) by the company Shin-Etsu;
* silicone elastomer particles, such as the products sold under the name Dowsil 9506 Cosmetic Powder by the company Dow Corning (INCI name: Dimethicone/Vinyl Dimethicone Crosspolymer);
* Methylsilanol/Silicate Crosspolymer particles, for example in the form of bowls such as those sold notably under the name TAK-110 by the company Takemoto Oil & Fat;

- Polyamide particles, such as Nylon®, in particular Nylon 12, Nylon 6/12; such as the nylon powders sold under the names Orgasol 2002 EXS NAT COS, Orgasol 4000 EXD NAT COS Caresse, by the company Arkema;

- Tetrafluoroethylene polymer (Teflon ^â ) particles.

Preferably, if the composition comprises any, the organic filler may be chosen from cellulose particles, particles of N-(C8-C22 acyl)amino acids, such as lauroyl lysine, and also mixtures thereof.

In accordance with a particular embodiment of the invention, the content of organic filler ranges from 2% to 10% by weight, preferentially from 3% to 8% by weight, relative to the total weight of the composition.

According to a particularly advantageous embodiment of the present invention, it may be that the composition does not comprise polymeric organic fillers, considered to be microplastics. It will be recalled that, for the purposes of the invention, the term “microplastics” means solid particles, having a stable form, of polymer comprising carbon atoms in the polymer chain (backbone), of synthetic origin or of chemically modified natural origin, insoluble in water (i.e.: less than 2 g/l; OECD Directive 105), with a size less than 5 mm (and with a size less than 15 mm for fibers). The term "stable form" denotes particles remaining solid in the composition and after its use. For example, polymer particles forming a film in the composition or when said composition is used are not considered to be of stable form. Thus, preferably, it may be that the composition according to the invention does not comprise particles of acrylic polymers or copolymers, acrylonitriles, polyurethanes, polyamides, tetrafluoroethylene polymers, silicone polymers, as described previously. If, however, the composition were to comprise any, their content would preferably be less than 5% by weight, more particularly less than 2% by weight and advantageously less than 1% by weight, relative to the total weight of the composition. Preferably, if the composition comprises them, the content of organic fillers of the abovementioned microplastic type is less than or equal to 0.01% by weight, relative to the total weight of the composition, and very advantageously, the composition is devoid organic fillers/.

Preferably, the composition may comprise at least one mineral filler chosen from kaolin, mica, calcium carbonate and silica, and mixtures thereof. The composition may also comprise at least one organic filler, particularly cellulose, N-(C8-C22 acyl)amino acids, lauroyl lysine, and mixtures thereof.

The total filler content advantageously represents from 2% to 30% by weight, and preferentially from 2% to 25% by weight, relative to the total weight of the composition.

COSMETIC ADDITIVES

The compositions according to the invention may include additives commonly used in care and/or makeup products, such as active agents such as vitamins, for example vitamins A, E, C and B3, adenosine, hyaluronic acid and salts thereof; UV-screening agents; waxes; pasty compounds; hydrophilic thickeners; hydrophobic thickeners other than the clays described previously, for instance hydrophobic silicas, such as the compounds having the following INCI names: Silica Silylate, Silica Dimethyl Silylate; surfactants other than the abovementioned nonionic hydrocarbon-based surfactants with an HLB of less than or equal to 8; film-forming agents; dextrin esters; fragrances; preserving agents; and mixtures thereof. Preferably, the composition does not comprise any compound of polyphenol type. The term “polyphenol” denotes any compound having in its chemical structure at least two benzene groups, in free or fused form, each benzene group comprising at least one hydroxyl (OH) group, preferably at least 2 hydroxyl groups, or even at least 3 (OH) groups. In particular, the composition does not comprise any tannic acid, or if it does, its content does not exceed 0.5% by weight, relative to the total weight of the composition.

It is a matter of routine practice to adjust the nature and amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.

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

Wax

The composition according to the invention may comprise at least one polar or apolar hydrocarbon-based wax, a silicone wax, or mixtures thereof.

For the purposes of the present invention, the term “wax” means a lipophilic compound, which is solid at room temperature, with a reversible solid/liquid change of state, which has a melting point of greater than or equal to 30°C that may be up to 120°C.

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

The measuring protocol is as follows:
A sample of 5 mg of wax is placed in a crucible and subjected to a first temperature rise ranging from -20°C to 120°C, at a heating rate of 10°C/minute, is then cooled from 120°C to -20°C at a cooling rate of 10°C/minute and is lastly subjected to a second temperature rise ranging from -20°C to 120°C at a heating rate of 5°C/minute.
During the second temperature rise, the melting point of the solid fatty substance is measured, which corresponds to the temperature of the most endothermic peak observed on the melting curve, representing the variation in the difference in power absorbed as a function of the temperature.
The enthalpy of fusion of the wax (∆Hf), corresponding to the integral of the entire melting curve obtained, may also be measured. This enthalpy of fusion of the wax is the amount of energy required to cause the compound to change from the solid state to the liquid state. It is expressed in J/g.

Hydrocarbon-based wax

The waxes may be of plant, mineral, animal and/or synthetic origin.

In particular, the waxes have a melting point preferably greater than or equal to 35°C and better still greater than or equal to 40°C.

Apolar wax

For the purposes of the present invention, the term “apolar hydrocarbon-based wax” means a wax constituted solely of carbon and hydrogen atoms and free of heteroatoms, for instance N, O, Si, P, etc.

As examples of apolar waxes that are suitable for use in the invention, mention may notably be made of hydrocarbon-based waxes, for instance microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes and microwaxes, notably polyethylene waxes.

Polar wax

The polar waxes may notably be hydrocarbon-based or silicone waxes.

For the purposes of the present invention, the term “polar hydrocarbon-based wax” means a wax of which the chemical structure is formed essentially of, or even constituted of, carbon and hydrogen atoms, and which comprises at least one heteroatom more particularly chosen from oxygen, optionally nitrogen, or mixtures thereof. It may thus contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The term “silicone wax” means an oil comprising at least one silicon atom and notably comprising Si-O groups.

According to a first preferred embodiment, the polar wax is a hydrocarbon-based wax.

A wax chosen from ester waxes and alcohol waxes is preferred as polar hydrocarbon-based wax.

According to the invention, the term “ester wax” means a wax comprising at least one ester function. The ester waxes may also be hydroxylated.

According to the invention, the term “alcohol wax” means a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.

Use may notably be made, as ester wax, alone or as mixtures, of:
i) waxes of formula R₁COOR₂ in which R₁ and R₂ represent linear, branched or cyclic aliphatic chains, the number of atoms of which ranges from 6 to 50, notably from 10 to 50, which may contain a heteroatom, for instance O or N, and the melting point of which ranges more particularly from 30°C to 120°C. In particular, use may be made, as ester wax, of a C₂₀-C₄₀ alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C₂₀-C₄₀ alkyl stearate. Such waxes are notably sold under the names Kester Wax K 82 P^®, Hydroxypolyester K 82 P^®, Kester Wax K 80 P^® or Kester Wax K82H by the company Koster Keunen. Use may also be made of stearyl heptanoate and stearyl caprylate and mixtures thereof;
ii) bis(1,1,1-trimethylolpropane) tetrastearate,
iii) diester waxes of a dicarboxylic acid of general formula R³-(-OCO-R⁴-COO-R⁵), in which R³ and R⁵ are identical or different, preferably identical, and represent a C₄-C₃₀ alkyl group and R⁴ represents a linear or branched C₄-C₃₀ aliphatic group which may or may not contain one or more unsaturations. Preferably, the C₄-C₃₀ aliphatic group is linear and unsaturated;
iv) mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils notably containing linear or branched C₈-C₃₂ fatty chains, for instance hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil or hydrogenated coconut kernel oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold in the Phytowax Castor range, for example Phytowax Castor 22L73^®, or else the waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, such as those of the Phytowax Olive range, for example Phytowax Olive 18L57, sold by the company Sophim. Such waxes are notably described in patent application FR2792190;
v) waxes corresponding to the partial or total esters, preferably total esters, of a saturated, optionally hydroxylated, C₁₆-C₃₀ carboxylic acid with glycerol. The term “total esters” means that all the hydroxyl functions of glycerol are esterified. Examples that may be mentioned include trihydroxystearine (or glyceryl trihydroxystearate), tristearine (or glyceryl tristearate) and tribehenine (or glyceryl tribehenate), alone or as a mixture. Among the suitable compounds, mention may be made of triesters of glycerol and of 12-hydroxystearic acid, or hydrogenated castor oil, for instance Thixcin R and Thixcin E sold by Elementis Specialties,
vi) Mention may also be made of waxes of animal or plant origin, such as beeswax, synthetic beeswax, carnauba wax, candelilla wax, rice bran wax, ouricury wax, esparto grass wax, cork fiber wax, sugar cane wax, Japan wax, sumac wax, montan wax, orange wax, laurel wax, or sunflower wax, in particular in refined form;
vii) mention may also be made of natural or synthetic polyalkylenated or polyglycerolated hydrocarbon-based waxes, of animal or plant origin; the number of (C₂-C₄) oxyalkylene units may range from 2 to 100, the number of glycerol units may range from 1 to 20. Examples that may be mentioned include polyoxyethylenated beeswaxes, such as PEG-6 beeswax or PEG-8 beeswax; polyoxyethylenated carnauba waxes, such as PEG-12 carnauba; polyoxyethylenated or polyoxypropylenated and hydrogenated or non-hydrogenated lanolin waxes, such as PEG-30 lanolin or PEG-75 lanolin; PPG-5 lanolin wax glyceride; polyglycerolated beeswaxes, notably polyglyceryl-3 beeswax, the Acacia Decurrens/Jojoba/Sunflower Seed Wax/Polyglyceryl-3 Esters mixture, polyglycerolated plant waxes, such as mimosa, jojoba or sunflower waxes, and mixtures thereof (Acacia Decurrens/Jojoba/Sunflower Seed Wax Polyglyceryl-3 Esters),

According to another embodiment, the polar wax may be an alcohol wax. As alcohol waxes, mention may be made of mixtures of saturated linear C₃₀-C₅₀ alcohols, for instance the wax Performacol 550 Alcohol from New Phase Technologies, stearyl alcohol and cetyl alcohol, or mixtures thereof.

Preferably, if the composition comprises any, the wax is chosen from hydrocarbon-based waxes. More particularly, it is chosen from polar hydrocarbon-based waxes such as animal or plant waxes, animal or plant waxes obtained by catalytic hydrogenation of animal or plant oils; ester waxes such as waxes corresponding to the partial or total, preferably total, esters of a saturated, optionally hydroxylated, C₁₆-C₃₀ carboxylic acid with glycerol; and also mixtures thereof.

Silicone wax

The term “silicone wax” means an oil comprising at least one silicon atom and notably comprising Si-O groups.

As silicone wax, examples that may be mentioned include siliconized beeswax, mixtures comprising a compound of C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane (INCI name) type, for example the product Dow Corning SW-8005 C30 Resin Wax sold by the company Dow Corning. Mention may also made of mixtures comprising a compound of the C30-45 Alkyl Methicone (INCI name) type, for instance the product Dow Corning® AMS-C30 Cosmetic Wax. Preferably, the silicone wax is C30-45 alkyldimethylsilyl polypropylsilsesquioxane. It should be noted that this wax is not considered as a film-forming polymer of the silicone resin type.

The wax content, if the composition comprises any, advantageously ranges from 0.1% to 5% by weight, in particular from 0.2% to 3% by weight, relative to the total weight of the composition.

According to one embodiment, the composition comprises at least one wax chosen from total esters of a saturated, optionally hydroxylated C₁₆-C₃₀ carboxylic acid with glycerol. The term “total esters” means that all the hydroxyl functions of glycerol are esterified. By way of example, mention may be made of glyceryl trihydroxystearate (or trihydroxystearine), glyceryl tristearate (or tristearin), glyceryl tribehenate (or tribehenin), alone or as mixtures, preferably glyceryl tribehenate.

If the composition comprises any, the content of total ester of an optionally hydroxylated, saturated C16-C30 carboxylic acid with glycerol represents from 0.1% to 3% by weight and more particularly from 0.2% to 2% by weight, relative to the total weight of the composition.

Preferably, if the composition comprises any, the silicone wax content does not exceed 3% by weight relative to the total weight of the composition. Preferably, if the composition comprises any, the silicone wax content is between 0.1% and 2% by weight relative to the total weight of the composition; preferably, it does not comprise any.

Pasty compound

The composition according to the invention may also comprise at least one compound which is pasty at room temperature and atmospheric pressure.

For the purposes of the present invention, the term “pasty” refers to a lipophilic compound with a reversible solid/liquid change of state, notably having in the solid state an anisotropic crystal organization, and including at room temperature a liquid fraction and a solid fraction.

In other words, the starting melting point of the pasty compound may be lower than room temperature. The liquid fraction of the pasty compound, measured at room temperature, may represent 9% to 97% by weight of the pasty compound. This fraction that is liquid at room temperature preferably represents between 15% and 85%, more preferably between 40% and 85%, by weight.

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

The pasty compound may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin.

The pasty compound(s) may in particular be chosen from:
- lanolin and derivatives thereof, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, and oxypropylenated lanolins,
- petroleum jelly (also known as petrolatum),
- ethers of pentaerythritol and of C₂-C₄, polyalkylene glycol, for example the compounds having the following INCI names: PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether, and mixtures thereof. Mention may be made, for example, of the mixture sold under the name Lanolide by the company Vevy,
- liposoluble polyethers resulting from polyetherification between one or more C₂-C₁₀₀ and preferably C₂-C₅₀ diols. Among the liposoluble polyethers, consideration is given in particular, to copolymers of ethylene oxide and/or of propylene oxide with long-chain C₆-C₃₀ alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or propylene oxide to alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will notably be made of the product having the INCI name PEG-45/Dodecyl Glycol Copolymer sold, for example, under the brand name Elfacos ST9 by the company Akzo Nobel,
- esters resulting from the condensation of a preferably saturated, linear or branched, C₆-C₁₀ dicarboxylic acid and of an ester of diglycerol and of optionally hydroxylated, preferably saturated, linear or branched, C₆-C₂₀ monocarboxylic acids, in particular the diester obtained by condensation of adipic acid and of a mixture of esters of diglycerol with a mixture of C₆-C₂₀ fatty acids, such as caprylic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, notably sold under the reference Softisan® 649 by the company Cremer Oleo (INCI name: Bis-Diglyceryl Polyacyladipate-2),
- triglycerides of fatty acids which are optionally hydrogenated (totally or partially), saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated, preferably C₁₂-C₁₈; for instance the glycerides of saturated C₁₂-C₁₈ fatty acids sold under the name Softisan 100® by the company Cremer Oleo (INCI name: Hydrogenated Coco-Glycerides),
- esters of diol dimer, or of polyol, and of diacid dimer, for instance:
* esters of dimer of dilinoleyl alcohol and of dilinoleic acid, the hydroxyl groups of which are esterified with a mixture of phytosterols, of behenyl alcohol and of isostearyl alcohol, for example the ester sold under the name Plandool G by the company Nippon Fine Chemical (INCI name: Bis-Behenyl / Isostearyl / Phytosteryl Dimer Dilinoleyl Dimer Dilinoleate);
* esters of dilinoleic acid and of a mixture of phytosterols, of isostearyl alcohol, of cetyl alcohol, of stearyl alcohol and of behenyl alcohol, for example the ester sold under the name Plandool H or Plandool S by the company Nippon Fine Chemical (INCI name: Phytosteryl/Isostearyl/Cetyl/Stearyl/Behenyl Dimer Dilinoleate);
- butters of plant origin, such as mango butter, such as the product sold under the name Lipex 203 by the company Aarhuskarlshamn, shea butter, in particular the product whose INCI name is Butyrospermum Parkii Butter, such as the product sold under the reference Sheasoft^® by the company Aarhuskarlshamn, cupuacu butter (Rain Forest RF3410 from the company Beraca Sabara), murumuru butter (Rain Forest RF3710 from the company Beraca Sabara), cocoa butter; and also orange wax, for instance the product sold under the reference Orange Peel Wax by the company Koster Keunen,
- totally or partially hydrogenated plant oils, for instance hydrogenated soybean oil, hydrogenated coconut kernel oil, hydrogenated rapeseed oil, mixtures of hydrogenated plant oils such as the mixture of hydrogenated soybean, coconut kernel, palm and rapeseed plant oil, for example the mixture sold under the reference Akogel^® by the company Aarhuskarlshamn (INCI name Hydrogenated Vegetable Oil), the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50®, partially hydrogenated olive oil, for instance the compound sold under the reference Beurrolive by the company Soliance,
- hydrogenated castor oil esters, such as hydrogenated castor oil dimer dilinoleate, for example Risocast-DA-L sold by Kokyu Alcohol Kogyo, and hydrogenated castor oil isostearate, for example Salacos HCIS (V-L) sold by Nisshin Oil,
- and mixtures thereof;

If the composition comprises at least one pasty compound,its/their content ranges from 0.5% to 5% by weight and preferably from 0.5% to 3% by weight, relative to the total weight of the composition.

Dextrin ester

The composition may optionally comprise at least one ester of dextrin and of a fatty acid, in particular a C12 to C24, preferably C14 to C18, fatty acid, or mixtures thereof. More preferentially, the dextrin ester is an ester of dextrin and of a C12-C18 and in particular C14-C18 fatty acid. Preferably, the dextrin ester is chosen from dextrin palmitate and dextrin myristate. These dextrin esters are, for example, commercially available, notably under the name Rheopearl from the company Chiba Flour Milling Co.

If the composition comprises any, their content ranges from 0.5% to 8% by weight, preferably from 0.5% to 5% by weight, relative to the total weight of the composition.

The invention also relates to a process for making up and/or caring for the skin and/or the lips, in particular the lips, in which the composition according to the invention is applied.

It is also pointed out that the compositions according to the invention more particularly comprise a cosmetically (or physiologically) acceptable medium, i.e. one which has a pleasant color, odor and feel and which does not give rise to any unacceptable discomfort, i.e. stinging, tautness or redness, that is liable to discourage the user from applying such compositions.

Throughout the description, including the claims, the expression “comprising a” should be understood as being synonymous with “comprising at least one”, unless otherwise specified; “at least one” meaning “one or more”.

The expressions “between ... and ...” and “ranging from ... to ...” should be understood as meaning limits included, unless otherwise specified.

Unless otherwise indicated, the contents are expressed as the active material of the ingredient(s) under consideration.

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

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

The starting materials are referred to by their chemical name or their INCI name.

EXAMPLES Protocol for measuring the viscosity

The viscosity measurement is performed with a sample of composition at 25°C, at least 24 hours after its manufacture (storage at room temperature), using a Rheomat RM180 viscometer equipped with a No. 2, 3 or 4 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the formulation, at a shear rate of 200 revolutions/minute (rpm).

Protocol for measuring the tack

Materials used :
* White supplale strip 150 cm×25 cm (Supplier: Soudotique, reference: DFSUP15025B)
* White supplale ring 38 mm diameter (Supplier: Soudotique, reference: DESUPDIAM38B)
* Stable Micro Systems Texturometer (model: TA.XT. plus) and its “Exponent” software
* Mobile measuring ring allowing the 38 mm diameter supplale ring to be attached.

Preparation of the deposit:
* Delineate the length of the deposit (10 cm) on a white supplale strip.
* Apply the composition packaged in a hot-water bottle with a dipping applicator, so as to obtain four layers, in the following manner:
a) remove the applicator without wiping off the excess on the edges and, on the “leather” side of the support, apply the composition along the 10 cm length. Make as many passes as required, always in the same direction, along the entire length and without turning the applicator over, to obtain a deposit of uniform thickness. (= application 1);
b) rotate the supplale strip through 180° (in such a manner that the second layer of composition is applied in the opposite direction);
c) remove the applicator without wiping the excess from the edges, and apply a new layer of composition over the preceding one, along the length of the 10 cm applied, under the same conditions as in step 1 (= application 2);
- repeat steps b) and c) twice;
* Leave to dry for 1h on a hotplate at 32°C.

Measure the tack with a texturometer :
The test parameters are indicated below:

Approach speed (or pre-speed)	1 mm/s
Speed (from detection of contact)	0.5 mm/s
Withdrawal speed (or post-speed)	40 mm/s
Force (and corresponding pressure)	800 g
Holding time	5 s
Trigger Force	5 g
Maximum following speed	5 mm/s

The tack is characterized by the disbonding work measured during discharge (tensile phase), corresponding to the peak force (expressed positively in g) and the area (expressed positively in g/sec) under the time axis.

The higher the peak force value, the tackier the deposit.

Three samples are prepared and two measurements are taken on the same sample: the first at the center of the sample, the second at a different point on the sample, not at the ends of the strip. A new white supplale ring is placed in the mobile for each new measurement.

The result is the mean of the three sample measurements.

Protocol for measuring the staying power and the transfer

1. Preparation of the test:

Support: Beige Supplale (2.5 x 5 cm) (sold by Soudotique).

Spread composition (D) over the entire surface three times in a row in order to have a uniform deposit. Repeat the operation on two other strips.
Allow the deposit to dry on a plate heated at 32°C for 45 minutes.
If necessary, take a photo of each support with the deposit (made up) before stressing.

2. Stresses:

Preparation of a paper tissue for each stress:
Fold each paper tissue twice along the long edge and then twice in the other direction to form a square.

Dry resistance:

Rub once with the folded tissue lengthwise against one of the three made-up supports; the force applied is that normally exerted when removing makeup from the skin or the lips.
Observe the state of the rubbed support and the used surface of the tissue, in particular the remaining color and the transferred color.
If necessary, take a photo.

It should be noted that the transfer resistance is evaluated with this stress.

If several passes are made, they should be performed with the same force and always in the same direction (i.e. after each pass, the tissue is lifted to be repositioned at the "start" of the strip so as to be reapplied on the deposit in the same way as in the previous pass). If necessary, take a photo between each step or only at the end of the evaluation. This type of process can be used to evaluate the overall resistance of the deposit.

Water resistance :

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

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

Oil resistance:

Perform the same protocol as for the water resistance, on the third made-up support, replacing the water with the same amount of olive oil (Refined Olive Oil - Aarhuskarlshamn).

Grading:

For each stress, record the result according to the table below:

Deposit grade	State of the deposit	Tissue grade	Surface of the tissue in contact with the deposit
- -	Total or partial removal of the deposit from the rubbed area; the surface of the support appears in places	5	Very intense coloring - very substantial to total color transfer
-	Partial removal resulting in significantly and visibly less intense coloring of the deposit.	4	Intense coloring - substantial color transfer
+	Decrease in color intensity of the deposit which is noticeable but does not reveal the support	3	Medium coloring - moderate color transfer
++	No substantial change in the deposit color	2	Slight coloring - little color transfer
+++	No variation in the deposit color	1	No coloring or barely visible coloring - very little or no color transfer

Example 1 1. Composition

The following composition, the list of ingredients and the mass percentage contents of which are collated in the table below, was prepared:

Phases	Ingredients (INCI name)	Composition 1
A1	Isododecane (Isodecane, Ineos)	16.89
A1	Trimethyl siloxysilicate (SR1000, Momentive Performance Materials)	5
A1	Nylon-611/Dimethicone copolymer (Dowsil 2-8179 Gellant, Dow)	3.33
A2	Polyglyceryl-6 polyricinoleate (SY-Glyster CRS-75, Sakamoto Yakuhin)	3.44
A2	Dicapryl ether	1.15
A3	Disteardimonium hectorite (Bentone 38 VCG, Elementis)	1.37
A4	Calcium carbonate (Omyacare Extra 35-OG, Omya)	5.75
B1	Water	30.76
B1	Pullulan (Cosmetic Grade Pullulan, Hayashibara)	7.69
B2	Glycerol	5
B2	Denatured alcohol	9.62
C	Mica (Mearlmica SV, Sun Chemicals)	2.5
C	Red 7 (Unipure Red LC 3079, Sensient)	7.5

2. Preparation of the compositions

Preparation of aqueous phase B: at room temperature, mix B1 for 5 minutes in a speedmixer at 3500 rpm, then add B2 and stir again for 5 minutes at 3500 rpm.
Preparation of the fatty phase: in a heating pan, place the ingredients of phase A1, with stirring using a Rayneri rotor-stator blender at 1000 rpm for 10 minutes at 60°C until totally dissolved, then pour in A2, then A3 once the mixture is homogenized, and continue stirring for 10 minutes. Allow the resulting mixture to cool to room temperature and add A4, with stirring for 10 minutes, until the fillers are well dispersed.
Preparation of the emulsion: at room temperature, slowly pour the aqueous phase B into the preceding preparation A, with stirring using a Rayneri rotor-stator blender.
Leave stirring for 5 min at 3500 rpm.
Preparation of phase C: place the ingredients of phase C in the bowl of an IKA MV20 mill and blend at maximum speed four times for 15 seconds, taking care after each 15 seconds to loosen any powder that may have adhered to the walls.
Add the resulting phase C with stirring using a Rayneri blender at 3500 rpm for a further 5 minutes until the composition is homogeneous.

3. Evaluation of the compositions

A homogeneous composition, which does not leach after 24 hours at room temperature, is obtained.

On making up the lips, composition 1 is applied very easily with a dipping applicator, affording a uniform, intense matte color.

The film obtained after drying is sparingly tacky, comfortable, does not transfer and does not migrate into the fine lines.

The deposit was evaluated in a test of resistance to mechanical stress and chemical attack (dry rubbing, water and oil) according to the staying power and transfer protocol detailed previously.

The table below collates the results obtained:

	Composition 1
Type of attack	Dry	Water	Oil
Grade: state of the deposit	+++	+++	++
Grade: surface state of the tissue in contact with the deposit	1	1	2

Surprisingly, composition 1 has very good staying power and shows little or no transfer, even though the silicone resin content is relatively low.

Comparative Example 2 1. Compositions

The following compositions, the list of ingredients and mass percentage contents of which are collated in the table below, were prepared. Composition 2 is in accordance with the invention; composition A is a comparative composition since it contains no pullulan.

Phases	Ingredients (INCI name)	Composition 2	Composition A
A1	Polyglyceryl-6 Polyricinoleate (SY-Glyster CRS-75, Sakamoto Yakuhin)	3.44	3.44
A1	Dicaprylyl ether (Cetiol OE, BASF)	1.15	1.15
A1	Undecane (and) Tridecane (Cetiol UT, BASF)	16.86	16.86
A1	Trimethyl siloxysilicate (SR1000, Momentive Performance Materials)	5	5
A1	Nylon-611/Dimethicone copolymer (Dowsil 2-8179 Gellant, Dow)	3.33	3.33
A2	Disteardimonium Hectorite (Bentone 38 VCG, Elementis)	1.37	1.37
A3	Calcium carbonate (Omyacare Extra 35-OG, Omya)	5.75	5.75
B1	Water	30.76	38.45
B1	Pullulan (Cosmetic Grade Pullulan, Hayashibara)	7.69	0
B2	Glycerol	5	5
B2	Denatured alcohol	10	10
C	Mica (Mearlmica SV, Sun Chemicals)	2.5	2.5
C	Red 7 (Unipure Red LC 3079, Sensient)	7.5	7.5

2. Preparation of the composition

Preparation of aqueous phase B: at room temperature, mix B1 for 5 minutes in a speedmixer at 3500 rpm, then add B2 and stir again for 5 minutes at 3500 rpm.
Preparation of the fatty phase: in a heating pan, place the ingredients of phase A1, with stirring using a Rayneri rotor-stator blender at 2000 rpm for 10 minutes at 75°C until totally dissolved, then, with continued stirring, pour in A2, then A3 once the mixture is homogenized.
Continue stirring for 10 minutes. Allow to cool and introduce A4, with stirring for a further 10 minutes until the fillers are well dispersed and the mixture has returned to room temperature.
Emulsification: at room temperature, slowly pour the aqueous phase B into the preceding preparation A, with stirring using a Rayneri rotor-stator blender.
Leave stirring for 5 min at 3300 rpm.
Preparation of phase C: place the ingredients of phase C in the bowl of an IKA MV20 mill and blend at maximum speed four times for 15 seconds, taking care after each 15 seconds to loosen any powder that may have adhered to the walls.
Add the resulting phase C with stirring using a Rayneri blender at 3300 rpm for a further 5 minutes until the composition is homogeneous.

3. Evaluation of the compositions

Composition	Comments
Composition 4 invention	Homogeneous composition, no leaching after 24 hours at room temperature. On making up the lips, the composition is applied very easily with a dipping applicator, affording a uniform, intense matte color. The film obtained after drying is sparingly tacky, comfortable, does not transfer and does not migrate into the fine lines.
Composition A comparative	Homogeneous composition, no leaching after 24 hours at room temperature. On making up the lips, the composition is applied very easily with a dipping applicator, affording a uniform, intense matte color. The film obtained after drying is tackier than composition 1, and transfers more after the oil test. The film does not migrate into the fine lines.

The table below collates the results obtained:

	Composition 1			Composition A
Type of attack	Dry	Water	Oil	Dry	Water	Oil
Grade: state of the deposit	+++	+++	++	+++	+++	++
Grade: surface state of the tissue in contact with the deposit	1	1	2	1	1	4

Claims

A cosmetic composition for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, in the form of a water-in-oil emulsion comprising:
- at least 3% by weight of pullulan relative to the total weight of the composition;
- at least 12% by weight, relative to the total weight of the composition, of at least a first apolar hydrocarbon-based oil comprising from 8 to 16 carbon atoms;
- at least one silicone film-forming polymer chosen from silicone resins, silicone acrylate copolymers, silicone acrylamide copolymers, and also mixtures thereof,
- at least one dyestuff.
The composition as claimed in claim 1, characterized in that the pullulan content is between 4% and 15% by weight, more particularly between 5% and 10% by weight, relative to the total weight of the composition.
The composition as claimed in either of the preceding claims, characterized in that the first apolar hydrocarbon-based oil is chosen from branched C8-C16 alkanes preferably such as isododecane, isodecane, isohexadecane, C8-9 isoalkane, C11-13 isoalkane, and mixtures thereof; from linear alkanes, preferably C8-C14 alkanes, and mixtures thereof, preferably such as n-dodecane, n-tetradecane, C9-12 alkane, the undecane-tridecane mixture; and also mixtures thereof; and preferably from isododecane, undecane, tridecane and C9-12 alkane, alone or as mixtures.
The composition as claimed in any one of the preceding claims, characterized in that the content of apolar hydrocarbon-based first oil(s) represents from 12% to 40% by weight and preferably from 12% to 35% by weight relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the film-forming polymer is chosen from:
- non-glycerolated silicone resins chosen from alkyl siloxysilicate, aryl siloxysilicate, alkylaryl siloxysilicate and polysilsesquioxane resins, and also mixtures thereof; more particularly from silicone resins having the following INCI names: Trimethyl siloxysilicate, Phenylpropyldimethyl siloxysilicate, Polymethylsilsesquioxane, Polypropylsilsesquioxane, and also mixtures thereof;
- glycerolated silicone resins, notably of formula:
(R¹ ₃SiO_1/2)_a(R²(CH₃)₂SiO_1/2)_b(R³ ₃SiO_1/2)_c(R¹ ₂SiO_2/2)_d(R¹SiO_3/2)_e(SiO_4/2)_f (1)
in which:
- each R¹, which may be identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof;
- each R² is a mono- or poly-glycerol group of the general formula (2) below
-(CH₂)₂—C_lH_2l—O—(CH₂CH(OH)CH₂O)_iR⁴ (2), in which R⁴ is a substituted or unsubstituted monovalent hydrocarbon-based group or a hydrogen atom, and the indices l and i are integers satisfying the conditions 0 ≤ l ≤ 15 and 0 < i ≤ 5,
- each R³ is an identical or different group of general formula (3), (4), (5) or (6) below:
—(CH₂)₂—C_mH_2m—(SiOR¹ ₂)j—SiR¹ ₃ (3)
—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ ₃)_3−k1) (4)
—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ ₃)_3−k2)_3−k1 (5)
—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ _k3(OSiR¹ ₃)_3−k3)_3−k2)_3−k1 (6)
in which
- each R¹, which may be identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted, amino-substituted or carboxyl-substituted group thereof;
- the indices m, j and k₁ to k₃ are integers that satisfy the following conditions: 0 ≤ m ≤ 5, 0 ≤ j ≤ 500, 0 ≤ k₁ ≤ 2, 0 ≤ k₂ ≤ 2 and 0 ≤ k₃ ≤ 2;
- the indices a, b, c, d, e and f are numbers that satisfy the following conditions: 0 ≤ a ≤ 400, 0 < b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0 < f ≤ 1000 and 0.5 ≤ (a+b+c)/f ≤ 1.5; and preferably of formula [(CH₃)₃SiO_1/2]_a[R(CH₃)₂SiO_1/2]_b(SiO_4/2)_f (21) in which R denotes the 3-glyceroxypropyl group of structure -C₃H₆OCH₂-CH(OH)CH₂OH; the indices a, b and f are integers which satisfy the conditions 0 ≤ a ≤ 400, 0 < b ≤ 30, 0 < f ≤ 1000 and 0.5 ≤ (a+b)/f ≤ 1.5;
- silicone acrylate copolymers chosen from vinyl polymers grafted with a carbosiloxane dendrimer, in particular having the INCI name Acrylates/Polytrimethylsiloxymethacrylate Copolymer, from copolymers including (meth)acrylic groups and polydimethylsiloxane groups, in particular having the INCI name Acrylates/Dimethicone Copolymer, and mixtures thereof;
- mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that the silicone film-forming polymer is chosen from non-glycerolated or glycerolated, and preferably non-glycerolated, silicone resins, in particular chosen from trimethyl siloxysilicate, polymethylsilsesquioxane, polypropylsilsesquioxane, and mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that the content of silicone film-forming polymer represents from 2% to 25% by weight and preferably from 3% to 20% by weight relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one mineral lipophilic thickener, in particular chosen from lipophilic clays, more particularly from lipophilic clays of the hectorite type comprising at least one quaternary ammonium group, bentonites comprising at least one quaternary ammonium group, or mixtures thereof, and preferably from disteardimonium hectorite, stearalkonium hectorite, Quaternium-18 hectorite, and also mixtures thereof, and even more preferentially disteardimonium hectorite.
The composition as claimed in any one of the preceding claims, characterized in that the content of mineral thickener represents from 0.2% to 4% by weight and preferably from 0.3% to 3% by weight relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the water content is at least 20% by weight, preferably between 20% and 50% by weight, and more preferably between 20% and 40% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the composition optionally comprises at least one second oil, different from the first oil(s), chosen from nonvolatile, polar or apolar hydrocarbon-based oils, from volatile or nonvolatile silicone oils, and also mixtures thereof.
The composition as claimed in the preceding claim, characterized in that the second oil is chosen from polar nonvolatile hydrocarbon-based oils such as:
- C10-C26 alcohols;
- ethers of formula ROR’ or carbonates of formula RO(CO)OR’, in which formulae the groups R and R’, which may be identical or different, represent a saturated or unsaturated, branched or unbranched, hydrocarbon-based group comprising not more than 16 carbon atoms;
- oils comprising one or more ester functions and comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon-based group comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; the ester oil may optionally comprise one or more ether or hydroxyl functions;
- liquid polyesters derived from the reaction of a monounsaturated or polyunsaturated acid dimer, the fatty acid comprising from 16 to 22 carbon atoms;
- and also mixtures thereof;
and preferably from plant oils; ester oils, comprising 1 to 4 ester functions, and comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon-based group, comprising at least 6 carbon atoms, preferably at least 8 carbon atoms; the ester oil may optionally comprise one or more ether or hydroxyl functions; ether oils of formula ROR’ in which R and R’, which may be identical or different, represent a saturated or unsaturated, branched or unbranched hydrocarbon-based group comprising not more than 16 carbon atoms; mixtures thereof.
The composition as claimed in either of claims 11 and 12, characterized in that the content of second oil(s), if the composition comprises any, does not exceed 15% by weight, and preferably ranges from 0.1% to 15% by weight relative to the total weight of the composition.
The composition as claimed in claim 11, characterized in that if the composition comprises at least one volatile or nonvolatile silicone oil, then their content does not exceed 5% by weight, advantageously does not exceed 3% by weight, and preferably does not exceed 1% by weight, relative to the total weight of the composition; preferably, the composition does not contain any.
The composition as claimed in any one of the preceding claims, characterized in that the dyestuff is chosen from pulverulent dyestuffs, liposoluble dyes, water-soluble dyes and mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one nonionic hydrocarbon-based or silicone surfactant with an HLB of less than or equal to 8, chosen from (poly)oxyethylenated or (poly)oxypropylenated C8-C30 alcohols, (poly)oxyethylenated or (poly)oxypropylenated C8-C30 esters, preferably polyhydroxylated C12-C20 fatty acid polyesters, which are polyoxyalkylenated, containing from 4 to 50 mol ethylene oxide, (C8-C30)alkyl and poly(C8-C30)alkyl sorbitan esters, (C8-C30)alkyl and poly(C8-C30)alkyl (poly)glycerol esters, alone or as mixtures; nonionic silicone surfactants chosen from oxyalkylenated (C2-C3) polydimethylmethylsiloxanes with an HLB ≤ 8, preferably having the following INCI names: PEG/PPG-8/8 Dimethicone, Bis-PEG/PPG-14/14 Dimethicone, PEG/PPG-18/18 Dimethicone, PEG/PPG-19/19 Dimethicone, PEG-3 Dimethicone, PEG-10 Dimethicone, and also mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one polyglycerolated nonionic hydrocarbon-based surfactant with an HLB ≤ 8, more particularly chosen from:
- polyglycerol esters of isostearic acid containing from 2 to 10 mol of glycerol units, such as polyglyceryl-4 isostearate, polyglyceryl-3 diisostearate; polyglyceryl-2 diisostearate, polyglyceryl-10 isostearate, polyglyceryl-2 triisostearate;
- polyglycerol esters of stearic acid containing from 2 to 3 mol of glycerol units, such as polyglyceryl-2 sesquistearate, polyglyceryl-3 distearate, polyglyceryl-2 stearate;
- polyglycerol esters of oleic acid containing from 2 to 3 mol of glycerol units, such as polyglyceryl-2 oleate, polyglyceryl-3 oleate, polyglyceryl-2 dioleate; polyglyceryl-3 dioleate;
- polyglyceryl polyricinoleate(s) containing from 3 to 6 mol of glycerol units, such as polyglyceryl-3 polyricinoleate; polyglyceryl-5 polyricinoleate; polyglyceryl-6 polyricinoleate;
- mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one polyglycerolated, nonionic hydrocarbon-based surfactant chosen from polyglyceryl polyricinoleate(s) containing from 3 to 6 mol of glycerol units, in particular polyglyceryl-6 polyricinoleate.
The composition as claimed in any one of claims 16 to 18, characterized in that the content of hydrocarbon-based or silicone surfactant(s), preferably nonionic hydrocarbon-based surfactants, represents from 2% to 10% by weight and preferably from 2% to 7% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one saturated or unsaturated, linear or branched C2-C8 and preferably C3-C6 polyol that is liquid at room temperature, comprising from 2 to 6 hydroxyl groups; more particularly chosen from glycerol, diglycerol, linear or branched, saturated C3-C8 glycols or alkanediols, in particular propylene glycol, propanediol, butylene glycol, pentanediol, pentylene glycol, caprylyl glycol or dipropylene glycol, and also mixtures thereof, and preferably glycerol.
The composition as claimed in the preceding claim, characterized in that the polyol content ranges from 3% to 20% by weight and in particular from 4% to 15% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one C2-C6, more particularly C2-C4, monoalcohol, preferably chosen from ethanol, isopropanol, tert-butanol or butanol, or mixtures thereof, and preferably at least ethanol.
The composition as claimed in the preceding claim, characterized in that the monoalcohol content represents from 3% to 20% by weight and preferably from 5% to 15% by weight relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one wax chosen from total esters of an optionally hydroxylated, saturated C16-C30 carboxylic acid with glycerol, preferably glyceryl trihydroxystearate, glyceryl tristearate or glyceryl tribehenate, alone or as a mixture, preferably glyceryl tribehenate.
The composition as claimed in the preceding claim, characterized in that the content of waxes chosen from total esters of an optionally hydroxylated, saturated C16-C30 carboxylic acid with glycerol represents from 0.1% to 3% by weight and more particularly from 0.2% to 2% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that it comprises:
- at least one mineral filler chosen from silica, perlite, zeolites, carbonate or hydrogen carbonate of alkaline-earth metals such as calcium or magnesium, hydroxyapatite, kaolin, talc, synthetic or natural mica, boron nitride, glass or ceramic microcapsules, barium sulfate, diatomaceous earth, mixtures thereof; preferably chosen from kaolin, mica, calcium carbonate and silica, and also mixtures thereof;
- organic fillers chosen from natural or synthetic micronized waxes, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, polysaccharide powders, cellulose, N-acylamino acids containing from 8 to 22 carbon atoms, polyhdyroxyalkanoates, particles of acrylic (co)polymers, acrylonitrile (co)polymers, polyurethane, silicone polymers, polyamide, tetrafluoroethylene, and mixtures thereof, preferably chosen from cellulose, C8-C22 N-acylamino acids, and mixtures thereof;
- mixtures thereof.
The composition as claimed in the preceding claim, characterized in that the content of mineral filler represents from 2% to 20% by weight and preferentially from 2% to 15% by weight relative to the total weight of the composition.
The composition as claimed in claim 26, characterized in that the content of organic filler represents from 2% to 10% by weight and more particularly from 3% to 8% by weight relative to the total weight of the composition.
A process for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, in which the composition as claimed in any one of the preceding claims is applied.