FR3134970A1 - Makeup kit for eyebrows and the skin around the eyebrows comprising an anhydrous film-forming composition and a 3-layer makeup composition and makeup process - Google Patents

Abstract

Makeup kit for eyebrows and the skin around the eyebrows comprising an anhydrous film-forming composition and a makeup composition and 3-layer makeup process. The present invention relates to a kit for makeup of keratin materials, in particular, eyebrows and the skin around the eyebrows, comprising:1) a first anhydrous film-forming composition (A) comprising, in particular in a physiologically acceptable medium:i) an oily phase comprising at least one hydrocarbon oil, preferably volatile; andii) at least one hydrophobic film-forming polymer different from silicone acrylate copolymers; and 2) a second composition (B) comprising, in particular in a physiologically acceptable medium:i) at least one polyphenol said phenol groups of polyphenol X; andiii) at least one mono-alcohol having 2 to 8 carbon atoms; and iv) at least one uncoated iron oxide pigment.

Description

Makeup kit for eyebrows and the skin around the eyebrows comprising an anhydrous film-forming composition and a 3-layer makeup composition and makeup process

The present invention aims to propose for the field of makeup of keratin materials, in particular eyebrows and the skin around the eyebrows, a new makeup kit with two compositions (A) and (B) which is particularly interesting with regard to its technical performances. and the aesthetic result that it provides to the user when applied to them and in particular to the eyebrows.

The invention also relates to a cosmetic process for making up keratin materials, in particular the eyebrows and the skin around the eyebrows, comprising at least a first step of applying a first layer with an anhydrous film-forming composition (A) which will be detailed below on said keratin materials, a second step of application to the layer formed by composition (A) of at least a second layer of a makeup composition (B) which will be detailed below, followed by application of a third layer with composition (A).

To obtain coloring of keratin materials, in particular of the eyebrows, numerous eyebrow makeup products are known from the prior art. They can be based on makeup products: pencils, powders, hot melts, ointments, etc. as well as on the use of direct dyes, but these products do not permanently dye the skin around the eyebrows and the results evolve over time. daytime.

There are also products based on oxidation coloring but require mixing at the time of use. This type of product does not allow the result to be projected before the rinsing step and also does not allow the result obtained to be corrected.

A solution also consists of applying a water-resistant makeup product based on the combination of an MQ type silicone resin with a high molecular weight silicone resin but the makeup result of this solution lasts a maximum of two days (WUNDERBROW 2 ® product range from Wonder 2).

A final solution known from the prior art consists of applying products containing a self-tanning active ingredient such as dihydroxyacetone DHA, associated or not with direct dyes, but this solution is limited in terms of color offering and the colorings are mainly orange.

Eyebrow coloring is an engaging act that can scare users for several reasons. The modification of the eyebrow and in particular its color strongly impacts the perception of the face. Users generally fear chemistry and want a surface makeup act with a semi-permanent result rather than a long-lasting coloring such as oxidation coloring as used in the field of hair coloring.

Users of products for coloring keratin materials such as eyebrows are looking for a surface makeup gesture with a semi-permanent result, that is to say, removable after a few days, while maintaining control over the final result and particular allowing it to be viewed in advance. In fact, users want to be able to make corrections or touch-ups in the event of overflows during application before fixing the result over several days.

Double gesture makeup routines are well known to those skilled in the art. They consist of adding color with a first makeup composition also called base coat and then applying on this first layer a second transparent fixing composition also called top coat and intended to protect this color. However, superimposing the two layers is delicate because the application of the top coat must not remove the base coat. In addition, this superposition often generates a thick deposit which then becomes uncomfortable because it is too present on the skin.

There therefore remains a need to find a multi-stage makeup process for keratin materials, in particular the eyebrows and the skin around the eyebrows, which does not present the aforementioned drawbacks, which is easy to implement and which leads to a fine deposit. comfortable, holds well on the surface of the made-up keratin material and whose color does not transfer.

Unexpectedly, the inventors have found that it is possible to achieve these objectives with a cosmetic process for making up keratin materials, in particular the eyebrows and the skin around the eyebrows, comprising at least the following 3 steps:
- the application of a first layer with an anhydrous film-forming composition (A) comprising, in particular in a physiologically acceptable medium:
i) an oily phase comprising at least one hydrocarbon oil, preferably volatile; And
ii) at least one hydrophobic film-forming polymer different from silicone acrylate copolymers; And
- the application of a second layer with a composition (B) comprising, in particular in a physiologically acceptable medium:
i) at least one polyphenol X comprising at least two different phenol groups, and
ii) at least one polyoxyethylenated compound Y capable of forming at least two hydrogen bonds with said phenol groups of polyphenol X; And
iii) at least one mono-alcohol having 2 to 8 carbon atoms; And
iv) at least one uncoated iron oxide type pigment; And.
- applying a third layer of composition (A) to the layer formed by composition (B).

The inventors were thus able to find a makeup process allowing the superposition of three layers with only two compositions. This superposition is made possible thanks to the layer of ethanolic colored composition (B) which is incompatible with the volatile hydrocarbon oil of the first layer of composition (A). The application of the first coat does not need to be precise. The application of color is easier on the film deposited by the first composition compared to direct application of color to the skin. This superposition is possible because the color remains insensitive to the application of the last layer. The color is durable with very good comfort.

This discovery is the basis of the invention.

Objects of the invention

Thus, a first object of the present invention is a makeup kit for keratin materials, in particular eyebrows and the skin around the eyebrows, comprising:
1) a first anhydrous film-forming composition (A) comprising, in particular in a physiologically acceptable medium:
i) an oily phase comprising at least one hydrocarbon oil, preferably volatile; And
ii) at least one hydrophobic film-forming polymer different from silicone acrylate copolymers; And
2) a second composition (B) comprising, in particular in a physiologically acceptable medium:
i) at least one polyphenol X comprising at least two different phenol groups, and
ii) at least one polyoxyethylenated compound Y capable of forming at least two hydrogen bonds with said phenol groups of polyphenol X; And
iii) at least one mono-alcohol having 2 to 8 carbon atoms; And
iv) at least one pigment of the uncoated iron oxide type.

A second object of the present invention relates to a cosmetic process for making up keratin materials, in particular eyebrows and the skin around the eyebrows, comprising at least:
- the application of a first layer with a composition (A) as defined above on said keratin materials, and
- the application of a second layer with a composition (B) as defined above on the layer formed by composition (A); And
- applying a third layer of composition (A) to the second layer formed by composition (B).

Definitions

In the context of the present invention, the term “keratin material” means in particular the skin around the eyebrows and the eyebrows. This term “keratin materials”, within the meaning of the present invention, extends to synthetic false eyebrows.

By "physiologically acceptable", we mean compatible with the skin and/or its appendages, which has a pleasant color, odor and touch and which does not generate unacceptable discomfort (tingling, tightness), likely to distract the consumer from 'use this composition.

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

By “room temperature” we mean 25°C.

By “atmospheric pressure”, we mean 760 mm of Hg or 105 Pascals.

Anhydrous film-forming composition (A)

The first anhydrous film-forming composition (A) comprises, in particular in a physiologically acceptable medium:
i) an oily phase comprising at least one hydrocarbon oil, preferably volatile; And
ii) at least one hydrophobic film-forming polymer different from silicone acrylate copolymers.

For the purposes of the present invention, the expression "anhydrous composition" designates any composition containing less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water. relative to its total weight, and in particular a composition free of water.

By “silicone acrylate copolymer” is meant a copolymer comprising monomers capable of forming a polyorganosiloxane and monomers of the (meth)acrylic type.

Oily phase

By oil, we mean a non-aqueous compound, immiscible with water, liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg).

By hydrocarbon oil, we mean an oil comprising mainly carbon and hydrogen atoms and not including any silicon atom.

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

Hydrophobic film-forming polymers

Among the hydrophobic film-forming polymers, we will preferably choose those chosen from:
(i) silicone resins
(ii) silicone polyamides
(iii) oily dispersions; the respective definitions of which are indicated below.

Silicone resin

The composition (A) according to the invention comprises at least one silicone resin.

More generally, the term resin means a compound whose structure is three-dimensional. Silicone resins are also called silicone resins or “siloxane resins”. Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

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

The letter M represents the Monofunctional unit of formula R ₁ R ₂ R ₃ SiO _1/2 , the silicon atom being connected to a single oxygen atom in the polymer comprising this unit.

The letter “D means a Difunctional unit R ₁ R ₂ SiO _2/2 in which the silicon atom is connected to two oxygen atoms.

The letter T represents a Trifunctional unit R ₁ Si _3/2 .

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

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

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

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

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

MQ resins:

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

As an example of MQ silicone resins of the Trimethylsiloxysilicates type, we can cite those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the company Wacker, under the name “KF-7312J®” by the company Shin -Etsu, “DC 749®”, “DC 593®” by the Dow Corning company.

T resins:

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

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

MQT resins:

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

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

The MQ-T-propyl resin preferably comprises the units:

(i) (R1 ₃ SiO _1/2 ) _a
(ii) (R2 ₂ SiO _2/2 ) _b
(iii) (R3SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d
with
Ri1, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group,
a, b, c and d being mole fractions,

a being between 0.05 and 0.5,

b being between zero and 0.3,

c being greater than zero,

d being between 0.05 and 0.6,

a + b + c + d = 1,

provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

Preferably the siloxane resin comprises the units:

(i) (R1 ₃ SiO _1/2 ) _a

(ii) (R3SiO _3/2 ) _c and

(iv) (SiO _4/2 ) _d

with R1 and R3 independently representing an alkyl group having 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,

provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.

The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of
A) an MQ resin comprising at least 80 mol% of units (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d
R1 representing an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,

a and d being greater than zero,

the a/d ratio being between 0.5 and 1.5; and of

B) a propyl resin T comprising at least 80% by moles of (R3SiO _3/2 ) _c units,

R3 representing an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,

c being greater than zero,

provided that at least 40 mol% of the R3 groups are propyl groups,

where the mass ratio A/B is between 95:5 and 15:85, preferably the mass ratio A/B is 30:70.

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

Preferably, the composition according to the invention comprises, as silicone resin, at least one resin of the MQ type, more particularly of the Trimethylsiloxysilicate type, such as those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the Wacker company, under the name KF-7312J® by the Shin-Etsu company, DC 749®, DC 593® by the Dow Corning company.

According to a particular embodiment of the invention, the silicone resin is present in composition (A) in a resin dry matter content ranging from 4 to 35% by weight relative to the total weight of the composition, preferably ranging from 6% to 30% by weight and more preferably from 8% to 25% by weight relative to the total weight of composition (A).

Siliconized polyamide

The first composition (A) of the makeup kit according to the invention comprises at least one silicone polyamide.

Silicone polyamides are preferably solid at room temperature (25°C) and atmospheric pressure (760 mm Hg).

For the purposes of the invention, the term polymer means a compound having at least 2 repeating units, preferably at least 3 repeating units and better still 10 repeating units.

The silicone polyamides of the composition of the invention may be polymers of the polyorganosiloxane type such as for example those described in documents US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680 .

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

According to a first variant, the silicone polymers are polyorganosiloxanes as defined above and whose units capable of establishing hydrogen interactions are arranged in the polymer chain.

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

in which: G' represents C(O) when G represents -C(O)-NH-Y-NH-, and G' represents –NH- when G represents –NH-C(O)-YC(O)-

R ⁴ , R ⁵ , R ⁶ and R ⁷ , identical or different, represent a group chosen from:

hydrocarbon groups, linear, branched or cyclic, in C ₁ to C ₄₀ , saturated or unsaturated, which may contain in their chain one or more atoms of oxygen, sulfur and/or nitrogen, and which may be substituted in part or totally by fluorine atoms,

C ₆ to C ₁₀ aryl groups, optionally substituted by one or more C ₁ to C ₄ alkyl groups,

polyorganosiloxane chains containing or not one or more oxygen, sulfur and/or nitrogen atoms,

_{the _}

Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, saturated or unsaturated, C ₁ to C ₅₀ , which may contain one or more oxygen, sulfur and/or nitrogen atoms, and/ or carry as a substituent one of the following atoms or groups of atoms: fluorine, hydroxy, C ₃ to C ₈ cycloalkyl, C ₁ to C ₄₀ alkyl, C ₅ to C ₁₀ aryl, phenyl optionally substituted by 1 to 3 C ₁ to C ₃ alkyl, C ₁ to C ₃ hydroxyalkyl and amino C ₁ to C ₆ alkyl groups, or Y represents a group corresponding to

, and which may contain one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and

R ⁸ represents a C ₁ to C ₅₀ alkyl group, linear or branched, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups
m and n are integers ranging from 1 to 1000, preferably from 1 to 700 and even better from 6 to 200. Preferably, m is an integer ranging from 50 to 150 and n ranges from 1 to 500, preferably from 1 to 100 and better still from 4 to 25.

According to one embodiment of the invention, 80% of the R ⁴ , R ⁵ , R ⁶ and R ⁷ of the polymer are preferably chosen from the methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of the R ⁴ , R ⁵ , R ⁶ and R ⁷ of the polymer are methyl groups.

According to the invention, Y can represent various divalent groups, possibly also comprising one or two free valences to establish bonds with other units of the polymer or copolymer. Preferably, Y represents a group chosen from:

linear C ₁ to C ₂₀ alkylene groups, preferably C ₁ to C ₁₀ ,

branched alkylene groups which may contain rings and unconjugated unsaturations, at C ₃₀ to C ₅₆ ,

C ₅ -C ₆ cycloalkylene groups,

phenylene groups optionally substituted by one or more C ₁ to C ₄₀ alkyl groups,

C ₁ to C ₂₀ alkylene groups, comprising from 1 to 5 amide groups,

C ₁ to C ₂₀ alkylene groups, comprising one or more substituents, chosen from hydroxyl, C ₃ to C ₈ cycloalkane, C ₁ to C ₃ hydroxyalkyl and C ₁ to C ₆ alkylamine groups,

the polyorganosiloxane chains of formula (2) or (3):

(2)

(3)
in which R ⁴ , R ⁵ , R ⁶ , R ⁷ , T and m are as defined above.

According to the second variant, the polyorganosiloxanes can be polymers comprising at least one unit corresponding to formula (II):

(II)
in which

R ⁴ and R ⁶ , identical or different, are as defined above for formula (I),

R ¹⁰ represents a group as defined above for R ⁴ and R ⁶ , or represents the group of formula -XGR ¹² in which X and G are as defined above for formula (I) and R12 represents an atom hydrogen or a linear, branched or cyclic, saturated or unsaturated, C ₁ to C ₅₀ hydrocarbon group optionally comprising in its chain one or more atoms chosen from O, S and N, optionally substituted by one or more fluorine atoms and/or one or more hydroxyl groups, or a phenyl group optionally substituted by one or more C ₁ to C ₄ alkyl groups,

R ¹¹ represents the group of formula -XGR ¹² in which X, G and R ¹² are as defined above,

m ₁ is an integer ranging from 1 to 998, and

m ₂ is an integer ranging from 2 to 500.

According to a particular embodiment of the invention, the silicone polyamide can be a homopolymer, that is to say a polymer comprising several identical units, in particular units of formula (I) or of formula (II).

According to another particular embodiment of the invention, it is also possible to use a silicone polyamide consisting of a copolymer comprising several different units of formula (I), that is to say a polymer in which at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , X, G, Y, m and n is different in one of the patterns. The copolymer can also be formed of several units of formula (II), in which at least one of R ⁴ , R ⁶ , R ¹⁰ , R ¹¹ , m ₁ and m ₂ is different in at least one of the units .

It is also possible to use a polymer comprising 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) being able to be identical or different from each other. others.

According to a variant of the invention, it is also possible to use a polymer further comprising at least one hydrocarbon unit comprising two groups capable of establishing hydrogen interactions chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino and their combinations.

These copolymers can be block polymers, block polymers or graft polymers.

According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of formula
–C(O)NH- and –HN-C(O)-.

In this case, the film-forming agent may be a polymer comprising at least one unit of formula (III) or (IV)

Or

in which R ⁴ , R ⁵ , R ⁶ , R ⁷ , X, Y, m and n are as defined above.

In these polyamides of formula (III) or (IV), m ranges from 1 to 700, in particular from 15 to 500 and in particular from 50 to 200 and n particularly ranges from 1 to 500, preferably from 1 to 100 and better still from 4 to 25; And

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

Y is preferably a linear or branched alkylene chain or one which may comprise cycles and/or unsaturations, having from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, and better still from 2 to 6 carbon atoms , in particular of 6 carbon atoms.

In formulas (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following elements:
1 to 5 amide, urea, urethane, or carbamate groups, a C ₅ or C ₆ cycloalkyl group, and a phenylene group optionally substituted by 1 to 3 identical or different C ₁ to C ₃ alkyl groups.

In formulas (III) and (IV), the alkylene groups can also be substituted by at least one element chosen from the group consisting of:

a hydroxy group,

a C ₃ to C ₈ cycloalkyl group,

one to three C ₁ to C ₄₀ alkyl groups,

a phenyl group optionally substituted by one to three C ₁ to C ₃ alkyl groups,

a C ₁ to C ₃ hydroxyalkyl group, and

a C ₁ to C ₆ aminoalkyl group.

In these formulas (III) and (IV), Y can also represent:
[Chem 6]

where R ⁸ represents a polyorganosiloxane chain, and T represents a group of formula:

in which a, b and c are independently integers ranging from 1 to 10, and R ¹³ is a hydrogen atom or a group such as those defined for R ⁴ , R ⁵ , R ⁶ and R ⁷ .

In formulas (III) and (IV), R ⁴ , R ⁵ , R ⁶ and R ⁷ preferably represent, independently, a linear or branched C ₁ to C ₄₀ alkyl group, preferably a CH ₃ , C ₂ H ₅ , nC ₃ H ₇ or isopropyl, a polyorganosiloxane chain or a phenyl group optionally substituted by one to three methyl or ethyl groups.

According to a preferred embodiment, the silicone polyamide comprises at least one unit of formula (III) and/or (IV).

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

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

^{in which} _{_ _} at 300.

In this formulation, the units can be structured to form either a block copolymer, a random copolymer, or an alternating copolymer. In this copolymer, the units can be not only of different lengths but also of different chemical structures, for example having different Ys. In this case, the polymer can correspond to formula (VI):

in which R ⁴ to R ⁷ , X, Y, m ₃ m ₄ , n and p have the meanings given above and Y1 is different from Y but chosen from the groups defined for Y.

As before, the different units can be structured to form either a block copolymer, a random copolymer, or an alternating copolymer.

In this first embodiment of the invention, the film-forming agent may also consist of a graft copolymer. Thus, the polyamide with silicone units can be grafted and possibly crosslinked by silicone chains with amide groups. Such polymers can be synthesized with trifunctional amines.

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

in which X ¹ and X ² which are identical or different, have the meaning given for X in formula (I), is only as defined in formula (I), Y and T are as defined in formula ( I), R ¹⁴ to R ²¹ are groups chosen from the same group as R ⁴ to R ⁷ , m ₅ and m ₆ are numbers located in the range from 1 to 1,000, and p is an integer ranging from 2 to 500.

In formula (VII), we prefer that:

p is from 1 to 25, better still from 1 to 7,

R ¹⁴ to R ²¹ are methyl groups,

T responds to one of the following formulas:

in which R ²² is a hydrogen atom or a group chosen from the groups defined for R ⁴ to R ⁷ , and R ²³ , R ²⁴ and R ²⁵ are independently alkylene groups, linear or branched, more preferably, at the formula :
[Chem 12]

in particular with R ²³ , R ²⁴ and R ²⁵ representing -CH ₂ -CH ₂ -,

m ₁ and m ₂ range from 15 to 500, and better still from 15 to 45,

X ¹ and X ² represent -(CH ₂ ) ₁₀ -, and

Y represents -CH ₂ -.

These grafted silicone pattern polyamides of formula (VII) can be copolymerized with polyamide-silicones of formula (II) to form block copolymers, alternating copolymers or random copolymers. The percentage by weight of grafted silicone units (VII) in the copolymer can range from 0.5 to 30% by weight.

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

According to a variant embodiment of the invention, a copolymer of silicone polyamide and hydrocarbon polyamide can be used, i.e. a copolymer comprising units of formula (III) or (IV) and hydrocarbon polyamide units. In this case, the polyamide-silicone units can be arranged at the ends of the hydrocarbon polyamide.

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

in which R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a C ₁ to C ₄₀ alkyl group, linear or branched, preferably a CH ₃ , C ₂ H ₅ , nC ₃ H ₇ or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted by one to three methyl or ethyl groups, and m ranges from 1 to 700, in particular from 15 to 500 and in particular from 50 to 200 and n ranges in particular from 1 to 500, preferably from 1 to 100 and even better from 4 to 25.

Preferably, according to this embodiment, the groups R ⁴ , R ⁵ , R ⁶ and R ⁷ represent methyl groups, one of X and Y represents an alkylene group of 6 carbon atoms and the other an alkylene group. of 11 carbon atoms, n representing the degree of polymerization (DP) of the polymer.

As an example of such silicone polyamides, mention may be made of the compounds marketed by the company Dow Corning under the name DC 2-8179 GELLANT® (DP 100) and DC 2-8178 GELLANT® (DP 15) whose INCI name is NYLON-611/DIMETHICONE COPOLYMER.

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

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

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

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

According to a preferred embodiment, a silicone polyamide polymer with the INCI name: NYLON-611/DIMETHICONE COPOLYMER marketed by the company Dow Corning under the name DC 2-8179 GELLANT® (DP 100) is used.

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

The content of silicone polyamide, expressed as active material, preferably varies from 4 to 30% by weight, more preferably from 5 to 25% by weight, more particularly from 8 to 25% by weight relative to the weight of the composition. (HAS).

According to a particular form of the invention, the composition (A) according to the invention may comprise at least one mixture of a silicone polyamide as described above in association with a silicone resin as defined above.

Preferably, said mixture consists of a silicone polyamide with the INCI name: NYLON-611/DIMETHICONE POLYMER with a silicone resin MQ with the INCI name Trimethoxysiloxysilicate.

According to a particular form of the invention, the silicone polyamide/silicone resin mixture is present in composition (A) in a mass ratio of silicone polyamide to silicone resin ranging from 0.3 to 0.8 and more preferably from 0.4 to 0.7. According to a particular form of the invention, the silicone polyamide and silicone resin mixture is present in composition (A) in a content ranging from 8 to 50% by weight, preferably from 10 to 45% by weight and more preferably from 12 at 40% by weight relative to the weight of composition (A).

Oily dispersions

The composition (A) according to the invention comprises at least one oily dispersion comprising at least:
i) particles comprising:

a) at least one ethylenic copolymer of a ₁ ) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl, and of a ₂ ) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid groups , sulfonic acid and/or aryl such as benzyl; in particular a ₂ ) is a (C ₁ -C ₄ )(alkyl)acrylic acid, more particularly the copolymers of (C ₁ -C ₄ )alkyl (meth)acrylate and (meth)acrylic acid; And
ii) at least one polymeric stabilizing agent chosen from:
b) polymers of (C ₁ -C ₆ )(alkyl)acrylate monomers of (C ₃ -C ₁₂ )cycloalkyl such as isobornyl (meth)acrylates; And
c) copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl) acrylate of (C ₃ -C ₁₂ ) cycloalkyl such as (meth) acrylate of (C ₁ -C ₄ ) alkyl; And
iii) at least one hydrocarbon oil, preferably a volatile hydrocarbon oil.

The dispersions according to the invention therefore consist of particles, generally spherical, of at least one polymer i) stabilized on the surface by one or more stabilizing agents ii), in a non-aqueous medium.

In order to obtain the dispersion, it is proposed to polymerize particular monomers capable of forming the polymeric core i) in the presence of a statistical polymeric stabilizing agent ii) comprising mainly a soluble part ii) and a minority an insoluble part i) in the dispersion medium i.e. in the hydrocarbon liquid fatty substance(s) iii) possibly containing iv) water.

Preferably, said particles i) are not, or only slightly, crosslinked.

The polymer particles i) and the stabilizing agent(s) ii) are preferably found in the liquid hydrocarbon fatty substance(s) iii) in an amount of between 2 and 40% by weight, in particular between 4 and 35 % by weight of soluble monomer (that forming the stabilizing agent(s) ii)) and between 60% and 98% by weight, in particular from 65 to 96% by weight of insoluble monomer (that forming the particles i )).

Polymer particles i)

The particle(s) i) of the dispersion of the process of the invention consist(s) of one or more ethylenic copolymer(s) resulting from the polymerization
a ₁ ) of at least one (C ₁ -C ₄ )(alkyl)acrylate monomer of (C ₁ -C ₄ )alkyl and a ₂ ) of at least one ethylenic monomer comprising one or more carboxy, anhydride, acid groups phosphoric, sulfonic and/or aryl acid; in particular a ₂ ) is a (C ₁ -C ₄ ) (alkyl)acrylic acid.

Preferably the particle(s) i) is(are) made up of an ethylenic polymer core derived from copolymers a), as defined above.

By “ ethylenic copolymer ” we mean a polymer resulting from the polymerization of two monomers: monomer a ₁ ) (C ₁ -C ₄ )(alkyl)acrylate of
(C ₁ -C ₄ ) alkyl and a ₂ ) ethylenic monomer comprising one or more carboxy, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as phenyl.

By “ ethylenic monomer ” is meant a compound comprising at least one ethylenic unsaturation –(R _a )C=C(R _b )–, –C(R _a )=C(R _b )–R _c or >C=C( R _a )–R _b , with R _a , R _b , and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ ) alkyl group such as methyl, preferably hydrogen.

The ethylenic compound may also be a cyclic compound, preferably having 5 or 6 members, and comprising ethylenic unsaturation.

By ethylenic monomer comprising “ one or more carboxy , anhydride, phosphoric acid, sulfonic acid and/or aryl groups ” is meant that the monomer is substituted on one of the carbon atoms of the polymeric monomer by one or more groups, preferably a single group. , chosen from carboxy
–C(O)-OH, phosphoric acid –OP(O)(OH) ₂ or –P(O)(OH) ₂ , and sulfonic acid
–OS(O) ₂ -OH or –S(O) ₂ -OH, maleic anhydride, and aryl such as phenyl.

According to one embodiment of the invention, the particle(s) i) comprise a) ethylenic copolymers of a ₁ ) (C ₁ -C ₄ ) (alkyl)acrylate of
(C ₁ -C ₄ ) alkyl, and a ₂ ) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as benzyl.

More particularly the ethylenic monomers a ₂ ) comprising one or more carboxy, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3), (4):

(1) R ₁ (R ₂ )C=C(R ₃ )-Acid with R ₁ , R ₂ and R ₃ representing a hydrogen atom or a CO ₂ H, H ₂ PO ₄ , or SO ₃ H group, and Acid representing a carboxy group, phosphoric acid, sulfonic acid, preferably carboxy, preferably carboxy, preferably (1) represents (5) H ₂ C=C(R)-C(O)-OH with R represents an atom hydrogen, or a (C ₁ -C ₄ ) alkyl group such as methyl;

(2) H ₂ C=C(R)-C(O)-N(R')-Alk-Acid with R and R', identical or different, represent a hydrogen atom, or a group (C ₁ -C ₄ ) alkyl; Alk represents a group
(C ₁ -C ₆ ) alkylene optionally substituted by at least one group chosen from Acid as defined above and hydroxy; and Acid is as defined above, preferably carboxy or sulfonic acid;

(3) Ar-(Ra) C=C(Rb)-Rc with Ra, Rb and Rc, identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, and Ar represents a group aryl, preferably benzyl, optionally substituted by at least one acidic group CO ₂ H, H ₂ PO ₄ , or SO ₃ H, preferably substituted by a CO ₂ H group, or SO ₃ H)
(4) Maleic anhydride of formula (4a) and (4b):

Formulas (4b) and (4b) in which R _a , R _b and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, preferably R _a , R _b , and R _c represent a hydrogen atom. Preferably an ethylenically unsaturated anhydride monomer of the invention is of formula (4b) and more preferably is maleic anhydride; and more particularly a ₂ ) is chosen from (1) and (4), in particular (4) and (5).

According to a particular variant of the invention, a ₂ ) is a (C ₁ -C ₄ )(alkyl)acrylic acid, more particularly b) is(are) copolymers of (meth)acrylate of (C ₁ -C ₄ ) alkyl and (meth)acrylic acid.

According to another variant of the invention a ₂ ) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrene sulfonic acid, vinylbenzoic acid, vinyl phosphoric acid, acrylic acid, acrylaminopropane sulfonic acid, acrylamido glycolic acid, and their salts, more preferably a ₂ ) represents maleic anhydride.

The salts can be chosen from alkali metal salts, for example sodium, potassium; alkaline earth metal salts, for example calcium, magnesium, strontium, metal salts, for example zinc, aluminum, manganese, copper; ammonium salts of formula NH ₄ ⁺ ; quaternary ammonium salts; salts of organic amines, such as for example the salts of methylamine, diethylamides, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis-(2-hydroxyethyl)amine, tri-(2- hydroxyethyl)amine; lysine and arginine salts.

According to a preferred embodiment of the invention, the (C ₁ -C ₄ )(alkyl)acrylate monomer(s) of (C ₁ -C ₄ )alkyl a ₁ ) are chosen from those of formula (VIII):

(VIII)

Formula (VIII) in which:

R representing a hydrogen atom or (C ₁ -C ₄ ) alkyl group such as methyl, and

R' representing a (C ₁ -C ₄ ) alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, preferably methyl, ethyl or i-butyl,

preferably (VIII) represents a C ₁ -C ₄ alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate.

According to another particular embodiment of the invention, the polymer constituting the particles i) is an ethylene acrylate copolymer a) resulting from the polymerization:
- a ₁ ) of at least one monomer of formula (VIII) as defined above, preferably C ₁ -C ₄ alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and methacrylate d isobutyl; And
- a ₂ ) of at least one monomer chosen from (1), (2), (3), and (4) as defined above and preferably of formula (IX) as well as its salts:

(IX)
Formula (IX) in which R as defined above, in particular (IX) represents acrylic acid.

According to a preferred embodiment of the invention, the quantity of a ₂ ) in particular of compound (IX) and in particular of acrylic acid is greater than 2.5% by weight relative to the total weight of the particle i), more particularly between 3% and 35% by weight relative to the weight of monomers of particle i), even more particularly between 5% and 25% by weight and the polymer of particles i), better between 10% and 15 % by weight and the polymer of the particles i).

In particular a) is a copolymer resulting from the copolymerization a ₂ ) of acrylic acid with a ₁ ) one or more C ₁ -C ₄ alkyl (meth)acrylate monomers, preferably of at least 2 different monomers ( C ₁ -C ₄ alkyl meth)acrylate, in particular chosen from methyl (meth)acrylate, ethyl (meth)acrylate and butyl (meth)acrylate, isobutyl (meth)acrylate .

According to another preferred embodiment of the invention, the polymer constituting the particles i) is an ethylene acrylate copolymer a) resulting from the polymerization:

- at least two different monomers: of formula (VIII) as defined above, preferably C ₁ -C ₄ alkyl acrylate such as methyl acrylate, ethyl acrylate, ((meth )isobutyl acrylate; and

- at least one monomer chosen from (1), (2), (3), and (4) as defined above, preferably of formula (IX) as defined above.

According to a particular embodiment of the invention, the polymer of particles i) is a polymer derived from monomers a ₁ ) of C ₁ -C ₄ alkyl (meth)acrylate.

Advantageously, a linear or branched C ₁ -C ₄ alkyl acrylate monomer is used, preferably linear in particular in (C ₁ -C ₃ ). Preferably a) is chosen from methyl acrylate and ethyl acrylate.

The monomers a ₁ ) are preferably chosen from methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate and more preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate.

According to another particular embodiment of the invention, the polymer constituting the particles i) is an acrylate copolymer a) derived from:
a ₁ ) of at least one monomer of formula (VIII) as defined above; And
a ₂ ) of at least one ethylenically unsaturated anhydride monomer, in particular of formula (4) as defined above.

Particularly the polymer of particles a) is a polymer a ₁ ) of C ₁ -C ₄ alkyl (meth)acrylate monomer, linear or branched, preferably linear in particular of (C ₁ -C ₃ ) alkyl and a ₂ ) of anhydride monomer with ethylenic unsaturation.

The monomers a ₁ ) are preferably chosen from methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate.

Advantageously, a monomer or two different monomers a ₁ ) of C ₁ -C ₄ alkyl acrylate, linear or branched, are used, preferably linear, in particular in (C ₁ -C ₃ ). Preferably a ₁ ) is chosen from methyl acrylate and ethyl acrylate.

According to a particular embodiment, one or two different monomers of branched (C ₃ -C ₄ ) alkyl (meth)acrylate are used. Preferably a1) is chosen from isobutyl acrylate and isobutyl methacrylate.

According to a particular form of the invention, the ethylenically unsaturated anhydride compound(s) a ₂ ) of the invention are chosen from the derivatives of maleic anhydride (4a) and itaconic anhydride (4b) as defined above.

More preferably, the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and even more preferably is maleic anhydride.

The polymer of the particles can be chosen from: methyl acrylate/maleic anhydride copolymers; ethyl acrylate/maleic anhydride copolymers; and methyl acrylate/ethyl acrylate/maleic anhydride copolymers.

According to a preferred embodiment of the invention, the copolymer(s) of the particles i) of the oily dispersion comprise, from 80 to 95% by weight, of the ingredient a ₁ ) and from 5 to 20% by weight of the ingredient a ₂ ), relative to the total weight of the copolymer(s).

More particularly the polymer of particles i) preferably comprises from 80 to 93% by weight of ingredient a ₁ ) in particular C ₁ -C ₄ alkyl (meth)acrylate and from 7 to 20% by weight, of ingredient a ₂ ) relative to the total weight of polymer i). More preferably, the polymer of particles i) preferably comprises from 85 to 93% by weight, more particularly 87% to 92% by weight, even more preferably from 85% to 90% by weight, of ingredient a1) in particular of C ₁ -C ₄ alkyl (meth)acrylate and 10 to 20% by weight of ingredient a ₂ ) relative to the total weight of the polymer.

Advantageously, the polymer of particles i) is a non-crosslinked polymer.

According to one embodiment of the invention, the copolymers i) are chosen from:
- methyl acrylate/ethyl acrylate/acrylic acid copolymers and its salts;
- methyl acrylate/ethyl acrylate/maleic anhydride copolymers;
- methyl acrylate/acrylic acid copolymers and its salts;
- ethyl acrylate/acrylic acid copolymers and its salts;
- methyl acrylate/maleic anhydride copolymers; And
- ethyl acrylate/maleic anhydride copolymers.
- isobutyl acrylate/acrylic acid copolymers and its salts
- isobutyl acrylate/isobutyl methacrylate/acrylic acid copolymers and its salts.

The polymer of particles i) of the dispersion preferably has a number average molecular weight ranging from 2,000 to 10,000,000 g/mol.

The polymer of particles i) may be present in the oily dispersion in a content ranging from 20 to 60% by weight, relative to the total weight of the dispersion, in particular between 21% to 58.5% by weight, relative to the total weight of the dispersion, preferably ranging from 30 to 50% by weight, relative to the total weight of the dispersion, more preferably ranging from 36% to 42% by weight relative to the total weight of the oily dispersion.

Preferably the particle(s) i) consist of a copolymer of a ₁ ) and a ₂ ).

According to a particular embodiment of the invention, the particles i) consist of copolymers resulting from the polymerization of monomers a ₁ ) and a ₂ ) with a weight ratio a ₁ ) / a ₂ ) inclusively between 4.4 and 20, more particularly between 5.5 and 19, preferably between 6.5 and 16, even more preferably between 6.6 and 15.6.

The polymer particle(s) i) of the oily dispersion preferably have a number average size ranging from 5 to 600 nm, in particular ranging from 10 to 500 nm, and better still ranging from 20 to 400 nm.

The stabilizing agent(s) ii)

The oily dispersion according to the invention also comprises one or more stabilizing agents ii). Preferably only one type of stabilizing agent ii) is used in the invention.

The stabilizing agent(s) of the invention consist(s) of ethylenic polymers chosen from b) polymers of (C ₁ -C ₆ )(alkyl)acrylate monomers of (C ₃ -C ₁₂ )cycloalkyl; and c) copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl and c ₂ ) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ ) alkyl. Preferably the stabilizing agent(s) of the invention is(are) made up of ethylenic polymers chosen from c) copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl and c ₂ ) (C ₁ -C ₄ )(alkyl) acrylate of (C ₁ -C ₄ )alkyl.

According to a preferred embodiment of the invention, the stabilizing agent ii) is(are) made up of ethylenic polymers chosen from:
b) polymers of monomers of formula H ₂ C=C(R)-C(O)-O-R'' (X) with R representing a hydrogen atom or (C ₁ -C ₄ ) alkyl group such as methyl, and R'' representing a (C ₅ -C ₁₀ )cycloalkyl group such as norbornyl, or isobornyl, preferably isobornyl; And
c) copolymers of c ₁ ) H ₂ C=C(R)-C(O)-O-R'' (X) in which R and R'' have the same meanings indicated previously in b) and of
c ₂ ) H ₂ C=C(R)-C(O)-O-R' (VIII) in which R has the same meaning as that in formula (X) and R' represents a group (C ₁ -C ₄ ) alkyl.

According to a particular embodiment, the stabilizing agent(s) of the invention is(are) made up of ethylenic polymers chosen from b) polymers of (C ₁ -C ₆ )(alkyl)acrylate monomers ( C ₃ -C ₁₂ ) cycloalkyl, particularly of formula (X) as defined above.

According to another particular embodiment of the invention, the stabilizing agent(s) of the invention is(are) made up of ethylenic polymers chosen from c) copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl particularly of formula (X) as defined previously and of c ₂ ) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl particularly of formula (VIII) as defined previously.

According to a particular form of the invention, the ingredient c ₂ ) is a (C _{1 -C 4} ) (alkyl) acrylate monomer of (C ₁ -C ₄ ) alkyl in particular of formula (VIII) more particularly chosen from (meth )methyl acrylate and (meth)ethyl acrylate, more preferably methyl (meth)acrylate.

According to another particular form of the invention, ingredient c ₂ ) is a mixture of several different monomers (C ₁ -C ₄ )(alkyl) acrylate of (C ₁ -C ₄ ) alkyl, in particular 2 different monomers (C ₁ -C ₄ )(alkyl) acrylate of (C ₁ -C ₄ ) alkyl in particular of formula (VIII) more particularly chosen from methyl (meth) acrylate and ethyl (meth) acrylate.

Particularly the stabilizing agent ii) is chosen from b) polymers of (C ₁ -C ₆ )(alkyl) acrylate of (C ₃ -C ₁₂ ) cycloalkyl monomers; and c) random copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl and c ₂ ) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ - C ₄ )alkyl with a weight ratio c ₁ )/c ₂ ) greater than 4. Advantageously, said weight ratio ranges from 4.5 to 19. More advantageously, said weight ratio c ₁ )/c ₂ ) ranges from 5 to 15 , more preferably said weight ratio ranges from 5.5 to 12.

More particularly, the stabilizing agent ii) is a polymer chosen from b) the homopolymer of isobornyl (meth)acrylate and c) the random copolymers c ₁ ) of isobornyl (meth)acrylate and c ₂ ) of ( C ₁ -C ₄ alkyl meth)acrylate preferably present in a weight ratio (isobornyl meth)acrylate / C 1 -C 4 alkyl (meth) _acrylate (( _{c 1 )} /c ₂ )) greater than 4. Advantageously, said weight ratio c ₁ ) /c ₂ ) ranges from 4.5 to 19. Advantageously, said weight ratio
c ₁ )/c ₂ ) ranges from 5 to 15, more preferably said weight ratio c ₁ )/c ₂ ) ranges from 5.5 to 12.

For these random copolymers, the defined weight ratio makes it possible to obtain a stable polymer dispersion, particularly after storage for 7 days at room temperature.

Advantageously, the stabilizing agent is chosen from: b) isobornyl acrylate homopolymers, c) random isobornyl acrylate/methyl acrylate copolymers, isobornyl acrylate/methyl acrylate random copolymers, ethyl, and random copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate according to the weight ratio described above.

The stabilizing polymer ii) preferably has a number average molecular weight ranging from 10,000 to 400,000 g/mol, preferably ranging from 20,000 to 200,000 g/mol.

The stabilizer ii) is in contact with the surface of the polymer particles i) and thus makes it possible to stabilize these particles on the surface to maintain these particles in dispersion in the medium of the oily dispersion.

More particularly the stabilizing agent(s) ii) are chosen from c) the copolymers of:
c ₁ ) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl; And
c ₂ ) (C ₁ -C ₄ )(alkyl) acrylate of (C ₁ -C ₄ ) alkyl;
with 80 to 95% by weight of ingredient c1) in particular isobornyl (meth)acrylate and 5 to 20% by weight of ingredient c2) in particular methyl acrylate and ethyl acrylate relative to total weight of the stabilizing agent.

More preferably, the stabilizing agent(s) ii) comprise from 85 to 94% by weight, more particularly 87% to 93% by weight, of ingredient c ₁ ) in particular isobornyl (meth)acrylate and from 10 to 20 % by weight of ingredient c ₂ ) in particular ethyl acrylate and/or ethyl acrylate relative to the total weight of the polymer.

Advantageously, the set ii) stabilizing agent(s) + i) particle(s) of polymer(s) present in the oily dispersion comprises from 5 to 60%, in particular comprises from 10 to 40% by weight of polymers b) or c) and from 60 to 90%, in particular from 61 to 89% by weight of polymers a), relative to the total weight of the whole ii) stabilizing agent(s) + i) particle(s) of polymer(s).

Preferably, the set ii) stabilizing agent(s) + i) particle(s) of polymer(s) present in the dispersion comprises from 15 to 30% by weight of polymers b) or c) and from 70 to 85% by weight of polymers a), relative to the total weight of the assembly ii) stabilizing agent(s) + i) polymer particle(s).

Preferably, the stabilizing agent(s) ii) and the particle(s) i) have a number average molecular weight (Mn) of between 1000 and 1,000,000 g/mol, in particular between 5,000 and 500,000 g/mol and again better between 10,000 and 300,000 g/mol.

The oily dispersion according to the invention is ultimately formed of polymeric particles, of fairly large diameter i.e. preferably greater than 100 nm, and leads to film-forming deposits, shiny and resistant to fatty substances at room temperature (25°C), which are interesting especially for makeup applications.

The final particle size is greater than 100 nm. In particular an average size in number ranging from 100 nm and 600 nm; more particularly ranging from 150 nm to 500 nm, even more particularly ranging from 160 nm to 400 nm.

The average particle size is determined by conventional methods known to those skilled in the art. A MALVERN® brand NanoZS laser particle size analyzer (particularly well suited to submicron dispersions) makes it possible to measure the size distribution of these samples. The operating principle of this type of device is based on dynamic light scattering (DLS), also called quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS).

The sample is pipetted into a single-use plastic tank (4 transparent sides, 1 cm side and 4 ml capacity) placed in the measuring cell. The data are analyzed on the basis of a cumulant method which leads to a unimodal particle size distribution characterized by an average diameter in intensity d(nm) and a polydispersity factor in sizes Q. The results can also be expressed in the form of data statistics such as D10; D50 (median), D90 and mode.

Other particle sizing techniques make it possible to obtain this type of information, such as the analysis of individual particle tracking (Nanoparticle Crackings Analysis, NTA), laser diffraction (DL), acoustic extinction spectroscopy (AES). , Doppler velocimetry by spatial filter or even image analysis.

The hydrocarbon oil(s) iii)

The oily medium of the polymer dispersion comprises at least one hydrocarbon oil iii).

Hydrocarbon oil is a liquid oil at room temperature (25°C) and atmospheric pressure.

By hydrocarbon oil, we mean an oil formed essentially, or even made up, of carbon and hydrogen atoms, and possibly of oxygen or nitrogen atoms, and not containing any silicon or fluorine atom. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

Advantageously, the hydrocarbon oil(s) of the invention are formed solely of carbon and hydrogen atoms.

The hydrocarbon oil can be chosen from non-volatile hydrocarbon oils.

By "non-volatile oil" is meant an oil remaining on the keratin fiber at room temperature (25°C) and atmospheric pressure for at least several hours and in particular having a vapor pressure less than 10 ^-3 mm Hg (0.13 Pa).

These oils may be hydrocarbon oils.

The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and phosphorus atoms.

As non-volatile hydrocarbon oil, we can in particular cite:
- hydrocarbon oils of plant origin such as triesters of fatty acids and glycerol whose fatty acids can have chain lengths varying from C ₄ to C ₂₄ , the latter being able to be linear or branched, saturated or unsaturated; these oils are in particular wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oil. sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, cancholy, passionflower, muscat rose; or even the triglycerides of caprylic/capric acids such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
- linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, polydecenes, polybutenes, hydrogenated polyisobutene such as Parléam, squalane;
- synthetic ethers having 10 to 40 carbon atoms;
- synthetic esters such as oils of formula R ₁ COOR ₂ in which R ₁ represents the remainder of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain in particular branched containing from 1 to 40 carbon atoms provided that R ₁ + R ₂ is ≥ 10, such as for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C ₁₂ alcohol benzoate at C ₁₅ , hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethyl-hexyl palmitate, isostearate isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters;
- fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol;
- higher fatty acids such as oleic acid, linoleic acid, linolenic acid; and their mixtures.

According to a particularly preferred form of the invention, the hydrocarbon oil will be chosen from volatile hydrocarbon oils as defined above. In particular, the volatile hydrocarbon oil is isododecane.

Preferably the liquid hydrocarbon oil(s) iii) are found in the dispersion of the invention in an amount of between 15% by weight and 80% by weight, more preferably between 20% and 60% by weight relative to the total weight of said oily dispersion. According to a particular embodiment of the invention the ratio by weight of the sum of the ingredients [i) + ii)] / iii) is less than or equal to 1, more particularly [i) + ii]] / iii) the ratio mass is between 0.5 and 1.

The polymer particles i) of the dispersion preferably have an average size, in particular in number, ranging from 50 to 500 nm, in particular ranging from 75 to 400 nm, and better still ranging from 100 to 250 nm.

Generally speaking, the dispersion according to the invention can be prepared in the following manner, given by way of example.

Dispersion preparation method

Without being limiting, in general, the dispersion according to the invention can be prepared in the following manner:

- The polymerization is carried out in dispersion in a non-aqueous medium, that is to say by precipitation of the polymer being formed, with protection of the particles formed with one or more stabilizing agents ii), preferably a single type of agent stabilizer ii) chosen from b) and c) as defined above.

- In a first step, the stabilizing polymer (or stabilizing agent ii)) is prepared by mixing the monomer(s) constituting the stabilizing polymer b) or c), with iv) a radical initiator, in a solvent called synthesis solvent, and by polymerizing these monomers; Then

- In a second step, the monomers constituting the polymer of particles i) are added to the stabilizing polymer ii) formed in the previous step and the polymerization of these added monomers is carried out in the presence of the radical initiator.

- In a third step, water is added and all ingredients i) + ii) are stirred in the reactor before removing the dispersion. When the non-aqueous medium is a non-volatile hydrocarbon oil iii), the polymerization can be carried out in an apolar organic solvent (synthesis solvent) then add the non-volatile hydrocarbon oil (which must be miscible with said synthesis solvent) and distill selectively the synthesis solvent.

The synthesis solvent may consist of hydrocarbon oil iii) associated with an additional solvent chosen in particular from esters with a linear or branched hydrocarbon aliphatic chain, having from 3 to 8 carbon atoms in total such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate.

At the end of step 1, when the synthesis solvent is a mixture, the additional solvent including the aliphatic hydrocarbon chain esters as defined above is removed by a conventional method of those skilled in the art such as distillation. The polymers of particles i) are found in hydrocarbon oil iii).

We therefore choose a synthesis solvent such that the monomers of the polymeric stabilizing agent(s) ii), and the radical initiator iv), are soluble therein, and the polymer particles i) obtained are insoluble therein so that they precipitate therein. during their training.

In particular, we choose the synthesis solvent which is apolar and volatile organic, preferably chosen from volatile hydrocarbon oils iii) in particular alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.

When the non-aqueous medium is a volatile hydrocarbon oil iii), the polymerization can be directly carried out in said oil which therefore also plays the role of synthesis solvent. The monomers must also be soluble there, as well as the radical initiator, and the polymer of particles i) obtained must be insoluble there.

The monomers are preferably present in the synthesis solvent, before polymerization, at a rate of 15% to 45% by weight. All of the monomers can be present in the solvent before the start of the reaction, or part of the monomers can be added as the polymerization reaction progresses.

The polymerization is preferably carried out in the presence iv) of one or more radical initiators which can be any initiator known to those skilled in the art for radical polymerization such as peroxide, azo initiators, redox (redox) couples, and photochemical initiators.

We can in particular cite those of type:
- peroxide in particular chosen from tert-Butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from Akzo Nobel; Or
- azo in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2'-azo-bis(2-amidinopropane) dihydrochloride.

The polymerization is preferably carried out at a temperature ranging from 70 to 110°C and at atmospheric pressure.

The polymer particles i) are stabilized on the surface, when they form during polymerization, thanks to the stabilizing agent ii).

The stabilization can be carried out by any known means, and in particular by direct addition of the stabilizing agent ii), during the polymerization.

The stabilizing agent ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of particles i). However, it is also possible to add it continuously, in particular when the monomers of particles i) are also added continuously.

It is possible to use from 2 to 40% by weight, particularly from 3 to 30% by weight, more particularly from 4 to 25% by weight of the stabilizing agent(s) ii) relative to the total weight of monomers used (stabilizing agents ii). ) + polymer particles i), and preferably from 4.5 to 20% by weight.

The dispersion of polymer particles i) advantageously comprises from 30 to 65% by weight of dry matter, relative to the total weight of said dispersion, and preferably from 40 to 60% by weight relative to the total weight of said dispersion.

According to a preferred embodiment of the invention the dispersion of the invention comprises no more than 3% by weight of surfactants relative to the total weight of the dispersion, preferably no more than 2% by weight of surfactants relative to the weight total of the dispersion, more particularly not more than 1% by weight of surfactants relative to the total weight of the dispersion, even more preferably the composition does not comprise more than 0.5% by weight of surfactants relative to the total weight of the dispersion. dispersion, even better the mixture does not include surfactant.

In a particular method of preparation, the statistical stabilizing polymer ii) is prepared in a first step. This stabilizing polymer is soluble in a non-polar organic solvent of the alkane type such as isododecane.

Then, in a second step, the particles of polymer i) are synthesized in the presence of the stabilizing polymer ii).

Preferably, a solution of stabilizing polymer ii) is prepared in the hydrocarbon oil(s) iii) for the final dispersion, and the polymerization of the monomers which form the core of the particle is carried out, in the presence of this stabilizer ii).

The stabilizing polymer ii) can be prepared by radical polymerization optionally in the presence of polymerization initiator iv) as defined above.

In a second step, the monomers which form the core of particle i) can be polymerized in the presence of said stabilizing polymer ii). This second step can be a conventional radical polymerization.

The dispersions are carried out in the presence of one or more hydrocarbon oil(s) iii) preferably in a non-polar organic solvent, in particular of the alkane type such as in isododecane, according to an industrially realistic process.

The dispersions according to the invention are therefore ultimately formed of polymeric particles, of fairly large diameter (preferably greater than 100 nm), and will lead to film-forming deposits, shiny and resistant to fatty substances at the observation temperature (25 °C).

Advantageously, the oily dispersion may comprise a plasticizing agent chosen from trin-butyl citrate, tripropylene glycol monomethyl ether (INCI name: PPG-3 Methyl Ether), trimethyl pentaphenyl trisiloxane (sold under the name DOW CORNING PH-1555 HRI COSMETIC FLUID® by the company Dow Corning). These plasticizers improve the mechanical resistance of the polymer film.

The plasticizing agent is preferably present in the oily dispersion in a content ranging from 5 to 50% by weight, relative to the total weight of the polymer particles.

Preferably, we will use a dispersion in iii) in particular isododecane of particles i) of surface-stabilized polymer chosen from:
- a dispersion in isododecane of particles of methyl acrylate/ethyl acrylate/acrylic acid copolymer (24.5/62.8/12.7) stabilized by a statistical copolymer stabilizer isobornyl acrylate/methyl acrylate/ ethyl acrylate (92/4/4); the oily dispersion containing in total (stabilizer + particles) 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate;
-a dispersion in isododecane of particles of methyl acrylate/ethyl acrylate/acrylic acid copolymer (11.7/75.6/12.7) stabilized by a statistical copolymer stabilizer isobornyl acrylate/methyl acrylate/ ethyl acrylate (92/4/4); the oily dispersion containing in total (stabilizer + particles) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate;
- a dispersion in isododecane of particles of methyl acrylate/ethyl acrylate/maleic anhydride copolymer (50/37.2/12.8) stabilized by a statistical copolymer stabilizer isobornyl acrylate/methyl acrylate/acrylate ethyl (92/4/4); the oily dispersion containing in total (stabilizer ii) + particles i)) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.

More preferably, we will use a dispersion in isododecane of particles of methyl acrylate/ethyl acrylate/acrylic acid copolymer (11.7/75.6/12.7) stabilized by a statistical copolymer stabilizer isobornyl acrylate/ methyl acrylate/ethyl acrylate (92/4/4); the oily dispersion containing in total (stabilizer ii) + particles i)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate, such as the INCI name product: ACRYLATES/ISOBORNYL ACRYLATE COPOLYMER sold under the trade name MEXOMERE PBM® from the company NOVEAL.

The composition (A) according to the invention preferably comprises a dry matter content (or active material) of polymers of particle i) + dispersant polymers ii) according to the invention ranging from 10 to 45% by weight relative to the total weight of composition (A), and more preferably ranging from 15 to 40% by weight relative to the total weight of composition (A).

According to a particularly preferred embodiment of the invention, the composition (A) comprises at least one hydrophobic film-forming polymer chosen from silicone polyamides and/or silicone resins, preferably a silicone polyamide NYLON-611/DIMETHICONE COPOLYMER and/or a resin. silicone type MQ Trimethoxysiloxysilicate.

More particularly, composition (A) comprises at least one mixture of silicone polyamide and silicone resin, and even more particularly a silicone polyamide NYLON-611/DIMETHICONE COPOLYMER and a Trimethoxysiloxysilicate silicone resin.

According to a preferred mode, the total quantity of volatile hydrocarbon oil(s) is greater than or equal to 20% by weight, more preferably ranging from 30 to 80% by weight, and more particularly ranging from 35 to 75% by weight relative to the total weight of composition (A).

According to a preferred embodiment of the invention, the total quantity of non-volatile hydrocarbon oil(s) is less than or equal to 10% by weight, more preferably less than or equal to 5% by weight relative to to the total weight of the composition (A).

According to a particular embodiment of the invention, composition (A) is free of non-volatile oil.

Coloring Matter

According to a particular embodiment of the invention, the composition (A) additionally comprises at least one coloring material, synthetic, natural or of natural origin.

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

The coloring material(s) are preferably present in composition (A) at contents less than or equal to 5.0% by weight, relative to the total weight of composition (A).

Pigments

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

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

By “mineral pigment” we mean any pigment which meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue. , chromium hydrate and ferric blue, titanium dioxide, metal powders such as aluminum powder and copper powder. The following mineral pigments can also be used: Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₂ O ₃ , TiO, ZrO ₂ mixed with TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , CeO ₂ , ZnS.

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

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

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

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

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

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

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

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

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

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

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

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

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

According to a particular mode, the composition (A) according to the invention comprises at least one uncoated pigment.

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

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

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

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

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

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

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

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

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

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

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

When the pigment comprises a lipophilic or hydrophobic coating, the latter is preferably present in the fatty phase of the composition according to the invention.

According to a particular embodiment of the invention, the pigments can be coated according to the invention with at least one compound chosen from silicone surfactants; fluorinated surfactants; fluoro-silicone surfactants; metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and their mixtures.

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

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

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

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

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

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

Among the organic dyes, we can cite cochineal carmine. We can also cite the products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570) , D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

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

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

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

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

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

The fat-soluble dye(s) are preferably present at contents of less than 4% by weight, or even less than 2% by weight, more preferably ranging from 0.01 to 2% by weight, and even better from 0.02 to 1 .5% by weight relative to the total weight of composition (A).

Makeup composition (B)

The second makeup composition (B) comprises, in particular in a physiologically acceptable environment:
i) at least one polyphenol X comprising at least two different phenol groups, and
ii) at least one polyoxyethylenated compound Y capable of forming at least two hydrogen bonds with said phenol groups of polyphenol X; And
iii) at least one mono-alcohol having 2 to 8 carbon atoms; And
iv) at least one uncoated iron oxide type pigment

According to a particular mode, the first composition (B) may comprise water.

The quantity of water is then preferably less than or equal to 25% by weight, more preferably less than or equal to 15%, and more particularly less than or equal to 5% by weight relative to the total weight of the composition ( B).

The composition may contain demineralized water, or even 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 thermal water.

The pH of composition (B) is, in this case, preferably less than 6, more preferably between 2 and 6 and more particularly between 2 and 5.

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

According to a particular mode, composition (B) can be free of water.

Oily Phase

Composition (B) of the invention may additionally comprise an oily phase.

The term "oil phase" means a liquid phase at room temperature (25°C) and at atmospheric pressure comprising oils, waxes, pasty bodies as well as possibly all organic solvents and ingredients which are soluble or miscible in said phase.

The oil or oils may be chosen from mineral, vegetable, synthetic oils, in particular chosen from hydrocarbon and/or silicone and/or fluorinated oils, volatile or non-volatile, and their mixtures.

By “oil”, we mean a liquid fatty substance at room temperature (25°C) and atmospheric pressure (760mm Hg or 101325 Pa). Oil can be volatile or non-volatile.

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

The term “fluorinated oil” means an oil comprising at least one fluorine atom.

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

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

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

Volatile hydrocarbon oils

As an example of a volatile hydrocarbon oil which can be used in the invention, the following can be cited:
- hydrocarbon oils having 8 to 16 carbon atoms, and in particular C ₈ -C ₁₆ isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane ), isododecane, isohexadecane, and for example oils sold under the trade names Isopars® or Permetyls®, branched C ₈ -C ₁₆ esters, iso-hexyl neopentanoate, and mixtures thereof . Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Solt® by the company SHELL, can also be used; volatile linear alkanes such as those described in the patent application of the company Cognis DE10 2008 012 457 and like that sold under the trade name CETIOL ULTIMATE® by the company BASF. We can also cite the dodecane/tetradecane mixture in the weight ratio 85/15 marketed by the company BIOSYNTHIS under the reference VEGELIGHT 1214® as well as the mixture of volatile linear alkanes in C9-C12 - INCI name: C9-12 ALKANE tel than the product marketed by the company BIOSYNTHIS under the reference VEGELIGHT SILK®.

Non-volatile hydrocarbon oils

As an example of a non-volatile hydrocarbon oil which can be used in the invention, the following can be cited:
- linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, petroleum jelly, polydecenes, polybutenes, polyisobutenes, hydrogenated or not such as Parleam, squalane;
- synthetic ethers having 10 to 40 carbon atoms such as dicaprylyl ether;
- triglycerides consisting of esters of fatty acids and glycerol, in particular the fatty acids of which may have chain lengths varying from C ₄ to C ₃₆ , and in particular from C ₁₈ to C ₃₆ , these oils being able to be linear or branched, saturated or unsaturated; these oils may in particular be heptanoic or octanoic triglycerides, wheat germ, sunflower, grape seed, sesame (820.6 g/mol), corn, apricot, castor, shea, avocado, olive, soy, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, cancholy, passionflower, muscat rose; shea oil; or even caprylic/capric acid triglycerides such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel
- linear aliphatic hydrocarbon esters of formula RCOOR' in which RCOO represents a carboxylic acid residue comprising from 2 to 40 carbon atoms, and R' represents a hydrocarbon chain containing from 1 to 40 carbon atoms, such as octanoate cetostearyl, isopropyl alcohol esters such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethyl-hexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoates, and in particular isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 4-diheptanoate and 2-hexyl ethyl palmitate, alkyl benzoate, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyl-2-docecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate , oleyl erucate; lauroyl isopropyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate;
- polyesters obtained by condensation of dimer and/or trimer of unsaturated fatty acid and diol such as those described in patent application FR 0 853 634, such as in particular dilinoleic acid and 1,4- butanediol. In particular, we can cite in this respect the polymer marketed by Biosynthis under the name Viscoplast 14436H® (INCI name: Dilinoleic Acid/Butane diol Copolymer), or even copolymers of polyols and diacid dimers, and their esters, such as Hailuscent ISDA ®,
- di-alkyl carbonates, the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate marketed under the name
Cetiol CC®, by Cognis;
- esters of linear fatty acids having a total carbon number ranging from 35 to 70 such as pentaerythrityl tetrapelargonate,
- aromatic esters such as tridecyl trimellitate, C ₁₂ -C ₁₅ alcohol benzoate, 2-phenyl ethyl ester of benzoic acid, butyl octyl salicylate,
- esters and polyesters of dimer diol and mono-or dicarboxylic acid, such as esters of dimer diol and fatty acid and esters of dimer diol and dimer dicarboxylic acid, such as Lusplan DD-DA5® and Lusplan DD-DA7® marketed by the company NIPPON FINE CHEMICAL and described in application US 2004-175338, the content of which is incorporated into this application by reference;
- fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyl decanol, 2-undecyl pentadecanol, oleic alcohol;
- di-alkyl carbonates, the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate marketed under the name
Cetiol CC®, by Cognis; And
- and their mixtures.

Non-volatile silicone oils

Among the non-volatile silicone oils, mention may be made of silicone oils such as non-volatile polydimethylsiloxanes (PDMS); phenyl silicones such as phenyl trimethicones, phenyl dimethicones, diphenyl dimethicones, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, trimethylsiloxyphenyl dimethicone, diphenylsiloxy phenyl trimethicone, as well as mixtures thereof.

Volatile, linear or cyclic silicone oils

As linear volatile silicone oils, mention may be made of octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and their mixtures.

As cyclic volatile silicone oils, mention may be made of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane and their mixtures.

According to a preferred embodiment of the invention, the total quantity of non-volatile oil(s) is less than or equal to 10% by weight, more preferably, in particular less than or equal to 5.0% by weight, or even less than 2.0% by weight, relative to the total weight of the composition (B).

According to a particular embodiment of the invention, the composition (B) of the invention may be free of non-volatile oil.

According to a preferred embodiment of the invention, the total quantity of volatile oil(s) is less than or equal to 10% by weight, more preferably, in particular less than or equal to 5.0% by weight relative to the total weight of the composition (B).

According to a particular embodiment of the invention, the composition (B) of the invention may be free of volatile oil.

Polyphenol

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

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

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

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

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

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

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

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

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

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

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

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

We will use more particularly as polyphenol X, tannic acid the commercial product sold under the name Brewtan F® by the company Anijomoto Omnichem Nv.

.According to a particular embodiment, the polyphenol(s) of the invention is(are) present in an amount greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0 % by weight, and more particularly greater than or equal to 2.0% by weight relative to the total weight of the composition (B).

According to a particular embodiment, the polyphenol(s) of the invention (is) are present in an amount ranging from 1.0 to 30.0% by weight, and more particularly ranging from 2.0 at 30% by weight relative to the total weight of the composition (B).

Polyoxyethylenated compound Y

The polyoxyethylenated Y compounds according to the invention comprise in their chemical structure at least two ethoxylene groups, capable of forming at least two hydrogen bonds with the phenol groups of the polyphenol X comprising at least two different phenols.

For the purposes of the present invention, the term "polyoxyethylenated compound" means any molecule comprising in its chemical structure at least one chain comprising oxyethylene units -(OCH ₂ CH ₂ ) _n .

In a preferred embodiment, the molar mass of compound Y is greater than 200 g/mol, or even greater than 350 g/mol.

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

As examples of compounds Y capable of reacting with polyphenols
(1) polyoxyethylene waxes, in particular chosen from polyoxyethylenated ester waxes such as polyoxyethylene jojoba wax (120 EO) (INCI name: Jojoba Wax PEG-120 Esters), PEG-8 Beeswax, PEG-60 Lanolin, PEG -75 Lanolin, PPG-12-PEG-50 Lanolin;
(2) Polyoxyethylene waxes, in particular chosen from polyoxyethylenated ester waxes such as polyoxyethylene jojoba wax (120 EO) (INCI name: Jojoba Wax PEG-120 Esters), PEG-8 Beeswax, PEG-60 Lanolin, PEG -75 Lanolin, PPG-12-PEG-50 Lanolin,
(6) polyethylene glycols of the H(O-CH ₂ -CH ₂ ) _n -OH type
in particular chosen from PEG-6, PEG-8, PEG-14M, PEG-20, PEG-45M, PEG-90, PEG-90M, PEG-150, PEG-180, PEG-220;
(3) Poloxamers of the HO-(CH ₂ -CH ₂ -O) _n -(CHCH ₃ -CH ₂ -O)O-(CH ₂ -CH ₂ -O) _p -H type, in particular chosen from Poloxamer 124, Poloxamer 184, Poloxamer 338, Poloxamer 124, Poloxamer 184, Poloxamer 184, Poloxamer 338;
(4) polypropylene glycols alkyl ethers of type:
C _n H _2n+1 -(OC(CH ₃ )H-CH ₂ ) _o -(O-CH ₂ -CH ₂ ) _p -OH
in particular chosen from PPG-26-Buteth-26, PPG-5-Ceteth-20, PPG-6-Decyltetradeceth-30.
(5) Compounds of type:
H(OC(C _n H _2n+1 )-CH ₂ )o-(CH ₂ -CH ₂ -O) _p -(CH ₂ -C(C _q H _2q+1 )HO) _r H
in particular PEG-45/Dodecyl Glycol Copolymer.
(6) compounds of the type: C _n H _2n+1 -(O-CH ₂ -CH ₂ )oO-CH ₂ -C(C _p H _2p+1 )HOH
in particular Ceteareth-60 Myristyl Glycol;
(7) polyoxyethylenated glycerins, in particular polyoxyethylenated glycerin 26 EO (Glycereth-26);
(8) alkylpolyethylene glycols of type C _n H _2n+1 -(O-CH ₂ -CH ₂ ) _o -OH, in particular chosen from Ceteth-2, Ceteth-10, Ceteth-20, Ceteth-25 , Isoceteth-20, Laureth-2, Laureth-3, Laureth-4, Laureth-12, Laureth-23, Oleth-2, Oleth-5, Oleth-10, Oleth-20, Oleth-25, Deceth-3, Deceth-5, Beheneth-10, Steareth-2, Steareth-10, Steareth-20, Steareth-21, Steareth- 100, Ceteareth-12, Ceteareth-15, Ceteareth-20, Ceteareth-25, Ceteareth-30, Ceteareth-33, Coceth-7, Trideceth-12;
(9) Polyoxyethylenated alkylphosphates, in particular chosen from Trilaureth-4 Phosphate, Ceteth-10 Phosphate, Oleth-10 Phosphate, PPG-5-Ceteth-10 Phosphate;.
(10) polyoxyethylenated alkylamines of the type
CH ₃ -(CH ₂ ) _n -(CH=CH) _o -(CH) _p -N((CH ₂ -CH ₂ -O)H) _q ((CH ₂ -CH ₂ -O) _r H), in particular: PEG-2-Oleamine;
(11) polyethylene glycol and fatty acid esters of the type
C _n H _2n+1 -(CH=CH ₂ )oC _p H _2p -CO-(O-CH ₂ -CH ₂ ) _n -OH or
C _n H _2n+1 -(CH=CH) _o -C _p H _2p -CO-(O-CH ₂ -CH ₂ ) _q -O-CO-C _r H _2r+1 or
C _n H _2n+1 -(CH=CH) _o -CO-(O-CH ₂ -CH ₂ ) _q -OC _n H _2n+1 or
C _n H _2n+1 -O-CH(alkyl)-(CH ₂ ) _p -(O-CH ₂ -CH ₂ ) _q -O-CO-C _r H _2r+1
in particular chosen from PEG-6 Isostearate, PEG-6 Stearate, PEG-8 Stearate, PEG-8 Isostearate, PEG-20 Stearate, PEG-30 Stearate, PEG-32 Stearate, PEG-40 Stearate, PEG-75 Stearate, PEG-100 Stearate, PEG-8 Distearate, PEG-150 Distearate, Mereth-3 Myristate, PEG-4 Olivate, Propylene Glycol Ceteth-3 Acetate, PEG-30 Dipolyhydroxystearate ;
(12) Polyoxyethylenated carboxylic acids of the type
C _n H _2n+1 -(O-CH ₂ -CH ₂ ) _o -COOH, in particular chosen from PEG-7 Capric Acid, PEG-6 Caprylic Acid, PEG-7 Caprylic Acid, Laureth-5 Carboxylic Acid , Laureth-11 Carboxylic Acid, Laureth-12 Carboxylic Acid;
(13) polyoxyethylenated alkylglycerides, in particular chosen from PEG-6 Caprylic/Capric Glycerides, PEG-60 Almond Glycerides, PEG-10 Olive Glycerides, PEG-45 Palm Kernel Glycerides, PEG-70 Mango Glycerides;
(14) polyoxyethylenated alkylglucoses, in particular chosen from Methyl-Gluceth-10, Methyl-Gluceth-20;
(15) polyoxyethylenated sugar esters such as PEG-120 Methyl Glucose Dioleate, PEG-20 Methyl Glucose Sesquistearate.
(16) polyoxyethylenated and polyoxypropylenated alkyl glycol ethers such as PPG-1-PEG-9 Lauryl Glycol Ether.
(17) polyoxyethylenated pentaerythritol esters and ethers, in particular PEG-150 Pentaerythrityl Tetrastearate.
(18) polysorbates, in particular chosen from Polysorbate-20, Polysorbate-21, Polysorbate-60, Polysorbate-61, Polysorbate-80, Polysorbate-85.
(19) polyoxyethylenated polyamines, in particular PEG-15 Cocopolyamine.
(20) polyoxyethylenated dihydrocholesteryl esters. structure:
[Chem 17]


in particular Dihydrocholeth-30.
(21) optionally hydrogenated esters of glycerol and polyoxyethylenated fatty acids chosen from PEG-7 Glyceryl Cocoate, PEG-30 Glyceryl Cocoate, PEG-200 Glyceryl Stearate, PEG-200 Hydrogenated Glyceryl Palmitate;
(22) polyoxyethylenated hydrogenated castor oils such as PEG-40 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil,
(23) polyethylene glycol propylene glycol fatty acid ester ethers such as PEG-55 Propylene Glycol Oleate
(24) Polyoxyethylenated butters, in particular polyoxyethylene shea butter such as PEG-50 Shea Butter;
(25) Polyoxyalkylenated silicones, in particular chosen from PEG/PPG-17/18 Dimethicone, PEG/PPG-18/18 Dimethicone, Trideceth-9 PG-Amodimethicone, PEG/PPG-22/24 Dimethicone;
(26) Polyoxyalkylenated silanes, in particular chosen from Bis-PEG-18 Methyl Ether Dimethyl Silane, Bis-PEG-18 Methyl ether Dimethyl Silane;
(2) polyoxyethylenated acrylate copolymers, in particular the copolymer with the INCI name: Acrylate/Palmeth-25 Acrylate Copolymer;
(27) polyoxyalkylenated alkanediols such as PEG-8 Caprylyl Glycol;
(28) polyoxyethylenated rapeseed amides and sterols (Rapeseed), in particular chosen from PEG-4 Rapeseed Amide, PEG-5 Rapeseed Sterol.
(29) polyoxyethylenated lanolins such as Laneth-15;
(30) sorbitol and polyoxyethylene fatty acid esters such as PEG-40 Sorbitan Peroleate;
(31) Polyoxyethylenated glycerol esters such as Glycereth-25 PCA Isostearate;
(32) their mixtures.

According to a preferred mode, the compound(s) Y will be chosen from non-ionic compounds.

According to a preferred mode, the compound(s) Y will be chosen from
i) polyethylene glycols, in particular PEG-180;
ii) polyoxyethylenated hydrogenated castor oils, in particular PEG-40 Hydrogenated Castor Oil;
iii) optionally hydrogenated esters of glycerol and polyoxyethylenated fatty acids, in particular PEG-7 Glyceryl Cocoate
iv) polysorbates, in particular Polysorbate 80;
v) their mixtures.

According to a preferred embodiment, compound Y is a polysorbate, in particular Polysorbate 80.

According to a preferred embodiment, the compound(s) Y of the invention is(are) present in an amount greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0 % by weight, in particular greater than or equal to 2.0% by weight, more particularly in an amount ranging from 3 to 30% by weight, and even better ranging from 4 to 20%. relative to the total weight of the composition ( B).

According to a preferred embodiment of the invention, the molar ratio of the reactive hydroxyl groups (OH) of the polyphenol to 20, more preferably from 1/2 to 15, and more particularly from 3/4 to 3.

Mono-alcohol

The composition according to the invention comprises at least at least one mono-alcohol comprising from 2 to 8 carbon atoms, in particular from 2 to 6 carbon atoms, and in particular from 2 to 4 carbon atoms such as ethanol, isopropanol, propanol or butanol, and mixtures thereof, and more particularly ethanol.

The mono-alcohol(s) comprising from 2 to 8 carbon atoms is (are) then preferably present at contents ranging from 40 to 95% by weight, and more preferably ranging from 40 to 80% by weight. , and more particularly from 45 to 80% by weight relative to the total weight of the composition (B).

Pigment

The composition according to the invention comprises at least one pigment of the iron oxide type (INCI Name Iron Oxide).

By “pigment” is meant particles insoluble in the medium of the composition, intended to color and/or opacify the composition and/or the resulting deposit.

By “uncoated pigment” is meant any pigment not treated with a surfactant covering it partially or completely by being absorbed, adsorbed or grafted onto said pigment.

According to a preferred embodiment, the pigment(s) are present in an amount of up to 35.0% by weight, more preferably up to 25.0% by weight and more particularly ranging from 4 to 25% by weight. relative to the total weight of the composition (B).

According to a particular embodiment, the uncoated pigments used according to the invention are chosen from yellow iron oxides (CI 77492), red iron oxides, black iron oxides (CI47499), and mixtures thereof.

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

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

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

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

In the context of the present invention, the pigments are more particularly black iron oxides (CI 77499).

Cosmetic compositions

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

Cosmetic additives

Compositions (A) and (B) of the makeup kit of the invention may contain additives usual in cosmetics. We can cite in particular antioxidants, preservatives, neutralizers, cosmetic active ingredients such as emollients, moisturizers, vitamins, sun filters and their mixtures.

The compositions (A) and (B) of the makeup kit of the invention according to the invention can be makeup products for keratin materials such as, in particular, eyebrows and the skin around them as eyebrow makeup products.

Such compositions are prepared in particular according to the general knowledge of those skilled in the art.

Packaging and applicators

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

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

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

The container can be associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US patent 4,887,622. It can also be in the form of a comb comprising a plurality of application elements, obtained in particular by molding. Such combs are described for example in patent FR 2 796 529. The applicator can be in the form of a brush, as described for example in patent FR 2 722 380. The applicator can be in the form of a block of foam or elastomer. The applicator can be free (sponge) or attached to a rod carried by the closure element, as described for example in US patent 5,492,426. The applicator can be integral with the container, as described for example in patent FR 2 761 959.

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

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

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

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

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

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

Throughout the description, including the claims, the expression "comprising one" must be understood as being synonymous with "comprising at least one", unless the contrary is specified. The expressions “between… and…” and “ranging from… to…” must be understood inclusive, unless otherwise specified. The invention is illustrated in more detail by the examples and figures presented below. Unless otherwise indicated, the quantities indicated are expressed as a mass percentage.

Example 1: Makeup kit: composition (A1) and composition (B1)

Anhydrous film-forming composition (A1)

The following anhydrous film-forming composition (A1) was prepared.

.[Tables 1] Ingredients (INCI name) (A1)
(invention) Phase ISODODECANE qsp 100 HAS TRIMETHYLSILOXYSILICATE
(SR 1000® from MOMENTIVE PERFORMANCE MATERIALS) 17.5 DISTEARDIMONIUM HECTORITE (and) PROPYLENE CARBONATE
(BENTONE GEL ISD V® from ELEMENTIS) 26 B ISODODECANE 20 NYLON-611/DIMETHICONE COPOLYMER
(DOW CORNING 2-8179 GELLANT®) 11 VS

Method of preparation

Phase A was prepared by mixing the ingredients of this phase at room temperature until a transparent and homogeneous phase was obtained.

In a pan, the ingredients of phases B and C were placed and mixed at a temperature of 95°C until a homogeneous mixture was obtained. Phase A was then added. Once the mixture was homogeneous, it was cooled with stirring until it returned to room temperature.

Makeup composition (B1)

We prepared the following makeup composition B1

.[Tables 2]
Phases Ingredients B1
(invention) (has) Tannic acid
(Brewtan F® - Anijomoto Omnichem Nv) 5 Ethanol 75 Polysorbate-80
(TWEEN-80-LQ® from CRODA)a 5 (b) Black iron oxide
(CI 77499)
SUNPURO C33-7001® from SUN 15

Preparation protocol

Phase (a) was prepared at room temperature (25°C) by dissolving the tannic acid as well as the Polysorbate-80 in ethanol. Once the mixture is homogeneous, phase (b) based on the pigment is added to this preparation with stirring to obtain a black and homogeneous composition.

3 layers were successively applied to the area of skin to be made up with, in order, composition (A1), composition (B1) then composition (A1).

The gestures proved easy to implement. We obtained a comfortable fine deposit on the made-up skin area, which held well for a few days and whose color did not transfer.

Claims (37)

Makeup kit for keratin materials, in particular eyebrows and the skin around the eyebrows, including:
1) a first anhydrous film-forming composition (A) comprising, in particular in a physiologically acceptable medium:
i) an oily phase comprising at least one hydrocarbon oil, preferably volatile; And
ii) at least one hydrophobic film-forming polymer different from silicone acrylate copolymers; And
2) a second composition (B) comprising, in particular in a physiologically acceptable medium:
i) at least one polyphenol X comprising at least two different phenol groups, and
ii) at least one polyoxyethylenated compound Y capable of forming at least two hydrogen bonds with said phenol groups of polyphenol X; And
iii) at least one mono-alcohol having 2 to 8 carbon atoms; And
iv) at least one pigment of the uncoated iron oxide type. Makeup kit according to any one of claims 1 to 7, where composition (A) comprises at least one hydrophobic film-forming polymer chosen from:
1) a silicone resin
2) a silicone polyamide
3) an oily dispersion comprising at least:
i) particle(s) comprising:
a) at least one ethylenic copolymer of a ₁ ) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl, and of a ₂ ) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid groups , sulfonic acid and/or aryl such as benzyl; in particular a ₂ ) is a (C ₁ -C ₄ )(alkyl)acrylic acid, more particularly the copolymers of (C ₁ -C ₄ )alkyl (meth)acrylate and (meth)acrylic acid; And
ii) at least one polymeric stabilizing agent chosen from:
b) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalyl monomers such as isobornyl (meth)acrylates; And
c) copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl) acrylate of (C ₃ -C ₁₂ ) cycloalkyl such as (meth) acrylate of (C ₁ -C ₄ ) alkyl; And
iii) at least one hydrocarbon oil, preferably a volatile hydrocarbon oil. Makeup kit according to claim 2, where the silicone resin is of the MQ type and chosen from a resin of the Trimethylsiloxysilicate type. Makeup kit according to claim 2, where the silicone polyamide corresponds to the following formula (III):

in which R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a C ₁ to C ₄₀ alkyl group, linear or branched, preferably a CH ₃ , C ₂ H ₅ , nC ₃ H ₇ or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted by one to three methyl or ethyl groups, and m ranges from 1 to 700, or from 15 to 500, or from 50 to 200 and n ranges from 1 to 500, or from 1 to 100 and better still from 4 to 25; preferably a silicone polyamide has the INCI name: NYLON-611/DIMETHICONE COPOLYMER. Makeup kit according to claim 2, wherein the composition (A) comprises at least one dispersion in isododecane of particles of methyl acrylate/ethyl acrylate/acrylic acid copolymer (11.7/75.6/12.7 ) stabilized by a statistical copolymer stabilizer isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4); the oily dispersion containing in total (stabilizer ii) + particles i)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate. Makeup kit according to one of the preceding claims where the volatile hydrocarbon oil in composition (A) is isododecane. Makeup kit according to one of the preceding claims, where the hydrophobic film-forming polymer is a mixture of silicone polyamide NYLON-611/DIMETHICONE COPOLYMER and Trimethylsiloxysilicate silicone resin. Makeup kit according to one of the preceding claims, where the total quantity of volatile hydrocarbon oil(s) in composition (A) is greater than or equal to 20% by weight, more preferably ranging from 30 to 80% by weight. weight, and more particularly ranging from 35 to 75% by weight relative to the total weight of the composition (A). Makeup kit according to one of the preceding claims, where the total quantity of the total quantity of non-volatile hydrocarbon oil(s) is less than or equal to 10% by weight, more preferably less than or equal at 5% by weight relative to the total weight of composition (A). Makeup kit according to one of the preceding claims, where composition (A) is free of non-volatile oil. Makeup kit according to one of the preceding claims, where composition (A) additionally comprises at least one coloring material, in particular chosen from mineral or organic pigments, coated or uncoated, fat-soluble dyes, and mixtures thereof. Makeup kit according to claim 11, wherein the coloring material(s) are preferably present in composition (A) at contents less than or equal to 5.0% by weight, relative to the total weight of composition (A). Makeup kit according to one of the preceding claims, where composition (B) additionally comprises water. Makeup kit according to claim 2, where the quantity of water is less than or equal to 30% by weight, and more preferably varies from 5 to 30% by weight, and more particularly from 8 to 25% relative to the total weight of composition (B). Makeup kit according to claim 13 or 14, where the pH of composition (B) is less than 6, more preferably between 2 and 6 and more particularly between 2 and 5. Makeup kit according to any one of the preceding claims, where composition (B) additionally comprises an oily phase. Makeup kit according to claim 16, where the total quantity of non-volatile oil(s) in composition (B) is less than or equal to 10% by weight, more preferably, in particular less than or equal to 5, 0% by weight, or even less than 2.0% by weight, relative to the total weight of the composition (B). Makeup kit according to claim 16, wherein composition (B) is free of non-volatile oil. Makeup kit according to claim 16, where the total quantity of volatile oil(s) in composition (B) is less than or equal to 10% by weight, more preferably, in particular less than or equal to 5, 0% by weight relative to the total weight of composition (B). Makeup kit according to claim 16, wherein composition (B) is free of volatile oil. Makeup kit according to any one of the preceding claims, where the polyphenol X is chosen from catechic tannins, in particular chosen from gallotannins and ellagitannins. Makeup kit according to any one of claims 1 to 20, where the polyphenol X is epigallocatechin., in particular a green tea extract comprising at least 45% by weight of epigallocatechin relative to the weight of said extract. Makeup kit according to any one of claims 1 to 20, where the polyphenol to the total weight of said extract. Makeup kit according to any one of claims 1 to 20, where the polyphenol X is tannic acid. Makeup kit according to any one of the preceding claims, where the polyphenol(s) X are present in an amount greater than or equal to 0.8% by weight, preferably greater than or equal to 1.0% by weight, and more particularly greater than or equal to 2.0% by weight relative to the total weight of the composition (B). Makeup kit according to any one of the preceding claims, where the polyphenol(s) 2.0 to 30% by weight relative to the total weight of the composition (B). Makeup kit according to any one of the preceding claims, where the molar mass of compound Y is greater than 200 g/mol, or even greater than 350 g/mol. Makeup kit according to any one of the preceding claims, where the compound Y in the medium of composition (B), does not contain an anionic group in their chemical structure, and in particular are non-ionic. Makeup kit according to any one of the preceding claims, where compound Y is chosen from
i) polyethylene glycols, in particular PEG-180;
ii) polyoxyethylenated hydrogenated castor oils, in particular PEG-40 Hydrogenated Castor Oil;
iii) optionally hydrogenated esters of glycerol and polyoxyethylenated fatty acids, in particular PEG-7 Glyceryl Cocoate
iv) polysorbates, in particular Polysorbate 80;
v) their mixtures. Makeup kit according to any one of the preceding claims, where compound Y is a polysorbate, in particular Polysorbate 80. Makeup kit according to any one of the preceding claims, where the compound(s) Y is(are) present in an amount greater than or equal to 0.8% by weight, preferably greater than or equal to 1 .0% by weight, in particular greater than or equal to 2.0% by weight, more particularly in an amount ranging from 3 to 30% by weight, and even better ranging from 4 to 20%. relative to the total weight of the composition (B). Makeup kit according to any one of the preceding claims, where the molar ratio of the reactive hydroxyl groups (OH) of the polyphenol from 1/3 to 20, more preferably from 1/2 to 15, and more particularly from 3/4 to 3. Makeup kit according to any one of the preceding claims, in which the mono-alcohol containing 2 to 8 carbon atoms is chosen from ethanol, isopropanol, propanol or butanol, and mixtures thereof, and more particularly is ethanol. Makeup kit according to any one of the preceding claims, where the mono-alcohol(s) comprising 2 to 8 carbon atoms is(are) present at contents ranging from 40 to 95% by weight, and more preferably ranging from 40 to 80% by weight, and more particularly from 45 to 80% by weight relative to the total weight of composition (B). A makeup kit according to any preceding claim, wherein the uncoated iron oxide(s) is(are) present in an amount of up to 35.0% by weight, plus preferably up to 25.0% by weight and more particularly ranging from 4 to 25% by weight relative to the total weight of composition (B). Makeup kit according to any one of the preceding claims, where the pigment(s) present in composition (B) are black iron oxides. Cosmetic process for making up keratin materials, in particular the eyebrows and the skin around the eyebrows, comprising at least:
- the application to said keratin materials of a first layer with a composition (A) as defined according to any one of claims 1 to 12, and
- the application of a second layer of a composition (B) as defined according to any one of claims 1, 13 to 34, on the layer formed by composition (A); And
- applying a third layer of composition (A) to the second layer formed by composition (B).