FR3117786A1 - DISPERSION COMPRISING A POLYMERIC PARTICLE, A STABILIZING AGENT WITH A C3-C12 CYCLOALKYL GROUP, AN OIL AND WATER, PROCESS FOR THE TREATMENT OF KERATIN MATERIALS USING THE DISPERSION - Google Patents

Abstract

Title: DISPERSION COMPRISING A POLYMERIC PARTICLE, A STABILIZING AGENT WITH A C 3 -C 12 CYCLOALKYL GROUP, AN OIL AND WATER, PROCESS FOR THE TREATMENT OF KERATIN MATERIALS USING THE DISPERSION The present invention relates to a dispersion (A) comprising at least one particle i) consisting of ethylenic polymer, ii) at least one polymeric stabilizing agent comprising a (C3-C12) cycloalkyl group, and iii) at least one liquid hydrocarbon fatty substance at 20°C and 1 atmosphere. The invention also relates to a process for treating keratin materials, in particular human materials such as skin or hair, implementing the application to said materials of at least one dispersion A); a method of preparing the dispersion, a multi-compartment kit comprising the ingredients i) to iii). The dispersion (A), and the process for treating keratin materials as defined above, make it possible to obtain a treatment of said materials that is resistant in particular to shampoos, sebum), sweat, and/or water, but also to fatty substances, in particular food, such as oils.

Description

DISPERSION COMPRISING A POLYMERIC PARTICLE, A STABILIZING AGENT WITH A C3-C12 CYCLOALKYL GROUP, AN OIL AND WATER, PROCESS FOR THE TREATMENT OF KERATIN MATERIALS USING THE DISPERSION

The present invention relates to a dispersion (A) comprising at least one particle i) consisting of ethylenic polymer, ii) at least one polymeric stabilizing agent comprising a (C ₃ -C ₁₂ )cycloalkyl group, iii) at least one hydrocarbon fatty substance liquid at 20°C and 1 atmosphere, and iv) water. A subject of the invention is also a method for treating keratin materials, in particular human materials such as the skin or the hair, the eyelashes, the eyebrows, implementing the application to said materials of at least one dispersion (A); and a method of preparing the dispersion, a multi-compartment kit comprising ingredients i) to iv).

During the aging process, different signs appear on the skin, very characteristic of this aging, resulting in particular in a modification of the structure and functions of the skin. The main clinical signs of skin aging are in particular the appearance of fine lines and deep wrinkles, which increase with age.

It is known to treat these signs of aging by using anti-aging cosmetic compositions. However, these active agents have the drawback of only being effective for the treatment of wrinkles after repeated applications. However, it is increasingly sought to obtain an immediate effect from the active agents used, leading rapidly to a smoothing of wrinkles and fine lines and/or to the disappearance of signs of fatigue.

Cosmetic products often require the use of a film-forming polymer to obtain a deposit of the product on keratin materials with good cosmetic properties. In particular, it is necessary for the film-forming deposit to have good hold, in particular for the deposit not to transfer on contact with fingers, clothing, as well as good hold in contact with water, in particular rain. or during the shower or even that the deposit is insensitive to perspiration or to sebum, as well as to the fatty substances of food, in particular food fatty substances such as oils.

It is known to use dispersions of polymer particles in organic media such as hydrocarbon oils. The polymers are used in particular as a film-forming agent in make-up products such as mascaras, eyeliners, eye shadows or lipsticks. Document EP 0 749 747 describes in the examples dispersions in hydrocarbon oils (paraffin oil, isododecane) of acrylic polymers stabilized with polystyrene/copoly(ethylene-propylene) diblock copolymers. The film obtained after application of the dispersion to the skin is not very shiny. Document FR 1362795 also describes the use of dispersions of surface-stabilized polymer particles containing hydrocarbon oils for making up the lips and eyelashes. Document WO 2010/046229 describes dispersions in isododecane of acrylic polymers stabilized with stabilizing polymers. Document FR 1 362 795 describes the use of a dispersion of surface-stabilized polymer particles containing hydrocarbon oils for making up the lips and eyelashes.

In the field of dyeing keratin fibers, it is already known to dye keratin fibers by various techniques using direct dyes for non-permanent dyes or dye precursors for permanent dyes.

Non-permanent coloring or direct coloring consists in dyeing the keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules with an affinity for keratin fibres. They are applied to the keratin fibers for the time necessary to obtain the desired coloration, then rinsed off.

The conventional dyes which are used are in particular dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane type or natural dyes.

Some of these dyes can be used under lightening conditions, which makes it possible to obtain visible colorations on dark hair.

It is also known to dye keratin fibers permanently by oxidation dyeing. This coloring technique consists in applying to the keratin fibers a composition containing dye precursors such as oxidation bases and couplers. These precursors under the action of an oxidizing agent will form one or more colored species in the hair.

The variety of molecules involved in oxidation bases and couplers makes it possible to obtain a rich palette of colors and the resulting colorations are generally permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing.

To be visible on dark hair, these two coloring techniques require prior or simultaneous bleaching of the keratin fibres. This bleaching step implemented with an oxidizing agent such as hydrogen peroxide or persalts leads to a significant degradation of the keratin fibres, which alters their cosmetic properties. The hair then tends to become rough, more difficult to disentangle and more fragile.

Another coloring method consists in bringing a surface coloring in particular with the help of pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colorations, especially on dark hair, since the pigment on the surface masks the natural color of the fiber. The use of pigment for coloring keratin fibers is for example described in patent application FR 2 741 530, which recommends the use for the temporary coloring of keratin fibers of a composition comprising at least one dispersion of particles of film-forming polymer comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.

The colors obtained by this method of coloring are generally not very tenacious and are eliminated fairly quickly with shampoo.

It is also known from patent application FR 2 907 678 to produce colored coatings for the hair from a composition comprising a polysiloxane/polyurea block copolymer and a pigment. However, with such a composition, the coatings obtained may sometimes lack homogeneity and the individualization of the hair after combing is not always satisfactory.

Document FR 3 014 875 describes the use of a dispersion of C ₁ -C ₄ alkyl (meth)acrylate polymer particles surface-stabilized with a polymeric stabilizing agent of isobornyl (meth)acrylate in a non-aqueous medium. containing an oil. The deposits obtained from this technology are not always satisfactory, particularly in terms of resistance to sebum.

Document FR 3 029 786 is concerned with dispersions for making up polymer particles stabilized by at least one stabilizing agent which is a C 8 alkyl (meth)acrylate homopolymer or a C ₈ alkyl (meth)acrylate copolymer. C ₈ alkyl (2-ethylhexyl) and C ₁ -C ₄ alkyl (meth)acrylate. These dispersions are not always satisfactory in terms of resistance to fatty substances and sebum, which can be a hindrance to their use in making up the lips, for example. In addition, these dispersions may have a feel that is considered too "sticky" after application to keratin materials, which may be prohibitive for certain applications such as lip or eyelash makeup...

Thus, the object of the present invention is to provide a composition for treating keratinous materials, in particular the skin, preferably human skin, and more preferably the skin of the face, which is non-sticky and has good resistance to external aggressions, and over time, does not disgorge, resistant to sweat, sebum, insensitive to oils such as cooking oils. In addition, the composition may comprise cosmetic active agents such as those for obtaining a tightening effect on the skin, body, face and hair care, Ultra-Violet (UV) protection, face make-up, lips, and eyelashes, eyebrows, and hair. Said composition may be intended in particular for care and/or makeup, especially for makeup of the lips.

Furthermore, consumers are demanding aqueous galenics, containing as few volatile compounds as possible. In the hair field, for example, it is always desirable, when possible, to replace volatile compounds with water in the compositions used, in particular in hairdressing salons. Environmental issues also lead to reducing the use of volatile compounds as much as possible. Thus, one of the aims of the present invention is to provide a composition with a reduced content of volatile compounds. Another object is to provide a film-forming composition containing an aqueous phase opening the way to a wider formulation field. For reasons related to the environment, but also to avoid potentially altering the keratin materials in the long run, it is desirable to put as few surfactants as possible in the cosmetic composition.

Another object of the present invention is to provide a composition for the treatment of keratinous fibers, in particular human fibers such as the hair, the eyelashes, the eyebrows, exhibiting good resistance to aggressions such as brushing, not bleeding, resistant to sweat and sebum, to light and bad weather, remanent to shampoos and to the various aggressions that said fibers may undergo without degradation of said fibers and while retaining perfectly individualized keratin fibers.

The technical problem was solved by the use of a dispersion (A) for the treatment of keratin materials, in particular α) keratin fibers, in particular human, such as hair, eyelashes, eyebrows or β) human skin, in particular of the lips, in which the dispersion (A), comprises:
i) one or more particle(s) comprising one or more polymer(s) chosen from a) one or more ethylenic copolymer(s) 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, sulphonic acid and/or aryl groups; in particular a ₂ ) is a (C ₁ -C ₄ )(alkyl)acrylic acid; And
ii) one or more polymeric stabilizing agent(s) chosen from:
b) polymers of (C ₁ -C ₆ )(C ₃ -C ₁₂ )cycloalkyl (alkyl)acrylate monomers; 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 (C ₁ -C ₄ ) alkyl; And
iii) one or more hydrocarbon-based liquid fatty substance(s);
iv) water; And
v) optionally one or more cosmetic active ingredient(s) chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, in particular the skin, and j) UV filters (A) and/or (B) as well as m) mixtures thereof;
it being understood that the amount of water is greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the dispersion.

More particularly, the subject of the invention relates to the use of the dispersion (A) as defined above for the treatment of keratin materials, in particular human materials such as the hair, the eyelashes, eyebrows, or the skin, preferably for coloring keratin fibers and/or the shaping of keratin fibers such as the hair, or for making up the skin or for caring for the skin or providing an immediate non-coloured effect.

A subject of the invention is also the dispersion (A) as defined previously, as well as a process for treating keratin materials, preferably α) keratin fibers, in particular human fibers such as the hair, the eyelashes, eyebrows or β) the human skin, in particular the lips, comprising the application to said materials of a dispersion (A), as defined above. A subject of the invention is also a kit or device comprising several compartments comprising the ingredients i) to iv) as defined above.

A subject of the invention is also a composition, preferably cosmetic, comprising the dispersion (A) as defined previously, the process for applying said composition to keratin materials.

A subject of the invention is also a process for treating keratin materials, preferably α) keratin fibres, in particular human ones, such as hair, eyelashes, eyebrows or β) human skin, in particular the lips, comprising the application to said materials of at least one dispersion (A), as defined previously, preferably after application of the dispersion (A) to the keratin materials, the composition is left to dry on the said keratin materials, either in the open air or in the using heating devices used in cosmetics such as a hair dryer

The dispersion (A), and the process for treating keratin materials as defined above, make it possible to obtain a treatment of said materials that is resistant in particular to shampoos, sebum, sweat, and/or water, but also to fatty substances in particular food such as oils. In addition, the dispersion is easy to implement in compositions, in particular cosmetic compositions, is easy to manufacture and remains stable over time. Indeed, the dispersion (A) in accordance with the present invention makes it possible to obtain deposits that are very resistant to external attacks, in particular sebum and fatty substances that are found in food, in particular liquid fatty substances such as oils. vegetables and in particular olive oil. It appears that the make-up produced with at least one dispersion (A), in particular lip make-up, is particularly resistant to external attacks such as liquid fatty substances, in particular vs. vegetable oils such as olive oil. In addition, the makeups obtained with the dispersions (A) are very aesthetic and shiny. In addition, these dispersions of polymer particles are found at a high dry matter content in the hydrocarbon-based liquid fatty substance(s) iii). It appears that the application of the dispersions (A) of the invention to the keratin fibers makes it possible to obtain coatings that are resistant to external aggressions (sun, water, shampoos, perspiration, sebum, etc.).

In addition, when the composition comprises one or more dye(s) and/or pigment(s), the colored keratin materials have a visible coloring on all types of materials, in particular on dark keratin materials, in a persistent manner on soaps, shower gels , or shampoos while preserving the physical qualities of the keratin material. Such coloring is in particular resistant to the external aggressions that the keratin fibres, in particular the hair, such as brushing and perspiration may undergo. The use of dispersion (A) on keratin materials, in particular on keratin fibres, makes it possible to obtain a smooth and homogeneous deposit. Furthermore, it has surprisingly been observed that the keratin fibers remained perfectly individualized and could be styled without any problem.

Within the meaning of the present invention, and unless a different indication is given:
- an " alkyl radical " is a saturated C ₁ -C ₈ hydrocarbon group, linear or branched, in particular C ₁ -C _6, preferably C ₁ -C ₄ such as methyl, ethyl, n-propyl, isopropyl or i-propyl, n-butyl, isobutyl or i-butyl and tert-butyl or t-butyl;
- an “ alkylene radical ” is a divalent C ₁ -C ₈ saturated hydrocarbon group, linear or branched, in particular C ₁ -C _6, preferably C ₁ -C ₄ such as methylene, ethylene or propylene;
- a “ cycloalkyl ” radical is a saturated cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, and which can be substituted by a or several (C ₁ -C ₄ )alkyl groups such as methyl such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, preferably the cycloalkyl radical is an isobornyl group.
- a “ cyclic ” radical is a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms such as cyclohexyl or phenyl;
- an “ aryl ” radical is an aromatic unsaturated cyclic radical, comprising from 6 to 12 carbon atoms, mono or bicyclic, fused or not, preferably the aryl group comprises 1 ring and 6 carbon atoms such as phenyl;
- an " aryloxy " radical is an aryl-oxy radical , i.e. aryl-O- with aryl as defined above, preferably phenoxy;
- an “ aryl(C ₁ -C ₄ )al c oxy ” radical is an aryl-(C ₁ -C ₄ )alkyl-O— radical, preferably benzoxy;
- By “ keratin materials ” is meant particularly the skin (keratinized epithelium) and human keratin fibers such as the hair, the eyelashes, eyebrows, and body hair, preferably the hair, the eyebrows and the eyelashes, even more preferably the hair;
- by “ individualized ” keratin fibers is meant keratin fibers, in particular hair which, after application of the composition and drying, is not stuck together (or is all separated from one another) and therefore does not form clusters of fibers;
- the term " insoluble monomer " therefore means any monomer whose homopolymer or copolymer is not in soluble form, that is to say completely dissolved at a concentration greater than 5% by weight at room temperature (20 °C) in said medium. However, the so-called “ insoluble ” monomers can, as monomers, be soluble or insoluble in the liquid hydrocarbon fatty substance(s) iii), it being understood that they become insoluble after polymerization in the liquid hydrocarbon fatty substance(s) iii);
- By “ ethylenic homopolymer ” is meant a polymer resulting from the polymerization of identical monomers;
- By “ ethylenic copolymer ” is meant a polymer resulting from the polymerization of different monomers, in particular at least 2 different monomers. Preferably, the ethylenic copolymer of the invention is derived from 2 or 3 different monomers;
- By “ ethylenic monomer ” is meant an organic compound comprising one or more unsaturations of the >C=C< types, conjugated or not, capable of polymerizing;
- by “ soluble monomer ”, is meant any monomer whose homopolymer or copolymer, preferably homopolymer, is soluble at least to 5% by weight, at 20° C., in the hydrocarbon liquid fatty substance(s) iii) of the dispersion . The homopolymer is completely dissolved in the carbonaceous liquid(s) iii), visually at 20° C., ie no deposit, nor precipitate, nor agglomerate, nor insoluble sediment is noted visually.
- by "fatty substance " is meant an organic compound which is immiscible in water at ordinary room temperature (25° C.) and at atmospheric pressure (760 mm Hg) (solubility less than 5% and preferably 1 % even more preferably at 0.1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as, for example, ethanol, ether, vaseline oil or decamethyl cyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids because salified fatty acids constitute soaps that are generally soluble in aqueous media;
- “ liquid ” fatty substance is understood to mean in particular a fatty substance that is liquid at 25° C. and 1 atmosphere, preferably said fatty substance has a viscosity less than or equal to 7000 centipoise at 20° C.;
- by “ hydrocarbon ” fatty substance is meant a fatty substance which comprises at least 50% by weight, in particular from 50 to 100% by weight, for example from 60 to 99% by weight, or even from 65 to 95% by weight, or even from 70 to 90% by weight, relative to the total weight of said fatty substance, of carbonaceous compound, having an overall solubility parameter according to HANSEN's solubility space of less than or equal to 20 (MPa)1/2, or d a mixture of such compounds;
- The global solubility parameter δ according to the HANSEN solubility space is defined in the article "Solubility parameter values" by Grulke, in the work "Polymer Handbook" 3 ^rd edition, Chapter VII, pages 519-559 by the relation δ = ( d _D ² + d _P ² + d _H ² ) ^1/2 in which: - d _D characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular collisions, - d _P characterizes the forces DEBYE interactions between permanent dipoles, - d _H characterizes the specific interaction forces (type of hydrogen bonds, acid/base, donor/acceptor, etc.); The definition of solvents in the three-dimensional solubility space according to HANSEN is described in the article by HANSEN: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967);
- “ oil ” means a fatty substance that is liquid at room temperature at room temperature (25° C.) and atmospheric pressure;
- by " hydrocarbon oil " is meant an oil formed essentially, or even consisting, of carbon and hydrogen atoms, and optionally of oxygen and nitrogen atoms, and not containing any silicon or of fluorine. It may contain hydroxy, ester, ether, carboxylic acid, amine and/or amide groups;
- “ volatile oil ” means an oil (or non-aqueous medium) capable of evaporating on contact with keratin materials, in particular the skin, in less than one hour, at ambient temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, liquid at ambient temperature, having in particular a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular, having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ^-3 to 300 mm Hg), and preferably ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 10mmHg);
- “ non-volatile oil ” means an oil having a vapor pressure of less than 0.13 Pa at room temperature and at atmospheric pressure;
- By “ silicone oil ” is meant an oil comprising at least one silicon atom, and in particular at least one Si—O group. The silicone oil can be volatile or non-volatile;
- By “ dispersing agent ” is meant a compound which makes it possible to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them, bearing one or more functionalities having a strong affinity for the surface of the particles to be dispersed; in particular, they can cling physically or chemically to the surface of the pigments. These dispersing agents also have at least one functional group that is compatible or soluble in the continuous medium. Said agent can be charged, it can be anionic, cationic, zwitterionic or neutral;
- by " pigment ", we mean all the pigments providing color to keratinous materials, of synthetic or natural origin, the solubility of the pigments in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0 0.05% by weight, and preferably less than 0.01%;
- By " lacquer " is meant the dyes adsorbed on insoluble particles, the assembly 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, mention may be made of cochineal carmine
- By “ hair dyes ” is meant oxidation dyes, and direct dyes used to color keratin fibres, in particular human fibres, such as the hair.
- By “ anhydrous ” dispersion or composition is meant a dispersion or composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular free of water; where appropriate, such small amounts of water can in particular be supplied by ingredients of the composition which can contain residual amounts thereof;
- by " special effect pigments ", we mean pigments which generally create a colored appearance (characterized by a certain nuance, a certain liveliness and a certain clarity) which is not uniform and changes according to the conditions of observation ( light, temperature, viewing angles, etc.). They are thereby opposed to colored pigments which provide a uniform opaque, semi-transparent or transparent classic shade; And
- by " sub-micronic " or in English " sub-micronic " means pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micronmeter (μm), in particular between 0, 1 and 0.9 μm, and preferably between 0.2 and 0.6 μm.
- By “ thickening polymer ” is meant a polymer which is introduced at 1% by weight into an aqueous or aqueous-alcoholic solution containing 30% ethanol, and at pH=7 or into an oil chosen from petroleum jelly, myristate d isopropyl or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps, preferably at least 500 cps, at 25° C. and at a shear rate of 1 s ⁻¹ . This viscosity can be measured using a cone/plane viscometer (Haake R600 rheometer or the like). The thickening polymers can thicken the aqueous phase and/or the fatty phase, preferably the aqueous phase;
- By " organic " thickening polymer is meant a thickening polymer as defined above which consists of carbon, hydrogen, and optionally nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine, bromine as well as phosphorus, alkali metals such as sodium, potassium, or alkaline earth metals such as magnesium or calcium. The organic polymers according to the invention do not include silicon;
- By the expression “ non-cellulose organic thickening polymer ”, is meant according to the invention, an organic thickening polymer not comprising a cellulose unit;

Dispersion (A)

The dispersion (A) of the invention comprises i) one or more particles of at least one surface-stabilized polymer with ii) at least one stabilizing agent in a preferably anhydrous medium, additionally containing iii) at least one fatty substance hydrocarbon liquid and iv) water.

In order to obtain the dispersion (A), it is proposed to polymerize particular monomers capable of forming the polymeric core i) in the presence of a polymeric random stabilizing agent ii) mainly comprising 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) optionally containing iv) water.

The dispersions according to the invention consist of particles, generally spherical, and of at least one surface-stabilized polymer.
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 hydrocarbon-based liquid 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 which forms the stabilizing agent(s) ii)) and between 60% and 98% by weight, in particular from 65 to 96% by weight of insoluble monomer (that which forms the particles i )).

By “ soluble ” monomer is meant in the present description any monomer whose polymer, in particular the homopolymer, is soluble, at 5% by weight, at 20° C., and at atmospheric pressure in the liquid hydrocarbon medium consisting of liquid fatty substances ( s) hydrocarbon(s) iii) of the dispersion. The polymer, in particular the homopolymer, is completely dissolved in the liquid carbonaceous medium, visually at 20° C. (no apparent visible deposit, no agglomerate or insoluble sediment observed with the eye).

By “ insoluble ” monomer is meant any monomer whose polymer, in particular the homopolymer, is not in soluble form, that is to say completely dissolved at a concentration greater than 5% by weight at room temperature (20°C ) in said liquid hydrocarbon medium consisting of hydrocarbon liquid fatty substance(s) iii).

Preferably, the monomers i) capable of forming the polymeric core of the particle are chosen from monomers which are insoluble in the liquid hydrocarbon-based medium consisting of liquid hydrocarbon-based fatty substance(s) iii). The insoluble monomers represent in particular 100% by weight of the total weight of the monomers forming the polymer core of the particle.

Polymer particles i)

The particle(s) i) of the dispersion (A) of the invention consists of one or more ethylenic copolymer(s) resulting from the polymerization:
a1) at least one monomer (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl and
a2) at least one ethylenic monomer comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups; in particular a2) is an acid
(C ₁ -C ₄ ) (alkyl)acrylic.

Preferably, the particle(s) i) consists of an ethylenic polymer core derived from copolymers a), as defined previously.

By " ethylenic copolymer " is meant a polymer resulting from the polymerization of at least two monomers chosen from one or more monomers a1) (C ₁ -C ₄ )(alkyl) acrylate (C ₁ -C ₄ )alkyl and one or more a2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic 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 can 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, sulphonic 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 , selected 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 or particles i) comprise a) ethylenic copolymers of a1) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl, and of a2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups such as benzyl.

More particularly, the ethylenic monomers a2) comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups are chosen from (1) , (2) , (3) and (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, phosphoric acid, sulphonic acid, preferably carboxy, preferably (1) represents (5) H ₂ C=C(R)-C(O)-OH with R representing a hydrogen atom, 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' , which are identical or different, represent a hydrogen atom, or a group (C ₁ -C ₄ ) alkyl; Alk represents a (C ₁ -C ₆ )alkylene group optionally substituted by at least one group chosen from Acid as defined previously and hydroxy; and Acid is as defined above, preferably carboxy or sulphonic acid;
(3) Ar-(R _a )C=C(R _b )-R _c with R _a , R _b and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group , and Ar represents an aryl group, preferably benzyl, optionally substituted by at least one CO ₂ H, H ₂ PO ₄ or SO ₃ H acid group, preferably substituted by a CO ₂ H or SO ₃ H group,
(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 a2) is chosen from (1) and (4) , in particular (4) and (5) .

According to a particular variant of the invention, a2) 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 a2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, acrylamiopropanesulfonic acid, acrylamidoglycolic acid, and their salts, more preferably a2) 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; the salts of organic amines, such as for example the salts of methylamine, of diethylamides, of trimethylamine, of triethylamine, of ethylamine, of 2-hydroxyethylamine, of bis-(2-hydroxyethyl)amine, of tri-(2- hydroxyethyl)amine; lysine and arginine salts.

According to a preferred embodiment of the invention, the (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl a1) monomer(s) are chosen from those of formula (I): Formula (I) in which:
- R representing a hydrogen atom or a (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 (I) 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 ethylenic acrylate copolymer a) resulting from the polymerization:
- a1) of at least one monomer of formula (I) as defined above, preferably C ₁ -C ₄ alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl; And
- a2) of at least one monomer chosen from (1) , (2) , (3) , and (4) as defined above and preferably of formula (II) as well as its salts: Formula (II) in which R as defined above, in particular (II) represents acrylic acid.

According to a preferred embodiment of the invention, the amount of a2) in particular of compound (II) and in particular of acrylic acid is greater than 2.5% by weight relative to the total weight of the particle i), plus particularly comprised between 3% and 35% by weight relative to the weight of monomers of the particle i), even more particularly comprised between 5% and 25% by weight and the polymer of the particles i), better comprised between 10% and 15% by weight and the polymer of the particles i).

In particular a) is a copolymer resulting from the copolymerization a2) of acrylic acid with a1) one or more C ₁ -C ₄ alkyl (meth)acrylate monomers, preferably of at least 2 different monomers (meth) C ₁ -C _{4 alkyl 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 ethylenic acrylate copolymer a) resulting from the polymerization:
- at least two different monomers: of formula (I) as defined above, preferably C ₁ -C ₄ alkyl acrylate such as methyl acrylate, ethyl acrylate, ((meth)acrylate isobutyl; and
- at least one monomer chosen from (1) , (2) , (3) , and (4) as defined above, preferably of formula (II) as defined above.

According to a particular embodiment of the invention, the polymer of the particles i) is a polymer resulting from monomers a1) of C ₁ -C ₄ alkyl (meth)acrylate.

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

The monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl, 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:
a1) at least one monomer of formula (I) as defined previously; And
a2) of at least one ethylenically unsaturated anhydride monomer in particular of formula (4) as defined previously.

In particular, the polymer of the particles a) is a polymer a1) of C ₁ -C ₄ alkyl (meth)acrylate monomer, linear or branched, preferably linear in particular of (C ₁ -C ₃ )alkyl and a2) of ethylenically unsaturated anhydride monomer.

The monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate.

Advantageously, one monomer or two monomers a1) different from C ₁ -C ₄ alkyl acrylate, linear(s) or branched(s), preferably linear(s) in particular (C ₁ -C ₃ ). Preferably a1) is chosen from methyl acrylate and ethyl acrylate.

According to particular embodiment, one or two different branched (C ₃ -C ₄ )alkyl (meth)acrylate monomers 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) a2) of the invention are chosen from derivatives of maleic anhydride (4a) and of itaconic anhydride (4b) as defined previously.

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 dispersion comprise, from 80 to 95% by weight, of the ingredient a1) and from 5 to 20% by weight of the ingredient a2), relative to the total weight of the copolymer(s).

More particularly, the polymer of the particles i) preferably comprises from 80 to 93% by weight of ingredient a1), in particular of C ₁ -C ₄ alkyl (meth)acrylate and from 7 to 20% by weight of ingredient a2) relative to the total weight of polymer i). More preferentially, the polymer of the particles i) preferably comprises from 85 to 93% by weight, more particularly 87% to 92% by weight, even more preferentially from 85% to 90% by weight, of the ingredient a1) in particular of C ₁ -C ₄ alkyl (meth)acrylate and 10 to 20% by weight of ingredient a2) 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 the particles i) of the dispersion preferably has a number average molecular weight ranging from 2,000 to 10,000,000.

The polymer of the particles i) may be present in the dispersion (A) 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, by 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 dispersion (A) .

Preferably, the particle(s) i) consist of a copolymer of a1) and a2).

According to a particular embodiment of the invention, the particles i) consist of copolymers resulting from the polymerization of monomers a1) and a2) with a weight ratio a1) / a2) is 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 or particles i) of the dispersion (A) preferably have a number-average size ranging from 5 and 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 dispersion (A) according to the invention also comprises one or more stabilizing agents ii). Preferably only one type of stabilizer ii) is used in the invention.

The stabilizing agent(s) of the invention is (are) constituted by ethylenic polymers chosen from b) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; and c) copolymers of c1) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl and c2) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ ) alkyl. Preferably, the stabilizing agent(s) of the invention is (are) composed of ethylenic polymers chosen from c) copolymers of c1) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ ) cycloalkyl and c2) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl.

According to a preferred embodiment of the invention, the stabilizing agent ii) consists of ethylenic polymers chosen from:
b) polymers of monomers of formula H ₂ C=C(R)-C(O)-O-R'' (III) with R representing a hydrogen atom or a (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) the copolymers of c1) H ₂ C=C(R)-C(O)-O-R'' (III) and of c2) H ₂ C=C(R)-C(O)-O-R' ( I)
with R, R' and R'' as defined previously.

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

According to another particular embodiment of the invention, the stabilizing agent(s) of the invention consist(s) of ethylenic polymers chosen from c) copolymers of c1) (C ₁ -C ₆ ) (C ₃ -C ₁₂ )cycloalkyl (alkyl)acrylate _, particularly of formula (III) as _defined previously and of (C ₁ -C ₄ )(c2)alkyl)acrylate, particularly of formula (I) as previously defined.

According to a particular form of the invention, ingredient c2 is a monomer (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl in particular of formula (I) more particularly chosen from (meth)acrylate methyl and ethyl (meth)acrylate, more preferably methyl (meth)acrylate.

According to another particular form of the invention, ingredient c2 is a mixture of several different monomers (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, in particular 2 different monomers (C ₁ -C (C ₁ -C ₄ )alkyl ₄ )(alkyl)acrylate in particular of formula (I) more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate.

In particular, the stabilizing agent ii) is chosen from b) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; and c) random copolymers of c1) (C ₁ -C ₆ )(alkyl)acrylate of (C ₃ -C ₁₂ )cycloalkyl and c2) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ ) alkyl with a c1/c2 weight ratio greater than 4. Advantageously, said weight ratio ranges from 4.5 to 19. More advantageously, said c1/c2 weight ratio 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 (meth) acrylate of isobornyl and c) the random copolymers c1) of (meth) acrylate of isobornyl and of c2) of (meth) C ₁ -C ₄ alkyl acrylate preferably present in an isobornyl (meth)acrylate/C 1 -C ₄ (c1 _/ c2) alkyl (meth)acrylate weight ratio greater than 4. Advantageously, said c1/c2 weight ratio ranges from 4.5 to 19. Advantageously, said c1/c2 weight ratio ranges from 5 to 15, more preferably said c1/c2 weight ratio ranges from 5.5 to 12.

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

Advantageously, the stabilizing agent is chosen from: b) homopolymers of isobornyl acrylate, c) random copolymers of isobornyl acrylate/methyl acrylate, random copolymers of isobornyl acrylate/methyl acrylate, ethyl, and isobornyl acrylate/methyl acrylate/ethyl acrylate random copolymers 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, preferably ranging from 20,000 to 200,000.

The stabilizer ii) is in contact with the surface of the particles i) of polymer and thus makes it possible to stabilize these particles at the surface for the maintenance of these particles in dispersion in the medium of the dispersion (A).

More particularly, the stabilizing agent(s) ii) are chosen from c) copolymers of:
c1) (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl; And
c2) (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl;
with from 80 to 95% by weight of ingredient c1) in particular isobornyl (meth)acrylate and from 5 to 20% by weight of ingredient c2) in particular methyl acrylate and ethyl acrylate with respect to the total weight of stabilizer.
More preferably, the stabilizing agent(s) ii) comprise from 85 to 94% by weight, more particularly 87% to 93% by weight, of ingredient c1), in particular of isobornyl (meth)acrylate and from 10 to 20% by weight of ingredient c2) 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 dispersion (A) 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 whole ii) stabilizing agent(s)+i) particle(s) of polymer(s).

According to a particular embodiment of the invention, the dispersion (A) is such that the set ii) stabilizing agent(s) + i) particle(s) of polymer(s) are present in the dispersion (A ) from 2% to 40% by weight, in particular from 4% to 35% by weight, preferably from 4.5% to 30% by weight relative to the total weight of the dispersion (A).

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

The dispersion (A) according to the invention is ultimately formed of polymer 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 particularly interesting for make-up applications.

The final particle size is greater than 100 nm. In particular a number-average size 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 model NanoZS laser particle sizer (particularly well suited to submicronic dispersions) is used 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 granulometry techniques make it possible to obtain this type of information, such as analysis of individual particle tracking (Nanoparticle Tracking Analysis, NTA), laser diffraction (DL), acoustic extinction spectroscopy (AES) , Doppler velocimetry by spatial filter or image analysis.

The liquid hydrocarbon fatty substance(s) iii)

The dispersion of polymer particles (A) according to the invention also comprises iii) one or more hydrocarbon-based liquid fatty substances in which said particles are dispersed.

According to a particular embodiment, the hydrocarbon-based liquid fatty substance(s) iii) of the invention is (are) chosen from hydrocarbons, in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluorinated oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, silicones; in particular the hydrocarbon-based liquid fatty substance(s) are preferably volatile hydrocarbon-based oils or are a mixture of different volatile oils, preferably chosen from isododecane and octyldodecanol, more particularly isododecane .

The liquid hydrocarbon fatty substances iii) are in particular chosen from C ₆ -C ₁₆ hydrocarbons or having more than 16 carbon atoms up to 50 carbon atoms, preferably between C ₆ and C ₁₆ , and in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides, fatty alcohols, fatty acid and/or fatty alcohol esters, silicones.

It is recalled that within the meaning of the invention, the alcohols, esters and fatty acids have more particularly one or more hydrocarbon groups, linear or branched, saturated or unsaturated, comprising 6 to 50 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds can comprise one to three carbon-carbon double bonds, conjugated or not.

As regards the C ₆ -C ₁₆ alkanes, the latter are linear, branched, possibly cyclic. By way of example, mention may be made of hexane, undecane, dodecane, tridecane, isoparaffins such as isohexadecane, isodecane isododecane, and their mixtures such as the combination of undecane and tridecane as for example CETIOL UT®. The linear or branched hydrocarbons with more than 16 carbon atoms can be chosen from paraffin oils, petroleum jelly, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parléam®.

Among the liquid hydrocarbon fatty substances iii) having an overall solubility parameter according to the HANSEN solubility space of less than or equal to 20 (MPa) ^1/2 , mention may be made of oils, which can be chosen from natural or synthetic oils , hydrocarbon, optionally branched, alone or as a mixture.

According to a very advantageous embodiment, the dispersion (A) according to the invention comprises one or more liquid fatty substances which is (are) one or more hydrocarbon oil(s). The hydrocarbon oil(s) may be volatile or non-volatile.

According to a preferred embodiment of the invention, the hydrocarbon-based liquid fatty substance(s) are hydrocarbon-based oils which are volatile or are a mixture of different volatile oils .

According to another particular embodiment, the liquid hydrocarbon fatty substance(s) iii) are a mixture of a volatile oil and a non-volatile oil such as an isododecane/octyldodecanol mixture

The hydrocarbon oil can be chosen from:
hydrocarbon oils having from 8 to 14 carbon atoms, and in particular:
- branched C ₈ -C ₁₄ alkanes such as C ₈ -C ₁₄ isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example the oils sold under the trade names Isopars' or Permetyls,
- linear alkanes, for example such as n-undecane (C11), n-dodecane (C12), n-tridecane (C13) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97 , as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and n-tridecane (C13) obtained in examples 1 and 2 of application WO 2008/155059 from the company Cognis , and mixtures thereof, also marketed under the name CETIOL UT®.
- hydrocarbon oils of plant origin such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which may have chain lengths varying from C ₄ to C ₂₄ , the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or alternatively wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soy, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or caprylic/capric acid triglycerides such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810 ^® , 812 ^® and 818 ^® ,
- synthetic ethers having 10 to 40 carbon atoms;
- linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam ®, squalane, paraffin oils, and mixtures thereof,

Dispersion (A) in addition to the liquid hydrocarbon fatty substance, may comprise a silicone oil. If silicone oil is in the dispersion (A), preferably it is in an amount which does not exceed 10% by weight relative to the weight of the dispersion (A), more particularly in an amount less than 5% and more preferably 2%.

In particular, the dispersion (A) comprises at least one hydrocarbon-based liquid fatty substance iii) chosen from:
- vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower, sesame or rapeseed, macadamia, soybean oil, sweet almond oil, calophyllum, palm, grapeseed, corn, arara, cotton, apricot, avocado, jojoba, olive or cereal germ;
- hydrocarbons and in particular linear, branched and/or cyclic alkanes, volatile or non-volatile, such as C ₅ -C ₆₀ isoparaffins, possibly volatile such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or 'ISOPARs'; or paraffin oils, petroleum jelly, or hydrogenated polyisobutylene; especially isododecane
- ethers having 6 to 30 carbon atoms;
- aliphatic fatty monoalcohols having 6 to 30 carbon atoms, the hydrocarbon chain not comprising any substitution group, such as oleic alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleic alcohol; in particular octyldodecanol; - polyols having 6 to 30 carbon atoms, such as hexylene glycol; And
- their mixtures.

Advantageously, the liquid hydrocarbon fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.

Preferably, the dispersion (A) comprises at least one liquid hydrocarbon fatty substance iii) apolar, preferably chosen from:
- linear or branched C ₈ -C ₃₀ alkanes, in particular C ₁₀ -C ₂₀ , more particularly C ₁₀ -C ₁₆ alkanes, volatile or non-volatile; preferably volatile
- cyclic, non-aromatic, C ₅ -C ₁₂ alkanes; volatile or non-volatile; preferably volatile, and
- their mixtures.

The hydrocarbon-based liquid fatty substance(s) are preferably chosen from hydrocarbon-based oils having from 8 to 16 carbon atoms, in particular having from 10 to 14 carbon atoms, preferably volatile, more particularly the apolar oils, described previously.
Among the branched C ₈ -C ₁₆ alkanes, in particular C ₁₀ -C ₁₄ suitable as liquid hydrocarbon fatty substances iii) in the dispersion of the invention, mention may be made of:
- isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane and for example the oils sold under the trade names of Isopars' or from Permetlys;
- linear alkanes, for example such as n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures, the mixture undecane-tridecane, mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ) from Cognis, and mixtures thereof.

Preferably, the liquid hydrocarbon fatty substance(s) iii) of the invention are apolar, more particularly isododecane.

According to another advantageous embodiment of the invention, the liquid hydrocarbon fatty substance(s) are a mixture of non-volatile oil and volatile oil, preferably the mixture comprises isododecane as volatile oil, or a mixture of in particular of undecane and tridecane.

In particular, in the mixture, the non-volatile oil is a phenyl silicone oil preferably chosen from pentaphenyl silicone oils.

Preferably, the liquid hydrocarbon fatty substance(s) iii) are present 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 dispersion (A).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 mass ratio is between 0.5 and 1.

Preferably, use will be made of 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 random copolymer stabilizer isobornyl acrylate/methyl acrylate/ ethyl acrylate (92/4/4); the 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 copolymer of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) stabilized by a stabilizer random copolymer of isobornyl acrylate/methyl acrylate/ ethyl acrylate (92/4/4); the 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 copolymer of methyl acrylate/ethyl acrylate/maleic anhydride (50/37.2/12.8) stabilized by a stabilizer random copolymer of isobornyl acrylate/methyl acrylate/acrylate of ethyl (92/4/4); the dispersion containing in total (stabilizer ii)+particles i)) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.

More preferably, use will be made of a dispersion in isododecane of particles of methyl acrylate/ethyl acrylate/acrylic acid copolymer (11.7/75.6/12.7) stabilized by a random copolymer stabilizer isobornyl acrylate/ methyl acrylate/ethyl acrylate (92/4/4); the dispersion containing in total (stabilizer ii) + particles i)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.

The amount of particles i) in the dispersion (A) of the invention preferably varies from 20% to 50% by weight, more preferably from 25 to 45% by weight relative to the total weight of the dispersion.

Dispersion preparation method (A)

Without this being limiting, in general, the dispersion according to the invention can be prepared in the following way:
- The polymerization is carried out in " dispersion " by precipitation of the polymer during formation, with protection of the particles formed with one or more stabilizing agents ii), preferably a single type of stabilizing agent ii) chosen from b) and c) as previously defined.
- In a first step, the stabilizing polymer (or stabilizing agent ii)) is prepared by mixing the monomer or monomers constituting the stabilizing polymer b) or c), with vi) a radical initiator, in a solvent called synthetic solvent, and by polymerizing these monomers; Then
- In a second step, to the stabilizing polymer ii) formed in the previous step, the monomers constituting the polymer of the particles i) are added and the polymerization of these added monomers is carried out in the presence of the radical initiator.- In a third step, the water is added and all the ingredients i)+ii) are stirred in the reactor before leaving the dispersion.

When the synthetic solvent is a non-volatile liquid hydrocarbon fatty substance iii), the polymerization can be carried out in an apolar organic solvent (synthesis solvent) then add the non-volatile liquid hydrocarbon fatty substance (which must be miscible with said synthetic solvent ) and selectively distilling the synthesis solvent.

The synthetic solvent may consist of liquid hydrocarbon fatty substances 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 method conventional to those skilled in the art, such as distillation. The polymers particles i) and the stabilizing agents ii) are found in the hydrocarbon liquid fatty substance iii).

Dispersion (A) optionally contains one or more cosmetic active agents v).

The cosmetic active agent(s) v) chosen from f) dyes and/or pigments; g) active ingredients for caring for keratin materials, in particular the skin, and h) UV filters as well as j) mixtures thereof can be added during the first stage. According to another variant, the said cosmetic active ingredient(s) is (are) added during the second stage or after the second stage.

According to another variant, the said cosmetic active ingredient(s) is (are) added during the third step.

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

In particular, the synthetic solvent which is apolar and volatile organic is chosen, preferably chosen from alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.

According to another variant, a mixture of:
- an apolar solvent as defined above, in particular isododecane
- a polar solvent chosen in particular from esters such as (C ₁ -C ₄ ) alkoxide (C ₁ -C ₄ ) alkyl, for example ethyl acetate.

When the synthesis solvent is a hydrocarbon liquid fatty substance iii) volatile, the polymerization can be carried out directly in said oil which therefore also acts as a synthesis solvent. The monomers must also be soluble therein, as well as the radical initiator, and the polymer of the particles i) obtained must be insoluble therein.

According to a particular form of the invention, the synthetic solvent is a mixture of liquid fatty substances such as iii) and in particular isodecane with an additional solvent chosen in particular from esters with a hydrocarbon or branched aliphatic chain, having from 3 to 8 carbon atoms in total such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and in particular ethyl acetate, said additional solvent being chosen to have a point boiling point lower than that of liquid fat. When the synthesis of the stabilizers ii) and the particles i) is complete, the additional solvent is removed and a mixture i) and ii) is obtained in the liquid fatty substance. The monomers are preferably present in the synthetic 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 preferentially carried out in the presence vi) of one or more radical initiators which can be any initiator known to those skilled in the art for radical polymerization such as peroxidic or azo initiators, oxidation-reducing (redox) couples, and photochemical initiators.

Mention may in particular be made of initiators vi) of the 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 AkzoNobel; 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 at the surface, when they form during the polymerization, thanks to the stabilizing agent ii) prepared beforehand.

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

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

It is possible to use from 2 to 40% by weight, particularly from 4 to 35% by weight, of the stabilizing agent(s) relative to the total weight of monomers used (stabilizing agents ii) + polymer particles i)), and of preferably 4.5 to 30% by weight.

The dispersion of polymer particles (A) 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.

The composition according to the invention preferably comprises a content of dry matter (or active matter) of particle polymers i) + dispersant polymers ii) ranging from 10 to 80% by weight, relative to the total weight of the dispersion (A) , and preferably ranging from 15 to 60% by weight, in particular 20 to 50% by weight, relative to the total weight of the dispersion (A).

In a particular method of preparation, the random stabilizing polymer ii) is prepared in a first step. This stabilizing polymer is soluble in an apolar organic solvent of the alkane type such as isododecane.

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

Preferably, a solution of stabilizing polymer ii) is prepared in the liquid hydrocarbon fatty substance(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 vi) as defined previously.

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

In a third step, water or an aqueous composition is preferably added with stirring, at room temperature and at atmospheric pressure.

The dispersions are produced in the presence of one or more liquid hydrocarbon fatty substances iii) preferably in an apolar organic solvent, in particular of the alkane type such as in isododecane, according to an industrially realistic process.

According to a preferred embodiment of the invention, the method is carried out according to the following 3 steps:

For the preparation of these new dispersions, a process was implemented:

Step 1: Synthesis of the polymer particles in the hydrocarbon oil iii)
In a first step, the synthesis of the polymer particles is carried out in hydrocarbon oil, preferably apolar volatile oil iii).

An additional solvent can be mixed with the volatile polar hydrocarbon oil and will be chosen from chain esters having from 3 to 8 carbon atoms in total such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate

The dispersion of the polymeric particles in the hydrocarbon oil iii) or the hydrocarbon oil/short chain ester mixture can be prepared as follows:

The polymerization is carried out in " dispersion ", that is to say by precipitation of the polymer during formation, with protection of the particles i) formed with one or more stabilizing agents ii), preferably a stabilizing agent.

Stage 1 , the stabilizing polymer ii) (or stabilizing agent ii) is prepared by mixing the monomer or monomers constituting the stabilizing polymer with a radical initiator vi), in a solvent called a synthetic solvent, and by polymerizing these monomers;

Step 2 , the monomers constituting the polymer of the particles are added to the stabilizing polymer formed in the previous step and the polymerization of these added monomers is carried out in the presence of the radical initiator vi).

The polymerization is preferably carried out in the presence vi) of one or more radical initiators vi) as defined previously

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

The polymer particles are stabilized on the surface, when they form during the polymerization, thanks to the stabilizer.

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

At the end of this step 1, the short chain ester is removed by distillation. Thus, the polymer of the particles is found in the volatile polar hydrocarbon oil.

Stage 3: The water is added and stirred with the polymer of the particles+volatile polar hydrocarbon-based oil assembly before removing the dispersion from the reactor.

The polymer according to the invention finds a very particular application in the cosmetics field, in particular in the field of make-up and in particular in eye make-up (mascara, eyeshadow, liner) and in lipsticks.

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).

In addition, said dispersion being in an oily medium with the presence of water, it becomes easy to formulate it in cosmetic compositions based on an oily medium commonly used in cosmetics, in particular in the fatty phases of emulsions, but also in the aqueous emulsion phases to make it possible to solubilize the water-soluble or hydrophilic active agents.

According to another particular embodiment of the invention, the method is carried out according to the following 3 steps:

For the preparation of these new dispersions, a process was implemented:

Step 1 : Synthesis of the stabilizing polymer ii)

The polymer forming the stabilizing agent ii) is synthesized in an apolar and volatile hydrocarbon oil iii), and optionally at least one additional polar solvent such as a chain ester having from 3 to 8 carbon atoms in total such as acetate ethyl acetate, methyl acetate, propyl acetate, or n-butyl acetate.

The polymerization is preferably carried out in the presence of at least one radical initiator vi) as defined above.

2nd step : Adding water

Before the preparation of i) in particular the core of the polymer particles i), water iv) is added to the medium containing the stabilizing polymer(s) ii), the volatile apolar hydrocarbon-based oil iii) and optionally the additional solvent. Step 3: Synthesis of the core of the polymer particles

The preparation of i) and in particular of the core of the polymer particles i) is preferably carried out in the presence of at least one radical initiator vi) as defined previously.

At the end of this step 3, the additional solvent(s) is (are) removed by distillation. Thus, the polymer particles i) + ii) are found in the volatile apolar hydrocarbon oil iii) in the presence of water iv).

The dispersion (A) according to the invention finds an application for caring for and/or making up the skin and/or lips and/or for caring for, styling and/or coloring keratin fibres, preferably the hair .

The dispersion according to the invention finds a very particular application in the cosmetics field, in particular in the field of make-up and in particular in lipsticks, glosses (lip gloss) and eye shadows and mascaras.

Water iv)

The dispersion (A) comprises water iv). Preferably, the amount of water in the dispersion is between 5% and 49% by weight, relative to the total weight of the dispersion, particularly between 10% and 47% by weight, more particularly between 15% and 48% by weight, more preferably between 18 and 45%, even more preferably between 20 and 44% by weight, relative to the total weight of the dispersion.

According to a particular embodiment of the invention when the dispersion (A) comprises one or more copolymer(s) a) derived from a1) and a2), with a2) representing an ethylenic compound comprising one or more anhydride groups such as d maleic anhydride, then the dispersion does not contain:
- thiolated compound(s) chosen from a) an emulsion made with a fluid silicone which comprises thiol groups (Supplier ref: KM-9769) - SHIN-ETSU, b) Mercaptopropyl)Methylsiloxane - Dimethylsiloxane Copolymers (CAS Number : [102783-03-9]); Supplier ref: SMS-042, GELEST, and c) Mercaptopropyl)Methylsiloxane - Dimethylsiloxane Copolymers (CAS Number: [102783-03-9]) Supplier ref: SMS-992: GELEST or- of selected amino compound(s) (s) from Poly(dimethylsiloxane),bis(3-aminopropyl) terminated (PDMS-diNH ₂ )(CAS Number: 106214-84-0) and BIS-CETEARYL AMODIMETHICONE, 2-[(2-aminoethyl)amino]propyl Me, di-Me, [(C ₁₄ - ₂₀ -alkyldimethylsilyl)oxy]-terminated (CAS Number: 1126942-72-0) (Mn = 50,000 g/mol)polyamino compounds having more than one primary amine and/or amine group secondary.

More particularly the dispersion (A) does not include polyamino compounds having several primary amine groups and / or secondary amine, and does not include amino alkoxysilane when a2) is an ethylenic compound comprising one or more anhydride groups such as anhydride maleic. Even more particularly the dispersion (A) does not contain a compound comprising one or more amino groups –NH ₂ when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride.

More particularly the dispersion (A) does not comprise a thiolated polymer when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride. Even more particularly the dispersion does not contain a compound comprising one or more thiol groups when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride
.

By " thiolated polymer " is meant a homopolymer, copolymer, star, combe, brush and dendritic comprising one or more thiol groups which may be present as terminal or pendent groups.

According to a particular embodiment of the invention, the ratio by weight of the liquid hydrocarbon fatty substance(s) iii)/water iv) is between 0.2 and 10, more particularly between 0.5 and 8, preferably between 0.6 and 7, more preferably between 0.7 and 6.

The water suitable for the invention can be tap water, distilled water, spring water, floral water, such as blueberry water and/or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and/or thermal water.

The dispersion may further comprise one or more water-soluble solvents.

By “ water-miscible solvent ” according to the present invention, is meant a compound that is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25° C. and atmospheric pressure).

The water-miscible solvents that can be used in the dispersion (A) of the invention can also be volatile.

Among the water-miscible solvents that can be used in the composition according to the invention, mention may be made in particular of lower monoalcohols having from 2 to 5 carbon atoms, such as ethanol and isopropanol, glycols having from 3 to 8 carbon atoms such as hexylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol.

The water can also comprise any water-soluble or water-dispersible compound compatible with an aqueous phase, such as additional film-forming polymers, surfactants and mixtures thereof.

By “ surfactant ” is meant a “ surfactant ” or “ surfactant ” which is a compound capable of modifying the surface tension between two surfaces, surfactants are amphiphilic molecules, ie which have two parts of different polarity, one lipophilic and apolar and the other hydrophilic and polar. Surfactants can be nonionic, anionic, amphoteric, cationic or nonionic active.

According to a preferred embodiment of the invention, the dispersion of the invention does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferably not 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, even better the mixture does not include surfactant.

The cosmetic active ingredient(s) v)

According to a particular embodiment of the invention, the dispersion of the invention (A) comprises one or more cosmetic active ingredient(s) chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials and j) UV screening agents (A) and/or (B) as well as k) mixtures thereof.

According to a preferred embodiment of the present invention, the cosmetic active ingredient(s) of the invention is (are) chosen from f) pigments.

According to a particular embodiment of the present invention, the cosmetic active ingredient(s) of the invention is (are) chosen from h) active ingredients for the care of keratin materials, preferably active ingredients for the care of the skin.

According to yet another particular embodiment of the present patent application, the cosmetic active ingredient(s) of the invention is (are) chosen from j) UV(A) and/or UV( B) and their mixture.

According to a particular embodiment of the invention, the dispersion (A) comprises iv) one or more cosmetic active agents chosen from pigment(s).

The pigment(s) represent more particularly from 0.5 to 40% by weight of the total weight of the dispersion (A), and preferably from 1 to 20% by weight.

The pigments are solid, white or colored particles, naturally insoluble in the liquid hydrophilic and lipophilic phases usually used in cosmetics or rendered insoluble by formulation in the form of a lacquer, where appropriate. More particularly pigments with little or no solubility in hydro-alcoholic media.

The pigments which can be used are in particular chosen from the organic and/or inorganic pigments known in the art, in particular those which are described in the encyclopedia of chemical technology by Kirk-Othmer and in the encyclopedia of industrial chemistry by Ullmann. Mention may in particular be made, as pigments, of organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, "Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a20_243.pub3

These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

The pigments can for example be chosen from mineral pigments, organic pigments, lakes, special effect pigments such as nacres or glitter, and mixtures thereof.

The pigment can be an inorganic pigment. By mineral pigment, we mean any pigment that meets the definition of the Ullmann encyclopedia in the chapter inorganic pigment. Mention may be made, among the mineral pigments useful in the present invention, of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment.

By organic pigment, we mean any pigment that meets the definition of the Ullmann encyclopedia in the organic pigment chapter.

The organic pigment can in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, compounds of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525 , 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2,679,771.

By way of example, mention may also be made of organic pigment pigment pastes such as the products sold by the company HOECHST under the name:
- YELLOW COSMENYL IOG: Pigment YELLOW 3 (Cl 11710);
- COSMENYL G YELLOW: Pigment YELLOW 1 (Cl 11680);
- ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);
- COSMENYL RED R: Pigment RED 4 (Cl 12085);
- CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);
- VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);
- GREEN COSMENYL GG: Pigment GREEN 7 (Cl 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

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

The organic pigment can also be a lake. By lacquer, we mean the dyes adsorbed on insoluble particles, the assembly 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 dyes, we can mention carminic acid. Mention may also be made of the dyes 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, mention may be made of the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment may also be a special effect pigment. By special effect pigments, we mean pigments that generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is not uniform and changes according to the conditions of observation (light, temperature , viewing angles, etc.). They are therefore opposed to colored pigments which provide a uniform opaque, semi-transparent or classic transparent shade.

There are several types of special effect pigments, those with a low refractive index such as fluorescent or photochromic pigments, and those with a higher refractive index such as nacres, interference pigments or glitter.

As examples of special effect pigments, mention may be made of pearlescent pigments such as mica covered with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica covered with titanium and iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide, mica covered with titanium and an organic pigment as defined previously as well as pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, mention may be made of Cellini nacres marketed by BASF (Mica-TiO ₂ -lacquer), Prestige marketed by Eckart (Mica-TiO ₂ ), Prestige Bronze marketed by Eckart (Mica-Fe2O3) Colorona marketed by Merck ( Mica-TiO ₂ -Fe ₂ O ₃ ).

Mention may also be made of the gold-colored nacres marketed by the company BASF under the name of Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne) ; the mother-of-pearl bronzes marketed in particular by the company MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres in particular marketed by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper sheen in particular marketed by the company BASF under the name Copper 340A (Timica); nacres with a red sheen in particular marketed by the company MERCK under the name Sienna fine (17386) (Colorona); nacres with a yellow sheen in particular marketed by the company BASF under the name Yellow (4502) (Chromalite); nacres of a red tint with a gold sheen in particular marketed by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres in particular marketed by the company BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen in particular marketed by the company BASF under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl in particular marketed by the company MERCK under the name Matte blue (17433) (Microna), white mother-of-pearl with sheen silver in particular marketed by the company MERCK under the name Xirona Silver and the orange-pink golden-green nacres in particular marketed by the company MERCK under the name Indian summer (Xirona) and mixtures thereof.

Still by way of example of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

Particles with a glass substrate coated with titanium oxide are in particular sold under the name METASHINE MC1080RY by the company TOYAL.

Finally, as examples of nacres, mention may also be made of polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). One can also consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

The special effect pigments can also be chosen from reflective particles, that is to say in particular particles whose size, structure, in particular the thickness of the layer or layers which constitute it and their physical and chemical natures, and the surface finish, allow them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, that is i.e. brighter points that contrast with their surroundings by seeming to shine.

The reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them and more particularly so as to optimize this effect in terms of color rendering. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or reflection.

These particles can have various shapes, in particular be in the form of platelets or globular, in particular spherical.

The reflective particles, whatever their shape, may or may not have a multilayer structure and, in the case of a multilayer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

When the reflective particles do not have a multilayer structure, they may be composed for example of metal oxides, in particular titanium or iron oxides obtained by synthesis.

When the reflective particles have a multilayer structure, these may for example comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, in particular of at least one metal or metallic material . The substrate can be monomaterial, multimaterial, organic and/or inorganic.

More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and mixtures thereof, this list not being limiting.

The reflective material may comprise a layer of metal or of a metallic material.

Reflective particles are described in particular in the documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, mention may also be made of particles comprising a borosilicate substrate coated with silver.

Particles with a glass substrate coated with silver, in the form of platelets, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Particles with a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by this same company.

It is also possible to use particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium, said substrate being coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium, chromium oxide, silicon oxides and mixtures thereof.

Mention may be made, by way of example, of the aluminum, bronze or copper powders coated with SiO ₂ marketed under the name VISIONAIRE by the company ECKART.

Mention may also be made of pigments with an interference effect not fixed on a substrate, such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the Quantum Dots Corporation.

The variety of pigments which can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic and interference effects.

The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferably between 30 nm and 50 μm.

The pigments can be dispersed in the composition using a dispersing agent.

The dispersing agent serves to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, bearing one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can cling physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C ₈ to C ₂₀ fatty acid and of polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid stearate) are used. ) with a molecular weight of approximately 750 g/mole, such as that sold under the name Solsperse 21,000 by the company Avecia, the polygyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or the acid polyhydroxystearic such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures.

As other dispersant which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17000 sold by the company Avecia, mixtures of polydimethylsiloxane/oxypropylene such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

The pigments used in the composition can be surface-treated with an organic agent.

Thus the pigments previously surface-treated useful in the context of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electro-chemical, mechano-chemical or mechanical nature, with an organic agent such as those which are described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64 before being dispersed in the composition in accordance with the invention. These organic agents can for example be chosen from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethylmethacrylates; polymers and copolymers containing acrylate units; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

The surface-treated pigments useful in the composition may also have been treated with a mixture of these compounds and/or have undergone several surface treatments.

The surface-treated pigments useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art or found as such in commerce.

Preferably, the surface-treated pigments are covered by an organic layer.

The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

The surface treatment can thus be carried out, for example, by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or the fillers. This method is described in particular in US patent 4,578,266.

Preferably, an organic agent bound to the pigments covalently will be used.

The surface treatment agent can represent from 0.1 to 50% by weight of the total weight of the surface-treated pigment, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight. weight of the total weight of surface-treated pigment.

Preferably, the surface treatments of the pigments are chosen from the following treatments:
- a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW - a Methicone treatment such as the SI surface treatment marketed by LCW;
- a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;
- a Dimethicone/Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW;
- a Magnesium Myristate treatment such as the MM surface treatment marketed by LCW;
- an Aluminum Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;
- a Perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW;
- an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi;
- a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito;
- an acrylate copolymer/dimethicone and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;
- a Polymethylhydrogen siloxane/Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;
- an Acrylate/Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito;
- an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;
- an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;
- a Perfluoroalkyl Phosphate/Isopropyl Titanium Triisostearate treatment such as the PF+ITT surface treatment marketed by Daito.

According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in particulate form of sub-micron size in the coloring composition.

According to one embodiment, the dispersing agent and the pigment(s) are present in an amount (dispersant: pigment) of between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or better between 1.75:3 and 3:1.

The dispersing agent(s) can therefore have a silicone skeleton, such as silicone polyether and dispersants of the amino-silicone type, different from the alkoxysilanes previously described. Suitable dispersing agents include:
- amino-silicones, ie silicones comprising one or more amino groups such as those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee polymers,
- silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,
- polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

According to one particular embodiment, the dispersing agent(s) are of the amino-silicone type, different from the alkoxysilanes previously described and are cationic.

Preferably, the pigment(s) is (are) chosen from inorganic, mixed inorganic-organic or organic pigments.

In a variant of the invention, the pigment(s) according to the invention are organic pigments, preferably organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment or pigments according to the invention are mineral pigments.

The composition may comprise one or more direct dye(s).

By " direct dye " is meant natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber.

They can be ionic or nonionic, preferably cationic or nonionic.

Examples of suitable direct dyes which may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

The direct dyes are preferably cationic direct dyes. Mention may be made of the cationic hydrazono dyes of formulas (V) and (VI), the cationic azo dyes (VII) and (VIII) below: (V) (VI) (VII) (VIII)
formulas (V) to (VIII) in which:
- Het ⁺ represents a cationic heteroaryl radical, preferentially with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by at least one (C ₁ -C ₈ )alkyl group such as methyl;
- Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(C ₁ -C ₈ )alkyl-ammonium such as trimethylammonium;
- Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron-donating groups such as i) (C ₁ -C ₈ )alkyl optionally substituted, ii) (C ₁ -C ₈ )alkoxy optionally substituted, iii) (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C ₁ -C ₈ )alkylamino, v) N-(C ₁ -C ₈ ) alkyl-N-aryl (C ₁ -C ₈ ) alkylamino optionally substituted or else Ar represents a julolidine group;
- Ar' ' represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl optionally substituted, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl )amino, (C ₁ -C ₈ )alkoxy or phenyl;
- Ra and Rb , identical or different, representing a hydrogen atom or a (C ₁ -C ₈ )alkyl group optionally substituted, preferably by a hydroxyl group;
or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a hydroxyl group;
- Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulphate.

Particular mention may be made of direct dyes with cationic charge, endocyclic azo and hydrazono of formula (V) to (VIII) as defined above. More particularly, the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably the following direct dyes: (IX) (X)
formulas (IX) and (X) in which:
- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;
- R ² and R ³ , which are identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; And
- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl) amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R ⁴ is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferably CH,
- Q- is an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

In particular, the dyes of formula (IX) and (X) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives with Q′ an anionic counterion as defined previously, particularly halide such as chloride or an alkyl sulphate such as methyl sulfate or mesyl.

Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

According to one embodiment of the invention, the dyes are fat-soluble. They are for example chosen from Sudan red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C orange 5, quinoline yellow, annatto. Water-soluble dyes are for example beet juice, methylene blue.

Preferably, the cosmetic active ingredient(s) v) are chosen from the following pigments carbon black, iron oxides, in particular black, and micas coated with iron oxide, red iron oxides (iron(III) oxide, also called ferric oxide), triarylmethane pigments in particular blue and violet such as BLUE 1 LAKE, azo pigments in particular red such as D&C RED 7, alkali metal salts of lithol red such as the calcium salt of lithol red B.

According to a particular embodiment of the invention, the quantity of pigments varies from 0.5% up to 40%, and preferably from 1 to 20% relative to the weight of the dispersion (A) comprising them.

According to a particular embodiment of the invention, the dispersion (A) comprises iv) one or more cosmetic active agents chosen from hair dyes.

Among the hair dyes we can mention:
- oxidation dyes which are generally chosen from one or more oxidation bases, optionally combined with one or more coupling agents.
By way of example, the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and the corresponding addition salts optionally combined with coupling agents, it is in particular chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents as well as the corresponding addition salts.
- direct dyes, in particular azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures. Direct dyes can be anionic, cationic or neutral.
- natural dyes chosen in particular from hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein as well as extracts or decoctions containing these natural dyes.

The hair dye(s) represent more particularly from 0.001 to 10% by weight of the total weight of the composition of dispersion (A), and preferably from 0.005 to 5% by weight relative to the total weight of dispersion (A).

Preferably, the pigment(s) of the invention are chosen from carbon black, iron oxides, in particular red, brown or black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, such as BLUE 1 LAKE, the azo pigments, in particular red, such as D&C RED 7 alkali metal salt of lithol red such as the calcium salt of lithol red B, more preferably the pigment(s) used are chosen from red iron oxides and azo pigments, in particular red, such as D&C RED 7 .

According to a particular embodiment of the invention, the quantity of pigments varies from 0.5% up to 40%, and preferably from 1 to 20% relative to the weight of the composition and dispersion (A) comprising them.

Process for treating keratin materials from the dispersion (A):

According to an advantageous variant of the invention, the process of the invention is a process for treating keratin fibres, in particular human hair, preferably the hair, which implements the application to said fibers of at least one dispersion (A) as defined previously.

According to one particular embodiment of the invention, after application of the dispersion (A) to the keratin materials, the composition is left to dry on the said keratin materials, either in the open air, or with the aid of heating devices used in cosmetics such as a hair dryer.

According to a particular embodiment of the invention, the method for treating keratin fibers is a treatment for shaping said fibers.

More particularly, the process for treating keratin fibers implements at least one shaping step, in particular:
- in a first step of the process, the keratin fibers are shaped using conventional shaping means, for example with curlers or a brush of particular shape (cylindrical), then
- in a second step, the dispersion (A) is applied to said fibers, the mode of application preferably being carried out using a spray, then
- in a third step, said fibers are dried in the open air or dried using conventional devices used in cosmetics, then
- the shaping means is removed from said fibers optionally followed by a rinsing step, a shampoo step and then a step of drying in the open air or then dried using conventional devices.

Once the dispersion (A) has been applied, before the third step, rinsing or shampooing may optionally be performed.

Dispersion (A) can be applied to dry or wet, preferably dry, keratin fibres.

It is also possible by the process for treating keratin fibers of the invention to achieve shaping while providing one or more cosmetic active agents to said fibers, for example to color by applying at least one dye and/or pigment, and/ or to apply at least one UV(A) and/or UV(B) filter, and/or to apply at least one care active ingredient to said fibres. It suffices to apply a dispersion (A) comprising at least one cosmetic agent v) as defined above. It also appears that the shaping is persistent and furthermore the cosmetic active ingredient(s) iv) applied are also persistent, in particular vs. the successive shampoos and the rays of light.

After the application of the dispersion (A), the fibers can be left to dry or dried, for example at a temperature greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is greater than 45°C and less than 100°C.

Preferably, if the fibers are dried, they are dried, in addition to a supply of heat, with an air flow obtained using a conventional device used in cosmetics such as a helmet, a hair dryer, a hair straightener, a climazon….

During drying, a mechanical action on the locks can be exerted such as combing, brushing, the passage of the fingers. This operation can also be carried out once the fibers have dried, naturally or not.

When the drying step is implemented with a helmet or a hair dryer, the drying temperature is between 40°C and 110°C, preferably between 50°C and 90°C.

According to one embodiment of the method for treating keratin fibers of the invention, the hair undergoes treatment with a straightening iron. This treatment is then carried out once said hair is dry, the temperature of the straightening iron treatment is between 110°C and 220°C, preferably between 140°C and 200°C.

Dispersion (A) can be applied to dry or wet keratin fibres, as well as to all types of fibres, light or dark, natural or colored, permed, bleached or straightened.

According to a particular embodiment of the method of the invention, the fibers are washed before application of the dispersion (A).

The application to the fibers can be carried out by any conventional means, in particular by means of a comb, a paintbrush, a brush or the fingers.

According to a preferred embodiment of the invention, the step of applying the dispersion (A) is carried out on dry keratin fibres.

According to another particular embodiment of the method of the invention, the step of applying the dispersion (A) is carried out on damp or wet keratin fibers.

Preferably, after application of the dispersion (A), the wait is between 1 minute and 2 hours, in particular between 5 minutes and 1 hour, more particularly between 10 minutes and 30 minutes, preferably in the open air and at room temperature.

According to another particular embodiment of the invention, the process for treating keratin fibres, in particular human fibers such as the hair, is a process for coloring said fibers comprising at least one step of applying to said fibers a dispersion (A) as defined previously which comprises h) at least one dye, and/or j) at least one pigment, followed by a drying step. Once the dispersion (A) of the invention has been applied to the keratin fibres, rinsing and/or shampooing may optionally be carried out.

Dispersion (A) can be applied to dry or wet keratin fibres, preferably dried in the open air or dried using conventional devices used in cosmetics as defined above.

According to a particular embodiment of the invention, the process for treating keratin materials is a treatment of the skin and/or the eyelashes, eyebrows implementing the application to the skin and/or the eyelashes, eyebrows the dispersion (A ) as defined above, followed by a step of drying in the open air or else dried using conventional devices used in cosmetics as defined above, preferably in the open air.

According to a particular embodiment of the invention, the process for treating keratin materials is a process for making up the skin and/or the eyelashes, eyebrows implementing a step of applying the dispersion (A) comprising at least one dye and/or at least one pigment, preferably at least one pigment.

The dispersion (A) according to the invention may also comprise a cosmetic additive chosen from perfumes, preservatives, fillers, waxes, moisturizers, vitamins, ceramides, antioxidants, anti-free radical agents, polymers different from a), b), c), d) and e), thickeners, coloring matters different from f) dyes and g) pigments.

Preferably, the first step of the process of the invention is the application of the dispersion (A) in one or more apolar solvents, in particular isododecane.

vii) thickening agent(s)

According to an advantageous variant of the invention, the dispersion (A) further comprises vii) one or more thickening agent(s) chosen from organic thickening polymers and thickening mono/di/triglycerides.

By “ thickening ” agent is meant that the agent in question, polymer or triglyceride, introduced at 1% by weight into an aqueous or hydroalcoholic solution containing 30% ethanol, and at pH=7 or into an oil chosen from Vaseline oil, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps, preferably at least 500 cps, at 25° C. and at a shear rate of 1 s ^-1 . This viscosity can be measured using a cone/plane viscometer (Haake R600 rheometer or the like). The thickening polymers can thicken the aqueous phase and/or the fatty phase, preferably the aqueous phase.

According to a particular embodiment of the invention, the thickening agent or agents are organic polymers.

By " organic " thickening polymer is meant a thickening polymer as defined above which consists of carbon, hydrogen, and optionally nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine, bromine as well as phosphorus, alkali metals such as sodium, potassium, or alkaline earth metals such as magnesium or calcium. The organic polymers according to the invention do not include silicon.

The organic thickening polymers according to the invention can be of natural or synthetic origin.

The thickening agents can be anionic, cationic, amphoteric or nonionic polymers, associative or not, with sugar units or not.

By “ sugar ” unit is meant within the meaning of the present invention a unit derived from a carbohydrate of formula C _n (H ₂ O) _n-1 or (CH ₂ O) _n which can optionally be modified by substitution, and/or by oxidation and/or dehydration. The sugar units which can enter into the composition of the thickening polymers of the invention are preferably derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulphate; anhydrogalactose sulfate and fructose.

The thickeners can thicken the aqueous phase, i.e. in water or in the liquid fatty substance(s) iii).

Preferably, the polymers structuring the oily phase via physical interactions are chosen from polyamides, silicone polyamides, mono- or poly-alkyl esters of saccharide or polysaccharide, amide derivatives of N-acylated amino acids, copolymers comprising an alkylene sequence or styrene, these copolymers possibly being di-block, tri-block, multi-block, radial-block polymers also called star copolymers, or even comb polymers.

According to one embodiment, the thickening polymers carry in the backbone at least one crystallizable block.

They are still polymers that are soluble or dispersible in oil or oily phase by heating above their melting point pF. These polymers are in particular block copolymers consisting of at least 2 blocks of different chemical nature, one of which is crystallizable.

As polymers bearing in the skeleton at least one crystallizable sequence suitable for the implementation of the invention, mention may be made of:
i). The polymers defined in document US-A-5,156,911;
ii). Olefin or cycloolefin block copolymers with a crystallizable chain, such as those resulting from the block polymerization of:
- cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo(2,2,1)heptene 2), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethyl- norbornene, 5,5,6- trimethyl norbornene, 5-ethylidene-norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene, dicyclopentadiene, and mixtures thereof;
- with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1- eicosene or mixtures thereof. These block copolymers may in particular be (ethylene/norbornene) block copolymers and (ethylene/propylene/ethylidene-norbornene) block terpolymers.

It is also possible to use those resulting from the block copolymerization of at least 2 α-olefins in C ₂ -C ₁₆ and better still in C ₂ -C ₁₂ , such as those mentioned above and in particular the block bipolymers of ethylene and of 1-octene.

Particularly, the copolymers have at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers may, in addition, have two crystallizable sequences of different chemical nature. The preferred copolymers are those which possess both, at room temperature, a crystallizable block and an amorphous block which is both hydrophobic and lipophilic distributed sequentially; mention may be made, for example, of non-crosslinked or (partially) crosslinked semi-crystalline polymers, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the liquid oily phase by heating above their melting point. It can then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It can also be a physical crosslinking which can then be due either to the establishment of hydrogen or dipolar type bonds between groups carried by the polymer, such as for example the dipolar interactions between ionomers carboxylates, these interactions being in weak quantity and carried by the backbone of the polymer; or to a phase separation between the crystallizable blocks and the amorphous blocks carried by the polymer.

Preferably, the semi-crystalline polymers suitable for the invention are non-crosslinked. As a specific example of a semi-crystalline polymer that can be used in the composition according to the invention, mention may be made of the Intelimer® products from the company Landec described in the “Intelimer® polymers” brochure. These polymers are in solid form at room temperature (25°C). They carry crystallizable side chains and present the monomer. Mention may in particular be made of “Landec IP22®”, having a melting point pF of 56° C., which is a viscous product at room temperature, impermeable, non-sticky.

2) According to one embodiment, the thickening agent(s) are chosen from mono-/polyalkylesters of saccharide or polysaccharide

Among the saccharide or polysaccharide mono or polyalkyl esters suitable for the implementation of the invention, mention may be made of the alkyl or polyalkyl esters of dextrin or inulin.

It may be in particular a mono- or poly-ester of dextrin and at least one fatty acid and in particular corresponding to the following formula (XI) : (XI)
Formula (XI) in which:
- n is an integer ranging from 3 to 200, in particular ranging from 20 to 150, and in particular ranging from 25 to 50,
- R ₁ , R ₂ and R ₃ , which are identical or different, are chosen from hydrogen or an acyl group (RC(O)-) in which the radical R is a hydrocarbon group, linear or branched, saturated or unsaturated, possessing from 7 to 29, in particular from 7 to 21, in particular from 11 to 19, more particularly from 13 to 17, even 15, carbon atoms, provided that at least one of the said radicals R ₁ , R ₂ or R ₃ is different from hydrogen.

In particular, R ₁ , R ₂ and R ₃ can represent hydrogen or an acyl group (RC(O)-) in which R is a hydrocarbon radical as defined previously, provided that at least two of the said radicals R ₁ , R ₂ or R ₃ are identical and different from hydrogen. All of the radicals R ₁ , R ₂ and R ₃ may represent an identical or different, and in particular identical, acyl group (RC(O)). In particular, n described above advantageously varies from 25 to 50, in particular is equal to 38 in the general formula of the saccharide ester which can be used in the present invention.

In particular when the R ₁ , R ₂ and/or R ₃ radicals, which are identical or different, contain an acyl group (RC(O)), these can be chosen from caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoaracic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, palmitoleic, hexadecenoic, palmitoleic, hexadecenoic oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic, stearolic, and mixtures thereof.

Preferably, at least one dextrin palmitate is used as ester of dextrin and of fatty acid(s). This can be used alone or mixed with other esters.

Advantageously, the ester of dextrin and fatty acid has a degree of substitution less than or equal to 2.5 on the basis of a glucose unit, in particular varying from 1.5 to 2.5, preferably from 2 to 2 ,5. The weight-average molecular weight of the dextrin ester may in particular be from 10,000 to 150,000, in particular from 12,000 to 100,000 and even from 15,000 to 80,000.

Dextrin esters, in particular dextrin palmitates, are commercially available under the name RHEOPEARL TL or RHEOPEARL KL from the company Chiba Flour.

According to another particular embodiment of the invention, the thickening agent(s) contained in dispersion (A) is (are) chosen from mono/di/tri glycerides mono/di/tri glycerides of which at least one hydrogen atom of a hydroxy group of glycerol has been substituted by the group –C(O)-R ^a , with R ^a representing a carbonyl hydrocarbon chain, linear or branched, cyclic or acyclic, saturated or unsaturated, comprising 8 to 40 carbon atoms, said hydrocarbon chain possibly being substituted by one or more hydroxy groups.

Preferably, the thickening agents vii) are chosen from triglycerides tri-substituted by –C(O)-R^Towith R^Toas defined previously, more particularly chosen from trihydroxystearin. In particular, the thickening agent(s) is (are) chosen from: 1) block polymers of at least 2 C α-olefins₂-VS₁₆and better in C₂-VS₁₂, preferably, non-crosslinked semi-crystalline polymers, more particularly semi-crystalline polymers, 2) saccharide or polysaccharide mono-/polyalkylesters, particularly dextrin esters, in particular dextrin palmitates, 3) mono/polyalkylesters of saccharide or polysaccharide, di/tri glycerides mono/di/tri glycerides in which at least one hydrogen atom of a glycerol hydroxy group has been substituted by the –C(O)-R group^To, with R^Torepresenting a carbonyl hydrocarbon chain, linear or branched, cyclic or acyclic, saturated or unsaturated, comprising from 8 to 40 carbon atoms, said hydrocarbon chain possibly being substituted by one or more hydroxy groups, preferably chosen from triglycerides tri-substituted by -HORN^Towith R^Toas defined previously, more particularly chosen from trihydroxystearin.

Preferably, the thickener(s) is or are present in the dispersion according to the invention in a content ranging from 0.01 to 15% by weight, more preferably from 0.1 to 7% by weight, even more preferably from 1 to 6% by weight relative to the total weight of the dispersion.

The set

The invention also relates to a kit or device with several separate compartments comprising:
- in a compartment: a dispersion comprising the ingredients i) to iii), and optionally vii) as defined above,
- in one or more distinct compartments are distributed the following ingredients v): f) colorants, g) pigments; h) active ingredients for the care of keratin materials, in particular the skin and/or j) UV filters (A) and/or (B), and
iv) water, being in the dispersion, and/or with ingredients f) to h) and/or in another compartment.

The packaging assembly for the compositions is, in a known manner, any packaging suitable for storing cosmetic compositions (bottles, tube, spray bottle, aerosol bottle in particular).

The invention is further illustrated in the following examples.

EXAMPLES
The following dispersions (A) were made:
[Table 1]:

Examples

Polymer particles (i + ii)
Isododecane (iii)
Water (iv)
Example 1-1

30
50
20
Example 1-2

30
30
40

Example 2
30
30
40

Example 3-1

30
50
20
Example 3-2

30
30
40
Example 4

30
30
40
Example 5

37.5
37.5
25

Table 1: Composition by weight of the various exemplified dispersions of the invention

All of the monomers used for the various examples for i), ii) and the polymerization initiator vi) are summarized in Tables 2 and 3 below:
[Table 2]:
Monomers
CASE Supplier
Isobornyl Acrylate
5888-33-5 Sigma Aldrich
Methyl Acrylate
96-33-3 Sigma Aldrich
Ethyl Acrylate
140-88-5 Sigma Aldrich
Acrylic Acid
79-10-7 Sigma Aldrich
Maleic Anhydride
108-31-6 Sigma Aldrich Table 2: Monomers used in the various examples
[Table 3]: Name INCI name Intelimer C ₁₂ -C ₂₂ ALKYL ACRYLATE/HYDROXYETHYLACRYLATE COPOLYMER Trihydroxystearin TRIHYDROXYSTEARIN
TRIESTER OF GLYCERINE AND HYDROXYSTEARIC ACID Dextrin palmitate DEXTRIN PALMITATE Table 3: thickening agents
[Table 4]:
Radical initiator
CASE
Supplier

Trigonox 21S
3006-82-4 Akzo Nobel Table 4: Polymerization initiator used in the various examples

For all the dispersions, an evaluation of the cosmetic properties on a dry film was carried out.

A film is made on a contrast card with a film puller (speed: 50 mm/s - cylinder: 100 μm). The film is left to dry for 24 h at room temperature. Once dry, the film has a thickness of about 30-50 µm.

On the dry film, an evaluation of the resistance to water / olive oil / sebum aggressors is carried out:

Measurement of resistance to water and fatty substances.

3 drops of olive oil or water or sebum have been deposited on the dry film present on the black part of the contrast card (one for each observation time of resistance to the aggressor), each drop corresponds to approximately 30 µL of aggressor (Use of a micropipette).

The drop is left in contact with the dry film for 20 minutes. After the time has elapsed, the drop of olive oil, water or sebum is wiped off and an observation of the deterioration of the polymer film is made. If the film has been attacked by the drop of aggressor, the polymer film is considered non-resistant to this aggressor.

Example 1: Obtaining dispersion with variable amounts of water

Step 1: Synthesis of the dispersion of polymeric particles in isododecane

First, the synthesis of the polymeric particles is carried out in isododecane.

The polymeric particles are formed as a whole (Stabilizer ii + particles i) at 10% Acrylic Acid, 10% Methyl Acrylate, 60% Ethyl Acrylate and 20% Isobornyl Acrylate. The synthesis of these dispersions was carried out in a controlled reactor of 6 liters. The synthesis is carried out in two steps:
During a first step, Isobornyl Acrylate is polymerized in Isododecane / Ethyl Acetate (60/40) in the presence of a small amount of Methyl Acrylate / Ethyl Acrylate and a radical initiator (T21S). In the first step, the Isobornyl Acrylate/Methyl Acrylate/Ethyl Acrylate mass ratio is 92/4/4.
During the second step, the rest of the Methyl Acrylate/Ethyl Acrylate and the Acrylic Acid are poured in the presence of Isododecane/Ethyl Acetate (60/40) and radical initiator (T21S).

After stripping, the polymer is at a dry extract of 50% in isododecane.

The ratios used to obtain the stabilizer and the core are summarized in [Table 5]: Mass percentage
Stabilizer - Heart Monomer Mass percentage in the stabilizer
and the heart Stabilizer ii) 21 Isobornyl Acrylate 92 Methyl acrylate 4 Ethyl acrylate 4 Heart i) 79 Methyl Acrylate 11.7 Ethyl acrylate 75.6 Acrylic Acid 12.7 Table 5: Specific ratios in the stabilizer and the core for the polymeric particles of example 1

Quantity of reagents:
Step 1.1:
[Table 6]: Reagents Mass (g) Isobornyl Acrylate 315.2 Methyl Acrylate 12.5 Ethyl Acrylate 12.5 T21S 3.4 Isododecane / AcOEt (60/40) 900

Isododecane/ethyl acetate added between the two steps:
[Table 7]: Reagent Mass (g) Isododecane / AcOEt (60/40) 900

Step 1.2:
[Table 8]: Reagents Mass (g) Mass added in beaker for casting (g) Methyl Acrylate 145 174 Ethyl Acrylate 934 1120 Acrylic Acid 157 188.4 T21S 12.36 14.83 Isododecane / AcOEt (60/40) 1236 1483.2 Tables 8: Quantities of reagents used for Example 1

Experimental protocol :
Isododecane / Ethyl Acetate (60/40), Isobornyl Acrylate, Methyl Acrylate / Ethyl Acrylate and T21S are introduced into the reactor at the bottom of the tank. The medium is heated to 90° C. (Setpoint on the medium), under argon and with stirring.
After 2 hours of heating, the NMR indicates a consumption of 97% of Isobornyl Acrylate (Consumption of Methyl Acrylate: 96% and Ethyl Acrylate: 96%).
After 2 hours of reaction, isododecane / ethyl acetate (60/40) are introduced into the base stock. Heat to 90°C in the middle.
Once the medium has reached 90°C, Methyl Acrylate / Ethyl Acrylate / Acrylic Acid, Isododecane / Ethyl Acetate (60/40), and T21S are introduced over 2 hours by pouring. At the end of the casting the medium is milky.
After 7 hours of synthesis, we obtain a consumption of Methyl Acrylate / Ethyl Acrylate / Acrylic Acid of 99% (Consumption of Isobornyl Acrylate: 100%).
3 L of isododecane and ethyl acetate are then stripped (the NMR indicates that there are no more monomers and the ethyl acetate is completely removed from the dispersion). The dry extract is 50%.
Step 2: Adding water at the end of the synthesis
In a second step, keeping the polymer in the reactor, water is added
[Table 9]: Ingredients Mass percentage of active ingredient in the final dispersion Example 1-1
invention Example 1-2
invention Example 1-3
comparative Polymeric particle i) + ii) 30 30 25 Water iv)
20 40 50 Isododecane iii)
50 30 25 Appearance of formulas Homogeneous white dispersion Stable Homogeneous white dispersion Stable Unstable dispersion Presence of a strong white precipitate Table 9: Influence of the amount of water on the stability of the final dispersion
Subsequently, an evaluation of the cosmetic properties of the different stable dispersions was carried out. Measurements of sensitivity to fatty substances (Olive oil and sebum) and to water are summarized in Table 10:
[Table 10]: Example number Water resistance Olive oil resistance Sebum resistance Example 1-1 ++ ++ + Example 1-2 ++ ++ + Table 10: Cosmetic properties of example 1
(-): no resistance, (+) resistance, (++), very significant resistance after passage of the same cotton fabric soaked in the same quantity of sebum, olive oil, or water.

• Lors d’une première étape, l’Acrylate d’Isobornyle est mis à polymériser dans l’Isododécane / Acétate d’éthyle (60/40) en présence d’une petite quantité d’Acrylate d’Ethyle et d’un amorceur radicalaire (T21S). En première étape, le ratio massique Acrylate d’Isobornyle / Acrylate d’Ethyle est 92/8.
• Lors de la seconde étape, le reste de l’Acrylate d’Ethyle et l’Anhydride Maléique sont coulés en présence d’Isododécane / Acétate d’éthyle (60/40) et d’amorceur radicalaire (T21S).

Après un stripping, le polymère se trouve à un extrait sec de 50 % dans l’Isododécane.
Les ratios employés pour obtenir le stabilisant et le cœur sont résumés dans le Tableau 11 :
[Tableau 11] : Pourcentage massique
Stabilisant - Cœur Monomère Pourcentage massique dans le stabilisant
et le coeur Stabilisant ii) 22 Acrylate d’Isobornyle 92 Acrylate d’éthyle 8 Cœur i) 78 Acrylate d’Ethyle 87 Anhydride maléïque 13 Quantité de réactifs :
Etape 1.1 :
[Tableau 12] : Réactifs Masse (g) Acrylate d’Isobornyle 50 Acrylate d’Ethyle 4 T21S 0,54 Isododécane / AcOEt (60/40) 96 Isododécane/Acétate d’éthyle ajouté entre les deux étapes :
[Tableau 13] : Réactif Masse (g) Isododécane / AcOEt (60/40) 80 Etape 1.2 :
[Tableau 14] : Réactifs Masse (g) Masse ajoutée dans le bécher pour la coulée (g) Acrylate d’Ethyle 171 196.65 Anhydride Maléique 25 28,7 T21S 1.96 2,25 Isododécane / AcOEt (60/40) 196 225,4 Tableaux 14 : Quantités de réactifs utilisés pour l’exemple 2
Protocole expérimental :
Dans le réacteur en pied de cuve, sont introduits l’Isododécane / Acétate d’éthyle (60/40), l'Acrylate d’Isobornyle, l'Acrylate d’Ethyle et le T21S. Le milieu est chauffé à 90°C (Consigne sur le milieu), sous argon et sous agitation.
Après 2h de chauffe, la RMN indique une consommation de 97% de l'Acrylate d’Isobornyle (Consommation de l’Acrylate d’Ethyle : 97%).
Après 2h de réaction, dans le pied de cuve, de l’Isododécane / Acétate d’éthyle (60/40), sont introduits. On chauffe à 90 °C dans le milieu.
Une fois le milieu à 90 °C, on introduit en 1h par une coulée l'Acrylate d’Ethyle / Anhydride Maléique, l’Isododécane / Acétate d’éthyle (60/40), et le T21S. A la fin de la coulée le milieu est laiteux. L
Après 7 h de synthèse il reste des traces des monomères de départ.
On réalise ensuite un stripping de 1L d’Isododécane et de l’acétate d’éthyle (la RMN indique qu'il n'y a plus de monomères et l’acétate d’éthyle est totalement retiré de la dispersion). L’extrait sec est de 50%.
Etape 2 : Ajout d’eau en fin de synthèse
Dans un second temps, en conservant le polymère dans le réacteur, de l’eau est ajoutée en fin de manip. Un essai a été réalisé avec introduction de 40% d’eau. Il est résumé dans le Tableau 15 :
[Tableau 15] : Exemple 2 - Ingrédients Pourcentage massique en matière active dans la dispersion finale Particule polymérique i) + ii) 30 Eau iv) 40 Isododécane iii) 30
Aspect des formules

Formule blanche homogène et stable Tableau 15 : Nouvelle dispersion contenant de l’anhydride maléique – exemple 2
Une dispersion stable a été obtenue contenant jusqu’à 40 % d’eau.
Par la suite, une évaluation des propriétés cosmétiques de la nouvelle dispersion a été effectuée. Les mesures de la sensibilité aux corps gras (Huile d’olive et sébum) et à l’eau sont résumées dans le Tableau 16 : N° de l’exemple Résistance à l’eau Résistance à l’huile d’olive Résistance au sébum Exemple 2 ++ ++ + Tableau 16 : Propriétés cosmétiques de l’exemple 2
(-) : pas de résistance, (+) résistance, (++), résistance très significative après passage d’un même tissé en coton imbibé de la même quantité de sébum, d’huile d’olive, ou d’eau.The dispersions containing less volatile hydrocarbon iii) oil of example 1-1 and 1-2 lead to a deposit resistant to sebum and very significantly resistant to water, to olive oil.
Example 2: Dispersion for polymeric particles containing maleic anhydride
Step 1 : Synthesis of the dispersion of polymeric particles in isododecane
First, the synthesis of the polymeric particles is carried out in isododecane.
The dispersions are formed as a whole (Stabilizer ii + particles i) with 10% Maleic Anhydride, 70% Ethyl Acrylate and 20% Isobornyl Acrylate. The synthesis of these dispersions was carried out in a controlled reactor of 1 liter. The synthesis is carried out in two steps:

• During a first step, Isobornyl Acrylate is polymerized in Isododecane / Ethyl Acetate (60/40) in the presence of a small amount of Ethyl Acrylate and a radical initiator (T21S). In the first step, the Isobornyl Acrylate/Ethyl Acrylate mass ratio is 92/8.
• During the second step, the rest of the Ethyl Acrylate and Maleic Anhydride are cast in the presence of Isododecane/Ethyl Acetate (60/40) and radical initiator (T21S).

After stripping, the polymer is at a dry extract of 50% in isododecane.
The ratios used to obtain the stabilizer and the core are summarized in Table 11:
[Table 11]: Mass percentage
Stabilizer - Heart Monomer Mass percentage in the stabilizer
and the heart Stabilizer ii) 22 Isobornyl Acrylate 92 Ethyl acrylate 8 Heart i) 78 Ethyl Acrylate 87 Maleic anhydride 13 Quantity of reagents:
Step 1.1:
[Table 12]: Reagents Mass (g) Isobornyl Acrylate 50 Ethyl Acrylate 4 T21S 0.54 Isododecane / AcOEt (60/40) 96 Isododecane/ethyl acetate added between the two steps:
[Table 13]: Reagent Mass (g) Isododecane / AcOEt (60/40) 80 Step 1.2:
[Table 14]: Reagents Mass (g) Mass added in beaker for casting (g) Ethyl Acrylate 171 196.65 Maleic Anhydride 25 28.7 T21S 1.96 2.25 Isododecane / AcOEt (60/40) 196 225.4 Tables 14: Quantities of reagents used for Example 2
Experimental protocol :
Isododecane/Ethyl Acetate (60/40), Isobornyl Acrylate, Ethyl Acrylate and T21S are introduced into the reactor at the bottom of the tank. The medium is heated to 90° C. (Setpoint on the medium), under argon and with stirring.
After 2 hours of heating, the NMR indicates a consumption of 97% of Isobornyl Acrylate (Consumption of Ethyl Acrylate: 97%).
After 2 hours of reaction, isododecane / ethyl acetate (60/40) are introduced into the base stock. Heat to 90°C in the middle.
Once the medium has reached 90°C, the Ethyl Acrylate/Maleic Anhydride, Isododecane/Ethyl Acetate (60/40), and T21S are introduced over 1 hour by pouring. At the end of the casting the medium is milky. I
After 7 hours of synthesis, traces of the starting monomers remain.
1L of isododecane and ethyl acetate are then stripped (the NMR indicates that there are no more monomers and the ethyl acetate is completely removed from the dispersion). The dry extract is 50%.
2nd step : Addition of water at the end of the synthesis
In a second step, keeping the polymer in the reactor, water is added at the end of the manipulation. A test was carried out with the introduction of 40% water. It is summarized in Table 15:
[Table 15]: Example 2 - Ingredients Mass percentage of active ingredient in the final dispersion Polymeric particle i) + ii) 30 Water iv) 40 Isododecane iii) 30
Appearance of formulas

Homogeneous and stable white formula Table 15: New dispersion containing maleic anhydride – example 2
A stable dispersion was obtained containing up to 40% water.
Subsequently, an evaluation of the cosmetic properties of the new dispersion was carried out. Measurements of sensitivity to fatty substances (Olive oil and sebum) and to water are summarized in Table 16: Example number Water resistance Olive oil resistance Sebum resistance Example 2 ++ ++ + Table 16: Cosmetic properties of example 2
(-): no resistance, (+) resistance, (++), very significant resistance after passage of the same cotton fabric soaked in the same quantity of sebum, olive oil, or water.

• Lors d’une première étape, l’Acrylate d’Isobornyle est mis à polymériser dans l’Isododécane / Acétate d’éthyle (60/40) en présence d’une petite quantité d’Acrylate de Méthyle / Acrylate d’Ethyle et d’un amorceur radicalaire (T21S). En première étape, le ratio massique Acrylate d’Isobornyle / Acrylate de Méthyle / Acrylate d’Ethyle est 92/4/4.
• Lors de la seconde étape, le reste de l’Acrylate de Méthyle / Acrylate d’Ethyle et l’Acide Acrylique sont coulés en présence d’Isododécane / Acétate d’éthyle (60/40) et d’amorceur radicalaire (T21S).

Après un stripping, le polymère se trouve à un extrait sec de 50 % dans l’Isododécane.
Les ratios employés pour obtenir le stabilisant et le cœur sont résumés dans le Tableau 17 : Pourcentage massique
Stabilisant - Cœur Monomère Pourcentage massique dans le stabilisant
et le coeur Stabilisant ii) 21 Acrylate d’Isobornyle 92 Acrylate de méthyle 4 Acrylate d’éthyle 4 Cœur i) 79 Acrylate de Méthyle 24,5 Acrylate d’éthyle 62,8 Acide Acrylique 12,7 Tableau 17 : Ratios spécifiques dans le stabilisant et le cœur pour la dispersion de l’exemple 3
Quantité de réactifs :
Etape 1.1 : Réactifs Masse (g) Acrylate d’Isobornyle 315,2 Acrylate de Méthyle 12,5 Acrylate d’Ethyle 12,5 T21S 3,4 Isododécane / AcOEt (60/40) 900 Isododécane/Acétate d’éthyle ajouté entre les deux étapes : Réactif Masse (g) Isododécane / AcOEt (60/40) 900 Etape 1.2 : Réactifs Masse (g) Masse ajoutée dans le bécher pour la coulée (g) Acrylate de Méthyle 303 364 Acrylate d’Ethyle 776 931 Acide Acrylique 157 188,4 T21S 11 13 Isododécane / AcOEt (60/40) 1236 1483,2 Tableaux 20 : Quantités de réactifs utilisés pour l’exemple 3
Protocole expérimental :
Dans le réacteur en pied de cuve, sont introduits l’Isododécane / Acétate d’éthyle (60/40), l'Acrylate d’Isobornyle, l'Acrylate de Méthyle / Acrylate d’Ethyle et le T21S. Le milieu est chauffé à 90 °C (Consigne sur le milieu), sous argon et sous agitation.
Après 2h de chauffe, la RMN indique une consommation de 98% de l'Acrylate d’Isobornyle (Consommation de l’Acrylate de Méthyle : 96% et l’Acrylate d’Ethyle : 98 %).
Après 2h de réaction, dans le pied de cuve, de l’Isododécane / Acétate d’éthyle (60/40), sont introduits. On chauffe à 90 °C dans le milieu.
Une fois le milieu à 90 °C, on introduit en 2h par une coulée l'Acrylate de Méthyle / Acrylate d’Ethyle / Acide Acrylique, l’Isododécane / Acétate d’éthyle (60/40), et le T21S. A la fin de la coulée le milieu est laiteux.
Après 7 h de synthèse on obtient une consommation de l'Acrylate de Méthyle / Acrylate d’Ethyle / Acide Acrylique de 99 % (Consommation de l'Acrylate d’Isobornyle : 100 %).
On réalise ensuite un stripping de 3L d’Isododécane et de l’acétate d’éthyle (la RMN indique qu'il n'y a plus de monomères et l’acétate d’éthyle est totalement retiré de la dispersion). L’extrait sec est de 50 %.
Etape 2 : Ajout d’eau en fin de synthèse
Dans un second temps, en conservant le polymère dans le réacteur, de l’eau est ajoutée en fin de manip. 2 essais ont été réalisés. Ils sont résumés dans le Tableau 21 : Ingrédients Pourcentage massique en matière active dans la dispersion finale Exemple 3-2 Exemple 3-3 Particule polymérique i) + ii) 30 30 Eau iv) 20 40 Isododécane iii) 50 30 Aspect des formules Formule blanche homogène
Stable Formule blanche homogène
stable Tableau 21 : Influence de la quantité d’eau– exemple 3
Evaluation des propriétés cosmétiques des différentes dispersions stables a été effectuée. Les mesures de la sensibilité aux corps gras (Huile d’olive et sébum) et à l’eau sont résumées dans le Tableau 22 : N° de l’exemple Résistance à l’eau Résistance à l’huile d’olive Résistance au sébum Exemple 3-1 ++ ++ + Exemple 3-2 ++ ++ + Tableau 22 : Propriétés cosmétiques de l’exemple 3
(-) : pas de résistance, (+) résistance, (++), résistance très significative après passage d’un même tissé en coton imbibé de la même quantité de sébum, d’huile d’olive, ou d’eau.The dispersion of example 2 leads to a deposit resistant to sebum and very significantly resistant to water, and to olive oil.
Example 3: Obtaining dispersion with variable amounts of water for polymeric particles containing more acrylic acid (20%)
Step 1 : Synthesis of the dispersion of polymeric particles in isododecane
First, the synthesis of the polymeric particles is carried out in isododecane.
The dispersions are formed as a whole (Stabilizer ii + particles i) at 10% Acrylic Acid, 20% Methyl Acrylate, 50% Ethyl Acrylate and 20% Isobornyl Acrylate. The synthesis of these dispersions was carried out in a controlled reactor of 6 liters. The synthesis is carried out in two steps:

• During a first step, Isobornyl Acrylate is polymerized in Isododecane / Ethyl Acetate (60/40) in the presence of a small amount of Methyl Acrylate / Ethyl Acrylate and a radical initiator (T21S). In the first step, the Isobornyl Acrylate/Methyl Acrylate/Ethyl Acrylate mass ratio is 92/4/4.
• During the second step, the rest of the Methyl Acrylate/Ethyl Acrylate and the Acrylic Acid are poured in the presence of Isododecane/Ethyl Acetate (60/40) and radical initiator (T21S).

After stripping, the polymer is at a dry extract of 50% in isododecane.
The ratios used to obtain the stabilizer and the core are summarized in Table 17: Mass percentage
Stabilizer - Heart Monomer Mass percentage in the stabilizer
and the heart Stabilizer ii) 21 Isobornyl Acrylate 92 Methyl acrylate 4 Ethyl acrylate 4 Heart i) 79 Methyl Acrylate 24.5 Ethyl acrylate 62.8 Acrylic Acid 12.7 Table 17: Specific ratios in the stabilizer and the heart for the dispersion of example 3
Quantity of reagents:
Step 1.1: Reagents Mass (g) Isobornyl Acrylate 315.2 Methyl Acrylate 12.5 Ethyl Acrylate 12.5 T21S 3.4 Isododecane / AcOEt (60/40) 900 Isododecane/ethyl acetate added between the two steps: Reagent Mass (g) Isododecane / AcOEt (60/40) 900 Step 1.2: Reagents Mass (g) Mass added in beaker for casting (g) Methyl Acrylate 303 364 Ethyl Acrylate 776 931 Acrylic Acid 157 188.4 T21S 11 13 Isododecane / AcOEt (60/40) 1236 1483.2 Tables 20: Quantities of reagents used for example 3
Experimental protocol :
Isododecane / Ethyl Acetate (60/40), Isobornyl Acrylate, Methyl Acrylate / Ethyl Acrylate and T21S are introduced into the reactor at the bottom of the tank. The medium is heated to 90° C. (Setpoint on the medium), under argon and with stirring.
After 2 hours of heating, the NMR indicates a consumption of 98% of Isobornyl Acrylate (Consumption of Methyl Acrylate: 96% and Ethyl Acrylate: 98%).
After 2 hours of reaction, isododecane / ethyl acetate (60/40) are introduced into the base stock. Heat to 90°C in the middle.
Once the medium has reached 90°C, Methyl Acrylate / Ethyl Acrylate / Acrylic Acid, Isododecane / Ethyl Acetate (60/40), and T21S are introduced over 2 hours by pouring. At the end of the casting the medium is milky.
After 7 hours of synthesis, a consumption of Methyl Acrylate / Ethyl Acrylate / Acrylic Acid of 99% is obtained (Consumption of Isobornyl Acrylate: 100%).
A stripping of 3L of isododecane and ethyl acetate is then carried out (the NMR indicates that there are no more monomers and the ethyl acetate is completely removed from the dispersion). The dry extract is 50%.
2nd step : Addition of water at the end of the synthesis
In a second step, keeping the polymer in the reactor, water is added at the end of the manipulation. 2 tests were carried out. They are summarized in Table 21: Ingredients Mass percentage of active ingredient in the final dispersion Example 3-2 Example 3-3 Polymeric particle i) + ii) 30 30 Water iv) 20 40 Isododecane iii) 50 30 Appearance of formulas Homogeneous white formula
Steady Homogeneous white formula
steady Table 21: Influence of water quantity – example 3
Evaluation of the cosmetic properties of the different stable dispersions was carried out. Measurements of sensitivity to fatty substances (Olive oil and sebum) and to water are summarized in Table 22: Example number Water resistance Olive oil resistance Sebum resistance Example 3-1 ++ ++ + Example 3-2 ++ ++ + Table 22: Cosmetic properties of example 3
(-): no resistance, (+) resistance, (++), very significant resistance after passage of the same cotton fabric soaked in the same quantity of sebum, olive oil, or water.

• Lors d’une première étape, l’Acrylate d’Isobornyle est mis à polymériser dans le Cétiol UT / Acétate d’éthyle (60/40) en présence d’une petite quantité d’Acrylate de Méthyle / Acrylate d’Ethyle et d’un amorceur radicalaire (T21S). En première étape, le ratio massique Acrylate d’Isobornyle / Acrylate de Méthyle / Acrylate d’Ethyle est 92/4/4.
• Lors de la seconde étape, le reste de l’Acrylate de Méthyle / Acrylate d’Ethyle et l’Acide Acrylique sont coulés en présence de Cétiol UT / Acétate d’éthyle (60/40) et d’amorceur radicalaire (T21S).

Après un stripping, le polymère se trouve à un extrait sec de 50 % dans le Cétiol UT.
Les ratios employés pour obtenir le stabilisant et le cœur sont résumés dans le Tableau 23 : Pourcentage massique
Stabilisant - Cœur Monomère Pourcentage massique dans le stabilisant
et le cœur Stabilisant 21 Acrylate d’Isobornyle 92 Acrylate de méthyle 4 Acrylate d’éthyle 4 Cœur 79 Acrylate de Méthyle 11,7 Acrylate d’éthyle 75,6 Acide Acrylique 12,7 Tableau 23 : Ratios spécifiques dans le stabilisant et le cœur pour les particules polymériques de l’exemple 4
Quantité de réactifs :
Etape 1.1 : Réactifs Masse (g) Acrylate d’Isobornyle 315,2 Acrylate de Méthyle 12,5 Acrylate d’Ethyle 12,5 T21S 3,4 Cétiol UT / AcOEt (60/40) 900 Cétiol UT/Acétate d’éthyle ajouté entre les deux étapes : Réactif Masse (g) Cétiol UT / AcOEt (60/40) 900 Etape 1.2 : Réactifs Masse (g) Masse ajoutée dans le bécher pour la coulée (g) Acrylate de Méthyle 145 174 Acrylate d’Ethyle 934 1120 Acide Acrylique 157 188,4 T21S 12.36 14,83 Cétiol UT / AcOEt (60/40) 1236 1483,2 Tableaux 26 : Quantités de réactifs utilisés pour l’exemple 4
Protocole expérimental :
Dans le réacteur en pied de cuve, sont introduits le Cétiol UT / Acétate d’éthyle (60/40), l'Acrylate d’Isobornyle, l'Acrylate de Méthyle / Acrylate d’Ethyle et le T21S. Le milieu est chauffé à 90 °C (Consigne sur le milieu), sous argon et sous agitation.
Après 2h de chauffe, la RMN indique une consommation de 97 % de l'Acrylate d’Isobornyle (Consommation de l’Acrylate de Méthyle : 96 % et l’Acrylate d’Ethyle : 96%).
Après 2h de réaction, dans le pied de cuve, le Cétiol UT / Acétate d’éthyle (60/40), sont introduits. On chauffe à 90 °C dans le milieu.
Une fois le milieu à 90 °C, on introduit en 2h par une coulée l'Acrylate de Méthyle / Acrylate d’Ethyle / Acide Acrylique, le Cétiol UT / Acétate d’éthyle (60/40), et le T21S. A la fin de la coulée le milieu est laiteux.
Après 7h de synthèse on obtient une consommation de l'Acrylate de Méthyle / Acrylate d’Ethyle / Acide Acrylique de 99 % (Consommation de l'Acrylate d’Isobornyle : 100%).
On réalise ensuite un stripping de 3L de Cétiol UT et de l’acétate d’éthyle (la RMN indique qu'il n'y a plus de monomères et l’acétate d’éthyle est totalement retiré de la dispersion). L’extrait sec est de 50 %.
Etape 2 : Ajout d’eau en fin de synthèse
Dans un second temps, en conservant le polymère dans le réacteur, de l’eau est ajoutée en fin de manip. Un essai a été réalisé. Il est résumé dans le Tableau 27 : Ingrédients Pourcentage massique en matière active dans la dispersion finale Exemple 4 Particule polymérique i) + ii) 30 Eau iv) 40 Cétiol UT iii) (undecane et tridecane) 30 Aspect des formules Formule blanche homogène - Stable Tableau 27 : Nouvelle dispersion contenant du Cétiol UT – exemple 4
Par la suite, une évaluation des propriétés cosmétiques de la nouvelle dispersion a été effectuée. Les mesures de la sensibilité aux corps gras (Huile d’olive et sébum) et à l’eau sont résumées dans le Tableau 28 : N° de l’exemple Résistance à l’eau Résistance à l’huile d’olive Résistance au sébum Exemple 4 ++ ++ + Tableau 28 : Propriétés cosmétiques de l’exemple 4
(-) : pas de résistance, (+) résistance, (++), résistance très significative après passage d’un même tissé en coton imbibé de la même quantité de sébum, d’huile d’olive, ou d’eau.
La dispersion de l’exemple 4 conduit à un dépôt résistant au sébum et très significativement résistant à l’eau, et à l’huile d’olive.
Exemple 5 : Modification de l’ordre d’introduction de l’eau :
Pour cet exemple, dans un premier temps, le polymère stabilisant est synthétisé. Par la suite, l’eau ajoutée avant la synthèse du cœur des particules polymériques.
Les particules polymériques sont formées dans leur ensemble (Stabilisant i + particules ii) à 10 % Acide Acrylique, 10 % d’Acrylate de Méthyle, 60 % d’Acrylate d’Ethyle et à 20 % d’Acrylate d’Isobornyle.
Après un stripping de l’acétate d’éthyle, le polymère se trouve à un extrait sec de 37,5 % dans isododécane iii) / eau iv).
Les ratios employés pour obtenir le stabilisant et le cœur sont résumés dans le Tableau 28 : Pourcentage massique
Stabilisant - Cœur Monomère Pourcentage massique dans le stabilisant
et le cœur Stabilisant 21 Acrylate d’Isobornyle 92 Acrylate de méthyle 4 Acrylate d’éthyle 4 Cœur 79 Acrylate de Méthyle 12,2 Acrylate d’éthyle 75 Acide Acrylique 12,8 Tableau 28 : Ratios spécifiques dans le stabilisant et le cœur pour les particules polymériques de l’exemple 5
Quantité de réactifs :
Etape 1 : Réactifs Masse (g) Acrylate d’Isobornyle 50 Acrylate de Méthyle 2 Acrylate d’Ethyle 2 T21S 0.52 Isododécane / AcOEt (60/40) 110.7 Etape 2 : Isododécane/Acétate d’éthyle et eau ajoutés Réactif Masse (g) Isododécane / AcOEt (60/40) 110 Eau 167 Etape 3 : Réactifs Masse (g) Masse ajoutée dans le bécher pour la coulée (g) Acrylate de Méthyle 24 27.6 Acrylate d’Ethyle 147 169 Acide Acrylique 25 28.8 T21S 1.96 2.25 Isododécane / AcOEt (60/40) 196 225.4 Tableaux 31 : Quantités de réactifs utilisés pour l’exemple 5
Protocole expérimental :
Dans le réacteur en pied de cuve, sont introduits l'Isododécane/AcOEt, l'Acrylate Isobornyle, l'Acrylate d’éthyle / Acrylate de Méthyle et le T21S. Un bullage d’argon dans le milieu est effectué pendant 10 minutes. Le milieu est chauffé à 90 °C (Consigne bain d’huile) et sous agitation.
Après 2 h de chauffe, la RMN indique une consommation de 99 % de l'Acrylate d’Isobornyle
Après 2 h de réaction, dans le pied de cuve, l’isododécane / Acétate d’éthyle (60/40) et l’eau, sont introduits. On chauffe à 90 °C dans le milieu.
Une fois le milieu à 90 °C, on introduit par une coulée en 1h, l'Acrylate de Méthyle / Acrylate d’Ethyle / Acide Acrylique, l’isododécane / Acétate d’éthyle (60/40), et le T21S. A la fin de la coulée le milieu est laiteux. L’extrait sec est de 30 %.
Après 7 h de synthèse on obtient une consommation de l'Acrylate de Méthyle / Acrylate d’Ethyle / Acide Acrylique de 99 % (Consommation de l'Acrylate d’Isobornyle : 100 %).
Un stripping de l’acétate d’éthyle est réalisé.
La dispersion finale présente la composition, Tableau 32 : Ingrédients Pourcentage massique en matière active dans la dispersion finale Exemple 5 Particule polymérique i) + ii) 37,5 Eau iv) 25 Isododécane iii) 37,5 Aspect des formules Formule blanche homogène - Stable Tableau 32 : Composition de la dispersion finale – exemple 5
Par la suite, une évaluation des propriétés cosmétiques de la dispersion obtenue selon un autre procédé a été effectuée. Les mesures de la sensibilité aux corps gras (Huile d’olive et sébum) et à l’eau sont résumées dans le Tableau 33 : N° de l’exemple Résistance à l’eau Résistance à l’huile d’olive Résistance au sébum Exemple 5 ++ ++ + Tableau 33 : Propriétés cosmétiques de l’exemple 5
La dispersion de l’exemple 5 conduit à un dépôt résistant au sébum et très significativement résistant à l’eau, et à l’huile d’olive.
Ajout d’épaississant
Des formulations ont été réalisées en ajoutant un épaississant. Trois épaississants ont été ajoutés, selon le Tableau 3 :The dispersions containing less volatile hydrocarbon iii) oil of example 3-1 and 3-2 lead to a deposit resistant to sebum and very significantly resistant to water, to olive oil.
.
Example 4:Obtaining dispersion with variable amounts of water for polymeric particles synthesized in Cetiol UT
Step 1 : Synthesis of the dispersion of polymeric particles in isododecane
Initially, the synthesis of the polymeric particles is carried out in Cetiol UT/AcOEt.
The polymeric particles are formed as a whole (Stabilizer ii + particles i) with 10% Acrylic Acid, 10% Methyl Acrylate, 60% Ethyl Acrylate and 20% Isobornyl Acrylate. The synthesis of these dispersions was carried out in a controlled reactor of 6 liters. The synthesis is carried out in two steps:

• During a first step, Isobornyl Acrylate is polymerized in Cetiol UT / Ethyl Acetate (60/40) in the presence of a small amount of Methyl Acrylate / Ethyl Acrylate and a radical initiator (T21S). In the first step, the Isobornyl Acrylate/Methyl Acrylate/Ethyl Acrylate mass ratio is 92/4/4.
• During the second step, the rest of the Methyl Acrylate/Ethyl Acrylate and the Acrylic Acid are poured in the presence of Cetiol UT/Ethyl Acetate (60/40) and radical initiator (T21S).

After stripping, the polymer is at a dry extract of 50% in Cetiol UT.
The ratios used to obtain the stabilizer and the core are summarized in Table 23: Mass percentage
Stabilizer - Heart Monomer Mass percentage in the stabilizer
and the heart Stabilizing 21 Isobornyl Acrylate 92 Methyl acrylate 4 Ethyl acrylate 4 Heart 79 Methyl Acrylate 11.7 Ethyl acrylate 75.6 Acrylic Acid 12.7 Table 23: Specific ratios in the stabilizer and the core for the polymeric particles of example 4
Quantity of reagents:
Step 1.1: Reagents Mass (g) Isobornyl Acrylate 315.2 Methyl Acrylate 12.5 Ethyl Acrylate 12.5 T21S 3.4 Cetiol UT / AcOEt (60/40) 900 Cetiol UT/Ethyl acetate added between the two steps: Reagent Mass (g) Cetiol UT / AcOEt (60/40) 900 Step 1.2: Reagents Mass (g) Mass added in beaker for casting (g) Methyl Acrylate 145 174 Ethyl Acrylate 934 1120 Acrylic Acid 157 188.4 T21S 12.36 14.83 Cetiol UT / AcOEt (60/40) 1236 1483.2 Tables 26: Quantities of reagents used for Example 4
Experimental protocol :
Into the reactor at the bottom of the tank, are introduced Cetiol UT / Ethyl Acetate (60/40), Isobornyl Acrylate, Methyl Acrylate / Ethyl Acrylate and T21S. The medium is heated to 90° C. (Setpoint on the medium), under argon and with stirring.
After 2 hours of heating, the NMR indicates a consumption of 97% of Isobornyl Acrylate (Consumption of Methyl Acrylate: 96% and Ethyl Acrylate: 96%).
After 2 hours of reaction, in the base stock, Cetiol UT / Ethyl acetate (60/40), are introduced. Heat to 90°C in the middle.
Once the medium is at 90°C, Methyl Acrylate / Ethyl Acrylate / Acrylic Acid, Cetiol UT / Ethyl Acetate (60/40), and T21S are introduced over 2 hours by pouring. At the end of the casting the medium is milky.
After 7 hours of synthesis, we obtain a consumption of Methyl Acrylate / Ethyl Acrylate / Acrylic Acid of 99% (Consumption of Isobornyl Acrylate: 100%).
A stripping of 3L of Cetiol UT and ethyl acetate is then carried out (the NMR indicates that there are no more monomers and the ethyl acetate is completely removed from the dispersion). The dry extract is 50%.
2nd step : Addition of water at the end of the synthesis
In a second step, keeping the polymer in the reactor, water is added at the end of the manipulation. A test was carried out. It is summarized in Table 27: Ingredients Mass percentage of active ingredient in the final dispersion Example 4 Polymeric particle i) + ii) 30 Water iv) 40 Cetiol UT iii) (undecane and tridecane) 30 Appearance of formulas Homogeneous white formula - Stable Table 27: New dispersion containing Cetiol UT – example 4
Subsequently, an evaluation of the cosmetic properties of the new dispersion was carried out. Measurements of sensitivity to fatty substances (Olive oil and sebum) and to water are summarized in Table 28: Example number Water resistance Olive oil resistance Sebum resistance Example 4 ++ ++ + Table 28: Cosmetic properties of Example 4
(-): no resistance, (+) resistance, (++), very significant resistance after passage of the same cotton fabric soaked in the same quantity of sebum, olive oil, or water.
The dispersion of example 4 leads to a deposit resistant to sebum and very significantly resistant to water, and to olive oil.
Example 5 : Modification of the order of water introduction:
For this example, initially, the stabilizing polymer is synthesized. Subsequently, the water added before the synthesis of the core of the polymer particles.
The polymeric particles are formed as a whole (Stabilizer i + particles ii) with 10% Acrylic Acid, 10% Methyl Acrylate, 60% Ethyl Acrylate and 20% Isobornyl Acrylate.
After stripping with ethyl acetate, the polymer has a solids content of 37.5% in isododecane iii) / water iv).
The ratios used to obtain the stabilizer and the core are summarized in Table 28: Mass percentage
Stabilizer - Heart Monomer Mass percentage in the stabilizer
and the heart Stabilizing 21 Isobornyl Acrylate 92 Methyl acrylate 4 Ethyl acrylate 4 Heart 79 Methyl Acrylate 12.2 Ethyl acrylate 75 Acrylic Acid 12.8 Table 28: Specific ratios in the stabilizer and the core for the polymeric particles of example 5
Quantity of reagents:
Step 1 : Reagents Mass (g) Isobornyl Acrylate 50 Methyl Acrylate 2 Ethyl Acrylate 2 T21S 0.52 Isododecane / AcOEt (60/40) 110.7 Step 2: Isododecane/Ethyl acetate and water added Reagent Mass (g) Isododecane / AcOEt (60/40) 110 Water 167 Step 3: Reagents Mass (g) Mass added in beaker for casting (g) Methyl Acrylate 24 27.6 Ethyl Acrylate 147 169 Acrylic Acid 25 28.8 T21S 1.96 2.25 Isododecane / AcOEt (60/40) 196 225.4 Tables 31: Quantities of reagents used for Example 5
Experimental protocol :
Isododecane/AcOEt, Isobornyl Acrylate, Ethyl Acrylate/Methyl Acrylate and T21S are introduced into the reactor at the bottom of the tank. Argon bubbling in the medium is carried out for 10 minutes. The medium is heated to 90°C (oil bath setpoint) and stirred.
After 2 hours of heating, the NMR indicates a consumption of 99% of Isobornyl Acrylate
After 2 hours of reaction, the isododecane/ethyl acetate (60/40) and water are introduced into the base stock. Heat to 90°C in the middle.
Once the medium has reached 90°C, Methyl Acrylate/Ethyl Acrylate/Acrylic Acid, isododecane/ethyl acetate (60/40), and T21S are introduced over 1 hour. At the end of the casting the medium is milky. The dry extract is 30%.
After 7 hours of synthesis, a consumption of Methyl Acrylate / Ethyl Acrylate / Acrylic Acid of 99% is obtained (Consumption of Isobornyl Acrylate: 100%).
A stripping of ethyl acetate is carried out.
The final dispersion shows the composition, Table 32: Ingredients Mass percentage of active ingredient in the final dispersion Example 5 Polymeric particle i) + ii) 37.5 Water iv) 25 Isododecane iii) 37.5 Appearance of formulas Homogeneous white formula - Stable Table 32: Composition of the final dispersion – example 5
Subsequently, an evaluation of the cosmetic properties of the dispersion obtained according to another process was carried out. Measurements of sensitivity to fatty substances (Olive oil and sebum) and to water are summarized in Table 33: Example number Water resistance Olive oil resistance Sebum resistance Example 5 ++ ++ + Table 33: Cosmetic properties of example 5
The dispersion of example 5 leads to a deposit resistant to sebum and very significantly resistant to water, and to olive oil.
Addition of thickener
Formulations have been made by adding a thickener. Three thickeners were added, according to Table 3:

Process of obtaining:

• Mesure de collant: le collant est mesuré via une bille en caoutchouc viton venant en contact avec le dépôt à une vitesse de 5mm/s sous une force de 1N et pendant un temps de 5s. La mesure est reproduite 5 fois. Le collant a été mesurée principalement sur le dépôt réalisé sur FP40
• Mesure de collant au cours du séchage: Une goutte de 10 µL de formule est déposée sur carte de contraste. Le collant est mesuré via une bille en caoutchouc viton venant en contact avec le dépôt chaque minute à une vitesse de 5mm/s sous une force de 1N et pendant un temps de contact de 5 s.
• Sensibilité aux agresseurs eau / sébum: La sensibilité à l’eau et au sébum est évaluée après avoir déposé une goutte d’agresseur (10 μl pour le sébum et 20μl pour l’eau) sur la surface du dépôt réalisé sur la carte de contraste. Les évaluations sont faites après 20 minutes de contact entre l’agresseur et le dépôt.

Résultats :
Mesure de collant sur FP40 et sensibilité sébum/eau
[Tableau 35] : Exemple 1 Exemple 8 Exemple 9 Exemple 10 Collant sur FP40 (N) 0,23 0,02 0,03 0,11 Sensibilité à l’eau ++ ++ ++ ++ Sensibilité au sébum + ++ ++ + Tableau 35 : Mesures de collant sur FP40 et de sensibilité à l’eau/sébum suite à l’ajout d’épaississant par comparaison avec une même formule sans épaississant
(-) : pas de résistance, (+) résistance, (++), résistance très significative après passage d’un même tissé en coton imbibé de la même quantité de sébum, d’huile d’olive, ou d’eau.
Il apparait que l’ajout d’épaississant a permis d’améliorer la sensibilité au sébum, cet effet est plus marqué lors de l’ajout des épaississants trihydroxystéarine et intelimer. Pour ces 2 épaississants, le test de goutte révèle une meilleure résistance au sébum et le collant sur FP40 est plus faible. Pour le dextrine palmitate, l’effet est moins visible sur le test de goutte mais détecté via le test de collant sur FP40 avec une diminution de ce collant.
Mesures de collant au cours du séchage
Il a été observé et mesuré que l’ajout d’épaississant permet de modifier les profils de collant au cours du séchage. Dans le cas de la dispersion sans épaississant, le profil de collant tend vers maximum et reste à ce maximum sur un long pallier. Lors de l’ajout des épaississants, le pic de collant atteint un maximum à une valeur significativement plus faible avant de revenir à 0. Step 1 :The first step consists in carrying out the synthesis of the polymeric particles in isododecane. This step is identical to step 1 of example 1
2nd step :The medium containing the polymeric particles in the isododecane is cooled to 25°C. Water is added. The medium is stirred at 2500 rpm.
Step 3:The thickener is introduced while heating to 80°C and stirring at 1500 rpm. The medium is maintained at 80°C for 20 minutes with stirring and then cooled under the same stirring conditions.
The composition of the final formulas is, Table 34:
[Table 34]: Ingredients Mass percentage of active ingredient Example 8 Example 9 Example 10 Polymer particles i) + ii)
from example 1 30 30 30 Thickener vii) Intellimer vii) 5 Trihydroxystearin vii) 5 Dextrin palmitate (vii) 5 Isododecane iii) 45 45 45 Water iv) 20 20 20 Table 32: Composition of formulas with thickener
Ratings
Preparation of deposits
Initially, a deposit is made on a contrast card (for example that sold under the reference byko-charts by the company BYK-gardner) and also on the elastomeric support of the FP40 type. FP40 (Trellborg, N4I01) is an elastomeric butadiene-acrylonitrile copolymer substrate containing diethylhexyl sebacate oil as plasticizer. When a polymer conveyed in isododecane is applied to this substrate, an extraction of the plasticizer is carried out mimicking the contribution / impact of sebum on the coating.
A volume V of formula is deposited to obtain a dry deposit of 30 μm. The formula is left to dry for 7 days, at a temperature of 25° C. and a relative humidity RH=45%.
Evaluation protocols:

• Stickiness measurement : the stickiness is measured via a Viton rubber ball coming into contact with the deposit at a speed of 5mm/s under a force of 1N and for a time of 5s. The measurement is repeated 5 times. The stickiness was measured mainly on the deposit made on FP40
• Stickiness measurement during drying : A drop of 10 µL of formula is placed on a contrast card. The stickiness is measured via a viton rubber ball coming into contact with the deposit every minute at a speed of 5 mm/s under a force of 1 N and for a contact time of 5 s.
• Sensitivity to water/sebum aggressors : The sensitivity to water and sebum is evaluated after depositing a drop of aggressor (10 μl for sebum and 20 μl for water) on the surface of the deposit made on the contrast card . Assessments are made after 20 minutes of contact between the attacker and the depot.

Results :
Stickiness measurement on FP40 and sebum/water sensitivity
[Table 35]: Example 1 Example 8 Example 9 Example 10 Sticky on FP40 (N) 0.23 0.02 0.03 0.11 Water sensitivity ++ ++ ++ ++ Sensitivity to sebum + ++ ++ + Table 35: Measurements of stickiness on FP40 and sensitivity to water/sebum following the addition of thickener compared with the same formula without thickener
(-): no resistance, (+) resistance, (++), very significant resistance after passage of the same cotton fabric soaked in the same quantity of sebum, olive oil, or water.
It appears that the addition of thickener has improved sebum sensitivity, this effect is more marked when the thickeners trihydroxystearin and intelimer are added. For these 2 thickeners, the drop test reveals better resistance to sebum and the stickiness on FP40 is lower. For dextrin palmitate, the effect is less visible on the drop test but detected via the stickiness test on FP40 with a decrease in this stickiness.
Stickiness measurements during drying
It has been observed and measured that the addition of thickener makes it possible to modify the stickiness profiles during drying. In the case of the dispersion without thickener, the stickiness profile tends towards maximum and remains at this maximum over a long plateau. When adding thickeners, the stickiness peak peaks at a significantly lower value before returning to 0.

Claims (22)

Dispersion (A), which includes:
i) one or more particle(s) comprising one or more polymer(s) chosen from:
a) one or more ethylenic copolymer(s) 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, sulphonic acid and/or aryl groups; in particular a ₂ ) is a (C ₁ -C ₄ )(alkyl)acrylic acid; And
ii) one or more polymeric stabilizing agent(s) chosen from:
b) polymers of (C ₁ -C ₆ )(C ₃ -C ₁₂ )cycloalkyl (alkyl)acrylate monomers; 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 (C ₁ -C ₄ ) alkyl; And
iii) one or more hydrocarbon-based liquid fatty substance(s);
iv) water; And
v) optionally one or more cosmetic active ingredient(s) chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, in particular the skin, and j) UV filters (A) and/or (B) as well as m) mixtures thereof;
it being understood that the amount of water is greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the dispersion. Dispersion (A), according to the preceding claim, in which the particle(s) i) is (are) composed of an ethylenic polymer core derived from copolymers a), as defined in the preceding claim, and ii) of one or more polymeric surface stabilizer(s) derived from polymer b) or from copolymers c) as defined in the preceding claim. Dispersion (A), according to claim 1 or 2, in which the polymer(s) constituting the particles i) is (are) chosen from ethylenic acrylate copolymers a1) resulting from the polymerization of monomer ( s) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl of formula (I) :
H ₂ C=C(R)-C(O)-O-R' (I)
Formula (I) in which:
- R representing a hydrogen atom or a (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; particularly methyl, ethyl or isobutyl, preferably (I) is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate; and more preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate and isobutyl (meth)acrylate; more preferably (I) represents preferably represents methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate. Dispersion (A), according to any one of the claims, in which the polymer(s) constituting the particles i) is (are) chosen from among the ethylenic copolymers of b1) (C ₁ -C ₄ )(alkyl) acrylate of (C ₁ -C ₄ )alkyl, and of b2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups such as benzyl particularly chosen from (1) , (2) , ( 3) , and (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, phosphoric acid, sulphonic acid, preferably carboxy, preferably (1) represents (5) H ₂ C=C(R)-C(O)-OH with R representing a hydrogen atom, 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', which are identical or different, represent a hydrogen atom, or a group (C ₁ -C ₄ ) alkyl; Alk represents a (C ₁ -C ₆ )alkylene group optionally substituted by at least one group chosen from Acid as defined above and hydroxy; and Acid is as defined above, preferably carboxy or sulphonic acid;
(3) Ar-(R ^a )C=C(R ^b )-R ^c with R ^a , R ^b and R ^c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group , and Ar represents an aryl group, preferably benzyl, optionally substituted by at least one CO ₂ H, H ₂ PO ₄ or SO ₃ H acid group, preferably substituted by a CO ₂ H or SO ₃ H group,
(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;
more particularly a2) is chosen from (1) and (4), preferably (4) in particular (5) Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the ethylenic monomer(s) a2) comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups is (are) chosen among crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid , acrylamidopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid and their salts, even more preferentially a2) represents acrylic acid and its salts or maleic anhydride, more preferentially acrylic acid. Dispersion (A), according to any one of the preceding claims, in which the quantity of a2) 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 the particle i), even more particularly between 5% and 25% by weight and the polymer of the 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 of acrylic acid with one or more C ₁ -C ₄ alkyl (meth)acrylate monomers, preferably of two different C ₁ alkyl (meth)acrylate monomers -C _4, in particular chosen from methyl (meth)acrylate, and ethyl (meth)acrylate. Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the stabilizing agent(s) ii) consists of ethylenic polymers chosen from:
b) polymers of monomers of formula H ₂ C=C(R)-C(O)-O-R'' (III) with R representing a hydrogen atom or a (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) the copolymers of c1) H ₂ C=C(R)-C(O)-O-R'' (III) and of c2) H ₂ C=C(R)-C(O)-O-R' ( I) with R, R' and R'' as defined previously and claim 3; in particular, the stabilizing agent ii) is chosen from: isobornyl acrylate homopolymers, isobornyl acrylate/methyl acrylate random copolymers, isobornyl acrylate/ethyl acrylate random copolymers, and isobornyl acrylate/methyl acrylate/ethyl acrylate random copolymers according to the weight ratio described above. Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the stabilizing agent(s) ii) is (are) chosen from polymers of monomers
(C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl; 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 c ₁ /c ₂ weight ratio greater than 4, advantageously, said weight ratio ranges from 4.5 to 19, preferably, said c1/c2 weight ratio ranges from 5 to 15, more preferably said weight ratio ranges from from 5.5 to 12. Dispersion according to any one of the preceding claims, in which the dispersion is such that the polymer of the particles i) comprises from 80% to 93% by weight, of the ingredient a ₁ ), in particular of alkyl (meth)acrylate in C ₁ -C ₄ and from 7% to 20% by weight of ingredient a ₂ ) relative to the total weight of polymer i); more preferentially, the polymer of the particles i) preferably comprises from 85 to 93% by weight, more particularly 87% to 92% by weight, even more preferentially from 85% to 90% by weight, of the ingredient a ₁ ) in particular of C ₁ -C ₄ alkyl (meth)acrylate and from 10 to 20% by weight of ingredient a ₂ ) relative to the total weight of polymer i). Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the stabilizing agent or agents ii) are chosen from c) copolymers of c ₁ ) (C ₁ -C ₆ )(alkyl) acrylate (C ₃ -C ₁₂ )cycloalkyl and c ₂ ) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl with from 85% to 94% by weight of the ingredient c ₁ ) in particular of isobornyl (meth)acrylate and from 5% to 20% by weight of ingredient c ₂ ) relative to the total weight of the stabilizer; more preferentially, the stabilizing agent(s) ii) comprise from 85% to 98% by weight, more particularly 87% to 94% by weight, of ingredient c ₁ ) in particular of isobornyl (meth)acrylate and of 10% to 20% by weight of ingredient c ₂ ) relative to the total weight of the stabilizer. Dispersion (A) according to any one of the preceding claims, in which the polymer of the particles i) is present in a content ranging from 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 dispersion (A). Dispersion (A), according to any one of the preceding claims, in which the set ii) stabilizing agent(s) + i) particle(s) of polymer(s) are present in the dispersion (A) of 2 % to 40% by weight, in particular from 4% to 35% by weight, preferably from 4.5% to 30% by weight relative to the total weight of the dispersion (A). Dispersion (A), according to any one of the preceding claims, in which the hydrocarbon liquid fatty substance(s) iii) is (are) chosen from
hydrocarbons, in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, silicones; in particular the liquid hydrocarbon fatty substance(s) are preferably volatile hydrocarbon oils or are a mixture of different volatile oils, preferably chosen from isododecane and octyldodecanol, more particularly isododecane Dispersion (A), according to any one of the preceding claims, in which the hydrocarbon-based liquid fatty substance(s) iii) is (are) chosen from:
non-polar oils, i.e. formed solely of carbon and hydrogen atoms, preferably the dispersion (A) comprises at least one non-polar hydrocarbon-based liquid fatty substance iii), preferably chosen from:
- linear or branched C ₈ -C ₃₀ alkanes, in particular C ₁₀ -C ₂₀ , more particularly C ₁₀ -C ₁₆ alkanes, volatile or non-volatile; preferably volatile
- cyclic, non-aromatic, C ₅ -C ₁₂ alkanes; volatile or non-volatile; preferably volatile, and
- their mixtures;
preferably chosen from hydrocarbon oils having from 8 to 16 carbon atoms, in particular having from 10 to 14 carbon atoms, in particular chosen from:
- isoalkanes of petroleum origin such as isododecane;
- linear alkanes, such as undecane (C ₁₁ ), n-dodecane (C ₁₂ ), n-tridecane (C ₁₃ ) and n-tetradecane (C ₁₄ ), as well as their mixtures, the undecane-tridecane mixture, mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ).
preferentially, the liquid hydrocarbon fatty substance(s) iii) are apolar, more particularly isododecane. Dispersion (A), according to any one of the preceding claims, in which the hydrocarbon-based liquid fatty substance(s) iii) is (are) present in the dispersion in a content of between 15% by weight and 80% by weight, more preferably between 20% and 60% by weight relative to the total weight of said dispersion (A); in particular 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 mass ratio is between 0.5 and 1. Dispersion (A), according to any one of the preceding claims, in which the quantity of water iv) in the dispersion is between 5% and 49% by weight relative to the total weight of the dispersion, more particularly between 10% and 47% by weight, between 15% and 48% by weight, preferably between 18% and 45%, even more preferably between 20% and 40% by weight, relative to the total weight of the dispersion (A). Dispersion (A), according to any one of the preceding claims, which additionally comprises vii) one or more thickening agent(s) chosen from organic thickening polymers and thickening mono/di/triglycerides; in particular the thickening agent(s) is (are) chosen from: 1) block polymers of at least 2 C α-olefins₂-VS₁₆and better in C₂-VS₁₂, preferably, non-crosslinked semi-crystalline polymers, more particularly semi-crystalline polymers, 2) saccharide or polysaccharide mono-/polyalkylesters, particularly dextrin esters, in particular dextrin palmitates, 3) mono/polyalkylesters of saccharide or polysaccharide, di/tri glycerides mono/di/tri glycerides in which at least one hydrogen atom of a glycerol hydroxy group has been substituted by the –C(O)-R group^To, with R^Torepresenting a carbonyl hydrocarbon chain, linear or branched, cyclic or acyclic, saturated or unsaturated, comprising from 8 to 40 carbon atoms, said hydrocarbon chain possibly being substituted by one or more hydroxy groups, preferably chosen from triglycerides tri-substituted by -HORN^Towith R^Toas defined previously, more particularly chosen from trihydroxystearin. Dispersion (A), according to any one of the preceding claims, in which the said dispersion does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferably not 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, even better the mixture does not include a surfactant. Dispersion (A), according to any one of the preceding claims, in which the cosmetic active ingredient(s) iv) is (are) chosen from:
- organic and mineral or inorganic pigments,
- special effect pigments such as fluorescent, thermochromic, photochromic pigments, nacres, coated or uncoated, in the form of powder or pigment paste, lacquers, flakes or mixtures thereof;
- said pigments can be dispersed in the product using a dispersing agent and the pigments can be surface-treated with an organic agent;
in particular, the cosmetic active ingredient(s) iv) is (are) chosen from:
- the organic pigments nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone;
- white or colored organic pigments which are chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments codified in the Color Index under the BLUE 1 LAKE Cl 42090, 69800, 69825, 73000, 74100, 74160 pigment references, the yellow pigments codified in the Color Index under the Cl references 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47000, green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, 71105, red pigments codified in the Color Index under the references CI 12085 , 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, Pigments obtained by polymerization indole or phenolic derivatives;
- mineral pigments or inorganic pigments chosen iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide;
preferably, the cosmetic active ingredient(s) iv) is (are) chosen from carbon black, iron oxides, in particular red, brown or black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, such as BLUE 1 LAKE, azo pigments, in particular red, such as D&C RED 7 alkali metal salt of lithol red such as the calcium salt of lithol red B, more preferably the pigment(s) used are chosen from red iron oxides and azo pigments, in particular red ones, such as D&C RED 7 . Process for treating keratin materials, preferably α) keratin fibres, in particular human ones, such as hair, eyelashes, eyebrows or β) human skin, in particular the lips, comprising the application to said materials of at least one dispersion ( A), as defined in any one of the preceding claims, preferably after application of the dispersion (A) to the keratin materials, the composition is left to dry on the said keratin materials, either in the open air or using heating devices used in cosmetics such as a hair dryer Kit or device with several separate compartments comprising:
- in a compartment: the dispersion (A) comprising the ingredients i) to iii) as defined in any one of claims 1 to 16 and optionally vii) as defined in claim 17, and
- in one or more separate compartments are distributed the following ingredients: f) dyes, g) pigments; h) active ingredients for caring for keratin materials, in particular the skin, and/or j) UV filters (A) and/or (B) as defined in any one of Claims 1 or 19. Use of a dispersion (A) as defined in any one of Claims 1 to 19 for the treatment of keratin materials, in particular α) keratin fibers, in particular human fibers such as hair, eyelashes, eyebrows or β) human skin in particular of the lips, comprising the application to the said materials of at least one dispersion (A), for coloring the keratin fibers and/or shaping the keratin fibers such as the hair, or for making up the skin.