FR3137291A1 - Aerosol coloring device based on silicone acrylic copolymer, a coloring agent and a propellant gas of the dimethyl ether type - Google Patents

Abstract

Aerosol coloring device based on silicone acrylic copolymer, a coloring agent and a propellant gas of dimethyl ether type. The present invention relates to an aerosol device comprising a composition for coloring keratin fibers such as hair comprising one or more copolymers silicone acrylics, one or more coloring agents and at least one propellant chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases, as well as a coloring process using said composition.

Description

Aerosol coloring device based on silicone acrylic copolymer, a coloring agent and a propellant gas of the dimethyl ether type

The present invention relates to an aerosol device comprising a composition for coloring keratin fibers such as hair comprising one or more silicone acrylic copolymers, one or more coloring agents and at least one propellant chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases, as well as a coloring process using said composition.

In the field of coloring keratin fibers, in particular human ones, it is already known to color keratin fibers by different techniques using direct dyes or pigments for non-permanent colorings or dye precursors for permanent colorings.

There are essentially three types of hair coloring processes:

a) so-called permanent coloring which has the function of bringing about a significant modification of the natural color and which uses oxidation dyes which penetrate into the hair fiber and form the dye by a process of oxidative condensation;

b) non-permanent, semi-permanent or direct coloring, which does not involve the condensation, oxidative process and resists 4 or 5 shampoos; consists of dyeing keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules with an affinity for keratin fibers.

c) temporary coloring which gives rise to a modification of the natural color of the hair which lasts from one shampoo to another and which serves to beautify or correct a shade already obtained. It can also be compared to a “make-up” process.

For this last type of coloring, it is known to use pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible coloring on dark hair since the pigment on the surface masks the natural color of the fiber.

Temporary hair coloring and/or makeup compositions can be difficult to apply, leading to a non-homogeneous distribution of the coloring composition on the keratin fibers and therefore a non-uniform color on the keratin fibers. It is known to use devices in aerosol form comprising pigment-based compositions to color keratin fibers more homogeneously. For example, patent application FR 3 104 428 describes an aerosol device comprising a pigment-based composition.

However, such devices comprising compositions for temporary coloring and/or makeup of the hair may have the disadvantage of transferring, that is to say of being deposited at least in part, leaving traces, on certain supports with which they can come into contact with, in particular clothing or the skin. This results in poor performance of the applied film, requiring regular renewal of the application of the composition. Furthermore, the appearance of these unacceptable traces can dissuade certain people from using this type of coloring.

In addition, the colorings obtained by this coloring method may have the disadvantage of having low resistance to shampoos.

Thus, the aim of the present invention is to develop a device for coloring keratin fibers such as hair having the advantage of forming a deposit resistant to transfer, in particular which is not deposited, at least in part, on the supports with which the composition is brought into contact, such as the skin (the hands and the face in particular) and/or clothing, and which is residual to shampoos and to the various attacks that the hair may undergo while having good properties cosmetics in terms of softness or suppleness of the hair.

The applicant has surprisingly discovered that all of these objectives can be achieved by the device according to the present invention.

The present invention therefore relates to an aerosol device comprising:
- at least one pressurized container comprising:
a) at least one composition comprising:
i) one or more siliconized acrylic copolymers, and
ii) one or more coloring agent(s) chosen from pigments, direct dyes, and mixtures thereof, and,
b) at least one propellant chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases, and,
- a means for delivering the composition.

The composition according to the invention is preferably a composition for coloring keratin fibers such as hair.

The invention also relates to a process for coloring keratin fibers such as hair, comprising the application to said keratin fibers of a composition delivered from a device as defined above, possibly followed by drying.

Thanks to the aerosol device according to the invention, a uniform and chromatic coloring on the hair is quickly and easily obtained over the entire hair in a manner that is persistent with shampoos while preserving the physical qualities of the hair such as softness or the flexibility of the hair.

In addition, the composition obtained by the aerosol device according to the invention has good resistance to transfer and the deposition on the supports with which the composition is brought into contact, such as the skin and/or clothing is limited.

By “ remanent coloring with shampoo ” is meant for the purposes of the present invention that the coloring obtained persists after shampooing.

By “ keratin fibers ” is particularly meant human keratin fibers such as hair, eyelashes, eyebrows, and body hair, preferably hair, eyebrows and eyelashes, even more preferably hair.

For the purposes of the present invention, “ hair ” means the hair of the head. This term does not correspond to hair, eyebrows, or eyelashes

The expression “ at least one ” means one or more.

Unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “between” and “ranging from… to…”.

The invention is not limited to the examples illustrated. The characteristics of the different examples can in particular be combined in variants not illustrated.

For the purposes of the present invention and, unless otherwise indicated,
- an “ alkyl ” radical designates a linear or branched saturated radical containing for example from 1 to 20 carbon atoms;
- a “ hydroxyalkyl ” radical designates an alkyl radical as defined above, said alkyl radical comprising an OH group;
- an “ alkylene ” radical designates a divalent saturated hydrocarbon group in C ₂ -C ₄ , linear or branched, such as methylene, ethylene, or propylene;
- a “ cycloalkyl ” or “ alicycloalkyl ” radical designates a mono or polycyclic saturated cyclic hydrocarbon group, preferably monocyclic, comprising from 1 to 3 cycles, preferably 2 cycles, and comprising from 3 to 24 carbon atoms, in particular comprising 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, or norbornyl , in particular cyclopropyl, cyclopentyl or cyclohexyl. It being understood that the cycloalkyl radical can be substituted by one or more (C ₁ -C ₄ ) alkyl groups such as methyl, preferably the cycloalkyl radical is then an isobornyl group,
- a “ cycloalkylene ” radical designates a divalent cycloalkyl group with “ cycloalkyl ” as defined above, preferably C ₃ -C ₁₂ ;
- an “ aryl ” radical is an unsaturated and aromatic hydrocarbon cyclic radical, comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms, mono/bi/or tri/cyclic, fused or not, preferably the aryl group comprises 1 ring with 6 carbon atoms such as phenyl, naphthlyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical can be substituted by one or more (C ₁ -C ₄ ) alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl, preferably the aryl group represents phenyl;
- an “ arylene ” radical is a divalent aryl radical with “ aryl ” as defined above, preferably arylene represents phenylene;
- an “ aryloxy ” radical designates an aryl-oxy radical with “ aryl ” as defined above;
- an “ alkoxy ” radical designates an alkyl-oxy radical with “ alkyl ” as defined above.

When the propellant(s) b) are present in composition a), the total weight of the composition corresponds to the total weight of composition a).

When the propellant(s) b) are not present in the composition a), the total weight of the composition corresponds to the weight of the composition a) + the weight of the propellant(s) b).

In the description below, the total weight of the composition corresponds to the weight of the composition a) + the weight of the propellant(s) b).

Unless otherwise indicated, when compounds are mentioned in the present application, we also mean their optical isomers, their geometric isomers, their tautomers, their salts, alone or in mixture.

Detailed description of the invention Device according to the invention: Siliconized acrylic copolymer

The composition used in the context of the device according to the invention comprises one or more silicone acrylic copolymers.

Preferably, said silicone acrylic copolymer(s) comprise:
- at least one acrylic or methacrylic or crotonic pattern; And
- at least one polydimethylsiloxane unit (PDMS).

For the purposes of the present invention, the term “ polydimethylsiloxanes ” (also called in abbreviation, PDMS), in accordance with general acceptance, means any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and/or polycondensation. suitably functionalized silanes, and essentially constituted by a repetition of main units in which the silicon atoms are linked together by oxygen atoms (Si-O-Si siloxane bond), comprising methyl radicals directly linked by via a carbon atom on said silicon atoms.

The PDMS chains which can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, that is to say the PDMS can have for example a polymerizable radical group on each of the two ends of the chain or having a polymerizable radical group on one end of the chain and a terminal trimethylsilyl group on the other end of the chain.

By “ polymerizable radical group ” is meant a radical capable of polymerizing with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable radical group.

Preferably, the polymerizable radical group comprises at least one vinyl group.

Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable radical group comprising at least one vinyl group, preferably at least two polymerizable radical groups comprising at least one vinyl group, preferably located on at least one of the ends of chain.

As indicated above, said silicone acrylic copolymer(s) comprise at least one acrylic or methacrylic or crotonic unit, that is to say at least one unit comprising a carboxylic group.

By “ carboxylic group ” is meant a COOH or COO- functional group, the counterion of the COO- group being able to be chosen from alkali metals, alkaline earth metals, quaternary ammoniums.

Preferably, said silicone acrylic copolymer(s) comprise:
- at least one acrylic or methacrylic or crotonic unit, and at least one acrylic ester or methacrylic ester or vinyl ester unit; And
- at least one polydimethylsiloxane unit (PDMS).

More preferably, said siliconized acrylic copolymer(s) comprise:
- at least one crotonic unit and at least one unit chosen from an alkyl crotonate unit, the alkyl radical being a linear or branched, saturated radical containing from 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms; and their mixtures; And
- at least one polydimethylsiloxane unit (PDMS).

By “ crotonic unit ” is meant a unit derived from a crotonic acid monomer or one of its salts.

By “ alkyl crotonate unit ” is meant a unit derived from a crotonic acid ester monomer, having a saturated linear or branched alkyl radical containing from 1 to 20 carbon atoms.

By “ vinyl alkyl ester unit ” is meant a unit derived from a vinyl ester monomer having a linear or branched, saturated alkyl radical containing from 2 to 20 carbon atoms.

By “ vinyl acetate unit ” is meant a unit derived from a vinyl acetate monomer.

According to a preferred embodiment, said silicone acrylic copolymer(s) comprise:
- at least one crotonic unit, at least one vinylacetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms , And
- at least one polydimethylsiloxane unit (PDMS).

According to a particularly preferred embodiment, said silicone acrylic copolymer(s) comprise:
- at least one crotonic unit, at least one vinylacetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms, and
- at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising at least one vinyl group.

More preferably, the composition comprises one or more silicone acrylic copolymers comprising:
- at least one crotonic unit, at least one vinylacetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms ; And
- at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising at least one vinyl group.

Even more preferably, the composition comprises one or more silicone acrylic copolymers comprising:
- at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms; And
- at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising at least one vinyl group.

Among the silicone acrylic copolymers which can be used in the context according to the invention, mention may be made of the compound sold by the company Wacker Chemie AG under the trade name Belsil® P1101, INCI name Crotonic Acid/Vinyl C8-12 Isoalkyl Esters/VA /Bis-Vinyldimethicone Crosspolymer.

Advantageously, the total quantity of silicone acrylic copolymer(s) ranges from 0.01 to 30% by weight, preferably from 0.05 to 20% by weight, more preferably from 0.1 to 15% by weight, better from 0.5 to 10% by weight, even better from 0.5 to 5% by weight relative to the total weight of the composition.

Coloring agent

The composition used in the context of the device according to the invention comprises one or more coloring agent(s) chosen from pigments, direct dyes, and mixtures thereof.

Preferably, the composition used in the context of the device according to the invention comprises one or more pigments.

By “ pigment ” we mean all pigments providing color to keratin materials. Their solubility in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

The pigments which can be used are in particular chosen from organic and/or mineral 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.

They can be natural, of natural origin, or not.

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, lacquers, pigments with special effects such as pearls or flakes, and their mixtures.

The pigment may be a mineral pigment. By mineral pigment, we mean any pigment that meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of 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 which meets the definition of the Ullmann encyclopedia in the organic pigment chapter.

The organic pigment may in particular be chosen from the compounds nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo , 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 C 11680, 11710, 19140, 20040, 21100, 21100, 47000, 47005, the green pigments codified in the color index under the references Cl 61565, 61570, 74260, The orange pigments codified in the color index under the references CI 11725, 45370, 71105, the red pigments codified in the color index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525 , 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, pigments obtained by oxidative polymerization of indolic, phenolic derivatives such that they are described in the FR patent 2,679,771.

By way of example, we can also cite organic pigment pigment pastes such as the products sold by the company HOECHST under the name:
- COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);
- COSMENYL YELLOW G: 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);
- VERT COSMENYL GG: Pigment GREEN 7 (Cl 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

The pigments according to the invention can also be in the form of composite pigments such as they are 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 fixation organic pigments on the core, and at least one organic pigment at least partially covering the core.

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

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

Among the dyes, we can cite carminic acid. We can also cite 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, we can cite the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment can also be a special effect pigment. By special effect pigments, we mean pigments which generally create a colored appearance (characterized by a certain nuance, a certain vividness and a certain clarity) which is non-uniform and changes depending on the observation conditions (light, temperature , observation angles, etc.). They are therefore opposed to colored pigments which provide a classic uniform opaque, semi-transparent or 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 pearlescent, interference pigments or glitter.

As examples of special effect pigments, mention may be made of pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated 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 above as well as pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, we can cite Cellini pearls marketed by BASF (Mica-TiO ₂ -lacquer), Prestige marketed by Eckart (Mica-TiO ₂ ), Prestige Bronze marketed by Eckart (Mica-Fe ₂ O ₃ ) Colorona marketed by Merck (Mica-TiO ₂ -Fe ₂ O ₃ ).

We can also cite gold-colored mother-of-pearl, notably marketed by the company BASF under the name Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne) ; bronze mother-of-pearl sold 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); orange pearls marketed 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); brown colored mother-of-pearl sold in particular by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper reflection, notably marketed by the company BASF under the name Copper 340A (Timica); mother-of-pearl with a red reflection, notably marketed by the MERCK company under the name Sienna fine (17386) (Colorona); mother-of-pearl with a yellow reflection, notably marketed by the company BASF under the name Yellow (4502) (Chromalite); red pearls with a gold reflection, notably marketed by the company BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl sold in particular by the company BASF under the name Tan opal G005 (Gemtone); black mother-of-pearl with a gold reflection, 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 a gold reflection silver, in particular marketed by the MERCK company under the name Xirona Silver and the pinkish-golden green orange mother-of-pearl, in particular marketed by the MERCK company under the name Indian summer (Xirona) and their mixtures.

Still as an example of nacre, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

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

Finally, as examples of mother-of-pearl, we can also cite polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). We 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(s) which constitute it and their physical and chemical nature, and the surface condition, allow them to reflect incident light. This reflection can, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when it is applied to the support to be made up, highlighting points visible to the naked eye, this is i.e. brighter points that contrast with their environment by appearing to glow.

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 being in the shape of platelets or globular, in particular spherical.

The reflective particles, whatever their shape, may have a multilayer structure or not 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 can be composed for example of metal oxides, in particular titanium or iron oxides obtained by synthesis.

When the reflective particles have a multilayer structure, they may for example comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated by at least one layer of a reflective material, in particular 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 their mixtures, this list not being limiting.

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

Reflective particles are described in particular in 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, we can also cite particles comprising a borosilicate substrate coated with silver.

Particles with a silver-coated glass substrate, 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 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 metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, etc. 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 their mixtures.

As an example, we can cite aluminum, bronze or copper powders coated with SiO ₂ marketed under the name VISIONAIRE by the company ECKART.

We can also cite pigments with an interference effect not fixed on a substrate such as liquid crystals (Helicones HC from Wacker), interference holographic flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether substances which fluoresce 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, carrying 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 pigments. These dispersants also have at least one compatible or soluble functional group in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C8 to C20 fatty acid and of polyols such as glycerol, diglycerin, such as poly(12-hydroxystearic) acid stearate are used. molecular weight of approximately 750g/mole such as that sold under the name Solsperse 21,000 by the company Avecia, polygyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by the company Henkel or even polyhydroxystearic acid such than that sold under the reference Arlacel P100 by the company Uniqema and their mixtures.

As another 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 17 000 sold by the company Avecia, mixtures of poly dimethylsiloxane/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 previously surface-treated pigments useful in the context of the invention are pigments which have totally or partially undergone 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 according to 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 commercially as is.

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 surfactant molecules 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 fillers. This method is described in particular in US patent 4,578,266.

Preferably, an organic agent linked to the pigments in a covalent manner will be used.

The surface treatment agent can represent from 0.1 to 50% by weight of the total weight of the pigment treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight. weight of the total weight of the 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 Perfluoroalkyl 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 submicron size in composition B.

By “ sub-micron ” or in English “ sub-micronic ” we mean pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (µm), in particular between 0.1 and 0.9 µm, and preferably between 0.2 and 0.6 µm.

According to one embodiment, the dispersing agent and the pigment(s) are present in quantity (dispersant: pigment), according to a weight ratio, 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) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone type dispersants. 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 silicones (PDMS) 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 a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are cationic.

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

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

Preferably, the pigment(s) are chosen from iron oxides, in particular red, brown or black. As an example of iron oxide, we can cite iron oxide sold by the company Sun Chemical under the name SunPuro® Red Iron Oxide.

Direct dye

The composition used in the context of the device according to the invention may comprise one or more direct dye(s).

By “ direct dye ” we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes which will diffuse superficially on the fiber.

They can be ionic or non-ionic, preferably cationic or non-ionic.

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. We can mention the cationic hydrazono dyes of formulas (I) and (II), the cationic azo dyes (III) and (IV) below:
(I),
(II),
(III),
(IV),
formulas (I) to (IV) in which:
- Hét+ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally preferentially substituted 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-donor groups such as i) (C ₁ -C ₈ ) optionally substituted alkyl, ii) (C ₁ -C ₈ ) optionally substituted alkoxy, 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 ) optionally substituted alkyl-N-aryl(C ₁ -C ₈ )alkylamino or Ar represents a julolidine group;
- Ar'' represents an optionally substituted (hetero)aryl group such as optionally substituted phenyl or pyrazolyl, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl) groups )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 the Ra substituent with a Het+ substituent and/or Rb with an Ar substituent 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 mineral anionic counterion such as a halide or an alkyl sulfate.

Particularly, mention may be made of direct dyes with cationic endocyclic azo and hydrazono charges of formula (I) to (IV) as defined above; more particularly, the cationic direct dyes with endocyclic cationic charges described in patent applications WO 95/15144, WO 95/01772 and EP-714954; preferably the following direct dyes:
(V)
(VI),
Formulas (V) and (VI) in which:
- R ¹ represents a (C ₁ -C ₄ ) alkyl group such as methyl;
- R ² and R ³ , 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 donor group such as (C ₁ -C ₈ ) optionally substituted alkyl, (C ₁ -C ₈ ) optionally substituted alkoxy, (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 counterion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

Particularly, the dyes of formula (V) and (VI) 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 a alkyl sulfate such as methyl sulfate or mesytyl.

The direct dyes can be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances. By anionic direct dyes is meant any direct dye comprising in its structure at least one CO ₂ R or SO ₃ R substituent with R designating a hydrogen atom or a cation coming from a metal or an amine, or an ammonium ion . The anionic dyes can be chosen from direct nitrate acid dyes, azo acid dyes, azinic acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoids and natural acid dyes.

As acid dyes useful for the invention, mention may be made of the dyes of formulas (VII), (VII'), (VIII), (VIII'), (IX), (IX'), (X), (X). '), (XI), (XII), (XIII) and (XIV) following:

1. diaryl anionic azo dyes of formula (VII) or (VII'):
   (VII),
   (VII'),
   formulas (VII) and (VII') in which:
   - R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ , identical or different, represent a hydrogen atom or a group chosen from:
   - alkyl;
   - alkoxy, alkylthio;
   - hydroxy, mercapto;
   - nitro, nitroso;
   - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
   - (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
   - (O)CO--, M+ with M+ as defined previously;
   - R''-S(O) ₂ -, with R'' representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group;
   - R'''-S(O) ₂ -X'- with R''' representing an alkyl or optionally substituted aryl group, X' as defined above;
   - (di)(alkyl)amino;
   - aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+ and iv) alkoxy with M+ as defined above;
   - optionally substituted heteroaryl; preferably a benzothiazolyl group;
   - cycloalkyl, in particular cyclohexyl;
   - Ar-N=N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups, (O) ₂ S(O-)-, M+ or phenylamino;
   - or two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused group benzo A'; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a benzo B' fused group; with A' and B' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X'' and Ar as defined previously;
   - W represents a sigma σ bond, an atom of oxygen, sulfur, or a divalent radical i) –NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together with the carbon atom which carries them form a cycloalkyl spiro; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl;
   it being understood that formulas (VII) and (VII') comprise at least one sulfonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical (O)CO--, M+ on one of the rings A, A ', B, B' or C; preferably sodium sulfonate.

As an example of dyes of formula (VII) we can cite: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3 ; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; Food yellow 3 or sunset yellow;

and as an example of dyes of formula (VII') we can cite: Acid Red 111, Acid Red 134, Acid yellow 38;

b) the azo anionic pyrrazolone dyes of formula (VIII) and (VIII'):
(VIII),
(VIII'),
formulas (VIII) and (VIII') in which:
- R ₁₁ , R ₁₂ and R ₁₃ , identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or -(O) ₂ S(O-), M+ with M+ as defined above;
- R ₁₄ represents a hydrogen atom, an alkyl group or a -C(O)O-, M+ group with M+ as defined above;
- R ₁₅ represents a hydrogen atom;
- R ₁₆ represents an oxo group in which case R' ₁₆ is absent, or R ₁₅ with R ₁₆ together form a double bond;
- R ₁₇ and R ₁₈ , identical or different, represent a hydrogen atom, or a group chosen from:
- (O) ₂ S(O-)-, M+ with M+ as defined previously;
- Ar-OS(O) ₂ - with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups;
- R ₁₉ and R ₂₀ , together form either a double bond or a benzo D' group, optionally substituted;
- R' ₁₆ , R' ₁₉ and R' ₂₀ , identical or different, represent a hydrogen atom or an alkyl or hydroxy group;
- R ₂₁ represents a hydrogen atom, an alkyl, or alkoxy group;
- Ra and Rb, identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group;
- Y represents either a hydroxy group or an oxo group;
- represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;
it being understood that formulas (VIII) and (VIII') comprise at least one sulfonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+ on one of the rings D or E ; preferably sodium sulfonate;

As an example of dyes of formula (VIII) we can cite: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as an example of dyes of formula (VIII') we can cite: Acid Yellow 17;

c) the anthraquinone dyes of formula (IX) and (IX'):
(IX),
(IX'),
formulas (IX) and (IX') in which:
- R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- hydroxy, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferably substituted by one or more groups chosen from alkyl and (O) ₂ S(O-)-, M+ with M+ as defined above;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O) ₂ S(O-)-, M+ with M+ as defined above;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino
- (O) ₂ S(O-)-, M+ with M+ as defined previously;
- Z' represents a hydrogen atom or an NR ₂₈ R ₂₉ group with R ₂₈ and R ₂₉ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- polyhydroxyalkyl such as hydroxyethyl;
- aryl optionally substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-)-, M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°, X'' as defined above, preferably R° represents an alkyl group;
- cycloakyl, in particular cyclohexyl;
- Z represents a group chosen from hydroxy and NR' ₂₈ R' ₂₉ with R' ₂₈ and R' ₂₉ , identical or different, represent the same atoms or groups as R ₂₈ and R ₂₉ as defined above;
it being understood that formulas (IX) and (IX') comprise at least one sulfonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate;

As an example of dyes of formula (IX) we can cite: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT purple No. 2; and as an example of dyes of formula (IX') we can cite: Acid Black 48;

d) nitrate dyes of formula (X), (X'):
(X),
(X'),
formulas (X) and (X') in which:
- R ₃₀ , R ₃₁ and R ₃₂ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;
- hydroxy, mercapto;
- nitro, nitroso;
- polyhaloalkyl;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°; X, X' and X'' as defined previously;
- (O) ₂ S(O-)-, M+ with M+ as defined previously;
- (O)CO--, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R ₃₀ , R ₃₁ and R ₃₂ represent a hydrogen atom;
- Rc and Rd, identical or different, represent a hydrogen atom or an alkyl group;
- W is as defined previously; W particularly represents a –NH– group;
- ALK represents a linear or branched divalent alkylene group, C ₁ -C ₆ ; particularly ALK represents a –CH ₂ -CH ₂ - group;
- n is 1 or 2;
- p represents an integer inclusively between 1 and 5;
- q represents an integer inclusively between 1 and 4;
- u is 0 or 1;
- when n is 1, J represents a nitro, or nitroso group; particularly nitro;
- when n is 2, J represents an atom of oxygen, sulfur, or a divalent radical –S(O)m– with m representing an integer 1 or 2; preferably J represents a radical –SO ₂ –;
- M' represents a hydrogen atom or a cationic counterion;
- present or absent represents a benzo group optionally substituted by one or more R ₃₀ groups as defined above,
it being understood that formulas (X) and (X') comprise at least one sulfonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate.

As an example of dyes of formula (X) we can cite: Acid Brown 13; Acid Orange 3; as an example of dyes of formula (X') we can cite: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitro benzene acid sulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7;

e) triarylmethane dyes of formula (XI):
(XI),
formula (XI) in which:
- R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ , identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted by a (O)mS(O-)-, M+ group with M+ and m as defined above;
- R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
- or two contiguous groups R ₄₁ with R ₄₂ or R ₄₂ with R ₄₃ or R ₄₃ with R ₄₄ together form a fused group benzo: I'; with I' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; with M+, R°, X, X', X'' as defined previously; particularly R ₃₇ to R ₄₀ represent a hydrogen atom, and R ₄₁ to R ₄₄ , identical or different, represent a hydroxy group or (O) ₂ S(O-)-, M+; and when R ₄₃ with R ₄₄ together form a benzo group, it is preferentially substituted by a (O) ₂ S(O-)- group;
it being understood that at least one of the rings G, H, I or I' comprise at least one sulfonate radical (O) ₂ S(O-)- or a carboxylate radical -C(O)O-; preferably sulfonate.

As an example of dyes of formula (XI) we can cite: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

f) dyes derived from xanthene of formula (XII):
(XII),
formula (XII) in which:
- R ₄₅ , R ₄₆ , R ₄₇ and R ₄₈ , identical or different, represent a hydrogen atom or a halogen atom;
- R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
particularly R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ represent a hydrogen or halogen atom;
- G represents an oxygen or sulfur atom or an NRe group with Re as defined above; particularly G represents an oxygen atom;
- L represents an O-, M+ alkoxide; a thioalkoxide S-, M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined above; M+ is particularly sodium or potassium;
- L' represents an oxygen atom, sulfur or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl or aryl group optionally substituted; L' particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O)mS(O-)-, M+ with m and M+ as defined above;
- Q and Q', identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
- M+ is as defined previously.

As an example of dyes of formula (XII), we can cite: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

g) dyes derived from indole of formula (XIII):
(XIII),
formula (XIII) in which:
- R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ and R ₆₀ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
- G represents an oxygen or sulfur atom or an NRe group with Re as defined above; particularly G represents an oxygen atom;
- Ri and Rh, identical or different, represent a hydrogen atom or an alkyl group;
it being understood that formula (XIII) comprises at least one sulfonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate.

As an example of dyes of formula (XIII), we can cite: Acid Blue 74;

h) dyes derived from quinoline of formula (XIV):
(XIV),
formula (XIV) in which:
- R ₆₁ represents a hydrogen atom, a halogen atom or an alkyl group;
- R ₆₂ , R ₆₃ , and R ₆₄ , identical or different, represent a hydrogen atom or an (O) ₂ S(O-)-, M+ group with M+ representing a hydrogen atom or a cationic counterion ;
or R ₆₁ with R ₆₂ , or R ₆₁ with R ₆₄ , together form a benzo group optionally substituted by one or more groups (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a counter -cationic ion;
it being understood that formula (XIV) comprises at least one sulfonate radical (O) ₂ S(O-)-, M+ preferably sodium sulfonate.

As an example of dyes of formula (XIV) we can cite: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

Among the natural direct dyes which 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, apigenidin, orceins. We can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

Preferably, the direct dyes are chosen from anionic direct dyes.

The coloring agent(s) may be present in a total quantity ranging from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of the composition, preferably the coloring agent(s) are chosen from pigments.

The pigment(s) may be present in a total quantity ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 0.5 to 10% by weight relative to the total weight of the composition.

The direct dye(s) may be present in a total amount ranging from 0.001 to 10% by weight of the total weight of the composition, preferably from 0.005 to 5% by weight relative to the total weight of the composition.

Organic solvents:

The composition used in the context of the device according to the invention may comprise one or more organic solvents.

As an organic solvent, mention may for example be made of lower C ₁ -C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

Preferably, the composition according to the invention comprises one or more organic solvents chosen from lower C ₁ -C ₄ alkanols, more preferably ethanol.

When present, the organic solvents are present in a total content preferably inclusively between 0.5 and 95% by weight relative to the total weight of the composition, more preferably between 1 and 50% by weight, even more preferably between 2 and 20% by weight relative to the total weight of the composition.

Additives

The composition used in the context of the device according to the invention may contain any adjuvant or additive usually used.

Among the additives likely to be contained in the composition, mention may be made of reducing agents, softeners, dispersants, moisturizing agents, UV filters, peptizers, solubilizers, perfumes, proteins, vitamins, polymers. different from the polymer previously described, preservatives, oils, waxes and their mixtures.

The composition according to the invention may comprise water which may preferably be present in a content of less than 5% by weight, more preferably less than 1% by weight relative to the weight of the composition.

More preferably, the composition does not include water added during the preparation of the composition. Any water present may correspond to the residual water provided by the mixed ingredients.

According to a preferred embodiment, the composition according to the invention is an anhydrous liquid.

Device :

The aerosol device comprises at least one pressurized container comprising at least one propellant chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases.

The propellant(s) may or may not be present in the composition as described above.

The container of the device according to the invention can have rigid walls and directly contain the composition as described above.

Alternatively, the container may be rigid-walled and contain a flexible-walled pocket which contains the composition as described above.

According to this configuration, the composition in the bag may not include a propellant, the latter(s) being in the volume defined between the rigid walls of the container and the bag.

Preferably, the composition contained in the bag also comprises at least one propellant.

The device comprises means for delivering the compositions, the means comprising at least one dispensing valve which surmounts the container.

The valve is in selective fluid communication with the interior of the container via an inlet port of the valve, the communication being established in response to actuation of an actuation means, such as a push button.

When the device comprises a container with rigid walls which contains a flexible pocket, the valve is then provided with two inlet orifices, one of the orifices being able to communicate with the interior of the pocket and the other with the volume defined between the pocket and the rigid walls of the container.

When the container does not contain a pocket, it is equipped with a dip tube allowing the composition to be conveyed to the inlet port of the dispensing valve.

When the container contains a bag, the inlet port of the valve opens into the bag.

The device may include at least one diffuser which covers the valve. The push button may be part of the diffuser.

The diffuser may be provided with one or more distribution conduit(s) intended to convey the composition(s) to one or more distribution orifices.

Documents US 3,917,121, US 4,720,046, and WO 00/76880 disclose examples of devices.

The diffuser may include a single outlet orifice and diffusion branches which radiate from said orifice. Alternatively, the diffuser includes a plurality of outlet orifices. Advantageously, the outlet orifices can be arranged so as to obtain a diffusion grid.

Preferably, the pressurized container of the device according to the invention has rigid walls and directly contains the composition.

Preferably, the composition comprises at least one propellant chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases.

It should be noted that in the context of the invention, the propellant(s) can be used to allow the expulsion of the composition(s).

The propellant(s) are present in the pressurized container according to the invention preferably in a total content ranging from 1 to 99% by weight, more preferably from 10 to 98% by weight, better still from 40 to 97% by weight, better still from 70 to 96% by weight relative to the total weight of the composition (packaged in the aerosol device).

Preferably, the propellant(s) are present in the pressurized container according to the invention in a total quantity ranging from 1 to 99% by weight, more preferably from 10 to 98% by weight, better still from 40 to 97% by weight, better still from 70 to 96% by weight, relative to the total weight of the composition.

The propellant(s) is(are) chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases.

Preferably, the hydrocarbon gas(es) are propane, n-butane, and isobutane.

Advantageously, the coloring composition which is delivered from the pressurized container is in liquid form.

Coloring process:

The invention also relates to a process for coloring keratin fibers such as hair, comprising the application to said keratin fibers of a composition delivered from a device as defined above, possibly followed by drying.

The composition delivered by the aerosol device described above can be used on dry or wet keratin fibers, as well as on all types of fibers, light or dark, natural or colored, permed, bleached or straightened.

According to a particular embodiment of the process of the invention, the fibers are washed before application of the composition described above.

Thanks to the device according to the invention, the application is homogeneous over the entire hair.

The coloring process is generally carried out at room temperature (between 15 to 25°C).

After application of the composition, 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 220°C.

Drying, if carried out, can be carried out immediately after application or after an exposure time which can range from 1 minute to 30 minutes.

Preferably, if the fibers are dried, they are dried, in addition to heat, with an air flow. This air flow during drying improves the individualization of the sheathing.

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

The method according to the invention can thus include a step of applying heat to the keratin fibers using a heating tool.

The heat application step of the process of the invention can be implemented using a helmet, a hair dryer, a straightening or curling iron, a climazon, etc.

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

When the heat application step is carried out with a hair straightener, the drying temperature is between 110 and 220°C, preferably between 140 and 200°C.

The present invention will now be described more specifically by means of examples, which are in no way limiting the scope of the invention. However, the examples make it possible to support specific characteristics, variants, and preferred embodiments of the invention.

EXAMPLES

The compositions as described below were prepared: the quantities are expressed in g of raw material as is/100g, unless otherwise stated.

Compositions A1 A2 Crotonic Acid/Vinyl C ₈ - ₁₂ Isoalkyl Esters/VA/Bis-Vinyldimethicone Crosspolymer ⁽¹⁾ 2 2 IRON OXIDES (and) IRON OXIDES (and)TRIETHOXYCAPRYLYLSILANE (and) IRON OXIDES ⁽²⁾ 1.2 1.2 Clay 0.1 0.1 Ethanol QSP 100 QSP 100 Dimethyl ether 95 - n-butane - 95

(1) sold by the company Wacker Chemie AG under the trade name Belsil® P1101 (with 50% active ingredient in ethanol),
(2) sold by the company SENSIENT under the name 28510 BROWN BLEND.

Aerosol device:

Composition A1 is packaged in an aerosol device with dimethyl ether, in propellant/juice proportions 95/5. This composition A1 corresponds to the composition according to the invention.

Composition A2 is packaged in an aerosol device with n-butane in propellant/juice proportions 95/5. This A2 composition corresponds to the comparative composition.

The aerosol devices used include a 35x88 can equipped with a valve adapted to the propellant.

Composition A1 and composition A2 are delivered in liquid form at the outlet of the aerosol devices.

3g of composition A1 is applied to strands of 90% white natural hair.

3g of composition A2 is applied to strands of 90% white natural hair.

The hair strands are then left to dry at room temperature for 24 hours.

Color retention with shampoos:

The strands of hair thus colored are then subjected to a shampoo test in order to evaluate the tenacity (the persistence) of the coloring obtained with the shampoo, according to the shampoo protocol described below.

Shampoo protocol:

The hair strands are washed using a standard shampoo (Garnier Ultra Doux).

The hair strands are then rinsed, combed and dried with a hairdryer.

Results

The persistence of the color of the highlights was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).

In this L*a*b* system, L* represents the color intensity, a* indicates the green/red color axis and b* the blue/yellow color axis.

The persistence of the coloring is evaluated by the color difference ΔE between the colored strands before shampooing, then after having undergone 1 shampoo according to the protocol described above. The lower the value of ΔE, the more the color persists after shampooing.

The value of ΔE is calculated according to the following equation:

In this equation, L*a*b* represent the values measured after hair coloring and after shampooing, and L ₀ *a ₀ *b ₀ * represent the values measured after hair coloring but before shampooing.

Devices Number of shampoos L* has* b* ΔE A1 (Invention) 0 25.5 4.3 6.7 - 1 41.2 4.7 10.8 16.2 A2 (Comparison) 0 26.8 4.8 7.5 - 1 49.1 2.4 10.7 22.7

The strands of hair treated with the aerosol device according to the invention and washed with a shampoo have lower ΔE values than those of the strands of hair treated with the comparative device.

Thus, the colored sheathing obtained with the device according to the invention has improved persistence with shampoos.

In addition, the aerosol device according to the invention makes it possible to quickly and easily obtain uniform and chromatic coloring on the hair over the entire hair and which has good resistance to transfer.

Claims (13)

Aerosol device comprising:
- at least one pressurized container comprising:
a) at least one composition comprising:
i) one or more siliconized acrylic copolymers, and
ii) one or more coloring agent(s) chosen from pigments, direct dyes, and mixtures thereof, and,
b) at least one propellant chosen from dimethyl ether and mixtures of dimethyl ether with one or more hydrocarbon gases, and,
- a means for delivering the composition. Device according to claim 1, characterized in that the silicone acrylic copolymer(s) comprise:
- at least one acrylic or methacrylic or crotonic pattern; And
- at least one polydimethylsiloxane unit (PDMS). Device according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) comprise:
- at least one crotonic unit and at least one unit chosen from an alkyl crotonate unit, the alkyl radical being a linear or branched, saturated radical containing from 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms; and their mixtures; And
- at least one polydimethylsiloxane unit (PDMS). Device according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) comprise:
- at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 18 carbon atoms, and
- at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising at least one vinyl group. Device according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) comprise:
- at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms; And
- at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising a vinyl group. Device according to any one of the preceding claims, characterized in that the total quantity of siliconized acrylic copolymer(s) ranges from 0.01 to 30% by weight, preferably from 0.05 to 20% by weight. weight, more preferably from 0.1 to 15% by weight, better still from 0.5 to 10% by weight, even better from 0.5 to 5% by weight relative to the total weight of the composition. Device according to any one of the preceding claims, characterized in that the total quantity of coloring agent(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of the composition, preferably the coloring agent(s), are chosen from pigments. Device according to any one of the preceding claims, characterized in that the composition comprises one or more organic solvents chosen from lower C ₁ -C ₄ alkanols, more preferably ethanol. Device according to claim 8, characterized in that the organic solvents are present in a total content inclusively between 0.5 and 95% by weight relative to the total weight of the composition, more preferably between 1 and 50% by weight, again more preferably between 2 and 20% by weight relative to the total weight of the composition. Device according to any one of the preceding claims, in which the container has rigid walls and directly contains the composition. Device according to any one of the preceding claims, characterized in that the hydrocarbon gas(es) are propane, n-butane, and isobutane. Device according to any one of the preceding claims, characterized in that the propellant(s) are present in the pressurized container in a total quantity ranging from 1 to 99% by weight, more preferably from 10 to 98% by weight, better 40 to 97% by weight, better still 70 to 96% by weight, relative to the total weight of the composition. Process for coloring keratin fibers, such as hair, comprising the application to said keratin fibers of a composition delivered from a device according to any one of claims 1 to 12, optionally followed by drying.