FR3109304A1 - PROCESS FOR DENSIFICATION OF KERATINIC FIBERS BASED ON ACRYLIC SILICONE COPOLYMER AND A COLORING AGENT - Google Patents

Abstract

PROCESS FOR DENSIFYING KERATINIC FIBERS BASED ON SILICONE ACRYLIC COPOLYMER AND A COLORING AGENT The present application relates to a process for coloring an area of skin supporting keratin fibers, consisting in applying to said area of skin, and optionally on said keratin fibers, a composition comprising at least one silicone acrylic copolymer, and at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

Description

METHOD FOR DENSIFYING KERATIN FIBERS BASED ON SILICONE ACRYLIC COPOLYMER AND A COLORING AGENT

The subject of the present invention is a process for the visual densification of keratin fibers, more particularly hair and most especially their roots, beard hair, mustache, eyelashes and eyebrows, by coloring at least one area of the skin supporting said keratin fibers and optionally coloring said keratin fibers. More particularly, the method consists in coloring the skin which supports the keratin fibers using a composition comprising at least one silicone acrylic copolymer, at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

It is known to use, in the cosmetics industry, compositions which make it possible to visually densify keratin fibers such as hair or body hair such as eyelashes, eyebrows, beard or mustache hair.

For example, for a visual densification of the eyebrows, it is known to use felt-tip pens or tattoo pens to draw lines imitating the presence of eyelashes and to visually fill out the eyebrows, in particular when they are sparse. However, these products cannot always modify the initial color of the eyebrows and the color provided is not very persistent over time and not very resistant to water or sweat.

Furthermore, it is possible to carry out a permanent coloring of keratin fibers such as the hairs of the eyebrows or of the mustache using so-called oxidation colorings which consist in applying to the hair one or more dye precursors and an agent oxidant.

However, these methods do not result in providing sufficient densification where the density of the keratin fibers is lower and/or irregular.

Thus, the aim of the present invention is to propose a method making it possible to obtain a visual, natural densification effect of the keratin fibres, and which lasts over time.

This object is achieved with the present invention, the subject of which is a process consisting in coloring, using a particular composition, at least one zone of the skin which supports the keratin fibers and optionally in also coloring the said keratin fibers.

The subject of the present invention is a process for dyeing an area of skin supporting keratin fibers, consisting in applying to said area of skin, and optionally to said keratin fibers, a composition comprising:
a) at least one silicone acrylic copolymer comprising at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from an acrylic or methacrylic group having from 1 to 6 carbon atoms, and
- at least one alkyl acrylate or methacrylate unit, and,
b) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

The present invention also relates to a kit for coloring an area of skin supporting keratin fibres, comprising a coloring composition as defined above, and a makeup-removing composition as defined below.

The expression " at least one " means one or more.

By “ keratinous fibers ”, is meant in particular the hair, the hairs such as the eyelashes, the eyebrows, the hairs of the beard or mustache.

The area of the skin which supports the keratinous fibers can be the skin of the scalp, the skin at the level of the eyebrows, the eyelashes, the skin of the face which bears the hairs of the beard, mustache, the sideburns of the hair on the time.

The process according to the invention makes it possible to obtain, by coloring the skin close to the keratin fibres, an effect of visual densification of the keratin fibres. The coloration obtained is resistant to shampoos or washing, or to external aggressions that the fibers may suffer, such as brushing and perspiration. In particular, it makes it possible to obtain a smooth and homogeneous deposit.

Furthermore, this composition makes it possible to obtain the skin and the colored keratinous fibers which can be easily removed either immediately after the application of the coloring composition or either after a certain time, i.e. a few days to a few weeks, after the application of the coloring composition.

The invention is not limited to the examples illustrated. The characteristics of the various examples can in particular be combined within variants that are not illustrated.

The composition according to the invention is preferably a composition for coloring an area of skin supporting keratin fibres, such as the hair.

Siliconized acrylic copolymer

The process according to the invention comprises a composition comprising at least one silicone acrylic copolymer comprising at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from an acrylic or methacrylic group having from 1 to 6 carbon atoms, and
- at least one alkyl acrylate or methacrylate unit.

Preferably, the copolymer according to the invention is insoluble in water. By insoluble in water is meant, within the meaning of the present invention, a compound that is insoluble in water at ordinary temperature (25° C.) and at atmospheric pressure (760 mm Hg or 1.013.105 Pa). Preferably, the copolymer according to the invention has a solubility in water of less than 5%, better still less than 1% and even more preferentially less than 0.1%.

By “ alkyl acrylate or methacrylate unit ”, is meant a unit derived from an alkyl acrylate or methacrylate monomer.

Preferably, the silicone acrylic copolymer comprises at least two alkyl acrylate or methacrylate units.

The term “ polydimethylsiloxanes ” (also abbreviated as PDMS) is intended to denote, in accordance with general acceptance, any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are interconnected by oxygen atoms (siloxane bond -Si-O-Si-), comprising methyl radicals directly bonded via of 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 two polymerizable radical groups, preferably located on each end of the chain, that is to say that the PDMS can have for example a radical group polymerizable on each of the two ends of the chain.

By " polymerizable radical group " is meant a radical capable of polymerizing with other polymerizable radical groups or monomers.

By “ end of the chain ”, is meant the terminal group of the polydimethylsiloxane unit consisting of a dimethylsiloxane group, the polydimethylsiloxane unit comprising two ends each having a terminal group (ie dimethylsiloxane group).

Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable radical group located on each end of the chain, the polymerizable radical group being chosen from an acrylic or methacrylic group having from 1 to 6 carbon atoms.

Preferably, the polymerizable radical group is a CH ₂ =CH-CO-O-R1- group, where R1 represents an alkyl radical comprising from 1 to 3 carbon atoms.

The copolymers used in the composition are generally obtained according to the usual methods of polymerization and grafting, for example by radical polymerization (A) of a polyalkylsiloxane comprising at least two polymerizable radical groups (for example located on each end of the chain) and (B) at least one acrylic or methacrylic monomer, such as acrylic acid, methacrylic acid or one of their esters, as described for example in documents US-A-5,061,481 and US-A-5,219,560.

Preferably, the composition comprises at least one silicone acrylic copolymer, comprising at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from an acrylic or methacrylic group having from 1 to 6 carbon atoms, and,
- at least one alkyl acrylate or methacrylate unit, the alkyl radical comprising from 1 to 30 carbon atoms, preferentially from 1 to 22 carbon atoms, better still 1 to 10 carbon atoms, and more preferentially 2 to 6 carbon atoms .

Preferably, the composition comprises at least one silicone acrylic copolymer, comprising at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from a CH ₂ = CH – CO – O – R1- group, where R1 represents an alkyl radical comprising from 1 to 3 carbon atoms; And
- at least one C ₁ -C ₃₀ alkyl acrylate or methacrylate unit, preferably C ₁ -C ₂₂ , preferably C ₁ -C ₁₀ , better still C ₂ -C ₆ .

Even more particularly, the composition according to the invention comprises at least one silicone acrylic copolymer comprising at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from a CH ₂ = CH – CO – O – R1- group, where R1 represents an alkyl radical comprising from 1 to 3 carbon atoms; And
- at least one C ₁ -C ₂₂ alkyl acrylate or methacrylate unit, preferably C ₁ -C ₁₀ , better still C ₂ -C ₆ .

Even more particularly, the silicone acrylic copolymer according to the invention is a copolymer with the INCI name isobutylmethacrylate/bis-hydroxypropyl dimethicone acrylate copolymer, such as for example the compound marketed by the company GRANT INDUSTRIES under the name GRANACRYSIL BMAS.

It is an isobutyl methacrylate/bis-hydroxypropyl dimethicone acrylate copolymer, in solution in isododecane.

The silicone acrylic copolymer(s) may be present in a total amount varying from 1% to 50% by weight, preferably from 2% to 40% by weight, plus preferably from 3% to 35% by weight, better still from 5% to 30% by weight relative to the total weight of the composition.

Coloring Agent :

The process according to the invention comprises a composition comprising at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

Preferably, the composition according to the invention comprises one or more pigments.

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

The pigments which can be used are chosen in particular 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.

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, 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, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type compounds, 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 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 pearls marketed by BASF (Mica-TiO2-lacquer), Prestige marketed by Eckart (Mica-TiO2), Prestige Bronze marketed by Eckart (Mica-Fe2O3) Colorona marketed by Merck (Mica- TiO2-Fe2O3).

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 SiO2 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.

By “sub-micronic” or in English “sub-micronic” is meant pigments whose particle size has been micronized by the 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 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 backbone, such as silicone polyether and dispersants of the amino-silicone type. 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 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”, we mean 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 (I) and (II), the cationic azo dyes (III) and (IV) below:

(I)

(II)

(III)

(IV)

formulas (I) to (IV) 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 (I) to (IV) 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:

(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 , 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 (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 an alkyl sulphate such as methyl sulfate or mesyl.

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 originating from a metal or an amine, or an ammonium ion . The anionic dyes can be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

As acid dyes according to the invention, mention may be made of the dyes of formulas (VII), (VII'), (VIII), (VIII'), (IX), (IX'), (X), (X' ), (XI), (XII), (XIII) and (XIV) as follows:

a) diaryl anionic azo dyes of formula (VII) or (VII'):

(VII)

(VII')

formula (VII) and (VII') in which:
- R ₇ , R ₈ , R ₉ , R ₁₀ , R′ ₇ , R′ ₈ , R′ ₉ and R′ ₁₀ , which are 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 above;
- 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 optionally substituted alkyl or aryl group, X' as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy with M+ as defined above;
- optionally substituted heteroaryl; preferentially 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, (O)2S(O-)-, M+ or phenylamino groups;
- or else two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused benzo A'group; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a fused group benzo B'; with A' and B' optionally substituted with 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 above;

- W represents a sigma σ bond, an oxygen or sulfur atom, 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 else Ra and Rb form together with the carbon atom which carries them a cycloalkyl spiro; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl;
it being understood that the formulas (VII) and (VII') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical (O)CO--, M+ on one of the rings A, A ', B, B' or C; preferentially sodium sulfonate;

By way of example of dyes of formula (VII), mention may be made of: 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 by way of example of dyes of formula (VII'), mention may be made of: Acid Red 111, Acid Red 134, Acid yellow 38.

b) the anionic azo 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)₂S(O-), M+ with M+ as previously defined;
-R ₁₄ represents a hydrogen atom, an alkyl group or a -C(O)O- group, M+ with M+ as defined above;
-R ₁₅ represents a hydrogen atom;
-R ₁₆ represents an oxo group in which case R'₁₆is absent, or elseR ₁₅ withR ₁₆ together form a double bond;
-R ₁₇ and R ₁₈ , which are identical or different, represent a hydrogen atom, or a group chosen from:
- (O)₂S(O-)-, M+ with M+ as previously defined;
- Ar-O-S(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 group D', optionally substituted;
-R' ₁₆ , R' ₁₉ and R' ₂₀ , which are identical or different, represent a hydrogen atom or an alkyl or hydroxy group;
-R ₂₁ represents a hydrogen atom, an alkyl or alkoxy group;
-R _To and R _b identical or different, are as defined above, preferably R_Torepresents a hydrogen atom and R_brepresents an aryl group;
-Yrepresents 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 the formulas (VIII) and (VIII') comprise at least one sulphonate 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 examples of dyes of formula (VIII), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (VIII'), mention may be made of: Acid Yellow 17;

c) 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, halogen atom, or a group chosen from:
- alkyl;
- hydroxy, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferentially 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)2S(O-)-, M+ with M+ as defined above;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino
- (O) ₂ S(O-)-, M+ with M+ as defined above;

Z' represents a hydrogen atom or an NR28R29 group with R28 and R29, which are 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) ₂ S(O-)-, M+ with M+ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°, X, X' and X'' as defined above, preferably R° represents an alkyl group;
- cycloalkyl; in particular cyclohexyl;

Z represents a group chosen from hydroxy and NR′28R′29 with R′28 and R′29, which are identical or different, represent the same atoms or groups as R28 and R29 as defined previously;
it being understood that the formulas (IX) and (IX') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate;

Examples of dyes of formula (IX) include: 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 #2; and by way of example of dyes of formula (IX′), mention may be made of: Acid Black 48;

d) nitro dyes of formula (X), (X'):

(X)

(X')

formulas (X) and (X') in which:
- R ₃₀ , R ₃₁ and R ₃₂ , which are identical or different, represent a hydrogen or 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 above;
- (O)CO--, M+ with M+ as defined above;
- (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 an –NH– group;
- ALK represents a divalent linear or branched, C ₁ -C ₆ alkylene group; particularly ALK represents a -CH ₂ -CH ₂ - group;
- n is 1 or 2;
- p represents an integer comprised inclusively between 1 and 5;
- q represents an integer comprised inclusively between 1 and 4;
- u is 0 or 1;
- when n is 1, J represents a nitro or nitroso group; especially nitro;
- when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –S(O)m– with m representing an integer 1 or 2; preferably J represents a -SO2- radical;
- M' represents a hydrogen atom or a cationic counterion;
- present or absent represents a benzo group optionally substituted by one or more R30 groups as defined above
it being understood that the formulas (X) and (X') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate.

By way of example of dyes of formula (X), mention may be made of: Acid Brown 13; Acid Orange 3; as examples of dyes of formula (X'), mention may be made of: 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;

d) triarylmethane dyes of formula (XI):

(XI)

formula (XI) in which:
- R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ , which are 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 an (O) _m S(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 above;
- or else two contiguous groups R ₄₁ with R ₄₂ or R ₄₂ with R ₄₃ or R ₄₃ with R ₄₄ together form a fused benzo group: 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;
in particular R ₃₇ to R ₄₀ represent a hydrogen atom, and R ₄₁ to R ₄₄ , which are identical or different, represent a hydroxy or (O) ₂ S(O-)-, M+ group; and when R ₄₃ with R ₄₄ together form a benzo group, it is preferentially substituted by an (O) ₂ S(O-)- group;
it being understood that at least one of the rings G, H, I or I' comprises at least one sulphonate radical (O) ₂ S(O-)- or a carboxylate radical -C(O)O-; preferentially sulfonate;

By way of example of dyes of formula (XI), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50;

e) dyes derived from xanthene of formula (XII):

(XI)

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 , which are identical or different, represent a hydrogen or 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 above;
particularly R ₅₃ R ₅₄ , R ₅₅ and R ₄₈ 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 alcoholate O-, M+; an S-, M+ thioalcoholate 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 or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; L' represents in particular an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O) _m S(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;

By way of example of dyes of formula (XII), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

f) dyes derived from indole of formula (XIII):

(XIII)

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 previously; particularly G represents an oxygen atom;
- Ri and Rh, identical or different, represent a hydrogen atom or an alkyl group;
it being understood that the formula (XIII) comprises at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate

Examples of dyes of formula (XIII) include: Acid Blue 74.

g) dyes derived from quinoline of formula (XIV):

(XIV)

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

By way of example of dyes of formula (XIV), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

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.

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

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

The pigment(s) may be present in a total content ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 1 to 10% by weight relative to the total weight of the composition .

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

Silicone resin

The method according to the invention comprises a composition which may comprise at least one silicone resin.

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

The silicone resin(s) according to the invention can be chosen from silicone resins having a molecular weight of between 300 and 100,000 g/mol, preferably between 300 and 50,000 g/mol, more preferably between 300 and 30,000 g/mol. soft. The term "molecular weight" means average molecular weight (Mw).

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

The letter “M” represents the monofunctional unit of formula R1R2R3SiO _1/2 , the silicon atom being linked to a single oxygen atom in the polymer comprising this unit.

The letter "D" means a Difunctional unit R1R2SiO _2/2 in which the silicon atom is connected to two oxygen atoms

The letter “T” represents a Trifunctional unit of formula R1SiO _3/2 .

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

In the units M, D, T defined above, R, namely R1, R2 and R3, represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a group hydroxyl.

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

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

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

MQ Resins:

As an example of silicone resins of the MQ type, mention may be made of the alkylsiloxysilicates of formula [(R1) ₃ SiO _1/2 ]x(SiO ₂ )y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R1 represents a radical as defined previously, and is preferably an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

As an example of solid silicone resins of the MQ type of the trimethylsiloxysilicate type, mention may be made of those marketed under the reference SR1000®, E 1 170-002® or SS 4230® by the company General Electric, under the reference TMS 803®, WACKER 803® and 804® by Wacker, under the name "KF-7312J®" by Shin-Etsu, "DC 749®", "DC 593®" by Dow Corning, under the name Silsoft 74 by Momentive Performance Materials.

As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151® marketed by General Electric). The preparation of such resins is described in particular in patent US5817302.

T-resins:

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

Preferably, it is possible to use polymethylsilsesquioxane resins in which R represents a methyl group, such as for example those marketed:
- by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: polymer comprising repeating units CH ₃ SiO _3/2 (T units), which may also comprise up to 1% by weight of units (CH ₃ ) ₂ SiO _2/2 (D units) and having an average molecular weight of approximately 10000 g/mol, or
- by the company SHIN-ETSU under the references KR 220L® which are composed of T units of formula CH ₃ SiO _3/2 and have end groups Si OH (silanol), under the reference KR-242A® which comprise 98% of T units and 2% of dimethyl D units and have Si-OH terminal groups or under the reference KR 251® comprising 88% of T units and 12% of dimethyl D units and have Si-OH terminal groups Oh or
- by the company GRANT INDUSTRIES under the name GRANRESIN PMSQ ID with 80% polymethylsilsesquioxane in isododecane.

MQT resins:

As a resin comprising MQT units, those cited in document US Pat. No. 5,110,890 are known in particular.

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

The MQ-T-propyl resin preferably comprises the units:
(i) (R1 ₃ SiO _1/2 ) _a
(ii) (R2 ₂ SiO _2/2 ) _b
(iii) (R3SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d

With R1, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon or a phenyl group.
a, b, c and d being molar fractions,
a being between 0.05 and 0.5,
b being between zero and 0.3,
c being greater than zero,
d being between 0.05 and 0.6,
a+b+c+d=1,
provided that more than 40 mole % of the R3 groups of the siloxane resin are propyl groups.

Preferably, the siloxane resin comprises the units:
(i) (R1 ₃ SiO _1/2 ) _a
(iii) (R3SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d
With R1 and R3 independently representing an alkyl group having 1 to 8 carbon atoms, R1 preferably being a methyl group and R3 preferably being a propyl group,
a being between 0.05 and 0.5, preferably between 0.15 and 0.4,
c being greater than zero, preferably between 0.15 and 0.4,
d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or even between 0.2 and 0.55,
a + b + c + d = 1, and a, b, c and d being molar fractions,
provided that more than 40 mole % of the R3 groups of the siloxane resin are propyl groups.

The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of:
A) an MQ resin comprising at least 80% by mole of (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _{d units}
R1 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
a and d being greater than zero,
the a/d ratio being between 0.5 and 1.5; And
B) a propyl T resin comprising at least 80% by mole of (R3SiO _3/2 ) _c units,
R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
c being greater than zero,
provided that at least 40% by mole of the R3 groups are propyl groups,
where the A/B mass ratio is between 95:5 and 15:85, preferably the A/B mass ratio is 30:70.

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

Preferably, the composition according to _the invention comprises, as silicone resin, at least one silicone resin of type T, better still a silicone resin of polysilsesquioxane type of formula (RSiO _3/2 ) _x in which x is greater than 100 and the group R is an alkyl group having from 1 to 10 carbon atoms, more preferably at least one silicone resin of the polymethylsilsesquioxane type.

According to a preferred embodiment of the invention, the silicone resin is present in the composition in a content ranging from 0.01% to 10% by weight, preferably ranging from 0.05% to 5% by weight, more preferably ranging from 0.05% to 3% by weight relative to the total weight of the composition.

Oils

The method according to the invention comprises a composition which may comprise one or more oil(s).

Preferably, the composition comprises one or more oil(s) chosen from alkanes.

By “oil”, is meant a fatty substance that is liquid at ambient temperature (25° C.) and at atmospheric pressure (760 mm Hg or 1.013×10 ⁵ Pa).

The oil can be volatile or non-volatile.

By "volatile oil" is meant an oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. Volatile oil is a volatile cosmetic oil, liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm ² /min, limits included (see protocol for measuring the evaporation rate indicated in the text below).

By “non-volatile oil”, is meant an oil remaining on the skin or the keratin fiber at ambient temperature and atmospheric pressure. More specifically, a non-volatile oil has an evaporation rate strictly lower than 0.01 mg/cm ² /min (see protocol for measuring the evaporation rate indicated in the text below).

Preferably, the composition comprises one or more oil(s) chosen from C ₈ -C ₁₆ alkanes and/or mixtures thereof.

As regards the C ₈ -C ₁₆ alkanes, the latter can be linear, branched, possibly cyclic.

Mention may in particular be made of branched C ₈ -C ₁₆ alkanes such as C ₈ -C ₁₆ iso-alkanes (also called isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the names commercial Isopars or Permetyls, and mixtures thereof.

Mention may also be made of linear alkanes, preferably of plant origin, comprising from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms, and more particularly from 11 to 13 carbon atoms.

By way of example of a linear alkane suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), -pentadecane (C15), and mixtures thereof, and in particular the mixture of n -undecane (C11) and n-tridecane (C13) described in example 1 of application WO2008/155059 from Cognis.

Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures.

By way of example of alkanes suitable for the invention, mention may be made of the alkanes described in patent applications WO 2007/068371 and WO2008/155059. These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.

According to a particular embodiment, the composition comprises isododecane. Such a compound is for example isododecane sold under the reference ISODODECANE by INEOS.

Preferably, the composition according to the invention comprises one or more oil(s) chosen from C ₈ -C ₁₆ alkanes, more preferably from isododecane, isohexadecane, tetradecane and/or mixtures thereof.

More preferentially, the composition comprises isododecane.

The composition according to the invention may comprise one or more oils present in a total amount of between 10% and 99% by weight, preferably between 20% and 95% by weight, better still between 30% and 90% by weight relative to the total weight of the composition.

The composition according to the invention may comprise water present in a content ranging from 0% to 30% by weight, more preferably from 0% to 20% by weight relative to the total weight of the composition.

The composition according to the invention may comprise less than 2% by weight of water, or even less than 0.5% by weight of water relative to the total weight of the composition.

Preferably, the composition does not include water.

Additives :

The method according to the invention comprises a composition which may contain any adjuvant or additive usually used.

Among the additives which may be contained in the composition, mention may be made of reducing agents, thickening agents, softeners, antifoaming agents, moisturizing agents, UV filters, peptizers, solubilizers, perfumes, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers, preservatives, oils, waxes and mixtures thereof.

The composition according to the invention may in particular be in the form of a suspension, dispersion, gel, emulsion, in particular oil-in-water (O/W) or water-in-oil (W/O) emulsion, or multiple (W/O/W or polyol/O/W or O/W/O), in the form of cream, foam, stick, dispersion of vesicles in particular of ionic or nonionic lipids, biphase or multiphase lotion.

The person skilled in the art will be able to choose the appropriate galenic form, as well as its method of preparation, on the basis of his general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand of the intended application for the composition.
Process for coloring and removing make-up and/or cleaning an area of skin bearing keratin fibers

The present invention relates to a method for dyeing an area of skin supporting keratin fibers, consisting in applying to said area of skin, and optionally to said keratin fibers, a dye composition as described above.

The composition described above can be used on an area of skin supporting dry or wet keratin fibers and on all types of skin and fibers.

The application on the skin can be carried out using a brush, a felt, or a brush.

The application to the keratin fibers of the skin zone can be implemented by any conventional means, in particular by means of a comb, a brush, a brush such as a mascara brush or the fingers .

The application to the skin and the keratin fibres, where applicable, can be carried out using the same means of application or using a different means.

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. According to a particular embodiment, this temperature is greater than 45°C and less than 220°C.

A drying step can be carried out at the level of the zone of skin supporting the keratin fibers immediately after the application of the composition or after an exposure time which can range from 1 minute to 30 minutes.

During drying, a mechanical action on the zone of skin supporting keratin fibers 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.

The drying step can for example be implemented with a helmet or a hair dryer.

Preferably, the method according to the invention comprises a step of applying to said area of skin a makeup-removing composition comprising at least one hydrocarbon-based oil.

Thus, the method according to the invention may comprise a step of applying a makeup-removing composition to an area of skin supporting keratin fibers. This step can take place following the coloring of the area of skin supporting keratin fibers with the coloring composition as described above, optionally after a defined time, i.e. days or weeks, after application of the coloring composition on said area of skin.

The makeup-removing composition may correspond to a makeup-removing composition conventionally used in cosmetics. Preferably, the makeup-removing composition comprises at least one hydrocarbon-based oil.

Preferably, the hydrocarbon oil or oils are chosen from synthetic esters of formula R ₁ COOR ₂ in which R ₁ represents the residue of a fatty acid comprising from 8 to 29 carbon atoms, and R ₂ represents a hydrocarbon chain, branched or not, containing from 3 to 30 carbon atoms, and mixtures thereof, more preferably from isopropyl myristate, isononyl isononanoate and/or mixtures thereof.

Preferably, the application of the coloring composition to said area of skin is carried out before the application of a makeup-removing composition.

The application of the makeup-removing composition can be carried out on an area of skin supporting dry or wet keratin fibers as well as on all types of skin.

The make-up removal process is generally carried out at room temperature (between 15 and 25°C).

The application of the makeup-removing composition can be carried out immediately after the application of the coloring composition (i.e. a few minutes to a few hours after the application of the coloring composition), or in the days or weeks which follow the application of the coloring composition.

The makeup-removing composition can be applied using any suitable medium, in particular capable of absorbing it, for example a fibrous makeup-removing disc, for example a woven or non-woven, wadding, a flocked film, a sponge, a wipe, or a twist-on or injection-molded mascara applicator brush.

The make-up-removing composition can be contained in a container and withdrawn as and when each make-up removal. As a variant, the makeup-removing composition impregnates the support used for removing makeup, it being possible in this case for the support to be packaged, for example, in a sealed packaging.

After using the makeup-removing composition, the skin area may not be rinsed off. Alternatively, it may be. Rinsing can be done for example with running water, without adding soap.

The present invention will now be described more specifically by means of examples, which are in no way limiting of the scope of the invention. However, the examples support specific features, variations, and preferred embodiments of the invention.

Example

The following compositions are prepared:

Coloring composition: Compositions (g /100g)

Composition AT B Isobutylmethacrylate/bis-hydroxypropyl dimethicone acrylate copolymer (with 40% active ingredient in isododecane) ⁽¹⁾ 25 25 Polymethylsilsesquioxane (and) Isododecane ⁽²⁾ - 0.25 pigment 6 6 Isododecane Qsp 100 Qsp 100

(1) sold under the trade name Granacrysil BMAS by the company Grant industries,
(2) sold under the name Granresin PMSQ-ID by the company Grant Industries,

Protocol:

Composition A and composition B are applied with the finger to areas of skin bearing keratin fibers (this is a forearm with hair) at the rate of 2 mg per cm ² of skin.

The areas of skin covered by composition A and by composition B are then dried quickly with a hair dryer.

After a few seconds, the hairs on the skin areas are dry, colored and visually appear denser.

In addition, the color on the hair and skin is persistent with water and a few washes with soap.

Claims (13)

Process for dyeing an area of skin supporting keratin fibers, consisting in applying to said area of skin, and optionally to said keratin fibers, a composition comprising:
a) at least one silicone acrylic copolymer comprising at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from an acrylic or methacrylic group having from 1 to 6 carbon atoms, and
- at least one alkyl acrylate or methacrylate unit, and,
b) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof. Process according to Claim 1, characterized in that the silicone acrylic copolymer comprises at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from an acrylic or methacrylic group having from 1 to 6 carbon atoms and,
- at least one alkyl acrylate or methacrylate unit, the alkyl radical comprising from 1 to 30 carbon atoms, preferentially from 1 to 22 carbon atoms, better still 1 to 10 carbon atoms, and more preferentially 2 to 6 carbon atoms . Process according to any one of the preceding claims, characterized in that the silicone acrylic copolymer comprises at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from a CH ₂ = CH – CO – O – R1- group, where R1 represents an alkyl radical comprising from 1 to 3 carbon atoms; And
- at least one C ₁ -C ₃₀ alkyl acrylate or methacrylate unit, preferably C ₁ -C ₂₂ , preferably C ₁ -C ₁₀ , better still C ₂ -C ₆ . Process according to any one of the preceding claims, characterized in that the silicone acrylic copolymer comprises at least the following units:
- at least one polydimethylsiloxane (PDMS) unit comprising at least two polymerizable radical groups chosen from a CH ₂ = CH – CO – O – R1- group, where R1 represents an alkyl radical comprising from 1 to 3 carbon atoms; And
- at least one C ₁ -C ₂₂ alkyl acrylate or methacrylate unit, preferably C ₁ -C ₁₀ , better still C ₂ -C ₆ . Process according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) is (are) present in a total quantity varying from 1% to 50% by weight , preferably from 2% to 40% by weight, more preferably from 3% to 35% by weight, better still from 5% to 30% by weight relative to the total weight of the composition. Process according to any one of the preceding claims, characterized in that the composition comprises at least one silicone resin, the silicone resin preferably being a T-type silicone resin, better still a silicone resin of the polysilsesquioxane type of formula (RSiO _3/2 ) x in which x is greater than 100 and the group R is an alkyl group having from 1 to 10 carbon atoms, and more preferably at least one silicone resin of the polymethylsilsesquioxane type . Process according to Claim 6, characterized in that the silicone resin is present in the composition in a content ranging from 0.01% to 10% by weight, preferably ranging from 0.05% to 5% by weight, more preferably ranging from 0.05% to 3% by weight relative to the total weight of the composition. Process according to any one of the preceding claims, characterized in that the composition comprises one or more oil(s), preferably one or more oil(s) chosen from C ₈ -C ₁₆ alkanes, more preferably from isododecane, isohexadecane, tetradecane and/or mixtures thereof. Method according to any one of the preceding claims, characterized in that it implements a step of applying to the said area of skin a makeup-removing composition comprising at least one hydrocarbon-based oil. Process according to Claim 9, characterized in that the hydrocarbon oil(s) is (are) chosen from synthetic esters of formula R ₁ COOR ₂ in which R ₁ represents the residue of a fatty acid containing from 8 to 29 carbon atoms, and R ₂ represents a hydrocarbon chain, branched or not, containing from 3 to 30 carbon atoms, and mixtures thereof. Process according to any one of Claims 9 or 10, characterized in that the hydrocarbon oil(s) is (are) chosen from isopropyl myristate, isononyl isononanoate and /or mixtures thereof. Process according to any one of Claims 9 to 11, characterized in that the application of the coloring composition as defined according to any one of Claims 1 to 8 to the said area of skin is carried out before the application of the make-up remover composition. Kit for coloring an area of skin supporting keratin fibres, comprising:
- a coloring composition as defined according to any one of claims 1 to 8, and
- a makeup-removing composition as defined according to any one of claims 9 to 11.