COMPOSITION AND DYEING PROCESS OF KERATINOUS FIBERS

FR3157178B3Active Publication Date: 2026-01-02LOREAL SA
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Patent Information

Application Number
FR2024000876
Authority / Receiving Office
FR · FR
Patent Type
Utility models
Current Assignee / Owner
Priority Date
2023-12-20
Filing Date
2024-01-30
Publication Date
2026-01-02
Estimated Expiration
2034-01-30

AI Technical Summary

Technical Problem

Existing hair dyeing methods, particularly temporary dyeing, struggle with poor water resistance and durability against external agents such as sebum, perspiration, brushing, and rubbing actions.

Method used

A composition comprising at least one protein, at least one alkoxysilane, and at least one coloring agent, which forms a persistent colored coating on keratinous fibers like hair, enhancing water resistance and durability.

Benefits of technology

The composition effectively forms a long-lasting colored coating on hair that withstands water and various hair-related stresses, such as brushing and rubbing, improving the durability of the hair color.

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Abstract

COMPOSITION AND PROCESS FOR DYEING KERATINOUS FIBERS The present invention relates to a composition comprising: a) at least one protein; b) at least one alkoxysilane; and c) at least one coloring agent selected from pigments, direct dyes, and mixtures thereof. The present invention also relates to a process for dyeing keratinous fibers such as hair, comprising applying said composition to the keratinous fibers such as hair. Figure for abstract: none
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Description

Title of the invention: COMPOSITION AND PROCESS FOR DYEING KERATINOUS FIBERS Technical field

[0001] The present invention relates to a composition. In particular, the present invention relates to a composition for dyeing keratinous fibers such as hair. The present invention also relates to a process for dyeing keratinous fibers, such as hair. STATE OF THE ART

[0002] Many people have long been looking to change their hair color, and especially to hide their gray hair.

[0003] In the field of dyeing keratinous fibers, in particular human keratinous fibers, it is already known to dye keratinous fibers by means of various techniques using direct dyes or pigments for non-permanent dyeing, or dye precursors for permanent dyeing.

[0004] There are basically three types of processes for dyeing hair: a. “permanent” dyeing, the function of which is to make a substantial change to the natural color and which uses oxidation dyes which penetrate the hair fibers and form the dye by a process of oxidative condensation; b. non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists of dyeing the hair with dye compositions containing direct dyes; c. temporary dyeing, which results in a change in the natural hair color that remains from one shampoo to the next, and which serves to enhance or correct a shade that has already been achieved. It can also be likened to a "makeup" process.

[0005] The temporary dyeing process involves the use of pigments. Specifically, the use of pigments on the surface of keratinous fibers generally makes it possible to obtain visible colorations on dark hair, because the surface pigment masks the natural color of the fibers.

[0006] However, the colorations obtained by this dyeing process have the disadvantage of having poor resistance to water and also to external agents, such as sebum, perspiration, brushing and / or rubbing actions.

[0007] There is therefore a need to develop a composition for dyeing keratinous fibers such as hair which is capable of forming a coating on keratinous fibers such as hair which is persistent with respect to water and to the various attack factors to which keratinous fibers such as hair may be subjected such as brushing and / or rubbing actions. Summary of the invention

[0008] An objective of the present application is to provide a composition for dyeing keratinous fibers such as hair which is capable of forming a coating on the keratinous fibers such as hair which is persistent with respect to water and to the various attack factors to which the keratinous fibers such as hair may be subjected such as brushing and / or rubbing actions.

[0009] Another objective of the present application is to provide a process for dyeing keratinous fibers such as hair.

[0010] Thus, the present invention provides a composition, preferably for dyeing keratinous fibers such as hair, comprising: a. at least one protein; b. at least one alkoxysilane; and c. at least one coloring agent chosen from pigments, direct dyes and their mixtures.

[0011] The present invention also relates to a process for dyeing keratinous fibers such as hair comprising applying the composition as described above to the keratinous fibers such as hair.

[0012] It has been found that the composition according to the present invention forms a colored coating on the hair which is persistent with respect to water and to the various attack factors to which the hair may be subjected such as brushing and / or rubbing actions.

[0013] Preferably, the composition according to the present invention is a composition for dyeing hair.

[0014] Other subjects and characteristics, aspects and advantages of the present invention will become even more apparent upon reading the detailed description and examples which follow. DETAILED DESCRIPTION OF THE INVENTION

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art in the field to which the present invention pertains. Where the definition of a term in the present invention conflicts with the meaning commonly understood by those skilled in the art in the field to which the present invention pertains, the definition described herein invention will apply.

[0016] As used herein, unless otherwise indicated, the limits of a range of values ​​are included within that range, particularly in the expressions "between...and..." and "from...to...".

[0017] Furthermore, the expression “at least one” used in the present description is equivalent to the expression “one or more”.

[0018] Throughout this application, the term "comprising" should be interpreted to encompass all specifically mentioned features as well as optional, additional, and unspecified features. As used herein, the use of the term "comprising" also discloses the embodiment in which no features other than the specifically mentioned features are present (i.e., "consisting of").

[0019] Unless otherwise specified, all numerical values ​​expressing an amount of ingredients and the like which are used in the description and claims are to be understood as being modified by the term "about". Accordingly, unless otherwise specified, the numerical values ​​and parameters described herein are approximate values ​​which, if necessary, can be changed depending on the desired objective.

[0020] As used herein, molecular weight indicates weight average molecular weight.

[0021] In the present invention, all percentages refer, unless otherwise specified, to a percentage by weight.

[0022] The term "keratinous fibers" or "keratin fibers" herein refers to fibers containing keratin as a principal constituent, and examples include hair, eyelashes, eyebrows, and the like.

[0023] For the purposes of the present invention, and unless otherwise indicated: • an “alkyl” radical denotes a linear or branched saturated radical containing, for example, from 1 to 30 carbon atoms; • an “aminoalkyl” radical denotes an alkyl radical as defined above, said alkyl radical comprising an NH2 group; • a “hydroxyalkyl” radical denotes an alkyl radical as defined above, said alkyl radical comprising an OH group; • an alkylene radical*” denotes a linear or branched divalent saturated C1-C10 hydrocarbon group, such as methylene, ethylene or propylene; • a “cycloalkyl” or “alicycloalkyl” radical denotes a monocyclic or polycyclic saturated cyclic hydrocarbon group, preferably monocyclic, comprising from 1 to 3 cycles, preferably 2 cycles, and comprising from 3 to 40 carbon atoms, comprising in particular from 3 to 24 carbon atoms, more particularly from 3 to 20 carbon atoms, even more particularly particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, or isobornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted by one or more alkyl groups (C1-C4) such as methyl; preferably, the cycloalkyl radical is then an isobornyl group; • an “aryl” radical is a monocyclic, bicyclic or tricyclic hydrocarbon cyclic radical, fused or not, unsaturated and aromatic, comprising from 6 to 30 carbon atoms, preferably between 6 and 14 carbon atoms, more preferably between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 cycle of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted by one or more alkyl groups (C1-C4) such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, the aryl group represents a phenyl; • an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined previously; • an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously.

[0024] The composition according to the present invention comprises: a. at least one protein; b. at least one alkoxysilane; and c. at least one coloring agent chosen from pigments, direct dyes and their mixtures. Proteins

[0025] The composition of the present invention comprises at least one protein.

[0026] Preferably, the protein has a molecular weight of at least 10 kDa. More preferably, the protein has a molecular weight of at least 15 kDa.

[0027] As used herein, 1 kDa is equivalent to 1000 g / mol

[0028] Said protein may be of animal or plant origin.

[0029] Said protein may or may not be hydrolyzed.

[0030] Preferably, the composition according to the invention comprises at least one non-hydrolyzed protein, more preferably at least one non-hydrolyzed protein with a molecular weight of at least 10 kDa.

[0031] The term "hydrolyzed protein" as used herein means the product of the hydrolysis of homogeneous or heterogeneous proteins, or their respective components, derivatives or combinations thereof.

[0032] The term "non-hydrolyzed protein" as used herein means protein that is not hydrolyzed.

[0033] Protein sources useful for the composition of the present invention include, but are not limited to, plants and their respective components, seeds, animal bones, connective tissue, animal keratin, bovine and porcine collagen, human hair, wool, silk, elastin, reticulin, milk, eggs, wheat, corn, soy, oats, casein, albumin or any collagen or keratin substance, or derivatives thereof.

[0034] Preferably, the protein is selected from silk protein, pea protein, soy protein, wheat protein, corn protein, collagen, and mixtures thereof, which are non-hydrolyzed.

[0035] More preferably, the protein is chosen from corn protein, collagen and their mixtures, which are non-hydrolyzed, even more preferably from corn protein, in particular zein, which is non-hydrolyzed.

[0036] According to a preferred embodiment, the composition of the present invention comprises at least one protein chosen from corn protein, collagen and mixtures thereof, the proteins are non-hydrolyzed and have a molecular weight of at least 10 kDa.

[0037] According to a further preferred embodiment, the composition of the present invention comprises at least one protein chosen from corn protein, collagen and mixtures thereof, the proteins are non-hydrolyzed and have a molecular weight of at least 15 kDa.

[0038] We can cite Arorganic-zein sold by the company AROMA HOLLY LIMITED.

[0039] Advantageously, the protein is present in the composition according to the present invention in an amount ranging from 0.1% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight, more preferably from 1% by weight to 10% by weight, even more preferably from 1.5% by weight to 8% by weight, relative to the total weight of the composition. Alkoxysilanes

[0040] The composition according to the present invention comprises at least one alkoxysilane.

[0041] According to a preferred embodiment, the composition comprises at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I1) below, their oligomers and / or their mixtures: (D Rs

[0042] in which: • Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy; or an aryl group containing from 6 to 12 carbon atoms; • Rb and Rc, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and in particular from 1 to 4 carbon atoms, in particular an ethyl group, it being understood that if Ra does not represent an alkoxy group, then Rb and Rc cannot simultaneously represent a hydrogen atom; • Rd and Re, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and in particular from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms; • A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted by at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH; • Q represents a carbonyl group (CO); • p denotes an integer ranging from 0 to 1.

[0043] Among the alkoxysilanes of formula (I), their oligomers and / or their mixtures, mention may in particular be made of 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldiethoxysilane (APMDES), 3-ureidopropyltrimethoxysilane and N-cyclohexylaminomethyltriethoxysilane.

[0044] APTES can be purchased for example from the company Dow Corning under the name Xiameter OFS-6011 Silane or from the company Momentive Performance Materials under the name Silsoft A-l100 or from the company Shin-Etsu under the name KBE-903.

[0045] The compounds of formula (I) may also designate Dynasylan SIVO 210 or Dynasylan 1505 sold by the company Evonik.

[0046] 3-Ureidopropyltrimethoxysilane can be purchased, for example, from the company Gelest under the reference SIU9058.0.

[0047] N-cycloheylaminomethyltriethoxysilane can be purchased, for example, from the company Wacker under the name Geniosil XL 926.

[0048] Among the alkoxysilanes of formula (!), their oligomers and / or their mixtures, mention may in particular be made of N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine (CAS registration number: 74956-86-8), N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine (CAS registration number: 457065-96-2), 1,2-ethanediamine, Nl-[3-(triethoxysilyl)propyl]-Nl-[3-(trimethoxysilyl)propyl]- (CAS registration number: 1638528-78-5), and mixtures thereof.

[0049] Preferably, the alkoxysilane or alkoxysilanes, their oligomers and / or their mixtures are chosen from the compounds of formula (I) below:

[0050] in which: • Ra represents an alkyl group containing from 1 to 10 carbon atoms, in particular from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy; • Rb and Rc, which may be the same or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, such as an ethyl; • Rd and Re, which are identical, represent a hydrogen atom or Rd denotes a hydrogen atom and Re denotes a C5-C6 cycloalkyl radical such as cyclohexyl; • A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted by at least one heteroatom chosen from O, S and NH or a carbonyl group (CO), preferably NH; • r denotes an integer equal to 0.

[0051] Preferably, the alkoxysilane or alkoxysilanes, their oligomers and / or their mixtures are chosen from the compounds of formula (I) in which Ra represents an ethoxy group, Rb and Rc are identical and represent an ethyl, Rd and Re represent a hydrogen atom, A represents a propylene and r denotes an integer equal to 0.

[0052] According to a preferred embodiment, the alkoxysilane of formula (I), its oligomers and / or its mixtures, is 3-aminopropyltriethoxysilane (APTES).

[0053] The alkoxysilane or alkoxysilanes of formula (I) or of formula (!), their oligomers and / or their mixtures may be present in a total amount ranging from 0.1% by weight to 30% by weight, preferably from 0.3% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight, better still from 0.8% by weight to 10% by weight and still better still from 0.8% by weight to 5% by weight, relative to the total weight of the composition.

[0054] According to another preferred embodiment, the composition according to the invention comprises at least one alkoxysilane of formula (II) below, its oligomers and / or its mixtures: R (H) "s

[0055] in which: • Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy; or an aryl group containing from 6 to 12 carbon atoms; • Rb represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and in particular from 1 to 4 carbon atoms, in particular an ethyl group; • Rc represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by a group aryl; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as ethoxy; or an aryl group containing from 6 to 12 carbon atoms;

[0056] it being understood that if Ra and Rc do not represent an alkoxy group, then Rb cannot represent a hydrogen atom; • k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3; • Rf represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms; or a group of formula (IIa) below:

[0057] Rn. ° (Ha)

[0058] in which Rn represents a hydroxyl group (OH); an alkyl group containing from 1 to 10 carbon atoms, preferably a methyl.

[0059] Among the alkoxysilanes of formula (II), their oligomers and / or their mixtures, mention may in particular be made of tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane, and their mixtures.

[0060] TEOS can for example be purchased from the company Evonik under the name Dynasylan® A or Dynasylan® A SQ.

[0061] MTES can be purchased for example from the company Evonik under the name Dynasylan® MTES.

[0062] DMDES can be purchased, for example, from the company Gelest under the reference SID3404.0.

[0063] Preferably, the alkoxysilane or alkoxysilanes of formula (II), their oligomers and / or their mixtures are such that: • Ra represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methoxy or an ethoxy; or an alkyl group containing from 1 to 10 carbon atoms optionally substituted by an aryl group, preferably from 1 to 2 carbon atoms optionally substituted by an aryl group; • Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, such as methyl or ethyl; Rc represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy; k denotes an integer ranging from 0 to 3, preferably equal to 0; Rf represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms, such as a methyl or an ethyl.

[0064] More preferably, the alkoxysilane or alkoxysilanes of formula (II), their oligomers and / or their mixtures are such that: Ra represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as methyl or ethyl; Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as methyl or ethyl; Rc represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy; k denotes an integer equal to 0; R represents an alkyl group containing from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms, such as methyl or ethyl.

[0065] According to a preferred embodiment, the alkoxysilane of formula (II), its oligomers and / or its mixtures, is methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES).

[0066] The alkoxysilane or alkoxysilanes of formula (II), their oligomers and / or their mixtures may be present in a total amount ranging from 0.1% by weight to 30% by weight, preferably from 0.3% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight, better still from 0.8% by weight to 10% by weight and still better still from 0.8% by weight to 5% by weight, relative to the total weight of the composition.

[0067] Preferably, the composition according to the invention comprises at least one alkoxysilane of formula (I), its oligomers and / or its mixtures, more preferably 3-aminopropyltriethoxy silane (APTES).

[0068] According to a preferred embodiment, the alkoxysilane or alkoxysilanes is / are present in a total amount ranging from 0.1% by weight to 30% by weight, preferably from 0.3% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight, better still from 0.8% by weight to 10% by weight and still better still from 0.8% by weight to 5% by weight, relative to the total weight of the composition.

[0069] According to a preferred embodiment, the alkoxysilane or alkoxysilanes of formula (I), their oligomers and / or their mixtures are present in a total amount ranging from 0.1% by weight to 30% by weight, preferably from 0.3% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight, better still from 0.8% by weight to 10% by weight and still better still from 0.8% by weight to 5% by weight, relative to the total weight of the composition. Coloring agent

[0070] The composition of the present invention comprises at least one coloring agent chosen from pigments, direct dyes and their mixtures. Pigments

[0071] Preferably, the coloring agent is chosen from pigments.

[0072] Preferably, the composition according to the invention comprises one or more pigments.

[0073] The term "pigment" refers to any pigment that gives color to keratinous 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% by weight.

[0074] The pigments which can be used are in particular chosen from organic and / or mineral pigments known in the art, in particular those described in the Encyclopedia of Chemical Technology by Kirk-Othmer and in the Encyclopedia of Industrial Chemistry by Ullmann.

[0075] They can be natural, of natural origin or non-natural.

[0076] The pigments may for example be in the form of powder or pigment paste. They may be coated or uncoated.

[0077] The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, special effect pigments such as mother-of-pearl or glitter flakes, and mixtures thereof.

[0078] The pigment may be a mineral pigment. The term "mineral pigment" means any pigment that meets the definition in Ullmann's Encyclopedia in the chapter on inorganic pigments. Inorganic pigments used in the present invention include iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0079] The pigment may be an organic pigment. The term "organic pigment" means any pigment that meets the definition in Ullmann's Encyclopedia in the chapter on organic pigments.

[0080] The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone.

[0081] In particular, the white or colored organic pigments may be chosen, for example, from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the color index under the references CI 42090, 69800, 69825, 74100 and 74160, the yellow pigments codified in the color index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the color index under the references CI 61565, 61570 and 74260, the orange pigments codified in the color index under the references CI 11725, 45370, and 71105, the red pigments codified in the color index under the references CI 12085, CI 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, and 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives in patent FR 2 679 771..

[0082] Other examples that may be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:

[0083] - Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);

[0084] - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);

[0085] - Cosmenyl Orange GR: Orange 43 pigment (CI 71105);

[0086] - Cosmenyl Red R: Red 4 pigment (CI 12085);

[0087] - Cosmenyl Carminé FB: Red 5 pigment (CI 12490);

[0088] - Cosmenyl Violet RL: Violet 23 pigment (CI 51319);

[0089] - Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);

[0090] - Cosmenyl Green GG: Green 7 pigment (CI 74260);

[0091] - Cosmenyl Black R: Black 7 pigment (CI 77266).

[0092] The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed in particular of particles including an inorganic core, at least one binder for fixing the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

[0093] The organic pigment may also be a lake. The term "lake" refers to dyes adsorbed onto insoluble particles, the resulting assembly remaining insoluble during use.

[0094] The mineral substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium borosilicate. aluminum and aluminum.

[0095] Among the dyes, we can cite carminic acid. Other products known as: D&C Red 21 (CI 45380), D&C Orange 5 (CI 45370), D&C Red 27 (CI 45410), D&C Orange 10 (CI 45425), D&C Red 3 (CI 45430), D&C Red 4 (CI 15510), D&C Red 33 (CI 17200), D&C Yellow 5 (CI 19140), D&C Yellow 6 (CI 15985), D&C Green 5 (CI 61570), D&C Yellow 10 (CI 77002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42090).

[0096] An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850:1).

[0097] The pigment may also be a special effect pigment. The term "special effect pigments" means pigments that generally create a colored appearance (characterized by a certain shade, vividness and luminance level) that is non-uniform and changes depending on viewing conditions (light, temperature, viewing angles, etc.). They are thus distinguished from colored pigments that provide a standard uniform, opaque, semi-transparent or transparent shade.

[0098] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a high refractive index, such as pearlescent pigments, interference pigments and glitter flakes.

[0099] Examples of special effect pigments that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above, as well as pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include Cellini pearlescent pigments sold by BASF (mica-TiO2 lake), Prestige pearlescent pigments sold by Eckart (mica-TiO2), Prestige Bronze pearlescent pigments sold by Eckart (mica-Fe2O3) and Colorona pearlescent pigments sold by Merck (mica-TiO2-Fe2O3).

[0100] Mention may also be made of the gold-colored mother-of-pearl sold in particular by the company BASF under the names Brillant gold 212G (TIMICA®), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze mother-of-pearl sold in particular by the company Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange mother-of-pearl sold in particular by the company Engelhard under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the names Passion orange (Colorona) and Matte Orange (17449). (Microna); brown mother-of-pearl sold in particular by BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with copper highlights sold in particular by BASF under the name Copper 340A (Timica), mother-of-pearl with red highlights sold in particular by Merck under the name Sienna fine (17386)(Colorona); mother-of-pearl with yellow highlights sold in particular by Engelhard under the name Yellow (4502) (Chromalite); red mother-of-pearl with golden highlights sold in particular by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl sold in particular by BASF under the name Tan opale G005 (Gemtone);black mother-of-pearl with golden highlights sold in particular by the company Engelhard under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl sold in particular by the company Merck under the name Matte blue (17433) (Microna), white mother-of-pearl with silver highlights sold in particular by the company Merck under the name Xirona Silver and green-gold pink-orange mother-of-pearl sold in particular by the company Merck under the name Indian summer (Xirona), and mixtures thereof.;

[0101] Still as examples of pearlescent agents, we can also cite particles including a borosilicate substrate coated with titanium oxide.

[0102] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.

[0103] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, in particular those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multi-layer pigments based on synthetic substrates, such as alumina, silica, sodium calcium borosilicate, aluminum calcium borosilicate and aluminum.

[0104] The special effect pigments may also be chosen from reflective particles, i.e. in particular particles whose size, structure, in particular the thickness of the layer(s) of which they are composed, as well as their physical and chemical nature and their surface state, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create, on the surface of the composition or mixture, when it is applied to the support to be formed, points of over-luminosity which are visible to the naked eye, namely brighter points which contrast with their environment by appearing to sparkle.

[0105] The reflective particles may be chosen so as not to significantly alter the coloring effect generated by the coloring agents with which they are combined, 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 tint.

[0106] These particles can have various shapes and can in particular be in the form of platelet or globular form, especially in spherical form.

[0107] The reflective particles, whatever their shape, may or may not have a multi-layer structure and, in the case of a multi-layer structure, may have, for example, at least one layer of uniform thickness, in particular of a reflective material.

[0108] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, in particular synthetically obtained titanium or iron oxides.

[0109] When the reflective particles have a multi-layer structure, they may comprise, for example, 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 at least one metal or metallic material. The substrate may consist of one or more organic and / or inorganic materials.

[0110] More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

[0111] The reflective material may include a layer of metal or metallic material.

[0112] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0113] Again, as an example of reflective particles including a mineral substrate coated with a metal layer, one can also cite particles including a borosilicate substrate coated with silver.

[0114] Silver-coated glass substrate particles, in platelet form, are sold under the name Microglass Metashine REFSX 2025 PS by Toyal. Nickel / chromium / molybdenum alloy coated glass substrate particles are sold under the names Crystal Star GF 550 and GF 2525 by the same company.

[0115] It is also possible to use particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metallic oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides, and mixtures thereof.

[0116] Examples that may be cited include aluminum powder, bronze powder or SiO2 coated copper powder sold under the name Visionaire by the company Eckart.

[0117] Mention may also be made of pigments having an interference effect which are not attached to a substrate, for example, liquid crystals (Helicones HC from Wacker) and holographic interference glitter flakes (Geometry Pigments or Spectra f / x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances that fluoresce in daylight or produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots sold, for example, by the company Quantum Dots Corporation.

[0118] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors, as well as particular optical effects such as metallic effects or interference effects.

[0119] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferably between 30 nm and 50 pm.

[0120] The pigments may be dispersed in the composition by means of a dispersant.

[0121] The dispersant serves to protect the dispersed particles against their agglomeration or flocculation. This dispersant 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, the dispersant may attach physically or chemically to the surface of the pigments. These dispersants also contain at least one functional group which is compatible with the continuous medium or soluble therein.In particular, 12-hydroxy stearic acid esters and in particular C8 to C20 fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.

[0122] As other dispersants which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for example Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane / oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.

[0123] The pigments used in the composition may be surface treated with an organic agent.

[0124] Thus, the previously surface-treated pigments which are useful in the context of the invention are pigments which have been entirely or partially subjected to a surface treatment of a chemical, electronic, electrochemical, mechanical nature. chemical or mechanical with an organic agent, such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53 to 64, before being dispersed in the composition according to the invention.These organic agents may be chosen, for example, 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 and 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 polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

[0125] Surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.

[0126] Surface-treated pigments that are useful in the context of the present invention may be prepared according to surface treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

[0127] Preferably, the surface-treated pigments are coated with an organic layer.

[0128] The organic agent with which the pigments are treated may 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.

[0129] The surface treatment can therefore 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.

[0130] An organic agent covalently bonded to the pigments will preferably be used.

[0131] The agent for surface treatment may represent from 0.1% by weight to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% by weight to 30% by weight and even more preferably from 1% by weight to 20% by weight relative to the total weight of the surface-treated pigment.

[0132] Preferably, the surface treatments of the pigments are chosen from the following treatments: • a PEG-silicone treatment, for example the AQ surface treatment sold by LCW; • a methicone treatment, for example the SI surface treatment sold by LCW; • a dimethicone treatment, for example the Covasil 3.05 surface treatment sold by LCW; • a dimethicone / trimethyl siloxysilicate treatment, for example Covasil 4.05 surface treatment sold by LCW; • a magnesium myristate treatment, for example the MM surface treatment sold by LCW; • an aluminum dimyristate treatment, such as the MI surface treatment sold by Miyoshi; • a treatment with perfluoropolymethyl isopropyl ether, for example the FHC surface treatment sold by LCW; • an isostearyl sebacate treatment, for example the HS surface treatment sold by Miyoshi; • a perfluoroalkyl phosphate treatment, for example the PF surface treatment sold by Daito; • an acrylate / dimethicone and perfluoroalkyl phosphate copolymer treatment, for example the FSA surface treatment sold by Daito; • a polymethylhydrogensiloxane / perfluoroalkyl phosphate treatment, for example the FS01 surface treatment sold by Daito; • an acrylate / dimethicone copolymer treatment, for example the ASC surface treatment sold by Daito; • an isopropyl titanium triisostearate treatment, for example the ITT surface treatment sold by Daito; • an acrylate copolymer treatment, for example the APD surface treatment sold by Daito; • a perfluoroalkyl phosphate / isopropyl titanium triisostearate treatment, for example the PF + ITT surface treatment sold by Daito.

[0133] According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in the form of submicron-sized particles.

[0134] The term "submicron" or "submicronic" describes pigments having a particle size that has been micronized by a micronization process and having an average particle size of less than one micrometer (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

[0135] According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersant:pigment), according to a weight ratio, of between 1:4 and 4:1, in particular between 1.5:3.5 and 3.5:1 or better still between 1.75:3 and 3:1.

[0136] The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and amino silicone dispersants. Suitable dispersants that may be mentioned include: • aminosilicones, namely silicones comprising one or more amino groups such as those sold 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, sold by Genesee Polymers, • silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043, sold by Evonik, • polydimethylsiloxane (PDMS) silicones bearing carboxyl groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones 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.

[0137] According to a particular embodiment, the dispersant(s) is(are) of amino silicone type and is(are) cationic.

[0138] Preferably, the pigment(s) is(are) chosen from mineral, mixed mineral-organic or organic pigments.

[0139] In a variant of the invention, the pigments are organic pigments, preferably organic pigments surface-treated with an organic agent chosen from silicone compounds.

[0140] In another variant of the invention, the pigments are mineral pigments. Direct dyes

[0141] The composition according to the present invention may comprise one or more direct dyes.

[0142] The term "direct dyeing" means natural and / or synthetic dyes, other than oxidation dyes. These are dyes which spread superficially on the fiber.

[0143] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0144] Examples of suitable direct dyes that 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 as mixtures.

[0145] 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, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, api- genidin and orceins. Extracts or decoctions containing these natural dyes can also be used, particularly poultices or extracts based on henna.

[0146] The coloring agent(s) may be present in a total content ranging from 0.001% by weight to 20% by weight and preferably from 0.005% by weight to 15% by weight relative to the total weight of the composition according to the invention.

[0147] The pigment(s) may be present in a total content ranging from 0.05% by weight to 20% by weight, preferably from 0.1% by weight to 15% by weight and better still from 0.5% by weight to 10% by weight, relative to the total weight of the composition according to the invention.

[0148] The direct dye(s) may be present in a total content ranging from 0.001% by weight to 10% by weight relative to the total weight of the composition, preferably from 0.005% by weight to 5% by weight relative to the total weight of the composition according to the invention. Organic solvents

[0149] The composition of the present invention may comprise at least one organic solvent.

[0150] Preferably, the organic solvent is chosen from C2-C8 monoalcohols, C2-C8 glycols, C2-C8 fatty acids, and mixtures thereof.

[0151] As used herein, the C2-C8 monohydric alcohols may be saturated or unsaturated, and linear or branched.

[0152] Preferably, the organic solvent is selected from a saturated, linear or branched C2-C6 monoalcohol, for example, ethanol, propanol, butanol, isopropanol and isobutanol.

[0153] As used herein, C2-C8 glycols may be saturated or unsaturated, and linear or branched.

[0154] Preferably, the organic solvent is chosen from saturated, linear or branched C2-C6 glycols, for example, ethylene glycol, propylene glycol, butylene glycol, isoprene glycol, hexylene glycol, caprylyl glycol.

[0155] As used herein, the C2-C8 fatty acids may be saturated or unsaturated, and linear or branched, optionally a hydrogen atom bonded to a carbon atom is substituted with a hydroxyl group. Examples of C2-C8 fatty acids include acetic acid, lactic acid, citric acid, butyric acid, valeric acid, pentanoic acid, caproic acid, heptyl acid, and caprylic acid.

[0156] More preferably, the organic solvent is chosen from ethanol, propylene glycol, acetic acid, lactic acid, and mixtures thereof.

[0157] More preferably still, the organic solvent is chosen from ethanol, propylene glycol, and their mixtures.

[0158] Advantageously, the organic solvent is present in the composition of the present invention in an amount ranging from 5% by weight to 90% by weight, preferably from 10% by weight to 85% by weight, more preferably from 20% by weight to 80% by weight, relative to the total weight of the composition.

[0159] In certain preferred embodiments, the organic solvent is chosen from C2-C8 monoalcohols, in particular ethanol, present in the composition of the present invention in an amount ranging from 10% by weight to 85% by weight, preferably from 15% by weight to 80% by weight, more preferably from 15% by weight to 70% by weight, relative to the total weight of the composition.

[0160] In certain preferred embodiments, the organic solvent is chosen from C2-C8 glycols, in particular propylene glycol, present in the composition of the present invention in an amount ranging from 10% by weight to 85% by weight, preferably from 15% by weight to 80% by weight, more preferably from 20% by weight to 70% by weight, relative to the total weight of the composition. Water

[0161] Preferably, the composition of the present invention further comprises water.

[0162] Advantageously, water is present in the composition of the present invention in an amount ranging from 5% by weight to 80% by weight, preferably from 10% by weight to 70% by weight, more preferably from 15% by weight to 60% by weight, relative to the total weight of the composition. Adjuvants

[0163] The composition according to the present invention may also comprise one or more cosmetic adjuvants.

[0164] For example, the composition may include one or more additives well known in the art, such as antioxidants, pH adjusters, and preservatives.

[0165] A person skilled in the art can choose these optional additional compounds and their amount such that the advantageous properties intrinsically associated with the invention are not, or not substantially, adversely affected by the contemplated addition(s).

[0166] According to a preferred embodiment, the composition according to the present invention comprises, relative to the total weight of the composition: a. from 0.1% by weight to 20% by weight of at least one protein selected from silk protein, pea protein, soy protein, wheat protein, corn protein, collagen, and mixtures thereof, the proteins are non-hydrolyzed and have a molecular weight of at least 10 kDa; b. from 0.1% by weight to 30% by weight of at least one alkoxysilane chosen from the compounds of formula (I) or of formula (!') as described above, their oligomers and / or their mixtures; and c. from 0.05% by weight to 20% by weight of at least one pigment.

[0167] According to a preferred embodiment, the composition according to the present invention comprises, relative to the total weight of the composition: a. from 1.5% by weight to 8% by weight of at least one corn protein, which is unhydrolyzed and has a molecular weight of at least 15 kDa; b. from 0.8% by weight to 5% by weight of 3-aminopropyltriethoxysilane (APTES); and c. from 0.5% by weight to 10% by weight of at least one pigment chosen from mineral, mixed mineral-organic or organic pigments. Preparation and use

[0168] The composition according to the present invention can be prepared by conventional methods in the cosmetic field and can be used for dyeing hair.

[0169] The present invention also relates to a process for dyeing keratinous fibers such as hair comprising the application of the composition as described above to the keratinous fibers such as hair.

[0170] The process can be repeated several times to obtain the desired coloring. EXAMPLES

[0171] The following examples are given for the purpose of illustration of the present invention and should not be construed as limiting the scope.

[0172] The main raw materials used, their trade names and suppliers have been listed in Table 1.

[0173] [Tableauxl] INCI Name Trade Name Supplier Zein Arorganic-zein AROMA HOLLY LIMITED Red 30 COVASOP RED W 3773 SENSIENT Aminopropyl triethoxysilane KBE-903 SHIN ETSU Inventive Example 1 and Comparative Examples 1-2

[0174] The compositions according to inventive example (EI) 1 and comparative examples (CE) 1-2 were prepared with the components listed in Table 2 (the contents were expressed as percentages by weight of ingredients relative to the total weight of each composition, unless otherwise indicated - MA: Active Material):

[0175] [Tables2] Ingredients El. 1 EC. 1 EC. 2 Zein 3.6 3.6 - Red 30 2.4 MA 2.4 MA 2.4 MA Ethanol 20 20 20 Water 26 26 26 Aminopropyl triethoxysilane 1 - 1 Propylene glycol QS100 QS100 QS100

[0176] The composition of inventive example 1 is a composition according to the present invention.

[0177] The composition of Comparative Example 1 does not comprise at least one al-koxysilane.

[0178] The composition of comparative example 2 does not comprise at least one protein.

[0179] Preparation procedure:

[0180] The compositions listed above were prepared as follows: 1. Mixing organic solvents and water with stirring for 5 minutes to obtain a solvent mixture; 2. preheating the solvent mixture in a water bath at 50°C for 5 minutes; 3. addition of protein (if any) into the solvent mixture with stirring for 10 minutes to obtain a homogeneous system; 4. addition of aminopropyl triethoxysilane (if applicable) into the homogeneous system with stirring for 5 minutes; 5. Cooling to room temperature, then adding pigment into the homogeneous system with stirring for 10 minutes to obtain a homogeneous composition. Assessment Water resistance

[0181] 1.5 g of the test sample was applied to a 3 g lock of black hair natural, then the hair strand was dried with a hairdryer. Then, 0.5 g of water was sprayed onto the hair strand, then the hair was wiped with a cloth and the color stain on the cloth was assigned a score according to the following standard by 6 professional hairdressers, then the scores were averaged:

[0182] 1: almost complete color transfer to the cloth;

[0183] 2: significant color stain on the cloth;

[0184] 3: with color stain on the cloth, but the color level is acceptable;

[0185] 4: a small stain of color on the cloth but not obvious;

[0186] 5: no color stain on the cloth.

[0187] The water resistance scores of the compositions of Inventive Example 1 and Comparative Examples 1-2 have been summarized in Table 3.

[0188] [Tables3] Properties ELI EC. 1 EC. 2 Water resistance 4.5 2.3 1

[0189] It can be seen from Table 3 that the composition according to the present invention forms a colored coating on the hair which is persistent with respect to water and to the various attack factors to which the hair may be subjected such as brushing and / or rubbing actions.

Claims

Claims

1.

2.

3. Composition, preferably for dyeing keratinous fibers such as hair, comprising: a) at least one protein; (b) at least one alkoxysilane; and (c) at least one coloring agent chosen from pigments, direct dyes and their mixtures. The composition of claim 1, wherein the protein is selected from silk protein, pea protein, soy protein, wheat protein, corn protein, collagen and mixtures thereof, which are non-hydrolyzed and have a molecular weight of at least 10 kDa. Composition according to any one of claims 1 to 2, in which the composition comprises at least one alkoxysilane chosen from the compounds of formula (I) or formula (I1) below, their oligomers and / or their mixtures: in which: - Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy; or an aryl group containing from 6 to 12 carbon atoms; - Rb and Rc, which may be the same or different, represent a

4. hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and in particular from 1 to 4 carbon atoms, in particular an ethyl group, it being understood that if Ra does not represent an alkoxy group, then Rb and Rc cannot simultaneously represent a hydrogen atom; - Rd and Re, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and in particular from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms; - A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted by at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH; - Q represents a carbonyl group (CO); - r denotes an integer ranging from 0 to 1. Composition according to claim 3, in which the alkoxysilane or alkoxysilanes, their oligomers and / or their mixtures are chosen from the compounds of formula (I) below: in which: - Ra represents an alkyl group containing from 1 to 10 carbon atoms, in particular from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy; - Rb and Rc, which may be the same or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, such as an ethyl; - Rd and Re, which are identical, represent a hydrogen atom or Rd denotes a hydrogen atom and Re denotes a C5-C6 cycloalkyl radical such as cyclohexyl; - A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted by at least one heteroatom chosen from 0, S and NH or a carbonyl group (CO), preferably NH; - r denotes an integer equal to 0.

5. Composition according to any one of claims 3 or 4, in which the alkoxysilane or alkoxysilanes, their oligomers and / or their mixtures are chosen from the compounds of formula (I) in which Ra represents an ethoxy group, Rb and Rc are identical and represent an ethyl, Rd and Re represent a hydrogen atom, A represents a propylene and r denotes an integer equal to 0.

6. A composition according to any one of claims 1 to 5, wherein the composition comprises one or more pigments selected from mineral, mixed mineral-organic or organic pigments.

7. Composition according to any one of claims 1 to 6, further comprising at least one organic solvent, preferably chosen from C2-C8 monoalcohols, C2-C8 glycols, C2-C8 fatty acids and mixtures thereof, more preferably chosen from ethanol, propylene glycol, acetic acid, lactic acid, and mixtures thereof.

8. A composition according to claim 1, comprising, relative to the total weight of the composition, a) from 0.1% by weight to 20% by weight of at least one protein selected from a silk protein, a pea protein, a soy protein, a wheat protein, a corn protein, collagen, and mixtures thereof, the proteins being non-hydrolyzed and having a molecular weight of at least 10 kDa; b) from 0.1% by weight to 30% by weight of at least one alkoxysilane selected from the compounds of formula (I) or formula (I1) according to any one of claims 3 to 5, their oligomers and / or their mixtures; and c) from 0.05% by weight to 20% by weight of at least one pigment.

9. A composition according to claim 1, comprising, relative to the total weight of the composition, a) from 1.5% by weight to 8% by weight of at least one corn protein, which is unhydrolyzed and has a molecular weight of at least 15 kDa; b) from 0.8% by weight to 5% by weight of 3-aminopropyltriethoxysilane (APTES); and (c) from 0.5% by weight to 10% by weight of at least one pigment chosen from mineral, mixed mineral-organic or organic pigments.

10. A process for dyeing keratinous fibers such as hair comprising applying the composition according to any one of claims 1 to 9 to the keratinous fibers such as hair.