WO2023187158A1

WO2023187158A1 - Process for dyeing the hair

Info

Publication number: WO2023187158A1
Application number: PCT/EP2023/058455
Authority: WO
Inventors: Arnaud Bonnamy; Alexis LIARD
Original assignee: L'oreal
Priority date: 2022-03-31
Filing date: 2023-03-31
Publication date: 2023-10-05
Also published as: FR3133999A1

Abstract

A subject of the present invention is a process for dyeing keratin fibres such as the hair, comprising the application to the keratin fibres of at least one composition A comprising at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') and at least one alkoxysilane of formula (II), and the application to the keratin fibres of at least one composition B comprising at least one film-forming polymer. Said composition A and/or composition B comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof. Said composition A and/or composition B comprise at least one amino silicone.

Description

Title:

PROCESS FOR DYEING THE HAIR

Technical field of the invention

A subject of the present invention is a process for dyeing keratin fibres such as the hair, comprising the application to the keratin fibres of at least one composition A comprising at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I’) and at least one alkoxysilane of formula (II), and the application to the keratin fibres of at least one composition B comprising at least one film-forming polymer. Said composition A and/or composition B comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof. Said composition A and/or composition B comprise at least one amino silicone.

Context of the invention

In the field of dyeing of keratin fibres, in particular human keratin fibres, it is already known practice to dye keratin fibres via various techniques starting from direct dyes or pigments for non-permanent dyeing or from dye precursors for permanent dyeing. There are essentially three types of process for dyeing the hair: a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair fibre and forms the dye via an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing, which does not employ the oxidative condensation process and withstands 4 or 5 shampoo washes; it consists in dyeing keratin fibres with dye compositions containing direct dyes; c) temporary dyeing, which gives rise to a modification to the natural colour of the head of hair which remains from one shampoo wash to the next, and which serves to enhance or correct a shade which has already been obtained. It may also be likened to a “makeup” process. For the latter type of dyeing, it is known practice to use pigments. Specifically, the use of pigment on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair, since the surface pigment masks the natural colour of the fibre.

However, the colourings obtained by this dyeing method have the drawback of resulting in hair that that feels unnatural and/or uncosmetic, the hair thus dyed possibly in particular lacking softness and/or manageability.

The need thus remains to have available a process for dyeing keratin fibres, in particular the hair, which has the advantage of producing a uniform and smooth coloured coating on the hair, while at the same time exhibiting good cosmetic properties in terms of softness or manageability of the hair.

The applicant has discovered, surprisingly, that all of these objectives can be achieved through the process according to the present invention.

Summary of the invention

A subject of the present invention is a process for dyeing keratin fibres such as the hair, comprising the following steps: a) applying to the keratin fibres at least one composition A comprising:

- at least one alkoxy silane chosen from the compounds of formula (I) or of formula (I’) as described below, oligomers thereof and/or mixtures thereof, and

- at least one alkoxysilane of formula (II) as described below, oligomers thereof and/or mixtures thereof, and b) applying to the keratin fibres at least one composition B comprising:

- at least one film-forming polymer, composition A and/or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and composition A and/or composition B comprising at least one amino silicone. The present invention also relates to a device for dyeing keratin fibres such as the hair, comprising several compartments containing:

- in a first compartment, a composition A comprising:

- at least one alkoxysilane of formula (II) as described below, oligomers thereof and/or mixtures thereof,

- in a second compartment, a composition B according to the invention comprising:

- at least one film-forming polymer, composition A and/or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, and composition A and/or composition B comprising at least one amino silicone.

Through the use of this process, coloured coatings are obtained on the hair that make it possible to obtain a colouring that is visible on all types of hair while at the same time exhibiting good cosmetic properties in terms of softness or manageability of the hair.

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

Unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions "between" and "ranging from ... to ..." .

The expression "keratin fibres" is understood particularly to mean human keratin fibres, such as the hair, eyelashes, eyebrows and body hair, preferentially the hair, eyebrows and eyelashes, more preferentially still the hair.

For the purposes of the present invention, the term ^hai^ is intended to mean the hair on the head. This term does not correspond to body hair, the eyebrows or the eyelashes.

For the purposes of the present invention, the term "silicone" denotes any organosilicon polymer or oligomer of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or by polycondensation of suitably functionalized silanes, and constituted essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond -Si-O-Si-), hydrocarbon-based radicals, which are optionally substituted, being directly bonded via a carbon atom to said silicon atoms.

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 “amino alkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

- a “hydroxy alky I” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

- an “alkylene” radical denotes a linear or branched divalent saturated C1-C10 hydrocarbon-based group such as methylene, ethylene or propylene;

- a “cycloalkyl” or “alicycloalkyl” radical denotes a cyclic saturated monocyclic or bicyclic, preferably monocyclic, hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 40 carbon atoms, in particular comprising from 3 to 24 carbon atoms, more particularly from 3 to 20 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, norbomyl or isobornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobornyl group;

- an "aryl" radical is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic hydrocarbon-based cyclic radical, comprising from 6 to 30 carbon atoms, preferably between 6 and 14 carbon atoms, more preferentially between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted with one or more (Ci-C4)alkyl groups 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. Unless otherwise indicated, when compounds are mentioned in the present application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the salts thereof, alone or as a mixture.

The invention is not limited to the illustrated examples. The characteristics of the various examples may notably be combined within variants which are not illustrated.

Detailed description of the invention

Process according to the invention

Composition A

Alkoxysilane of formula (I) or of formula (T):

Composition A according to the invention comprises at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I’) below, oligomers thereof and/or mixtures thereof:

in which:

- Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, it being possible for said alkyl group to be substituted with 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 R_a does not represent an alkoxy group, then Rb and Rc cannot simultaneously represent a hydrogen atom;

- Rd and R_e, 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 with at least one heteroatom chosen from O, S and NH or a carbonyl group (CO), preferably NH;

- Q represents a carbonyl group (CO);

- r denotes an integer ranging from 0 to 1.

Mention may in particular be made, among the alkoxysilanes of formula (I), oligomers thereof and/or mixtures thereof, of 3-aminopropyltriethoxysilane (APTES), 3- aminopropylmethyldiethoxy silane (APMDES), 3-ureidopropyltrimethoxysilane and N- cy clohexy laminomethy Itriethoxy silane .

APTES may be purchased, for example, from Dow Coming under the name Xiameter OFS-6011 Silane or from Momentive Performance Materials under the name Silsoft A- 1100 or from Shin-Etsu under the name KBE-903.

The compounds of formula (I) can also denote Dynasylan SIVO 210 or Dynasylan 1505, which are sold by Evonik.

3 -Ureidopropyltrimethoxy silane may be purchased, for example, from Gelest under the name SIU9058.0.

N-Cyclohexylaminomethyltriethoxysilane may be purchased, for example, from Wacker under the name Geniosil XL 926. Among the alkoxy silanes of formula (I’), oligomers thereof and/or mixtures thereof, mention may in particular be made of N,N-Bis[3- (trimethoxysilyl)propyl]ethylenediamine (CAS RN: 74956-86-8), N1,N1-Bis[3- (triethoxysilyl)propyl]-l,2-ethanediamine (CAS RN: 457065-96-2), 1,2-ethanediamine, Nl-[3-(triethoxysilyl)propyl]-Nl-[3-(trimethoxysilyl)propyl]- (CAS RN: 1638528-78- 5), and mixtures thereof.

Preferably, the alkoxysilane(s), oligomers thereof and/or mixtures thereof are chosen from the compounds of formula (I) below:

in which:

- Ra represents an alkyl group containing from 1 to 10 carbon atoms, notably 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 identical 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 R_e denotes a Cs-Ce 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 with at least one heteroatom chosen from O,

5 and NH or a carbonyl group (CO), preferably NH;

- r denotes an integer equal to 0.

Preferably, the alkoxysilane(s), oligomers thereof and/or mixtures thereof are chosen from the compounds of formula (I) in which R_a represents an ethoxy group, Rb and Rc are identical and represent an ethyl, Rd and Re represent a hydrogen atom, A represents a propyl and r denotes an integer equal to 0.

According to one preferred embodiment, the alkoxysilane of formula (I), oligomers thereof and/or mixtures thereof is 3-aminopropyltriethoxysilane (APTES).

The alkoxysilane(s) of formula (I) or of formula (I’), oligomers thereof and/or mixtures thereof may be present in a total amount ranging from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, preferentially from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 1.5% to 15% by weight, relative to the total weight of composition A.

According to one preferred embodiment, the alkoxysilane(s) of formula (I), oligomers thereof and/or mixtures thereof is (are) present in a total amount ranging from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, preferentially from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 1.5% to 15% by weight, relative to the total weight of composition A.

Alkoxysilane of formula (II):

Composition A according to the invention comprises at least one alkoxysilane of formula (II) below, oligomers thereof and/or mixtures thereof:

in which:

- 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 preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, it being possible for said alkyl group to be substituted with 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; it being understood that, if R_a 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 notably from 1 to 4 carbon atoms; or a group of formula (Ila) below:

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

Among the alkoxysilanes of formula (II), oligomers thereof and/or mixtures thereof, mention may notably be made of tetraethoxy silane (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), dimethyldiethoxy silane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxy methyltriethoxy silane and mixtures thereof.

TEOS may be purchased, for example, from Evonik under the name Dynasylan® A or Dynasylan® A SQ. MTES may be purchased, for example, from Evonik under the name Dynasylan® MTES.

DMDES may be purchased, for example, from Gelest under the reference SID3404.0.

Preferably, the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof 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 with an aryl group, preferably 1 to 2 carbon atoms, optionally substituted with an aryl group;

- Rb represents an alkyl 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 methyl or an 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 notably from 1 to 4 carbon atoms such as a methyl or an ethyl.

More preferentially, the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof are such that:

- Ra represents an alkyl 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 methyl or an ethyl;

- Rb represents an alkyl 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 methyl or an ethyl; - R_c 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;

- Rf represents 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.

According to one preferred embodiment, the alkoxysilane of formula (II), oligomers thereof and/or mixtures thereof is methyltrimethoxysilane (MTMS) or methyltriethoxy silane (MTES).

The alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof may be present in a total amount ranging from 0.5% to 90% by weight, preferably from 1% to 75%, preferentially from 3% to 45% by weight, better still from 5% to 40% by weight, relative to the total weight of composition A.

Organic solvents:

Composition A according to the invention may comprise one or more organic solvents.

Examples of organic solvents that may be mentioned include lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance glycerol, 2- butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

Preferably, composition A according to the invention comprises ethanol.

The organic solvent(s) may be present in a total amount ranging from 1% to 70% by weight, preferably from 5% to 55% by weight, more preferentially from 10% to 50% by weight, relative to the total weight of composition A according to the invention.

Composition B: Film-forming polymer:

Composition B according to the invention comprises at least one film-forming polymer.

Preferably, the film-forming polymer(s) are chosen from hydrophilic film-forming polymers, hydrophobic film-forming polymers, and mixtures thereof.

For the purposes of the invention, the term “polymer” means a compound corresponding to the repetition of one or more units (these units being derived from compounds known as monomers). This or these unit(s) are repeated at least twice and preferably at least three times.

The term "hydrophobic polymer" is intended to mean a polymer having a solubility in water at 25°C of less than 1% by weight.

The term "hydrophilic polymer" is intended to mean a polymer having a solubility in water at 25 °C of greater than or equal to 1% by weight.

The term "film-forming" polymer is intended to mean a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, notably on keratin materials, and preferably a cohesive film.

According to one preferred embodiment, the film-forming polymer(s) are chosen from hydrophobic film- forming polymers.

In one particularly preferred embodiment, the hydrophobic film-forming polymer is a polymer chosen from the group comprising:

- film-forming polymers that are soluble in an organic solvent medium, in particular liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and forms a single homogeneous phase when it is incorporated into the medium;

- film-forming polymers that are dispersible in an organic solvent medium, which means that the polymer forms an insoluble phase in the organic medium, the polymer remaining stable and/or compatible once incorporated into this medium. In particular, such polymers may be in the form of non-aqueous dispersions of polymer particles, preferably dispersions in silicone oils or hydrocarbon-based oils; in one embodiment, the non-aqueous polymer dispersions comprise polymer particles stabilized on their surface with at least one stabilizing agent; these non-aqueous dispersions are often referred to as NADs;

- film-forming polymers in the form of aqueous dispersions of polymer particles, which means that the polymer forms an insoluble phase in water, the polymer remaining stable and/or compatible once incorporated into the water, the polymer particles possibly being stabilized at their surface with at least one stabilizing agent. These polymer particles are often referred to as “latex”; in this case, the composition must comprise an aqueous phase.

Mention may be made, among the hydrophobic film-forming polymers which can be used in the composition of the present invention, of synthetic polymers of radical or of polycondensate type, polymers of natural origin and mixtures thereof.

The hydrophobic film-forming polymers that may be mentioned in particular include acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose-based polymers such as nitrocellulose, silicone polymers, acrylamide-type polymers, and polyisoprenes.

Non-ionic hydrophobic film-forming polymers, amphoteric hydrophobic film- forming polymers, anionic hydrophobic film- forming polymers or cationic hydrophobic filmforming polymers may be used.

Preferably, the hydrophobic film-forming polymer(s) according to the invention are chosen from acrylic acid copolymers, methacrylic acid copolymers, acrylic acid ester homopolymers or copolymers, methacrylic acid ester homopolymers or copolymers, acrylic acid amide homopolymers or copolymers, methacrylic acid amide homopolymers or copolymers, vinylpyrrolidone copolymers, vinyl alcohol copolymers, vinyl acetate copolymers, ethylene homopolymers or copolymers, propylene homopolymers or copolymers, styrene homopolymers or copolymers, polyurethanes, polyesters and/or polyamides. The hydrophobic film-forming polymer can be chosen from homopolymers and copolymers of olefins such as cyclic olefins; of butadiene; of isoprene; of styrene; of vinyl ethers, esters or amides; of (meth)acrylic acid esters or amides containing a linear, branched or cyclic C1-C20 alkyl group, a Ce-Cio aryl group or a C2-C6 hydroxyalkyl group.

The hydrophobic film-forming polymer can be in particular chosen from homopolymers and copolymers which can be obtained from monomers chosen from the group constituted of isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl or phenyl acrylate, or mixtures thereof.

Mention may be made for example of the ethylene/sodium acrylate copolymer sold under the trade name Ecosmooth Satin® by Dow.

The hydrophobic film-forming polymer can be in particular chosen from homopolymers and copolymers which can be obtained from amides of acid monomers; mention may be made of (meth)acrylamides, and notably N-alkyl (meth)acrylamides, in particular of C2- C12 alkyl, such as N-ethylacrylamide, N-(t-butyl)acrylamide, N-octylacrylamide; N- di(Ci-C4) alkyl (meth)acrylamides, and perfluoroalkyl (meth)acrylates.

Mention may also be made of copolymers of which the CTFA (4th Ed., 1991) name is Octylacrylamide/acrylates/butylaminoethyl-methacrylate copolymer, such as the products sold under the name Amphomer® or Lovocryl® 47 by National Starch, and also copolymers of which the CTFA name is Acrylates/octylacrylamide copolymer, such as the products sold under the name Dermacryl® LT or Dermacryl® 79 by National Starch.

According to one preferred embodiment, the hydrophobic film-forming polymer(s) according to the invention are chosen from anionic copolymers. Preferably, the anionic copolymers according to the invention are copolymers of acrylic acid, of methacrylic acid or of (meth) acrylic acid esters containing a linear, branched or cyclic Ci-C₆ alkyl group, as described under the INCI name Acrylates.

Such copolymers are sold by Rohm and Haas under the name Aculyn®33.

Copolymers of unsaturated ethylenic acid esters and of alkoxylated fatty alcohols can also be used according to the invention. Such unsaturated ethylenic acid esters are in particular acrylic acid, methacrylic acid and itaconic acid, and such alkoxylated fatty alcohols are in particular steareth-20 and ceteth-20.

Mention will be made for example of Aculyn®22 (Acrylates/steareth-20 Methacrylate Copolymer), Aculyn®28 (Acrylates/Beheneth-25 Methacrylate Copolymer), Structure 2001® (Acrylates/Steareth-20 Itaconate Copolymer), Structure 3001® (Acrylates/Ceteth-20 Itaconate Copolymer), Structure Plus®

(Acrylates/ Aminoacrylates/C 10-30 Alkyl PEG-20 Itaconate Copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C 10-30 Alkyl acrylate Crosspolymer), Synthalen W2000® (Acrylates/ Palmeth-25 Acrylate Copolymer) or Soltex OPT (acrylates/Ci2-22 alkyl methacrylate copolymer) sold by Rohm and Haas.

The hydrophobic film-forming polymer can also be chosen from homopolymers and copolymers which can be obtained from vinyl monomers. Mention may be made of homopolymers or copolymers of N-vinylpyrrolidone, vinylcaprolactam, N-(Ci-Ce)alkyl vinylpyrroles, vinyloxazoles, vinylthiazoles, vinylpyrimidines or vinylimidazoles.

As examples of vinylpyrrolidone copolymers that may be used in the invention, mention may be made of copolymers of VP/vinyl laurate, VP/vinyl stearate, butylated polyvinylpyrrolidone (PVP), VP/hexadecene sold by ISP under the name Ganex V216, VP/eicosene sold by ISP under the name Ganex V220, VP/triacontene or VP/acrylic acid/lauryl methacrylate.

The hydrophobic film-forming polymer can also be chosen from homopolymers and copolymers which can be obtained from olefins such as ethylene, propylene, butenes, isoprene, butadienes. In one embodiment, the hydrophobic film-forming polymer according to the invention is a block copolymer comprising at least one block constituted of styrene units or styrene derivatives (for example methylstyrene, chlorostyrene or chloromethylstyrene). The copolymer comprising at least one styrene block may be a diblock or triblock copolymer, or even a multiblock copolymer, in starburst or radial form. The copolymer comprising at least one styrene block may also comprise, for example, an alkylstyrene (AS) block, an ethylene/butylene (EB) block, an ethylene/propylene (EP) block, a butadiene (B) block, an isoprene (I) block, an acrylate (A) block, a methacrylate (MA) block or a combination of these blocks. The copolymer comprising at least one block constituted of styrene units or styrene derivatives can be a diblock or triblock copolymer, and in particular of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as those sold or manufactured under the name Luvitol HSB by BASF SE.

Preferably, the hydrophobic film-forming polymer(s) according to the invention are chosen from vinylpyrrolidone (co)polymers, vinyl alcohol (co)polymers, vinyl acetate (co)polymers, carboxyvinyl (co)polymers, acrylic acid (co)polymers, methacrylic acid (co)polymers, acrylic acid ester (co)polymers, ethylene (co)polymers, acrylamide (co)polymers, and mixtures thereof.

More preferentially, the hydrophobic film-forming polymer(s) are chosen from vinylpyrrolidone copolymers, acrylamide copolymers, acrylic acid ester homopolymers or copolymers, ethylene homopolymers or copolymers, and mixtures thereof.

According to another preferred embodiment, the film-forming polymer(s) are chosen from hydrophilic film-forming polymers.

Non-ionic hydrophilic film- forming polymers, anionic hydrophilic film-forming polymers or cationic hydrophilic film-forming polymers may be used.

The hydrophilic film- forming polymer can be chosen from vinylpyrrolidone (co)polymers, vinyl alcohol (co)polymers, vinyl acetate polymers, carboxyvinyl (co)polymers, acrylic acid (co)polymers, methacrylic acid (co)polymers, natural gums, polysaccharides and/or acrylamide (co)polymers. Preferably, the hydrophilic film-forming polymer is chosen from vinylpyrrolidone homopolymers (PVP) and/or vinylpyrrolidone copolymers, preferentially vinylpyrrolidone homopolymers (PVP).

Mention may be made of the vinylpyrrolidone homopolymers (PVP) sold under the name Luviskol® by BASF SE, in particular Luviskol® K 90 or Luviskol® K 85 by BASF SE.

The PVP K30 polymers sold by Ashland Inc. (ISP, POI Chemical) may also be used. PVP K30 is a polyvinylpyrrolidone polymer that is soluble in cold water and has the CAS number CAS 9003-39-8 and a molecular weight of 40000 g/mol.

Other vinylpyrrolidone homopolymers suitable for the invention are sold under the trade name Luvitec K 17, Luvitec K 30, Luvitec K 60, Luvitec K 80, Luvitec K 85, Luvitec K 90 and Luvitec K 115 by BASF SE.

Mention may also be made of the vinylpyrrolidone/vinyl ester copolymers sold under the name Luviskol® by BASF SE, in particular the non-ionic polymers Luviskol® VA64 and Luviskol® VA73 (vinylpyrrolidone /vinyl acetate copolymers).

Mention may also be made of styrene/vinylpyrrolidone copolymers, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/DMAPA acrylates copolymers, and vinylpyrrolidone/vinyl caprolactam/DMAPA acrylates copolymers. The vinylpyrrolidone/vinyl caprolactam/DMAPA acrylates copolymers may be sold by Ashland Inc. under the trade name Aquaflex® SF-40.

The vinylpyrrolidone/DMAPA acrylates copolymers may be sold by Ashland Inc. under the trade name Styleze CC-10.

By way of vinylpyrrolidone copolymers, mention may be made of the copolymers obtained by reacting N-vinylpyrrolidone with at least one monomer chosen from N- vinylformamide, vinyl acetate, ethylene, propylene, acrylamide or vinylcaprolactam.

According to one preferred embodiment, the hydrophilic film-forming polymer(s) are chosen from vinylpyrrolidone homopolymers (PVP), vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/styrene copolymers, vinylpyrrolidone/ethylene copolymers, vinylpyrrolidone/propylene copolymers, vinylpyrrolidone/vinyl caprolactam copolymers, vinylpyrrolidone/vinylformamide copolymers, vinylpyrrolidone/vinyl alcohol copolymers, and mixtures thereof.

Preferably, the film-forming polymer(s) are chosen from vinylpyrrolidone homopolymers (PVP), vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/styrene copolymers, vinylpyrrolidone/ethylene copolymers, vinylpyrrolidone/propylene copolymers, vinylpyrrolidone/vinyl caprolactam copolymers, vinylpyrrolidone/vinylformamide copolymers, vinylpyrrolidone/vinyl alcohol copolymers, acrylamide copolymers, acrylic acid ester homopolymers or copolymers, ethylene homopolymers or copolymers, and mixtures thereof.

More preferentially, the film-forming polymer(s) are chosen from vinylpyrrolidone homopolymers (PVP), acrylamide copolymers, acrylic acid ester homopolymers or copolymers, ethylene homopolymers or copolymers, and mixtures thereof.

The film- forming polymer(s) may be present in a total amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight and better still from 1% to 20% by weight, relative to the total weight of composition B.

Amino silicone:

Composition A and/or composition B comprises (comprise) at least one amino silicone.

The term “amino silicone” denotes any silicone including at least one primary, secondary, tertiary amine or a quaternary ammonium group.

The weight-average molecular masses of these amino silicones may be measured by gel permeation chromatography (GPC) at room temperature (25°C), as polystyrene equivalent. The columns used are p styragel columns. The eluent is THF and the flow rate is 1 ml/min. 200 pl of a 0.5% by weight solution of silicone in THF are injected. Detection is performed by refractometry and UV-metry.

Preferably, the amino silicone(s) that may be used in the context of the invention are chosen from: a) the poly siloxanes corresponding to formula (A):

in which x’ and y’ are integers such that the weight-average molecular weight (Mw) is between 5000 and 500 000 approximately; b) the amino silicones corresponding to formula (B):

R'_aG3-_a-Si(OSiG₂)n-(OSiGbR'2-b)m-O-SiG3-_a-R'_a (B) in which:

- G, which may be identical or different, denotes a hydrogen atom or a group from among phenyl, OH, Ci-Cs alkyl, for example methyl, or Ci-Cs alkoxy, for example methoxy;

- a, which may be identical or different, denotes 0 or an integer from 1 to 3, in particular 0,

- b denotes 0 or 1, in particular 1,

- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10;

- R’, which may be identical or different, denotes a monovalent radical of formula - CqH2qL in which q is a number ranging from 2 to 8 and L is an amine group, optionally quatemized, chosen from the following groups:

-N(R")₂; -N+(R")₃ A-; -NR"-Q-N(R")₂ and -NR"-Q-N+(R")₃ A-, in which R”, which may be identical or different, denotes hydrogen, phenyl, benzyl, or a saturated monovalent hydrocarbon-based radical, for example a Ci-C₂o alkyl radical; Q denotes a linear or branched group of formula C_rH_2r, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A" represents a cosmetically acceptable anion, notably a halide such as fluoride, chloride, bromide or iodide. Preferably, the amino silicone(s) are chosen from the amino silicones of formula (B).

Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to formulae (C), (D), (E), (F), (G) below and/or the amino silicones comprising at least one unit of formula (L), in particular the amino silicones of formula (N) below.

According to a first embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones known as “trimethylsilyl amodimethicone” corresponding to formula (C):

in which m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10.

According to a second embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (D) below:

in which:

- m and n are numbers such that the sum (n + m) ranges from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n possibly denoting a number from 0 to 999, notably from 49 to 249 and more particularly from 125 to 175, and m possibly denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5;

- Ri, R2 and R3, which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Ri to R3 denoting an alkoxy radical. Preferably, the alkoxy radical is a methoxy radical.

The hydroxy /alkoxy mole ratio preferably ranges from 0.2: 1 to 0.4: 1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.

The weight-average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1 000 000 and more particularly from 3500 to 200 000.

According to a third embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (E) below:

in which:

- p and q are numbers such that the sum (p + q) ranges from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250; p possibly denoting a number from 0 to 999 and notably from 49 to 349 and more particularly from 159 to 239, and q possibly denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5;

- Ri and R2, which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Ri or R2 denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

The hydroxy /alkoxy mole ratio generally ranges from 1:0.8 to 1:1.1 and preferably from 1:0.9 to 1:1 and more particularly is equal to 1:0.95.

The weight- average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200 000, even more particularly from 5000 to 100000 and more particularly from 10 000 to 50000.

The commercial products comprising silicones of structure (D) or (E) may include in their composition one or more other amino silicones the structure of which is different from formula (D) or (E).

A product containing amino silicones of structure (D) is sold by Wacker under the name Belsil® ADM 652.

A product containing amino silicones of structure (E) is sold by Wacker under the name Fluid WR 1300® or under the name Belsil® ADM LOG 1. When these amino silicones are used, one particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil-in-water emulsion may comprise one or more surfactants. The surfactants may be of any nature but are preferably cationic and/or non-ionic. The number- average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, notably as amino silicones of formula (E), use is made of microemulsions with a mean particle size ranging from 5 nm to 60 nm (limits included) and more particularly from 10 nm to 50 nm (limits included). Thus, use may be made according to the invention of the amino silicone microemulsions of formula (E) sold under the names Finish CT 96 E® or SLM 28020® by Wacker.

According to a fourth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (F) below:

in which:

- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1 000000 and even more particularly from 3500 to 200000. Another silicone corresponding to formula (B) is, for example, the Xiameter MEM 8299 Emulsion from Dow Coming (INCI name: amodimethicone and trideceth-6 and cetrimonium chloride).

According to a fifth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (G) below:

in which:

- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1,999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10;

- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1 000 000 and even more particularly from 1000 to 200000.

A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning; c) the amino silicones corresponding to formula (H):

in which:

- R5 represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl or C2-C18 alkenyl radical, for example methyl;

- Re represents a divalent hydrocarbon-based radical, notably a Ci-Cis alkylene radical or a divalent Ci-Cis, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;

- Q" is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate;

- r represents a mean statistical value ranging from 2 to 20 and in particular from 2 to 8;

- s represents a mean statistical value ranging from 20 to 200 and in particular from 20 to 50.

Such amino silicones are notably described in patent US 4 185 087. d) the quaternary ammonium silicones of formula (I):

in which:

- R7, which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl radical, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl;

- Re represents a divalent hydrocarbon-based radical, notably a Ci-Cis alkylene radical or a divalent Ci-Cis, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond; - Rs, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci- Cis alkyl radical, a C2-C18 alkenyl radical or a radical -R6-NHCOR7;

- X" is an anion such as a halide ion, in particular chloride, or an organic acid salt, in particular acetate;

- r represents a mean statistical value ranging from 2 to 200 and in particular from 5 to 100.

These silicones are described, for example, in patent EP-A 0 530 974; e) the amino silicones of formula (J):

in which:

- Ri, R2, R3 and R4, which may be identical or different, denote a C1-C4 alkyl radical or a phenyl group,

- R⁵ denotes a C1-C4 alkyl radical or a hydroxyl group,

- n is an integer ranging from 1 to 5,

- m is an integer ranging from 1 to 5, and

- x is chosen such that the amine number ranges from 0.01 to 1 meq/g; f) multiblock polyoxyalkylene amino silicones, of the type (AB)n, A being a polysiloxane block and B being a polyoxyalkylene block including at least one amine group.

Said silicones are preferably formed from repeating units having the following general formulae:

[-(SiMe₂O)xSiMe₂-R-N(R”)- R’ -O(C2H₄O)_a(C3H₆O)b-R’ -N(H)-R-] or alternatively

[-(SiMe₂O)_xSiMe₂-R-N(R")- R'-O(C2H₄O)_a(C3H₆O)b-] 1 in which:

- a is an integer greater than or equal to 1, preferably ranging from 5 to 200 and more particularly ranging from 10 to 100;

- b is an integer between 0 and 200, preferably ranging from 4 to 100 and more particularly between 5 and 30;

- x is an integer ranging from 1 to 10000 and more particularly from 10 to 5000;

- R” is a hydrogen atom or a methyl;

- R, which may be identical or different, represent a linear or branched divalent C2-C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a -CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R denotes a -CH2CH2CH2OCH2CH(OH)CH2- radical;

- R’, which may be identical or different, represent a linear or branched divalent C2-C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R’ denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a radical CH₂CH2CH2OCH₂CH(OH)CH2-; preferentially, R’ denotes -CH(CH₃)-CH₂-.

The siloxane blocks preferably represent between 50 mol% and 95 mol% of the total weight of the silicone, more particularly from 70 mol% to 85 mol%.

The amine content is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.

The weight-average molecular mass (Mw) of the silicone is preferably between 5000 and 1 000000 and more particularly between 10000 and 200000.

Mention may notably be made of the silicones sold under the name Silsoft A- 843 or Silsoft A+ by Momentive; g) the amino silicones of formula (K):

in which:

- A represents a hydroxyl, -O-Si(CH3)3, -O-Si(CH3)2OH or -O-Si(CH3)2OCH3 group,

- D represents a hydrogen atom, or a -Si(CH3)3, -Si(CH3)2OH or -Si(CH3)2OCH3 group, - b, n and c, independently of one another, are integers between 0 and 100 with n>0 and b+c>0, and at least one of the following conditions is met: A represents a hydroxyl group (OH) or D represents a hydrogen atom.

In formula (K), the siloxane units bearing the indices b, c and n are distributed randomly, i.e. it is not necessarily a question of block copolymers; h) the amino silicones comprising at least one unit of formula (L):

According to one preferred embodiment, the amino silicone according to the invention comprises at least one unit of formula (L) below:

According to a more preferred embodiment, the amino silicone according to the invention comprises at least one unit of formula (L) and at least one unit of formula (M) below:

(M).

Preferably, the amino silicone according to the invention is an amino silicone substituted with at least one 4-morpholinomethyl group.

Mention may be made for example of the amodimethicone/morpholinomethyl silsesquioxane copolymer sold under the trade name Belsil ADM 8301E by Wacker.

The amino silicone substituted with at least one 4-morpholinomethyl group which can be used according to the invention has the formula (N) below:

(N) in which:

- Ri represents a -CH₃, OH, -OCH₃, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH₃)₂ group,

- R2 represents a -CH3, OH or -OCH3 group,

- B represents a hydroxyl, -O-Si(CH3)3, -O-Si(CH3)2OH or -O-Si(CH3)2OCH3 group, - D represents a hydrogen atom, or a -Si(CH₃)3, -Si(CH3)2OH or -Si(CH3)2OCH3 group,

- a, b and c, independently of one another, are integers between 0 and 1000 with a+b+c > 0,

- m and n, independently of one another, are integers between 1 and 1000, with at least one of the following conditions being met: B represents a hydroxyl group (OH) or D represents a hydrogen atom.

Preferably a>0 or b>0, more preferentially a>0 and b>0.

The amino silicone of formula (N) can have trimethylsilyl end groups (D or B = - Si(CH₃)₃) or dimethylsilylhydroxy end groups, or trimethylsilyl end groups on one side and dimethylsilylhydroxy end groups on another side.

According to one preferred embodiment, the amino silicone according to the invention is an amino silicone substituted with at least one 4-morpholinomethyl of formula (N) chosen from:

B= -O-Si(CH₃)₂OH and D= -Si(CH₃)₃

B= -O-Si(CH₃)₂OH and D= -Si(CH₃)₂OH

B= -O-Si(CH₃)₂OH and D= -Si(CH₃)₂OCH₃

B= -Si(CH₃)₃ and D= -Si(CH₃)₂OH

B= -Si(CH₃)₂OCH₃ and D= -Si(CH₃)₂OH i) and mixtures thereof.

Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to formula (D) or the amino silicones comprising at least one unit of formula (L), in particular the amino silicones of formula (N).

Preferably, composition A and/or composition B comprises (comprise) at least one amino silicone chosen from the amino silicones of formula (D) or the amino silicones comprising at least one unit of formula (L), in particular the amino silicones of formula (N).

The amino silicone(s) may be present in a total amount ranging from 0.1% to 35%, preferably from 1% to 25%, more preferentially from 3% to 20% and even more preferentially from 5% to 17% by weight relative to the total weight of composition A and/or composition B.

Non-associative non-ionic cellulose-based polymer Composition A and/or composition B according to the invention can comprise at least one non-ionic, preferably non-associative, cellulose-based polymer.

The non-associative non-ionic cellulose-based polymer is different from the filmforming polymers mentioned above.

According to the invention, the term “cellulose-based polymer” means any polysaccharide polymer having, in its structure, sequences of glucose residues joined together via beta- 1,4 bonds.

According to the invention, the term “non-associative cellulose-based polymer” means that the cellulose-based polymers do not include any Cx-Cao fatty chains.

The non-associative non-ionic cellulose-based polymers may be chosen from (Ci- C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); hydroxy(Ci-C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed hydroxy(Ci-C4)alkyl(Ci-C4)alkylcelluloses, such as hydroxypropylmethylcelluloses (for example Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example Bermocoll E 481 FQ from AkzoNobel), and hydroxybutylmethylcelluloses, and also mixtures thereof.

Preferably, the non-associative non-ionic cellulose-based polymer(s) are chosen from hydroxy(Ci-C4)alkylcelluloses.

More preferentially, the non-associative non-ionic cellulose-based polymer(s) are hydroxy ethylcellulose and/or hydroxypropylcellulose.

More preferentially, composition A and/or composition B comprises (comprise) hydroxy ethylcellulose and/or hydroxypropylcellulose.

In particular, mention may be made of the hydroxy ethylcellulose sold by Ashland Inc. under the trade name Natrosol 250 HHR PC.

The non-associative non-ionic cellulose-based polymer(s) can be present in a total amount preferably ranging from 0.01% to 10% by weight, preferentially from 0.05% to 5% by weight and better still from 0.1% to 3% by weight relative to the total weight of composition A and/or composition B.

nd/or composition B according to the invention comprises (comprise) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

Preferably, composition A according to the invention comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

Preferably, composition A and/or composition B according to the invention comprises (comprise) one or more pigments.

Preferably, the colouring agent(s) are chosen from pigments.

The term "pigment” is understood to mean any pigment that gives colour 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% by weight.

The pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry.

They may be natural, of natural origin, or non-natural.

These pigments may be in pigment powder or paste form. They may be coated or uncoated.

The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.

The pigment may be a mineral pigment. The term “mineral pigment” means any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on organic pigments.

The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds. In particular, the white or coloured organic pigments may be chosen 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, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771. Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by Hoechst under the names:

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

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

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

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

- Cosmenyl Carmine FB: Red 5 pigment (CI 12490);

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

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

- Cosmenyl Green GG: Green 7 pigment (CI 74260); - Cosmenyl Black R: Black 7 pigment (CI 77266).

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 notably be composed of particles including a mineral core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium. Among the dyes, mention may be made of 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 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42090).

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).

The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.

Several types of pigments with special effects exist: 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 flakes. Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica covered with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the Cellini nacres sold by BASF (mica-TiO2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2O3), and Colorona sold by Merck (mica-TiO2-Fe2O3).

Mention may also be made of the gold-coloured nacres sold notably by BASF under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); the orange nacres sold notably by BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold notably by BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CE4509 (Chromalite); the nacres with a copper tint sold notably by BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by BASF under the name Sunstone G012 (Gemtone); the pink nacres sold notably by BASF under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold notably by BASF under the name Nu antique bronze 240 AB (Timica), the blue nacres sold notably by Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold notably by Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by Merck under the name Indian summer (Xirona), and mixtures thereof.

Still as examples of nacreous agents, mention may also be made of particles including a borosilicate substrate coated with titanium oxide. Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by Toyal.

Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles of which the size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. brighter points that contrast with their environment, making them appear to sparkle. The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.

These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.

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

When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically. When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and/or mineral materials. More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

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

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

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

Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by Toyal. Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.

Use may also be made of particles comprising a metal substrate, such as silver, aluminium, 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 metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiO2 sold under the name Visionaire by Eckart.

Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by Quantum Dots Corporation. The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.

The size of the pigment used in the composition according to the present invention is generally between 5 nm and 200 pm, preferably between 7 nm and 80 pm and more preferentially between 10 nm and 50 pm.

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

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 thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of Cs to C20 fatty acid and 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 Avecia, polyglyceryl-2 dipoly hydroxy stearate (CTFA name) sold under the reference Dehymyls PGPH by Henkel, or else poly hydroxy stearic acid such as the product sold under the reference Arlacel Pl 00 by Uniqema, and mixtures thereof.

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

The pigments used in the composition may be surface-treated with an organic agent. Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxy stearic acid, stearyl alcohol, hydroxy stearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

The 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.

The 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.

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

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

The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.

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

The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment. Preferably, the surface treatments of the pigments are chosen from the following treatments:

- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;

- a methicone treatment, for instance the SI surface treatment sold by LCW;

- a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;

- a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;

- a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;

- an aluminium dimyristate treatment, for instance the MI surface treatment sold by Miyoshi;

- a perfluoropolymethyl isopropyl ether treatment, for instance the LHC surface treatment sold by LCW;

- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;

- a perfluoroalkyl phosphate treatment, for instance the PE surface treatment sold by Daito;

- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the ESA surface treatment sold by Daito;

- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the ES01 surface treatment sold by Daito;

- an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;

- an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito;

- an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;

- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PL + ITT surface treatment sold by Daito. According to one particular embodiment of the invention, the dispersant is present with organic or inorganic pigments in submicron- sized particulate form in the dye composition.

The term “submicron- sized” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

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

The dispersant(s) may thus have a silicone backbone, such as silicone polyether and dispersants of amino silicone type other than the amino silicones or alkoxysilanes of formula (I) or of formula (I’) described previously in the application. Among the suitable dispersants that may be mentioned are: amino silicones, i.e. 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, poly dimethylsiloxane (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.

According to one particular embodiment, the dispersant(s) are of amino silicone type other than the amino silicones or alkoxy silanes of formula (I) or of formula (I’) described previously in the application and are cationic.

Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments. In one variant of the invention, the pigment(s) according to the invention are organic pigments. In another variant of the invention, the pigment(s) according to the invention are mineral pigments.

Composition A and/or composition B according to the invention can comprise one or more direct dye(s).

The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes which will spread superficially over the fibre.

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

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 in the form of mixtures.

The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (III) and (IV) and the azo cationic dyes (V) and (VI) below:

H&⁺-C a)=»-M<Rb)-Ar Q

(III)

in which formulae (III) to (VI):

- Het⁺ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cs)alkyl group such as methyl;

- Ar⁺ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-Cs)alkylammonium, such as trimethylammonium; - Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cs)alkyl, ii) optionally substituted (Ci-Cs)alkoxy, iii) (di)(Ci- Cs)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-Cs)alkylamino, v) optionally substituted N-(Ci-Cs)alkyl-N-aryl(Ci- Cs)alkylamino or alternatively Ar represents a julolidine group;

- Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci- Cs)alkyl, hydroxyl, (di)(Ci-Cs)(alkyl)amino, (Ci-Cs)alkoxy or phenyl groups;

- Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci- Cs)alkyl group which is optionally substituted, preferentially with 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 that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group which is optionally substituted with a hydroxyl group;

- Q" represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.

In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (III) to (VI) as defined previously, more particularly the cationic direct dyes bearing an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP 714 954, preferentially the following direct dyes:

in which formulae (VII) and (VIII):

- R¹ represents a (Ci-C4)alkyl group such as methyl;

- R² and R³, which may be identical or different, represent a hydrogen atom or a (Ci- C4)alkyl group, such as methyl; and

- R⁴ represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cs)alkyl, optionally substituted (Ci-Cs)alkoxy, or (di)(Ci- Cs)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R⁴ is a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferentially CH,

- Q- is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

In particular, the dyes of formulae (VII) and (VIII) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof with Q’ being an anionic counterion as defined previously, particularly halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesityl.

The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. The term “anionic direct dye” means any direct dye including in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes. As acid dyes according to the invention, mention may be made of the dyes of formulae (IX), (IX’), (X), (X’), (XI), (XI’), (XII), (XII’), (XIII), (XIV), (XV) and (XVI) below: a) the diaryl anionic azo dyes of formula (IX) or (IX’):

in which formulae (IX) and (IX’):

- R7, Rs, R9, Rio, R'7, R'S, R'9 and R' 10, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

- (O)₂S(O’)-, M⁺ with M⁺ representing a hydrogen atom or a cationic counterion;

- (O)CO -, M⁺ with M⁺ as defined previously;

- R”-S(O)2-, with R” representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or ary l(alkyl) amino group; preferentially a phenylamino or phenyl group; - R’”-S(0)2-X’- with R’” representing an alkyl group, aryl group which is optionally substituted, X’ as defined previously;

- (di)(alkyl)amino;

- ary l(alkyl) amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O')-, M⁺ and iv) alkoxy with M⁺ as defined previously;

- optionally substituted heteroaryl; preferentially a benzothiazolyl group;

- cycloalkyl; notably cyclohexyl;

- Ar-N=N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl, (O)2S(O')-, M⁺ or phenylamino groups;

- or alternatively two contiguous groups R7 with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A'; and R'7 with R's or R's with R'9 or R'9 with R'10 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O')-, M⁺; iv) hydroxyl; 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 ary l(alkyl) amino; with M⁺, R°, X, X', X" and Ar as defined previously;

- W represents a sigma bond c, 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, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb together form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (IX) and (IX’) comprise at least one sulfonate radical (O)₂S(O’)-, M⁺ or one carboxylate radical (O)CO -, M⁺ on one of the rings A, A’, B, B’ or C; preferentially sodium sulfonate.

As examples of dyes of formula (IX), 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 as examples of dyes of formula (IX’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (X) and (X’):

in which formulae (X) and (X’):

- Rn, R12 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O‘), M⁺ with M⁺ as defined previously;

- Ri4 represents a hydrogen atom, an alkyl group or a group -C(O)O", M⁺ with M⁺ as defined previously;

- Ris represents a hydrogen atom;

- Ri6 represents an oxo group, in which case R'i6 is absent, or alternatively R15 with Ri6 together form a double bond; - Ri7 and Ris, which may be identical or different, represent a hydrogen atom, or a group chosen from:

- (O)2S(O’)-, M⁺ with M⁺ as defined previously;

- Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;

- R19 and R20 together form either a double bond, or a benzo group D' which is optionally substituted;

R'i6, R’i9 and R' 20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;

- R21 represents a hydrogen atom or an alkyl or alkoxy group;

- Ra and Rb, which may be identical or different, are as defined previously; preferentially, Ra represents a hydrogen atom and Rb represents an aryl group;

- Y represents either a hydroxyl group or an oxo group;

> — - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that formulae (X) and (X’) comprise at least one sulfonate radical (O)₂S(O’)-, M⁺ or one carboxylate radical -C(O)O-, M⁺ on one of the rings D or E; preferentially sodium sulfonate.

As examples of dyes of formula (X), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as an example of a dye of formula (X’), mention may be made of: Acid Yellow 17; c) the anthraquinone dyes of formulae (XI) and (XI’):

(XD in which formulae (XI) and (XI’):

- R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- hydroxyl, mercapto;

- alkoxy, alkylthio;

- optionally substituted aryloxy or optionally substituted arylthio, preferentially substituted with one or more groups chosen from alkyl and (O)2S(O')-, M⁺ with M⁺ as defined previously;

- ary l(alkyl) amino optionally substituted with one or more groups chosen from alkyl and (O)2S(O')-, M⁺ with M⁺ as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- (O)2S(O’)-, M⁺ with M⁺ as defined previously;

- Z' represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl;

- aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O')-, M⁺ with M⁺ as defined previously; iii) R°- C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group;

- cycloalkyl; notably cyclohexyl;

- Z represents a group chosen from hydroxyl and NR'2sR'29 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (XI) and (XI’) comprise at least one sulfonate radical (O)2S(O')-, M⁺ or one carboxylate radical C(O)O", M⁺; preferentially sodium sulfonate. As examples of dyes of formula (XI), mention may be made of: 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 Violet No. 2; and, as an example of a dye of formula (XI’), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (XII) and (XII’):

in which formulae (XII) and (XII’):

- R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: - alkyl;

- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;

- hydroxyl, 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)2S(O’)-, M⁺ with M⁺ as defined previously;

- (O)CO -, M⁺ with M⁺ as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R30, R31 and R32 represent a hydrogen atom;

- Rc and Rd, which may be 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 linear or branched divalent Ci-Ce alkylene group; in particular, ALK represents a -CH2-CH2- group;

- n is 1 or 2;

- p represents an integer inclusively between 1 and 5;

- q represents an integer inclusively between 1 and 4;

- u is 0 or 1 ;

- when n is 1, J represents a nitro or nitroso group; particularly nitro

- when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(O)_m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;

- M' represents a hydrogen atom or a cationic counterion;

CT , which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously it being understood that formulae (XII) and (XII’) comprise at least one sulfonate radical (O)2S(O')-, M⁺ or one carboxylate radical -C(O)O-, M⁺; preferentially sodium sulfonate.

As examples of dyes of formula (XII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XII’), mention may be made of: Acid Yellow 1, the sodium salt of 2, 4-dinitro-l-naphthol-7- sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4’-N,N-(2”-hydroxyethyl)amino-2’- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7; e) the triarylmethane dyes of formula (XIII):

in which formula (XIII):

- R33, R34, R35 and R36, which may be 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 with a group (O)mS(O')-, M⁺ with M⁺ and m as defined previously;

- R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxyl, mercapto; - nitro, nitroso;

- (O)2S(O’)-, M⁺ with M⁺ representing a hydrogen atom or a cationic counterion;

- (O)CO -, M⁺ with M⁺ as defined previously;

- or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: I’; with I’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O')-, M⁺; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’-C(X)-X”-; with M⁺, R°, X, X’ and X” as defined previously; in particular, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxyl group or (O)2S(O')-, M⁺; and when R43 with R44 together form a benzo group, it is preferentially substituted with an (O)2S(O')- group; it being understood that at least one of the rings G, H, I or I' comprises at least one sulfonate radical (O)2S(O')- or one carboxylate radical -C(O)O"; preferentially sulfonate. As examples of dyes of formula (XIII), 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; f) the xanthene-based dyes of formula (XIV):

in which formula (XIV):

- R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;

- R49, Rso, Rsi and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- (O)₂S(O')-, M⁺ with M⁺ representing a hydrogen atom or a cationic counterion;

- (O)CO -, M⁺ with M⁺ as defined previously; particularly, R53, R54, R55 and R48 represent a hydrogen or halogen atom;

- G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly G represents an oxygen atom;

- L represents an alkoxide O', M⁺; a thioalkoxide S', M⁺ or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and M⁺ as defined previously; M⁺ is particularly sodium or potassium;

- L' represents an oxygen or sulfur atom or an ammonium group: N⁺RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom, an alkyl group, aryl group which is optionally substituted; L' particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O)_mS(O')-, M⁺ groups with m and M⁺ as defined previously; - Q and Q', which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q' represent an oxygen atom;

- M⁺ is as defined previously.

As examples of dyes of formula (XIV), 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; g) the indole-based dyes of formula (XV):

- R53, R54, R55, R56, R57, R58, R59 and Reo, which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

- nitro, nitroso;

- (O)CO -, M⁺ with M⁺ as defined previously;

- Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XV) comprises at least one sulfonate radical (O)2S(O- )-, M+ or one carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate. As examples of dyes of formula (XV), mention may be made of: Acid Blue 74. h) the quinoline-based dyes of formula (XVI):

- Rei represents a hydrogen or halogen atom or an alkyl group;

- R62, R63 and R64, which may be identical or different, represent a hydrogen atom or a group (O)2S(O')-, M⁺ with M⁺ representing a hydrogen atom or a cationic counterion; or alternatively Rei with R62, or Rei with R64, together form a benzo group optionally substituted with one or more groups (O)2S(O')-, M⁺ with M⁺ representing a hydrogen atom or a cationic counterion; it being understood that formula (XVI) comprises at least one sulfonate radical (O)2S(O )-, M⁺, preferentially sodium sulfonate.

As examples of dyes of formula (XVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

Among the natural direct dyes that may 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, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts.

Preferably, the direct dyes are chosen from anionic direct dyes. The colouring agent(s) may be present in a total amount ranging from 0.001% to 20%, preferably from 0.005% to 15% by weight and better still from 0.005% to 10% by weight, relative to the total weight of composition A and/or composition B.

The pigments may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 0.5% to 10% by weight, relative to the total weight of composition A and/or composition B.

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

Solvent:

Composition A and/or composition B according to the invention may comprise water. Preferably, water is present in a content ranging from 0.1% to 95% by weight, more preferentially from 1% to 90% by weight and better still from 10% to 85% by weight relative to the total weight of composition A and/or composition B.

When composition A and/or composition B according to the invention comprises (comprise) water, the pH of composition A and/or composition B is preferably alkaline. For the purpose of adjusting the pH, composition A and/or composition B may comprise an alkaline agent.

Preferably, composition A and/or composition B according to the invention comprises an alkaline agent.

The pH of the compositions is measured at room temperature.

As alkaline agent, mention may be made of aqueous ammonia, alkanolamines and/or basic amino acids.

Preferably, the alkanolamine(s) are chosen from monoethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N- dimethylaminoethanolamine, 2-amino-2-methyl-l -propanol, triisopropanolamine, 2- amino-2-methyl- 1 ,3-propanediol, 3-amino- 1 ,2-propanediol, 3-dimethylamino- 1 ,2- propanediol and trishydroxymethylaminomethane. More preferentially, the alkanolamine(s) are chosen from monoethanolamine and/or 2- amino -2-methy 1- 1 -prop anol .

For the purposes of the invention, the term “amino acid” is understood to mean organic compounds having two functional groups: both a carboxyl -COOH or carboxylate group and an amine -NH2 group, it being possible for the amine group to be optionally methylated, that is to say in the -NR² or N⁺R³ form, where at least one R = CH3. Preferably, the amino acid(s) are chosen from aminocarboxylic acids such as alphaaminocarboxylic acid.

The term “basic amino acid’ is intended to mean amino acids having an isoelectric point above 7.

Preferably, the basic amino acids(s) are chosen from arginine, lysine, ornithine and/or histidine, more preferentially arginine and/or lysine.

According to one particular embodiment, composition A and/or composition B can comprise an inorganic alkaline agent, preferably chosen from ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium meta-silicate, potassium silicate, sodium carbonate and/or potassium carbonate.

Preferably, composition A and/or composition B comprises (comprise) an alkaline agent chosen from aqueous ammonia, monoethanolamine, 2-amino-2-methyl-l -propanol, arginine and/or lysine.

Composition A and/or composition B can also comprise acidifying agents for adjusting the pH.

Preferably, the acidifying agents are chosen from citric acid, lactic acid, acetic acid and/or mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid and mixtures thereof.

Additives: Composition A and/or composition B according to the invention may also contain any adjuvant or additive customarily used.

Mention may be made, among the additives capable of being contained in the composition, of reducing agents, thickening agents other than the polymers previously described, softeners, antifoaming agents, moisturizing agents, UV- screening agents, peptizers, dispersants, fragrances, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, preservatives, waxes and mixtures thereof.

Composition A and/or composition B may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W/O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or non-ionic lipids, a two-phase or multi-phase lotion, an anhydrous liquid or an anhydrous gel.

According to one particular embodiment, composition A according to the invention is an anhydrous liquid or an anhydrous gel.

According to one particular embodiment, composition B according to the invention is a dispersion.

Those skilled in the art may choose the appropriate presentation form, and also the method for preparing it, on the basis of their general knowledge, taking into account firstly the nature of the constituents used, notably their solubility in the support, and secondly the intended application for composition A and/or composition B.

According to one preferred embodiment, composition A according to the invention comprises at least one alkoxysilane of formula (I) as described previously, at least one alkoxysilane of formula (II) as described previously, and at least one pigment.

According to a more preferred embodiment, composition A according to the invention comprises 3-aminopropyltriethoxysilane (APTES), methyltrimethoxy silane (MTMS) or methyltriethoxy silane (MTES) and at least one pigment. According to one preferred embodiment, composition B according to the invention comprises at least one film-forming polymer chosen from vinylpyrrolidone homopolymers (PVP), vinylpyrrolidone copolymers, acrylamide copolymers, acrylic acid ester homopolymers or copolymers, ethylene homopolymers or copolymers, and mixtures thereof, and at least one amino silicone chosen from the amino silicones corresponding to formula (D) or the amino silicones comprising at least one unit of formula (L), in particular the amino silicones of formula (N).

According to a more preferred embodiment, composition B according to the invention comprises at least one film-forming polymer chosen from vinylpyrrolidone homopolymers (PVP), acrylamide copolymers, acrylic acid ester homopolymers or copolymers, ethylene homopolymers or copolymers, and mixtures thereof, and at least one amino silicone chosen from the amino silicones corresponding to formula (D) or the amino silicones comprising at least one unit of formula (L), in particular the amino silicones of formula (N).

Process for treating keratin fibres

- at least one alkoxy silane chosen from the compounds of formula (I) or of formula (I’) as described previously, oligomers thereof and/or mixtures thereof, and

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof, and b) applying to the keratin fibres at least one composition B comprising:

- at least one film-forming polymer as described previously, composition A and/or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and composition A and/or composition B comprising at least one amino silicone as described previously. Preferably, composition A and composition B according to the invention are compositions for dyeing keratin fibres such as the hair.

Composition A and composition B can be applied simultaneously or sequentially. Preferably, composition A and composition B are applied sequentially.

Thus, preferably, composition A is first of all applied to the keratin fibres, followed by composition B in a second step.

According to one preferred embodiment, the process for dyeing keratin fibres such as the hair comprises: i) applying to said keratin fibres composition A according to the invention comprising:

- at least one alkoxy silane chosen from the compounds of formula (I) or of formula (I’) as described previously, oligomers thereof and/or mixtures thereof,

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof, and

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying to said keratin fibres composition B according to the invention comprising:

- at least one film-forming polymer as described previously, and

- at least one amino silicone as described previously, v) optionally a leave-on time of from 10 seconds to 20 minutes, notably from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition B according to the invention on said fibres, vi) optionally a step of washing, rinsing, draining and vii) optionally a step of drying and/or heating the keratin fibres for example at a temperature of greater than or equal to 30°C. According to another preferred embodiment, the process for dyeing keratin fibres such as the hair comprises: i) applying to said keratin fibres composition A or composition B according to the invention comprising:

- at least one alkoxy silane chosen from the compounds of formula (I) or of formula (I’) as described previously, oligomers thereof and/or mixtures thereof

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof,

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof,

- at least one amino silicone as described previously, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying composition B according to the invention comprising:

- at least one film- forming polymer as described previously; v) optionally a leave-on time of from 10 seconds to 20 minutes, notably from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition B according to the invention on said fibres, vi) optionally a step of washing, rinsing, draining and vii) optionally a step of drying and/or heating the keratin fibres for example at a temperature of greater than or equal to 30°C.

According to another preferred embodiment, the process for dyeing keratin fibres such as the hair comprises: i) applying to said keratin fibres composition A or composition B according to the invention comprising:

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof, and - at least one amino silicone as described previously, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying composition B according to the invention comprising:

- at least one film-forming polymer as described previously, and

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, v) optionally a leave-on time of from 10 seconds to 20 minutes, notably from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition B according to the invention on said fibres, vi) optionally a step of washing, rinsing, draining and vii) optionally a step of drying and/or heating the keratin fibres for example at a temperature of greater than or equal to 30°C.

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying composition B according to the invention comprising:

- at least one film- forming polymer as described previously;

- at least one amino silicone as described previously, v) optionally a leave-on time of from 10 seconds to 20 minutes, notably from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition B according to the invention on said fibres, vi) optionally a step of washing, rinsing, draining and vii) optionally a step of drying and/or heating the keratin fibres for example at a temperature of greater than or equal to 30°C.

- at least one film-forming polymer as described previously, and

- at least one film- forming polymer as described previously;

- at least one amino silicone as described previously, and

The term “step of rinsing” is intended to mean applying water to the keratin fibres.

Compositions A and B according to the invention can be used on wet or dry keratin fibres, and also on all types of fair or dark, natural or dyed, permanent-waved, bleached or relaxed, fibres. According to one particular embodiment of the process of the invention, the fibres are washed before applying compositions A and B according to the invention.

The applying of compositions A and B according to the invention to the keratin fibres may be carried out by any conventional means, in particular by means of a comb, a fine brush, a coarse brush or with the fingers.

The dyeing process, i.e. application of compositions A and B according to the invention to the keratin fibres, is generally carried out at room temperature (between 15 and 25°C). After application of composition A or composition B to the keratin fibres, it is preferable to have a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A or composition B on said fibres.

According to one particular embodiment, the process for dyeing keratin fibres such as the hair comprises: i) preparing composition A according to the invention by mixing a first composition A' and a second composition A" in which the first composition A' comprises:

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof and the second composition A" comprises:

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, ii) applying to said keratin fibres composition A according to the invention, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying composition B according to the invention comprising:

- at least one film-forming polymer as described previously, and

In order to allow better preservation of composition A', the latter preferably comprises a low water content or is anhydrous.

Preferably, composition A' comprises a water content of between 0.001% and 10% by weight, better still between 0.5% and 10% by weight, more preferentially between 1% and 8% by weight relative to the total weight of composition A'.

Composition A" can also contain water.

According to another particular embodiment, the process for dyeing keratin fibres such as the hair comprises: i) preparing composition A according to the invention by mixing a first composition A' and a second composition A" in which the first composition A' comprises:

- at least one amino silicone as described previously, ii) applying to said keratin fibres composition A or composition B according to the invention, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying composition B according to the invention comprising:

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, ii) applying to said keratin fibres composition A or composition B according to the invention, ii) optionally a leave-on time of from 10 seconds to 20 minutes, in particular from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition A on said fibres, iii) optionally a step of washing, rinsing, draining or drying said fibres, iv) applying composition B according to the invention comprising:

- at least one film-forming polymer as described previously, and

According to one particular embodiment, the process for dyeing keratin fibres such as the hair comprises: i) preparing composition A according to the invention by mixing a first composition A', a second composition A" and a third composition A'" in which the first composition A' comprises:

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof, and the second composition A" comprises:

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, the third composition A'" comprises:

- at least one film- forming polymer as described previously; v) optionally a leave-on time of from 10 seconds to 20 minutes, notably from 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, of composition B according to the invention on said fibres, vi) optionally a step of washing, rinsing, draining and vii) optionally a step of drying and/or heating the keratin fibres for example at a temperature of greater than or equal to 30°C. After application of compositions A and B according to the invention and before an optional step of applying heat to the keratin fibres, the keratin fibres can be subjected to a drying step, for example, using a hairdryer.

The drying step can be carried out for a period of between 20 seconds and 5 minutes.

The drying step may be performed using absorbent paper, a hairdryer or a styling hood or by drying naturally.

Preferably, the drying step is carried out using a hairdryer at a temperature of greater than or equal to 30°C, more particularly at a temperature of greater than 30°C and less than 110°C.

After application of compositions A and B according to the invention to the keratin fibres, there may be a waiting time of at least 10 seconds, preferably of at least 30 seconds, before the step of drying the keratin fibres.

After application of compositions A and B according to the invention and optionally a step of drying the keratin fibres, the process according to the invention may comprise a step of applying heat to the keratin fibres using a heating tool.

Preferably, the process according to the invention does not comprise a step of applying heat to the keratin fibres using a heating tool in addition to the optional drying step.

The heat application step of the process of the invention may be performed using a hood, a hairdryer, a straightening iron, a curling iron, a Climazon, etc.

Preferably, the heat application step of the process of the invention is performed using a hairdryer and/or a straightening iron, more preferentially using a hairdryer.

During the step of applying heat to the keratin fibres, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.

When the step of applying heat to the keratin fibres is performed using a hood or a hairdryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

When the step of applying heat to the keratin fibres is performed using a straightening iron, the temperature is preferably between 110°C and 240°C, preferably between 110°C and 200°C. According to one particular embodiment, the process for dyeing keratin fibres such as the hair, according to the invention, implements a step of dyeing the keratin fibres, consisting in applying to said fibres a composition (G) comprising at least one amino silicone as described previously.

Composition (G) may comprise water or an organic solvent. Preferably, composition (G) comprises a total amount of water or organic solvent ranging from 30% to 99% by weight, relative to the total weight of composition (G).

Preferably, composition (G) is applied to the keratin fibres before applying composition A and composition B according to the invention to the keratin fibres.

Multi-compartment device (kit)

The present invention also relates to a device for dyeing keratin fibres such as the hair, comprising several compartments containing:

- in a first compartment, a composition A comprising:

- at least one film-forming polymer, composition A and/or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and composition A and/or composition B comprising at least one amino silicone.

According to one preferred variant of the invention, the dyeing device according to the invention is a device for dyeing keratin fibres such as the hair, comprising several compartments containing:

- in a first compartment, a composition A comprising: - at least one alkoxy silane chosen from the compounds of formula (I) or of formula (I’) as described previously, oligomers thereof and/or mixtures thereof, and

- at least one film-forming polymer as described previously, and

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, composition A and/or composition B comprising at least one amino silicone as described previously.

- in a first compartment, a composition A comprising:

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof;

- at least one hydrophobic film-forming polymer as described previously, and composition A and/or composition B comprising at least one amino silicone as described previously.

- in a first compartment, a composition A' comprising:

- at least one alkoxysilane of formula (II) as described previously, oligomers thereof and/or mixtures thereof, - in a second compartment, a composition A" comprising:

- in a third compartment, a composition B according to the invention comprising:

- at least one film-forming polymer as described previously, and composition A' and/or composition A" and/or composition B comprising at least one amino silicone as described previously.

- in a first compartment, a composition A' comprising:

- in a second compartment, a composition A" comprising:

- at least one film-forming polymer as described previously, and

- at least one amino silicone as described previously.

According to another preferred variant of the invention, the dyeing device according to the invention is a device for dyeing keratin fibres such as the hair, comprising several compartments containing:

- in a first compartment, a composition A' comprising:

- in a second compartment, a composition A" comprising:

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, - at least one amino silicone as described previously, and

- at least one film- forming polymer as described previously.

- in a first compartment, a composition A' comprising:

- in a second compartment, a composition A" comprising:

- at least one film-forming polymer as described previously, and

- at least one amino silicone as described previously.

According to one particular variant of the invention, the dyeing device according to the invention is a device for dyeing keratin fibres such as the hair, comprising several compartments containing:

- in a first compartment, a composition A' comprising:

- in a second compartment, a composition A" comprising:

- in a third compartment, a composition A'" comprising:

- at least one amino silicone as described previously and

- in a fourth compartment, a composition B according to the invention comprising: - at least one film- forming polymer as described previously.

The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific characteristics, variants and preferred embodiments of the invention.

Example

In the examples, the temperature is given in degrees Celsius and corresponds to room temperature (20°C-25°C), unless otherwise indicated, and the pressure is atmospheric pressure, unless otherwise indicated.

The following compositions are prepared (in g/100 g of unmodified starting material,

AM: Active Material): [Table 1]

[Table 2]

[Table 3]

1. Sold under the trade name KBE-903 by Shin-Etsu;

2. Synthetic Fluorophlogopite (and) Titanium Dioxide (and) Tin Oxide sold under the trade name Syncrystal Silk Silver by Eckart;

3. Sold under the trade name Belsil ADM 4000 E by Wacker;

4. Sold under the trade name Ecosmooth Satin by Dow Coming.

Protocol:

Comparative compositions Al' and Al", on the one hand, compositions A2' and A2" according to the invention and compositions A3' and A3" according to the invention, on the other hand, are mixed in a 50/50 ratio in order to obtain compositions Al, A2 and A3.

Comparative composition Al and compositions A2 and A3 according to the invention are applied with the fingers to locks of dry chestnut brown hair (TD4) in a proportion of 1 g of composition per gramme of lock.

The locks of hair are left for 2 min at room temperature.

Comparative composition Bl is then applied to the locks of hair treated with composition Al, in a proportion of 1 g of composition per gramme of lock. Compositions B2 and B3 according to the invention are then applied to the locks of hair treated with composition A2 or composition A3, respectively, in a proportion of 1 g of composition per gramme of lock.

The locks of hair are left for 5 min at room temperature.

The locks of hair are then dried with a hairdryer for 2 minutes. The locks of hair are left at room temperature for 24 hours before being evaluated by a panel of 8 experts.

Sensory evaluation:

For each lock of dyed hair, a panel of 8 experts evaluated the manageability and softness of the locks of hair.

A grade of between 0 and 5 was attributed for each of the two criteria for each lock of dyed hair.

A grade equal to 0 means that the hair is hardened, does not allow itself to be easily folded (poor manageability); and the perceived coating of the hair is crisp and rough and bumps are felt along the hair (poor perceived softness).

A grade equal to 5 means that the hair is easy to fold without resistance (good manageability) and the perceived coating of the hair is smooth (good perceived softness).

An average of the scores is calculated for each lock of dyed hair.

Results:

[Tables 4]

The hair dyed with compositions A2+B2 or A3+B3 according to the invention, comprising at least one amino silicone, exhibits better manageability of the hair and softness of the hair compared to the hair dyed with comparative composition Al + Bl not comprising any amino silicon. Thus, the coloured coating of the keratin fibres that is obtained with compositions A2+B2 or A3+B3 according to the invention exhibits good cosmetic properties in terms of softness or manageability of the hair.

Claims

1. Process for dyeing human keratin fibres such as the hair, comprising the following steps: a) applying to the keratin fibres at least one composition A comprising:

- at least one alkoxy silane chosen from the compounds of formula (I) or formula (I’) below, oligomers thereof and/or mixtures thereof:

(D in which:

- 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;

- Q represents a carbonyl group (CO);

- r denotes an integer ranging from 0 to 1, and

- at least one alkoxysilane of formula (II) below, oligomers thereof and/or mixtures thereof:

in which:

- k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;

in which R_n represents a hydroxyl group (OH); an alkyl group containing from 1 to 10 carbon atoms, preferably a methyl, and b) applying to the keratin fibres at least one composition B comprising:

2. Process according to Claim 1, in which the alkoxysilane(s), oligomers thereof and/or mixtures thereof are chosen from the compounds of formula (I) in which:

- Rd and R_e, which are identical, represent a hydrogen atom or Rd denotes a hydrogen atom and Re denotes a Cs-Ce cycloalkyl radical such as cyclohexyl;

5 and NH or a carbonyl group (CO), preferably NH;

- r denotes an integer equal to 0.

3. Process according to either one of the preceding claims, in which the alkoxysilane(s), oligomers thereof and/or mixtures thereof are chosen from the compounds of formula (I) in which R_a represents an ethoxy group, Rb and Rc are identical and represent an ethyl, Rd and R_e represent a hydrogen atom, A represents a propyl and r denotes an integer equal to 0.

4. Process according to any one of the preceding claims, in which the alkoxysilane(s) of formula (I) or of formula (I’), oligomers thereof and/or mixtures thereof is (are) present in a total amount ranging from 0.1% to 40% by weight, preferably from 0.5% to 30% by weight, preferentially from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 1.5% to 15% by weight, relative to the total weight of composition A.

5. Process according to any one of the preceding claims, in which the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof are such that:

- k denotes an integer equal to 0;

- Rf represents an alkyl group containing from 1 to 10 carbon atoms and in particular 1 to 4 carbon atoms, such as a methyl or an ethyl; preferably methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES).

6. Process according to any one of the preceding claims, in which the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof is (are) present in a total amount ranging from 0.5% to 90% by weight, preferably from 1% to 75% by weight, preferentially from 3% to 45% by weight and better still from 5% to 40% by weight, relative to the total weight of composition A.

7. Process according to any one of the preceding claims, in which the film-forming polymer(s) are chosen from vinylpyrrolidone homopolymers (PVP), acrylamide copolymers, acrylic acid ester homopolymers or copolymers, ethylene homopolymers or copolymers, and mixtures thereof.

8. Process according to any one of the preceding claims, in which the film-forming polymer(s) is (are) present in a total amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight and even more better still from 1% to 20% by weight, relative to the total weight of composition B.

9. Process according to any one of the preceding claims, in which composition A and/or composition B comprises (comprise) at least one amino silicone chosen from the amino silicones of formula (D) below:

in which:

- Ri, R2 and R3, which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Ri to R3 denoting an alkoxy radical; preferably, the alkoxy radical is a methoxy radical; or the amino silicones comprising at least one unit of formula (L) below:

10. Process according to any one of the preceding claims, in which the amino silicone(s) is (are) present in a total amount ranging from 0.1% to 30%, preferably from 1% to 25%, more preferentially from 3% to 20% and even more preferentially from 5% to 17% by weight relative to the total weight of composition A and/or composition B.

11. Process according to any one of the preceding claims, in which composition A and/or composition B comprises (comprise) at least one non-associative non-ionic cellulose-based polymer chosen from hydroxy(Ci-C4)alkylcelluloses, preferably hydroxy ethylcellulose and/or hydroxypropylcellulose.

12. Process according to Claim 11, in which the non-associative non-ionic cellulose- based polymer(s) is (are) present in a total amount preferably ranging from 0.01% to 10% by weight, preferentially from 0.05% to 5% by weight and better still from 0.1% to 3% by weight relative to the total weight of composition A and/or composition B.

13. Process according to any one of the preceding claims, in which the colouring agent(s) are present in a total amount ranging from 0.001% to 20%, preferably from 0.005% to 15% by weight and better still from 0.005% to 10% by weight relative to the total weight of composition A and/or composition B; preferably, the colouring agent(s) are chosen from pigments.

14. Device for dyeing keratin fibres such as the hair, comprising several compartments containing:

- in a first compartment, a composition A comprising: - at least one alkoxy silane chosen from the compounds of formula (I) or of formula (I’) as described according to any one of Claims 1 to 4, oligomers thereof and/or mixtures thereof, and

- at least one alkoxy silane of formula (II) as described according to any one of Claims 1, 5 or 6, oligomers thereof and/or mixtures thereof,

- at least one film-forming polymer as described according to either one of Claims 7 and 8, composition A and/or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, and composition A and/or composition B comprising at least one amino silicone as described according to either one of Claims 9 and 10.