FR3139721A1 - Hair coloring process comprising the application of a composition A comprising two alkoxysilanes, and the application of a composition B comprising a film-forming polymer - Google Patents

Abstract

Hair coloring process comprising the application of a composition A comprising two alkoxysilanes, and the application of a composition B comprising a film-forming polymer The subject of the present invention is a process for coloring keratin fibers such as hair, comprising the application to the keratin fibers 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 fibers of at least one composition B comprising at least one film-forming polymer. Said composition A and/or composition B comprise at least one insoluble fiber. Said composition A and/or composition B comprise at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof.

Description

Hair coloring process comprising the application of a composition A comprising two alkoxysilanes, and the application of a composition B comprising a film-forming polymer. Technical field of the invention

The present invention relates to a process for coloring keratin fibers such as hair, comprising the application to the keratin fibers of at least one composition A comprising at least one alkoxysilane chosen from the compounds of formula (I) or formula (I') and at least one alkoxysilane of formula (II), and the application to the keratin fibers of at least one composition B comprising at least one film-forming polymer. Said composition A and/or composition B comprise at least one insoluble fiber. Said composition A and/or composition B comprise at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof.

Background of the invention

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

There are basically three types of hair coloring processes:
(a) so-called permanent colouring, the function of which is to bring about a significant change in the natural colour and which uses oxidation dyes which penetrate the hair fibre and form the dye by a process of oxidative condensation;
b) non-permanent, semi-permanent or direct coloring, which does not involve the oxidative condensation process and is resistant to 4 or 5 shampoos; consists of dyeing keratin fibers with dye compositions containing direct dyes.
(c) temporary coloring which results in a change in the natural color of the hair that lasts from one shampoo to the next and which serves to enhance or correct a shade already obtained. It can also be likened to a “make-up” process.

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

However, the colors obtained by this coloring method have the disadvantage of having low resistance to shampoos as well as to external agents such as sebum, perspiration, brushing and/or friction.

There is therefore a need for a process for coloring keratin fibers, particularly hair, which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating that is resistant to shampoos and various aggressions that the hair may undergo such as brushing and/or friction without damaging the hair.

Thus, the aim of the present invention is to develop a process for coloring keratin fibers, in particular hair, which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating that is resistant to shampoos and various aggressions that the hair may undergo such as brushing and/or rubbing without damaging the hair.

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

The present invention relates to a process for coloring keratin fibers such as hair, comprising the following steps:
a) the application to keratin fibres of at least one composition A comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described below, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described below, its oligomers and/or their mixtures, and
b) the application to the keratin fibres of at least one composition B comprising at least one film-forming polymer as described below,
composition A and/or composition B comprising at least one insoluble fiber as described below, and
composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures.

The present invention also relates to a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described below, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described below, its oligomers and/or their mixtures,
- in a second compartment, a composition B according to the invention comprising at least one film-forming polymer as described below,
composition A and/or composition B comprising at least one insoluble fiber as described below, and
composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures.

By using this process, we obtain colored coatings on the hair that are resistant to shampoos and external aggressions that the hair may undergo such as blow-drying and perspiration.

For the purposes of the present invention, the term “ permanent coloring after shampooing ” means that the coloring obtained persists after at least one shampoo.

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

Unless otherwise indicated, the limits of a range of values are included in that range, particularly in the expressions “ between ” and “ ranging from … to … ”.

By “ keratin fibers ” we mean in particular human keratin fibers such as hair, eyelashes, eyebrows, and body hair, preferably hair, eyebrows and eyelashes, even more preferably hair.

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

For the purposes of the present invention, the term " silicone " means any organosilicon polymer or oligomer with a linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or by polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond -Si-O-Si-), optionally substituted hydrocarbon radicals being directly linked 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 “ aminoalkyl ” radical denotes an alkyl radical as defined above, said alkyl radical comprising an NH2 group;
- a “ hydroxyalkyl ” radical denotes an alkyl radical as defined above, said alkyl radical comprising an OH group;
- an “ alkylene ” radical denotes a divalent saturated _C1 - _C10 hydrocarbon group, linear or branched, such as methylene, ethylene, or propylene;
- a " cycloalkyl " or " alicycloalkyl " radical denotes a monocyclic or polycyclic saturated cyclic hydrocarbon group, preferably monocyclic, comprising from 1 to 3 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, norbornyl, or isobornyl, in particular cyclopropyl, cyclopentyl or a cyclohexyl. it being understood that the cycloalkyl radical may be substituted by one or more (C ₁ -C ₄ )alkyl groups such as methyl, preferably the cycloalkyl radical is then an isobornyl group,
- an “ aryl ” radical is an unsaturated and aromatic hydrocarbon cyclic radical, comprising from 6 to 30 carbon atoms, preferably between 6 and 14 carbon atoms, more preferably between 6 and 12 mono/bi/or tri/cyclic carbon atoms, fused or not, preferably the aryl group comprises 1 cycle with 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted by one or more (C ₁ -C ₄ )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 above;
- an “ alkoxy ” radical denotes an alkyl-oxy radical with “ alkyl ”, as defined above.

Unless otherwise indicated, when compounds are mentioned in this application, their optical isomers, their geometric isomers, their tautomers, their salts, alone or in mixture, are also meant.

The invention is not limited to the examples illustrated. The characteristics of the different examples may in particular be combined within non-illustrated variants.

Detailed description of the invention Composition A Alkoxysilane of formula (I) or of formula (I’):

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

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

APTES can for example be purchased from DOW CORNING 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.

Compounds of formula (I) may also designate DYNASYLAN SIVO 210 or DYNASYLAN 1505 sold by the company EVONIK.

3-ureidopropyltrimethoxysilane can for example be purchased from the company Gelest under the name SIU9058.0.

N-cyclohexylaminomethyl triethoxysilane can, for example, be purchased from WACKER under the name GENIOSIL XL 926.

Among the alkoxysilanes of formula (I’), their oligomers and/or their mixtures, 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]-1,2-ethanediamine (CAS RN: 457065-96-2), 1,2-ethanediamine, N1-[3-(triethoxysilyl)propyl]-N1-[3-(trimethoxysilyl)propyl]- (CAS RN: 1638528-78-5), and their mixtures.

Preferably, the alkoxysilane(s), their oligomers and/or their mixtures are chosen from the compounds of the following formula (I):
(I)
in which:
- R _a represents an alkyl group having from 1 to 10 carbon atoms, in particular from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group having from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy;
- R _b and R _c , identical or different, represent an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms such as an ethyl;
- R _d and R _e , identical, represent a hydrogen atom or R _d denotes a hydrogen atom and Re denotes a C5-C6 cycloalkyl radical such as cyclohexyl;
- A independently represents an alkylene group having from 1 to 10 linear or branched carbon atoms, which may be interrupted by at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
- r denotes an integer equal to 0.

Preferably, the alkoxysilane(s), their oligomers and/or their mixtures are chosen from the compounds of formula (I) in which R _a represents an ethoxy group, R _b and R _c are identical and represent an ethyl, R _d and R _e represent a hydrogen atom, A represents a propylene and r denotes an integer equal to 0.

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

The alkoxysilane(s) of formula (I) or of formula (I'), their oligomers and/or their mixtures 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, even better still from 1.5 to 15% by weight relative to the total weight of composition A.
According to a preferred embodiment, the alkoxysilane(s) of formula (I), their oligomers and/or their mixtures 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, 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 the following formula (II), its oligomers and/or their mixtures:
(II)
in which:
-R _has represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group having 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 having from 6 to 12 carbon atoms;
-R _b represents a hydrogen atom or an alkyl group having 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;
-R _c represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group having 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 having from 6 to 12 carbon atoms;
it being understood that ifR _has AndR _c do not represent an alkoxy group, thenR _b cannot represent a hydrogen atom;
-kdenotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;
-R _f represents a hydrogen atom; an alkyl group having from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms; or a group of the following formula (IIa):
(IIa)
in whichRnrepresents a hydroxy group (OH); an alkyl group having from 1 to 10 carbon atoms, preferably a methyl.

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

TEOS can for example be purchased from the company EVONIK under the name Dynasylan® A or Dynasylan® A SQ.

MTES can for example be purchased from the company EVONIK under the name Dynasylan® MTES.

DMDES can for example be purchased from the company GELEST under the reference SID3404.0.

Preferably, the alkoxysilane(s) of formula (II), their oligomers and/or their mixtures are such that:
- R _a represents an alkoxy group having 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 having from 1 to 10 carbon atoms optionally substituted by an aryl group, preferably 1 to 2 carbon atoms optionally substituted by an aryl group;
- R _b represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms such as a methyl or an ethyl;
- R _c represents an alkoxy group having 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 having from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms such as a methyl or an ethyl.

More preferably, the alkoxysilane(s) of formula (II), their oligomers and/or their mixtures are such that:
- R _a represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms such as methyl or ethyl;
- R _b represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms such as methyl or ethyl;
- R _c represents an alkoxy group having 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 having from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms such as a methyl or an ethyl.

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

The alkoxysilane(s) of formula (II), its oligomers and/or their mixtures 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 are C ₁ -C ₄ lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as glycerol, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols, such as 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 preferably 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 called monomers). This or these units are repeated at least twice and preferably at least 3 times.

By " hydrophobic polymer " is meant a polymer having a solubility in water at 25°C of less than 1% by weight.

By " hydrophilic polymer " is meant a polymer having a solubility in water at 25°C greater than or equal to 1% by weight.

By “ film-forming ” polymer is meant a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on keratin materials, and preferably a cohesive film.

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

In a particularly preferred embodiment, the hydrophobic film-forming polymer is a polymer selected from the group comprising:
- film-forming polymers soluble in an organic solvent medium, in particular liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and will form a single homogeneous phase when incorporated into the medium.
- film-forming polymers dispersible in an organic solvent medium, this 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 or hydrocarbon oils; in one embodiment, the non-aqueous polymer dispersions comprise polymer particles stabilized on their surface by at least one stabilizing agent; these non-aqueous dispersions are often called “NAD ( non-aqueous dispersions )”.
- film-forming polymers in the form of aqueous dispersions of polymer particles, this means that the polymer forms a water-insoluble phase, the polymer remaining stable and/or compatible once incorporated into water, the polymer particles being able to be stabilized on their surface by at least one stabilizing agent. These polymer particles are often called "latex"; in this case, the composition must comprise an aqueous phase.

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

As hydrophobic film-forming polymer, mention may be made in particular of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose, silicone polymers, acrylamide-type polymers, polyisoprenes.

Nonionic, amphoteric, anionic or cationic hydrophobic film-forming polymers can be used.

Preferably, the hydrophobic film-forming polymer(s) according to the invention are chosen from acrylic acid copolymers, methacrylic acid copolymers, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, vinylpyrrolidone copolymers, vinyl alcohol copolymers, vinyl acetate copolymers, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and/or polyamides.

The hydrophobic film-forming polymer may be chosen from homopolymers and copolymers of olefins such as cycloolefins; butadiene; isoprene; styrene; vinyl ethers, esters or amides; esters or amides of (meth)acrylic acid containing a linear, branched or cyclic C ₁ -C ₂₀ alkyl group, a C ₆ -C ₁₀ aryl group or a C ₂ -C ₆ hydroxyalkyl group.

The hydrophobic film-forming polymer may in particular be chosen from homopolymers and copolymers may be obtained from monomers chosen from the group consisting 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.

For example, we can cite the ethylene/sodium acrylate copolymer marketed under the trade name ECOSMOOTH SATIN® by the Dow company.

The hydrophobic film-forming polymer may be chosen in particular from homopolymers and copolymers which may be obtained from amides of acid monomers; mention may be made of (meth)acrylamides, and in particular N-alkyl (meth)acrylamides, in particular _C2 - _C12 alkyl such as N-ethyl acrylamide, Nt-butyl acrylamide, N-octyl acrylamide; N-dialkyl (C1-C4) (meth)acrylamides, perfluoroalkyl (meth)acrylates.

We can also cite the copolymers whose CTFA name (4th Ed., 1991) is Octylacrylamide/acrylates/butylaminoethyl-methacrylate copolymer, such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by the company NATIONAL STARCH as well as the copolymers whose CTFA name is Acrylates/octylacrylamide copolymer, such as the products sold under the name DERMACRYL® LT or DERMACRYL® 79 by the company NATIONAL STARCH.
According to a 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, methacrylic acid or (meth)acrylic acid esters containing a linear, branched or cyclic C ₁ -C ₆ alkyl group, as described under the INCI name Acrylates.

Such copolymers are marketed by the company ROHM AND HAAS under the name Aculyn®33.

Copolymers of unsaturated ethylenic acid esters and 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.

We will cite, for example, Aculyn®22 (Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn®28 (Acrylates/Beheneth-25 Methacrylate Copolymer), Structure 2001® (Acrylates/Steareth-20 Itaconate Copolymer), Structure 3001® (Copolymer Acrylates/Ceteth-20 Itaconate), Structure Plus® (Acrylates/Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C10-30 Alkyl acrylate Crosspolymer), Synthalen W2000® (Acrylates/Palmeth-25 Acrylate Copolymer) Or SOLTEX OPT (acrylate/C copolymer ₁₂ - ₂₂ alkyl methacrylate) marketed by the company ROHM AND HAAS.

The hydrophobic film-forming polymer may also be chosen from homopolymers and copolymers which may be obtained from vinyl monomers. Examples include homopolymers or copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl N-alkyl(C1-C6) pyrroles, vinyl oxazoles, vinyl thiazoles, vinylpyrimidines or vinylimidazoles.

Examples of vinylpyrrolidone copolymers that can be used in the invention include VP/vinyl laurate copolymer, VP/vinyl stearate copolymer, butylated polyvinylpyrrolidone (PVP), VP/hexadecene marketed by ISP under the name Ganex V216, VP/eicosene marketed 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 consisting of styrene or styrene-derived units (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, star or radial copolymer. The copolymer comprising at least one styrene block may further comprise, for example, an alkylstyrene block (AS), an ethylene/butylene block (EB), an ethylene/propylene block (EP), a butadiene block (B), an isoprene block (I), an acrylate block (A), a methacrylate block (MA) or a combination of these blocks. The copolymer comprising at least one block consisting of styrene or styrene-derived units may be a diblock or triblock copolymer, and in particular of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as those marketed or manufactured under the name “Luvitol HSB” by the company BASF SE.

Preferably, the hydrophobic film-forming polymer(s) according to the invention are chosen from vinylpyrrolidone (co)polymers, vinylalcohol (co)polymers, vinylacetate (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 preferably, the hydrophobic film-forming polymer(s) are chosen from polyvinylpyrrolidone copolymers, acrylamide copolymers, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of ethylene and mixtures thereof.

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

Nonionic, anionic or cationic hydrophilic film-forming polymers can be used.

The hydrophilic film-forming polymer may be chosen from vinylpyrrolidone (co)polymers, vinylalcohol (co)polymers, vinylacetate 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 (PVP) homopolymers and/or vinylpyrrolidone copolymers, more preferably vinylpyrrolidone (PVP) homopolymers.

Examples include vinylpyrrolidone (PVP) homopolymers marketed under the name Luviskol® K by BASF SE, in particular Luviskol® K 90 or Luviskol® K 85 by BASF SE.

The polymer PVP K30 marketed by Ashland Inc. (ISP, POI Chemical) can also be used. PVP K30 is a cold water soluble polyvinylpyrrolidone polymer with CAS number 9003-39-8 and molecular weight 40,000 g/mol.

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

We can also mention the vinylpyrrolidone/vinyl ester copolymers marketed under the name Luviskol® by the company BASF SE, in particular the non-ionic polymers Luviskol® VA64 and Luviskol® VA73 (vinylpyrrolidone/vinyl acetate copolymers).

Other examples include styrene/vinylpyrrolidone copolymers, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/DMAPA acrylate copolymers, vinylpyrrolidone/vinyl caprolactam/DMAPA acrylate copolymers.

Vinylpyrrolidone/vinyl caprolactam/DMAPA acrylate copolymers may be marketed by Ashland Inc. under the trade name Aquaflex® SF-40.

Vinylpyrrolidone/DMAPA acrylate copolymers may be marketed by Ashland Inc. under the trade name Styleze CC-10.

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

According to a 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 (PVP) homopolymers, 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, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of ethylene and mixtures thereof.

More preferably, the film-forming polymer(s) are chosen from vinylpyrrolidone (PVP) homopolymers, 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, even better from 1 to 20% by weight, relative to the total weight of composition B.

Composition A and/or B Insoluble fiber

Composition A and/or composition B according to the invention comprises (comprise) at least one insoluble fiber.

The insoluble fiber(s) are different from the film-forming polymers previously described.

By “ fiber ” is meant an object of length L and diameter D, D representing the diameter of the circle in which the section of the fiber is inscribed, such that L is greater than D, more preferably very large compared to D. In particular, the ratio L/D (or form factor) is chosen so as to be between 3.5 and 2500, more preferably between 5 and 500, better still between 5 and 150.

For the purposes of the present invention, the term " insoluble fiber " denotes a fiber that is not soluble in the medium in which said fiber is dispersed, said medium often being the solvent of the cosmetic composition, such as water or an organic solvent.

By " insoluble in the medium " is meant, for the purposes of the present invention, a compound insoluble in said medium at ordinary temperature (25°C) and at atmospheric pressure (760 mm Hg or 1.013.10 ⁵ Pa) (solubility less than 5% by weight, preferably 1% by weight, even more preferably 0.1% by weight).

The insoluble fiber(s) according to the invention preferably have a length ranging from 0.1 µm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.1 mm to 3 mm. They have a section included in a circle with a diameter ranging from 1 nm to 500 µm, preferably from 100 nm to 100 µm, and better still from 1 µm to 50 µm.

The insoluble fiber(s) may be flexible or rigid, short or long, unitary or organized, for example braided.

Their shape can be any and in particular circular, trilobed, multilobed or polygonal (triangular, rectangular, square, hexagonal or octagonal) section depending on the specific application envisaged.

According to a preferred embodiment, the insoluble fiber(s) according to the invention have a triangular, circular, rectangular or trilobed section.

The insoluble fibre(s) according to the invention may be fibres of synthetic origin, fibres of natural origin, fibres of mixed origin, i.e. of natural/synthetic origin, and mixtures thereof.

The insoluble fibre(s) of natural origin may in particular be chosen from flax, wool, cotton, silk, lignin, chitosan, insoluble collagen, bamboo or cellulose fibres, for example extracted from wood, vegetables or algae, and mixtures thereof.

The insoluble fibre(s) of synthetic origin may in particular be chosen from cellulose derivatives, viscose, polyvinyl derivatives, polyesters such as polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) or polypropylene (PP), polyamides such as Nylon®, or acrylic derivatives. In particular, the insoluble fiber(s) may be chosen from fibers of polyamide 6 (Nylon-6), polyamide 6,6 (Nylon-66), polyamide 12 (Nylon-12), modified cellulose, poly-p-phenylene terephthalamide, in particular Kevlar®, acrylic, aramid, carbon, polytetrafluoroethylene (Teflon®), polyvinyl or vinylidene chloride, polyvinyl alcohol, polyacrylonitrile, polyurethane, polyethylene phthalate, fibers formed from a mixture of polymers such as polyamide/polyester fibers, resorbable synthetic fibers, and mixtures thereof.

The insoluble fiber(s) may also be fibers of mixed origin, for example chosen from rayon fibers, polylactic acid (PLA), viscose/PET blend fibers, or viscose/polylactic acid (viscose/PLA) blend.

The insoluble fibre(s) may be in the form of a non-woven substrate comprising fibres of natural origin, fibres of synthetic origin, fibres of mixed origin and mixtures thereof.

A general description of nonwoven materials is given in the RIEDEL book " Nonwoven Bonding Methods & Materials ", Nonwoven World (1987). These substrates are obtained according to the usual processes of nonwoven preparation technology.

The insoluble fiber(s) may or may not be surface treated, coated or not.

As coated insoluble fibers that can be used in the invention, examples that may be mentioned include polyamide fibers coated with copper sulfide for an antistatic effect (for example, R-STAT fibers from the company Rhodia) or a surface treatment inducing color/hologram effects (for example, “Lurex” fiber from the company Sildorex).

Preferably, the insoluble fiber(s) according to the invention is (are) chosen from insoluble fibers of synthetic origin or insoluble fibers of mixed origin, more preferably from insoluble fibers of synthetic origin.

Preferably, the insoluble fiber(s) of synthetic origin according to the invention is (are) chosen from polyamide fibers, modified cellulose fibers, polyethylene fibers and their mixtures, more preferably from polyamide fibers such as Nylon-66.

For example, we can use Nylon-66 or Polyamide 6.6 in the form of fibers marketed by the company Utexbel under the trade name PULPE POLYAMIDE 12185 TAILLE 0.3 MM.

The insoluble fibre(s) may be present in a total amount ranging from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, better still from 0.5 to 3% by weight relative to the total weight of composition A and/or composition B.

Non-ionic non-associative cellulose polymer

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

The non-ionic non-associative cellulosic polymer is different from the film-forming polymers and fibers mentioned above.

According to the invention, the term “ cellulosic polymer ” means any polysaccharide polymer having in its structure chains of glucose residues united by beta-1,4 bonds.

By “ non-associative cellulose polymer ” is meant according to the invention that the cellulose polymers do not contain a _C8 - _C30 fatty chain.

The non-ionic non-associative cellulosic polymers may be selected from alkyl(C ₁ -C ₄ )celluloses, such as methylcelluloses and ethylcelluloses (e.g. Ethocel Standard 100 Premium from DOW CHEMICAL); hydroxyalkyl(C ₁ -C ₄ )celluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed hydroxyalkyl(C ₁ -C ₄ )alkyl(C ₁ -C ₄ )celluloses, such as hydroxypropylmethylcelluloses (e.g. Methocel E4M from DOW CHEMICAL), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (e.g. Bermocoll E 481 FQ from AKZO NOBEL), and hydroxybutylmethylcelluloses, and mixtures thereof.

Preferably, the non-associative non-ionic cellulose polymer(s) are chosen from hydroxyalkyl(C ₁ -C ₄ )celluloses.

More preferably, the non-associative non-ionic cellulose polymer(s) are hydroxyethylcellulose and/or hydroxypropylcellulose (HPC).

More preferably, composition A and/or composition B comprises (comprise) hydroxyethylcellulose and/or hydroxypropylcellulose (HPC).

In particular, mention may be made of hydroxyethylcellulose sold by Ashland Inc. under the trade name NATROSOL 250 HHR PC and hydroxypropylcellulose sold by Ashland Inc. under the trade name KLUCEL MF PHARM HYDROXYPROPYLCELLULOSE.

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

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

Coloring agent:

Composition A and/or composition B according to the invention comprises (comprise) at least one coloring agent chosen from pigments, direct dyes and their mixtures.

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

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

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

The term " pigment " means all pigments that impart color to keratin materials. Their solubility in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01% by weight.

The pigments which can be used are chosen in particular from organic and/or mineral pigments known in the art, in particular those which are described in the Kirk-Othmer encyclopedia of chemical technology and in the Ullmann encyclopedia of industrial chemistry.

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

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

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

The pigment may be a mineral pigment. By mineral pigment is meant any pigment that meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Among the mineral pigments useful in the present invention, mention may be made of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, titanium oxide and stannic oxide (tin oxide).

The pigment may be an organic pigment. By "organic pigment" we mean any pigment that meets the definition in the Ullmann encyclopedia in the organic pigment chapter.

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

In particular, the white or colored organic pigments 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 Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, 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, phenolic derivatives as described in patent FR 2 679 771.

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

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

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

Inorganic substrates on which dyes are adsorbed include, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

Among the colorants, we can cite carminic acid. We can also cite the colorants known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

Examples of lacquers include the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment can also be a special effect pigment. Special effect pigments are pigments that generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) that is non-uniform and changes depending on the observation conditions (light, temperature, observation angles, etc.). They are thus opposed to colored pigments that provide a conventional uniform opaque, semi-transparent or transparent shade.

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

Examples of special effect pigments include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above, as well as pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, we can cite Cellini pearlescent pigments marketed by BASF (Mica-TiO2-lacquer), Prestige marketed by Eckart (Mica-TiO2), Prestige Bronze marketed by Eckart (Mica-Fe2O3), Syncrystal marketed by Eckart (Mica-TiO2-SnO2), Colorona marketed by Merck (Mica-TiO2-Fe2O3).

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

As an example of mother-of-pearl, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

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

Finally, examples of nacres include polyethylene terephthalate flakes, including those marketed by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). Multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum can also be considered.

Special effect pigments may also be chosen from reflective particles, i.e. in particular particles whose size, structure, in particular the thickness of the layer(s) constituting them and their physical and chemical natures, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, i.e. brighter points which contrast with their environment by appearing to shine.

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

These particles can have various shapes, including being platelet-shaped or globular, particularly spherical.

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

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

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

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

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

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

Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, we can also cite particles comprising a borosilicate substrate coated with silver.

Platelet-shaped particles with a silver-coated glass substrate are sold under the name MICROGLASS METASHINE REFSX 2025 PS by TOYAL. Particles with a nickel/chromium/molybdenum alloy-coated glass substrate are sold under the name CRYSTAL STAR GF 550, GF 2525 by the same company.

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

Examples include aluminum, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

Other examples include interference pigments that are not fixed to a substrate, such as liquid crystals (Helicones HC from Wacker), interference holographic flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances that fluoresce in daylight or that produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the company Quantum Dots Corporation.

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

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

Pigments can be dispersed in the composition using a dispersing agent.

The dispersing agent serves to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can attach physically or chemically to the surface of the pigments. These dispersants also have at least one functional group compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C8 to C20 fatty acids and of polyols such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mole such as that sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures are used.

As another dispersant that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by the company Avecia, polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type, different from the alkoxysilanes of formula (I) or of formula (I’) previously described in the application and are cationic.

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

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

In another variant of the invention, the pigment(s) according to the invention are mineral pigments.

In another variant of the invention, the pigments according to the invention are special effect pigments, preferably pearlescent pigments, more preferably colored pearlescent pigments.

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

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

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 as mixtures.

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

Particularly, mention may be made of the direct dyes with endocyclic azo and hydrazono cationic charges of formula (III) to (VI) as defined above. More particularly, the direct cationic dyes with endocyclic cationic charges described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

Preferably, the following direct dyes:
(VII)
(VIII)
formulas (VII) and (VIII) in which:
- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;
- R ² and R ³ , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; and
- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R ⁴ is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferably CH,
- Q- is an anionic counterion as defined above particularly halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

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

The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances. Anionic direct dyes are understood to mean any direct dye comprising in its structure at least one CO ₂ R or SO ₃ R 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 acidic nitrated direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural 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) diaryl anionic azo dyes of formula (IX) or (IX'):
(IX)
(IX')
formula (IX) and (IX') in which:
- R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen atom, sulfur atom or NR with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
- R''-S(O) ₂ -, with R'' representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group;
- R'''-S(O) ₂ -X'- with R''' representing an alkyl group, optionally substituted aryl, X' as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+ and iv) alkoxy with M+ as defined above;
- optionally substituted heteroaryl; preferably a benzothiazolyl group;
- cycloalkyl; in particular cyclohexyl,
- Ar-N=N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O)2S(O-)-, M+ or phenylamino groups;
- or two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused group benzo A'; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a fused group benzo B'; with A' and B' optionally substituted by one or more groups selected from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X'' and Ar as defined previously;
- W represents a sigma σ bond, an oxygen atom, a sulfur atom, or a divalent radical i) –NR- with R as defined above, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, identical or different, representing a hydrogen atom or an aryl group, or else Ra and Rb form together with the carbon atom which carries them a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb form together a cyclohexyl;
it being understood that formulas (IX) and (IX') comprise at least one sulfonate radical (O) ₂ S(O-)-, M+ or one carboxylate radical (O)CO--, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate;

As an example of dyes of formula (IX), we can cite: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; Food yellow 3 or sunset yellow; and as an example of dyes of formula (IX') we can cite: Acid Red 111, Acid Red 134, Acid yellow 38.

(b) anionic pyrrazolone azo dyes of formula (X) and (X’):
(X)
(X’)
formulas (X) and (X’) in which:
-R ₁₁ , R ₁₂ and R ₁₃ , identical or different, represent a hydrogen atom, halogen, an alkyl group or -(O)₂S(O-), M+ with M+ as defined previously;
-R ₁₄ represents a hydrogen atom, an alkyl group or a -C(O)O-, M+ group with M+ as defined above;
-R ₁₅ represents a hydrogen atom;
-R ₁₆ represents an oxo group in which case R’₁₆is absent, or else R₁₅with R₁₆together form a double bond;
-R ₁₇ and R ₁₈ , 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; preferably a phenyl optionally substituted by one or more alkyl groups;
-R ₁₉ and R ₂₀ , together form either a double bond or a benzo D’ group, optionally substituted;
-R' ₁₆ , R' ₁₉ and R' ₂₀ , identical or different, represent a hydrogen atom or an alkyl or hydroxy group;
-R ₂₁ represents a hydrogen atom, an alkyl or alkoxy group;
-RaAndRbidentical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group;
-Yrepresents either a hydroxy group or an oxo group;
-represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;
it being understood that formulas (X) and (X’) comprise at least one sulfonate radical (O)₂S(O-)-, M+ or a carboxylate radical -C(O)O-, M+ on one of the rings D or E; preferably sodium sulfonate;

Examples of dyes of formula (X) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of dyes of formula (X') include: Acid Yellow 17;

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

Examples of dyes of formula (XI) include: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet No. 2; and examples of dyes of formula (XI') include: Acid Black 48;

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

Examples of dyes of formula (XII) include: Acid Brown 13; Acid Orange 3; examples of dyes of formula (XII') include: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid sodium salt, 2-piperidino 5-nitro benzene sulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7;

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

Examples of dyes of formula (XIII) include: 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) xanthene-derived dyes of formula (XIV):
(XIV)
formula (XIV) in which:
- R ₄₅ , R ₄₆ , R ₄₇ and R ₄₈ , identical or different, represent a hydrogen atom or a halogen atom;
- R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ , identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
particularly R ₅₃ R ₅₄ , R ₅₅ and R ₄₈ represent a hydrogen or halogen atom;
- G represents an oxygen atom, sulfur atom or an NRe group with Re as defined above; particularly G represents an oxygen atom;
- L represents an alcoholate O-, M+; a thioalcoholate S-, M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined above; M+ is particularly sodium or potassium;
- L' represents an oxygen atom, sulfur atom or an ammonium group: N+RfRg, with Rf and Rg , identical or different, representing a hydrogen atom, an alkyl group, optionally substituted aryl; L' particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O) _m S(O-)-, M+ with m and M+ as defined above;
- Q and Q' , identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
- M+ is as defined previously;

Examples of dyes of formula (XIV) include: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

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

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

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

Examples of dyes of formula (XVI) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

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

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

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

The pigment(s) may be present in a total amount ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 0.5 to 10% by weight relative to the total weight of 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, preferably from 0.005 to 5% by weight relative to the total weight of composition A and/or composition B.

Solvents :

Composition A and/or composition B used in the process according to the invention may comprise water.

Preferably, the water is present in a content ranging from 0.1% to 95% by weight, more preferably from 1% to 90% by weight, 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, more preferably, the pH of composition A and/or composition B is between 9 and 11.

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 an alkaline agent, we can cite ammonia, alkanolamines, and/or basic amino acids.

Preferably, the alkanolamine(s) are chosen from monoethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, trishydroxymethylaminomethane.

More preferably, the alkanolamine(s) are chosen from monoethanolamine and/or 2-amino-2-methyl-1-propanol.

For the purposes of the invention, the term " amino acid " means organic compounds having two functional groups: both a carboxyl group –COOH or carboxylate and an amine group –NH2, the amine group optionally being methylated, i.e. in the form –NR2 or N ⁺ R3, where at least one R=CH3.

Preferably, the amino acid(s) are chosen from aminocarboxylic acids such as alpha-aminocarboxylic acid.

By " basic amino acid " we mean amino acids having an isoelectric point greater than 7.

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

According to a particular embodiment, composition A and/or composition B may 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 metasilicate, potassium silicate, sodium carbonate and/or potassium carbonate.

Composition A and/or composition B may also include acidifying agents to adjust 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 usually used.

Among the additives that may be contained in the composition, mention may be made of reducing agents, thickening agents other than the polymers previously described, softeners, anti-foaming agents, moisturizing agents, UV filters, peptizers, dispersants, solubilizing agents, perfumes, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, preservatives, thickeners, fillers other than the insoluble fibers previously described, oils, waxes and mixtures thereof.

Composition A and/or composition B may be applied in particular to the hair in the form of a spray, cream, gel or mousse.

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

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

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

According to a more preferred embodiment, composition A according to the invention comprises 3-aminopropyltriethoxysilane (APTES), methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES), one or more polyamide fiber(s) such as Nylon-66 and at least one pigment.

According to a preferred embodiment, composition B according to the invention comprises at least one film-forming polymer chosen from vinylpyrrolidone (PVP) homopolymers, vinylpyrrolidone copolymers, acrylamide copolymers, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of ethylene and their mixtures and at least one insoluble fiber as described above.

According to a more preferred embodiment, composition B according to the invention comprises at least one film-forming polymer chosen from vinylpyrrolidone (PVP) homopolymers, acrylamide copolymers, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of ethylene and their mixtures, and one or more polyamide fiber(s) such as Nylon-66.

Process for treating keratin fibers

The present invention relates to a process for coloring keratin fibers such as hair, comprising the following steps:
a) the application to keratin fibres of at least one composition A comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
b) the application to the keratin fibres of at least one composition B comprising at least one film-forming polymer as described above,
composition A and/or composition B comprising at least one insoluble fiber, and
composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures.

Preferably, composition A and composition B according to the invention are compositions for coloring keratin fibers, such as hair.

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

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

According to a preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the application to said keratin fibers of composition A according to the invention comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures,
- at least one insoluble fiber as described above, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application to said keratin fibers of composition B according to the invention comprising at least one film-forming polymer as described above.
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

According to another preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the application to said keratin fibers of composition A according to the invention comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising:
- at least one film-forming polymer as described above, and
- at least one insoluble fiber as described above,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

According to another preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the application to said keratin fibers of composition A according to the invention comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
- at least one insoluble fiber as described above,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising:
- at least one film-forming polymer as described above, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

According to another preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the application to said keratin fibers of composition A according to the invention comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising:
- at least one film-forming polymer as described above,
- at least one insoluble fiber as described above, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

According to another preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the application to said keratin fibers of composition A according to the invention comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures,
- at least one insoluble fiber as described above, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising:
- at least one film-forming polymer as described above, and
- at least one insoluble fiber as described above,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

According to another preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the application to said keratin fibers of composition A according to the invention comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
- at least one insoluble fiber as described above,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising:
- at least one film-forming polymer as described above,
- at least one insoluble fiber as described above, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

The term “ rinsing step ” refers to the application of water to the keratin fibers.

Compositions A and B according to the invention can be used on dry or wet keratin fibres, as well as on all types of fibres, light or dark, natural or coloured, permed, bleached or straightened.

According to a particular embodiment of the process of the invention, the fibers are washed before application of compositions A and B according to the invention.

The application of compositions A and B according to the invention to keratin fibers can be carried out by any conventional means, in particular by means of a comb, a brush, a brush or with the fingers.

The coloring process, i.e. application of compositions A and B according to the invention to keratin fibers, is generally carried out at room temperature (between 15 and 25°C).

After applying composition A or composition B to the keratin fibres, it is preferable to have a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A or composition B on said fibres.

According to a preferred embodiment, the process for coloring keratin fibers such as hair comprises:
i) the preparation of 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 chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures and
the second composition A'' includes:
- at least one insoluble fiber as described above, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
ii) the application to said keratin fibres of composition A according to the invention,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising at least one film-forming polymer as described above,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

In order to allow better conservation of composition A’, it preferably has a low water content or is anhydrous.

Composition A’ may comprise a water content of between 0.001 and 10% by weight, better between 0.5 and 10% by weight, more preferably between 1 and 8% by weight relative to the weight of composition A’.

Composition A’’ may also contain water.

According to a particular embodiment, the process for coloring keratin fibers such as hair comprises:
i) the preparation of 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 chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
the second composition A'' comprises at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
ii) the application to said keratin fibres of composition A according to the invention,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising:
- at least one film-forming polymer as described above, and
- at least one insoluble fiber as described above,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

According to another particular embodiment, the process for coloring keratin fibers such as hair comprises:
i) the preparation of 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 chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
the second composition A'' comprises at least one coloring agent chosen from pigments, direct dyes, and their mixtures, and
the third composition A''' comprises at least one insoluble fiber as described above,
ii) the application to said keratin fibres of composition A according to the invention,
ii) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition A on said fibers,
iii) optionally a step of washing, rinsing, spinning or drying said fibers,
iv) the application of composition B according to the invention comprising at least one film-forming polymer as described above,
v) optionally a setting time of 10 seconds to 20 minutes, in particular 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B according to the invention on said fibers,
vi) optionally a washing, rinsing, spinning step and
vii) optionally a step of drying and/or heating the keratin fibres, for example at a temperature greater than or equal to 30°C.

After applying compositions A and B according to the invention and before a possible step of applying heat to the keratin fibres, the keratin fibres can be subjected to a drying step, for example using a hair dryer.

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

The drying step can be carried out using absorbent paper, a hair dryer, a hair dryer or even in the open air.

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

After applying compositions A and B according to the invention to the keratin fibres, it is possible to wait at least 10 seconds, preferably 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 fibers, the method according to the invention may comprise a step of applying heat to the keratin fibers using a heating tool.

Preferably, the method according to the invention does not include a step of applying heat to the keratin fibers using a heating tool in addition to the possible drying step.

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

Preferably, the heat application step of the method of the invention is carried out using a hair dryer and/or a hair straightener, more preferably using a hair dryer.

During the heat application stage on the keratin fibres, a mechanical action on the strands can be carried out such as combing, brushing, or passing the fingers through them.

When the step of applying heat to the keratin fibres is carried out using a helmet or a hair dryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.

When the step of applying heat to the keratin fibres is carried out using a hair straightener, the temperature is preferably between 110 and 240°C, preferably between 110 and 200°C.

Multi-compartment device (kit)

The present invention also relates to a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures,
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures,
- in a second compartment, a composition B according to the invention comprising at least one film-forming polymer as described above,
composition A and/or composition B comprising at least one insoluble fiber as described above,
composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures.

According to a preferred variant of the invention, the coloring device according to the invention is a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures, and
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
- in a second compartment, a composition B according to the invention comprising at least one film-forming polymer as described above,
composition A and/or composition B comprising at least one insoluble fiber as described above.

The present invention also relates to a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A' comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures;
- in a second compartment, a composition A'' comprising:
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
- in a third compartment, a composition B according to the invention comprising at least one film-forming polymer as described above, and
composition A' and/or composition A'' and/or composition B comprising at least one insoluble fiber as described above.

According to a preferred variant of the invention, the coloring device according to the invention is a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A' comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures;
- in a second compartment, a composition A'' comprising:
- at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
- at least one insoluble fiber as described above and
- in a third compartment, a composition B according to the invention comprising at least one film-forming polymer as described above.

According to another preferred variant of the invention, the coloring device according to the invention is a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A' comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures;
- in a second compartment, a composition A'' comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
- in a third compartment, a composition B according to the invention comprising:
- at least one film-forming polymer as described above, and
- at least one insoluble fiber as described above.

According to a particular variant of the invention, the coloring device according to the invention is a device for coloring keratin fibers such as hair, comprising several compartments containing:
- in a first compartment, a composition A' comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described above, their oligomers and/or their mixtures, and
- at least one alkoxysilane of formula (II) as described above, its oligomers and/or their mixtures;
- in a second compartment, a composition A'' comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures,
- in a third compartment, a composition A''' comprising at least one insoluble fiber as described above and
- in a fourth compartment, a composition B according to the invention comprising at least one film-forming polymer as described above.

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

Examples

In the examples, temperature is given in degrees Celsius, and corresponds to room temperature (20-25°C), unless otherwise stated, and pressure is atmospheric pressure, unless otherwise stated.
The following compositions are prepared (in g/100g of raw material as is): Composition HAS' 3-Aminopropyltriethoxysilane (APTES) ⁽¹⁾ 24 Methyltriethoxysilane (MTES) 72 Ethanol Qsp 100

Composition A1’’ (invention) A2’’ (invention) A3’’ (comparison) Pigment ⁽²⁾ 10 10 10 Hydroxypropylcellulose 4 4 4 Nylon-66 fibers ⁽³⁾ 1.5 - - Ethanol Qsp 100 Qsp 100 Qsp 100

Composition B1 (invention) B2 (invention) B3 (comparative) Ethylene/sodium acrylate copolymer ⁽⁴⁾ 15 15 15 Nylon-66 fibers ⁽³⁾ - 1.5 - Water Qsp 100 Qsp 100 Qsp 100

1. Sold under the trade name KBE-903 by the Shin Etsu company;
2. SYNTHETIC FLUORPHLOGOPITE (and) TITANIUM DIOXIDE (and) TIN OXIDE sold under the trade name SYNCRYSTAL SILK SILVER by the company Eckart;
3. Sold under the trade name PULPE POLYAMIDE 12185 SIZE 0.3MM by the company UTEXBEL (99% active material)
4. Sold under the trade name ECOSMOOTH SATIN by the Dow Corning company (at 25% active ingredient in water).

Protocol:

Compositions A’ and A1’’, compositions A’ and A2’’ and compositions A’ and A3’’ are mixed in a 50/50 ratio to obtain, respectively, compositions A1, A2 and A3.

The composition according to the invention A1, the composition according to the invention A2 and the comparative composition A3 are applied with the finger to locks of dry brown hair (HT4), at a rate of 1 g of composition per gram of lock.

The hair strands are left for 5 minutes at room temperature.

Composition B1, B2 or B3 is then applied with the finger to the strands of hair treated respectively with composition A1, composition A2 or composition A3, at a rate of 1 g of composition per gram of strand.

The hair strands are left for 5 minutes at room temperature.

The hair strands are then dried with a hair dryer for 2 minutes.

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

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

Shampoo protocol:

The following shampoo is performed on the strands obtained after applying the hair dryer.

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

The hair strands are then rinsed, combed and blow-dried.

Results :

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

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

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

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

In this equation, for the persistence of hair color after shampooing, L*, a*, b* represent the values measured after hair coloring and after shampooing, and L0*, a0*, b0* represent the values measured after hair coloring but before shampooing.

The results are shown in the table below:

Compositions Number of shampoos L* has* b* ΔE compared to wick before and after shampooing Composition A1 + B1 (invention) 0 37.5 1.7 0.1 - 1 37.1 1.8 0.1 0.4 Composition A2 + B2 (invention) 0 36.9 1.8 0.2 - 1 36.0 1.8 0.0 0.9 Composition A3 + B3 (comparison) 0 37.1 1.8 0.6 - 1 33.9 2.1 1.4 3.3

The locks of hair colored with the compositions A1 + B1 and A2 + B2 according to the invention comprising at least one insoluble fiber as described above and washed with a shampoo have low ΔE values compared to the locks of hair colored with the comparative composition A3 + B3 not comprising any insoluble fiber and washed with a shampoo.

Thus, the colored coating of the keratin fibers obtained with the compositions according to the invention comprising at least one insoluble fiber as described above, has good persistence to shampoos.

Claims (15)

Process for coloring keratin fibers such as hair comprising the following steps:
a) the application to keratin fibres of at least one composition A comprising:
- at least one alkoxysilane chosen from the compounds of formula (I) or formula (I’) below, their oligomers and/or their mixtures:
(I)
(I’)
in which:
-Rarepresents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group having 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 having from 6 to 12 carbon atoms;
-RbAndRc; identical or different represent a hydrogen atom; an alkyl group having 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 ifRadoes not represent an alkoxy group, thenRbAndRccannot simultaneously represent a hydrogen atom;
-RdAndD, identical or different, represent a hydrogen atom; an alkyl group having 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 having from 3 to 20 carbon atoms; an aryl group having from 6 to 12 carbon atoms; an aminoalkyl group having from 1 to 20 carbon atoms;
-HASindependently represents an alkylene group having from 1 to 10 linear or branched carbon atoms, which may be interrupted by at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH
-Qrepresents a carbonyl group (CO);
-rdenotes an integer ranging from 0 to 1, and
- at least one alkoxysilane of the following formula (II), its oligomers and/or their mixtures:
(II)
in which:
-R _has represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group having 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 having from 6 to 12 carbon atoms;
-R _b represents a hydrogen atom or an alkyl group having 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;
-R _c represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted by an aryl group; an alkoxy group having 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 having from 6 to 12 carbon atoms;
it being understood that ifRaAndRcdo not represent an alkoxy group, thenRbcannot represent a hydrogen atom
-kdenotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;
-R _f represents a hydrogen atom; an alkyl group having from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms; or a group of the following formula (IIa):
(IIa)
in whichRnrepresents a hydroxy group (OH); an alkyl group having from 1 to 10 carbon atoms, preferably a methyl, and
b) the application to the keratin fibres of at least one composition B comprising at least one film-forming polymer,
composition A and/or composition B comprising at least one insoluble fiber,
composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures. Process according to the preceding claim in which the alkoxysilane(s), their oligomers and/or their mixtures are chosen from the compounds of formula (I) in which:
- R _a represents an alkyl group having from 1 to 10 carbon atoms, in particular from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group having from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy;
- R _b and R _c , identical or different, represent an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms such as an ethyl;
- R _d and R _e , identical, represent a hydrogen atom or R _d denotes a hydrogen atom and Re denotes a C ₅ -C ₆ cycloalkyl radical such as cyclohexyl;
- A independently represents an alkylene group having from 1 to 10 linear or branched carbon atoms, which may be interrupted by at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
- r denotes an integer equal to 0. Process according to any one of the preceding claims, in which the alkoxysilane(s), their oligomers and/or their mixtures are chosen from the compounds of formula (I) in which R _a represents an ethoxy group, R _b and R _c are identical and represent an ethyl, R _d and R _e represent a hydrogen atom, A represents a propylene and r denotes an integer equal to 0. Process according to any one of the preceding claims, in which the alkoxysilane(s) of formula (I) or of formula (I’), their oligomers and/or their mixtures 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, even better still from 1.5 to 15% by weight, relative to the total weight of composition A. Process according to any one of the preceding claims, in which the alkoxysilane(s) of formula (II), their oligomers and/or their mixtures are such that:
-R _has represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms such as methyl or ethyl;
-R _b represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms such as methyl or ethyl;
-R _c represents an alkoxy group having 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
-kdenotes an integer equal to 0;
-R _f represents an alkyl group having from 1 to 10 carbon atoms and in particular from 1 to 4 carbon atoms such as a methyl or an ethyl,
preferably methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES). Process according to any one of the preceding claims, in which the alkoxysilane(s) of formula (II), its oligomers and/or their mixtures is (are) 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. Process according to any one of the preceding claims, in which the film-forming polymer(s) are chosen from vinylpyrrolidone (PVP) homopolymers, acrylamide copolymers, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of ethylene and mixtures thereof. 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, even better from 1 to 20% by weight, relative to the total weight of composition B. Method according to any one of the preceding claims, in which the insoluble fibre(s) is (are) chosen from insoluble fibres of synthetic origin or insoluble fibres of mixed origin, more preferably from insoluble fibres of synthetic origin. Method according to the preceding claim, in which the insoluble fiber(s) of synthetic origin is (are) chosen from polyamide fibers, modified cellulose fibers, polyethylene fibers and their mixtures, more preferably polyamide fibers such as Nylon-66. Process according to any one of the preceding claims, in which the insoluble fibre(s) is (are) present in a total amount ranging from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, better still from 0.5 to 3% by total weight of the composition comprising it. Process according to any one of the preceding claims, in which composition A and/or composition B comprises (comprise) at least one non-ionic non-associative cellulose polymer chosen from hydroxyalkyl(C ₁ -C ₄ )celluloses, preferably hydroxyethylcellulose and/or hydroxypropylcellulose. Process according to the preceding claim, in which the non-associative non-ionic cellulose 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, better still from 0.1 to 3% by weight relative to the total weight of composition A and/or composition B. Process according to any one of the preceding claims, in which the coloring agent(s) are present in a total amount ranging from 0.001 to 20%, preferably from 0.005% to 15% by weight, better still from 0.005 to 10% by weight relative to the total weight of composition A and/or composition B, preferably, the coloring agent(s) are chosen from pigments. Device for coloring keratin fibers such as hair comprising several compartments containing:
- in a first compartment, a composition A comprising:
at least one alkoxysilane chosen from the compounds of formula (I) or of formula (I') as described according to any one of claims 1 to 4, their oligomers and/or their mixtures;
at least one alkoxysilane of formula (II) as described according to any one of claims 1, 5 or 6, its oligomers and/or their mixtures;
- in a second compartment, a composition B comprising at least one film-forming polymer as described according to any one of claims 1, 7 or 8,
composition A and/or composition B comprising at least one insoluble fiber as described according to any one of claims 1, 9-11,
composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes and their mixtures.