Process for dyeing keratin hair fibres involving spraying keratin hair fibres with composition comprising (poly) carbodiimide compound and colorant using spray gun

Abstract

The present invention relates to a process for dyeing keratin hair fibres involving spraying keratin hair fibres with at least one composition (C) using a spray gun, comprising:-at least one (poly) carbodiimide compound; and-at least one colorant selected from the group consisting of pigments, direct dyes and mixtures thereof.

Description

Technical field

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which involves spraying the keratinous hair fibers with a composition C comprising at least one (poly)carbodiimide compound and a colorant using a spray gun. Background art

[0002] In the field of dyeing keratinous hair fibers, in particular human keratin fibers, it is known practice to dye keratinous hair fibers using direct dyes or pigments for non-permanent coloring or dye precursors for permanent coloring by various techniques.

[0003] Basically, there are three types of methods for dyeing keratinous hair fibers:

[0004] a) "Permanent" dyeing, which functions to provide a substantial change to the natural color and uses oxidation dyes that penetrate into the keratinous hair fibers and form a dyeing through an oxidative condensation process;

[0005] b) Non-permanent, semi-permanent or direct coloring, which does not use an oxidative condensation process and withstands four or five shampoo washes; it involves coloring the keratin fibers with a coloring composition containing a direct dye;

[0006] c) Temporary dyeing, which causes a change in the natural color of the keratinous hair fibers that remains from one shampoo wash to the next and is used to enhance or correct the tones already obtained. It can also be compared to a "make-up" process.

[0007] Another dyeing method involves the use of pigments. Specifically, the use of pigments on the surface of keratin fibers generally enables the obtaining of a coloring visible on dark keratinous hair fibers since the surface pigments mask the natural color of the fibers. However, the coloring obtained by this dyeing method has the drawback of having poor tolerance to shampoo washes and also to external agents such as sebum, sweat, brushing and / or friction.

[0008] Therefore, there is still a need for a method for dyeing keratinous hair fibers that has the following advantages: obtaining a uniform coloring coating on the keratinous hair fibers while forming a coating that is durable with respect to shampoo washes and the various stresses (such as brushing and / or friction) that the keratinous hair fibers may undergo, without compromising the cosmetic properties of the keratinous hair fibers.

[0009] Accordingly, an object of the present invention is to develop a method for dyeing keratinous hair fibers, which has the following advantages: obtaining a smooth and uniform coloring coating on the keratinous hair fibers, while forming a coating that is durable with respect to shampooing and various stresses (such as brushing and / or rubbing) that the keratinous hair fibers may undergo, without compromising the cosmetic properties of the keratinous hair fibers. Summary of the Invention

[0010] Accordingly, a subject of the present invention is a method for dyeing keratinous hair fibers, which involves spraying the keratinous hair fibers with at least one composition C using a spray gun, and the at least one composition comprises:

[0011] - at least one (poly)carbodiimide compound; and

[0012] - at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0013] By means of the method for dyeing keratinous hair fibers according to the present invention, coloring coatings are obtained on the keratinous hair fibers, and these coatings enable obtaining a coloring that is visible on all types of keratinous hair fibers and is durable with respect to shampooing, while retaining the physical quality of the keratinous hair fibers. Such coatings can withstand external stresses that the keratinous hair fibers may undergo, such as blow-drying and sweating. In particular, it allows for easily obtaining a thin and uniform deposit without any running phenomenon, and the deposit dries quickly.

[0014] Different from conventional aerosol devices (pressurized packaging of the composition to be sprayed), the composition can be stored in a non-pressurized form (i.e., at atmospheric pressure) in a container carried by or connected to the spray gun before use.

[0015] Another subject of the present invention is a spraying system, which comprises a spray gun and at least one compartment for containing the composition C. Description of the Drawings

[0016] The present invention can be more clearly understood by reading the following detailed description of the spray gun, its non-limiting usage examples, and examining the drawings, in which:

[0017] Figure 1 schematically and partially shows an example of the spray gun and the compressed air feeding system for the spray gun,

[0018] Figure 2 shows a perspective view of the spray gun. Detailed Description

[0019] ​​For the purposes of the present invention, the term "coloring persistent relative to shampooing" means that the coloring is persistent after one shampooing, preferably after three shampooings.

[0020] The term "at least one" means one or more.

[0021] Unless otherwise indicated, the limits of a range of values are included in the range, in particular in the expressions "between... and..." and "ranging from... to...".

[0022] The present invention is not limited to the examples shown. The features of the different examples can in particular be combined in variants not shown.

[0023] For the purposes of the present invention and unless otherwise indicated:

[0024] - "alkyl" denotes a straight-chain or branched-chain saturated group containing, for example, from 1 to 20 carbon atoms;

[0025] - "aminoalkyl" denotes an alkyl as defined previously, which alkyl contains an NH2 group;

[0026] - "hydroxyalkyl" denotes an alkyl as defined previously, which alkyl contains an OH group;

[0027] - "alkylene" denotes a straight-chain or branched-chain divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene or propylene;

[0028] - "cycloalkyl" or "alicyclic alkyl" denotes a cyclic saturated monocyclic or bicyclic, preferably monocyclic, hydrocarbon-based group containing from 1 to 3 rings, preferably 2 rings and containing from 3 to 24 carbon atoms, particularly containing from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, particularly cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl can be substituted by one or more (C1-C4) alkyls such as methyl; preferably, the cycloalkyl is isobornyl;

[0029] - "cycloalkylene" denotes a divalent cycloalkyl, where "cycloalkyl" is as defined previously, preferably C3-C 12 ;

[0030] - "Aryl" is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated and aromatic hydrocarbon-based cyclic group, which contains from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, aryl contains 1 ring having 6 carbon atoms, such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it should be understood that aryl can be substituted by one or more (C1-C4) alkyl groups such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, aryl represents phenyl;

[0031] - "Arylene" is a divalent aryl group, where "aryl" is as defined previously; preferably, arylene represents phenylene;

[0032] - "Heterocyclic" group denotes a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group, which contains one or more heteroatoms, preferably from 1 to 5 atoms selected from O, S or N, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furyl;

[0033] - "Heterocycloalkylene" is a divalent heterocyclic group, where "heterocyclic" is as defined previously;

[0034] - "Aryloxy" denotes aryl-oxy, where "aryl" is as defined previously;

[0035] - "Alkoxy" denotes alkyl-oxy, where "alkyl" is as defined previously;

[0036] - "Acetyloxy" denotes an ester group R-C(O)-O-, where R is an alkyl group as defined previously;

[0037] - "Reactive" group is a group capable of forming a covalent bond with another same or different group through a chemical reaction.

[0038] Unless otherwise indicated, when referring to a compound in this patent application, it also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or as a mixture.

[0039] The term "keratin hair fiber" means a keratin hair fiber or hair. In other words, the expressions "keratin hair fiber", "keratin hair fiber" and "hair" are equivalent in the subsequent part of the specification.

[0040] For the purposes of the present invention, the term "keratin hair fiber" means a keratin hair fiber on the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0041] Polycarbodiimide compound

[0042] The composition C used in the context of the method according to the invention contains at least one (poly)carbodiimide compound.

[0043] The composition may comprise at least two different (poly)carbodiimide compounds, which are present in the composition as a mixture.

[0044] The term "(poly)carbodiimide compound" means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100.

[0045] The term "carbodiimide group" means a divalent straight-chain triatomic moiety of the general formula -(N=C=N)-.

[0046] The (poly)carbodiimide compound according to the invention may optionally contain in its structure one or more reactive groups different from carbodiimide groups, which are selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups.

[0047] The reactive groups other than carbodiimide groups may be side groups or end groups. Preferably, the (poly)carbodiimide compound contains one or more end groups different from carbodiimide groups, preferably one or more end groups selected from: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups.

[0048] According to a specific embodiment, the (poly)carbodiimide compound is selected from the compounds of the following formula (I):

[0049]

[0050] wherein:

[0051] - X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0052] - R1 and R2 independently represent: a group selected from hydrocarbon-based groups, preferably alkyl groups, which may optionally be inserted with one or more heteroatoms; a group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups; and hydrocarbon-based groups, preferably alkyl groups, which may optionally be inserted with one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups;

[0053] - n indicates an integer ranging from 1 to 1000; and

[0054] - A is a monomer selected from the following compounds:

[0055]

[0056] According to another embodiment, the (poly)carbodiimide compound is selected from compounds of the following formula (I’):

[0057]

[0058] Wherein:

[0059] - X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0060] - Y1 and Y2 independently represent a group selected from saturated C1 to C 36 aliphatic groups or C6 to C 24A divalent organic group of an aromatic or alkylaromatic group, the aliphatic or aromatic group optionally containing one or more non-terminal heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof;

[0061] - Z1 and Z2 independently represent a reactive end group or an inert end group;

[0062] - As an inert end group, Z1 and Z2 can independently represent a saturated straight-chain, branched-chain or cyclic C1 to C 50 aliphatic group, or a C6 to C 18 aromatic group, the aliphatic and aromatic groups optionally containing from 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic group can be partially or fully fluorinated; in this variant, Z1 and Z2 contain a bonding group CG that connects Z1 to Y1 and Z2 to Y2, and this group CG can be a single covalent bond, a saturated C-C bond, an unsaturated covalent C-C bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a carbamate group, a thiocarbamate group or a urea group;

[0063] - As a reactive end group, Z1 and Z2 can be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimide group alkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups;

[0064] - Q represents an organic polymer or organic oligomer containing repeating units of saturated straight-chain, branched-chain or alicyclic groups, or aromatic groups or alkylaromatic groups, and these repeating units are coupled via carbonate, ester, ether, amide, carbamate or urea repeating bonds or combinations thereof;

[0065] - A represents a divalent aliphatic, aromatic, alkylaromatic or straight-chain, saturated, branched-chain or cyclic group containing 2 to 30 carbon atoms, which can optionally contain one or more non-terminal heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof in the aliphatic chain or aromatic chain;

[0066] - r indicates an integer equal to 0 or 1;

[0067] - m indicates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0068] -m’ denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0069] -n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, where m + (m’ * n) ≥ 2.

[0070] Preferably, Z1 and Z2 independently represent reactive end groups; more preferably, Z1 and Z2 independently represent a group selected from the following: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups.

[0071] Such (poly)carbodiimide compounds are, for example, sold by Stahl B.V under the name Permutex XR, or under the name RelcaLink10., or under the name Picassian XL, and Nisshinbo compounds are sold under the name Carbodilite with the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0072] Preferably, the (poly)carbodiimide compound is selected from compounds of the following formula (II):

[0073]

[0074] Wherein:

[0075] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0076] -R1 and R2 independently represent a hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0077] -n and z denote integers ranging from 1 to 20, where n + z ≥ 2 and w denotes an integer ranging from 1 to 3;

[0078] -L1 independently represents C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkylene group, C3-C 12Azaheterocycloalkyl or C6-C 14 Arylene, and mixtures thereof;

[0079] -E independently represents a group selected from the following:

[0080] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0081] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0082] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0083] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0084] The term "hydrocarbon-based group" means a saturated or unsaturated, straight-chain or branched-chain group containing from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated straight-chain group.

[0085] The hydrocarbon-based group may contain one or more cyclic groups.

[0086] The hydrocarbon-based group may be interrupted by one or more heteroatoms selected in particular from O, S or N, and / or substituted by one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or contain metal ions which may be introduced in the form of salts.

[0087] The term "heteroatom" means an oxygen O, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the chain of the hydrocarbon-based group contains heteroatoms, the heteroatoms are preferably selected from oxygen O, sulfur S or nitrogen N atoms.

[0088] Preferably, X1 and X2 independently represent an oxygen atom.

[0089] Preferably, R1 and R2 independently are selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has been removed, and mixtures thereof.

[0090] In a preferred embodiment, R1 and R2 independently are selected from the following groups (i) to (iv):

[0091] (i) A compound of the following formula (III):

[0092] R7-O-C(O)-C(R8)(H)-(III),

[0093] wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl group, and R8 is a hydrogen atom or a methyl group.

[0094] (ii) A compound of the following formula (IV):

[0095] R9-[O-CH2-C(H)(R 10 )] p -(IV),

[0096] wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group and p indicates an integer ranging from 1 to 3; preferably, R9 is a methyl group, an ethyl group or a butyl group, R 10 is a hydrogen atom or a methyl group and p is equal to 1.

[0097] (iii) A compound of the following formula (V):

[0098] (R 11 )2N-CH2-C(H)(R 12 )-(V),

[0099] wherein R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 is a methyl group, an ethyl group or a butyl group, and R 12 is a hydrogen atom or a methyl group.

[0100] (iv) A compound of the following formula (VI):

[0101] R 13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0102] wherein R 13 represents a C1-C4 alkyl group or a phenyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group and q indicates an integer ranging from 4 to 30; preferably, R 13 is a methyl group, an ethyl group or a butyl group, and R 14 is a hydrogen atom or a methyl group.

[0103] Preferably, R1 and R2 independently represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30.

[0104] According to an alternative embodiment, R1 and R2 are different, and one of the groups R1 or R2 represents a compound of formula (IV) as described above, and the other of the groups R1 or R2 represents a compound of formula (VI) as described above.

[0105] Preferably, in formula (IV), R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl and p is equal to 1.

[0106] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl and q indicates an integer ranging from 4 to 30.

[0107] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably methyl, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30.

[0108] Preferably, n indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0109] Preferably, z indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0110] Preferably, w is equal to 1.

[0111] Preferably, w is equal to 1 and n + z indicates an integer ranging from 4 to 10.

[0112] Preferably, L1 is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups such as methylene, ethylene and propylene, C3-C 15 cycloalkylenes such as cyclopentylene, cycloheptylene and cyclohexylene, C3-C 12 heterocycloalkylenes such as imidazolylene, pyrrolylene and furanylene, or C6-C 14 arylenes such as phenylene, and mixtures thereof.

[0113] For example, L1 may be selected from groups derived from the following: toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and phenylene diisocyanate, and mixtures thereof.

[0114] Preferably, L1 is selected from C3-C 15 subcycloalkyl or C6-C 14 arylene, and mixtures thereof, such as a compound of the following formula (VII):

[0115]

[0116] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to the following formula (VIII):

[0117]

[0118] According to another embodiment, when L1 is C6-C 14 arylene, L1 is not m-tetramethylxylylene represented by the following formula (IX):

[0119]

[0120] As previously indicated, E independently represents a group selected from the following:

[0121] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0122] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0123] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms; and

[0124] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

[0125] Preferably, R3 and R4 are independently selected from C6-C 14 arylene such as phenylene, C3-C 12Subcycloalkyl groups such as cyclopropylidene and cyclobutylidene, linear or branched C 11 -C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0126] More preferably, R3 and R4 are independently selected from linear or branched C1-C optionally interrupted by one or more heteroatoms 18 alkylene groups, such as methylene, butylene, propylene or ethylene.

[0127] Preferably, when R5 is not a covalent bond, R5 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 subcycloalkyl groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0128] Preferably, R6 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 subcycloalkyl groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0129] Preferably, E represents the group -O-R3-O-, where R3 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene, C3-C 12 subcycloalkyl, linear or branched C1-C 18 alkylene, and mixtures thereof.

[0130] More preferably, E represents the group -O-R3-O-, where R3 represents a linear or branched C1-C optionally interrupted by one or more heteroatoms 18 alkylene group, such as methylene, butylene, propylene or ethylene.

[0131] According to a specific embodiment, the (poly)carbodiimide compound is a copolymer derived from an α-methylstyryl isocyanate of the following formula (X):

[0132]

[0133] wherein R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms, and

[0134] n indicates an integer ranging from 2 to 100.

[0135] In this embodiment, the term "alkyl" is as defined previously.

[0136] In this embodiment, the term "cycloalkyl" is as defined previously.

[0137] In this embodiment, n may denote an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferably from 5 to 10.

[0138] According to another specific embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0139]

[0140] wherein R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms, or an aryl group containing from 6 to 24 carbon atoms.

[0141] "Alkyl", "cycloalkyl" and "aryl" are as defined previously.

[0142] According to a preferred embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I) or formula (II), wherein:

[0143] - X1 and X2 independently represent an oxygen atom;

[0144] - R1 and R2 independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has been removed, more preferably the compound of formula (VI) described previously, wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30;

[0145] - n and z (when they are present) denote integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0146] - L1 (when it is present) is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups, C3-C 15 subcycloalkyls, C3-C 12 subheterocycloalkyls or C6-C 14 subaryls, and mixtures thereof, preferably C3-C 15 subcycloalkyls;

[0147] - A (when it is present) is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups, C3-C 15 subcycloalkyls, C3-C12 Azaheterocycloalkyl or C6-C 14 Arylene, and mixtures thereof, preferably C3-C 15 Cycloalkylene;

[0148] -E (when present) independently represents a group selected from:

[0149] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0150] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof;

[0151] -When R5 is not a covalent bond, R5 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof; and

[0152] -R6 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

[0153] Preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0154] -X1 and X2 independently represent an oxygen atom;

[0155] -R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof;

[0156] -n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0157] -L1 is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Azaheterocycloalkyl or C6-C 14 Arylene, and mixtures thereof;

[0158] -E independently represents a group selected from:

[0159] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0160] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0161] - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and

[0162] - R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

[0163] More preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0164] - X1 and X2 independently represent an oxygen atom;

[0165] - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed;

[0166] - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0167] - L1 is C3-C 15 cycloalkylene;

[0168] - E independently represents a group selected from:

[0169] - O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0170] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0171] - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof; and

[0172] -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

[0173] Even more preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0174] -X1 and X2 independently represent an oxygen atom;

[0175] -R1 and R2 independently represent the following compound of formula (VI):

[0176] R 13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0177] wherein R 13 represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl, R 14 represents a hydrogen atom or C1-C4 alkyl, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0178] -n and z indicate integers ranging from 1 to 20, wherein n + z ranges from 4 to 10 and w is equal to 1;

[0179] -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane; and

[0180] -E represents the group -O-R3-O-, wherein R3 is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

[0181] Even more preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0182] -X1 and X2 independently represent an oxygen atom;

[0183] -R1 and R2 independently represent the following compound of formula (VI):

[0184] R 13 -[O-CH2-C(H)(R 14 )] q -(VI)

[0185] wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0186] -n and z indicate integers ranging from 1 to 20, where n + z ranges from 4 to 10 and w is equal to 1;

[0187] -L1 is a C3-C 15 cycloalkanediyl group, such as cyclopentanediyl, cycloheptanediyl, cyclohexanediyl and 4,4-dicyclohexylmethanediyl, preferably 4,4-dicyclohexylmethanediyl; and

[0188] -E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkanediyl group optionally inserted with one or more heteroatoms, such as methylene, propanediyl, butanediyl or ethanediyl.

[0189] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0190]

[0191] wherein L1 is 4,4-dicyclohexylmethanediyl, n and z indicate integers ranging from 1 to 20, where n + z ranges from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkanediyl group optionally inserted with one or more heteroatoms, such as methylene, propanediyl, butanediyl or ethanediyl, and r and s indicate integers ranging from 4 to 30.

[0192] Advantageously, the total amount of the (poly)carbodiimide compound ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% by weight and still better from 1% to 6% by weight relative to the total weight of composition C.

[0193] Colorant

[0194] Composition C used in the context of the method according to the invention comprises one or more colorants selected from pigments, direct dyes and mixtures thereof.

[0195] Preferably, composition C used in the context of the method according to the invention comprises one or more pigments.

[0196] The term "pigment" refers to any pigment that imparts color to keratin materials. They have a solubility in water at 25 °C and atmospheric pressure (760 mmHg) of less than 0.05% by weight, and preferably less than 0.01%.

[0197] Pigments that can be used are especially selected from organic and / or mineral pigments known in the art, especially those described in Kirk - Othmer’s Encyclopedia of Chemical Technology and Ullmann’s Encyclopedia of Industrial Chemistry.

[0198] They can be natural, of natural origin or non - natural.

[0199] These pigments can be in the form of pigment powders or pastes. They can be coated or uncoated.

[0200] Pigments can be selected, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as mother - of - pearl or glitter flakes, and mixtures thereof.

[0201] The pigment can be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann’s encyclopedia. Among the mineral pigments available in the present invention, iron oxides, chromium oxides, manganese violet, ultramarine, chromium hydrates, iron blue, and titanium oxides can be mentioned.

[0202] The pigment can be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann’s Encyclopedia.

[0203] Organic pigments can especially be selected from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, and quinophthalone compounds.

[0204] In particular, the white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments numbered with Color Index (CI) numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments numbered with Color Index numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments numbered with Color Index numbers CI 61565, 61570, 74260, orange pigments numbered with Color Index numbers CI 11725, 45370, 71105, red pigments numbered with Color Index numbers CI12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, such as the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0205] Examples that may also be mentioned include pigment pastes of organic pigments, such as products sold by Hoechst under the following names:

[0206] - Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710);

[0207] - Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680);

[0208] - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105);

[0209] - Cosmenyl Red R: Pigment Red 4 (CI 12085);

[0210] - Cosmenyl Carmine FB: Pigment Red 5 (CI 12490);

[0211] - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319);

[0212] - Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160);

[0213] - Cosmenyl Green GG: Pigment Green 7 (CI 74260);

[0214] - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0215] The pigments according to the invention can also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments can in particular consist of particles which include an inorganic core, at least one binder for attaching the organic pigment to the core and at least one organic pigment which at least partly covers the core.

[0216] The organic pigment can also be a lake. The term "lake" means a dye adsorbed on an insoluble particle, and the assembly thus obtained remains insoluble during use.

[0217] The inorganic substrate on which the dye is adsorbed is for example alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0218] Among these dyes, carminic acid can be mentioned. Dyes known under the following names can also be mentioned: 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 45425), 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 (CI15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42090).

[0219] Examples of lakes which can be mentioned are products known under the following names: D&C Red 7 (CI 15 850:1).

[0220] The pigment can also be a pigment with special effects. The term "pigment with special effects" means a pigment which generally produces a non-uniform coloured appearance (characterized by a certain chromaticity, a certain vivacity and a certain brightness level) which varies with the observation conditions (light, temperature, observation angle, etc.). Thus, they are different from coloured pigments which provide standard uniform opaque, translucent or transparent tones.

[0221] There are several types of special effects pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacre, interference pigments or glitter flakes.

[0222] Examples of pigments with special effects that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride; colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxides, mica coated with titanium and especially coated with iron blue or chromium oxides, mica coated with titanium and an organic pigment as previously defined, and also pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include nacre Cellini (mica - TiO2 - lake) sold by BASF, Prestige (mica - TiO2) sold by Eckart, Prestige Bronze (mica - Fe2O3) sold by Eckart, and Colorona (mica - TiO2 - Fe2O3) sold by Merck.

[0223] It is also possible to mention nacreous pigments sold, inter alia, by BASF under the names Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); nacreous pigments with a bronze colour sold, inter alia, by Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); nacreous pigments with an orange colour sold, inter alia, by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion orange (Colorona) and Matte orange (17449) (Microna); nacreous pigments with a brown colour sold, inter alia, by BASF under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacreous pigments with a copper colour tone sold, inter alia, by BASF under the name Copper 340A (Timica); nacreous pigments with a red colour tone sold, inter alia, by Merck under the name Sienna fine (17386) (Colorona); nacreous pigments with a yellow colour tone sold, inter alia, by BASF under the name Yellow (4502) (Chromalite); nacreous pigments with a red colour with a golden colour tone sold, inter alia, by BASF under the name Sunstone G012 (Gemtone); nacreous pigments with a pink colour sold, inter alia, by BASF under the name Tan opale G005 (Gemtone); nacreous pigments with a black colour with a golden colour tone sold, inter alia, by BASF under the name Nu antique bronze 240AB (Timica); nacreous pigments with a blue colour sold, inter alia, by Merck under the name Matte blue (17433) (Microna); nacreous pigments with a white colour with a silver colour tone sold, inter alia, by Merck under the name Xirona Silver; and nacreous pigments with a golden green pink orange colour sold, inter alia, by Merck under the name Indian summer (Xirona); and mixtures thereof.

[0224] Still as examples of nacreous pigments, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

[0225] Particles comprising a glass substrate coated with titanium oxide are in particular sold by Toyal under the name Metashine MC1080RY.

[0226] Finally, examples of nacre that can also be mentioned include polyethylene terephthalate glitter flakes, in particular those sold by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver glitter flakes). Multilayer pigments based on synthetic substrates can also be envisaged, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

[0227] Pigments with special effects can also be selected from reflective particles, i.e. in particular from particles whose size, structure, in particular the thickness of the layer they form, and their physical and chemical properties and surface state allow them to reflect incident light. If appropriate, when they are applied to the support to be made up, this reflection can have an intensity sufficient to produce highlights visible to the naked eye on the surface of the composition or mixture, i.e. points that make them appear to sparkle and are brighter in contrast to their surroundings.

[0228] Reflective particles can be chosen so as not to significantly modify the colouring effect produced by the colourants combined with them, and more particularly so as to optimize this effect in terms of colour reproduction. They can more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper colour or hue.

[0229] These particles can have different forms and can in particular be in the form of flakes or spheres, especially in the form of spheres.

[0230] Regardless of their form, the reflective particles can have or can not have a multilayer structure, and in the case of a multilayer structure, can have for example at least one layer of uniform thickness, especially of a reflective material.

[0231] When the reflective particles do not have a multilayer structure, they can be composed of, for example, metal oxides, especially titanium or iron oxides obtained synthetically.

[0232] When the reflective particles have a multilayer structure, they can include for example a natural or synthetic substrate, especially a synthetic substrate at least partially coated with at least one layer of reflective material, especially at least one metal or metallic material. The substrate can be made of one or more organic and / or mineral materials.

[0233] More particularly, it can be selected from glass, ceramics, graphite, metal oxides, alumina, silica, silicates (especially aluminosilicates and borosilicates), and synthetic mica, and mixtures thereof, this list not being limiting.

[0234] The reflective material may include a metal layer or a layer of a metallic material.

[0235] Reflective particles are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0236] In addition, as an example of reflective particles comprising a mineral substrate coated with a metal layer, mention may also be made of particles comprising a silver-coated borosilicate substrate.

[0237] Particles having a silver-coated glass substrate in the form of flakes are sold by Toyo Corporation under the name Microglass Metashine REFSX 2025PS. Particles having a glass substrate coated with a nickel / chromium / molybdenum alloy are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0238] Particles comprising a metallic substrate may also be used, said metallic substrate such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, said at least one metal oxide such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0239] Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiO2, which are sold by Eckart under the name Visionaire.

[0240] Interference pigments not attached to a substrate may also be mentioned, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectraf / x from Spectratek). Special effect pigments also include fluorescent pigments (whether these are substances that fluoresce in daylight or produce ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, for example sold by Quantum Dots Corporation.

[0241] The various pigments that can be used in the compositions according to the invention make it possible to obtain a wide range of colours, as well as specific optical effects, such as metallic or interference effects.

[0242] The size of the pigments used in the compositions according to the invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferably between 30 nm and 50 μm.

[0243] The pigment may be dispersed in the composition by a dispersant.

[0244] Dispersants are used to protect the dispersed particles from agglomeration or flocculation. The dispersants can be surfactants, oligomers, polymers or mixtures of several thereof carrying one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can become physically or chemically attached to the surface of the pigment. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, use is made of esters of, in particular, 12-hydroxystearic acid and of C8 to C20 fatty acids and of polyols such as glycerol or diglycerol, for example poly(12-hydroxystearic acid)stearate having a molecular weight of about 750 g / mol, such as the product sold under the name Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by Henkel, or polyhydroxystearic acids such as the product sold under the reference Arlacel P100 by Uniqema, and mixtures thereof.

[0245] As other dispersants 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 Avicia, and polydimethylsiloxane / propylene oxide mixtures, such as those sold under the references DC2-5185 and DC2-5225 C by Dow Corning.

[0246] The pigments used in the composition may be surface treated with an organic agent.

[0247] Thus, pigments that have been pre-surface-treated and are available in the context of the present invention are pigments that have been subjected, in whole or in part, to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic reagent and are then dispersed in the composition according to the present invention, such organic reagents being in particular those described in Cosmetics and Toiletries, February 1990, Volume 105, pages 53 - 64. These organic reagents can be selected, for example, from waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and their derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids such as aluminum stearate or aluminum laurate; metal alkoxides; polyethylene; (meth)acrylic polymers such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds such as silicones, in particular polydimethylsiloxane; organic fluorine compounds such as perfluoroalkyl ethers; fluorosilicone compounds.

[0248] The surface-treated pigments that can be used in the composition can also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.

[0249] The surface-treated pigments that can be used in the context of the present invention can be prepared according to surface treatment techniques well-known to those skilled in the art or can be commercially available as such.

[0250] Preferably, the surface-treated pigments are coated with an organic layer.

[0251] The organic reagent for treating the pigments can be attached to the pigments by evaporation of the solvent, by chemical reaction between the molecules of the surfactant or by formation of a covalent bond between the surfactant and the pigments.

[0252] The surface treatment can thus be carried out, for example, by a chemical reaction of the surfactant with the pigment surface and by formation of a covalent bond between the surfactant and the pigment or filler. This method is described in particular in patent US 4 578 266.

[0253] Preferably, an organic reagent that is covalently bonded to the pigment is used.

[0254] The reagent for surface treatment can be present in an amount, by weight, from 0.1% to 50%, preferably from 0.5% to 30% and even more preferably from 1% to 20% relative to the total weight of the surface-treated pigment.

[0255] Preferably, the surface treatment agent for the pigments is selected from the following treatment agents:

[0256] - PEG - silicone treatment agents, such as the AQ surface treatment agent sold by LCW;

[0257] - Polymethylsiloxane treatment agents, such as the SI surface treatment agent sold by LCW;

[0258] - Polydimethylsiloxane treatment agents, such as the Covasil 3.05 surface treatment agent sold by LCW;

[0259] - Polydimethylsiloxane / trimethylsilyl silicate treatment agents, such as the Covasil 4.05 surface treatment agent sold by LCW;

[0260] - Magnesium myristate treatment agents, such as the MM surface treatment agent sold by LCW;

[0261] - Aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi;

[0262] - Perfluoropoly(methyl isopropyl ether) treatment agents, such as the FHC surface treatment agent sold by LCW;

[0263] - Isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi;

[0264] - Perfluoroalkyl phosphate treatment agents, such as the PF surface treatment agent sold by Daito;

[0265] - Acrylate / polydimethylsiloxane copolymer and perfluoroalkyl phosphate treatment agents, such as the FSA surface treatment agent sold by Daito;

[0266] - Polymethylhydrosiloxane / perfluoroalkyl phosphate treatment agents, such as the FS01 surface treatment agent sold by Daito;

[0267] - Acrylate copolymer / polydimethylsiloxane treatment agents, such as the ASC surface treatment agent sold by Daito;

[0268] - Isopropyl triisostearoyl titanate treatment agents, such as the ITT surface treatment agent sold by Daito;

[0269] - Acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito;

[0270] - Perfluoroalkyl phosphate / isopropyl triisostearoyl titanate treatment agents, such as the PF + ITT surface treatment agent sold by Daito.

[0271] According to specific embodiments of the present invention, the dispersant is present together with organic or mineral pigments in the form of sub - micron - sized particles.

[0272] The term "submicron-sized" or "submicron" means that the pigment has a particle size that has been micronized by a micronization method and has an average particle size of less than one micron (μm), in particular between 0.1 and 0.9 μm and preferably between 0.2 and 0.6 μm.

[0273] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) according to a weight ratio between 1:4 and 4:1, in particular between 1.5:3.5 and 3.5:1 or even better between 1.75:3 and 3:1.

[0274] Thus, the dispersant can have a silicone backbone, such as silicone polyethers and dispersants of the amino silicone type other than the amino silicones mentioned below. Among the suitable dispersants, the following can be mentioned:

[0275] - Amino silicones, i.e., silicones containing one or more amine groups, such as those sold under the following names and index numbers: BYK LPX 21879 from BYK Chemie GmbH, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967, and GP-988-1 sold by Genesee Polymers,

[0276] - Silicone acrylates, such as those sold by Evonik RC 902, RC 922, RC 1041, and RC 1043,

[0277] - Carboxyl-bearing polydimethylsiloxane (PDMS) silicones such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 from Genesee Polymers, or RC 1401, RC 1403, RC 1412 from Evonik.

[0278] According to a specific embodiment, the dispersant is of the amino silicone type other than the amino silicones mentioned below and is cationic.

[0279] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments, or organic pigments.

[0280] In a variant of the present invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic reagent selected from silicone compounds. In another variant of the present invention, the pigment is a mineral pigment.

[0281] Preferably, the pigment is selected from iron oxides, especially red, brown or black iron oxides. As an example of iron oxide, mention may be made of the iron oxide sold by Sun Chemical under the name Red Iron Oxide.

[0282] Direct dyes

[0283] The composition C used in the context of the process according to the invention may comprise one or more direct dyes.

[0284] The term "direct dyes" means natural and / or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fiber.

[0285] They may be ionic or non-ionic, preferably cationic or non-ionic.

[0286] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl types; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, either alone or in the form of a mixture.

[0287] The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazinium cationic dyes of the following formulas (XIII) and (XIV) and the azo cationic dyes of the formulas (XV) and (XVI):

[0288] Het + -N(Ra)-N=C(Rb)-Ar, Q - (XIII),

[0289] Het + -C(Ra)=N-N(Rb)-Ar, Q (XIV),

[0290] Het + -N=N-Ar, Q - (XV),

[0291] Ar + -N=N-Ar”, Q - (XVI),

[0292] In formulas (XIII) to (XVI):

[0293] -Het +Denote cationic heteroaryls that preferably carry a cationic charge within the ring, such as imidazolium, indolium, or pyridinium, which are optionally preferably substituted by at least one (C1-C8) alkyl group such as methyl;

[0294] -Ar + Denote aryls that carry a cationic charge outside the ring, preferably ammonium, especially tri(C1-C8)alkylammonium such as trimethylammonium, such as phenyl or naphthyl;

[0295] -Ar represents an aryl group, especially a phenyl group, which is optionally preferably substituted by one or more electron-donating groups, such as i) an optionally substituted (C1-C8) alkyl group, ii) an optionally substituted (C1-C8) alkoxy group, iii) a (di)(C1-C8)(alkyl)amino group optionally substituted by a hydroxyl group on the alkyl, iv) an aryl(C1-C8)alkylamino group, v) an optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino group, or alternatively, Ar represents a julolidine group;

[0296] -Ar” represents an optionally substituted (hetero)aryl group, such as a phenyl or pyrazolyl group, which is optionally preferably substituted by one or more (C1-C8) alkyl groups, hydroxyl groups, (di)(C1-C8)(alkyl)amino groups, (C1-C8) alkoxy groups, or phenyl groups;

[0297] -Ra and Rb can be the same or different and represent a hydrogen atom or an (C1-C8) alkyl group optionally preferably substituted by a hydroxyl group;

[0298] Alternatively, the substituent Ra together with the substituent of Het+ and / or the substituent Rb together with the substituent of Ar form a (hetero)cycloalkyl group with the atoms carrying them; in particular, Ra and Rb represent a hydrogen atom or an (C1-C4) alkyl group optionally substituted by a hydroxyl group;

[0299] -Q- represents an organic or inorganic anion counterion, such as a halide ion or an alkyl sulfate.

[0300] In particular, azo and hydrazo direct dyes carrying a cationic charge within the ring as defined previously in formulas (XIII) to (XVI) can be mentioned, and more particularly, cationic direct dyes carrying a cationic charge within the ring as described in patent applications WO 95 / 15144, WO 95 / 01772, and EP 714 954, preferably the following direct dyes:

[0301]

[0302]

[0303] In formulas (XVII) and (XVIII):

[0304] -R 1 represents a (C1-C4) alkyl group such as methyl;

[0305] -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; and

[0306] -R 4 represents a hydrogen atom or an electron-donating group such as an optionally substituted (C1-C8) alkyl group, an optionally substituted (C1-C8) alkoxy group, or a (di)(C1-C8)(alkyl)amino group optionally substituted by a hydroxyl group on the alkyl; in particular, R 4 is a hydrogen atom;

[0307] -Z represents a CH group or a nitrogen atom, preferably CH;

[0308] -Q- is an anion counterion as previously defined, especially a halide ion such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0309] In particular, the dyes of formulas (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87, and Basic Orange 31 or derivatives thereof, where Q’ is an anion counterion as previously defined, especially a halide ion such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl.

[0310] Direct dyes may be selected from anionic direct dyes. The anionic direct dyes of the present invention are dyes that are usually called "acid" direct dyes due to their affinity for basic substances. The term "anionic direct dye" means any direct dye that includes at least one CO2R or SO3R substituent in its structure, where R indicates a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. Anionic dyes may be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigo dyes, and natural acid dyes.

[0311] As acid dyes that can be used in the present invention, the following dyes of formulas (XIX), (XIX’), (XX), (XX’), (XXI), (XXI’), (XXII), (XXII’), (XXIII), (XXIV), (XXV), and (XXVI) may be mentioned:

[0312] a) Diaryl anionic azo dyes of formula (XIX) or (XIX’):

[0313]

[0314] In formulas (XIX) and (XIX’):

[0315] - R7, R8, R9, R 10 , R’7, R’8, R’9 and R’ 10 may be the same or different and represent a hydrogen atom or a group selected from the following:

[0316] - alkyl;

[0317] - alkoxy, alkylthio;

[0318] - hydroxy, mercapto;

[0319] - nitro, nitroso;

[0320] - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R° represents a hydrogen atom or an alkyl or aryl group; X, X’ and X” may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0321] -(O)2S(O - )-, M + , where M + represents a hydrogen atom or a cationic counterion;

[0322] -(O)CO - -, M + , where M + is as previously defined;

[0323] - R”-S(O)2-, where R” represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferably phenylamino or phenyl;

[0324] - R”’-S(O)2-X’-, where R”’ represents an optionally substituted alkyl or aryl group and X’ is as previously defined;

[0325] -(di)(alkyl)amino;

[0326] - aryl(alkyl)amino, optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii)(O)2S(O - )-, M + and iv) alkoxy, where M + is as previously defined;

[0327] - optionally substituted heteroaryl; preferably benzothiazolyl;

[0328] - cycloalkyl, especially cyclohexyl;

[0329] - Ar-N=N-, where Ar represents an optionally substituted aryl group; preferably optionally substituted by one or more alkyl, (O)2S(O- )-,M + or a phenyl group substituted with a phenylamino group;

[0330] - alternatively, two adjacent groups R7 and R8, or R8 and R9, or R9 and R 10 together form a fused benzo group A'; and R'7 and R'8, or R'8 and R'9, or R'9 and R' 10 together form a fused benzo group B'; where A' and B' are optionally substituted with one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(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; where M + , R°, X, X', X'' and Ar are as defined previously;

[0331] - W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR-, where R is as defined previously, or ii) methylene -C(Ra)(Rb)-, where Ra and Rb may be the same or different and represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom carrying them form a spiroalkyl group; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl group;

[0332] It should be understood that formula (XIX) and (XIX') contain at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group (O)CO - -,M + ; preferably sodium sulfonate.

[0333] As examples of the dyes of formula (XIX), mention may be made of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow;

[0334] And, as examples of the dyes of formula (XIX'), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0335] b) Pyrazolone anion azo dyes of formula (XX) and (XX'):

[0336]

[0337] In formulae (XX) and (XX'):

[0338] -R 11 、R 12 and R 13 may be the same or different and represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O - ),M + where M + is as previously defined;

[0339] -R 14 represents a hydrogen atom, an alkyl group or the group -C(O)O - ,M + where M + is as previously defined;

[0340] -R 15 represents a hydrogen atom;

[0341] -R 16 represents an oxo group, in which case R' 16 is absent, or alternatively, R 15 and R 16 together form a double bond;

[0342] -R 17 and R 18 may be the same or different and represent a hydrogen atom or a group selected from:

[0343] -(O)2S(O - )-,M + , wherein M + is as defined previously;

[0344] -Ar-O-S(O)2-, wherein Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups;

[0345] -R 19 and R 20 together form a double bond, or an optionally substituted benzo group D';

[0346] -R' 16 , R' 19 and R' 20 may be the same or different and represent a hydrogen atom or an alkyl group or a hydroxyl group;

[0347] -R 21 represents a hydrogen atom or an alkyl group or an alkoxy group;

[0348] -Ra and Rb may be the same or different, as defined previously; preferably, Ra represents a hydrogen atom and Rb represents an aryl group;

[0349] -Y represents a hydroxyl group or an oxo group;

[0350] - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

[0351] It should be understood that formula (XX) and (XX') contain at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group -C(O)O - ,M + ; preferably sodium sulfonate.

[0352] As examples of the dyes of formula (XX), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of the dyes of formula (XX'), mention may be made of: Acid Yellow 17;

[0353] c) Anthraquinone dyes of formula (XXI) and (XXI'):

[0354]

[0355] In formula (XXI) and (XXI'):

[0356] -R 22 , R 23 , R 24, R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or a group selected from the following:

[0357] -alkyl;

[0358] -hydroxy, mercapto;

[0359] -alkoxy, alkylthio;

[0360] -optionally substituted aryloxy or arylthio, preferably substituted by one or more groups selected from alkyl and (O)2S(O - ), M + , where M + is as previously defined;

[0361] -aryl(alkyl)amino, optionally substituted by one or more groups selected from alkyl and (O)2S(O - ), M + , where M + is as previously defined;

[0362] -(di)(alkyl)amino;

[0363] -(di)(hydroxyalkyl)amino;

[0364] -(O)2S(O - ), M + , where M + is as previously defined;

[0365] -Z’ represents a hydrogen atom or the group NR 28 R 29 , where R 28 and R 29 may be the same or different and represent a hydrogen atom or a group selected from the following:

[0366] -alkyl;

[0367] -polyhydroxyalkyl, such as hydroxyethyl;

[0368] -aryl optionally substituted by one or more groups, especially the following: i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O - ), M + , where M + is as previously defined; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R°, X, X’ and X” are as previously defined, preferably R° represents alkyl;

[0369] -cycloalkyl, especially cyclohexyl;

[0370] -Z represents a group selected from hydroxy and NR' 28 R' 29 wherein R' 28 and R' 29 may be the same or different and represent an atom or group the same as R 28 and R 29 as previously defined;

[0371] It should be understood that formulae (XXI) and (XXI') contain at least one sulphonate group (O)2S(O - ),M + or a carboxylate group C(O)O - ,M + ; preferably sodium sulphonate.

[0372] As examples of the dyes of formula (XXI), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No.2; and, as examples of the dyes of formula (XXI'), mention may be made of: Acid Black 48;

[0373] d) Nitro dyes of formulae (XXII) and (XXII'):

[0374]

[0375]

[0376] In formulae (XXII) and (XXII'):

[0377] -R 30 、R 31 and R 32 may be the same or different and represent a hydrogen atom or a halogen atom or a group selected from:

[0378] -alkyl;

[0379] -alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;

[0380] -hydroxy, mercapto;

[0381] -nitro, nitroso;

[0382] -polyhaloalkyl;

[0383] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R°, X, X’, and X” are as previously defined;

[0384] -(O)2S(O - )-, M + where M + is as previously defined;

[0385] -(O)CO - -, M + where M + is as previously defined;

[0386] -(di)(alkyl)amino;

[0387] -(di)(hydroxyalkyl)amino;

[0388] -heteroalkyl, such as piperidino, piperazino, or morpholino; In particular, R 30 、R 31 and R 32 represent a hydrogen atom;

[0389] -Rc and Rd may be the same or different and represent a hydrogen atom or an alkyl group;

[0390] -W is as previously defined; W particularly represents an -NH- group;

[0391] -ALK represents a straight-chain or branched divalent C1-C6 alkylene group; In particular, ALK represents a -CH2-CH2- group;

[0392] -n is 1 or 2;

[0393] -p represents an integer between 1 and 5 inclusive;

[0394] -q represents an integer between 1 and 4 inclusive;

[0395] -u is 0 or 1;

[0396] -When n is 1, J represents a nitro or nitroso group; In particular, nitro;

[0397] -When n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O) m -, where m represents the integer 1 or 2; Preferably, J represents a -SO2- group;

[0398] -M’ represents a hydrogen atom or a cationic counterion;

[0399] - may be present or absent and represents optionally being substituted by one or more groups R as previously defined 30Substituted benzogroups;

[0400] It should be understood that formulae (XXII) and (XXII’) contain at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group C(O)O - ,M + ; preferably sodium sulfonate.

[0401] As examples of dyes of formula (XXII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII’), mention may be made of: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidyl-5-nitrobenzenesulfonic acid, 2-(4’-N,N-(2”-hydroxyethyl)amino-2’-nitro)anilinoethanesulfonic acid, the sodium salt of 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; External D&C Yellow 7 (EXT D&C Yellow 7);

[0402] e) Triarylmethane dyes of formula (XXIII):

[0403]

[0404] In formula (XXIII):

[0405] -R 33 、R 34 、R 35 and R 36 may be the same or different and represent a hydrogen atom or a group selected from: alkyl, optionally substituted aryl and optionally substituted aralkyl; in particular alkyl and optionally substituted benzyl by the group (O) m S(O - )-,M + where M + and m are as defined previously;

[0406] -R 37 、R 38 、R 39 、R 40 、R 41 、R 42 、R 43 and R 44 may be the same or different and represent a hydrogen atom or a group selected from:

[0407] -alkyl;

[0408] -alkoxy, alkylthio;

[0409] -(di)(alkyl)amino;

[0410] -hydroxy, mercapto;

[0411] - nitro, nitroso;

[0412] - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’, where R° represents a hydrogen atom or an alkyl or aryl group; X, X’ and X’’ may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0413] -(O)2S(O - )-, M + where M + represents a hydrogen atom or a cationic counterion;

[0414] -(O)CO - -, M + where M + is as previously defined;

[0415] - or alternatively, two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I’; where I’ is optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’-C(X)-X’’; where M + , R°, X, X’ and X’’ are as previously defined;

[0416] In particular, R 37 to R 40 represent a hydrogen atom, and R 41 to R 44 may be the same or different and represent hydroxy or (O)2S(O - )-, M + ; and when R 43 and R 44 together form a benzo group, it is preferably substituted by an (O)2S(O - )- group;

[0417] It should be understood that at least one of the rings G, H, I or I’ contains at least one sulfonic acid group (O)2S(O - )- or a carboxylic acid group -C(O)O - ; preferably sulfonic acid.

[0418] As examples of the dyes of formula (XXIII), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.

[0419] f) Xanthene-based dyes of formula (XXIV):

[0420]

[0421] In formula (XXIV):

[0422] -R 45 、R 46 、R 47 and R 48 may be the same or different and represent a hydrogen or halogen atom;

[0423] -R 49 、R 50 、R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or a group selected from:

[0424] -alkyl;

[0425] -alkoxy, alkylthio;

[0426] -hydroxy, mercapto;

[0427] -nitro, nitroso;

[0428] -(O)2S(O - )-,M + where M + represents a hydrogen atom or a cationic counterion;

[0429] -(O)CO - -,M + where M + is as previously defined;

[0430] In particular, R 49 、R 50 、R 51 and R 52 represent a hydrogen or halogen atom;

[0431] -G represents an oxygen or sulfur atom or the group NRe, where Re is as previously defined; in particular, G represents an oxygen atom;

[0432] -L represents an alkoxide O - ,M + ; a thiolate S - ,M +or the group NRf, where Rf represents a hydrogen atom or an alkyl group, and M + as defined above; M + is in particular sodium or potassium;

[0433] -L’ represents an oxygen or sulfur atom or an ammonium group: N + RfRg, where Rf and Rg may be the same or different, represent a hydrogen atom or an optionally substituted alkyl or aryl group; L’ in particular represents an oxygen atom or an optionally substituted phenylamino group by one or more alkyl groups or (O) m S(O - )-, M + group, where m and M + are as defined previously;

[0434] -Q and Q’ may be the same or different and represent an oxygen or sulfur atom; in particular, Q and Q’ represent an oxygen atom;

[0435] -M + is as defined previously.

[0436] As examples of the dyes of formula (XXIV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0437] g) indole-based dyes of formula (XXV):

[0438]

[0439] In formula (XXV):

[0440] -R 53 、R 54 、R 55 、R 56 、R 57 、R 58 、R 59 and R 60 may be the same or different and represent a hydrogen atom or a group selected from:

[0441] -alkyl;

[0442] -alkoxy, alkylthio;

[0443] -hydroxy, mercapto;

[0444] -nitro, nitroso;

[0445] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R° represents a hydrogen atom or an alkyl or aryl group; X, X’ and X” may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0446] -(O)2S(O - )-,M + , wherein M + represents a hydrogen atom or a cationic counterion;

[0447] -(O)CO - -,M + , wherein M + is as defined previously;

[0448] -G represents an oxygen or sulfur atom or the group NRe, where Re is as defined previously; in particular, G represents an oxygen atom;

[0449] -Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group;

[0450] It should be understood that formula (XXIII) contains at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group -C(O)O - ,M + ; preferably sodium sulfonate.

[0451] As an example of the dye of formula (XXV), mention may be made of: Acid Blue 74;

[0452] h) quinoline-based dyes of formula (XXVI):

[0453]

[0454] In formula (XXVI):

[0455] -R 61 represents a hydrogen or halogen atom or an alkyl group;

[0456] -R 62 、R 63 and R 64 may be the same or different and represent a hydrogen atom or the group (O)2S(O - )-,M + , wherein M + represents a hydrogen atom or a cationic counterion;

[0457] Alternatively, R 61 and R 62 , or R 61 and R 64 together form a benzo group, which is optionally substituted by one or more groups (O)2S(O - )-,M + , wherein M + represents a hydrogen atom or a cationic counterion;

[0458] It should be understood that formula (XXVI) contains at least one sulfonate group (O)2S(O - )-, M + , preferably sodium sulfonate.

[0459] As examples of the dyes of formula (XXVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0460] Among the natural direct dyes that can be used according to the present invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, gallic acid, protocatechaldehyde, indigo, indirubin, curcumin, penicillic acid, apigenidin and orcein. Extracts or decoctions containing these natural dyes can also be used and in particular poultices or extracts based on henna.

[0461] Preferably, the direct dye is selected from anionic direct dyes.

[0462] The colorant may be present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C; preferably, the colorant is selected from pigments.

[0463] The pigment may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and still better from 0.5% to 10% by weight, relative to the total weight of composition C.

[0464] The direct dye 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 C.

[0465] Compound containing at least one carboxyl functional group

[0466] Composition C used in the context of the method according to the present invention may also contain at least one compound containing at least one carboxyl functional group.

[0467] Preferably, the compound containing at least one carboxyl functional group is selected from silicone compounds containing at least one carboxyl, polyurethanes, acrylic polymers and mixtures thereof.

[0468] Polyurethane and acrylic polymer

[0469] According to a preferred embodiment, composition C contains at least one compound containing at least one carboxyl functional group, which is selected from polyurethanes, acrylic polymers and mixtures thereof.

[0470] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers and mixtures thereof.

[0471] Preferably, composition C comprises at least one compound containing at least one carboxyl functional group, which is in the form of an aqueous dispersion of particles of a polyurethane, an acrylic polymer and mixtures thereof.

[0472] The dispersion can be a simple dispersion in the aqueous medium of the cosmetic composition. As a particular case of the dispersion, mention may be made of latexes.

[0473] The aqueous dispersion of polymer particles can be selected from the aqueous dispersion of polyurethane particles.

[0474] More particularly, the polyurethane present in the aqueous dispersion used in the present invention is produced by the reaction of:

[0475] - a prepolymer of the following formula (A):

[0476]

[0477] wherein:

[0478] - R1 represents a divalent group of a dihydroxylated compound;

[0479] - R2 represents a group of an aliphatic or cycloaliphatic polyisocyanate;

[0480] - R3 represents a group of a low molecular weight diol, optionally substituted by one or more ionic groups;

[0481] - n represents an integer ranging from 1 to 5, and

[0482] - m is greater than 1;

[0483] - at least one chain extender according to the following formula (B):

[0484] H2N-R4-NH2 (B),

[0485] where R4 represents an alkylene or alkyleneoxy group not substituted by one or more ionic or potentially ionic groups; and

[0486] - at least one chain extender according to the following formula (C):

[0487] H2N-R5-NH2 (C),

[0488] where R5 represents an alkylene group substituted by one or more ionic or potentially ionic groups.

[0489] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number-average molecular weight of from about 700 to about 16,000, and preferably from about 750 to about 5,000. By way of example of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polybutadienes, polyhydroxylated polysulfides, and mixtures thereof. Preferably, the hydroxylated compounds are selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0490] The polyisocyanates that can be used according to the present invention are in particular selected from organic diisocyanates having a molecular weight of from about 112 to 1,000, and preferably from about 140 to 400.

[0491] Preferably, the polyisocyanates are selected from diisocyanates and more particularly from those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon-based group containing 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon-based group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon-based group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon-based group containing 6 to 15 carbon atoms.

[0492] Preferably, R2 represents an organic diisocyanate. As examples of organic diisocyanates, in particular the following may be selected: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methylcyclohexyl)methane, isomers of toluene diisocyanate (TDI) such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures with its isomers diphenylmethane 2,4-diisocyanate and optionally diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate, and mixtures thereof.

[0493] Preferably, the diisocyanate is an aliphatic and cycloaliphatic diisocyanate, and more preferably is selected from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, and mixtures thereof.

[0494] According to the present invention, the term "low molecular weight diol" refers to diols having a molecular weight from about 62 to 700, and preferably from 62 to 200. These diols can contain aliphatic, cycloaliphatic or aromatic groups. Preferably, they contain only aliphatic groups.

[0495] Preferably, R3 represents a low molecular weight diol containing more than 20 carbon atoms, more preferably selected from ethylene glycol, diethylene glycol, 1,2 - propanediol, 1,3 - propanediol, 1,4 - butanediol, 1,3 - butanediol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4 - cyclohexanedimethanol, 1,6 - hexanediol, bisphenol A (2,2 - bis(4 - hydroxyphenyl)propane), hydrogenated bisphenol A (2,2 - bis(4 - hydroxycyclohexyl)propane), and mixtures thereof.

[0496] The low molecular weight diol can optionally contain ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are particularly described in patent US 3,412,054. Such compounds are preferably selected from dimethylolbutyric acid, dimethylolpropionic acid, carboxyl - containing polycaprolactone diols, and mixtures thereof.

[0497] If a low molecular weight diol containing ionic or potentially ionic groups is used, they are preferably used in an amount such that there is less than 0.30 meq of COOH / gram of polyurethane in the polyurethane dispersion.

[0498] The prepolymer is chain - extended by two families of chain - extenders. The first class of chain - extenders corresponds to compounds of the general formula (B).

[0499] The chain - extenders of formula (B) are preferably selected from alkylenediamines such as hydrazine, ethylenediamine, propylenediamine, 1,4 - butanediamine, piperazine; alkylenediamine oxides such as 3 - {2 - [2 - (3 - aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diglycol or DPA - DEG, available from Tomah Products, Milton, Wisconsin), 2 - methyl - 1,5 - pentanediamine (Dytec A from DuPont), hexamethylenediamine, isophoronediamine, 4,4 - methylenebis(cyclohexylamine), ether amines of the DPA series available from Tomah Products, Milton, Wisconsin, such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3 - propylene glycol, dipropylamine 2 - methyl - 1,3 - propylene glycol, dipropylamine 1,4 - butanediol, dipropylamine 1,3 - butanediol, dipropylamine 1,6 - hexanediol, and dipropylamine cyclohexane - 1,4 - dimethanol; and mixtures thereof.

[0500] The second type of chain extender corresponds to compounds of general formula (C). Such compounds preferably have ionic or potential ionic groups and two groups that can react with isocyanate groups. Such compounds may optionally contain two groups that react with isocyanate groups and one group that is an ionic group or capable of forming an ionic group.

[0501] The ionic or potential ionic groups may preferably be selected from tertiary ammonium or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups, and sulfonate groups. At least partial conversion of groups that can be converted into tertiary ammonium or quaternary ammonium group salts may be carried out before or during mixing with water.

[0502] The chain extender of formula (C) is preferably selected from diamino sulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0503] The polyurethane that can be used according to the present invention may also optionally contain compounds (chain terminators) that are located at the chain ends and terminate the chain. Such compounds are particularly described in patents US 7 445 770 and / or US 7 452 770.

[0504] Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa·s at 23 °C, more preferably less than 1500, and even better less than 1000. Even more preferably, the aqueous polyurethane dispersion has a glass transition temperature of less than 0 °C.

[0505] Also preferably, based on the weight of the dispersion, the aqueous polyurethane dispersion has a polyurethane (or active material, or solid) content by weight of from 20% to 60%, more preferably from 25% to 55% by weight, and even better from 30% to 50% by weight. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferably from 25% to 55% by weight, and even better from 30% to 50% by weight relative to the total weight of the dispersion.

[0506] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) of less than or equal to -25 °C, preferably less than -35 °C, and more preferably less than -40 °C.

[0507] The polyurethane particles may have an average diameter ranging up to about 1000 nm, for example from about 50 nm to about 800 nm, and even better from about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size analyzer (such as Brookhaven BI90).

[0508] As non-limiting examples of aqueous polyurethane dispersions, mention may be made of those sold by Bayer under the name , such as C1000 (INCI name: Polyurethane-34), C1001 (INCI name: Polyurethane-34), C1003 (INCI name: Polyurethane-32), C1004 (INCI name: Polyurethane-35) and C1008 (INCI name: Polyurethane-48).

[0509] Also mention may be made of the following aqueous polyurethane dispersions: isophthalic acid / adipic acid copolymer / hexanediol / neopentyl glycol / dimethylolpropionic acid / isophorone diisocyanate (INCI name: Polyurethane-1, such as PUR, BASF), polyurethanes of polycarbonates, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (such as or DSM series, such as R989 and R-2202).

[0510] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be selected from the aqueous dispersions of particles of a compound having the INCI name Polyurethane-35 or a compound having the INCI name Polyurethane-34.

[0511] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0512] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds called monomers). The unit or units are repeated at least twice and preferably at least three times.

[0513] The term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film, and preferably an adhesive film, on a support, in particular on keratin hair fibers.

[0514] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide.

[0515] The units of (meth)acrylic monomers derived from the polymer may optionally be in the form of salts, in particular alkali metal salts, alkaline earth metal salts or ammonium salts, or organic base salts.

[0516] (Meth)acrylic acid ester (also known as (meth)acrylate) is advantageously selected from alkyl (meth)acrylates, especially C1-C 30 alkyl esters, preferably C1-C 20 alkyl esters and even better C1-C 10 alkyl esters; aryl (meth)acrylates, especially C6-C 10 aryl esters; and hydroxyalkyl (meth)acrylates, especially C2-C6 hydroxyalkyl (meth)acrylates.

[0517] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

[0518] Among the hydroxyalkyl (meth)acrylates, mention may be made of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0519] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0520] Particularly preferred (meth)acrylates are alkyl, preferably C1-C 30 、more preferably C1-C 20 、even better C1-C 10 、and even more particularly C1-C4 alkyl (meth)acrylates.

[0521] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0522] As (meth)acrylamide, examples that may be mentioned include (meth)acrylamide and also N-alkyl (meth)acrylamide, especially N-(C2-C 12 alkyl)(meth)acrylamide. Among the N-alkyl (meth)acrylamides that may be mentioned are N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide and N-undecylacrylamide.

[0523] The acrylic polymer according to the present invention may be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and (meth)acrylate.

[0524] Preferably, the acrylic polymer according to the invention comprises one or more units derived from the following monomers:

[0525] a) (meth)acrylic acid; and

[0526] b) C1 to C 30 and more preferably C1 to C 20 even better C1 to C 10 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0527] Preferably, the aqueous dispersion of acrylic polymer particles does not contain any surfactant.

[0528] The term "surfactant" refers to any reagent capable of changing the surface tension between two surfaces.

[0529] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and (meth)acrylic methyl ester or (meth)acrylic ethyl ester, in particular the copolymer of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the polyacrylate-2 crosslinked polymer sold by Lubrizol under the trade name Fixate Superhold Polymer, or the acrylate copolymer sold by Daito Kasei Kogyo under the trade name Daitosol 3000VP3, or the acrylate polymer sold by Daito Kasei Kogyo under the trade name Daitosol 3000SLPN-PE1.

[0530] The acrylic polymer may optionally comprise one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic esters and / or (meth)acrylamide monomers.

[0531] As additional monomers, mention will be made, for example, of styrene monomers, in particular styrene and α-methylstyrene, and preferably styrene.

[0532] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular a polymer selected from the copolymers resulting from the polymerization of at least one styrene monomer and at least one C1 to C 20 alkyl ester of (meth)acrylic acid, preferably a C1 to C 10 alkyl ester monomer of (meth)acrylic acid.

[0533] (meth)acrylic acid C1 to C 10The alkyl ester monomer may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.

[0534] As acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers, which are sold by BASF under the name Joncryl 77, by Akzo Nobel under the name Yodosol GH41F, and by Interpolymer under the name Syntran 5760CG.

[0535] Preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle.

[0536] More preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle, which comprises one or more units derived from the following monomers:

[0537] a) (meth)acrylic acid; and

[0538] b) C1 to C 30 , more preferably C1 to C 20 , still better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

[0539] Preferably, based on the weight of the dispersion, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or solid) content of from 20% to 60% by weight, more preferably from 22% to 55% by weight, and still better from 25% to 50% by weight.

[0540] Silicone acrylate copolymer

[0541] According to a specific embodiment, the silicone compound comprising at least one carboxyl group is selected from silicone acrylate copolymers.

[0542] Thus, according to a specific embodiment, the compound containing at least one carboxyl functional group is selected from silicone acrylate copolymers.

[0543] Preferably, the silicone acrylate copolymer comprises:

[0544] - at least one acrylic acid or methacrylic acid or crotonic acid unit; and

[0545] - at least one polydimethylsiloxane (PDMS) unit.

[0546] For the purposes of the present invention, the term "polydimethylsiloxane" (also abbreviated as PDMS) denotes any silicone polymer or oligomer having a linear structure with variable molecular weight, obtained by polymerizing and / or polycondensing appropriately functionalized silanes and consisting essentially of repeating main units in which silicon atoms are linked together via oxygen atoms (siloxane bond Si-O-Si-), containing methyl groups directly linked to said silicon atoms via carbon atoms.

[0547] The PDMS chains that can be used to obtain the copolymers used according to the present invention contain at least one polymerizable group, which is preferably located at at least one end of the chain, i.e., the PDMS can contain, for example, polymerizable groups at each of the two ends of the chain or a polymerizable group at one end of the chain and a trimethylsilyl end group at the other end of the chain.

[0548] The term "polymerizable group" means a group capable of polymerizing with other polymerizable groups or monomers. Preferably, the polydimethylsiloxane units contain at least one polymerizable group.

[0549] Preferably, the polymerizable group contains at least one vinyl group.

[0550] Preferably, the polydimethylsiloxane (PDMS) units contain at least one polymerizable group containing at least one vinyl group, preferably at least two polymerizable groups containing at least one vinyl group, which are preferably located at at least one chain end.

[0551] As previously pointed out, the silicone acrylate copolymer preferably contains at least one acrylic acid or methacrylic acid or crotonic acid unit, i.e., at least one unit containing a carboxyl group.

[0552] The term "carboxyl group" means COOH or COO - functional group, COO - The counterion of the group is preferably selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0553] Preferably, the silicone acrylate copolymer contains:

[0554] - at least one acrylic acid or methacrylic acid or crotonic acid unit, and at least one acrylate or methacrylate or vinyl ester unit; and

[0555] - at least one polydimethylsiloxane (PDMS) unit.

[0556] More preferably, the composition contains one or more silicone acrylate copolymers, which contain:

[0557] - At least one crotonic acid unit and at least one unit selected from the following: crotonic acid alkyl ester units, wherein the alkyl is a straight-chain or branched-chain saturated group containing from 1 to 20 carbon atoms; vinyl acetate units; vinyl alkyl ester units, wherein the alkyl is a straight-chain or branched-chain saturated group containing from 2 to 20 carbon atoms; and mixtures thereof; and

[0558] - At least one polydimethylsiloxane (PDMS) unit.

[0559] The term "crotonic acid unit" means a unit derived from a crotonic acid monomer or its salt.

[0560] The term "crotonic acid alkyl ester unit" means a unit derived from a crotonic acid ester monomer, which contains a saturated straight-chain or branched-chain alkyl group containing from 1 to 20 carbon atoms.

[0561] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer, which contains a saturated straight-chain or branched-chain alkyl group containing from 2 to 20 carbon atoms.

[0562] The term "vinyl acetate unit" means a unit derived from a vinyl acetate monomer.

[0563] According to a preferred embodiment, the silicone acrylic copolymer comprises:

[0564] - At least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (wherein the alkyl is a saturated straight-chain or branched-chain group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms), and

[0565] - At least one polydimethylsiloxane (PDMS) unit, which preferably contains at least one polymerizable group containing at least one vinyl.

[0566] According to a particularly preferred embodiment, the silicone acrylic copolymer comprises:

[0567] - At least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (wherein the alkyl is a straight-chain or branched-chain saturated group containing from 6 to 16 carbon atoms), and

[0568] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl.

[0569] More preferably, the composition comprises one or more silicone acrylic copolymers, which comprise:

[0570] - At least one crotonic acid unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit (wherein the alkyl group is a saturated straight-chain or branched-chain group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms); and

[0571] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl group.

[0572] Even more preferably, the composition contains one or more silicone-acrylic copolymers, which contain:

[0573] - At least one crotonic acid unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit (wherein the alkyl group is a saturated straight-chain or branched-chain group containing from 6 to 16 carbon atoms); and

[0574] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl group.

[0575] Among the silicone-acrylic copolymers that can be used in the context of the present invention, mention may be made of the compound sold by Wacker Chemie AG under the trade name P1101, having the INCI name Crotonic Acid / Vinyl C8 - 12 Isalkyl Ester / VA / Bis-Vinyl Polydimethylsiloxane Crosspolymer.

[0576] The total amount of the compound containing at least one carboxyl functional group preferably ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, still better from 1% to 15% by weight, and even more preferably from 2% to 10% by weight, relative to the total weight of composition C.

[0577] The total amount of the aqueous dispersion of the particles of the polymer selected from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, still better from 1% to 25% by weight, and even more preferably from 2% to 20% by weight, relative to the total weight of composition C.

[0578] According to a specific embodiment, the total amount of the aqueous dispersion of the acrylic polymer particles preferably ranges from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, still better from 1% to 25% by weight, and even more preferably from 2% to 20% by weight, relative to the total weight of composition C.

[0579] Advantageously, the total amount of the silicone acrylate copolymer ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, still better from 1% to 15% by weight and even more preferably from 2% to 10% by weight, relative to the total weight of composition C.

[0580] Organic solvent

[0581] Composition C according to the invention may comprise one or more organic solvents.

[0582] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, and also aromatic alcohols (especially aromatic monohydric alcohols such as benzyl alcohol or phenoxyethanol), and mixtures thereof.

[0583] The organic solvent may be present in a total amount between 0.01% and 75% by weight, preferably between 0.05% and 50% by weight and more preferably between 0.1% and 45% by weight and including the end values, relative to the total weight of composition C.

[0584] Composition C used in the context of the method according to the invention may be aqueous. The water content may range from 1% to 90% by weight, preferably from 10% to 80% by weight and more preferably from 20% to 75% by weight, relative to the total weight of composition C.

[0585] Additive

[0586] Composition C used in the context of the method according to the invention may contain any conventional adjuvants or additives.

[0587] Among the additives that may be included in the composition, reducing agents, softeners, antifoaming agents, humectants, UV screening agents, peptizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, thickeners, preservatives, silicones, oils, waxes other than silicone in the form of waxes and mixtures thereof may be mentioned.

[0588] Composition C used in the context of the method according to the invention may in particular be in the form of a suspension, a dispersion, a gel, an emulsion, especially an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or a multiple emulsion (W / O / W or polyol / O / W or O / W / O), in the form of a cream, a mousse, a stick, a vesicle dispersion, especially an ionic or non-ionic lipid vesicle dispersion, or a two-phase or multi-phase lotion.

[0589] A person skilled in the art can select a suitable presentation form, as well as its preparation method, based on their general knowledge, first considering the nature of the ingredients used, especially their solubility in the carrier, and secondly the intended application of the composition.

[0590] spray gun

[0591] As previously indicated, the composition C used in the context of the method according to the invention is sprayed onto the keratinous hair fibers using a spray gun.

[0592] To spray the composition just described, a spray gun system 1 as Figure 1 shown is used.

[0593] As shown in the figure, the spray gun system 1 may include a spray gun 2 connected to a compressed gas source, which compressed gas source may include, for example, an air compressor 4 connected to the spray gun 2 in a manner known per se via a pressure regulator 5 and a hose 15. The compressed gas source may also be a capsule of replaceable or refillable compressed gas (such as compressed air).

[0594] The spray gun 2 includes a gripping portion in a manner known per se. For example, when the spray gun is pen-shaped, the gripping portion is defined by the elongated body of the spray gun, or when the spray gun is pistol-shaped, the gripping portion is defined by a handle 10, as Figure 2 shown.

[0595] The spray gun 2 may carry a container 11 for containing the composition C to be sprayed, which container 11 is, for example, in the form of a removable bottle. As shown in the figure, the spray gun may include connecting means 30 at the top for receiving the container 11.

[0596] During the operation of the spray gun 2, the product is sucked up and flows into the spray gun via a collection channel before being sprayed.

[0597] The container 11 may be transparent or provided with graduations to allow the user to more easily visualize the amount of product available. The volume of the product contained in the container 11 is, for example, between 1 and 5000 mL, and preferably 1 to 1000 mL, even more preferably 1 to 500 mL.

[0598] Preferably, for example, the hose 15 connecting the spray gun to the compressor 4 and especially to the air regulator 5 is less than or equal to 5 m in length and has an inner diameter equal to 4 mm. The hose 15 is preferably fitted with quick-connect fittings.

[0599] As Figure 1 shown, the user may be recommended a spray gun 2 with several plugged and pre-filled containers 11, for example all containing the same product, to allow the user to quickly replace an empty container with a full one, for example to treat different people.

[0600] Container 11 can even contain different products, such as products with different compositions, which are intended for complementary or otherwise different treatments, and the user can select which one of the containers 11 corresponds to the treatment to be carried out.

[0601] The spraying parameters, in particular the flow rate of the carrier gas (preferably air) and / or the flow rate of the product to be sprayed, can be manually adjusted by the user each time the container 11 is changed, if necessary or during use, to obtain the desired visual effect.

[0602] The relative pressure of the compressed air entering the spray gun 2 can be between 0.2 and 3 bar, preferably between 0.4 and 1 bar, for example about 0.5 bar.

[0603] The nozzle 21 fitted to the spray gun is preferably chosen such that the average size of the droplets of the product to be sprayed is concentrated between 10 and 35 μm, for example a value of about 23 μm (size measured at 15 cm from the nozzle outlet).

[0604] The nozzle 21 can have an outlet diameter in the range, for example, from 0.1 to 1 mm, preferably from 0.2 to 0.7 mm.

[0605] In the example shown, the connecting device 30 suitable for a container 11 in the form of a bottle (including the neck fitted with a collar and a stopper 120) comprises an end piece for fixing to the body of the spray gun, for example an end piece of the quick - fitting type, so as to allow removable fixing to the body of the spray gun.

[0606] Needless to say, if the connecting device 30 is not removably fixed to the rest of the spray gun, or if a device other than a quick - coupling is used for removable fixing, this does not depart from the context of the present invention.

[0607] When the connecting device 30 is in place on the spray gun, the axis of the nozzle can be vertical, or inclined and directed towards the front or the rear of the spray gun.

[0608] The connecting device 30 can even be made in the form of part of the body of the spray gun, and the connecting device 30 does not necessarily project relative to the body of the spray gun.

[0609] Since the container 11 is fixed to the connecting device in a sealed manner, an air return circuit is provided to allow air to flow back into the container when it is emptied. The container is closed except for the product collection circuit and the air return circuit.

[0610] To use the spray gun 2, the user places the container 11 on the connecting device 30.

[0611] Before being placed on the spray gun, the container 11 is, for example, fitted with a plug 120, such as a nipple or a capping cap, and then the plug is separated from the container.

[0612] The spray gun 2 can include any spraying triggering device, for example in the form of a control member, such as a lever 13 actuated by the fingers of the hand of the user holding the spray gun, as Figure 2 shown. In this figure, the spray gun is a gravity spray gun. Using a suction spray gun is not beyond the scope of the present invention. In the latter case, it is sufficient for the connecting device 30 to be fitted with a system (for example, a tube 200 as shown by the dashed line in Figure 1 the figure) for connecting the first orifice to the inlet of the spray gun so as to allow suction.

[0613] As examples of spray guns to which the present invention can be applied, reference can be made to reference A4700 from Azteck, reference Kustom micron CM from Iwata, and reference "Evolution Infinity 2in 1" from Harder and Steenbeck, which are pen-grip type spray guns. It is also possible to use the "Kustom revolution TR" or "Studio series" spray guns from Iwata, or the spray guns from Harder&Steenbeck.

[0614] Needless to say, arrangements other than those just described are possible. For example, the same compressor can be used for several spray guns, and this compressor is located, for example, outside the room where the treatment is carried out in order to reduce noise pollution.

[0615] Preferably, the spray is circular, but various nozzles can be used in order to have a flat spray or a spray of another shape according to the visual effect to be obtained.

[0616] The compressor can be replaced by a compressed air supply, such as bottled compressed air or a cylinder of compressed or liquefied gas, for example carried on the spray gun and handled together with the spray gun during use.

[0617] In appropriate cases, several containers can be mounted on the spray gun.

[0618] The can carried by the spray gun can be replaced by a can connected to the spray gun by a pipe, and the product is sucked into the spray gun by the negative pressure generated by the circulation of the carrier gas in the spray gun through the Venturi effect. A pump can also be used to feed the product to be sprayed into the spray gun.

[0619] The use of the spray gun allows for easy modification of the operating parameters to vary the effects that can be optionally produced by the user during use; for example, the user can adjust the flow rate of the product jet according to the desired visual effect. In addition, when the spray gun is connected to a compressor, the volume of the gas (preferably air) used as a carrier is unlimited. The product to be sprayed can be easily updated, and different products can be easily used continuously with the same spray gun.

[0620] The flow rate of the composition being sprayed is advantageously less than or equal to 10 g / min.

[0621] Solution

[0622] The composition C described above can be used on wet or dry keratin hair fibers, as well as on any type of keratin hair fibers that are blond or brown, natural or dyed, permanently waved, bleached or relaxed.

[0623] According to a specific embodiment of the invention, the keratin hair fibers are washed before applying the composition C.

[0624] Preferably, a washing, rinsing, draining or drying step is carried out after applying the composition C to the keratin hair fibers.

[0625] More preferably, a drying step is carried out after spraying the composition C onto the keratin hair fibers.

[0626] As shown previously, the composition C is sprayed using the spray gun as described above.

[0627] The composition C is generally sprayed onto the keratin hair fibers at room temperature (between 15 °C and 25 °C).

[0628] After spraying the composition C onto the keratin hair fibers, it is possible to wait between 1 minute and 6 hours, particularly between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, and more preferably between 1 minute and 30 minutes before, for example, a washing, rinsing, draining and / or drying step.

[0629] After spraying the composition C, the keratin hair fibers can be left to dry or can be dried, for example, at a temperature greater than or equal to 30 °C.

[0630] Thus, the method according to the invention can include a step of applying heat to the keratin hair fibers using a heat tool.

[0631] The heat application step of the method of the invention can be carried out using a hood, a hair dryer, a straightener, a curler, a Climazon hood, etc.

[0632] Preferably, the heat application step of the method of the invention is carried out using a hair dryer.

[0633] When the method according to the invention involves a step of applying heat to keratinous hair fibers, the step of applying heat to the keratinous hair fibers is carried out after the application of composition C to the keratinous hair fibers.

[0634] During the step of applying heat to the keratinous hair fibers, a mechanical action such as combing, brushing or passing the fingers through can be exerted on the tress.

[0635] When the step of applying heat to the keratinous hair fibers is carried out using a hood or a hair dryer, the temperature is preferably between 30 °C and 110 °C, preferably between 50 °C and 90 °C.

[0636] When the step of applying heat to the keratinous hair fibers is carried out using a straightener, the temperature is preferably between 110 °C and 220 °C, preferably between 140 °C and 200 °C.

[0637] In a particular variant, the method according to the invention involves a step (c1) of applying heat using a hood, a hair dryer or a Climazon hood, preferably a hair dryer, and a step (c2) of applying heat using a straightener or a curler, preferably a straightener.

[0638] Step (c1) can be carried out before step (c2).

[0639] During step (c1), which is also called the drying step, the keratinous hair fibers can be dried, for example, at a temperature above or equal to 30 °C. According to a particular embodiment, this temperature is above 40 °C. According to a particular embodiment, this temperature is above 45 °C and below 110 °C.

[0640] Preferably, if the keratinous hair fibers are dried, they are dried with an air stream in addition to the supply of heat. This air stream during drying makes it possible to improve the separation of the tresses of the coating.

[0641] During drying, a mechanical action such as combing, brushing or passing the fingers through can be exerted on the tresses.

[0642] During step (c2), the passage of the straightener or the curler, preferably the straightener, can be carried out at a temperature ranging from 110 °C to 220 °C, preferably between 140 °C and 200 °C.

[0643] After the heating step, a shaping step can be carried out, for example using a straightener; the temperature for the shaping step can be between 110 °C and 220 °C, preferably between 140 °C and 200 °C.

[0644] Preferably, the invention is a method for dyeing keratinous hair fibers, the method comprising the following steps:

[0645] i) Spray the keratin hair fibers with at least one composition C using a spray gun as described above, the at least one composition comprising:

[0646] - at least one (poly)carbodiimide compound as previously described; and

[0647] - at least one colorant selected from pigments, direct dyes, and mixtures thereof; and then

[0648] ii) Optionally, allow the composition C to have a residence time on these keratin hair fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes; and then

[0649] iii) Optionally, wash, rinse, drain, and / or dry the keratin hair fibers.

[0650] Preferably, composition C further comprises at least one compound containing at least one carboxyl functional group.

[0651] Advantageously, spraying the composition C on the keratin hair fibers is repeated several times.

[0652] According to a preferred embodiment, the dyeing method according to the present invention is a method for dyeing keratin hair fibers, which comprises instantaneously mixing at least two compositions A and B during use to obtain composition C and spraying composition C on the keratin hair fibers using a spray gun as described above, wherein:

[0653] - Composition A comprises at least one (poly)carbodiimide compound as previously described;

[0654] - Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0655] Composition A and / or composition B may optionally comprise at least one compound containing at least one carboxyl functional group.

[0656] Preferably, composition B comprises at least one compound containing at least one carboxyl functional group.

[0657] Preferably, composition A does not comprise at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0658] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes, more preferably less than 10 minutes, still better less than 5 minutes before spraying on the keratin hair fibers.

[0659] The weight ratio between composition A and composition B preferably ranges from 0.1 to 10, preferably from 0.2 to 5 and more preferably from 0.5 to 2, or even from 0.6 to 1.5. In a specific embodiment, the weight ratio between composition A and composition B is equal to 1.

[0660] (The total amount of the (poly)carbodiimide compound preferably ranges from 0.01% to 40% by weight, more preferably from 0.1% to 30% by weight, still more preferably from 0.5% to 20% by weight and even more preferably from 1% to 12% by weight relative to the total weight of composition A.

[0661] When a compound containing at least one carboxyl functional group is present, its total amount preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 40% by weight, still more preferably from 1% to 30% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of composition B.

[0662] Spraying system

[0663] The present invention also relates to a spraying system, which comprises:

[0664] - A spray gun;

[0665] - At least one compartment for containing composition C, which composition comprises:

[0666] a) At least one (poly)carbodiimide compound as defined above;

[0667] b) At least one colorant selected from pigments, direct dyes and mixtures thereof.

[0668] The present invention also relates to a spraying system, which comprises:

[0669] - A spray gun;

[0670] - A plurality of compartments for containing:

[0671] Composition A in the first compartment, which comprises:

[0672] a) At least one (poly)carbodiimide compound as defined above;

[0673] Composition B in the second compartment, which comprises:

[0674] b) At least one colorant selected from pigments, direct dyes and mixtures thereof.

[0675] The present invention will now be described more specifically by way of examples, which do not limit the scope of the present invention in any way. However, these examples enable the support of specific features, variants and preferred embodiments of the present invention.

[0676] Example

[0677] The (poly)carbodiimide of the present invention is obtainable from commercial products or reagents which can be synthesized according to chemical reactions known to the person skilled in the art by synthesis methods known to the person skilled in the art. For example, reference may be made to the book Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D - 70469 Stuttgart, or US Patent US 4 284 730 or Canadian Patent Application CA2 509 861.

[0678] More specifically, the method for preparing the (poly)carbodiimide of the present invention involves in a first step a diisocyanate reagent (1):

[0679] O=C=N - L1 - N=C=O (1),

[0680] In formula (1), L1 is as previously defined, which in the presence of a carboimidation catalyst (2) (such as those described in US 4 284 730, especially phosphorus - based catalysts, in particular selected from cyclophosphene oxides and cyclophosphene sulfoxides, diaza - and oxa - phospholanes), preferably under an inert atmosphere (nitrogen or argon), and especially in a polar solvent (preferably an aprotic solvent such as THF, diglyme, triglyme, 1,4 - dioxane or DMF), at a temperature between room temperature and the reflux temperature of the solvent, preferably at about 140 °C, reacts to obtain a carbodiimide diisocyanate compound (3):

[0681] O=C=N - L1 - (N=C=N - L1) n - N=C=O (3),

[0682] In formula (3), L1 and n are as previously defined. A benzoyl halide such as benzoyl chloride may be added to deactivate the catalyst.

[0683] In order to obtain a "symmetrical" (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of a nucleophilic reagent R1 - X1 - H and then with 0.5 equivalent of the reagent H - E - H, where R1, X1 and E are as previously defined, to obtain the "symmetrical" compound (4) according to the present invention:

[0684] [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4),

[0685] In formula (4), R1, X1, L1, n and E are as defined previously. According to a variant of obtaining compound (4) from (3), 0.5 equivalents of the reagent H-E-H can be added first, and then 1 equivalent of the reagent R1-X1-H can be added.

[0686] To obtain an “asymmetric” (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of the nucleophilic reagent R1-X1-H, and then with 1 equivalent of the reagent H-E-H, where R1, X1 and E are as defined previously, to obtain compound (5):

[0687] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-H (5),

[0688] In formula (5), R1, X1, L1, n and E are as defined previously.

[0689] According to a variant of obtaining compound (5) from (3), 1 equivalent of the reagent R1-X1-H can be added first, and then 0.5 equivalent of the reagent H-E-H can be added.

[0690] During the third step, compound (5) is reacted with 1 equivalent of compound (6)

[0691] R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O(6), and the compound (6) is prepared in advance from compound (3’):

[0692] O=C=N-L1-(N=C=N-L1) z -N=C=O(3’),

[0693] In formula (3’), L1 and z are as defined previously, and it is reacted with 1 equivalent of the nucleophilic reagent R2-X2-H, where L1, R2, X2 and z are as defined previously, to obtain the asymmetric compound (7):

[0694] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-C(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2 (7),

[0695] In formula (7), R1, X1, L1, R2, X2, n, z and E are as previously defined.

[0696] One molar equivalent of the compound O═C═N-L1-(N═C═N-L1) z -N═C═O (3’) can be reacted with 1 / w molar equivalents of H-E-H, and then with 1 equivalent of the nucleophile R2-X2-H to obtain the compound (8):

[0697] H-[E-C(O)-NH-L1-(N═C═N-L1) z w -NH-C(O)-X2-R2 (8),

[0698] In formula (8), L1, R2, X2, z and E are as previously defined, and w is an integer between 1 and 3; more preferably, w = 1.

[0699] Then this last compound (8) can be reacted with 1 equivalent of the compound (4’):

[0700] R1-X1-C(O)-NH-L1-(N═C═N-L1) n -N═C═O (4’), (the compound (4’) can be synthesized by the reaction of 0.5 equivalent of the nucleophile R1-X1-H with 1 equivalent of the compound (3)), to obtain the (poly)carbodiimide (9) of the present invention:

[0701] R1-X1-C(O)-NH-L1-(N═C═N-L1) n -NH-C(O)-[E-C(O)-NH-L1-(N═C═N-L1) z w -NHC(O)-X2-R2 (9),

[0702] In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as previously defined.

[0703] (Poly)carbodiimide compounds and similarly all reaction intermediates and reagents can be purified by conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0704] Example 1: Method for synthesizing (poly)carbodiimide compounds

[0705] ​​50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide were placed in a 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer, and a reflux tube under stirring.

[0706] The reaction medium was heated at 140 °C for 4 h under nitrogen, and the reaction was monitored by infrared spectroscopy by means of the absorption of the isocyanate functional group between 2200 and 2300 cm -1 and then cooled to 120 °C.

[0707] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol was introduced into the reaction medium under stirring. The temperature of 120 °C was maintained until the isocyanate functional group had completely disappeared, monitored by infrared spectroscopy at 2200 - 2300 cm -1 and then cooled to room temperature.

[0708] After cooling to room temperature, the reaction medium was poured dropwise into a 500 mL glass beaker containing 85 g of distilled water under vigorous stirring to obtain the desired product in the form of a translucent yellow liquid.

[0709] Example 2

[0710] Compositions A and B as described in Tables 1 and 2 below were prepared: Unless otherwise mentioned, the amounts are expressed as g of starting material as obtained / 100 g. In the tables below, "a.m." means "active material".

[0711] [Table 1]

[0712]

[0713]

[0714] (1) Synthesis was carried out according to the synthesis method described in Example 1 (40% active material in water).

[0715] [Table 2]

[0716]

[0717] (2) Sold by Daito Kasei Kogyo Co., Ltd. under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active material)

[0718] (3) Sold by Dow Corning under the name Dow Corning HMW 2220 nonionic emulsion (divinyl polydimethylsiloxane / polydimethylsiloxane block copolymer as an aqueous emulsion) (60% active material)

[0719] Then, composition A and composition B are mixed at a mass ratio of 50 / 50 to obtain composition C according to the present invention.

[0720] Scheme

[0721] Two application methods are used.

[0722] According to the first method (referred to as method P1), composition C is manually applied to a lock of dry natural keratin hair fibers containing 90% white keratin hair fiber strands at a rate of 0.8 g of composition per gram of lock using a brush. Then the lock of keratin hair fibers is detangled and dried with a hair dryer, and then combed.

[0723] Therefore, this is a comparative method.

[0724] According to the second method (referred to as method P2), composition C is introduced into a cup, which is inserted into a spray gun (Iwata Studio series spray gun). Pressure is applied to the trigger to distribute the composition via compressed air at 0.5 bar at a distance of no more than 5 cm for a time sufficient to cover a lock of dry natural keratin hair fibers containing 90% white keratin hair fiber strands. Thus, composition C is sprayed onto the lock of keratin hair fibers. Then the lock of keratin hair fibers is detangled and dried with a hair dryer, and then combed.

[0725] Therefore, this is the method according to the present invention.

[0726] Shampoo washing scheme:

[0727] The lock of dyed keratin hair fibers is combed, moistened with water at 35 °C and then passed through the fingers five times for 5 seconds. Then the lock of keratin hair fibers is squeezed dry between two fingers.

[0728] A standard shampoo (Garnier Ultra Doux) is uniformly applied to the dyed lock at a ratio of 0.4 g of standard shampoo per gram of lock, and the lock of keratin hair fibers is gently massaged for 15 seconds along the length from the root to the tip (6 passes).

[0729] Then the lock of keratin hair fibers is placed on a watch glass and left to stand for 1 minute.

[0730] Next, the lock of keratin hair fibers is rinsed with water while passing it through the fingers (15 passes). Then the lock of keratin hair fibers is squeezed dry between two fingers, and then the next shampoo wash is carried out.

[0731] After several shampoo wash tests, the lock of keratin hair fibers is combed and dried with a hair dryer.

[0732] Result

[0733] The color fastness of the tress was evaluated using a Minolta CM3600A spectrophotometer colorimeter (light source D65, 10° angle, including specular reflection component) in the CIE L*a*b* system.

[0734] In this L*a*b* system, L* represents the intensity of the color, a* represents the green / red axis and b* represents the blue / yellow axis.

[0735] The color fastness was evaluated by the color difference ΔE between the colored tress before shampooing and then after undergoing three shampoo washes according to the protocol described above. The lower the ΔE value, the more color fast the color is with respect to shampoo washing.

[0736] The ΔE value was calculated according to the following equation:

[0737]

[0738] In this equation, L*a*b* represents the values measured after dyeing the keratin hair fibers and after shampoo washing, and L0*a0*b0* represents the values measured after dyeing the keratin hair fibers but before shampoo washing.

[0739] [Table 3]

[0740]

[0741] Tresses of keratin hair fibers treated by method P2 according to the invention and washed with three shampoo washes have a lower ΔE value than tresses of keratin hair fibers treated by the comparative method P1.

[0742] Therefore, the colored coating obtained by means of the method according to the invention shows improved fastness with respect to shampoo washing.

Claims

1. A method for dyeing keratin hair fibers, the method involving spraying the keratin hair fibers with at least one composition C using a spray gun, the at least one composition comprising: - one or more (poly)carbodiimide compounds; and - at least one colorant selected from pigments, direct dyes, and mixtures thereof.

2. The method according to claim 1, characterized in that, The (poly)carbodiimide compound is selected from compounds of the following formula (I): Wherein: - X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; - R1 and R2 independently represent: a group selected from hydrocarbon-based groups optionally inserted with one or more heteroatoms, preferably alkyl groups; a group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups; and hydrocarbon-based groups, preferably alkyl groups, which are optionally inserted with one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups; - n indicates an integer ranging from 1 to 1000; and - A is a monomer selected from the following compounds:

3. The method according to claim 1, characterized in that, The (poly)carbodiimide compound is selected from compounds of the following formula (II): Wherein: - X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; - R1 and R2 independently represent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w indicates an integer ranging from 1 to 3; -L1 independently represents C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkylene, C3-C 12 a heterocycloalkylene or C6-C 14 an arylene, and mixtures thereof; - E independently represents a group selected from: - O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; Where R3 and R4 independently represent divalent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms; - R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

4. The method according to claim 3, characterized in that The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently are selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof; - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w is equal to 1; -L1 is selected from C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkylidene, C3-C 12 a heterocycloalkylidene or C6-C 14 an arylidene, and mixtures thereof; - E independently represents a group selected from: - O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; -When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

5. The method according to claim 3 or 4, characterized in that, The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently are monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed; - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w is equal to 1; -L1 is C3-C 15 subcycloalkyl; - E independently represents a group selected from: - O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; -When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

6. The method according to any one of claims 3 to 5, characterized in that, The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently represent a compound of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers ranging from 1 to 20, where the range of n + z is from 4 to 10 and w is equal to 1; -L1 is a C3-C 15 subcycloalkyl group, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane; and -E represents the group -O-R3-O-, where R3 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

7. The method according to any one of claims 3 to 6, characterized in that The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently represent a compound of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30; - n and z indicate integers ranging from 1 to 20, where the range of n + z is from 4 to 10 and w is equal to 1; -L1 is a C3-C 15 subcycloalkyl group, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane, preferably 4,4-dicyclohexylmethane; and -E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkylene group, such as methylene, propylene, butylene or ethylene.

8. The method according to any one of claims 3 to 7, characterized in that, The (poly)carbodiimide compound is selected from the compounds of the following formula (XII): Wherein L1 is 4,4-dicyclohexylmethane, n and z denote integers ranging from 1 to 20, where the range of n + z is from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkylene group, such as methylene, propylene, butylene or ethylene, and r and s denote integers ranging from 4 to 30.

9. The method according to any one of the preceding claims, characterized in that, The total amount of the (poly)carbodiimide compound ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% by weight, and still better from 1% to 6% by weight relative to the total weight of composition C.

10. The method according to any one of the preceding claims, characterized in that, The total amount of the colorant ranges from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C; preferably, the colorant is selected from pigments.

11. The method according to any one of the preceding claims, characterized in that, Composition C further comprises at least one compound containing at least one carboxyl functional group.

12. The method according to claim 11, wherein The compound containing at least one carboxyl functional group is selected from silicone compounds containing at least one carboxyl group, polyurethanes, acrylic polymers, and mixtures thereof.

13. The method according to claim 11 or 12, characterized in that, The compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of polymer particles selected from polyurethanes, acrylic polymers, and mixtures thereof, preferably in the form of an aqueous dispersion of acrylic polymer particles, more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

14. The method according to the preceding claim, characterized in that, The acrylic polymer comprises one or more units derived from the following monomers: a) (Meth)acrylic acid; and b) C1 to C 30 , more preferably C1 to C 20 , still better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

15. The method according to any one of claims 11 to 14, characterized in that The total amount of the compound containing at least one carboxyl functional group ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, and still better from 2% to 10% by weight, relative to the total weight of composition C.

16. The method according to any one of claims 1 to 8, characterized in that The method comprises instantaneously mixing at least two compositions A and B in use to obtain composition C, and spraying composition C onto the keratinous hair fibers, wherein: - Composition A contains at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8; - Composition B contains at least one colorant selected from pigments, direct dyes, and mixtures thereof.

17. A spraying system, comprising: - A spray gun; - At least one compartment containing composition C, said composition comprising: a) At least one (poly)carbodiimide compound as defined in any one of claims 1 to 9; b) At least one colorant selected from pigments, direct dyes, and mixtures thereof.

18. A spraying system, comprising: - A spray gun; - A plurality of compartments containing: Composition A in a first compartment, which comprises: a) At least one (poly)carbodiimide compound as defined in any one of claims 1 to 8; Composition B in a second compartment, which comprises: b) At least one colorant selected from pigments, direct dyes, and mixtures thereof.

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