A method for coloring keratin fibers, comprising applying a composition comprising at least one (poly)carbodiimide compound and a composition comprising at least one associative polymer and a specific compound

Abstract

The present invention relates to a method for coloring hair keratinous fibers, comprising applying a composition A and a composition B to the hair keratinous fibers, wherein composition A comprises at least one (poly)carbodiimide compound and composition B comprises - at least one associative polymer and - at least one compound different from the associative polymer, containing at least one carboxylic acid group, and composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof, and composition A and composition B are applied simultaneously or successively to the hair keratinous fibers. The present invention also relates to a device for coloring hair keratinous fibers.

Description

Technical Field

[0001] The present invention relates to a method for coloring keratin fibers of hair, which comprises applying composition A and composition B to the keratin fibers of hair. Composition A contains at least one (poly)carbodiimide compound, and composition B contains at least one associative polymer and at least one compound containing at least one carboxylic acid group different from the associative polymer. Composition A and / or composition B contains at least one colorant selected from pigments, direct dyes, and mixtures thereof, and composition A and composition B are applied to the keratin fibers of hair simultaneously or sequentially.

[0002] The present invention also relates to an apparatus for coloring keratin fibers of hair.

Background Art

[0003] In the field of coloring hair, especially human hair, it is already known to color keratin fibers through various techniques using direct dyes or pigments for non-permanent coloring or dye precursors for permanent coloring.

[0004] There are essentially three methods for coloring hair. a) "Permanent" coloring: Its action can significantly modify the original color, penetrate into the hair fibers, and uses oxidation dyes that produce pigments through an oxidative condensation process. b) Non-permanent, semi-permanent or direct dyes: Do not use the oxidative condensation process and can withstand 4 to 5 shampoo washings. This involves coloring the keratin fibers with a coloring composition containing a direct dye. c) Temporary coloring: Modifies the original color of the hair, remains from the first shampoo wash to the next shampoo wash, and plays a role in enhancing or correcting the already obtained color tone. This can also be associated with the "makeup" method.

[0005] Regarding the last-mentioned type of coloring, a technique using colored polymers produced by grafting one or more dyes having the properties of azo, triphenylmethane, azine, indamine or anthraquinone onto a polymer chain is known. Such colored polymers are not entirely satisfactory, particularly with regard to the uniformity of the colored color and its resistance, and needless to say, with regard to the problems associated with their production, particularly reproducibility.

[0006] Another coloring method involves using pigments. Specifically, when pigments are used on the surface of keratin fibers, the pigments on the surface conceal the original color of the fibers, so that it is generally possible to achieve coloring that can be recognized on dark-colored hair. However, the coloring obtained by this coloring method has the drawback that it is inferior not only in resistance to shampoo washing but also in resistance to external agents such as sebum, sweat, brushing and / or friction.

[0007] Furthermore, temporary hair coloring compositions may further have a working quality that is not entirely satisfactory, particularly with regard to texture and the ease and / or uniformity of spreading on the head of the hair.

[0008] Therefore, there is still a need for a method of coloring hair keratin fibers, particularly hair, which has the advantage of obtaining a smooth and uniform coloring coating on the hair while at the same time forming a durable coating against various attack factors that the hair may be subjected to, such as shampoo washing and brushing and / or friction without deteriorating the hair, and the composition used in connection with said method has good stability and good working quality over time. Summary of the Invention Problems to be Solved by the Invention

[0009] Accordingly, an object of the present invention is to provide a method for coloring keratin fibers of hair, which has the advantage of obtaining a smooth and uniform coloring coating on the hair, while at the same time forming a durable coating against various attack factors that the hair may be subjected to, such as brushing and / or friction, with respect to shampooing and without deteriorating the hair. The composition used in relation to said method has good stability over time and good working quality, especially in terms of texture and ease and / or uniformity of spreading of the hair on the head. The object is to develop a method.

Means for Solving the Problems

[0010] Accordingly, one subject of the present invention is a method for coloring keratin fibers of hair, which comprises applying composition A and composition B to the keratin fibers of hair. Composition A contains at least one (poly)carbodiimide compound, and composition B - contains at least one associative polymer, and - at least one compound containing at least one carboxylic acid group, different from the associative polymer and composition A and / or composition B contain at least one colorant selected from pigments, direct dyes and mixtures thereof, and composition A and composition B are applied to the keratin fibers of hair simultaneously or sequentially.

[0011] In one variant of the present invention, the hair coloring composition C is obtained by immediate mixing during the use of at least one composition A as defined above and at least one composition B as defined above. In this variant, the hair coloring composition C obtained by mixing composition A and composition B is applied to the keratin fibers of hair.

[0012] In another variant, the composition A as defined above and the composition B as defined above are applied to the keratin fibers of hair simultaneously.

[0013] In another variant, compositions A and B are applied continuously to the keratin fibers of the hair, and composition A is optionally applied to the keratin fibers of the hair before composition B or vice versa.

[0014] The present invention also relates to an apparatus for coloring keratin fibers of the hair, the apparatus comprising - composition A as defined above, in a first compartment (E1), and - composition B as defined above, in a second compartment (E2), - optionally, composition D as defined below, in a third compartment (E3) and comprising at least two compartments for containing them.

Embodiments for Carrying out the Invention

[0015] By using this coloring method on the keratin fibers of the hair, a colored coating is obtained on the hair, which is persistent with respect to shampooing and at the same time makes it possible to obtain a visible coloring on all types of hair in a way that maintains the physical quality of the keratin fibers of the hair. This type of coating can withstand drying by blowing and external aggressors to which the hair may be exposed, such as sweat. Thereby, it is possible to obtain in particular a smooth and uniform deposit.

[0016] Furthermore, the compositions used in connection with the method for coloring keratin fibers according to the present invention have good stability over time, in particular after a storage period at room temperature or up to a temperature of 55°C.

[0017] Furthermore, the compositions used in connection with the method according to the present invention have good working quality, in particular with respect to texture and ease and uniformity of spreading on the hair, while at the same time minimizing running problems.

[0018] For the purposes of the present invention, the term "coloring showing persistence with respect to shampooing" means that the coloring obtained persists after one shampooing, preferably after three shampooings, more preferably after five shampooings.

[0019] The term "at least one" means one or more.

[0020] The present invention is not limited to the illustrated embodiments. The features of the various embodiments can be combined, in particular, within variants not illustrated.

[0021] For the purposes of the present invention, unless otherwise specified, the following applies: - The term "alkyl" refers to a straight-chain or branched saturated group containing, for example, from 1 to 20 carbon atoms; - The term "aminoalkyl" refers to an alkyl group as defined above in which the alkyl group contains an NH2 group; - The term "hydroxyalkyl" refers to an alkyl group as defined above in which the alkyl group contains an OH group; - The term "alkylene" refers to a straight-chain or branched divalent saturated C2-C4 hydrocarbon-based group such as methylene, ethylene or propylene; - The term "cycloalkyl" or "alicycloalkyl" refers to 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, in particular from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably from 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, and the cycloalkyl group may be substituted with one or more (C1-C4) alkyl groups such as methyl, in which case, preferably, the cycloalkyl group is an isobornyl group; - The term "cycloalkylene" refers to a divalent cycloalkyl group having the "cycloalkyl" defined above, preferably C3-C 12 and refers to a divalent cycloalkyl group; - The term "aryl" refers to a monocyclic, bicyclic or tricyclic, fused or unfused unsaturated aromatic hydrocarbon-based cyclic group containing 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the aryl group contains one ring having 6 carbon atoms, such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl. It is understood that the aryl group may be substituted with one or more (C1-C4) alkyl groups such as methyl, preferably tolyl, xylyl or methylnaphthyl. Preferably, the aryl group represents phenyl; - The term "arylene" refers to a divalent aryl group having the "aryl" defined above. Preferably, arylene represents phenylene; - The term "heterocyclic" refers to a saturated or unsaturated, non-aromatic or aromatic monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as imidazolyl, pyrrolyl and furanyl; - The term "heterocycloalkylene" refers to a divalent heterocyclic group having the "heterocyclic" defined above; - The term "aryloxy" refers to aryloxy having the "aryl" defined above; - The term "alkoxy" refers to an alkyloxy group having the "alkyl" defined above; - The term "acyloxy" refers to an ester group R-C(O)-O- where R is the alkyl group defined above; - The term "reactive" refers to a group that can form a covalent bond with another identical or different group by a chemical reaction.

[0022] The term "hair keratin fiber" means hair.

[0023] For the purposes of the present invention, the expression "hair" means the hair on the head. This does not refer to eyelashes, eyebrows and body hair.

[0024] Polycarbodiimide compound Composition A according to the invention, which is used in connection with a method for coloring keratin fibers according to the invention, comprises at least one (poly)carbodiimide compound.

[0025] This composition can comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0026] 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, and in particular the number of carbodiimide groups does not exceed 200, preferably does not exceed 150, more preferably does not exceed 100.

[0027] The "carbodiimide group" means a divalent linear three-atom moiety represented by the general formula -(N=C=N)-.

[0028] The (poly)carbodiimide compounds according to the invention can optionally comprise one or more reactive groups different from the carbodiimide groups, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloalkylsilyl, methacryloalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloalkyl, crotonylalkyl, alkyl epoxide, such as propyl epoxide or butyl epoxide and aziridine groups.

[0029] Reactive groups other than the carbodiimide group can be side groups or end groups. Preferably, the (poly)carbodiimide compound has one or more end groups different from the carbodiimide group, preferably alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonylalkyl, alkyl epoxide, such as propyl epoxide or butyl epoxide and one or more end groups selected from azacyclopropane groups.

[0030] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I):

Chemical formula

Chemical formula

[0031] According to another embodiment, the (poly)carbodiimide compound is of the following formula (Ia):

Chemical formula

[0032] Preferably, Z1 and Z2 independently represent reactive end groups. More preferably, Z1 and Z2 independently represent groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylylalkylsilyl, methacrylylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acrylylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane groups.

[0033] Such (poly)carbodiimide compounds are sold, for example, under the name Permutex XR or RelcaLink10 or Picassian XL by Stahl B.V., and Nisshinbo sells the compounds under the name Carbodilite by 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.

[0034] Preferably, the (poly)carbodiimide compound is of the following formula (II):

Chemical formula

[0035] The term "hydrocarbon-based group" means a saturated or unsaturated, straight-chain or branched 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.

[0036] The hydrocarbon-based group can include one or more cyclic groups.

[0037] The hydrocarbon-based group may in particular be intervened by one or more heteroatoms selected from O, S or N, and / or may be 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 may contain metal ions that can be incorporated in the form of salts.

[0038] The term "heteroatom" also means halogen atoms such as Cl, F, Br and I in addition to oxygen O, sulfur S or nitrogen N atoms. When a heteroatom is included in the chain of the hydrocarbon-based group, this heteroatom is preferably selected from oxygen O, sulfur S or nitrogen N atoms.

[0039] Preferably, X1 and X2 each independently represent an oxygen atom.

[0040] Preferably, R1 and R2 are each independently selected from dialkylamino alcohols excluding hydroxyl groups, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols and mixtures thereof.

[0041] In a preferred embodiment, R1 and R2 are independently selected from the following groups (i) to (iv). (i) The following formula (III): R7-O-C(O)-C(R8)(H)- (III) (In the formula, R7 represents a C1-C3 alkyl group, R8 represents a hydrogen atom or a C1-C3 alkyl group, preferably, R7 is methyl, and R8 is a hydrogen atom or methyl) of the compound. (ii) The following formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (In the formula, R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group, p represents an integer in the range of 1-3, preferably, R9 is methyl, ethyl or butyl, R 10 is a hydrogen atom or methyl, and p is equal to 1) of the compound. (iii) The following formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, R 12 represents a hydrogen atom or a C1-C4 alkyl group, preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl) of the compound. (iv) The following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, q represents an integer in the range of 4-30, preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl) of the compound.

[0042] Preferably, R1 and R2 independently represent a compound of formula (VI), where R 13represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30.

[0043] According to an alternative embodiment, R1 and R2 are different, and one of the R1 or R2 groups represents a compound of formula (IV) described above, and the other of the R1 or R2 groups represents a compound of formula (VI) described above.

[0044] 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.

[0045] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl, and q represents an integer in the range of 4 to 30.

[0046] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), where R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30.

[0047] Preferably, n represents an integer in the range of 1 to 20, more preferably 2 to 20.

[0048] Preferably, z represents an integer in the range of 1 to 20, more preferably 2 to 20.

[0049] Preferably, w is equal to 1.

[0050] Preferably, w is equal to 1, and n + z represents an integer in the range of 4 to 10.

[0051] Preferably, L1 is a divalent C1-C such as methylene, ethylene, and propylene 18 aliphatic hydrocarbon group, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 cycloalkylene group, C3-C such as imidazolene, pyrrolene, and furanylene 12 heterocycloalkylene group or C6-C such as phenylene 14 arylene group and a mixture thereof.

[0052] For example, L1 can be selected from groups derived from tolylene 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-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl-dimethyl-methane diisocyanate, and phenylene diisocyanate and mixtures thereof.

[0053] Preferably, L1 is a C3-C 15 cycloalkylene group or a C6-C 14 arylene group and mixtures thereof, such as compounds of the following formula (VII).

Chemical formula

[0054] Preferably, L1 is 4,4-dicyclohexylene methane corresponding to the following formula (VIII).

Chemical formula

[0055] According to another embodiment, when L1 is C6-C14 When it is an arylene group, L1 is not an m-tetramethylxylylene group represented by the following formula (IX). [Chemical formula]

[0056] As described above, E is independently - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- represents a group selected from, where R3 and R4 independently represent a divalent hydrocarbon group in which one or more heteroatoms are optionally interposed, - R5 independently represents a covalent bond or a divalent saturated hydrocarbon group in which one or more heteroatoms are optionally interposed, and - R6 independently represents a hydrogen atom or a hydrocarbon group in which one or more heteroatoms are optionally interposed.

[0057] Preferably, R3 and R4 are independently selected from C6-C arylene groups such as phenylene, C3-C cycloalkylene groups such as cyclopropylene and cyclobutylene, linear or branched C1-C alkylene groups such as methylene and ethylene, and mixtures thereof, in which one or more heteroatoms are optionally interposed. 14 arylene group, C3-C cycloalkylene groups such as cyclopropylene and cyclobutylene 12 linear or branched C1-C alkylene groups such as methylene and ethylene 18 and mixtures thereof.

[0058] More preferably, R3 and R4 are independently selected from linear or branched C1-C alkylene groups such as methylene, butylene, propylene or ethylene, in which one or more heteroatoms are optionally interposed. 18 and mixtures thereof.

[0059] Preferably, when R5 is not a covalent bond, R5 is optionally an arylene group such as phenylene, C3-C cycloalkylene groups such as cyclopropylene and cyclobutylene, in which one or more heteroatoms are optionally interposed, 14 arylene group, C3-C cycloalkylene groups such as cyclopropylene and cyclobutylene 12Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof. 18 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof.

[0060] Preferably, R6 is a C6-C arylene group such as phenylene, a C3-C cycloalkylene group such as cyclopropylene and cyclobutylene, a linear or branched C1-C alkylene group such as methylene and ethylene, with one or more heteroatoms optionally intervening, and mixtures thereof. 14 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof. 12 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof. 18 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof.

[0061] Preferably, E represents an -O-R3-O- group, where R3 is a C6-C arylene group, a C3-C cycloalkylene group, a linear or branched C1-C alkylene group such as methylene, butylene, propylene or ethylene, with one or more heteroatoms optionally intervening, and mixtures thereof. 14 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof. 12 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof. 18 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof.

[0062] More preferably, E represents an -O-R3-O- group, where R3 is a linear or branched C1-C alkylene group such as methylene, butylene, propylene or ethylene, with one or more heteroatoms optionally intervening. 18 Selected from a cycloalkylene group, a linear or branched C1-C alkylene group such as methylene and ethylene, and mixtures thereof.

[0063] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from α-methylstyryl isocyanate of the following formula (X):

Chemical formula

[0064] The term "alkyl group" in this embodiment is as defined above.

[0065] In the present embodiment, the term "cycloalkyl group" is as defined above.

[0066] In the present embodiment, n can represent an integer in the range of 2 to 50, preferably 3 to 30, and more preferably 5 to 10.

[0067] According to another specific embodiment, the (poly)carbodiimide compound is of the following formula (XI):

Chemical formula

[0068] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0069] According to a preferred embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I) or formula (II), wherein - X1 and X2 independently represent an oxygen atom, - R1 and R2 are independently selected from dialkylamino alcohols excluding hydroxyl groups, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols excluding hydroxyl groups, and more preferably, R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, and more preferably methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30, and is a compound of formula (VI) described above. - When n and z are present, they represent integers in the range of 1 to 20, where n + z ≧ 2, and w is equal to 1. - When L1 is present, it is a divalent C1 - C 18 aliphatic hydrocarbon group, C3 - C 15 cycloalkylene group, C3 - C 12 heterocycloalkylene group or C6 - C 14 arylene group and mixtures thereof, preferably selected from C3 - C 15 cycloalkylene groups. - When A is present, it is a divalent C1 - C 18 aliphatic hydrocarbon group, C3 - C 15 cycloalkylene group, C3 - C 12 heterocycloalkylene group or C6 - C 14 arylene group and mixtures thereof, preferably selected from C3 - C 15 cycloalkylene groups. - When E is present, it is independently - -O - R3 - O -; - S - R4 - S -; - R5 - N(R6) - R4 - N(R6) - R5 - representing a group selected from, where R3 and R4 are independently C6 - C with one or more heteroatoms optionally intervening 14 arylene group, C3 - C 12 cycloalkylene group, linear or branched C1 - C 18 alkylene group and mixtures thereof. - R5 is not a covalent bond. When R5 is present, it is a C6 - C with one or more heteroatoms optionally intervening 14 arylene group, C3 - C 12 cycloalkylene group, linear or branched C1 - C 18 alkylene group and mixtures thereof, and - When R6 is present, it is a C6 - C with one or more heteroatoms optionally intervening 14 arylene group, C3 - C 12 cycloalkylene group, linear or branched C1 - C 18 alkylene group and mixtures thereof.

[0070] Preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: - X1 and X2 each independently represent an oxygen atom, - R1 and R2 are each independently selected from a dialkylamino alcohol excluding a hydroxyl group, an alkyl ester of a hydroxycarboxylic acid, a monoalkyl ether of a (poly)alkylene glycol, and mixtures thereof, - n and z each represent an integer in the range of 1 to 20, where n + z ≧ 2, and w is equal to 1, - L1 is a divalent C1-C 18 aliphatic hydrocarbon-based group, C3-C 15 cycloalkylene group, C3-C 12 heterocycloalkylene group or C6-C 14 arylene group, and mixtures thereof, - E is independently - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- represents a group selected from, wherein R3 and R4 are each independently a C6-C 14 arylene group, C3-C 12 cycloalkylene group, a linear or branched C1-C 18 alkylene group, and mixtures thereof, in which one or more heteroatoms are optionally interposed, - When R5 is not a covalent bond, R5 is a C6-C 14 arylene group, C3-C 12 cycloalkylene group, a linear or branched C1-C 18 alkylene group, and mixtures thereof, in which one or more heteroatoms are optionally interposed, and - R6 is a C6-C 14 arylene group, C3-C 12 cycloalkylene group, a linear or branched C1-C 18 alkylene group, and mixtures thereof, in which one or more heteroatoms are optionally interposed.

[0071] More preferably, the (poly)carbodiimide compound is selected from the compounds of 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 hydroxyl group has been removed, - n and z represent integers in the range of 1 to 20, where n + z ≧ 2, and w is equal to 1, - L1 is a C3-C 15 cycloalkylene group, - E independently is - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- represents a group selected from, wherein R3 and R4 independently are C6-C 14 arylene groups, C3-C 12 cycloalkylene groups, linear or branched C1-C 18 alkylene groups and mixtures thereof, in which one or more heteroatoms are optionally intervening, - When R5 is not a covalent bond, R5 is a C6-C 14 arylene group, C3-C 12 cycloalkylene group, linear or branched C1-C 18 alkylene group and mixtures thereof, and - R6 is a C6-C 14 arylene group, C3-C 12 cycloalkylene group, linear or branched C1-C 18 alkylene group and mixtures thereof, in which one or more heteroatoms are optionally intervening.

[0072] Even more preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein - X1 and X2 independently represent an oxygen atom, - R1 and R2 independently are of the following formula (VI): R 13-[O-CH2-C(H)(R 14 )] q - (VI) represents a compound of, wherein R 13 represents a C1-C4 alkyl group or phenyl, 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 represents an integer in the range of 4 to 30, - n and z represent integers in the range of 2 to 20, where n + z is in the range of 4 to 10, and w is equal to 1, - L1 is a C3-C 15 cycloalkylene group such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, - E represents a -O-R3-O- group (wherein R3 is a C6-C 14 arylene group, a C3-C 12 cycloalkylene group, a linear or branched C1-C 18 alkylene group and mixtures thereof, optionally intervened by one or more heteroatoms).

[0073] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein - X1 and X2 independently represent an oxygen atom, - R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) represents a compound of, wherein R 13 represents a C1-C4 alkyl group or phenyl, 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 represents an integer in the range of 4 to 30, -n and z represent integers in the range of 1 to 20, preferably 2 to 20, n + z is in the range of 4 to 10, and w is equal to 1, - L1 is a C3-C cycloalkylene group such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane, 15 - E represents a -O-R3-O- group (wherein R3 represents a linear or branched C1-C alkylene group such as methylene, propylene, butylene or ethylene, in which one or more heteroatoms are optionally interposed). - E represents a -O-R3-O- group (wherein R3 represents a linear or branched C1-C alkylene group such as methylene, propylene, butylene or ethylene, in which one or more heteroatoms are optionally interposed). 18 - E represents a -O-R3-O- group (wherein R3 represents a linear or branched C1-C alkylene group such as methylene, propylene, butylene or ethylene, in which one or more heteroatoms are optionally interposed).

[0074] According to a preferred embodiment, the (poly)carbodiimide compound is of the following formula (XII):

Chemical formula

[0075] The total amount of the (poly)carbodiimide compound present in the composition A according to the present invention is preferably in the range of 0.01% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, still more preferably 0.5% by mass to 25% by mass, and even more preferably 2% by mass to 20% by mass based on the total mass of the composition A.

[0076] The total amount of the (poly)carbodiimide compound present in the hair coloring composition C according to the present invention is preferably in the range of 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 25% by mass, still more preferably 0.2% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass based on the total mass of the composition C.

[0077] Non-carboxylic acid anionic thickener Composition A may also contain a non-carboxylic acid anionic thickener.

[0078] For the purposes of the present invention, the term "non-carboxylic acid agent" means an agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylate functional group (-COO - ).

[0079] For the purposes of the present invention, the term "thickener" means a compound that increases the viscosity of the composition into which it is introduced by at least 20 cps, preferably at least 50 cps, at a shear rate of 1 s -1 (viscosity can be measured using a cone / plate viscometer, a Haake R600 rheometer, etc.) at room temperature (25 °C), atmospheric pressure, and up to a concentration of 0.05% by mass based on the total mass of the composition.

[0080] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, more preferably anionic polymers having a sulfone group.

[0081] For the purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic groups or anionized groups and does not contain a cationic group or cationized group.

[0082] Advantageously, the non-carboxylic acid anionic thickener is selected from anionic polymers containing at least one ethylenically unsaturated monomer having a sulfone group in free form or in partially or fully neutralized form.

[0083] These polymers may or may not be cross-linked. These are preferably cross-linked.

[0084] These polymers can be associative or non-associative, preferably non-associative.

[0085] It should be recalled that a "associative polymer" is a polymer that can reversibly associate with each other or with other molecules in an aqueous medium.

[0086] Their chemical structures more particularly include at least one hydrophilic zone and at least one hydrophobic zone.

[0087] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, straight-chain or branched hydrocarbon-based chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms.

[0088] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group can be derived from a fatty alcohol, for example, stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also represent a hydrocarbon-based polymer (for example, polybutadiene).

[0089] Ethylenically unsaturated monomers having a sulfonic acid group are particularly selected from vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1 - C 22 ) alkyl sulfonic acid, N-(C1 - C 22 ) alkyl (meth)acrylamide (C1 - C 22 ) alkyl sulfonic acid (such as undecylacrylamide methane sulfonic acid) and also in the form in which some or all of these are neutralized.

[0090] (meth)acrylamide (C1 - C 22)Alkylsulfonic acids, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and also their partially or fully neutralized forms are more preferentially used.

[0091] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0092] Among 2-acrylamido-2-methylpropanesulfonic acid copolymers, partially or fully neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide may be mentioned, and the products described in Example 1 of European Patent No. 503853 may be particularly mentioned, and the said document may be referred to with respect to these polymers.

[0093] Copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT10 by SEPPIC (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer), may also be mentioned.

[0094] Associative AMPS polymers are particularly C6-C 22It can be selected from statistical associative AMPS polymers modified by reaction with n-monoalkylamine or di-n-alkylamine and those described in WO 00 / 31154 pamphlet (which forms an essential part of the content of the specification), etc. These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected from, for example, (meth)acrylic acid derivatives such as their esters obtained with monoalcohol or mono- or polyalkylene glycol, (meth)acrylamide, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

[0095] Preferred polymers of this type are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0096] These same copolymers may also contain one or more ethylenically unsaturated monomers without aliphatic chains, such as (meth)acrylic acid derivatives, especially their esters obtained with monoalcohol or mono- or polyalkylene glycol, (meth)acrylamide, vinylpyrrolidone or mixtures of these compounds. These copolymers are particularly described in EP-A 750899, US 5089578 and the following published materials from Yotaro Morishima: - Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol.18, No.40, (2000), 323 - 336; - Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,Vol.33,No.10(2000),3694-3704; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte::salt effects on rheological behavior-Langmuir,Vol.16,No.12,(2000)5324-5332; -Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers-Polym.Preprint,Div.Polym.Chem.,40(2),(1999),220-221。

[0097] Among these polymers, the following can be mentioned: - Crosslinked or non-crosslinked, neutralized or non-neutralized copolymers containing 15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8 - C 16 ) alkyl (meth)acrylamide or (C8 - C 16 ) alkyl (meth)acrylate units with respect to the polymer, for example, those described in European Patent Application Publication No. A750899. - Copolymers containing 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, and 5 mol% to 80 mol% of n-(C6 - C 18) A terpolymer containing alkyl acrylamide units, for example, those described in U.S. Patent No. 5,089,578.

[0098] Completely neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecyl methacrylamide, for example, those described in the above Morishima paper, may also be mentioned.

[0099] Preferably, the non-carboxylic acid anionic thickener is selected from the sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymer (INCI name hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer) sold by SEPPIC.

[0100] Advantageously, the total amount of the non-carboxylic acid anionic thickener ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 2% by weight, based on the total weight of Composition A.

[0101] Associative polymer Composition B according to the invention used in connection with the method for coloring keratin fibers according to the invention contains at least one associative polymer.

[0102] The associative polymer is different from the aforementioned non-carboxylic acid anionic thickener.

[0103] It should be recalled that an "associative polymer" is a polymer that can reversibly associate with each other or with other molecules in an aqueous medium.

[0104] Their chemical structure more particularly contains at least one hydrophilic zone and at least one hydrophobic zone.

[0105] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, straight-chain or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms.

[0106] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group can be derived from a fatty alcohol, for example, stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also represent a hydrocarbon-based polymer (such as polybutadiene).

[0107] The associative polymer can be nonionic, anionic, cationic or amphoteric.

[0108] Preferably, the associative polymer is selected from anionic associative polymers.

[0109] Among the anionic associative polymers that can be mentioned, the following can be cited: - (a) Those containing at least 1 hydrophilic unit and at least 1 fatty chain allyl ether unit, more specifically those in which the hydrophilic unit is formed from an anionic ethylenically unsaturated monomer, more specifically those formed from a vinyl carboxylic acid, and most specifically those formed from acrylic acid or methacrylic acid or a mixture thereof.

[0110] Among these anionic associative polymers, those particularly preferred according to the present invention are polymers formed from 20% to 60% by mass of acrylic acid and / or methacrylic acid, 5% to 60% by mass of a lower alkyl (meth)acrylate, 2% to 50% by mass of a fatty chain allyl ether, and 0 to 1% by mass of a crosslinking agent (a well-known copolymerizable unsaturated polyethylene monomer such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylbisacrylamide).

[0111] Among the latter polymers, in particular, a crosslinked terpolymer of methacrylic acid, ethyl acrylate, and polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular, an aqueous 30% emulsion of a crosslinked terpolymer (40 / 50 / 10) of methacrylic acid, ethyl acrylate, and stearyl allyl ether, sold under the names Salcare SC 80 (registered trademark) and Salcare SC 90 (registered trademark) by Ciba, is most preferred.

[0112] - (b) i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type, and ii) those containing at least one hydrophobic unit of the type such as (C10-C30) alkyl esters of unsaturated carboxylic acids.

[0113] (C 10 ~C 30 ) alkyl esters of unsaturated carboxylic acids useful in the present invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0114] This type of anionic polymer is described and prepared, for example, by U.S. Patent No. 3,915,921 and U.S. Patent No. 4,509,949.

[0115] Among this type of anionic associative polymer, those composed of 95% by mass to 60% by mass of acrylic acid (hydrophilic unit), 4% by mass to 40% by mass of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by mass of a crosslinkable polymerizable monomer, or those described above, etc., 98% by mass to 96% by mass of acrylic acid (hydrophilic unit), 1% by mass to 4% by mass of C 10 ~C 30Those composed of an alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by mass of a crosslinkable polymerizable monomer will be more particularly used.

[0116] Among the above polymers, according to the present invention, the most particularly preferred ones are Pemulen TR1 (registered trademark), Pemulen TR2 (registered trademark), Carbopol 1382 (registered trademark), and even more preferably, the products sold by Goodrich under the trade name of Pemulen TR1 (registered trademark) and the products sold by SEPPIC under the name of Coatex SX (registered trademark).

[0117] Mention may also be made of the acrylic acid / lauryl methacrylate / vinyl pyrrolidone terpolymer sold by ISP under the name Acrylidone LM; - (c) Maleic anhydride / C 30 ~C 38 α-olefin / maleic acid alkyl terpolymer, for example, the product sold by Newphase Technologies under the trade name of Performa V1608 (registered trademark) (maleic anhydride / C 30 ~C 38 α-olefin / isopropyl maleate copolymer); - (d) Acrylic terpolymers containing the following: i) About 20% to 70% by mass of an α,β-monoethylenically unsaturated carboxylic acid [A], ii) About 20% to 80% by mass of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A], iii) About 0.5% to 60% by mass of a nonionic monourethane which is a reaction product of a surfactant having one hydroxyl group and a monoethylenically unsaturated monoisocyanate. For example, those described in European Patent Application Publication No. A-0173109, more specifically, the terpolymer described in Example 3, i.e., an aqueous 25% dispersion of a terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meth-isopropenylbenzyl isocyanate ethoxylate (40 EO). - (e) a copolymer containing, as monomers, an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylated fatty alcohol.

[0118] Preferably, these compounds also contain, as monomers, an ester of an α,β-monoethylenically unsaturated carboxylic acid and a C1-C4 alcohol.

[0119] Examples of this type of compound that may be mentioned are Aculyn22® sold by Roehm & Haas, a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylated stearyl methacrylate, and also Aculyn88 sold by Roehm & Haas.

[0120] Advantageously, the associative polymer different from the non-carboxylic acid anionic thickener is selected from acrylic associative polymers, more preferably carboxylic acid acrylic associative polymers.

[0121] Particularly preferably, the associative polymer different from the non-carboxylic acid anionic thickener is selected from copolymers containing, in their monomers, an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylated fatty alcohol.

[0122] Advantageously, the total amount of the associative polymer ranges from 0.1% by mass to 30% by mass, preferably from 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 10% by mass, even better from 0.2% by mass to 5% by mass, and even more specifically from 0.2% by mass to 2% by mass, based on the total mass of Composition B.

[0123] Advantageously, the total amount of the associative polymer ranges from 0.05% to 15% by mass, preferably from 0.05% to 10% by mass, more preferably from 0.1% to 5% by mass, and even more preferably from 0.1% to 1% by mass, based on the total mass of the hair coloring composition C.

[0124] Compound containing at least one carboxylic acid group Composition B according to the invention, which is used in connection with the method for coloring keratin fibers of the invention, comprises at least one compound different from the associative polymer containing at least one carboxylic acid group.

[0125] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is selected from silicone compounds containing at least one carboxyl group, polyurethanes, acrylic polymers, and mixtures thereof.

[0126] Polyurethanes and acrylic polymers: According to a preferred embodiment, composition B comprises one or more compounds different from the associative polymer containing at least one carboxylic acid group, selected from polyurethanes, acrylic polymers, and mixtures thereof.

[0127] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is in the form of an aqueous dispersion of polymer particles selected from polyurethanes, acrylic polymers, and mixtures thereof.

[0128] Preferably, composition B comprises one or more compounds different from the associative polymer containing at least one carboxylic acid group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers, and mixtures thereof.

[0129] Thus, in this embodiment, the polymer used in the aqueous dispersion of polymer particles is different from the associative polymer.

[0130] This dispersion can be a simple dispersion in which a cosmetic composition is dispersed in an aqueous medium. As a specific example of the dispersion, latex can be mentioned.

[0131] The aqueous dispersion of polymer particles can be selected from the aqueous dispersion of polyurethane particles.

[0132] More specifically, the polyurethane present in the aqueous dispersion used in the present invention is - The following formula (A)

Chemical formula

[0133] Among the hydroxylated compounds that can be used according to the present invention, particularly, compounds containing two hydroxyl groups and having a number average molecular weight of about 700 to about 16,000, preferably about 750 to about 5,000 can be mentioned. Examples of high molecular weight hydroxylated compounds include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0134] The polyisocyanate that can be used according to the present invention is particularly selected from organic diisocyanates having a molecular weight of about 112 to 1000, preferably about 140 to 400.

[0135] Preferably, the polyisocyanate is selected from diisocyanates, more specifically those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon group containing 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon group containing 6 to 15 carbon atoms.

[0136] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates can, in particular, be selected from the following: 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 - methyl - cyclohexyl)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 its diphenylmethane 2,4 - diisocyanate isomer, and optionally a mixture with the diphenylmethane 2,2’ - diisocyanate isomer, naphthalene 1,5 - diisocyanate and mixtures thereof.

[0137] Preferably, the diisocyanate is an aliphatic and cycloaliphatic diisocyanate, more preferably selected from 1,6 - hexamethylene diisocyanate, 3 - isocyanatomethyl - 3,5,5 - trimethylcyclohexane isocyanate and mixtures thereof.

[0138] The term "low - molecular - weight diol" according to the present invention refers to diols having a molecular weight of about 62 to 700, preferably 62 to 200. These diols can contain an aliphatic group, a cycloaliphatic group or an aromatic group. Preferably, they contain only aliphatic groups.

[0139] Preferably, R3 represents a low molecular weight diol containing more than 20 carbon atoms, more preferably ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, 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.

[0140] 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 described, in particular, in the patent US Patent No. 3412054. Compounds of this kind are preferably selected from dimethylolbutanoic acid, dimethylolpropionic acid, polycaprolactone diols containing carboxyl groups, and mixtures thereof.

[0141] When low molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that there is less than 0.30 meq of COOH per gram of polyurethane in the polyurethane dispersion.

[0142] The prepolymer is chain extended by using chain extenders belonging to two groups. The first group of chain extenders corresponds to compounds of general formula (B).

[0143] The chain extender of formula (B) is preferably an alkylene diamine such as hydrazine, ethylenediamine, propylenediamine, 1,4 - butylenediamine, piperazine; alkylene oxide diamine such as 3-{2-[2-(3 - aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diethylene glycol or DPA - DEG, available from Tomah Products, Milton, Wis.), 2 - methyl - 1,5 - pentanediamine (Dytec A from DuPont), hexanediamine, isophoronediamine, 4,4 - methylenedi(cyclohexylamine), ether - amines of the DPA series available from Tomah Products, Milton, Wis. 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 - propanediol, dipropylamine 2 - methyl - 1,3 - propanediol, dipropylamine 1,4 - butanediol, dipropylamine 1,3 - butanediol, dipropylamine 1,6 - hexanediol and dipropylamine cyclohexane - 1,4 - dimethanol and mixtures thereof.

[0144] A second group of chain extenders corresponds to compounds of general formula (C). Compounds of this type preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Compounds of this type can optionally contain two groups capable of reacting with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0145] Ionic or potentially ionic groups can preferably be selected from tertiary or quaternary ammonium groups or groups convertible thereto, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. At least partial conversion of groups convertible to salts of tertiary or quaternary ammonium groups can be carried out before or during mixing with water.

[0146] The chain extender of formula (C) is preferably selected from diaminosulfonates, 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.

[0147] The polyurethane that can be used according to the present invention can optionally also contain a compound (chain terminator) located at each chain end and terminating the chain. This kind of compound is described in particular in US Patent No. 7445770 and / or US Patent No. 7452770.

[0148] Preferably, the viscosity of the aqueous dispersion of polyurethane particles is less than 2000 mPa·s at 23 °C, more preferably less than 1500, even more preferably less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0 °C.

[0149] Also preferably, the polyurethane (or active substance or solid content) content of the aqueous polyurethane dispersion is 20% to 60% by mass, more preferably 25% to 55% by mass, even more preferably 30% to 50% by mass based on the mass of the dispersion. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably 20% to 60% by mass, more preferably 25% to 55% by mass, even more preferably 30% to 50% by mass based on the total mass of the dispersion.

[0150] Similarly preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is -25°C or lower, preferably less than -35°C, more preferably less than -40°C.

[0151] The average diameter of the polyurethane particles can range up to about 1000 nm, for example from about 50 nm to about 800 nm, even more preferably from about 100 nm to about 500 nm. These particle diameters can be measured using a laser particle size distribution measuring device (e.g., Brookhaven BI90).

[0152] Non-limiting examples of the aqueous polyurethane dispersion include those sold under the name Baycusan® by Bayer, such as Baycusan® C1000 (INCI name: Polyurethane-34), Baycusan® C1001 (INCI name: Polyurethane-34), Baycusan® C1003 (INCI name: Polyurethane-32), Baycusan® C1004 (INCI name: Polyurethane-35), and Baycusan® C1008 (INCI name: Polyurethane-48).

[0153] Aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, e.g., Luviset® PUR from BASF), polyurethane of polycarbonate, polyurethane of aliphatic polyester, and aliphatic polyurethane (e.g., the Neorez® series from DSM, such as Neorez® R989, Neorez® and R-2202) can also be mentioned.

[0154] According to a preferred embodiment, the aqueous dispersion of polyurethane particles can 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.

[0155] Preferably, the compound different from the associative polymer containing at least one carboxylic acid 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.

[0156] 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 known as monomers). This or these units are repeated at least twice, preferably at least three times.

[0157] The term "film-forming polymer" refers to a polymer that can form a macroscopically continuous film, preferably an agglomerative film, on a support, particularly a keratinous substance, either alone or in the presence of an auxiliary film-forming agent.

[0158] 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)acrylic acid esters and / or (meth)acrylic acid amides.

[0159] Units derived from the (meth)acrylic acid monomers of the polymer can optionally be in the form of salts, particularly alkali metal salts, alkaline earth metal salts or ammonium salts or organic base salts.

[0160] (Meth)acrylic acid esters (also known as (meth)acrylates) are preferably alkyl (meth)acrylates, particularly C1-C 30 Preferably C1-C 20 Even more preferably C1-C 10 Alkyl (meth)acrylates, aryl (meth)acrylates, particularly C6-C 10 Aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, particularly C2-C6 hydroxyalkyl (meth)acrylates.

[0161] Among alkyl (meth)acrylates, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and cyclohexyl (meth)acrylate can be mentioned.

[0162] Among hydroxyalkyl (meth)acrylates, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate can be mentioned.

[0163] Among aryl (meth)acrylates, benzyl acrylate and phenyl acrylate can be mentioned.

[0164] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , more preferably C1-C 20 , even more preferably C1-C 10 , and even more specifically C1-C4 alkyl (meth)acrylates.

[0165] According to the present invention, the alkyl group of the ester can be fluorinated or further perfluorinated, that is, part or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0166] Examples of (meth)acrylamides include, in addition to (meth)acrylamide, N-alkyl (meth)acrylamides, particularly N-(C2-C 12 alkyl)(meth)acrylamides. Among N-alkyl (meth)acrylamides, N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide, and N-undecylacrylamide can be mentioned.

[0167] The acrylic polymer according to the invention can be a homopolymer or a copolymer, preferably a copolymer, more preferably a copolymer of (meth)acrylic acid and (meth)acrylate.

[0168] Preferably, the acrylic polymer according to the invention comprises the following monomers: a) (meth)acrylic acid, and b) C1-C 30 , more preferably C1-C 20 , even more preferably C1-C 10 , even more specifically C1-C4 alkyl (meth)acrylate and comprises one or more units derived therefrom.

[0169] Preferably, the aqueous dispersion of acrylic polymer particles does not contain a surfactant.

[0170] The term "surfactant" refers to any agent capable of adjusting the surface tension between two surfaces.

[0171] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE or the polyacrylate-2 cross-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 3000 SLPN-PE1.

[0172] The acrylic polymer can optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide monomer.

[0173] Examples of the additional monomer would include styrene monomers, especially styrene and α-methylstyrene, preferably styrene.

[0174] In particular, the acrylic polymer can be a polymer selected from copolymers obtained by polymerizing a styrene / (meth)acrylate copolymer, especially at least one styrene monomer and at least one C1-C 20 preferably C1-C 10 alkyl (meth)acrylate monomer.

[0175] C1-C 10 The alkyl (meth)acrylate monomer can be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.

[0176] Examples of the acrylic polymer include styrene / (meth)acrylate copolymers sold by BASF under the name Joncryl 77, by Akzo Nobel under the name Yodosol GH41F, and by Interpolymer under the name Syntran 5760 CG.

[0177] Preferably, Composition B contains at least one aqueous dispersion of acrylic polymer particles.

[0178] More preferably, Composition B comprises the following monomers: a) (meth)acrylic acid, and b) C1-C 30 more preferably C1-C 20 even more preferably C1-C 10, and more specifically C1-C4 alkyl (meth)acrylate including at least one aqueous dispersion of acrylic polymer particles containing one or more units derived from

[0179] Preferably, the acrylic polymer (or active substance or solid content) content of the aqueous dispersion of acrylic polymer particles is 20% to 60% by mass, more preferably 22% to 55% by mass, and even better 25% to 50% by mass based on the mass of the dispersion.

[0180] The total amount of the compound different from the associative polymer containing at least one carboxylic acid group present in Composition B is preferably in the range of 0.2% to 60% by mass, more preferably 1% to 55% by mass, even better 5% to 50% by mass, and even more preferably 10% to 45% by mass based on the total mass of Composition B.

[0181] The total amount of the compound different from the associative polymer containing at least one carboxylic acid group is preferably in the range of 0.1% to 35% by mass, more preferably 0.5% to 30% by mass, even better 1% to 25% by mass, even more preferably 3% to 25% by mass, and even more preferably 10% to 25% by mass based on the total mass of the hair coloring composition C.

[0182] The total amount of the aqueous dispersion of polymer particles different from the aforementioned associative polymer selected from polyurethane, acrylic polymer and mixtures thereof is preferably in the range of 0.2% to 60% by mass, more preferably 1% to 55% by mass, even better 5% to 50% by mass, and even more preferably 10% to 45% by mass based on the total mass of Composition B.

[0183] According to certain embodiments, the total amount of the aqueous dispersion of acrylic polymer particles different from the associative polymer described above is preferably in the range of 0.2% to 60% by mass, more preferably 1% to 55% by mass, even better 5% to 50% by mass, and even more preferably 10% to 45% by mass based on the total mass of Composition B.

[0184] The total amount of the aqueous dispersion of polymer particles different from the associative polymer described above, selected from polyurethane, acrylic polymer and mixtures thereof, is preferably in the range of 0.1% to 35% by mass, more preferably 0.5% to 30% by mass, even better 1% to 25% by mass, even more preferably 3% to 25% by mass, and even better 10% to 25% by mass based on the total mass of Composition C.

[0185] According to certain embodiments, the total amount of the aqueous dispersion of acrylic polymer particles different from the associative polymer described above is preferably in the range of 0.1% to 35% by mass, more preferably 0.5% to 30% by mass, even better 1% to 25% by mass, even more preferably 3% to 25% by mass, and even better 10% to 25% by mass based on the total mass of the hair coloring composition C.

[0186] Colorant Composition A and / or Composition B according to the present invention used in connection with the method for coloring hair keratin fibers according to the present invention comprises at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0187] Preferably, Composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0188] Advantageously, Composition A and / or Composition B according to the present invention used in connection with the method for coloring hair keratin fibers according to the present invention comprises one or more pigments.

[0189] Preferably, Composition B according to the present invention comprises one or more pigments.

[0190] The term "pigment" refers to any pigment that imparts color to keratinous substances. Their solubility in water at atmospheric pressure (760 mmHg) of 25 °C is less than 0.05% by mass, preferably less than 0.01%.

[0191] The pigments that can be used are selected from organic and / or mineral pigments, especially those known in the art, especially those described in Kirk - Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry.

[0192] These can be natural or non - natural substances of natural origin.

[0193] These pigments can be in the form of pigment powders or pastes. They may or may not be coated.

[0194] The pigment can be selected from, for example, mineral pigments, organic pigments, lakes, pigments with special effects such as pearlescent agents or glitter flakes, and mixtures thereof.

[0195] The pigment can be a mineral pigment. The term "inorganic pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann’s encyclopaedia. Among the inorganic pigments for use in the present invention, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrates, ferric blue, and titanium oxides can be mentioned.

[0196] 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 encyclopaedia.

[0197] Organic pigments can be selected, in particular, from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0198] In particular, white or colored organic pigments can be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments classified under the reference numbers CI 42090, 69800, 69825, 74100, 74160 in the Color Index, yellow pigments classified under the reference numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005 in the Color Index, green pigments classified under the reference numbers CI 61565, 61570, 74260 in the Color Index, orange pigments classified under the reference numbers CI 11725, 45370, 71105 in the Color Index, red pigments classified under the reference numbers CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470 in the Color Index, and pigments obtained by oxidative polymerization of indole or phenol derivatives described in French Patent No. 2679771.

[0199] Examples of pigment pastes of organic pigments can also include products sold under the following names by Hoechst: - Cosmenyl Yellow 10G: Yellow 3 pigment (CI11710); - Cosmenyl Yellow G: Yellow 1 pigment (CI11680); - Cosmenyl Orange GR: Orange 43 pigment (CI 71105); - Cosmenyl Red R: Pigment Red 4 (CI 12085); - Cosmenyl Carmine FB: Pigment Red 5 (CI 12490); - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319); - Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160); - Cosmenyl Green GG: Pigment Green 7 (CI 74260); - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0200] The pigments in the present invention may be in the form of composite pigments as described in European Patent No. 1184426. These composite pigments may in particular be composed of particles comprising a core substance of an inorganic material, at least one binder for binding an organic pigment to the core substance, and at least one organic pigment covering at least a part of the core substance.

[0201] The organic pigment may be a lake. The term "lake" refers to a dye adsorbed on insoluble particles, so that the composite thus obtained remains insoluble in use.

[0202] The mineral substrate on which the dye is adsorbed is, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0203] Among the dyes, carminic acid can be mentioned. Dyes known by the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090) may also be mentioned.

[0204] Examples of lakes may include products known by the following names: D&C Red 7 (CI 15 850:1).

[0205] Pigments can also be pigments with special effects. The term "pigments with special effects" generally means pigments that are non-uniform and result in a colored appearance (characterized by a specific hue, a specific luster, and a specific level of brightness) that varies depending on the conditions of observation (light, temperature, angle of observation, etc.). As a result, they differ from colored pigments that exhibit standard uniform opaque, translucent, or transparent hues.

[0206] There are several types of pigments with special effects: those with a low refractive index such as fluorescent or photochromic pigments, and those with a high refractive index such as pearlescent agents, interference pigments, or glitter flakes.

[0207] Examples of pigments having 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 oxide, mica coated with iron oxide, mica coated with titanium and especially coated with ferric blue or chromium oxide, mica coated with titanium and coated with the organic pigments defined above, and pearlescent pigments based on bismuth oxychloride. Examples of pearlescent pigments that may be mentioned include Cellini (mica-TiO2-lake) sold by BASF, Prestige sold by Eckart (mica-TiO2), Prestige Bronze (mica-Fe2O3) sold by Eckart, and Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0208] Golden pearlescent pigments, especially those sold under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne) by BASF; bronze pearlescent pigments, especially those sold under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) by Merck and under the name Super bronze (Cloisonne) by BASF; orange pearlescent pigments, especially those sold under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) by BASF and under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna) by Merck; brown pearlescent pigments, especially those sold under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite) by BASF; copper-colored pearlescent pigments, especially those sold under the name Copper 340A (Timica) by BASF; red-colored pearlescent pigments, especially those sold under the name Sienna fine (17386) (Colorona) by Merck; yellow-colored pearlescent pigments, especially those sold under the name Yellow (4502) (Chromalite) by BASF; golden-red pearlescent pigments, especially those sold under the name Sunstone G012 (Gemtone) by BASF; peach-colored pearlescent pigments, especially those sold under the name Tan opale G005 (Gemtone) by BASF; golden-black pearlescent pigments, especially those sold under the name Nu-Antique Bronze 240 AB (Timica) by BASF; blue pearlescent pigments, especially those sold under the name Matte blue (17433) (Microna) by Merck; silver-colored white pearlescent pigments, especially those sold under the name Xirona Silver by Merck;And nacreous pearlescent agents that change to greenish-gold to pink to orange, in particular those sold by Merck under the name Indian summer (Xirona); and mixtures thereof may also be mentioned.;

[0209] As a further example of nacreous pearlescent agents, particles comprising a borosilicate substrate coated with titanium oxide may also be mentioned.

[0210] Particles comprising a glass substrate coated with titanium oxide are sold, in particular, by Toyal under the name Metashine MC1080RY.

[0211] Finally, as an example of nacreous pearlescent agents, polyethylene terephthalate glitter flakes, in particular those sold by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver glitter flakes) may also be mentioned. Synthetic substrates, for example, multilayer pigments based on alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum etc. can also be envisaged.

[0212] Pigments with special effects can also be selected from reflective particles, i.e., particles capable of reflecting incident light due to their size, structure, in particular the thickness of the layers that constitute them, as well as their physical and chemical properties and surface state. This reflection can, where appropriate, create highlight points visible to the naked eye on the surface of the composition or mixture when it is applied to the support on which it is formed, i.e., brighter points that appear to shine compared to their surroundings with sufficient intensity.

[0213] The reflective particles can be selected so as not to significantly change the color effect brought about by the colorant combined with it, and more specifically to optimize this effect from the perspective of color rendering. These can more specifically have colors or color shades of yellow, pink, red, bronze, orange, brown, gold and / or copper.

[0214] These particles can have various forms, particularly platelet or small spherical forms, especially spherical forms.

[0215] Regardless of their form, the reflective particles may or may not have a multilayer structure. In the case of a multilayer structure, for example, they may have at least one layer of a reflective material, particularly of uniform thickness.

[0216] When the reflective particles do not have a multilayer structure, they can be composed of metal oxides, particularly titanium oxide or iron oxide obtained by synthesis.

[0217] When the reflective particles have a multilayer structure, they can include, for example, a natural or synthetic substrate, particularly a synthetic substrate, at least partially coated with a reflective material, particularly at least one layer of at least one metal or metallic material. The substrate can be made from one or more organic and / or inorganic materials.

[0218] More specifically, this can be selected from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, particularly aluminosilicates and borosilicates, and synthetic mica, as well as mixtures thereof, but is not limited to this list.

[0219] The reflective material can include a layer of a metal or metallic material.

[0220] The reflective particles are particularly described in the documents of JP-A-09-188830, JP-A-10-158450, JP-A-10-158541, JP-A-07-258460, and JP-A-05-017710.

[0221] As a further example of reflective particles including an inorganic substrate coated with a metal layer, particles including a borosilicate substrate coated with silver can also be mentioned.

[0222] Particles of a small plate-shaped silver-coated glass substrate are sold by Toyal under the name Microglass Metashine REFSX 2025 PS. Particles of 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.

[0223] Particles containing a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, or titanium can also be used, and the substrate is coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0224] Examples thereof include aluminum powder, bronze powder, or copper powder coated with SiO2, sold by Eckart under the name Visionaire.

[0225] Pigments showing interference effects such as liquid crystals (Helicones HC from Wacker) or holographic glitter flakes (Geometric Pigments from Spectratek or Spectra f / x) that are not bound to the substrate can also be mentioned. Pigments with special effects include fluorescent pigments (which are either substances that fluoresce in daylight or substances that bring about ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots sold, for example, by Quantum Dots Corporation.

[0226] The diversity of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic effects or interference effects.

[0227] The size of the pigments used in the composition according to the present invention is generally from 10 nm to 200 μm, preferably from 20 nm to 80 μm, and more preferably from 30 nm to 50 μm.

[0228] The pigment can be dispersed in the composition by a dispersant.

[0229] The dispersant serves to prevent aggregation or soft aggregation of the dispersed particles. This dispersant can be a surfactant, oligomer, polymer or a mixture of several of these having one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, these can be physically or chemically bonded to the pigment surface. These dispersants also contain at least one functional group that is compatible with the continuous medium or soluble in the continuous medium. In particular, 12-hydroxystearic acid, especially esters of C8-C20 fatty acids and polyols such as glycerol or diglycerol, for example poly(12-hydroxystearic acid) stearate with a molecular weight of about 750 g / mol, for example a product sold under the name Solsperse 21000 from Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the trade symbol Dehymyls PGPH from Henkel or polyhydroxystearic acid, for example a product sold under the trade symbol Arlacel P100 from Uniqema and mixtures thereof are used.

[0230] Other dispersants that can be used in the composition of the present invention include quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17000 sold by Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold under the trade symbols DC2-5185 and DC2-5225 C by Dow Corning.

[0231] The pigment that can be used in the composition can be surface-treated with an organic agent.

[0232] Accordingly, the pre-surface-treated pigments useful in connection with the present invention are pigments that have been surface-treated, either fully or partially, with an organic agent to impart chemical, electronic, electrochemical, mechanochemical or mechanical properties, such as those described in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, and after such treatment, are dispersed in the compositions of the present invention. These organic agents include, for example, 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, especially polydimethylsiloxane; organic fluorine compounds such as perfluoroalkyl ethers; and fluorosilicone compounds, and can be selected therefrom.

[0233] The surface-treated pigments useful in the present composition can be those treated with a mixture of these compounds and / or can be those that have been surface-treated several times.

[0234] The surface-treated pigments useful in connection with 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.

[0235] Preferably, the surface-treated pigment is coated with an organic layer.

[0236] The organic agent for treating the pigment can be deposited on the pigment by evaporating the solvent, causing a chemical reaction between the molecules of the surface treatment agent, or forming a covalent bond between the surface treatment agent and the pigment.

[0237] Thus, the surface treatment can be carried out, for example, by causing a chemical reaction between a surface treatment agent and the pigment surface to generate a covalent bond between the surface treatment agent and the pigment or filler. This method is particularly described in U.S. Patent No. 4,578,266.

[0238] An organic agent that covalently bonds to the pigment will preferably be used.

[0239] The agent used for surface treatment can account for 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferably 1% to 20% by mass based on the total mass of the pigment to be surface-treated.

[0240] Preferably, the surface treatment agent for the pigment is selected from the following treatment agents: - PEG-silicone treatment agent, such as the AQ surface treatment agent sold by LCW; - Methicone treatment agent, such as the SI surface treatment agent sold by LCW; - Dimethicone treatment agent, such as the Covasil 3.05 surface treatment agent sold by LCW; - Dimethicone / trimethylsiloxysilicate treatment agent, such as the Covasil 4.05 surface treatment agent sold by LCW; - Magnesium myristate treatment agent, such as the MM surface treatment agent sold by LCW; - Aluminum dimyristate treatment agent, such as the MI surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - Perfluoropolyisopropylmethyl ether treatment, such as surface treatment using FHC sold by LCW; - Isostearyl sebacate treatment agent, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - Perfluoroalkyl phosphate treatment agent, such as the PF surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate / dimethicone copolymers and perfluoroalkyl phosphate treatment agents, such as the FSA surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Polymethylhydrogensiloxane / perfluoroalkyl phosphate treatment agents, such as the FS01 surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate / dimethicone copolymer treatment agents, such as the ASC surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Isopropyl titanate triisostearate treatment agents, such as the ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Perfluoroalkyl phosphate / isopropyl titanate triisostearate treatment agents, such as the PF+ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.

[0241] According to a particular embodiment of the present invention, the dispersant is present together with an organic or mineral pigment in the form of submicron-sized particles.

[0242] The term "submicron" or "submicron-sized" refers to pigments having a particle size comminuted by a comminution method and an average particle size of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, preferably 0.2 to 0.6 μm.

[0243] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, particularly 1.5:3.5 to 3.5:1 or even more preferably 1.75:3 to 3:1, depending on the mass ratio.

[0244] Thus, the dispersant may have a silicone backbone, such as a silicone polyether, and be an aminosilicone type dispersant. Suitable dispersants include the following: - Amino silicone, i.e., silicone containing one or more amino groups, for example, those sold by BYK under the name BYK LPX 21879, those sold by Genesee Polymers under the names and references of GP-4, GP-6, GP-344, GP-851, GP-965, GP-967, and GP-988-1. - Silicone acrylate, for example, Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043 sold by Evonik. - Polydimethylsiloxane (PDMS) silicone having a carboxyl group, for example, X-22162 and X-22370 by Shin-Etsu Chemical Co., Ltd., epoxy silicone, for example, GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.

[0245] According to a specific embodiment, the dispersant is of the amino silicone type and is cationic.

[0246] Preferably, the pigment is selected from mineral pigments, mineral-organic mixed pigments, or organic pigments.

[0247] In a variant of the present invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic agent selected from silicone compounds. In another variant of the present invention, the pigment is a mineral pigment.

[0248] Direct dye Composition B used in connection with the method according to the present invention may contain one or more direct dyes.

[0249] The term "direct dye" means natural and / or synthetic dyes other than oxidative dyes. These are dyes that will spread on the surface of the fiber.

[0250] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0251] Examples of suitable direct dyes include azo direct dyes, alone or in mixture form; (poly)methine dyes such as cyanine, hemicyanine and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes; and natural direct dyes.

[0252] The direct dyes are preferably cationic direct dyes. Examples thereof include hydrazonocationic dyes of the following formulas (XIII) and (XIV) and azocationic dyes of the formulas (XV) and (XVI). Het+-N(Ra)-N=C(Rb)-Ar,Q-(XIII), Het+-C(Ra)=N-N(Rb)-Ar,Q(XIV), Het+-N=N-Ar,Q-(XV), Ar+-N=N-Ar’’,Q-(XVI) In the formulas (XIII) to (XVI), - Het+ represents a cationic heteroaryl group such as imidazolium, indolium or pyridinium which preferably has a cationic charge in the ring and is optionally substituted with a (C1-C8) alkyl group such as at least one methyl, - Ar+ represents an aryl group such as phenyl or naphthyl which has a cationic charge outside the ring, preferably ammonium, especially tri(C1-C8) alkylammonium such as trimethylammonium, - Ar preferably represents one or more electron-donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8)alkylamino, v) an aryl group optionally substituted with an N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino optionally substituted with one or more of the above electron-donating groups, especially phenyl, or alternatively, Ar represents a julolidine group, - Ar’’ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, preferably substituted with one or more (C1-C8) alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8) alkoxy or phenyl groups, - Ra and Rb may be the same or different and each represents a hydrogen atom or an optionally (preferably hydroxyl-substituted) (C1-C8) alkyl group, or otherwise, Het + together with the substituents of Het and / or together with the substituents of Ra and / or Ar, form a (hetero)cycloalkyl together with the atoms bearing them, in particular, Ra and Rb each represents a hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group, - Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

[0253] In particular, azo and hydrazono direct dyes having an intra-ring cationic charge of the formulas (XIII)-(XVI) defined above, more specifically, cationic direct dyes having an intra-ring cationic charge described in International Publication No. WO 95 / 15144 pamphlet, International Publication No. WO 95 / 01772 pamphlet and European Patent No. EP 714954, preferably include the following direct dyes.

Chemical formula

[0254] 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, and Q’ is the anionic counterion defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0255] The direct dye can be selected from anionic direct dyes. The anionic direct dyes of the present invention are generally dyes referred to as "acid" direct dyes due to their affinity for alkaline substances. The term "anionic direct dye" means a direct dye containing at least one CO2R or SO3R substituent (wherein R represents a hydrogen atom or a cation or ammonium ion derived from a metal or an amine) in its structure. The anionic dye can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes, and natural acid dyes.

[0256] Examples of acid dyes useful in the present invention include dyes of the following formulas (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI). a) Diaryl anionic azo dyes of formula (XIX) or (XIX'); [Chemical formula] In formulas (XIX) and (XIX'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and are a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - nitro, nitroso; - R°-C(X)-X'-、R°-X'-C(X)-、R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, and X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - ),M + (wherein M + represents a hydrogen atom or a cationic counter ion); - (O)CO - (,M + (wherein M + is as defined above); - R''-S(O)2- (wherein R'' represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferably represents a phenylamino or phenyl group); - R'''-S(O)2-X'- (wherein R''' represents an optionally substituted alkyl or aryl group, and X' is as defined above); - (di)(alkyl)amino; - i) nitro, ii) nitroso, iii) (O)2S(O - )-, M + (wherein M + is as defined above), and iv) aryl(alkyl)amino optionally substituted with one or more groups selected from alkoxy; - heteroaryl optionally substituted, preferably a benzothiazolyl group; - cycloalkyl, especially cyclohexyl represents a group selected from, - Ar-N=N- (wherein Ar represents an optionally substituted aryl group, preferably phenyl optionally substituted with one or more alkyl, (O)2S(O - )-, M + or phenylamino groups), or 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’, and A’ and B’ are optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-X’’-; x) Ar-N=N-, and xi) aryl(alkyl)amino optionally substituted, and M + , R°, X, X’, X’’ and Ar are as defined above, - W is a sigma bond σ, an oxygen atom or a sulfur atom or a divalent group: i) -NR- (where R is as defined above) or ii) methylene-C(Ra)(Rb)- (where Ra and Rb (which may be the same or different) represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom to which they are attached form a spirocycloalkyl), preferably, W represents a sulfur atom or Ra and Rb together form cyclohexyl, Formulas (XIX) and (XIX') have at least one sulfonate group (O)2S(O - )-,M + or one carboxylate group (O)CO - -,M + and preferably contain sodium sulfonate is understood.

[0257] Examples of dyes of formula (XIX) include 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 may be mentioned, and examples of dyes of formula (XIX') include Acid Red 111, Acid Red 134, Acid Yellow 38 may be mentioned.

[0258] b) Pyrazolone anionic azo dyes of formula (XX) and (XX’):

Chem.

Chemical formula

[0259] Examples of the dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and an example of the dye of formula (XX’) may be Acid Yellow 17.

[0260] c) Anthraquinone dyes of formulas (XXI) and (XXI’):

Chemical formula

[0261] Examples of dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2 may be mentioned, and as an example of a dye of formula (XXI'), Acid Black 48 may be mentioned.

[0262] d) Nitro dyes of formulas (XXII) and (XXII'):

Chemical formula

Chemical formula

[0263] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3, and examples of dyes of formula (XXII’) include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4’-N,N-(2’’-hydroxyethyl)amino-2’-nitro)aniline ethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7.

[0264] e) Triarylmethane dyes of formula (XXIII):

Chemical Structure

[0265] Examples of dyes of formula (XXIII) may include 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.

[0266] f) Xanthene dyes of formula (XXIV):

Chemical formula

[0267] Examples of the dyes of formula (XXIV) may include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

[0268] g) Indole dyes of formula (XXV): [Chem.] In formula (XXV), - R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 may be the same or different and are a hydrogen atom or the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - nitro, nitroso; - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- (wherein R° represents a hydrogen atom or an alkyl or aryl group, and X, X’ and X’’ may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - ), M + (wherein M + represents a hydrogen atom or a cationic counterion); - (O)CO - , M + (wherein M + is as defined above) represents a group selected from - G represents an oxygen or sulfur atom or an NRe group (wherein Re is as defined above), and in particular, G represents an oxygen atom, - Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group, Formula (XXV) is understood to contain at least one sulfonate group (O)2S(O - ), M + or one carboxylate group -C(O)O - , M + , preferably sodium sulfonate.

[0269] As an example of the dye of formula (XXV), Acid Blue 74 may be mentioned.

[0270] h) Quinoline dyes of formula (XXVI): [Chemical formula] In formula (XXVI), - R 61 represents a hydrogen or halogen atom or an alkyl group, - R 62 , R 63 and R 64 may be the same or different and represent a hydrogen atom or an (O)2S(O - )-, M + group (wherein M + represents a hydrogen atom or a cationic counterion), or alternatively, R 61 and R 62 or R 61 and R 64 together form a benzoyl group optionally substituted with one or more (O)2S(O - )-, M + groups (wherein M + represents a hydrogen atom or a cationic counterion), It is understood that formula (XXVI) contains at least one sulfonate group (O)2S(O-),M+, preferably sodium sulfonate.

[0271] As examples of the dyes of formula (XXVI), Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5 may be mentioned.

[0272] Among the natural direct dyes that can be used according to the present invention, Lawson, Juglone, Alizarin, Purpurin, Carmic acid, Kermesic acid, Purpurogallin, Protocatechuic aldehyde, Indigo, Isatin, Curcumin, Spinulosin, Apigenidin, Orcein may be mentioned. Extracts or decoctions containing these natural dyes, particularly henna-based compresses or extracts, can also be used.

[0273] Preferably, the direct dye is selected from anionic direct dyes.

[0274] The colorant may be present in a total content in the range of 0.001% to 20% by mass, preferably 0.005% to 15% by mass, based on the total mass of Composition A and / or Composition B. Preferably, the colorant is selected from pigments.

[0275] The pigment may be present in a total content in the range of 0.05% to 20% by mass, preferably 0.1% to 15% by mass, more preferably 5% to 15% by mass, based on the total mass of Composition A and / or Composition B.

[0276] The direct dye can be present in a total content in the range of 0.001% to 10% by mass, preferably 0.005% to 5% by mass, based on the total mass of the composition.

[0277] The colorant can be present in a total amount in the range of 0.001% to 20% by mass, preferably 0.005% to 15% by mass, based on the total mass of the hair coloring composition C.

[0278] The pigment can be present in a total amount in the range of 0.05% to 20% by mass, preferably 0.1% to 15% by mass, more preferably 0.5% to 10% by mass, based on the total mass of the hair coloring composition C.

[0279] The direct dye can be present in a total content in the range of 0.001% to 10% by mass, preferably 0.005% to 5% by mass, based on the total mass of the hair coloring composition C.

[0280] Silicone One and / or the other of Compositions A and B may also contain at least one silicone.

[0281] The silicone is different from a compound containing at least one carboxylic acid group.

[0282] Preferably, one and / or the other of Compositions A and B contains at least one silicone selected from non - amino silicones, amino silicones, and mixtures thereof.

[0283] Silicones can be solid or liquid under atmospheric pressure (1.013×10 5 Pa) at 25 °C and can be volatile or non - volatile.

[0284] The silicones that can be used can be soluble or insoluble in the compositions according to the invention, and they can be in the form of oils, waxes, resins or gums, with silicone oils being preferred.

[0285] Silicones are described in detail, in particular, in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0286] Preferably, one and / or the other of Compositions A and B contains one or more silicones that are liquid at 25 °C and atmospheric pressure (1.013×10 5 Pa).

[0287] Volatile silicones are those having a boiling point of 60 °C to 260 °C (under atmospheric pressure) and can be more particularly selected from the following: i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5 silicon atoms, such as the following, - octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0288] Products sold under the name Volatile Silicone 7207 from Union Carbide or Silbione 70045 V 2 from Rhodia, under the name Volatile Silicone 7158 from Union Carbide or Silbione 70045 V 5 from Rhodia can be mentioned; - A dimethylsiloxane / methylalkylsiloxane type cyclic copolymer having the following chemical structure. [Chemical formula]

[0289] Preferably, it is cyclomethylsiloxane.

[0290] Volatile Silicone FZ 3109 sold by Union Carbide may be mentioned. - A mixture of cyclic silicone and a silicon-based organic compound, such as a mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and a mixture of octamethylcyclotetrasiloxane and 1,1'-oxy(2,2,2',2',3,3'-hexatrimethylsilyloxy)bisneopentane; ii) Generally, a linear polydialkylsiloxane containing 2 to 9 silicon atoms and having a viscosity at 25 °C of 5×10 -6 m 2 / s or less, such as decamethyltetrasiloxane.

[0291] Other silicones belonging to this classification are described in the article published in Cosmetics and Toiletries, Vol.91, Jan.76, pp.27~32, Todd&Byers, “Volatile silicone fluids for cosmetics”, and products sold under the name SH 200 by Toray Silicone can be cited.

[0292] Among non-volatile silicones, there may be mentioned polydialkylsiloxanes, especially polydimethylsiloxane (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and organopolysiloxanes (or organomodified polysiloxanes or alternatively organomodified silicones) containing one or more organic functional groups generally bonded via hydrocarbon-based groups in their structure, preferably selected from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups, either alone or as a mixture. Preferably, the non-volatile silicone is optionally selected from oxyethylenated and oxypropylenated polydimethyl / methylsiloxanes.

[0293] Organomodified silicones can be polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes modified with the above-mentioned organic functional groups. Polyalkylarylsiloxanes are especially selected from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0294] Among organomodified silicones, there may be mentioned organopolysiloxanes including the following: - Polyoxyethylene and / or polyoxypropylene groups optionally containing a C6 - C 24 alkyl group; for example, dimethicone copolyols, especially those sold under the name DC 1248 by Dow Corning or the oils Silwet® L722, L7500, L77 and L711 from Union Carbide; or (C12) alkylmethicone copolyols, especially those sold under the name Q2 5200 by Dow Corning; - Substituted or unsubstituted amine groups, especially C1 - C4 aminoalkyl groups; products sold under the names GP4 Silicone Fluid and GP7100 by Genesee or products sold under the names Q2 - 8220, DC929 or DC939 by Dow Corning may be mentioned; - A thiol group; for example, products sold under the names GP72A and GP71 by Genesee; - An alkoxylated group; for example, products sold under the name Silicone Copolymer F-755 by SWS Silicones and products sold under the names Abil Wax® 2428, 2434, and 2440 by Goldschmidt; - A hydroxylated group; for example, a polyorganosiloxane having a hydroxyalkyl group; - An acyloxyalkyl group; for example, a polyorganosiloxane described in U.S. Patent No. 4957732A; - A carboxylic acid type anionic group; for example, those described in European Patent No. 186507 or an alkylcarboxylic acid type anionic group, for example, product X-22-3701E from Shin-Etsu Chemical Co., Ltd. or a 2-hydroxyalkylsulfonate type or 2-hydroxyalkylthiosulfate type anionic group, for example, products sold under the names Abil® S201 and Abil® S255 by Goldschmidt; - A hydroxyacylamino group; for example, a polyorganosiloxane described in European Patent No. 342834; for example, Q2-8413, a product from Dow Corning, can be mentioned.

[0295] The silicone can also be selected from polydialkylsiloxanes, among which, mainly, polydimethylsiloxane having trimethylsilyl end groups can be mentioned. Among these polydialkylsiloxanes, the following commercially available products can be mentioned: - The 47 and 70047 series of Silbione® oil sold by Rhodia or Mirasil® oil, for example, 70047 V 500000 oil; - Oils of the Mirasil® series sold by Rhodia; - Oils from Dow Corning's 200 series, such as DC200 with a viscosity of 60,000 mm 2 / s; - Viscasil® oils from General Electric and certain oils from General Electric's SF series (SF 96, SF 18).

[0296] Polydimethylsiloxanes with dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as oils from the 48 series from Rhodia, can also be mentioned.

[0297] Polydialkylsiloxanes included in this classification also include products sold under the names Abil Wax® 9800 and 9801 from Goldschmidt, which are poly(C1 - C20)dialkylsiloxanes.

[0298] More specific products that can be used according to the present invention are mixtures such as the following: - A mixture produced from polydimethylsiloxane having hydroxy at the chain ends, i.e., dimethiconol (CTFA) and cyclic polydimethylsiloxane also known as cyclomethicone (CTFA), such as product Q2 - 1401 sold by Dow Corning. - A mixture produced from polydimethylsiloxane having hydroxy at the chain ends, i.e., dimethiconol (CTFA) and polydimethylsiloxane also known as dimethicone (CTFA), such as Xiameter® PMX - 1503 Fluid sold by Dow Corning.

[0299] Polyalkylaryl siloxanes are selected in particular from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes having a viscosity in the range of 1×10 -5 ~5×10 -2 m 2 / s at 25°C.

[0300] Among these polyalkylaryl siloxanes, products sold under the following names can be mentioned: - Silbione® oil of the 70 641 series from Rhodia; - 70633 and 763 series of Rhodorsil® oil from Rhodia; - Dow Corning 556 Cosmetic Grade Fluid, an oil from Dow Corning; - PK series of silicones from Bayer, such as product PK20; - PN and PH series of silicones from Bayer, such as products PN1000 and PH1000; - Certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0301] Preferably, one and / or the other of compositions A and B contains at least one aminosilicone. The term "aminosilicone" refers to any silicone containing at least one primary, secondary or tertiary amine or quaternary ammonium group.

[0302] The mass average molecular weight of these aminosilicones can be measured by gel permeation chromatography (GPC) at room temperature (25 °C) in terms of polystyrene. The column used is a μ-styragel column. The eluent is THF, and the flow rate is 1 ml / min. 200 μl of a solution containing 0.5% by mass of silicone in THF is injected. Detection is carried out by refractive index measurement and UV measurement.

[0303] Preferably, the aminosilicones that can be used in connection with the present invention are selected from the following: a) Formula (A):

Chemical formula

[0304] Preferably, the aminosilicone is selected from the aminosilicones of formula (B). Preferably, the aminosilicone of formula (B) is selected from the aminosilicones corresponding to the following formulas (C), (D), (E), (F) and / or (G).

[0305] According to the first embodiment, the amino silicone corresponding to formula (B) is selected from silicones known as "trimethylsilylamodimethicone" corresponding to formula (C): [Chemical formula] (wherein m and n are numbers such that the total (n + m) is in the range of 1 to 2000, particularly 50 to 150, n represents a number from 0 to 1999, particularly 49 to 149, and m represents a number from 1 to 2000, particularly 1 to 10).

[0306] According to the second embodiment, the amino silicone corresponding to formula (B) is selected from the following silicones of formula (D): [Chemical formula] wherein - m and n are numbers such that the total (n + m) is in the range of 1 to 1000, particularly 50 to 250, more specifically 100 to 200, n represents a number from 0 to 999, particularly 49 to 249, more specifically 125 to 175, and m represents a number from 1 to 1000, particularly 1 to 10, more specifically 1 to 5, - R1, R2 and R3 may be the same or different and represent a hydroxyl or C1 - C4 alkoxy group, and at least one of the R1 - R3 groups represents an alkoxy group).

[0307] Preferably, the alkoxy group is a methoxy group.

[0308] The molar ratio of hydroxyl / alkoxy is preferably in the range of 0.2:1 to 0.4:1, preferably 0.25:1 to 0.35:1, and more specifically 0.3:1.

[0309] The weight average molecular weight (Mw) of these silicones is preferably in the range of 2000 to 1000000, more specifically in the range of 3500 to 200000.

[0310] According to the third embodiment, the amino silicone corresponding to formula (B) is the following formula (E): [Chemical formula] selected from the silicones of, wherein - p and q are numbers such that the sum (p + q) is in the range of 1 to 1000, particularly in the range of 50 to 350, more particularly in the range of 150 to 250, and p can represent a number from 0 to 999, particularly from 49 to 349, more particularly from 159 to 239, and q can represent a number from 1 to 1000, particularly from 1 to 10, more particularly from 1 to 5, - R1 and R2 are different and represent a hydroxyl or a C1-C4 alkoxy group, and at least one of the R1 group or the R2 group represents an alkoxy group).

[0311] Preferably, the alkoxy group is a methoxy group.

[0312] The hydroxy / alkoxy molar ratio is generally in the range of 1:0.8 to 1:1.1, preferably in the range of 1:0.9 to 1:1, and more particularly is 1:0.95.

[0313] The mass average molecular weight (Mw) of the silicone is preferably in the range of 2000 to 200000, even more particularly in the range of 5000 to 100000, and more particularly in the range of 10000 to 50000.

[0314] Commercially available products containing the silicone of structure (D) or (E) can contain one or more other amino silicones having a structure different from formula (D) or (E) in their composition.

[0315] Products containing the amino silicone of structure (D) are sold by Wacker under the name Belsil® ADM 652.

[0316] Products containing the amino silicone of structure (E) are sold by Wacker under the name Fluid WR 1300® or the name Belsil® ADM LOG 1.

[0317] When these aminosilicones are used, a particularly advantageous embodiment consists in using them in the form of a water-in-oil emulsion. The water-in-oil emulsion may contain one or more surfactants. The surfactant can be of any nature, but is preferably cationic and / or nonionic. The number-average particle diameter of the silicone particles in the emulsion is generally in the range of 3 nm to 500 nm. Preferably, particularly as the aminosilicone of formula (E), a microemulsion with an average particle diameter in the range of 5 nm to 60 nm (including the boundary values), more particularly in the range of 10 nm to 50 nm (including the boundary values) is used. Thus, according to the present invention, the aminosilicone microemulsion of formula (E) sold under the names Finish CT 96 E (registered trademark) or SLM 28020 (registered trademark) from Wacker can be used.

[0318] According to a fourth embodiment, the aminosilicone corresponding to formula (B) has the following formula (F):

Chemical formula

[0319] The weight-average molecular weight (Mw) of these aminosilicones is preferably in the range of 2000 to 1000000, more particularly in the range of 3500 to 200000.

[0320] Another silicone corresponding to formula (B) is, for example, Xiameter MEM 8299 Emulsion from Dow Corning (INCI name: amodimethicone and trideceth-6 and cetrimonium chloride).

[0321] According to the fifth embodiment, the amino silicone corresponding to formula (B) is the following formula (G):

Chemical formula

[0322] The mass average molecular weight (Mw) of these amino silicones is preferably in the range of 500 to 1,000,000, more particularly in the range of 1000 to 200,000.

[0323] A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning.

[0324] c) Formula (H):

Chemical formula

[0325] This type of amino silicone is described in particular in US Patent No. 4,185,087.

[0326] - d) Formula (I):

Chemical formula

[0327] These silicones are described, for example, in the patent application European Patent Application Publication No. 0530974 A.

[0328] e) Formula (J):

Chemical formula

[0329] f) (AB) n type of multi-block polyoxyalkylene amino silicone (A is a polysiloxane block and B is a polyoxyalkylene block containing at least one amine group).

[0330] The silicone preferably has the following general formula: [-(SiMe2O) x SiMe2-R-N(R’’)-R’-O(C2H4O) a (C3H6O) b -R’-N(H)-R-] or alternatively, [-(SiMe2O)xSiMe2-R-N(R’’)-R’-O(C2H4O) a (C3H6O) b -] (In the formula, - a is an integer in the range of 1 or more, preferably 5 to 200, more specifically 10 to 100, - b is an integer in the range of 0 to 200, preferably 4 to 100, more specifically 5 to 30, - x is an integer in the range of 1 to 10000, more specifically 10 to 5000, - R’’ is a hydrogen atom or methyl, - R may be the same or different and is a linear or branched divalent C2-C hydrocarbon group optionally containing one or more heteroatoms such as oxygen, 12 preferably, R represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group or a -CH2CH2CH2OCH2CH(OH)CH2- group, and preferentially, R represents a -CH2CH2CH2OCH2CH(OH)CH2- group, - R’ may be the same or different and is a linear or branched divalent C2-C hydrocarbon group optionally containing one or more heteroatoms such as oxygen, 12 preferably, R’ represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group or a -CH2CH2CH2OCH2CH(OH)CH2- group, and preferentially, R’ represents -CH(CH3)-CH2-) and is formed from repeating units having

[0331] The siloxane block preferably represents 50 mol% to 95 mol%, more specifically 70 mol% to 85 mol% based on the total mass of the silicone.

[0332] The amine content is preferably 0.02 to 0.5 meq / g, more specifically 0.05 to 0.2 in a solution containing 30% of the copolymer in dipropylene glycol.

[0333] The mass average molecular weight (Mw) of the silicone is preferably 5000 to 1000000, more specifically 10000 to 200000.

[0334] In particular, mention may be made of silicones sold by Momentive under the name Silsoft A-843 or Silsoft A+.

[0335] g) and mixtures thereof.

[0336] Preferably, the aminosilicone of formula (B) is selected from aminosilicones corresponding to formula (E).

[0337] Preferably, the composition according to the invention comprises at least one aminosilicone having the INCI name amodimethicone, preferably introduced in the form of an emulsion or a microemulsion, together with a surfactant.

[0338] Preferably, the composition according to the invention comprises at least one aminosilicone having the INCI name amodimethicone, as an emulsion or a microemulsion, together with a surfactant having the INCI names trideceth-5 and trideceth-10.

[0339] The silicone may be present in a total amount in the range of 0.01% to 20% by weight, preferably 0.05% to 15% by weight, more preferably 0.1% to 10% by weight, and even more preferably 0.5% to 5% by weight, based on the total weight of Composition A and / or Composition B.

[0340] The silicone may be present in a total amount in the range of 0.01% to 20% by weight, preferably 0.05% to 15% by weight, more preferably 0.1% to 10% by weight, and even more preferably 0.5% to 5% by weight, based on the total weight of the hair coloring composition C.

[0341] The aminosilicone may be present in a total amount in the range of 0.01% to 20% by weight, preferably 0.05% to 15% by weight, more preferably 0.1% to 10% by weight, and even more preferably 0.5% to 5% by weight, based on the total weight of the hair coloring composition C.

[0342] Organic solvent One and / or the other of Composition A and B used in connection with the method according to the invention may comprise one or more organic solvents.

[0343] Examples of organic solvents include lower C1-C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, and diethylene glycol monoethyl ether and monomethyl ether; aromatic alcohols such as benzyl alcohol or phenoxyethanol; and mixtures thereof.

[0344] Preferably, the composition contains one or more organic solvents selected from C1-C4 lower alkanols, more preferably ethanol.

[0345] The organic solvent may be present in a total amount of 0.01% to 60% by weight, preferably 0.05% to 50% by weight, more preferably 0.1% to 45% by weight, based on the total weight of the hair coloring composition C.

[0346] The composition A and / or composition B according to the present invention is preferably aqueous. The water content may range from 20% to 99% by weight, preferably 50% to 98% by weight, more preferably 60% to 95% by weight, based on the total weight of the composition A and / or composition B.

[0347] Additives One and / or the other of the compositions A and B used in connection with the method according to the present invention may contain any conventional adjuvant or additive.

[0348] Among the additives that may be used are reducing agents, softening agents, antifoaming agents, moisturizing agents, UV screening agents, peptidizing agents, solubilizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the aforementioned polymers, preservatives, oils, waxes, and mixtures thereof.

[0349] One and / or the other of compositions A and B may in particular be in the form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion or a multiple emulsion (W / O / W type or polyol / O / W type or O / W / O type), a cream, a mousse, a stick, a vesicle, in particular a dispersion of ionic or non-ionic lipids or a two-phase or multiple-phase lotion.

[0350] Based on general knowledge, a person skilled in the art can select, in addition to the appropriate delivery form, a method for preparing it, first considering the nature of the components used, in particular their solubility in their carriers, and then considering the intended use of the composition.

[0351] Any application of composition D The method for coloring keratin fibers according to the present invention may also include the step of applying a composition D containing at least one silicone compound containing at least one carboxyl group to the keratin fibers of the hair.

[0352] Silicone compounds having a carboxyl functional group The term "carboxyl group" means COOH or COO - functional group, and the counterion of the COO - group can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0353] The silicone that can be used can be soluble or insoluble in composition D, and these can be in the form of oils, waxes, resins or rubbers, with silicone oils and rubbers being preferred.

[0354] Silicones are described in detail in particular in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0355] Preferably, the silicone compound containing at least one carboxyl group has the following formula (XXVII): [Chemical formula] (wherein, - R1 independently represents an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; a hydroxyl group; an alkoxy group containing 1 to 20 carbon atoms; or an aryl group containing 6 to 12 carbon atoms, - R2 independently represents an R4-COOM group (wherein, R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, and at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof is optionally interposed, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal or a quaternary ammonium NR’3 (wherein, R’ may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms)); a pyrrolidine group containing a carboxyl group COOH; or a Ra-(ORb)x-COOM group (wherein, Ra represents a linear or branched alkylene group containing 1 to 4 carbon atoms, Rb represents an alkyl group containing 1 to 4 carbon atoms, x is an integer in the range of 1 to 200, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal or a quaternary ammonium NR’3 (wherein, R’ may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms)), - R3 independently represents an alkyl group containing 1 to 20 carbon atoms; a hydroxyl group; an R4-COOM group (wherein, R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, and at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof is optionally interposed, and M represents a hydrogen atom; an alkali metal or an alkaline earth metal or a quaternary ammonium NR’3 (wherein, R’ may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms)); an alkoxy group containing 1 to 20 carbon atoms; an aryl group containing 6 to 12 carbon atoms or R a -(OR b ) x -COOM group (wherein, R arepresents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkyl group containing 1 to 4 carbon atoms, x is an integer in the range of 1 to 200, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal or a quaternary ammonium NR’3 (wherein R’ may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms)), - n represents an integer in the range of 1 to 1000, - p represents an integer in the range of 0 to 1000, It is understood that at least one of the R2 group and / or the R3 group contains a carboxyl group COOH or COOM (wherein M represents an alkali metal or an alkaline earth metal or a quaternary ammonium NR’3 (wherein R’ may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms)). is selected from organosiloxanes of

[0356] In particular, the silicone compound containing at least one carboxyl group is of the following formula (XXVIII): [Chemical formula] (wherein - R1 is independently a linear or branched alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, preferentially methyl, - R4 is independently a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally intervened by at least one heteroatom selected from a sulfur atom, a nitrogen atom, an oxygen atom and mixtures thereof; or a divalent R a -(OR b ) x - group (wherein R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer in the range of 1 to 200). - M independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium NR’3 (wherein R’ may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms), - n represents an integer in the range of 1 to 1000) of the organosiloxane; - The following formula (XXIX):

Chemical formula

Chemical formula

Chemical formula

[0357] Among the organosiloxanes of formula (XXVIII), polydimethylsiloxane (PDMS) having a carboxyl terminal group, for example, a compound sold under the trade name Silform INX by Momentive (INCI name: bis-carboxydecyl dimethicone) can be mentioned.

[0358] Among the organosiloxanes of formula (XXIX), polydimethylsiloxane (PDMS) having a carboxyl side group, for example, a compound sold under the trade name X-22-3701E by Shin-Etsu Chemical Co., Ltd. can be mentioned.

[0359] Among the organosiloxanes of formula (XXX), polydimethylsiloxane (PDMS) having a carboxyl terminal group, for example, a compound sold under the trade name X-22-3710 by Shin-Etsu Chemical Co., Ltd. can be mentioned.

[0360] Among the organosiloxanes of formula (XXXI), a compound sold under the trade name Grandsil SiW-PCA-10 by Grant Industries (INCI name: dimethicone (and) PCA dimethicone (and) butylene glycol (and) decyl glucoside) can be mentioned.

[0361] The silicone compound containing a carboxyl group may correspond to, for example, the compound described in European Patent No. 186507 in the name of Chisso Corporation, which is incorporated herein by reference.

[0362] Preferably, the silicone compound containing at least one carboxyl group is selected from the organosiloxanes of formula (XXVIII), the organopolysiloxanes of formula (XXIX), and mixtures thereof.

[0363] More preferably, the silicone compound containing at least one carboxyl group has the following formula (XXIXa):

Chemical formula

[0364] The total amount of the silicone compound containing at least one carboxyl group present in Composition D is preferably in the range of 0.01% to 20% by mass, more preferably 0.1% to 15% by mass, still more preferably 0.5% to 10% by mass, based on the total mass of Composition D.

[0365] oil Composition D can also contain one or more oils.

[0366] Preferably, Composition D contains one or more oils. More preferably, Composition D contains one or more oils selected from alkanes.

[0367] The term "oil" means a fatty substance that is liquid at room temperature (25 ° C) and atmospheric pressure (760 mmHg, i.e., 1.013 × 10 5 Pa).

[0368] The oil can be volatile or non-volatile.

[0369] The term "volatile oil" refers to an oil that can evaporate in less than 1 hour at room temperature and atmospheric pressure when in contact with the skin. The volatile oil is a cosmetic volatile oil that is liquid at room temperature. More specifically, the evaporation rate of the volatile oil is 0.01 to 200 mg / cm 2 / min (including the boundary values) (see the evaporation rate measurement procedure described later in the text).

[0370] The term "non-volatile oil" refers to an oil that remains on the skin or keratin fibers at room temperature and atmospheric pressure. More specifically, the evaporation rate of the non-volatile oil is strictly less than 0.01 mg / cm 2 / min (see the evaporation rate measurement procedure described later in the text).

[0371] Preferably, the composition comprises one or more oils selected from C6 - C 16 alkanes and / or mixtures thereof.

[0372] Regarding C6 - C 16 alkanes, these can be straight-chain or branched and optionally cyclic.

[0373] In particular, branched C8 - C 16 alkanes, such as C8 - C 16 isoalkanes (also known as isoparaffins), isododecane, isodecane or isohexadecane, for example oils sold under the trade names Isopar or Permethyl and mixtures thereof can be mentioned.

[0374] Also mentionable are linear alkanes containing 7 - 15 carbon atoms, in particular 9 - 14 carbon atoms, more specifically 11 - 13 carbon atoms, preferably of plant origin.

[0375] Examples of linear alkanes suitable for use in the present invention include n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15) and mixtures thereof, in particular the mixture of n-undecane (C11) and n-tridecane (C13) described in Example 1 of WO 2008 / 155059 pamphlet, a patent application by Cognis.

[0376] In addition to n-dodecane (C12) and n-tetradecane (C14), which are sold by Sasol under the product symbols Parafol 12-97 and Parafol 14-97 respectively, mixtures thereof may also be included.

[0377] Examples of alkanes suitable for use in the present invention include those described in the patent applications WO 2007 / 068371 pamphlet and WO 2008 / 155059 pamphlet. These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut oil or palm oil.

[0378] According to certain embodiments, the composition comprises isododecane. A compound of this kind is, for example, isododecane sold by Ineos under the product symbol Isododecane.

[0379] Preferably, composition D is C8-C 16 alkane, more preferably isododecane, isohexadecane, tetradecane and / or one or more oils selected from mixtures thereof.

[0380] More preferably, composition D comprises isododecane.

[0381] Composition D can comprise one or more oils present in a total amount of 30% to 99% by weight, preferably 50% to 99% by weight, even more preferably 70% to 99% by weight, based on the total weight of composition D.

[0382] Composition D can comprise at least one colorant selected from the pigments, direct dyes and mixtures thereof described above.

[0383] Procedure As shown above, compositions A and B can be applied to keratin fibers such as hair, sequentially, in any order or simultaneously.

[0384] According to one variant of the invention, compositions A and B are applied sequentially to keratin fibers such as hair in any order, i.e., composition A can be applied to the keratin fibers of the hair before composition B or vice versa.

[0385] According to a particular embodiment, the invention is a method of coloring keratin fibers of the hair, i) application of composition A or composition B to the keratin fibers of the hair, wherein composition A comprises at least one (poly)carbodiimide compound as described above, and composition B - at least one of the aforementioned associative polymers; - at least one compound different from the associative polymer having at least one of the aforementioned carboxylic acid groups; - at least one colorant selected from pigments, direct dyes and mixtures thereof including application of composition A or composition B to the keratin fibers of the hair, ii) application of composition B to the keratin fibers of the hair when composition A was applied during step i) or application of composition A to the keratin fibers of the hair when composition B was applied during step i) including.

[0386] Preferably, the invention is a method of coloring keratin fibers of the hair, i) application of composition A or composition B to the keratin fibers of the hair, wherein composition A comprises at least one (poly)carbodiimide compound as described above, and composition B - at least one of the aforementioned associative polymers; - at least one compound different from the associative polymer having at least one of the aforementioned carboxylic acid groups; - at least one colorant selected from pigments, direct dyes and mixtures thereof including application of composition A or composition B to the keratin fibers of the hair, ii) optionally, a leave-on time of 1 to 30 minutes, preferably 1 to 20 minutes, of the composition A or the composition B on the fibers; then, iii) Optionally, a step of washing, rinsing, draining or drying the fibers, preferably a drying step, then, iv) If composition A was applied during step i), then application of composition B to the hair keratin fibers or if composition B was applied during step i), then application of composition A to the hair keratin fibers, then, v) Optionally, a step of washing, rinsing, draining or drying the fibers, preferably a drying step, then, vi) Application of composition D, which contains at least one silicone compound containing at least one carboxyl group as described above, to the hair keratin fibers, then, vii) Optionally, a standing time of 1 minute to 30 minutes, preferably 1 to 20 minutes, on the fibers of composition D, then, viii) An optional step of washing, laundering, dehydrating or drying the fibers is included.

[0387] According to another variant of the invention, preferably, compositions A and B are applied simultaneously.

[0388] According to one embodiment, both composition A and composition B are applied simultaneously to hair keratin fibers such as hair.

[0389] According to another embodiment, compositions A and B are immediately mixed during use to obtain the hair coloring composition C.

[0390] The above hair coloring composition C and optional composition D can be used on wet or dry hair keratin fibers and any type of white or dark, natural or colored, permed, bleached or relaxed fibers.

[0391] According to a preferred embodiment, the hair coloring composition C and composition D are applied simultaneously to the hair keratin fibers.

[0392] According to another preferred embodiment, after applying the hair coloring composition C to the hair keratin fibers, composition D is applied to the hair keratin fibers.

[0393] According to another preferred embodiment, composition D is applied to the keratin fibers of the hair before applying the hair coloring composition C to the keratin fibers of the hair.

[0394] According to a specific embodiment of the present invention, the keratin fibers of the hair are washed before applying the hair coloring composition C and any composition D.

[0395] Preferably, after applying the hair coloring composition C to the keratin fibers of the hair and before applying the composition D to the keratin fibers of the hair, a washing, rinsing, draining or drying step is performed.

[0396] More preferably, after applying the hair coloring composition C to the keratin fibers of the hair and before applying the composition D to the keratin fibers of the hair, a drying step is performed.

[0397] The application to the fibers can be carried out via any standard means, in particular using a comb, a fine-toothed brush, a coarse-toothed brush, a sponge or the fingers.

[0398] The application of the hair coloring composition C and the optional component composition D to the keratin fibers of the hair is usually carried out at room temperature (15 - 25 °C).

[0399] After applying the hair coloring composition C to the keratin fibers of the hair, for example, before applying the composition D to the keratin fibers of the hair or, for example, before a washing, rinsing, dehydration or drying step, it can be left for 1 minute to 6 hours, in particular 1 minute to 2 hours, more specifically 1 minute to 1 hour, and more preferably 1 minute to 30 minutes.

[0400] Preferably, after applying the hair coloring composition C to the keratin fibers of the hair and before applying the composition D to the keratin fibers of the hair, there is no leave-on time.

[0401] After applying the hair coloring composition C and any composition D, the fibers can be dried, or can be dried at a temperature of 30 °C or higher, for example.

[0402] Accordingly, the method according to the present invention can include a step of applying heat to keratin fibers of hair using a heating appliance.

[0403] The step of applying heat in the method of the present invention can be carried out using a hood dryer, a hair dryer, a straight iron, a Climazon, etc.

[0404] Preferably, the step of applying heat in the method of the present invention is carried out using a hair dryer.

[0405] When the method of the present invention includes a step of applying heat to keratin fibers of hair, the step of applying heat to keratin fibers of hair is performed after applying the hair coloring composition C and any composition D to the keratin fibers of hair.

[0406] During the step of applying heat to keratin fibers of hair, a mechanical action such as combing, brushing or a hairbrush can be applied to the hair bundle.

[0407] When the step of applying heat to keratin fibers of hair is carried out using a hood dryer or a hair dryer, the temperature is preferably 30°C to 110°C, preferentially 50°C to 90°C.

[0408] When the step of applying heat to keratin fibers of hair is carried out using a straight iron, the temperature is preferably 110°C to 220°C, preferably 140°C to 200°C.

[0409] In a specific variant, the method of the present invention includes a step (b1) of applying heat using a hood dryer, a hair dryer or a Climazon, preferably a hair dryer, and a step (b2) of applying heat using a straight iron or a curling iron, preferably a straight iron.

[0410] Step (b1) can be carried out before step (b2).

[0411] During the implementation of step (b1), also known as the drying process, the fibers can be dried at a temperature of, for example, 30 °C or higher. According to a specific embodiment, this temperature exceeds 40 °C. According to a specific embodiment, this temperature exceeds 45 °C and is less than 110 °C.

[0412] Preferably, when drying the fibers, in addition to supplying heat, drying is carried out using an air flow. By using an air flow during drying in this way, it becomes possible to improve the separation of the coating of the tufts of hair.

[0413] During drying, a mechanical action such as combing, brushing or hand-combing can be applied to the tufts of hair.

[0414] During the implementation of step (b2), the temperature when sliding a straight iron or a curling iron is preferably in the range of 110 °C to 220 °C, preferably 140 °C to 200 °C.

[0415] After the drying process is completed, the shaping process can be carried out using, for example, a straight iron, and the temperature of the shaping process is 110 - 220 °C, preferably 140 - 200 °C.

[0416] Preferably, the present invention is a method for coloring keratin fibers of hair, for example hair, comprising mixing composition A and composition B to obtain a hair coloring composition C, and then i) application of the hair coloring composition C to the keratin fibers of the hair, wherein composition A contains at least one (poly)carbodiimide compound as described above, and composition B - at least one of the above-mentioned associative polymers; - at least one compound different from the associative polymer having at least one of the above-mentioned carboxylic acid groups; - at least one colorant selected from pigments, direct dyes and mixtures thereof including the application.

[0417] More preferably, the present invention is a method for coloring keratin fibers of hair, comprising obtaining a hair coloring composition C by mixing composition A and composition B, and then i) application of the hair coloring composition C to the keratin fibers of the hair, wherein composition A contains at least one (poly)carbodiimide compound as described above, and composition B - the at least one associative polymer described above; - at least one compound different from the associative polymer having at least one carboxylic acid group described above; - at least one colorant selected from pigments, direct dyes and mixtures thereof and - application of the hair coloring composition C to the keratin fibers of the hair, wherein one or the other of compositions A and B optionally further contains at least one silicone as described above, and then ii) optionally, allowing the hair coloring composition C to stand on the fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes, and then iii) optionally, washing, rinsing, dehydrating or drying the fibers, and then iv) application of a composition D containing at least one silicone compound containing at least one carboxyl group described above to the keratin fibers of the hair, and then v) optionally, allowing the composition D to stand on the fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes, and then vi) optionally, washing, rinsing, dehydrating or drying the fibers is included.

[0418] Preferably, the step of applying the hair coloring composition C to the keratin fibers of the hair is repeated several times.

[0419] According to a preferred embodiment, a method for coloring keratin fibers of hair is a method for coloring keratin fibers of hair, which comprises, at the time of use, immediately mixing at least two compositions A and B to obtain a hair coloring composition C, and applying the hair coloring composition C to the keratin fibers of the hair, - Composition A contains at least one of the (poly)carbodiimide compounds described above, - Composition B contains an aqueous dispersion of polymer particles selected from at least one of the associative polymers described above, at least one compound different from the associative polymers described above and containing at least one carboxylic acid group, preferably polyurethane, an acrylic polymer different from the associative polymers described above, and mixtures thereof, and at least one colorant selected from pigments, direct dyes, and mixtures thereof, Composition A and / or Composition B optionally contains at least one silicone as defined above.

[0420] Preferably, Compositions A and B are mixed preferably less than 15 minutes, more preferably less than 10 minutes, and even more preferably less than 5 minutes before application to keratin fibers of the hair.

[0421] The mass ratio of Composition A to Composition B is preferably in the range of 0.1 to 10, more preferably 0.2 to 5, even more preferably 0.5 to 2, and further 0.6 to 1.5. In certain embodiments, the mass ratio of Composition A to Composition B is equal to 1.

[0422] According to a particular embodiment, a method for coloring keratin fibers of the hair comprises, in use, immediately mixing at least two Compositions A and B to obtain a hair coloring composition C, and applying the hair coloring composition C to the keratin fibers of the hair, - Composition A contains at least one of the (poly)carbodiimide compounds described above, - Composition B contains an aqueous dispersion of polymer particles selected from at least one compound different from the associative polymers described above and containing at least one carboxylic acid group, preferably the polyurethane described above, an acrylic polymer different from the associative polymers described above, and mixtures thereof, at least one of the associative polymers described above, and at least one colorant selected from pigments, direct dyes, and mixtures thereof, Composition A and / or composition B optionally contain at least one silicone as defined above, and composition D is as described above, which is applied to the keratin fibers of the hair before and / or after applying the mixture of said compositions A and B to the hair keratin fibers.

[0423] The present invention also relates to an apparatus for coloring hair keratin fibers, - Composition A according to the invention as defined above in a first compartment (E1), - Composition B according to the invention as defined above in a second compartment (E2), - Optionally, composition D as defined above in a third compartment (E3) and comprises at least two compartments for containing them.

[0424] Here, the present invention will be described in more detail using examples, which in no way limit the scope of the present invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the present invention.

Examples

[0425] The (poly)carbodiimide of the present invention can be obtained via synthetic methods known to those skilled in the art, starting from commercially available products or reagents that can be synthesized according to chemical reactions also known to those skilled in the art. For example, reference can 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 No. 4284730 or Canadian Patent No. 2509861.

[0426] More specifically, the method for preparing the (poly)carbodiimide of the present invention comprises, in a first step, a diisocyanate reagent (1): O=C=N - L1 - N=C=O (1) (In formula (1), L1 is as defined above) is reacted in the presence of a carbodiimidization catalyst (2) such as those described in US Patent No. 4,284,730, particularly a phosphorus-based catalyst, particularly phosphorene oxide and phosphorene sulfoxide, and those selected from diaza- and oxaaza-phosphoranes, preferably in an inert atmosphere (nitrogen or argon), particularly preferably in an aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane or DMF, at a temperature from room temperature to the reflux temperature of the solvent, preferably at about 140 °C, to give a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O (3) (In formula (3), L1 and n are as defined above) is involved. To deactivate the catalyst, a benzoyl halide such as benzoyl chloride can be added.

[0427] In the second step of this preparation method, when obtaining a "symmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of a nucleophilic reagent R1-X1-H, and then with 0.5 eq. of the reagent H-E-H (wherein R1, X1 and E are as defined above), to give the "symmetric" compound (4) according to the present invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4) (In formula (4), R1, X1, L1, n and E are as defined above) is formed. According to one variant for obtaining compound (4) from (3), it is possible to first add 0.5 eq. of the reagent H-E-H and then 1 eq. of the reagent R1-X1-H.

[0428] In the second step of this preparation method, when obtaining an "asymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of a nucleophilic reagent R1-X1-H, and then with 1 eq. of the reagent H-E-H (wherein R1, X1 and E are as defined above), to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-H (5) (In formula (5), R1, X1, L1, n, and E are as defined above.) is produced.

[0429] According to one variant for obtaining compound (5) from (3), first 1 eq. of reagent R1-X1-H can be added, followed by 0.5 eq. of reagent H-E-H.

[0430] In the third step, compound (5) is reacted with 1 eq. of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6) (Said compound (6) is compound (3’): O=C=N-L1-(N=C=N-L1) z -N=C=O (3’) (wherein, in formula (3’), L1 and z are as defined above, and this is prepared using 1 eq. of the nucleophile R2-X2-H having L1, R2, X2, and z as defined above to obtain the asymmetric compound (7): 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) (In formula (7), R1, X1, L1, R2, X2, n, z, and E are as defined above.) is produced.

[0431] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O(3’) is reacted with 1 / w molar equivalent of H-E-H, followed by 1 eq. of the nucleophile R2-X2-H to obtain compound (8): H-[E-C(O)-NH-L1-(N=C=N-L1) z w -NH-C(O)-X2-R2(8) ​(In formula (8), L1, R2, X2, z, and E are as defined above, w is an integer from 1 to 3, and more preferably, w = 1) It is also possible to generate

[0432] Next, this last compound (8) is reacted with 1 eq. of compound (4'): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -N=C=O(4') to obtain a reaction (the compound (4') can be synthesized by reacting 0.5 eq. of the nucleophilic reagent R1-X1-H with 1 equivalent of compound (3)), and the (poly)carbodiimide (9) of the present invention: 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 -NH C(O)-X2-R2(9), (In formula (9), L1, R1, X1, R2, X2, n, z, w, and E are as defined above) can be generated.

[0433] (Poly)carbodiimide compounds and all reaction intermediates and reagents as well can be purified by conventional methods known to those skilled in the art, for example, extraction, precipitation, centrifugation, filtration, and / or chromatography using water and an organic solvent immiscible with water.

[0434] Example 1: Method for synthesizing (poly)carbodiimide compound Charge 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide into a 500 mL three-necked round-bottom flask equipped with a thermometer, stirrer, and reflux tube while stirring.

[0435] While monitoring the reaction by the absorption of isocyanate groups at 2200 - 2300 cm -1 heat the reaction medium at 140 °C in nitrogen for 4 hours, and then cool it to 120 °C.​

[0436] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol is introduced into the reaction medium while stirring. By infrared spectroscopy, 2200-2300 cm -1 is monitored, the temperature is maintained at 120 °C until the isocyanate groups have completely disappeared, and then it is cooled to room temperature.

[0437] After cooling to room temperature, the reaction medium is added dropwise with vigorous stirring to a 500 mL glass beaker containing 85 g of distilled water to obtain the desired product in the form of a translucent yellow liquid.

[0438] Example 2 The following compositions A1, A2, B1, B2, B3 and B4 were prepared: The amounts are expressed as g / 100 g of the starting materials obtained.

[0439] [Table 1]

[0440] [Table 2]

[0441] Therefore, compositions A1, A2, B1 and B2 are compositions used in connection with the method according to the invention. Therefore, these compositions are considered to be compositions according to the invention. Compositions B3 and B4 are comparative compositions.

[0442] The appearance of the compositions is observed at T0 after they have been prepared.

[0443] Compositions A1 and A2 are in the form of smooth-flowing gels.

[0444] Compositions B1 and B2 are in the form of viscous gels with fluidity.

[0445] Compositions B3 and B4 are in the form of very thick gels.

[0446] Next, the compositions are stored at 55 °C and atmospheric pressure for 10 days. Then, the stability of each composition is evaluated by visual observation.

[0447] It can be seen that compositions B3 and B4 were in the form of very brittle dry gels with many particles.

[0448] Therefore, the stability of compositions B3 and B4 is insufficient and unacceptable.

[0449] On the other hand, the stability of compositions B1 and B2 is acceptable.

[0450] The stability of compositions A1 and A2 is also acceptable.

[0451] Example 3: Compositions A1, A2, B1 and B2 described above in Example 2 were prepared.

[0452] Next, two mixtures are prepared.

[0453] Composition A1 and composition B1 are mixed in a 50 / 50 mass ratio to obtain a hair coloring composition C1.

[0454] Composition A2 and composition B2 are mixed in a 50 / 50 mass ratio to obtain a hair coloring composition C2.

[0455] Therefore, compositions C1 and C2 are compositions according to the present invention.

[0456] Next, the following composition D was prepared. The amounts are expressed as g / 100 g of the starting materials obtained.

[0457]

Table 3

[0458] Protocol: Each of the compositions C1 and C2 is applied to a tuft of dry natural hair containing 90% white hair at a rate of 0.5 g of the composition per gram of the tuft.

[0459] Next, the hair tresses are dried with a hair dryer and then combed.

[0460] Next, composition D is applied to the tuft of dried hair treated with compositions C1 and C2 at a rate of 0.5 g of the composition per gram of the tuft.

[0461] Next, the hair tresses are left at room temperature for 24 hours.

[0462] Then, the thus-colored hair tresses are subjected to several repeated shampoo washing tests to evaluate the fastness (persistence) of the colorant obtained with respect to shampoo washing according to the shampoo washing protocol described below.

[0463] Shampoo washing protocol: Comb the colored hair tresses, moisten them with water at 35°C, and then pass them through the fingers 5 times for 5 seconds. Next, wring the hair tresses dry between two fingers.

[0464] Apply a standard shampoo (Garnier Ultra Doux) uniformly to the colored hair tuft at a rate of 0.4 g of the standard shampoo per gram of the hair tuft, and gently knead it along the longitudinal direction of the hair tuft from the root to the tip for 15 seconds (6 times).

[0465] Then place the hair tuft in a watch glass and leave it for 1 minute.

[0466] Then, rinse the hair tuft with water while passing it through the fingers (15 times). Next, wring the hair tresses dry between two fingers before the next shampoo wash.

[0467] After finishing the test of performing several shampoo washes, comb the hair tuft and dry it with a hair dryer.

[0468] Results: The color persistence of the tufts of hair was evaluated in the CIE L*a*b* system using a Minolta Spectrophotometer CM3600A colorimeter (D65 light source, 10° angle, including the specular reflection component).

[0469] In this L*a*b* system, L* represents the color intensity, a* indicates the green / red axis, and b* indicates the blue / yellow axis.

[0470] The color persistence of the coloring is evaluated by the color difference ΔE before shampooing the dyed tufts of hair and then after performing shampoo washing 5 times according to the procedure described above. The lower the ΔE value, the higher the color persistence with respect to shampoo washing.

[0471] The ΔE value is determined according to the following formula.

Equation

[0472] In this formula, L*a*b* represents the values measured after performing shampoo washing after hair dyeing, and L0*a0*b0* represents the values measured before performing shampoo washing after hair dyeing.

[0473]

Table 4

[0474] The hair tresses treated with each of the compositions (C1 and C2)+D and washed with 5 shampoo washings have low ΔE values. Therefore, the coloring paints obtained using the compositions (C1 and C2)+D exhibit good persistence with respect to shampoo washing.

[0475] Furthermore, a smooth and uniform color coating on the hair is observed.

Claims

1. A method for coloring keratin fibers of hair, comprising applying Composition A and Composition B to the keratin fibers of hair, Composition A contains at least one (poly)carbodiimide compound selected from compounds of the following formula (II): 【Chemical Formula 1】 (wherein, - X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group, - R1 and R2 independently represent a hydrocarbon-based group in which one or more heteroatoms are optionally interposed, - n and z represent integers in the range of 1 to 20, where n + z ≥ 2, and w represents an integer in the range of 1 to 3, - L1 is independently selected from a divalent C1 - C18 aliphatic hydrocarbon-based group, a C3 - C15 cycloalkylene group, a C3 - C12 heterocycloalkylene group or a C6 - C14 arylene group and mixtures thereof, - E is independently -O - R3 - O -; -S - R4 - S -; -R5 - N(R6) - R4 - N(R6) - R5 - represents a group selected from, where - R3 and R4 independently represent a divalent hydrocarbon-based group in which one or more heteroatoms are optionally interposed, - R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group in which one or more heteroatoms are optionally interposed, - R6 independently represents a hydrogen atom or a hydrocarbon-based group in which one or more heteroatoms are optionally interposed) and Composition B contains - at least one associative polymer selected from anionic carboxylic acid acrylic associative polymers, - At least one compound containing at least one carboxylic acid group, different from the associative polymer, and selected from a silicone compound containing at least one carboxyl group, polyurethane, an acrylic polymer, and mixtures thereof, and comprising Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof, A method in which Composition A and Composition B are applied simultaneously or sequentially to the keratin fibers of the hair.

2. The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein - X １ and X ２ independently represent an oxygen atom, - R １ and R ２ are independently selected from dialkylamino alcohols from which a hydroxyl group has been removed, alkyl esters of hydroxycarboxylic acids, monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof, - n and z represent integers in the range of 1 to 20, where n + z ≧ 2, and w is equal to 1, - L1 is a divalent C １ to C １８ aliphatic hydrocarbon-based group, C ３ to C １５ cycloalkylene group, C ３ to C １２ heterocycloalkylene group or C ６ to C １４ arylene group, and mixtures thereof, - E is independently -O-R ３ -O-; -S-R ４ -S-; -R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - represents a group selected from, where - R3 and R4 are independently selected from C with one or more heteroatoms optionally intervening, ６ ~C １４ arylene group, C ３ ~C １２ cycloalkylene group, linear or branched C １ ~C １８ alkylene group, and mixtures thereof, - R ５ when not a covalent bond, R ５ is selected from C with one or more heteroatoms optionally intervening, ６ ~C １４ arylene group, C ３ ~C １２ cycloalkylene group, linear or branched C １ ~C １８ alkylene group, and mixtures thereof, and - R ６ is selected from C with one or more heteroatoms optionally intervening, ６ ~C １４ arylene group, C ３ ~C １２ cycloalkylene group, linear or branched C １ ~C １８ alkylene group, and mixtures thereof, characterized in that the method according to claim 1.

3. The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein - X １ and X ２ each independently represents an oxygen atom, - R １ and R ２ are each independently a monoalkyl ether of a (poly)alkylene glycol from which the hydroxyl group has been removed, - n and z each represent an integer in the range of 1 to 20, where n + z ≥ 2, and w is equal to 1, - L １ is a C ３ ~C １５ cycloalkylene group, - E is independently -O-R ３ -O-; -S-R ４ -S-; -R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - represents a group selected from, where, -R ３ and R ４ are independently a C ６ ~C １４ arylene group, a C ３ ~C １２ cycloalkylene group, a linear or branched C １ ~C １８ alkylene group and a mixture thereof, -R ５ is not a covalent bond, R ５ is a C ６ ~C １４ arylene group, a C ３ ~C １２ cycloalkylene group, a linear or branched C １ ~C １８ alkylene group and a mixture thereof, and -R ６ is a C ６ ~C １４ arylene group, a C ３ ~C １２ cycloalkylene group, a linear or branched C １ ~C １８ alkylene group and a mixture thereof, characterized in that the method according to claim 1 or 2.

4. The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein, -X １ and X ２ independently represent an oxygen atom, -R １ and R ２ independently represent the following formula (VI): R １３ - [O-CH ２ -C(H)(R １４ )] ｑ -(VI) represents a compound of, wherein R １３ represents a C １ to C ４ alkyl group or phenyl, R １４ represents a hydrogen atom or a C １ to C ４ alkyl group, and q represents an integer in the range of 4 to 30, - n and z represent integers in the range of 2 to 20, wherein n + z is in the range of 4 to 10, and w is equal to 1, - L １ is a C ３ to C １５ cycloalkylene group, and - E is a -O-R ３ -O- group (wherein R ３ represents a C ６ to C １４ arylene group, a C ３ to C １２ cycloalkylene group, a linear or branched C １ to C １８ alkylene group and a mixture thereof), which is characterized in that the method according to any one of claims 1 to 3.

5. The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein - X １ and X ２ each independently represents an oxygen atom, - R １ and R ２ each independently represents the following formula (VI): R １３ - [O-CH ２ -C(H)(R １４ )] ｑ -(VI) represents a compound of, wherein R １３ represents a C １ to C ４ alkyl group or phenyl, R １４ represents a hydrogen atom or a C １ to C ４ alkyl group, and q represents an integer in the range of 4 to 30, - n and z represent integers in the range of 1 to 20, where n + z is in the range of 4 to 10, and w is equal to 1, - L １ is a C ３ to C １５ cycloalkylene group, and - E is -O-R ３ -O- group (where R ３ represents a linear or branched C １ to C １８ alkylene group in which one or more heteroatoms are optionally interposed). The method according to any one of claims 1 to 4.

6. The (poly)carbodiimide compound is represented by the following formula (XII): 【Chemical formula 2】 (In the formula, L １ is 4,4-dicyclohexylene methane, n and z represent integers in the range of 1 to 20, where n + z is in the range of 4 to 10, E is -O-R ３ -O- group (where R ３ represents a linear or branched C １ to C １８ alkylene group in which one or more heteroatoms are optionally interposed), and r and s represent integers in the range of 4 to 30). The method according to any one of claims 1 to 5, characterized in that it is selected from the compounds of

7. The total amount of the (poly)carbodiimide compound is in the range of 0.01% by mass to 40% by mass based on the total mass of Composition A. The method according to any one of claims 1 to 6.

8. The total amount of the associative polymer is in the range of 0.1% by mass to 30% by mass based on the total mass of Composition B. The method according to any one of claims 1 to 7.

9. The method according to any one of claims 1 to 8, characterized in that the compound containing at least one carboxylic acid group, which is different from the associative polymer, is selected from polyurethane, acrylic polymer and mixtures thereof.

10. The method according to claim 9, characterized in that the compound containing at least one carboxylic acid group, which is different from the associative polymer, is in the form of an aqueous dispersion of polymer particles selected from polyurethane, acrylic polymer and mixtures thereof.

11. The acrylic polymer comprises the following monomers: a) (meth)acrylic acid, and b) C １ - C30 alkyl (meth)acrylate The method according to claim 10, characterized in that it comprises one or more units derived from.

12. The method according to any one of claims 1 to 11, characterized in that the total amount of the compound containing at least one carboxylic acid group, which is different from the associative polymer, ranges from 0.2% to 60% by mass based on the total mass of composition B.

13. The method according to any one of claims 1 to 12, characterized in that the content of the colorant ranges from 0.001% to 20% by mass based on the total mass of composition A and / or composition B.

14. The method according to any one of claims 1 to 13, characterized in that the content of the pigment ranges from 0.05% to 20% by mass based on the total mass of composition A and / or composition B.

15. The method according to any one of claims 1 to 14, characterized in that one and / or the other of compositions A and B also contains at least one silicone.

16. The method according to claim 15, wherein the silicone is present in a total amount in the range of 0.01% by mass to 20% by mass based on the total mass of composition A and / or composition B.

17. The method according to any one of claims 1 to 16, further comprising the step of applying a composition D containing at least one silicone compound containing at least one carboxyl group to the keratin fibers of the hair.

18. The method according to claim 17, wherein the total amount of the silicone compound containing at least one carboxyl group present in composition D is in the range of 0.01% by mass to 20% by mass based on the total mass of composition D.

19. The method according to claim 17 or 18, wherein composition D further contains one or more oils.

20. - Composition A as defined in any one of claims 1 to 7 or 13 to 16 in a first compartment (E1), - Composition B as defined in any one of claims 1 or 8 to 16 in a second compartment (E2), - Optionally, composition D as defined in any one of claims 17 to 19 in a third compartment (E3) An apparatus for coloring keratin fibers of the hair, comprising at least two compartments for containing

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