FR3105734A1 - Process for treating keratin fibers comprising the application of a composition comprising a particular compound and a step of supplying energy to said keratin fibers - Google Patents

Abstract

The present invention relates to a process for treating keratin fibers, in particular human keratin fibers, in particular the hair, comprising: a) a step of applying to the keratin fibers a composition comprising one or more compounds comprising at least two groups tetrazole, and optionally at least one coloring agent chosen from pigments, direct dyes and mixtures thereof; b) a step of providing energy to the keratin fibers chosen from a heat treatment using a heating means and / or irradiation by artificial or natural light radiation.

Description

Process for the treatment of keratin fibers comprising the application of a composition comprising a particular compound and a step of providing energy to said keratin fibers

The present invention relates to a process for treating keratin fibers, in particular the hair, comprising the application of a composition comprising at least one compound comprising at least two tetrazole groups, and optionally at least one coloring agent chosen from pigments, dyes direct and mixtures thereof, and a step of providing energy to the keratin fibers by heat treatment and/or by irradiation using artificial or natural radiation.

The invention also relates to said compound comprising at least two tetrazole groups, a composition comprising at least said compound according to the invention and the use of said composition for the care and/or repair of keratin fibres.

The invention also relates to a process for dyeing keratin fibers comprising the application of a composition comprising at least said compound according to the invention and at least one coloring agent chosen from pigments, direct dyes and mixtures thereof, and a step energy supply to keratinous fibers by heat treatment and/or by irradiation using artificial or natural radiation.

Prior techniques

Keratin fibres, in particular human keratin fibers such as the hair, are generally damaged and weakened by the action of external atmospheric agents such as light, the sun and bad weather, as well as by mechanical or chemical treatments such as brushing, combing, perms, straightening, repeated washing. Said keratinous fibers thus find themselves damaged by these various factors and may in the long run become dry, rough, brittle, dull, soft split ends and/or difficult to style.

Thus, to remedy these drawbacks, it is usual to have recourse to hair care products which use compositions intended to condition keratin fibres, in particular human keratin fibers such as the hair, in a suitable manner by providing them with satisfactory cosmetic properties, in particular smoothness, shine, softness to the touch (a natural feel, the hair is no longer rough), suppleness, lightness, good detangling properties making it easier to comb, good discipline of the hair which thus has a good formatting.

These hair care compositions can be, for example, conditioning shampoos, conditioners, masks, serums. However, the conditioner effect obtained fades during successive shampoos and does not exhibit satisfactory shampoo persistence. On the other hand, these compositions, if they improve the visual effect of the split ends and facilitate disentangling or brushing, do not generally have the effect of repairing the split ends. Thus the results obtained are not always satisfactory in terms of repair or prevention of breakage of keratin fibres, in particular split keratin fibres.

There is therefore a real need to develop a process for treating keratin fibers, in particular human keratin fibers such as the hair, and a composition, which are capable of protecting and/or repairing said fibers, and if possible, in a lasting manner against -to external agents.

In addition, it is interesting to find a way to treat damaged keratin fibers by repairing them, that is to say by improving the cosmetics of intrinsically damaged keratin fibers, while maintaining or even improving manageability (discipline), the anti-frizz and/or the remanence of the styling of said fibres. It is also interesting to prevent the breakage of natural keratin fibers, while maintaining or even improving the manageability (discipline), the anti-frizz and/or the persistence of the styling of said fibers.

Furthermore, in the field of dyeing keratin fibres, in particular human keratin fibers such as the hair, it is already known to dye keratin fibers by various techniques using direct dyes for non-permanent dyes or precursors of dyes for permanent coloring.

Non-permanent coloring or direct coloring consists in dyeing the keratin fibers with dye compositions containing direct dyes. The latter are applied to the keratin fibers for a time necessary to obtain the desired coloration, then rinsed.

The conventional dyes which are used are in particular dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane type or natural dyes.

Some of these dyes can be used under lightening conditions, which makes it possible to obtain visible colorations on dark hair.

Another coloring method is to use pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colorings on dark hair since the pigment on the surface masks the natural color of the fiber. These colorings obtained by this method of coloring can have the disadvantage of having a low resistance to water and/or shampoos as well as to external agents such as sebum, perspiration, mechanical actions such as brushing and / or friction. The colorations obtained can also generate staining and/or transfer, in particular when the fibers are wet.

In addition, temporary hair coloring compositions can also lead to an unnatural and/or non-cosmetic feel to the hair, the hair thus colored possibly lacking in softness and/or suppleness and/or softness. individualization in particular.

There therefore remains a real need to have a treatment for keratin fibers, in particular human keratin fibers such as the hair, and a composition, which are capable of protecting and/or repairing said fibers, and/or coloring them, and if possible, in a sustainable way with respect to external agents.

This object is achieved by the present invention, the subject of which is in particular a method for treating keratin fibers, in particular human keratin fibers, in particular the hair, comprising:
a) a step of applying to the keratin fibers a composition comprising one or more compounds comprising at least two tetrazole groups, and optionally at least one coloring agent chosen from pigments, direct dyes and mixtures thereof;
b) a step of supplying energy to the keratinous fibers chosen from a heat treatment using a heating means and/or irradiation by artificial or natural light radiation.

The Applicant has found, surprisingly, that the process according to the invention makes it possible to improve the cosmetic properties imparted to keratin fibres, in particular as regards the properties in terms of anti-breakage of the keratin fibres.

When the method uses at least one coloring agent, said method also leads to a visible coloring on all types of hair, said coloring being remanent to shampoos and preserving or improving the physical qualities of the keratin fibres, without altering the integrity treated fibers. Such a process is resistant to external aggressions that the hair may suffer such as blow-drying and/or sensitivity to humidity such as perspiration, atmospheric humidity.

Moreover, this process leaves the hair perfectly individualized, which can be styled without any problem. The hair after treatment can be subjected to shaping treatments, preferably temporary shaping.

In particular, the hair treated with the process according to the invention remains disciplined, including in a humid atmosphere, because the presence of frizz is not observed. Thus the hair is aligned, smooth and disentangles easily, which makes it easier to comb. The treated hair also has more body, i.e. it is not limp, and is therefore easier to style and retains its hold during styling. The treated hair has a good shape which remains persistent even after several shampoos.

Furthermore, the treated hair is also shiny and soft to the touch. They are less brittle and more resistant. The process according to the invention has the advantage of conferring good persistence after at least one shampoo of these good cosmetic properties for conditioning the hair, in particular after 10 successive shampoos. Also, the treated hair is conditioned in a durable way. After treatment, the hair is not loaded and has a natural feel.

A subject of the present invention is also compounds comprising at least two tetrazole groups as defined below as well as a composition comprising at least one such compound and optionally at least one coloring agent chosen from pigments, direct dyes and mixtures thereof. .

Another object of the present invention is the use of the composition according to the invention for the care and/or repair of keratin fibres.

Another object of the present invention is a composition comprising at least one compound comprising at least two tetrazole groups according to the invention and at least one coloring agent chosen from pigments, direct dyes and mixtures thereof, and the use of said composition for coloring keratin fibres, in particular human keratin fibers such as the hair.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the example which follow.

In the present description, the expression "at least one" is equivalent to the expression "one or more" and can be substituted therefor; the expression "included between" is equivalent to the expression "ranging from" and can be substituted therefor, and implies that the terminals are included.

By tetrazole unit or group or group is meant, within the meaning of the present invention, a tetrazolyl radical, optionally substituted by one or more radicals, identical or different, chosen from a C ₁ to C ₆ alkyl group or an aromatic group.

The term “keratin fibres”, within the meaning of the present invention, means the hair, the eyelashes, the hairs, and in particular the human keratin fibres, even more particularly the hair.

The term “individualized hair”, within the meaning of the present invention, means hair which, after application of a composition and drying, is not stuck together (or is all separated from each other) and therefore does not form pile of hair.

By “shampoo-resisting coloration” is meant, within the meaning of the present invention, that the coloration obtained persists after one shampoo, preferably after 3 shampoos, more preferably after 5 shampoos, even more preferably after 10 shampoos.

The expression "comprising a" must be understood as meaning "comprising at least one", unless the contrary is specified.

In the expression “chain containing an atom”, it is meant, within the meaning of the present invention, that the atom can be present throughout the chain, including at the ends of said chain.

In the expression “chain interrupted by an atom”, it is meant, within the meaning of the present invention, that the atom can be present throughout the chain, with the exception of the ends of said chain.

The invention is not limited to the examples illustrated. The characteristics of the various examples can in particular be combined within variants that are not illustrated.

Within the meaning of the present invention and unless otherwise indicated,

the term "alkyl" denotes a linear or branched, saturated hydrocarbon radical;

an “aryl” radical is an aromatic unsaturated cyclic radical, comprising from 6 to 20 carbon atoms, mono or bicyclic, fused or not, preferably the aryl group consists of a ring and contains 6 carbon atoms such as phenyl;

a "cycloalkyl" radical denotes a saturated cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 1 to 2 rings, more preferably 1 ring and comprising from 3 to 20 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl or isobornyl, the cycloalkyl radical possibly being substituted by one or more C ₁ to C ₄ alkyl groups, such as methyl;

the term "alkoxy" denotes an alkyl-oxy group, "alkyl" being as defined previously.

Process for treating keratinous fibers

The process for treating keratin fibers according to the invention comprises a step a) of applying to the keratin fibers a composition comprising at least one compound comprising at least two tetrazole groups and optionally at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

Compound comprising at least two tetrazole groups

It can be a non-polymeric organic molecule carrying at least two tetrazole groups, or a polymer carrying at least two tetrazole groups.

According to the invention, the names “polytetrazole compound”, “tetrazole compound”, “compound with tetrazole units” or “compound comprising at least two tetrazole groups” are equivalent.

The compound with tetrazole units can be aromatic, or heteroaromatic, or can comprise an aromatic radical.

The compound comprising at least two tetrazole groups according to the invention may also contain one or more heteroatoms chosen from O, S, N, and/or one or more functions chosen from esters, ketones, amides and ureas.

Preferably, said compound comprising at least two tetrazole groups according to the invention may also contain one or more heteroatoms chosen from O, N and/or one or more functions chosen from ester and amide functions.

According to a first variant, the compound with tetrazole units according to the invention designates a non-polymeric organic compound which can be represented by the following formula (A1): WW(TET) _n1 (A1), in which:
n ₁ denotes an integer greater than or equal to 2, preferably between 2 and 10, preferably between 2 and 5 and in particular 2;
WW denotes a multivalent (at least divalent) C ₂ to C ₃₀ radical, linear or branched or (hetero)cyclic, saturated, an aromatic radical, or a heteroaromatic cyclic radical, WW possibly also containing one or more heteroatoms such as O , N and/or one or more functions chosen from esters, ketones, amides, ureas, preferably esters, amides, and/or being substituted by one or more C ₁ to C ₁₀ alkyl groups, linear or branched, alkoxy C ₁ to C ₁₀ , linear or branched, it being understood that when the WW radical is substituted, the tetrazole groups can be carried by the substituent(s);
TET denotes a tetrazole group as defined above.

By cyclic radical is meant, within the meaning of the present invention, a saturated monocyclic, hydrocarbon-based or heterocyclic radical, a saturated or aromatic polycyclic radical, for example biphenyl, or condensed cycles, such as for example the naphthyl radical.

The molar mass of the compounds of formula (A1) is generally between 90 and 1500 g/mol.

According to a particular embodiment of the invention, the compound with tetrazole units of formula (A1) is such that n ₁ =2, and WW denotes a divalent saturated hydrocarbon radical C ₂ to C ₃₀ , linear or branched, optionally comprising one or more groups or heteroatoms chosen from O, S, N, CO, or their combinations such as -CO-O, -O-CO-, -CO-NH-, -NH-CO-.

According to a preferred embodiment, the compound containing tetrazole units of formula (A1) is such that n1=2 and is of formula (I) below. Thus, according to a preferred embodiment, said compound comprising at least two tetrazole groups has the following formula (I):
(I).

In this formula (I), A represents a hydrocarbon chain, linear or branched, saturated or unsaturated, C ₂ to C ₃₀ , optionally containing one or more groups or heteroatoms chosen from O, S, N, CO, or their combinations such as -CO-O, -O-CO-, -CO-NH-, -NH-CO-.

In this formula (I), R ₁ and R ₂ , which are identical or different, represent a C ₁ to C ₆ alkyl group or an aromatic group.

Preferably, A is of the following formula (IIA): -C(O)-X ₁ -BX ₂ -C(O)- (IIA),
in which:
X ₁ and X ₂ , which are identical or different, represent an oxygen atom or an NR group with R denoting a hydrogen atom or a C ₁ to C ₄ alkyl radical such as methyl;
B represents a linear or branched, saturated or unsaturated, C ₂ to C ₂₈ hydrocarbon chain, optionally interrupted by one or more heteroatoms chosen from O, S and N.

Preferably, B is C ₂ to C ₂₆ , more preferably C ₂ to C ₂₀ .

According to a particular embodiment, A has the following formula (IIIA): -C(O)-O-CH ₂ -CH ₂ -CH ₂ –[O-CH ₂ -CH ₂ -CH ₂ ] _n2 -OC(O )- (IIIA), in which n ₂ is an integer ranging from 1 to 8, preferably from 1 to 7; or of the following formula (IVA): -C(O)-NH-CH ₂ -CH ₂ -CH ₂ -[O-CH ₂ -CH ₂ ] _n3 -CH ₂ -NH-C(O)- (IVA), in which n ₃ is an integer ranging from 1 to 8, preferably from 1 to 7, more preferably from 1 to 3.

As indicated above, R ₁ and R ₂ , which are identical or different, represent a C ₁ to C ₆ alkyl group or an aromatic group. Preferably, R ₁ and R ₂ represent an aromatic group, preferably a phenyl group.

According to a second variant, the compound with tetrazole units according to the invention designates a polymeric compound, and which can be represented by the following formula (A2): POL(TET) _n4 (A2), in which:
n ₄ denotes an integer greater than or equal to 2, preferably between 2 and 1000, preferably between 2 and 500;
POL denotes a multivalent (at least divalent) carbon or silicone polymeric radical or comprising carbon and silicon atoms, POL possibly also comprising one or more heteroatoms such as O, N, S, and/or one or more functions chosen from the ester, ketone and amide functions, and/or be substituted by one or more C ₁ to C ₁₀ alkyl groups, linear or branched, C ₁ to C ₁₀ alkoxy, linear or branched, it being understood that when POL is substituted, the tetrazole groups can be carried by the substituent(s);
TET denotes a tetrazole group as defined above.

When POL designates a carbonaceous polymeric radical, the latter comprises at least 31 carbon atoms.

The molar mass of the compounds of formula (A2) is generally between 500 and 400,000 g/mol, preferably between 500 and 150,000 g/mol.

POL can designate a multivalent radical of the homopolymer or copolymer type; POL can refer to a star, comb, brush or dendritic polymeric radical.

The POL radical can be of natural origin (such as polysaccharides, peptides) or synthetic (such as acrylic polymers, polyesters, polyglycols).

The tetrazole units can be terminal and/or pendent groups.

According to a particular embodiment, POL can denote a polyglycol chain optionally terminated at each end by an ester or amide group. According to this mode, POL can designate a chain of formula -C(O)-X' ₁ -B ₁ -X' ₂ -C(O)- (IIB), in which:
X' ₁ and X' ₂ , which are identical or different, represent an oxygen atom or an NR' group with R' denoting a hydrogen atom or a C ₁ to C ₄ alkyl radical such as methyl, preferably a hydrogen;
B ₁ represents a linear or branched, saturated or unsaturated, C ₃₁ to C ₃₀₀₀ hydrocarbon chain, interrupted by one or more heteroatoms chosen from O, and optionally S and N.

Advantageously, B ₁ is interrupted by one or more oxygen atoms, preferably by several non-adjacent oxygen atoms.

According to a particular embodiment, B ₁ has the following formula (IIIB): -C(O)-O-CH ₂ -CH ₂ -CH ₂ –[O-CH ₂ -CH ₂ -CH ₂ ] _n5 -OC( O)- (IIIB), in which n ₅ is an integer ranging from 9 to 990, preferably from 9 to 500; or of the following formula (IVB): -C(O)-NH-CH ₂ -CH ₂ -CH ₂ -[O-CH ₂ -CH ₂ ] _n6 -CH ₂ -NH-C(O)- (IVB), in which n ₆ is an integer ranging from 9 to 1000, preferably from 9 to 500.

According to another particular embodiment, POL can denote a polymer of natural origin such as polysaccharides and polypeptides.

As an example of a polysaccharide that can be used for the preparation of the compounds containing tetrazole units of the invention, mention may be made of polysaccharides containing amine group(s), in particular those of average molecular weight MW less than or equal to to 400 KDa, in particular those with C ₅ -C ₇ osidic units, their α or β anomers, their optical isomers of L or D configuration, and more particularly polyhexosamines, whose osidic units are linked together between the carbon atoms 1 of one osidic unit and carbon 4 of the other osidic unit, denoted (1→4), such as the polysaccharide with amine group(s) of formula (Z1) below:
(Z1), in which:
the radicals _{R a} , R _b , R _c of each osidic unit can be identical or different;
n is an integer greater than or equal to 2, particularly between 3 and 2500, preferably between 10 and 2300;
R _a , R _b , and R _c , which are identical or different, represent a group i) hydroxy, ii) C ₁ to C ₄ alkoxy, the alkyl group of which may be optionally substituted in particular by one or more hydroxy groups, iii) carboxy, and iv) NR ₁₁ R ₂₁ with R ₁₁ and R ₂₁ , which are identical or different, representing i) a hydrogen atom, ii) a (C ₁ -C ₆ )alkyl group optionally substituted, preferably by one or more hydroxy groups or NH ₂ , iii) an aryl group such as phenyl, iv) an aryl(C ₁ -C ₄ )alkyl group such as benzyl, v) a (hetero)cyclo(C ₅ -C ₇ )alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidinyl, vi) a (hetero)cyclo(C ₅ -C ₇ )alkyl(C ₁ -C ₄ )alkyl group such as cyclohexylmethyl, vii) –C(Y)-(Y') _p -R' ₁₂ with Y and Y', identical or different, representing an oxygen, sulfur or N(R' ₂₁ ) atom, preferably oxygen, p=0 or 1, preferably 0; and R' ₁₂ and R' ₂₁ representing i) to vi) of R ₁₁ and R ₂₁ defined above, and in particular R' ₁₂ denoting a (C ₁ -C ₆ )alkyl group such as methyl, in particular R ₁₁ and R ₂₁ are chosen from a hydrogen atom and –C(O)-R′ ₁₂ in which R′ ₁₂ is as defined above; preferably R ₁₁ and R ₂₁ represent i) a hydrogen atom or ii) –C(O)-R' ₁₂ and R' ₁₂ represent a C ₁ to C ₄ alkyl group such as methyl;
it being understood that at least one of the R _a , R _b or Rc radicals of at least one osidic unit represents an NR ₁₁ R ₂₁ group and that at least one of the NR ₁₁ R ₂₁ groups of at least one osidic unit represents an NH ₂ group; preferably R _a of at least one osidic unit represents a group NR ₁₁ R ₂₁ with R ₁₁ which represents a hydrogen atom and R ₂₁ is chosen from i) a hydrogen atom or ii) a –C(O) group )-R' ₁₂ , and R _b and R _c represent a hydroxy group, it being understood that at least one of the NR ₁₁ R ₂₁ groups of at least one osidic unit represents an NH ₂ group.

More particularly, the polysaccharide containing amine group(s) has the following formula (Z2):
(Z2), in which:
R''' represents a hydrogen atom or a (C ₁ -C ₄ )alkylcarbonyl group such as acetyl CH ₃ -C(O)-;
R'' represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a carboxy group such as –CH(CO ₂ H)-CH ₃ ;
n is an integer greater than or equal to 2, particularly between 3 and 2500, preferably between 10 and 2300;
it being understood that in the polysaccharide (Z2) at least one osidic unit carries an amino group NH ₂ and at least one other osidic unit carries at least one N(H)-R' group with R' representing a group (C ₁ -C ₄ )alkylcarbonyl such as acetyl CH ₃ -C(O)-.

Preferably, the osidic units of formula (Z1) or (Z2) are of D configuration or also called D-glucopyrane. Particularly, the units of formula (Z1) or (Z2) are of β (beta) anomeric configuration. According to a particular embodiment, the polysaccharide containing amine groups is chosen from the compounds of formula (Z3) below:
(Z3), in which:
R _a , R _b , R _c are as defined for (Z1) above;
the radicals R _a , R _b , R _c of each osidic unit can be identical or different;
n is an integer greater than or equal to 2, particularly between 3 and 2500, preferably between 10 and 2300;
it being understood that in the polysaccharide (Z3) at least one of the R _a , R _b or R _c radicals of at least one osidic unit represents an NR ₁₁ R ₂₁ group and that at least one of the NR ₁₁ R ₂₁ groups of at at least one osidic unit represents an NH ₂ group; preferably at least one osidic unit carries a Ra amino NH ₂ group and at least one other osidic unit carries a Ra group which represents -N(H)-R' with R' representing a (C ₁ -C ₄ )alkylcarbonyl group such as as acetyl CH ₃ -C(O)-.

Preferably, the polysaccharide containing amine groups is chosen from chitin, chitosan and their derivatives, preferably chitosan.

More particularly, the polysaccharide containing amine groups is chosen from those of the following formula (Z4):
(Z4), in which:
R ₁₁ and R ₂₁ are as defined in formulas (Z1) and (Z3); And
n is an integer greater than or equal to 2, particularly between 3 and 3000, more particularly between 5 and 2500, preferentially between 10 and 2300;
it being understood that in the polysaccharide of formula (Z4) at least one osidic unit carries an amino group NH ₂ and at least one other osidic unit carries an N(H)-R' group with R' representing a group (C ₁ -C ₄ )alkylcarbonyl such as acetyl CH ₃ -C(O)-.

More particularly, the polysaccharide containing amine groups is chosen from the chitosans of formula (Z5) below:
(Z5), in which:
R′ ₁₁ represents a (C ₁ -C ₄ )alkyl group such as methyl;
n is an integer greater than or equal to 2, particularly between 3 and 3000, more particularly between 5 and 2500, preferentially between 10 and 2300;
p is greater than 0 and ranges up to 0.5, preferably from 0.05 to 0.3, and better still from 0.1 to 0.20 such as 0.15 with m+p being equal to 1;
it being understood that in chitosan at least one osidic unit carries an amino group NH ₂ and at least one other osidic unit carries an N(H)-R' ₁ group with R' representing a (C ₁ -C ₄ )alkylcarbonyl group such as acetyl CH ₃ -C(O)-.

For example, when m = 0.7, p = 0.3 this means that 70% of the amino groups are free (unsubstituted), and 30% of the amino groups are N-alkyl(C ₁ -C ₄ )carbonyl, in particular N-acetylated, corresponding to the chitosan polymer of formula (Z6) below:
(Z6),
with n which is as defined above, its α and β anomers, its optical isomers of L or D configuration and its solvates such as hydrates.

As an example of polymers of natural origin that can be used for the preparation of POL of compounds with tetrazole units according to the invention, mention may also be made of cellulose and collagen.

According to a particular form of the invention, POL is of formula (Z5).

According to another embodiment, the compound with tetrazole units according to the invention is such that POL designates a silicone polymeric radical.

The silicone polymeric radical can thus denote aminosilicone derivatives comprising at least two amine functions.

By way of example of aminosilicone derivatives comprising at least two amine functions, used to prepare the compounds with tetrazole units of the invention, mention may be made of:

a) the polysiloxanes of formula (WW1) below:
(WW1),
in which x' and y' are integers such that the weight average molecular weight (Mw) ranges from 5,000 to 300,000 g/mol; with y' greater than or equal to 2;

b) amino silicones of the following formula (WW2):
K' _a G _3-a -Si(OSiG ₂ ) _n -(OSiG _b K' _2-b ) _m -O-SiG _3-a -K' _a (WW2),
in which:
G, identical or different, denotes a hydrogen atom, a phenyl group, OH, C ₁ -C ₈ alkyl, for example methyl, or C ₁ -C ₈ alkoxy, for example methoxy,
a, identical or different, denotes 0 or an integer from 1 to 3, in particular 0,
b denotes 0 or 1, in particular 1,
m and n are numbers such that the sum (n + m) varies from 1 to 2000, in particular from 50 to 150, n being able to denote a number from 0 to 1999, and in particular from 49 to 149 and m being able to denote a number from 1 to 2000, and in particular from 1 to 10;
K', identical or different, denotes a monovalent radical of formula -C _q H _2q L in which q is a number ranging from 2 to 8, and L is an amino group - NH ₂ ;
Q denotes a group of formula C _r H _2r , linear or branched, r being an integer ranging from 2 to 6, preferably from 2 to 4;

c) multiblock polyoxyalkylenated amino silicones, of (AXBX) _n type, AX being polysiloxane and BX being a polyoxyalkylenated block comprising at least two amine groups;

d) amino silicones of formula (WW3) called “trimethylsilylamodimethicone”:
(WW3),
in which m and n are numbers such that the sum (n + m) varies from 1 to 2000, in particular from 50 to 150, n possibly denoting a number from 0 to 1999, and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10, with m greater than or equal to 2;

e) amino silicones of formula (WW4):
(WW4), in which:
m and n are numbers such that the sum (n+m) varies from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n possibly denoting a number from 0 to 999 and in particular from 49 to 249 and more particularly from 125 to 175 and m possibly denoting a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5; with m greater than or equal to 2;
Q ₁ , Q ₂ , Q ₃ , identical or different, represent a hydroxy or C ₁ -C ₄ alkoxy radical, at least one of the radicals Q ₁ to Q ₃ designating an alkoxy radical.

Preferably the alkoxy radical is a methoxy radical.

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

The weight-average molecular weight (Mw) of these silicones preferably ranges from 2,000 to 1,000,000, more particularly from 3,500 to 200,000;

f) amino silicones of the following formula (WW5):
(WW5), in which:
p and q are numbers such that the sum (p+q) varies from 1 to 1000, in particular from 50 to 350, and more particularly from 150 to 250; p possibly denoting a number from 0 to 999 and in particular from 49 to 349 and more particularly from 159 to 239 and q possibly denoting a number from 2 to 1000, in particular from 2 to 10 and more particularly from 2 to 5;
T ₁ , T ₂ , which are different, represent a C ₁ -C ₄ hydroxy or alkoxy radical, at least one of the T ₁ or T ₂ radicals designating an alkoxy radical.

Preferably the alkoxy radical is a methoxy radical.

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

The weight-average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200000 g/mol and even more particularly from 5000 to 100000 and more particularly from 10000 to 50000.

Commercial products comprising structural silicones (WW4) or (WW5) may include in their composition one or more other amino silicones whose structure is different from formulas (WW4) or (WW5):

g) amino silicones of the following formula (WW6):
(WW6), in which:
m and n are numbers such that the sum (n + m) varies from 1 to 2000 and in particular from 50 to 150, n being able to denote a number from 0 to 1999 and in particular from 49 to 149 and m being able to denote a number from 2 to 2000, and in particular from 2 to 10;
A denotes a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1000000 g/mol and even more particularly from 3500 to 200000;

h) amino silicones of the following formula (WW7):
(WW7), in which:
m and n are numbers such that the sum (n + m) varies from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and in particular from 49 to 149 and m possibly denoting a number from 2 to 2000, and in particular from 2 to 10;
A denotes a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1,000,000 g/mol and even more particularly from 1,000 to 200,000 g/mol;

i) amino silicones of the following formula (WW8):
(WW8), in which:
m and n are numbers ranging from 2 to 5000 and in particular, n being able to designate a number ranging from 10 to 2000 and in particular ranging from 100 to 1000 and in particular m being able to designate a number from 1 to 100;
S ₁ and S ₂ , identical or different, preferably identical, represent a linear or branched, saturated or unsaturated alkyl radical, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms. carbon;
A denotes a linear or branched alkylene radical having from 3 to 8 carbon atoms and preferably 4 carbon atoms, this radical is preferably branched.

Preferably, A comprises from 3 to 6 carbon atoms, better still 4 carbon atoms, preferably A is branched. In particular, A denotes the following divalent radicals: -CH ₂ CH ₂ CH ₂ - or –CH ₂ CH(CH ₃ )CH ₂ -.

Preferably, S ₁ and S ₂ , which are identical or different, represent a saturated linear alkyl radical, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms; in particular S ₁ and S ₂ denote dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, S ₁ and S ₂ , which are identical or different, are chosen from hexadecyl or octadecyl radicals.

Preferably, the amino silicones of formula (WW8) are such that:
n is a number ranging from 10 to 2000 and in particular from 100 to 1000;
m is a number ranging from 1 to 100;
S ₁ and S ₂ , which are identical or different, represent a saturated linear alkyl radical, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms; chosen in particular from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, S ₁ and S ₂ , which are identical or different, are chosen from hexadecyl or octadecyl radicals; And
A comprises 3 to 6 carbon atoms, preferably 4 carbon atoms; preferably A is branched; and more preferably A is chosen from the following divalent radicals: -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH(CH ₃ )CH ₂ -.

j) amino silicones of the following formula (WW9):
(WW9),
wherein the value of n is such that the weight average molecular weight (Mw) of the silicone ranges from 500 to 55000 g/mol.

The silicone polymeric radical can also denote polyhydroxylated silicone derivatives comprising at least two hydroxyl functions.

By way of example of polyhydroxylated silicones, mention may be made of the compounds of formula (WW10) below:
(WW10), in which:
V1, identical or different, independently represents a hydroxy group; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 to 2 carbon atoms such as a methyl; an alkoxy group having 1 to 2 carbon atoms; or a –(CH ₂ ) _s —Si(R ₄ ) ₃ group in which s denotes an integer ranging from 1 to 4 such as 2 and R ₄ independently denotes an alkoxy radical having from 1 to 2 carbon atoms;
V' ₂ and V'' ₂ independently represent an alkyl group having from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms such as a methyl;
a denotes an integer ranging from 0 to 10, b denotes an integer ranging from 0 to 500, with a+b≥4.

Among the silicones of formula (WW10), mention may be made of polydimethylsiloxanes (PDMS) with terminal hydroxy functions such as the compounds sold by the company Sigma Aldrich under the reference 481939 (Mn ~550, ~25 cSt), 481955 (~65 cSt ), or 481963 (~750 cSt).

Mention may also be made of the compounds sold by the company Gelest under the name DMS-S12 (16~32 cSt), DMS-S15 (45-85 cst), DMS-S21 (90-120 cst), DMS-S27 (700- 800 cst) or DMS-S31 (~1000 cSt).

Advantageously, the composition according to the invention comprises a mixture of at least two compounds comprising at least two tetrazole groups according to the invention.

It may be a mixture of compounds of structure WW(TET) _n1 , mixtures of compounds (POL(TET) _n4 or mixtures of at least one compound WW(TET) _n1 and at least one compound POL( TET) _n4 , in all proportions.

Preferably, the compounds comprising at least two tetrazole groups according to the invention are chosen from:
the compounds of formula (V) below, and mixtures thereof:
(V),
in which n ₇ is an integer ranging from 1 to 990, preferably from 1 to 100, more preferably from 1 to 45;
and the compounds of formula (VI) below, and mixtures thereof:
(VI),
in which n ₈ is an integer ranging from 1 to 1000, preferably from 1 to 100, more preferably from 1 to 3.

Preferably, n ₈ is an integer which can be 1, 2 or 3.

Very advantageously, the compound or compounds comprising at least two tetrazole groups according to the invention are chosen from the following compounds:
Compound 1
_n8 = 3 Compound 2
n ₇ = 1 Compound 3
n ₇ = 2 Compound 4
n ₇ = 3

their mixtures and the compounds of formula (V) as defined above, in which n ₇ is an integer ranging from 7 to 45.

Preferably, said compound or compounds comprising at least two tetrazole groups according to the invention are present in a content ranging from 0.01 to 15% by weight, preferably from 0.2 to 10% by weight relative to the total weight of the composition.

Coloring agent

The composition according to the invention optionally at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

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

The term “pigment” is understood to mean, within the meaning of the present invention, all the pigments providing color to keratin materials. Their solubility in water at 25° C. and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

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

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

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

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

The pigment can be an inorganic pigment. By "mineral pigment" is meant, within the meaning of the present invention, any pigment which meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment. By "organic pigment" is meant, within the meaning of the present invention, any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter.

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

In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525 , 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679771.

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

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

The organic pigment can also be a lake. By lacquer is meant, within the meaning of the present invention, the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use.

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

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

As examples of lacquers, mention may be made of the product known under the following name: D & C Red 7 (CI 15,850:1).

The pigment may also be a special effect pigment. By special effect pigments is meant, within the meaning of the present invention, pigments which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is not uniform and changes according to the observation conditions (light, temperature, observation angles, etc.). They are therefore opposed to colored pigments which provide a uniform opaque, semi-transparent or transparent classic shade.

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

As examples of special effect pigments, mention may be made of pearlescent pigments such as mica covered with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica covered with titanium and iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide, mica covered with titanium and an organic pigment as defined previously as well as pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, mention may be made of Cellini nacres marketed by BASF (Mica-TiO ₂ -lacquer), Prestige marketed by Eckart (Mica-TiO ₂ ), Prestige Bronze marketed by Eckart (Mica-Fe ₂ O ₃ ) Colorona marketed by Merck (Mica-TiO ₂ -Fe ₂ O ₃ ).

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

Still by way of example of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

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

Finally, as examples of nacres, mention may also be made of polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). One can also consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

The special effect pigments can also be chosen from reflective particles, that is to say in particular particles whose size, structure, in particular the thickness of the layer or layers which constitute it and their physical and chemical natures, and the surface finish, allow them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, that is i.e. brighter points that contrast with their surroundings by seeming to shine.

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

These particles can have various shapes, in particular be in the form of platelets or globular, in particular spherical.

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

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

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

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

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

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

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

Particles with a glass substrate coated with silver, in the form of platelets, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Particles with a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by this same company.

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

Mention may be made, by way of example, of the aluminum, bronze or copper powders coated with SiO ₂ marketed under the name VISIONAIRE by the company ECKART.

Mention may also be made of pigments with an interference effect not fixed on a substrate, such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the Quantum Dots Corporation.

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

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

The pigments can be dispersed in the composition according to the invention using a dispersing agent.

The dispersing agent serves to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, bearing one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can cling physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C ₈ to C ₂₀ fatty acid and of polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid stearate) are used. ) with a molecular weight of approximately 750 g/mole, such as that sold under the name Solsperse 21,000 by the company Avecia, the polygyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or the acid polyhydroxystearic such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures.

As other dispersant which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17000 sold by the company Avecia, mixtures of polydimethylsiloxane/oxypropylene such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

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

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

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

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

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

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

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

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

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

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

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

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

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

The dispersing agent(s) can therefore have a silicone skeleton, such as silicone polyether and dispersants of the amino-silicone type, different from the alkoxysilanes previously described. Suitable dispersing agents include:

amino-silicones i.e. silicones comprising one or more amino groups such as those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP -967 and GP-988-1, marketed by Genesee polymers,

silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP -607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

According to one particular embodiment, the dispersing agent(s) are of the amino-silicone type, different from the compounds described above and are cationic.

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

The composition can include at least one direct dye.

By "direct dye" is meant, within the meaning of the present invention, natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber.

They can be ionic or nonionic, preferably anionic, cationic or nonionic.

Examples of suitable direct dyes which may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

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

In particular, mention may be made of direct dyes with cationic charge, endocyclic azo and hydrazono of formula (VIII) to (XI) as defined above. More particularly, the cationic direct dyes with endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954, preferably the following direct dyes:
(XII),
(XIII),
formulas in which:
R ¹ represents a C1 to C4 alkyl group such as methyl;
R ² and R ³ , which are identical or different, represent a hydrogen atom or a C ₁ to C ₄ alkyl group such as methyl; And
R ⁴ represents a hydrogen atom or an electron-donating group such as optionally substituted C ₁ to C ₈ alkyl, optionally substituted C ₁ to C ₈ alkoxy, optionally substituted (di)(C ₁ -C ₈ )(alkyl)amino on the alkyl group(s) by a hydroxyl group; especially R ⁴ is hydrogen;
Z represents a CH group or a nitrogen atom, preferably CH;
Q- is an anionic counter ion as defined previously, particularly halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

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

The direct dyes can be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances. By anionic direct dyes is meant, within the meaning of the present invention, any direct dye comprising in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes can be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

As acid dyes according to the invention, mention may be made of the dyes of formulas (XIV), (XIV'), (XV), (XV'), (XVI), (XVI'), (XVII), (XVII' ), (XVIII), (XIX), (XX) and (XXI) following:

a) diaryl anionic azo dyes of formula (XIV) or (XIV'):
(XIV),
(XIV'),
formulas in which:
R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ , which are identical or different, represent a hydrogen atom or a group chosen from:
alkyl;
alkoxy, alkylthio;
hydroxy, mercapto;
nitro, nitroso;
R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, a alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
(O) ₂ S(O ^- )-, M+ with M+ representing a hydrogen atom or a cationic counterion;
(O)CO--, M+ with M+ as defined previously;
R''-S(O)2-, with R'' representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group;
R'''-S(O)2-X'- with R''' representing an optionally substituted alkyl or aryl group, X' as defined previously;
(di)(alkyl)amino;
aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+ and iv) alkoxy with M+ as defined previously;
optionally substituted heteroaryl; preferentially a benzothiazolyl group;
cycloalkyl; in particular cyclohexyl,
Ar-N=N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O) ₂ S(O-)-, M+ or phenylamino groups;
or else two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused group benzo A'; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a fused group benzo B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+; iv) hydroxy; (v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X'' and Ar as previously defined;
W represents a sigma σ bond, an oxygen or sulfur atom, or a divalent radical i) –NR- with R as previously defined, or ii) methylene -C(R _a )(R _b )- with R _a and R _b which are identical or different, representing a hydrogen atom or an aryl group, or else R _a and R _b together with the carbon atom which bears them form a spiro cycloalkyl; preferably W represents a sulfur atom or R _a and R _b together form a cyclohexyl;
it being understood that the formulas (XIV) and (XIV') comprise at least one sulfonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical (O)CO--, M+ on one of the rings A, A ', B, B' or C; preferentially sodium sulphonate.

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

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

By way of example of dyes of formula (XV), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (XV'), mention may be made of: Acid Yellow 17.

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

Examples of dyes of formula (XVI) 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 purple #2; and by way of example of dyes of formula (XVI′), mention may be made of: Acid Black 48.

d) nitro dyes of formula (XVII), (XVII'):
(XVII),
(XVII'),
formulas (XVII) and (XVII') in which:
R ₃₀ , R ₃₁ and R ₃₂ , which are identical or different, represent a hydrogen or halogen atom, or a group chosen from:
alkyl;
alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;
hydroxy, mercapto;
nitro, nitroso;
polyhaloalkyl;
R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°; X, X' and X'' as defined previously;
(O) ₂ S(O-)-, M+ with M+ as defined above;
(O)CO--, M+ with M+ as defined above;
(di)(alkyl)amino;
(di)(hydroxyalkyl)amino;
heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R ₃₀ , R ₃₁ and R ₃₂ represent a hydrogen atom;
R _c and R _d , which are identical or different, represent a hydrogen atom or an alkyl group;
W is as previously defined; W particularly represents an –NH– group;
ALK represents a linear or branched, C ₁ -C ₆ divalent alkylene group; particularly ALK represents a -CH ₂ -CH ₂ - group;
n is 1 or 2;
p represents an integer between 1 and 5;
q represents an integer between 1 and 4;
u is 0 or 1;
when n is 1, J represents a nitro or nitroso group; especially nitro;
when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –S(O) _m – with m representing an integer 1 or 2; preferably J represents a –SO ₂ – radical;
M' represents a hydrogen atom or a cationic counterion;
present or absent represents a benzo group optionally substituted by one or more R ₃₀ groups as defined previously;
it being understood that the formulas (XVII) and (XVII') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulphonate.

By way of example of dyes of formula (XVII), mention may be made of: Acid Brown 13; Acid Orange 3; as examples of dyes of formula (XVII'), mention may be made of: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitro benzene acid sulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7.

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

By way of example of dyes of formula (XVIII), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

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

By way of example of dyes of formula (XIX), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

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

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

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

By way of example of dyes of formula (XXI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

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

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

When they are present, the content of the pigment(s) advantageously ranges from 0.05 to 15% by weight, preferably from 0.1 to 10% by weight relative to the total weight of the composition according to the invention.

When they are present, the content of the direct dye(s) advantageously ranges from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight relative to the total weight of the composition according to the invention.

Additional components

Advantageously, the composition according to the invention may also comprise one or more silicones.

Preferably, the silicone(s) are chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organo-modified polysiloxanes comprising at least one functional group chosen from amino groups, hydroxyls, oxyalkylenated groups, aryl groups and alkoxy groups. .

The organopolysiloxanes are defined in more detail in the work by Walter NOLL “Chemistry and Technology of Silicones” (1968), Academie Press. They can be volatile or non-volatile.

The non-volatile silicones which can be used in the composition according to the invention can preferably be non-volatile polydialkylsiloxanes, polyorganosiloxanes modified with organofunctional groups chosen from amino groups, aryl groups, oxyalkylenated groups and alkoxy groups, as well as mixtures thereof.

According to a particular embodiment of the invention, the silicones are chosen from amino silicones. Preferably, said amino silicones are different from the amino silicones previously described.

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

Preferably, the amino silicone(s) capable of being used in the context of the invention are chosen from:

a) silicones called "trimethylsilylamodimethicone" corresponding to formula (C):

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

b) amino silicones of the following formula (J):
,
in which :
m and n are numbers ranging from 1 to 5000 and in particular, n being able to designate a number ranging from 10 to 2000 and in particular ranging from 100 to 1000 and in particular m being able to designate a number from 1 to 100;
R ₁ and R ₂ , identical or different, preferably identical, represent a linear or branched, saturated or unsaturated alkyl radical, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms. carbon;
A denotes a linear or branched alkylene radical having from 3 to 8 carbon atoms, preferably 4 carbon atoms, this radical is preferably branched.

Preferably, A comprises from 3 to 6 carbon atoms, better still 4 carbon atoms, preferably A is branched. In particular, A can denote the following divalent radicals: -CH ₂ CH ₂ CH ₂ - or –CH ₂ CH(CH ₃ )CH ₂ -.

Preferably, R ₁ and R ₂ , which are identical or different, represent a saturated linear alkyl radical, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms; in particular R1 and R2 denote dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, R ₁ and R ₂ , which are identical or different, are chosen from hexadecyl or octadecyl radicals.

Preferably, the amino silicones of formula (J) are such that:
n is a number ranging from 10 to 2000 and in particular from 100 to 1000;
m is a number ranging from 1 to 100;
R ₁ and R ₂ , which are identical or different, represent a saturated linear alkyl radical, comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms; chosen in particular from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, R1 and R2, which are identical or different, are chosen from the hexadecyl or octadecyl radicals; And
A comprises from 3 to 6 carbon atoms, preferably 4 carbon atoms; preferably A is branched; and more preferably A is chosen from the following divalent radicals: -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH(CH ₃ )CH ₂ -.

The amino silicones of formula (J) which are particularly preferred are those corresponding to the INCI name bis-cetearylamodimethicone. In particular, the amino silicones of formula (J) correspond to the silicone marketed by the company Momentive under the name Silsoft AX;

c) amino silicones of formula (K) below:
,
wherein the n value is such that the weight average molecular weight (Mw) of the silicone ranges from 500 to 55,000 g/mol.

As examples of amino silicones corresponding to the formula (K), mention may be made of those sold under the names “DMS-A11”, “DMS-A12”, “DMS-A15”, “DMS-A21”, “DMS-A31”. , “DMS-A32, “DMS-A35” by the company GELEST, “reference 481688” from Aldrich.

Advantageously, the composition according to the invention also comprises one or more silicones; preferably chosen from amino silicones, silicones with oxyalkylenated groups, and mixtures thereof.

The composition used in the process according to the invention may optionally also comprise one or more organic solvents.

By way of organic solvent, mention may be made, for example, of lower C ₂ -C ₄ alcohols, such as ethanol and isopropanol; polyols, in particular those having from 2 to 6 carbon atoms such as glycerin, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, polyol ethers such as 2- butoxyethanol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether; and their mixtures.

The content of the organic solvent(s), when they are present in the composition used in the process according to the invention, preferably ranges from 1 to 98% by weight, relative to the total weight of the composition.

According to a particular embodiment of the invention, the water content, when it is present in the composition used in the process according to the invention, ranges from 40 to 99.8% by weight of water with respect to the total weight of the composition.

According to another embodiment of the invention, the composition comprises a mixture comprising water and one or more organic solvents, preferably a water/ethanol mixture.

According to another embodiment, the composition is anhydrous. The term “anhydrous composition” is understood to mean a composition containing less than 2% by weight of water, or even less than 0.5% by weight of water, relative to the total weight of the composition, and in particular free of water; if necessary, such small amounts of water can in particular be introduced by ingredients of the composition which can contain residual amounts thereof

The composition according to the invention may also contain one or more additives usually used in cosmetics chosen from nonionic, anionic, amphoteric and cationic surfactants, vitamins and pro-vitamins including panthenol, fillers, oils, opacifying agents, sequestering agents, film-forming polymers, thickening agents, antioxidants, antifoaming agents, moisturizing agents, emollients, penetrating agents, perfumes and preservatives.

Preferably, when the additive(s) above are present in the composition according to the invention, the additive(s) are generally present in an amount comprised for each of them between 0.01 and 20% by weight relative to the composition weight.

Of course, those skilled in the art will take care to choose this or these possible additives in such a way that the advantageous properties intrinsically attached to the composition of the invention are not, or substantially not, altered by the addition or additions envisaged.

Energy intake

The method according to the invention further comprises a step b) of supplying energy to the keratin fibers chosen from a heat treatment using a heating means and/or irradiation by artificial or natural light radiation.

According to the invention, step b) can be a step of heat treatment of the keratin fibers using a heating means.

Preferably, the temperature of the heating means ranges from 60 to 230°C.

The heating means that can be used according to the invention can be chosen from those commonly used in the field of hair cosmetics.

Preferably, the heating means are chosen from hair dryers, irons such as straightening irons, steam irons, curling irons, pinking irons, curlers; preferentially among the irons.

It is also possible to combine several means of heating, such as in particular the use of a hair dryer, a heated brush or a helmet and then the use of an iron.

According to a particular embodiment of the invention, the heating means is chosen from hair dryers and heated helmets. According to this embodiment, the heating means can be applied to dry or wet keratin fibers.

More preferentially according to this embodiment of the invention, the temperature of the hair dryer or the heating cap is greater than or equal to 60° C., more preferentially still ranges from 60 to 100° C., even better from 70 to 80° C. .

Preferably, the duration of heat treatment of the keratin fibers using a hair dryer or a heated helmet is between 30 seconds and 60 minutes, more preferably between 1 minute and 45 minutes, more preferably still between 2 minutes and 30 minutes, even better between 3 minutes and 20 minutes.

According to another preferred embodiment of the invention, the heating means is chosen from irons. According to this embodiment, the heating means is applied to dry keratin fibers, that is to say keratin fibers previously dried in the air or using a device of the hair dryer or helmet type. heater whose temperature is below 80°C.

More preferably according to this embodiment of the invention, the temperature of the iron is greater than or equal to 100° C., more preferably still ranges from 100 to 230° C., more particularly from 120 to 230° C., even more particularly from 130 at 210°C, even better from 140 to 200°C, or even from 140 to 190°C.

Preferably, the duration of heat treatment of the keratinous fibers using an iron ranges from 100 milliseconds to 2 minutes, more preferably from 500 milliseconds to 1 minute, even more preferably from 1 second to 30 seconds, even better still from 3 seconds to 20 seconds, or even from 4 seconds to 10 seconds. This heating step can be repeated several times on each lock of keratin fibers.

According to a particular form of the invention, the step of heating with iron is carried out on dry keratin fibers, that is to say that a step of drying in the air or with a helmet or with a heated brush or with a hair dryer precedes the heat treatment stage with an iron.

By “iron”, is meant within the meaning of the present invention, a means for heating the keratin fibers in contact with said keratin fibers.

By way of example of irons that can be used according to the invention, mention may be made of all types of flat iron, and for example those described in patents US 5,957,140 and US 5,046,516.

The iron can be applied to said keratin fibers by successive strokes separated by a few seconds, or by displacement or progressive sliding along the keratin fibers.

Preferably, the iron is applied by continuous movement from the root to the tip of said keratin fibres, in one or more passes.

According to the invention, step b) can be a step of irradiating the keratin fibers with artificial or natural light radiation.

According to one embodiment, the light radiation is natural.

For the purposes of the invention, the term "natural light radiation" means light radiation from natural daylight (generated by the sun).

According to another embodiment of the invention, the light radiation is artificial, and can be continuous or non-continuous.

For the purposes of the invention, the term “artificial light radiation” means light radiation different from natural daylight (generated by the sun).

Preferably, the exposure of the keratin fibers to artificial light radiation is carried out at a wavelength ranging from 320 to 480 nm, preferably from 400 to 480 nm.

Preferably, the artificial light radiation has a quantity of energy per unit area greater than or equal to 1 J/cm ² , more preferably strictly greater than 1 J/cm ² , more preferably still ranges from 1.001 to 100 J/cm ² , even better from 2 to 50 J/cm ² , and particularly preferably from 3 to 10 J/cm ² .

Advantageously, the artificial light radiation is generated using a device chosen from arc lamps such as xenon lamps and mercury lamps, fluorescent lamps, incandescent lamps such as halogens, light-emitting diodes (LEDs), organic light-emitting diodes (LEDs), and lasers.

By way of example, mention may be made of the goLITE BLU from the company Philips, the Energylight HF 3319/01 lamp from the company Philips, the Dayvia White and Messa lamps from the company Solvital, the Lumino Plus lamp from the company Lanaform , the medibeam lamp from the Medibeam company, the M-LED 01 lamp from the Meimed company, the Lifemax light pod lamp from the Lifemax company, the Lite-Pad lamp from the Reicorp company, the Omnilux Clear-U and New-U lamps from Omnilux, the 1000W Xenon Arc lamp from Lot-Oriel and the Camag Box 3 lamp (4x8W) from Camag.

Preferably, the duration of exposure of the keratinous fibers to natural or artificial light radiation is greater than or equal to 5 seconds, more preferably ranges from 10 seconds to 60 minutes, even more preferably from 15 seconds to 55 minutes, even better still from 20 seconds to 45 minutes.

According to another preferred embodiment of the invention, the step of irradiation with artificial light radiation is carried out in static mode (that is to say for example that the lamp does not move relative to the hair such as a lamp placed fixed above the head). Preferably, the duration of exposure of the keratinous fibers to artificial light radiation is greater than or equal to 5 seconds, more preferably ranging from 10 seconds to 60 minutes, even more preferably from 15 seconds to 55 minutes, even better still from 20 seconds at 45 minutes.

According to a preferred embodiment, when the method according to the invention comprises step a) followed by step b), that is to say when step b) is implemented after step a ), the duration of exposure of the keratin fibers to artificial light radiation ranges from 5 seconds to 45 minutes; optionally a step of applying the composition according to the invention to said keratin fibers ranging from 1 second to 3 hours is carried out between step a) and step b); optionally a step of rinsing said keratin fibers is carried out in step b).

According to yet another preferred embodiment of the invention, the step of irradiation with artificial light radiation is carried out in dynamic mode (that is to say for example that the lamp moves relative to the hair). Preferably, the duration of exposure of the keratin fibers to artificial light radiation is the time required to pass the lamp over the hair and ranges from 100 milliseconds to 2 minutes, preferably from 500 milliseconds to 1 minute, more preferably from 1 second. to 30 seconds, more preferably still from 3 seconds to 20 seconds, even better from 4 seconds to 10 seconds. This step can be repeated as many times as necessary so that each exposed hair or group of hairs undergoes a cumulative exposure greater than 5 seconds and less than 1 hour, in particular from 20 seconds to 45 minutes.

According to a particular embodiment of the invention, step b) comprises a heat treatment using a heating means and irradiation by artificial or natural light radiation, preferably a heat treatment using a heating means followed by irradiation by artificial or natural light radiation, more preferably heat treatment using a heating means and irradiation by artificial light radiation, or even irradiation by a radiation device irradiation by heating light radiation.

Advantageously, the method according to the invention comprises step a) followed by step b), that is to say that step b) is implemented after step a).

Preferably, the composition applied in step a) is left to set for between 1 second and 3 hours before the implementation of treatment step b).

At the end of treatment step b), the keratin fibers are optionally rinsed with water or washed with a shampoo. The keratin fibers can then be dried or left to dry.

Advantageously, the composition is applied in step a) according to a ratio of bath weight of composition/weight of hair ranging from 0.5 to 1.

Compound comprising at least two tetrazole groups

Another object of the invention relates to the compound(s) comprising at least two tetrazole groups.

Preferably, these compounds are those of formula WW(TET) _n1 defined previously, in particular the compounds of formula (I), and those of formula POL(TET) _n4 , and mixtures thereof. More preferably, they are chosen from compounds of formula (V), compounds of formula (VI), and mixtures thereof.

The compounds comprising at least two tetrazole groups according to the invention have the same preferences and the same embodiments as those included in the composition applied in step a) of the method according to the invention described above.

Composition

A subject of the invention is also a composition comprising one or more compounds comprising at least two tetrazole groups according to the invention.

Preferably, said composition comprises at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

The composition according to the invention may comprise one or more compounds of WW(TET) _n1 structure, as defined above, one or more compounds of POL(TET) _n4 structure, as defined above, a mixture comprising at least one compound of WW(TET) _n1 structure and at least one compound of POL(TET) _n4 structure.

The composition according to the invention has the same preferences and the same embodiments as the composition applied in step a) of the method according to the invention described above.

The composition according to the invention can be in all the pharmaceutical forms conventionally used for hair application.

Another subject of the invention is the use of at least one compound according to the invention or of at least one composition according to the invention for the care and/or repair of keratin fibers, preferably the repair of fibers keratins, more preferably the repair of split ends.

The invention also relates to a process for dyeing keratin fibers comprising the application of at least one composition according to the invention, and comprising at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and a step of providing energy to the keratin fibers by heat treatment and/or by irradiation using artificial or natural radiation.

Another object of the invention is the use of the composition comprising one or more compounds comprising at least two tetrazole groups according to the invention and at least one coloring agent chosen from pigments, direct dyes and mixtures thereof, for coloring keratin fibers.

The following examples serve to illustrate the invention without however being limiting.

Examples

In the following text, the term “alkaline solubility (AS)”, within the meaning of the present invention, means the loss of mass of a sample of 100 mg of keratin fibers under the action of a decinormal sodium hydroxide solution during 30 mins at 65°C.

Example 1

1. Preparation of Compound 1

Compound 1 is the following compound, for which n8 = 3:

Compound 1 was prepared with the following ingredients and according to the following protocol with the ingredients indicated in Table 2:
n (mmol) m (mg) Volume (mL) ACTP 0.53 100 - DCC 0.53 109 - TTD 0.24 52.8 - _{CH2Cl2 _} - - 30

PTCA: 2-Phenyl-2H-tetrazole-5-carboxylic acid;
DCC: N,N′-Dicyclohexylcarbodiimide;
TTD: 4,7,10-trioxa-1,13-Tridecanediamine.

The PTCA dissolved in dichloromethane was added to a 50mL three-necked flask with magnetic stirring. Once dissolved, the DCC was added to the medium. The mixture was refluxed for 40 minutes. A CCM follow-up was carried out to follow the reaction: ethyl acetate. Rf PTCA=0; Rf compound solvent front = 0.83.

The TTD was added to the reaction medium via the dropping funnel. The reaction was maintained for 50 minutes after the addition of the diamine. The contents of the flask were then evaporated using a rotary evaporator. Compound 1 was purified by chromatography on a silica column using a heptane/AcOET solvent gradient. At the end of the purification, 58 mg of compound were obtained. HPLC/MS (Peak at 564) and NMR analyzes confirmed the expected structure.

2. Preparation of composition 1

Composition 1 was prepared from the ingredients indicated in Table 3 below, the amounts of which are expressed in% by weight of active ingredient (AM).

Composition 1 Compound 1 10 PEG-12 dimethicone (1) 0.4 Water/ethanol (50/50) Qsp 100%

(1) PEG-12 dimethicone: reference Xiameter OFX-0193 fluid from Dow Corning.

3. Evaluation of keratin fiber repair

A. Procedure – preparation of 4 locks

A lock of hair was moistened (bleached hair with an alkaline solubility value of 20) by soaking it in MilliQ water. The wick was then spread on a plastic film placed on a heating plate at 33°C. Composition 1 was applied to the lock with a 1:1 bath ratio (1 g of composition for 1 g of lock of hair). The lock was then kneaded with the fingers by making circular movements all along the lock (10 times). The wick was covered with aluminum foil, then the wick was left 2 minutes on each side on the heating plate. The lock was then combed out.

The lock of hair was then irradiated for 20 minutes (10 minutes on each side) with a UV lamp (power: 7 to 8 mW/cm2; wavelength: 254 nm).

Then, a shampoo was carried out with the DOP shampoo according to the following protocol: wetting of the locks with tap water at 38°C for 10 seconds, then application of the shampoo (0.4 g/g of hair), then massage of the wick for 15 seconds, then rinse with water for 20 seconds.

The lock is then dried under a helmet at 60° C. (10 minutes per gram of lock of hair). Finally, the wick was combed.

This is the lock treated according to the process according to the invention. It is called in the following wick A.

A second lock was prepared according to a procedure which differs from that above in that, during the step of irradiating the lock with the UV lamp, it was covered with aluminum foil. to protect it from UV radiation. It is a wick treated according to a comparative process. This wick is called comparative wick B.

A third wick has been prepared. On this lock, no composition was applied. It was shampooed with DOP shampoo, then dried under a hood at 60° C. (10 minutes per gram of lock of hair). Finally, the wick was combed. It is a wick treated according to a comparative process. This wick is called comparative wick C.

A fourth wick has been prepared. On this lock, no composition was applied. The lock of hair was irradiated for 20 minutes (10 minutes on each side) with a UV lamp (power: 7 to 8 mW/cm2; wavelength: 254 nm).

This lock was then shampooed with DOP shampoo, then dried under a hood at 60° C. (10 minutes per gram of lock of hair). Finally, the wick was combed. It is a wick treated according to a comparative process. This wick is called comparative wick D.

B. Study of hair breakage by the cyclic fatigue test

The cyclic fatigue technique is known to those skilled in the art for the breakage of keratin fibers (reference: https://www.diastron.com/app/uploads/2017/06/Dia-Stron-CYC801-Brochure. pdf). The principle of the test is to measure the number of extension cycles of a single fiber before the fibers break. The 30 mm long fibers were subjected to a constant tension (100 MPa) at a constant speed (40 mm/s). The studies were carried out at 25°C and 45% relative humidity. A Diastron CYC801 device from Diastron was used. A measurement series comprised 50 hairs. The results have been collated in Table 4 below.
Wick A (inv.) B (comp.) C (comp.) D (comp.) Number of cycles before breakage 12972 3457 4332 3026

The results above clearly show that the performance in terms of anti-hair breakage was better for the lock treated with the process according to the invention A than for the comparative locks B, C and D. Indeed, the lock treated with the method of the invention withstood more than 12,000 cycles while the comparative locks broke rapidly.

C. Differential scanning calorimetry study

The differential scanning calorimetry technique is known to those skilled in the art as a method which makes it possible to quantify the reinforcement of proteins in the cortex of keratin fibers. The principle of the test is to measure the denaturation temperature of proteins. The higher the protein denaturation temperature, the better the protein integrity of the cortex, resulting in less fiber breakage.

The denaturation temperature is directly related to the binding density of the keratin proteins present in the cortex. Thus, the lower the denaturation temperature, the lower the bond density of the proteins between them. In fact, the disulphide bridges break down, and the cortex is damaged. The test was performed and the results are collated in Table 5 below:
Wick A (inv.) C (comp.) D (comp.) Denaturation temperature (°C) 148.4 146.4 144.9

An increase in the denaturation temperature of the hair of 2° C. was observed for lock A compared to lock C. The application of composition 1 to lock A caused this increase. This means that a reinforcement of the protein network of the cortex has taken place. Protein bond density is higher, so bonds have formed within the cortex.

On the other hand, a significant reduction in the denaturation temperature was observed for lock D. The treatment of the lock by irradiation with UV light without application of composition 1 caused degradation of the fiber.

The results thus show that there was a better performance in terms of hair integrity, in comparison with the locks of hair treated with a comparative process.

The results clearly show that the performance in terms of anti-breakage of the hair was better for the lock treated with the process according to the invention.

Example 2

1. Preparation of compounds 2 to 5

Compound 2 is the following compound, for which n ₇ = 1:
.

Compound 3 is the following compound, for which n ₇ = 2:
.

Compound 4 is the following compound, for which n ₇ = 3:
.

Compound 5 is a mixture of 3 compounds, namely compounds 2, 3 and 4.

Compounds 2 to 4 were prepared with the following ingredients, indicated in Table 6 below and according to the following protocol:
n (mmol) m(g) Volume (mL) ACTP 26.3 5 - CO 39.4 - 3.4 PDP 13.1 3.5 - _{CH2Cl2 _} - - 50 Pyridine - - 50

PTCA: 2-Phenyl-2H-tetrazole-5-carboxylic acid;
CO: Oxalyl chloride;
PPD: Polypropandiol; SENSATIS H250 from ALLESSA.

The PTCA dissolved in dichloromethane was added to a three-necked flask with magnetic stirring. The reaction mixture was placed under argon (inert atmosphere). Once dissolved, the CO was added to the medium followed by a drop of N,N-dimethylformamide. The mixture was stirred for 1 hour.

A solution of PPD and pyridine was prepared and cooled to 0°C by an external ice bath. The solution with PTCA was added dropwise to the PPD solution via a dropping funnel. The reaction was stirred under an inert atmosphere for 20 hours and then the medium was poured into water. The aqueous phase was extracted with dichloromethane (2 times). The organic phase was washed with an aqueous solution of saturated sodium bicarbonate then a solution of 2N HCl. It was then dried over Na2SO4, filtered and concentrated under reduced pressure. Compounds 2 to 4 were obtained by purification using chromatography on a silica column using a 95/5 dichloromethane/ethyl acetate then 98/2 dichloromethane/methanol solvent gradient.

An identical process was carried out to obtain compound 5. Indeed, at the end of the protocol, compound 5, i.e. the mixture of compounds 2, 3 and 4, was isolated.

2. Preparation of compositions 2a, 2b, 2c

Compositions 2a to 2c were prepared from the ingredients indicated in Table 7 below, the amounts of which are expressed in% by weight of active ingredient (AM).
Compositions 2a 2b 2c Compound 2 0.25 - 0.25 Amodimethicone (2) 5 5 - Decamethylcyclopentasiloxane Qsp 100% Qsp 100% Qsp 100%

(2) Bis-Cetearyl Amodimethicone: Silsoft AX reference from Momentive.

3. Evaluation of the ease of combing and the persistence of the treatment

A. Procedure – preparation of 3 locks

Compositions 2a, 2b and 2c were applied to three different dry locks (natural hair, 2 g/20 cm in length), at the rate of 0.5 g of composition per gram of hair, each of the locks being placed on a heating plate at 33°C during application. The locks were then kneaded with the fingers by making circular movements all along the lock (5 times), then combed. Then, the locks were left to rest for 2 minutes (1 minute on each side) on the heating plate. The locks were then dried with a hair dryer.

The locks of hair were then irradiated for 20 minutes (10 minutes on each side) with a UV lamp (power: 7 to 8 mW/cm2; wavelength: 254 nm).

In the following, the locks have been called lock E (treated with composition 2a according to the invention), lock F (treated with comparative composition 2b), lock G (treated with composition 2c according to the invention).

B. Study of the remanence of the silicone on the locks

Locks E and F were analyzed by infrared (ATR-IR) before and after having been washed 10 times using a shampoo according to the following washing protocol: the locks were moistened 5 times, then a DOP shampoo was was applied to the locks (0.4g/g of hair), then the locks were kneaded 10 times with the fingers, making circular movements all along the lock, then the locks were rinsed 10 times under water , then the locks are dried with a hair dryer, then all the steps were repeated 9 times.

The method used makes it possible to quantify the quantity of silicone present on the surface of the lock of hair. After application of the compositions, a silicone film was formed on the surface of the lock. 10 shampoos were then performed. The thickness of the film decreased with repeated shampoos. The signal representing silicone on the infrared spectrum also decreased.

In this test, a ratiometric comparison, called ratio R, was carried out between a signal representing the amides of hair proteins (band at 1633 cm ^-1 in the infrared spectrum) and a signal representing the Si-O-Si bond silicone polymers (band at 1258 cm ^-1 ). If the ratio remains the same, this means that the quantity of silicone remains constant on the surface of the hair. On the other hand, if the ratio increases, this means that the quantity of silicone present decreases. The results have been collated in Table 8 below.

Wick E (composition 2a according to the invention) F (comparative composition 2b) Ratio R before shampoo 0.69 0.62 Ratio R after 10 shampoos 0.77 3.34

The results above show that the process according to the invention has made it possible to improve the persistence of the silicone on the wick with shampoos. Indeed, the quantity of silicone present on the lock E treated with the process of the invention resisted at least 10 shampoos unlike the deposit of silicone on the comparative lock F.

C. Study of ease of combing

The test consisted of combing each of the locks 3 times and comparing the gesture to that performed on a lock from the same batch, but which had not been irradiated with a UV lamp. Thus, lock E1 is a lock to which composition 2a has been applied, but which has not been irradiated. Similarly, lock F1 is a lock to which composition 2b was applied, but which was not irradiated. Finally, lock G1 is a lock to which composition 2c was applied, but which was not irradiated. The locks E1, F1 and G1 are therefore treated with a comparative process.

During this test, six combing scenarios are possible:
-2: very difficult on the whole wick;
-1: difficult on the whole wick, very difficult at the ends;
0: difficult at points;
+0.5: easy, with slight spike resistance;
+1: easy;
+2: very easy.

A control lock, called lock T, is the reference lock to which no composition has been applied, but which has been irradiated with a UV lamp. A rating of 0 was assigned to this lock because combing was difficult at the ends. Three evaluators gave their ratings. The results have been compiled in the table below.

Wick Note before shampoo Note after 1 shampoo Rating after 10 shampoos T 0 0 0 E (2a) 2 2 2 E1 (2a) -2 0 1 F1 (2b) 2 2 1 G (2c) 0.5 0.5 0 G1 (2c) 0 0 -1

The results clearly show that the lock E treated according to the process according to the present invention was easy to comb and the good combing properties conferred on the lock E resisted even after 10 shampooings.

4. Preparation of compositions 3a, 3b, 3c

Compositions 3a to 3c were prepared from the ingredients indicated in Table 10 below, the amounts of which are expressed in% by weight of active ingredient (AM).

Compositions 3a 3b 3c Compound 5 2 2 - Amodimethicone (3) 10 - 10 Ethanol 20 20 20 Decamethylcyclopentasiloxane Qsp 100% Qsp 100% Qsp 100%

(3) Poly(dimethylsiloxane)bis(3-aminopropyl) terminated (PDMS=25KDa) from the company Gelest (reference DMS-A31).

5. Evaluation of the anti-frizz of the hair

A. Procedure – preparation of 6 locks

Composition 3a was applied to a first lock and a second lock, composition 3b to a third lock and a fourth lock and composition 3c to a fifth lock and a sixth lock, at a rate of 1 g of composition per gram of hair . The application of the different compositions having taken place on a dry wick (natural hair, 2g/20 cm in length) placed on a heating plate at 33°C. The locks were then kneaded with the fingers by making circular movements all along the lock (5 times), then combed. Then, the locks were left to rest for 2 minutes (1 minute on each side) on the heating plate. The locks were then dried with a hair dryer and then combed.

Three of the six locks of hair were then smoothed with a straightening iron (“Babyliss Pro EP technology 5.0 the straightener” iron) at a temperature of 190° C. The passage of the iron was carried out three times per lock at a speed of 4 seconds for 10 cm of locks.

The three wicks concerned were the first, the third and the fifth wick. In the following, the locks smoothed with a straightening iron have been called lock H (treated with composition 3a according to the invention and smoothed with a straightening iron), lock I (treated with composition 3b according to the invention and smoothed with an iron hair straightener), section J (treated with comparative composition 3c and smoothed with a straightening iron).

The strands not straightened with a straightening iron are the second, fourth and sixth strands. In the following, these locks not smoothed with a straightening iron were called lock H1 (treated with composition 3a according to the invention and not smoothed with a straightening iron), lock I1 (treated with composition 3b according to the invention and not straightened with a straightening iron) and lock J1 (treated with comparative composition 3c and not straightened with a straightening iron).

B. Study of the anti-frizz of the hair

All the locks were placed in a glove box (closed box) with a relative humidity controlled at 80%. Measurements were made at time T0 and after 1 hour (T1).

Frizz was assessed by measuring the width of the locks at mid-height. The smaller the difference between the width at mid-height of the lock measured at time T1 and the width at mid-height at time T0 (Δ), the better the control of frizz. The results have been collated in Table 11 below.

Wick Δ (mm) H (3a) 11 H1 (3a) 23 I (3b) 17 I1 (3b) 25 Y (3c) 26 D1 (3c) 24

The results show that the locks treated with the process according to the invention (implementing a compound according to the invention and the heat of a straightening iron) (locks H and I) had less frizz than the locks not having undergone no heat treatment (locks H1 and I1), and that the locks to which compositions not containing a compound according to the invention) have been applied (locks J and J1).

6. Preparation of compositions 4a, 4b, 4c and 4d

Compositions 4a to 4d are prepared from the ingredients indicated in Table 12 below, the amounts of which are expressed in% by weight of active ingredient (AM).

Compositions 4a 4b 4c 4d Compound 2 0.2 - 0.2 - Amodimethicone (2) 4 4 4 4 Pigment Red 7 0.2 0.2 - - Pigment Black 2 (4) - - 0.2 0.2 Isododecane 40 40 40 40 Decamethylcyclopentasiloxane Qsp 100% Qsp 100% Qsp 100% Qsp 100%

(2) Bis-Cetearyl Amodimethicone: Silsoft AX reference from Momentive

(4) Pigment from DAITO KASEI KOGYO (reference ISD-CB2).

7. Color assessment

A. Procedure – Preparation of 4 locks

Composition 4a was applied to a first lock, composition 4b to a second lock, composition 4c to a third lock and composition 4d to a fourth lock, at a rate of 5 g of composition per gram of hair, application of the different compositions having taken place on a dry wick (natural hair, 1g/20 cm in length). The locks were then kneaded with the fingers by making circular movements all along the lock (5 times), then combed. Then, we let the locks sit for 15 minutes. The locks were then dried with a hair dryer.

The locks were then irradiated for 20 minutes (10 minutes on each side) with a UV lamp (Hamamatsu LightningCure LC-C1 365nm (OLED), power 120 mW/cm2).

B. Staining study

The color of the locks was then evaluated by colorimetry in the CIE L*a*b* system using a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) after coloring and before washing with shampoo then after washing 5 times with shampoo according to the following washing protocol: the locks were moistened 5 times, then a DOP shampoo was applied to the locks (0.4 g/g of hair), then the locks were mixed 10 times with the fingers by making circular movements all along the lock, then the locks were rinsed 15 times under water, then the locks are dried with a hair dryer, then all the steps were repeated 4 times.

In this L*a*b* system; L* represents the lightness of the color, a* indicates the green/red color axis and b* the blue/yellow color axis. The lower the value of L*, the darker and more powerful the coloration.

The lower the value of a* and the greener the color, the higher the value of a* the more red the color.

The lower the value of b* and the more blue the color, the higher the value of b* the more yellow the color.

The resistance of the color to repeated shampooing corresponding to the variation in color between the locks of hair before and after repeated shampooing is defined by (∆E**) according to the following equation:
ΔE** = √[(L1*-L*) ² + (a1*-a*) ² + (b1*-b*) ² ].

In this equation, L*, a* and b* represent the values measured on the locks of hair after coloring and L1*, a1* and b1* represent the values measured on the respective locks of hair washed with the shampoo.

The lower the value of ∆E**, the greater the resistance to shampoo of the colorations.

The results have been collated in Table 13 below:
Before shampoo Hair conditioner Compositions I* To* b* L1* a1* b1* OF** 4a 34.37 28.71 7.79 36.77 32.05 10.96 5.19 4b 27.58 29.26 10.6 40.72 17.63 5.05 18.40 4c 22.82 0.19 3.04 25.12 0.65 3.97 2.52 4d 15.69 0.39 1.5 29.96 0.15 3.52 14.41

The results show that the locks treated with a compound according to the invention (compositions 4a and 4c) exhibited a significantly improved resistance to shampooing of the colorations compared to the locks to which compositions not containing a compound according to the invention were applied. (compositions 4b and 4d).

Example 3

1. Preparation of Compound 6

Compound 6 is a mixture of compounds of formula (V), for which n ₇ is from 7 to 45:

Compound 6 was prepared with the following ingredients, indicated in Table 14, and according to the following protocol:
n (mmol) m(g) Volume (mL) ACTP 5.26 1 - CO 7.9 - 0.691 PPD-2 2.64 6.59 - _{CH2Cl2 _} - - 10 Pyridine - - 5

PTCA: 2-Phenyl-2H-tetrazole-5-carboxylic acid;
CO: Oxalyl chloride;
PPD-2: Velvetol: Polypropandiol from ALLESSA (molecular weight 500-2700 g/mol; CAS No. 345260-48-2).

The PTCA dissolved in dichloromethane was added to a three-necked flask with magnetic stirring. The reaction mixture was placed under argon (inert atmosphere). Once dissolved, CO was added to the medium, followed by a drop of N,N-dimethylformamide. The mixture was stirred for 1 hour.

A solution of PPD and pyridine was prepared and cooled to 0°C by an external ice bath. The solution with PTCA was added dropwise to the PPD solution via a dropping funnel. The reaction was stirred under an inert atmosphere for 20 hours and then the medium was poured into water. The aqueous phase was extracted with dichloromethane (2 times). The organic phase was washed with an aqueous solution of saturated sodium bicarbonate then a solution of 2N HCl. It was then dried over Na2SO4, filtered and concentrated under reduced pressure. Compound 6 was obtained by purification using chromatography on a silica column using a 95/5 dichloromethane/ethyl acetate then 98/2 dichloromethane/methanol solvent gradient.

2. Preparation of compositions 5a and 5b

Compositions 5a and 5b were prepared from the ingredients indicated in Table 15 below, the amounts of which are expressed in% by weight of active ingredient (AM).

Compositions 5a 5b Compound 6 0.6 - Ethanol 3 3 Water Qsp 100% Qsp 100%

3. Evaluation of the repair of the forks

A. Procedure

Each of the natural fibers used has been previously split in two longitudinally at the tip. The fibers used are fibers marketed by the company IHIP (Glendale, NY 11385, United States – Reference: Split End Hair, length 15cm).

The fibers were then soaked in composition 5a, or in composition 5b, for 30 seconds. Then the fibers were hung up and left to air dry. The fibers were then smoothed with a straightening iron (“Babyliss Pro EP technology 5.0 the straightener” iron) at a temperature of 190° C. The passage of the iron was carried out three times per fiber at a speed of 4 seconds for 10 cm of fiber.

In the following, the fibers soaked in composition 5a and smoothed have been called the fibers according to the invention, and the fibers soaked in composition 5b and smoothed have been called the comparative fibers.

B. Fork repair study

Observations were made using a magnification optical microscope (Model 175 X optical “MightyScope 1.3M Digital Microscope” marketed by the company Aven Inc, USA).

Microscopic observations of the fibers before soaking were carried out. Microscopic observations of the fibers according to the invention and of the comparative fibers were also carried out. The evolution of the fibers was then evaluated using the microscope. Specifically, fiber repair was assessed. If the two parts of the end of a fiber have been joined together, then the fiber is repaired. Otherwise, the fiber is not repaired.

It was found that three out of five fibers were repaired with respect to the fibers according to the invention, while no fibers were repaired with respect to the comparative fibers.

The results therefore show that the method according to the invention using a particular compound of formula (V) made it possible to repair the damaged forks.

Claims (25)

Process for the treatment of keratin fibres, in particular the hair, comprising:
a) a step of applying to the keratin fibers a composition comprising one or more compounds comprising at least two tetrazole groups, and optionally at least one coloring agent chosen from pigments, direct dyes and mixtures thereof;
b) a step of supplying energy to the keratinous fibers chosen from a heat treatment using a heating means and/or irradiation by artificial or natural light radiation. Process according to Claim 1, characterized in that the said compound comprising at least two tetrazole groups has the following formula (A1): WW(TET) _n1 (A1), in which:
WW denotes a multivalent C ₂ to C ₃₀ radical, linear or branched or (hetero)cyclic, saturated, an aromatic radical, or a heteroaromatic cyclic radical, WW possibly also containing one or more heteroatoms such as O, N and/or one or more functions chosen from esters, ketones, amides, ureas, preferably esters, amides, and/or be substituted by one or more C ₁ to C ₁₀ alkyl groups, linear or branched, C ₁ to C alkoxy ₁₀ , linear or branched, it being understood that when the WW radical is substituted, the tetrazole groups may be carried by the substituent(s);
TET denotes a tetrazole group;
n ₁ denotes an integer greater than or equal to 2, preferably between 2 and 10, preferably between 2 and 5 and in particular 2. Process according to Claim 1 or 2, characterized in that the said compound comprising at least two tetrazole groups has the following formula (I):
(I),
in which:
A represents a hydrocarbon chain, linear or branched, saturated or unsaturated, C ₂ to C ₃₀ , optionally containing one or more groups or heteroatoms chosen from O, S, N, CO, or their combinations such as -CO-O, -O -CO-, -CO-NH-, -NH-CO;
R ₁ and R ₂ , identical or different, represent a C ₁ to C ₆ alkyl group or an aromatic group. Process according to Claim 3, characterized in that A has the following formula (IIA): -C(O)-X ₁ -BX ₂ -C(O)- (IIA),
in which:
X ₁ and X ₂ , identical or different, represent an oxygen atom or an NR group with R denoting a hydrogen atom or a C ₁ to C ₄ alkyl radical such as methyl;
B represents a linear or branched, saturated or unsaturated, C ₂ to C ₂₈ hydrocarbon chain, optionally interrupted by one or more heteroatoms chosen from O, S and N. Process according to Claim 4, characterized in that B is interrupted by one or more oxygen atoms, preferably by several non-adjacent oxygen atoms. Process according to any one of Claims 3 to 5, characterized in that A has the following formula (IIIA): -C(O)-O-CH ₂ -CH ₂ -CH ₂ –[O-CH ₂ -CH ₂ -CH ₂ ] _n2 -OC(O)- (IIIA), in which n ₂ is an integer ranging from 1 to 8, preferably from 1 to 7; or of the following formula (IVA): -C(O)-NH-CH ₂ -CH ₂ -CH ₂ -[O-CH ₂ -CH ₂ ] _n3 -CH ₂ -NH-C(O)- (IVA), in which n ₃ is an integer ranging from 1 to 8, preferably from 1 to 7, more preferably from 1 to 3. Process according to any one of Claims 3 to 6, characterized in that R ₁ and R ₂ represent an aromatic group, preferably a phenyl group. Process according to Claim 1, characterized in that the said compound comprising at least two tetrazole groups has the following formula (A2): POL(TET) _n4 (A2), in which:
POL designates a multivalent carbon or silicone polymeric radical or one comprising carbon and silicon atoms, POL possibly also comprising one or more heteroatoms such as O, N, S, and/or one or more functions chosen from ester, ketone and amides, and/or be substituted by one or more C ₁ to C ₁₀ alkyl groups, linear or branched, C ₁ to C ₁₀ alkoxy, linear or branched, it being understood that when POL is substituted, the tetrazole groups can be carried by the substituent(s);
TET denotes a tetrazole group;
n ₄ denotes an integer greater than or equal to 2, preferably between 2 and 1000, preferably between 2 and 500. Process according to Claim 8, characterized in that POL is of the following formula (IIB): -C(O)-X' ₁ -B ₁ -X' ₂ -C(O)- (IIB), in which:
X' ₁ and X' ₂ , which are identical or different, represent an oxygen atom or an NR' group with R' denoting a hydrogen atom or a C ₁ to C ₄ alkyl radical such as methyl, preferably a hydrogen;
B ₁ represents a linear or branched, saturated or unsaturated, C ₃₁ to C ₃₀₀₀ hydrocarbon chain, interrupted by one or more heteroatoms chosen from O, and optionally S and N. Process according to Claim 9, characterized in that B ₁ is interrupted by one or more oxygen atoms, preferably by several non-adjacent oxygen atoms. Process according to Claim 9 or 10, characterized in that B ₁ has the following formula (IIIB): -C(O)-O-CH ₂ -CH ₂ -CH ₂ –[O-CH ₂ -CH ₂ -CH ₂ ] _n5 -OC(O)- (IIIB), in which n ₅ is an integer ranging from 9 to 990, preferably from 9 to 500; or of the following formula (IVB): -C(O)-NH-CH ₂ -CH ₂ -CH ₂ -[O-CH ₂ -CH ₂ ] _n6 -CH ₂ -NH-C(O)- (IVB), in which n ₆ is an integer ranging from 9 to 1000, preferably from 9 to 500. Process according to any one of the preceding claims, characterized in that the said compound comprising at least two tetrazole groups is chosen from the compounds of formula (V) below, and mixtures thereof:
(V),
in whichn ₇ is an integer ranging from 1 to 990, preferably from 1 to 100, more preferably from 1 to 45;
and the compounds of formula (VI) below, and mixtures thereof:
(VI),
in which n ₈ is an integer ranging from 1 to 1000, preferably from 1 to 100, more preferably from 1 to 3. Process according to any one of the preceding claims, characterized in that the said compound or compounds comprising at least two tetrazole groups are present in a content ranging from 0.01 to 15% by weight, preferably from 0.2 to 10% by weight relative to the total weight of the composition. Process according to any one of the preceding claims, characterized in that the composition additionally comprises one or more silicones; preferably chosen from amino silicones, silicones containing oxyalkylenated groups, and mixtures thereof. Method according to any one of the preceding claims, characterized in that the heating means is an iron; preferably the temperature of the iron is greater than or equal to 120°C, more preferably ranges from 120 to 230°C. Method according to any one of the preceding claims, characterized in that step b) is a step of irradiation with artificial light radiation, preferably at a wavelength ranging from 320 to 480 nm. Method according to the preceding claim, characterized in that the artificial light radiation is generated using a device chosen from arc lamps such as xenon lamps and mercury lamps, fluorescent lamps, incandescent such as halogens, light emitting diodes, organic light emitting diodes, and lasers. Compound comprising at least two tetrazole groups. Compound according to the preceding claim, characterized in that it is chosen from WW(TET) _n1 as defined in any one of Claims 2 to 7, POL(TET) _n4 as defined in any one of Claims 8 to 11, and mixtures thereof. Compound according to Claim 18 or 19, characterized in that it is chosen from the compounds of formula (V) as defined in Claim 12, the compounds of formula (VI) as defined in Claim 12 and mixtures thereof. Composition comprising one or more compounds as defined in any one of claims 18 to 20. Composition according to the preceding claim, characterized in that it comprises at least one coloring agent chosen from pigments, direct dyes and mixtures thereof. Use of at least one compound as defined in any one of Claims 18 to 20 or of at least one composition as defined in Claim 21 for the care and/or repair of keratin fibers, preferably the repair keratin fibres, more preferably the repair of hair split ends. Process for dyeing keratin fibers comprising the application of at least one composition as defined in Claim 22, and a step of supplying energy to the keratin fibers by heat treatment and/or by irradiation with the aid of artificial or natural. Use of the composition as defined in Claim 22 for dyeing keratin fibres.