WO2021136788A1

WO2021136788A1 - Process for treating keratin fibres, comprising the application of a composition comprising a particular compound comprising at least two tetrazoles groups

Info

Publication number: WO2021136788A1
Application number: PCT/EP2020/088000
Authority: WO
Inventors: Andrew Greaves
Original assignee: L'oreal
Priority date: 2019-12-30
Filing date: 2020-12-29
Publication date: 2021-07-08
Also published as: FR3105734B1; FR3105734A1

Abstract

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

Description

DESCRIPTION

PROCESS FOR TREATING KERATIN FIBRES, COMPRISING THE APPLICATION OF A COMPOSITION COMPRISING A PARTICULAR COMPOUND COMPRISING AT LEAST TWO TETRAZOLES GROUPS.

Technical field

The present invention relates to a process for treating keratin fibres, notably the hair, comprising the application of a composition comprising at least one compound comprising at least two tetrazole groups, and optionally at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, and a step of supplying energy to the keratin fibres 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 to the use of said composition for caring for and/or repairing keratin fibres.

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

Prior art

Keratin fibres, in particular human keratin fibres such as the hair, are generally damaged and weakened by the action of external atmospheric agents such as light, sun and bad weather, and also by mechanical or chemical treatments, such as brushing, combing, permanent-waving, relaxing and repeated washing. Said keratin fibres are thus damaged by these various factors and may in the long run become dry, coarse, brittle, dull, split, limp and/or difficult to style.

Thus, to overcome these drawbacks, it is common practice to resort to hair treatments which make use of compositions intended for appropriately conditioning keratin fibres, in particular human keratin fibres such as the hair, by giving them satisfactory cosmetic properties, notably smoothness, sheen, a soft feel (a natural feel; the hair is no longer coarse), suppleness, a lightweight feel, good disentangling properties leading to easy combing, and good manageability of the hair which is thus easy to shape.

These haircare compositions can, for example, be conditioning shampoos, hair conditioners, masks or serums. However, the conditioning effect obtained fades out in the course of successive shampoo washes and does not show satisfactory persistence on shampooing. Moreover, whereas these compositions improve the visual effect of split ends and facilitate disentangling or brushing, they generally have no effect on repairing split ends. Thus, the results obtained are not always satisfactory in terms of repairing or preventing breakage of the keratin fibres, notably split keratin fibres.

There is thus a real need to develop a process and a composition for treating keratin fibres, notably human keratin fibres such as the hair, which are capable of protecting and/or repairing said fibres, and if possible, in a long-lasting manner with respect to external agents.

It is also advantageous to find a means for treating damaged keratin fibres by repairing them, that is to say by improving the cosmetic nature of damaged keratin fibres intrinsically, while maintaining or even improving the manageability, the frizziness control and/or the persistence of the styling of said fibres. It is also advantageous to prevent the breakage of natural keratin fibres, while maintaining or even improving the manageability, the frizziness control and/or the persistence of the styling of said fibres.

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

Non-permanent dyeing or direct dyeing consists in dyeing keratin fibres with dye compositions containing direct dyes. These dyes are applied to the keratin fibres for a time necessary to obtain the desired colouring, and are then rinsed out.

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

Some of these dyes may be used under lightening conditions, which enables the production of colourings that are visible on dark hair.

Another dyeing method consists in using pigments. Specifically, the use of pigment on the surface of keratin fibres generally makes it possible to obtain visible colourings on dark hair, since the surface pigment masks the natural colour of the fibre. These colourings obtained via this dyeing method may have the drawback of having poor resistance to water and/or shampoo washing and also to external agents such as sebum, perspiration, and mechanical actions such as brushing and/or rubbing. The colourings obtained may also give rise to staining and/or transfer, in particular when the fibres are wet.

Furthermore, compositions for temporarily dyeing the hair may also lead to a hair feel that is uncosmetic and/or not natural; the hair thus dyed may notably lack softness and/or suppleness and/or strand separation.

There is thus a real need for a treatment and a composition for keratin fibres, notably human keratin fibres such as the hair, which are capable of protecting and/or repairing said fibres, and/or of dyeing them, and if possible, in a long-lasting manner with respect to external agents.

Disclosure of the invention

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

The Applicant has found, surprisingly, that the process according to the invention can improve the cosmetic properties given to the keratin fibres, in particular as regards the properties in terms of resistance to breakage of the keratin fibres.

When the process involves at least one colouring agent, said process also leads to a colouring that is visible on all types of hair, said colouring being persistent with respect to shampoo washing and preserving or improving the physical qualities of the keratin fibres, without impairing the integrity of the treated fibres. Such a process is resistant to the external attacking factors to which the hair may be subjected, such as blow-drying and/or sensitivity to moisture such as perspiration or atmospheric moisture.

Moreover, this process gives hair complete strand separation, enabling it to be styled without any problem. The hair after treatment can be subjected to shaping treatments, preferably temporary shaping treatments.

In particular, hair treated by means of the process according to the invention remains manageable, including in a humid atmosphere, since no presence of frizziness is observed. Thus, the hair strands are aligned, straight and disentangle easily, which makes them easier to comb. The treated hair also has more body, i.e. it is not limp, and is thus easier to style and maintains hold of the hairstyle The treated hair is easy to shape, this shaping of the hair persisting even after several shampoo washes.

Moreover, the treated hair is also shiny and soft to the touch. It is stronger and less brittle. The process according to the invention has the advantage of giving good persistence of these good hair-conditioning cosmetic properties after at least one shampoo wash, in particular after 10 successive shampoo washes. Thus, the treated hair is conditioned in a long-lasting manner. After treatment, the hair is not laden, and has a natural feel.

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

Another subject of the present invention is the use of the composition according to the invention for caring for and/or repairing keratin fibres.

Another subject 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 colouring agent chosen from pigments, direct dyes and mixtures thereof, and the use of said composition for dyeing keratin fibres, in particular human keratin fibres such as the hair.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

In the present description, the expression “at least one” is equivalent to the expression “one or more” and can be substituted for said expression; the expression “between” is equivalent to the expression “ranging from” and can be substituted for said expression, and implies that the limits are included.

For the purposes of the present invention, the term “tetrazole group” means a tetrazolyl radical, optionally substituted with one or more radicals, which may be identical or different, chosen from a Ci to Ce alkyl group or an aromatic group.

For the purposes of the present invention, the term “keratin fibres” means the hair, the eyelashes, bodily hair, and in particular human keratin fibres, even more particularly the hair.

For the purposes of the present invention, the term “hair with strand separation” means hair which, after application of a composition and drying, is not stuck together (or of which all the strands are separated from each other) and thus does not form clumps of hair.

For the purposes of the present invention, the term “colouring that is persistent with respect to shampoo washing” means that the colouring obtained persists after one shampoo wash, preferably after three shampoo washes, more preferentially after five shampoo washes, even more preferentially after ten shampoo washes.

The term “including a” should be understood as meaning “including at least one”, unless otherwise specified.

For the purposes of the present invention, the expression “chain containing an atom” means that the atom may be present throughout the chain, including at the ends of said chain.

For the purposes of the present invention, the expression “chain interrupted with an atom” means that the atom may be present throughout the chain, except for at the ends of said chain.

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

For the purposes of the present invention and unless otherwise indicated: the term “alkyl” denotes a saturated, linear or branched hydrocarbon-based radical; an “aryl” radical is a monocyclic or bicyclic, fused or non-fused, unsaturated cyclic aromatic radical comprising from 6 to 20 carbon atoms; preferably, the aryl group consists of 1 ring and contains 6 carbon atoms, such as phenyl; a “cycloalkyl” radical denotes a saturated cyclic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 to 2 rings, more preferentially 1 ring, and comprising from 3 to 20 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbomyl or isobornyl, the cycloalkyl radical possibly being substituted with one or more Ci to C4 alkyl groups such as methyl; the term “alkoxy” denotes an “alkyl-oxy” group with “alkyl” as defined previously.

Process for treating keratin fibres

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

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

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

The compound containing tetrazole units may be aromatic or hetero aromatic or may 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 and N and/or one or more functions chosen from ester, ketone, amide and urea functions.

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

According to a first variant, the compound bearing tetrazole units according to the invention denotes a non-polymeric organic compound which may be represented by formula (Al) below: WW(TET)_ni (Al), in which: m denotes an integer greater than or equal to 2, preferably between 2 and 10, preferably between 2 and 5, in particular 2;

WW denotes a linear or branched or (hetero)cyclic, saturated C2 to C30 multivalent (at least divalent) radical, an aromatic radical, or a heteroaromatic cyclic radical, WW also possibly containing one or more heteroatoms such as O and N and/or one or more functions chosen from ester, ketone, amide and urea functions, preferably ester and amide functions, and/or possibly being substituted with one or more linear or branched Ci to C10 alkyl groups, or linear or branched Ci to C10 alkoxy groups, it being understood that when the radical WW is substituted, the tetrazole groups may be borne by the substituent(s);

TET denotes a tetrazole group as defined above.

For the purposes of the present invention, the term “cyclic radical” means a hydrocarbon-based or heterocyclic saturated monocyclic radical, a saturated or aromatic polycyclic radical, for example biphenyl, or fused rings, for instance a naphthyl radical.

The molar mass of the compounds of formula (Al) is generally between 90 and 1500 g/mol. According to a particular embodiment of the invention, the compound bearing tetrazole units of formula (Al) is such that m = 2, and WW denotes a linear or branched, saturated divalent C2 to C30 hydrocarbon-based radical, optionally comprising one or more groups or heteroatoms chosen from O, S, N, CO, or combinations thereof such as -CO-O, -O-CO-, -CO-NH-, -NH-CO-.

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

(I).

In this formula (I), A represents a linear or branched, saturated or unsaturated C2 to C30 hydrocarbon-based chain, optionally containing one or more groups or heteroatoms chosen from O, S, N, CO, or combinations thereof such as -CO-O, -O- CO-, -CO-NH-, -NH-CO-. In this formula (I), Ri and R2, which may be identical or different, represent a C1-C6 alkyl group or an aromatic group.

Preferably, A is of formula (IIA) below: -C(0)-X_I-B-X₂-C(0)- (PA), in which:

Xi and X2, which may be identical or different, represent an oxygen atom or a group NR with R denoting a hydrogen atom or a Ci to C4 alkyl radical such as methyl;

B represents a linear or branched, saturated or unsaturated C2 to C28 hydrocarbon-based chain, optionally interrupted with one or more heteroatoms chosen from O, S and N.

Preferably, B is C2 to C26 and more preferentially C2 to C20. According to a particular embodiment, A is of formula (IIIA) below: -C(O)-

0-CH₂-CH₂-CH_2-[0-CH₂-CH₂-CH₂]_n2-0-C(0)- (IIIA), in which n₂ is an integer ranging from 1 to 8, preferably from 1 to 7; or of formula (IVA) below: -C(0)-NH- CH₂-CH₂-CH₂-[0-CH₂-CH₂]_n3-CH₂-NH-C(0)- (IVA), in which n is an integer ranging from 1 to 8, preferably from 1 to 7 and more preferentially from 1 to 3. As indicated above, Ri and R2, which may be identical or different, represent a Ci to Ce alkyl group or an aromatic group. Preferably, Ri and R2 represent an aromatic group, preferably a phenyl group.

According to a second variant, the compound bearing tetrazole units according to the invention denotes a polymeric compound and can be represented by formula (A2) below: POL(TET)_n4 (A2), in which:

P4 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) polymeric radical which is carbon-based or silicon-based or comprising carbon and silicon atoms, POL also possibly comprising one or more heteroatoms such as O, N or S, and/or one or more functions chosen from ester, ketone and amide functions, and/or possibly being substituted with one or more linear or branched Ci to C10 alkyl groups, or linear or branched Ci to C10 alkoxy groups, it being understood that when POL is substituted, the tetrazole groups may be borne by the substituent(s);

TET denotes a tetrazole group as defined above.

When POL denotes a carbon-based polymeric radical, this radical comprises at least 31 carbon atoms.

The molar mass of the compounds of formula (A2) is generally between 500 and 400000 g/mol and preferably between 500 and 150000 g/mol.

POL may denote a multivalent radical such as a homopolymer or copolymer; POL may denote a polymeric radical of star, comb, brush or dendritic type.

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

The tetrazole units may be end and/or side groups.

According to a particular embodiment, POL may denote a poly glycol chain optionally terminated at each end with an ester or amide group. According to this mode, POL may denote a chain of formula -C(0)-X’ I-BI-X’₂-C(0)- (IIB), in which:

X’ 1 and X’2, which may be identical or different, represent an oxygen atom or a group NR’ with R’ denoting a hydrogen atom or a Ci to C4 alkyl radical such as methyl, preferably a hydrogen atom;

Bi represents a linear or branched, saturated or unsaturated C31 to C3000 hydrocarbon-based chain, interrupted with one or more heteroatoms chosen from O, and optionally S and N. Advantageously, Bi is interrupted with one or more oxygen atoms, preferably with several non-adjacent oxygen atoms.

According to a particular embodiment, Bi is of formula (IIIB) below: -C(O)- 0-CH₂-CH₂-CH_2-[0-CH₂-CH₂-CH₂]_n5-0-C(0)- (IIIB), in which n₅ is an integer ranging from 9 to 990, preferably from 9 to 500; or of formula (IVB) below: -C(O)- NH-CH₂-CH₂-CH₂-[0-CH₂-CH₂]_n6-CH₂-NH-C(0)- (IVB), in which n₆ is an integer ranging from 9 to 1000, preferably from 9 to 500.

According to another particular embodiment, POL may denote a polymer of natural origin such as polysaccharides and polypeptides. As examples of polysaccharides that may be used for the preparation of the compounds bearing tetrazole units of the invention, mention may be made of polysaccharides bearing amine group(s), notably those with an average molecular weight MW of less than or equal to 400 kDa, notably those containing C5-C7 saccharide units, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and more particularly polyhexosamines, the saccharide units of which are connected together between the atoms of carbon 1 of one saccharide unit and of carbon 4 of the other saccharide unit, denoted as (1 4), such as the polysaccharide bearing amine group(s) of formula (Zl) below:

(Zl), in which: the radicals R_a, R_b and R_c of each saccharide unit may be identical or different; n is an integer greater than or equal to 2, particularly between 3 and 2500, preferentially between 10 and 2300;

R_a, R_b and R_c, which may be identical or different, represent a group from among: i) hydroxyl, ii) Ci to C4 alkoxy, the alkyl group of which may be optionally substituted notably with one or more hydroxyl groups, iii) carboxyl, and iv) NR11R21 with R11 and R21, which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C₆)alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH₂ groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, v) a (hetero)cyclo(Cs-C7)alkyl group such as cyclohexyl, morpholinyl, piperazinyl or piperidyl, vi) a (hetero)cyclo(C₅-C₇)alkyl(Ci-C₄)alkyl group such as cyclohexylmethyl, vii) -C(Y)-(Y’)_P-R’i₂ with Y and Y’, which may be identical or different, representing an oxygen atom, a sulfur atom or N(R’_2i), preferably oxygen, p = 0 or 1, preferably 0; and R’₁₂ and R’₂₁ representing i) to vi) of Rn and R₂₁ defined previously, and in particular R’₁₂ denoting a (Ci-C₆)alkyl group such as methyl; in particular, Rn and R₂₁ are chosen from a hydrogen atom and -C(0)-R’i₂ in which R’₁₂ is as defined previously; preferably, Rn and R₂₁ represent i) a hydrogen atom or ii) -C(0)-R’i₂ and R’₁₂ represents a Ci to C₄ alkyl group such as methyl; it being understood that at least one of the radicals R_a, R_b or R_c of at least one saccharide unit represents a group NR₁₁R₂₁ and that at least one of the groups NR₁₁R₂₁ of at least one saccharide unit represents an Nth group; preferably, R_a of at least one saccharide unit represents a group NR₁₁R₂₁ with Rn which represents a hydrogen atom and R₂₁ is chosen from i) a hydrogen atom or ii) a group -C(0)-R’ ₁₂, and R_b and R_c represent a hydroxyl group, it being understood that at least one of the groups NR₁₁R₂₁ of at least one saccharide unit represents an Nth group.

More particularly, the polysaccharide bearing amine group(s) is of formula (Z2) below:

(Z2), in which:

R’” represents a hydrogen atom or a (Ci-C₄)alkylcarbonyl group such as acetyl CH -C(0)-;

R’ ’ represents a hydrogen atom or a (Ci-C₄)alkyl group optionally substituted with a carboxyl group such as -CH(C0₂H)-Cth; n is an integer greater than or equal to 2, particularly between 3 and 2500, preferentially between 10 and 2300; it being understood that in the polysaccharide (Z2), at least one saccharide unit bears an Nth amino group and at least one other saccharide unit bears at least one group N(H)-R’ with R’ representing a (Ci-C₄)alkylcarbonyl group such as acetyl Cth- C(O)-. Preferably, the saccharide units of formula (Zl) or (Z2) are of D configuration, also referred to as D-glucopyran. Particularly, the saccharide units of formula (Zl) or (Z2) are of b (beta) anomeric configuration. According to a particular embodiment, the polysaccharide bearing amine groups is chosen from the compounds of formula (Z3) below:

(Z3), in which:

R_a, R_b and R_c are as defined for (Zl) previously; the radicals R_a, R_b and R_c of each saccharide unit may be identical or different; n is an integer greater than or equal to 2, particularly between 3 and 2500, preferentially between 10 and 2300; it being understood that, in the polysaccharide (Z3), at least one of the radicals R_a, R_b or R_c of at least one saccharide unit represents a group NR11R21 and that at least one of the groups NR11R21 of at least one saccharide unit represents an NH2 group; preferably, at least one saccharide unit bears a group Ra which represents an amino NH2 and at least one other saccharide unit bears a group Ra which represents -N(H)- R’ with R’ representing a (Ci -Chalky lcarbonyl group such as acetyl ϋ¾-(3(0)-.

Preferentially, the polysaccharide bearing amine groups is chosen from chitin, chitosan and derivatives thereof, preferably chitosan.

More particularly, the polysaccharide bearing amine groups is chosen from those of formula (Z4) below:

(Z4), in which:

Rii and R21 are as defined in formulae (Zl) 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 saccharide unit bears an amino group Nth and at least one other saccharide unit bears a group N(H)-R’ with R’ representing a (Ci -Chalky lcarbonyl group such as acetyl CH -C(0)-. More particularly, the polysaccharide bearing amine groups is chosen from the chitosans of formula (Z5) below:

which:

R’n represents a (Ci-C4)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 the chitosan at least one saccharide unit bears an amino group Nth and at least one other saccharide unit bears a group N(H)-R’i with R’ representing a (Ci -Chalky lcarbonyl group such as acetyl Cth-C(O)-.

For example, when m = 0.7, p = 0.3 this means that 70% of the amine groups are free (unsubstituted) and 30% of the amino groups are N-alkyl(Ci-C4)carbonyl groups, in particular N-acetyl groups, corresponding to the chitosan polymer of formula (Z6) below:

with n as defined previously, the a and b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.

As examples of polymers of natural origin that may be used for the preparation of POL of the compounds bearing 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 bearing tetrazole units according to the invention is such that POL denotes a silicon-based polymeric radical.

The silicon-based polymeric radical may thus denote amino silicone derivatives comprising at least two amine functions.

As examples of amino silicone derivatives comprising at least two amine functions, used for preparing the compounds bearing tetrazole units of the invention, mention may be made of: a) the polysiloxanes of formula (WW1) below:

in which x’ and y’ are integers such that the weight-average molecular weight (Mw) ranges from 5000 to 300000 g/mol; with y’ greater than or equal to 2; b) the amino silicones of formula (WW2) below:

K’aG3-a-Si(0SiG2)n-(0SiGbK’₂-b)m-0-SiG3-a-K’a (WW2), in which:

G, which may be identical or different, denotes a hydrogen atom or a group from among phenyl, OH, Ci-Cs alkyl, for example methyl, or Ci-Cs alkoxy, for example methoxy, a, which may be identical or different, denotes 0 or an integer from 1 to 3, in particular 0, b denotes 0 or 1, in particular 1, m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10;

K’, which may be identical or different, denotes a monovalent radical of formula -C_qth_qL in which q is a number ranging from 2 to 8 and L is an amino group -NH₂;

Q denotes a linear or branched group of formula C_rth_r, r being an integer ranging from 2 to 6, preferably from 2 to 4; c) multiblock polyoxyalkylene amino silicones, of the type (AXBX)_n, AX being polysiloxane and BX being a polyoxyalkylene block comprising at least two amine groups; d) the amino silicones of formula (WW3) known as “trimethylsilyl

in which m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10, with m greater than or equal to 2; e) the amino silicones of formula (WW4):

which: m and n are numbers such that the sum (n + m) ranges from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n possibly denoting a number from 0 to 999, notably from 49 to 249 and more particularly from 125 to 175, and m possibly denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5, with m greater than or equal to 2;

Qi, Q2 and Q3, which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Qi to Q3 denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

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

The weight-average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1 000000 and more particularly from 3500 to 200000; f) the amino silicones of formula (WW5) below:

which: p and q are numbers such that the sum (p + q) ranges from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250; p possibly denoting a number from 0 to 999, notably from 49 to 349 and more particularly from 159 to 239, and q possibly denoting a number from 2 to 1000, notably from 2 to 10 and more particularly from 2 to 5;

Ti and T2, which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals Ti or T2 denoting an alkoxy radical.

Preferably, the alkoxy radical is a methoxy radical.

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

The weight- average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200 000 g/mol, even more particularly from 5000 to 100 000 and more particularly from 10000 to 50000.

The commercial products comprising silicones of structure (WW4) or (WW5) may include in their composition one or more other amino silicones, the structure of which is different from formula (WW4) or (WW5). g) the amino silicones of formula (WW6) below:

(WW6), in which: m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 2 to 2000 and notably from 2 to 10;

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

The weight- average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1 000 000 g/mol and even more particularly from 3500 to 200 000; h) the amino silicones of formula (WW7) below:

which: m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 2 to 2000 and notably from 2 to 10;

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

The weight- average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1 000000 g/mol and even more particularly from 1000 to 200000 g/mol; i) the amino silicones of formula (WW8) below:

(WW8), in which: m and n are numbers ranging from 2 to 5000 and in particular n possibly denoting a number ranging from 10 to 2000 and notably ranging from 100 to 1000, and in particular m possibly denoting a number from 1 to 100;

Si and S2, which may be 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;

A denotes a linear or branched alkylene radical containing 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: -CH2CH2CH2- or -CH₂CH(CH )CH₂-.

Preferably, Si and S2, which may be 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, Si and S2 denote dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, Si and S2, which may be identical or different, are chosen from hexadecyl and octadecyl radicals.

Preferably, the amino silicones of formula (WW8) are such that: n is a number ranging from 10 to 2000 and notably from 100 to 1000; m is a number ranging from 1 to 100;

Si and S2, which may be identical or different, represent a saturated linear alkyl radical comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and preferably 12 to 20 carbon atoms; chosen in particular from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, Si and S2, which may be identical or different, are chosen from hexadecyl and octadecyl radicals; and A comprises from 3 to 6 carbon atoms and preferably 4 carbon atoms; preferably, A is branched; and more preferentially, A is chosen from the following divalent radicals: -CH₂CH₂CH₂- and -CH₂CH(CH )CH₂-. j) the amino silicones of formula (WW9) below:

(WW9), in which 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 may also denote polyhydroxylated silicone derivatives comprising at least two hydroxyl functions.

Examples of polyhydroxylated silicones that may be mentioned include the compounds of formula (WW10) below:

(WW10), in which:

VI, which may be identical or different, independently represents a hydroxyl group; an alkyl group containing from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, notably 1 to 2 carbon atoms such as a methyl; an alkoxy group containing from 1 to 2 carbon atoms; or a group -(CH₂)_s-Si(R4)3 in which s denotes an integer ranging from 1 to 4 such as 2 and R4 independently denotes an alkoxy radical containing from 1 to 2 carbon atoms;

V’₂ and V”₂ independently represent an alkyl group containing from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, notably 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) bearing hydroxyl end 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 having the structure WW(TET)_ni, mixtures of compounds POL(TET)_n4 or mixtures of at least one compound WW(TET)_ni and of 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 and more preferentially from 1 to 45; and the compounds of formula (VI) below, and mixtures thereof:

in which ns is an integer ranging from 1 to 1000, preferably from 1 to 100 and more preferentially from 1 to 3. Preferably, ns is an integer which may be equal to 1, 2 or 3.

Very advantageously, the compound(s) comprising at least two tetrazole groups according to the invention are chosen from the following compounds: [Table 1]

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

Preferably, said compound(s) 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.

Colouring agent

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

For the purposes of the present invention, the term “pigment” refers to any pigment that gives colour to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

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

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

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

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

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

The pigment may be an organic pigment. For the purposes of the present invention, the term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’ s encyclopaedia in the chapter on organic pigments.

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

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

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

Cosmenyl Yellow IOG: Yellow 3 pigment (Cl 11710);

Cosmenyl Yellow G: Yellow 1 pigment (Cl 11680);

Cosmenyl Orange GR: Orange 43 pigment (Cl 71105);

Cosmenyl Red R: Red 4 pigment (Cl 12085);

Cosmenyl Carmine FB: Red 5 pigment (Cl 12490);

Cosmenyl Violet RL: Violet 23 pigment (Cl 51319);

Cosmenyl Blue A2R: Blue 15.1 pigment (Cl 74160);

Cosmenyl Green GG: Green 7 pigment (Cl 74260);

Cosmenyl Black R: Black 7 pigment (Cl 77266).

The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed notably of particles including a mineral core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The organic pigment may also be a lake. For the purposes of the present invention, the term “lake” means dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (Cl 45 380), D&C Orange 5 (Cl 45 370), D&C Red 27 (Cl 45 410), D&C Orange 10 (Cl 45 425), D&C Red 3 (Cl 45 430), D&C Red 4 (Cl 15 510), D&C Red 33 (Cl 17 200), D&C Yellow 5 (Cl 19 140), D&C Yellow 6 (Cl 15 985), D&C Green (Cl 61 570), D&C Yellow 10 (Cl 77 002), D&C Green 3 (Cl 42053), D&C Blue 1 (Cl 42090). An example of a lake that may be mentioned is the product known under the following name: D & C Red 7 (Cl 15 850: 1).

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

Several types of pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiC -lake), Prestige sold by Eckart (mica-TiC ), Prestige Bronze sold by Eckart (mica-Fe203) and Colorona sold by Merck (mica-Ti02-Fe203).

Mention may also be made of the gold-coloured nacres sold notably by the company BASF under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by 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 notably 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 sold notably by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu antique bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.

Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.

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

The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle.

The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.

These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form. The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.

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

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

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

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

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

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

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

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

Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with S1O2 sold under the name Visionaire by the company Eckart.

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

The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.

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

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

The dispersant serves to protect the dispersed particles against their agglomeration or flocculation. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly( 12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipoly hydroxy stearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.

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

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

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

The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

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

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

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

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

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

Preferably, the surface treatments of the pigments are chosen from the following treatments: a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW; a methicone treatment, for instance the SI surface treatment sold by LCW; a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW; a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW; a magnesium myristate treatment, for instance the MM surface treatment sold by LCW; an aluminium dimyristate treatment, such as the MI surface treatment sold by

Miyoshi; a perfluoropolymethyl isopropyl ether treatment, for instance the LHC surface treatment sold by LCW; an isostearyl sebacate treatment, for instance the HS surface treatment sold by

Miyoshi; a perfluoroalkyl phosphate treatment, for instance the PL surface treatment sold by Daito; an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the LSA surface treatment sold by Daito; a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the LS01 surface treatment sold by Daito; an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito; an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito; an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito; a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PL + ITT surface treatment sold by Daito.

According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the dye composition. For the purposes of the present invention, the term “submicron” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

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

The dispersant(s) may thus have a silicone backbone, such as silicone polyether and dispersants of amino silicone type other than the alkoxysilanes described previously. Among the suitable dispersants, mention may be made of: amino silicones, i.e. silicones comprising one or more amino groups such as those sold under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, sold by Genesee Polymers, silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043, sold by Evonik, polydimethylsiloxane (PDMS) silicones bearing carboxyl groups such as X- 22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP- 504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.

According to a particular embodiment, the dispersant(s) are of amino silicone type, other than the compounds described previously, and are cationic.

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

The composition may comprise at least one direct dye.

For the purposes of the present invention, the term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre.

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

Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures. The direct dyes may be chosen from cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (VIII) and (IX) and the azo cationic dyes (X) and (XI) below:

Het+-C(Ra)=N-N(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); in which formulae (VIII) to (XI):

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

Ar+ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci- C8)alkylammonium, such as trimethylammonium;

Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted Ci to Cs alkyl, ii) optionally substituted Ci to Cs alkoxy, iii) (di)(Ci- C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(Ci-C8)alkyl-N-aryl(Ci- Cs)alkylamino or alternatively Ar represents a julolidine group;

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

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

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

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

in which formulae

R¹ represents a Cl to C4 alkyl group such as methyl;

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

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

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

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

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

The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. For the purposes of the present invention, the term “anionic direct dye” means any direct dye including in its structure at least one C02R or S03R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.

As acid dyes according to the invention, mention may be made of the dyes of formulae (XIV), (XIV’), (XV), (XV’), (XVI), (XVI’), (XVII), (XVII’), (XVIII), (XIX), (XX) and (XXI) below: a) the diaryl anionic azo dyes of formula (XIV) or (XIV’):

in which formulae: Hz/, RS, R9, Rio, R’7, R’s, R’9 and R’10, which may be identical or different, represent a hydrogen atom or a group chosen from: alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso;

R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group; (0)₂S(0 )-, M+ with M+ representing a hydrogen atom or a cationic counterion;

(O)CO -, M+ with M+ as defined previously; R”-S(0)2-, with R” representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;

R’”-S(0)2-X’- with R’” representing an alkyl or optionally substituted 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) (0)₂S(0-)-, M+ and iv) alkoxy with M+ as defined previously; optionally substituted heteroaryl; preferentially a benzothiazolyl group; cycloalkyl; especially cyclohexyl,

Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (0)₂S(0 )-, M⁺ or phenylamino groups; or alternatively two contiguous groups R₇ with Rs or Rs with R₉ or R₉ with Rio together form a fused benzo group A’; and R’₇ with R’s or R’s with R’₉ or R’₉ with R’₁₀ together form a fused benzo group B’; with A’ and B’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)₂S(0-)-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’- C(X)-X”-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X’, X” and Ar as defined previously;

W represents a sigma bond s, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(R_a)(R_b)- with R_a and R_b, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R_a and R_b form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or R_a and R_b together form a cyclohexyl; it being understood that formulae (XIV) and (XIV’) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A’, B, B’ or C; preferentially sodium sulfonate.

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

in which formulae (XV) and (XV’): Rii, Ri2 and R_B, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0)₂S(0-), M+ with M+ as defined previously;

Ri4 represents a hydrogen atom, an alkyl group or a group -C(0)0-, M+ with M+ as defined previously;

Ri5 represents a hydrogen atom; Ri₆ represents an oxo group, in which case R’ _½ is absent, or alternatively R15 with Ri₆ together form a double bond;

Ri7 and Ris, which may be identical or different, represent a hydrogen atom, or a group chosen from:

(0)₂S(0-)-, M+ with M+ as defined previously; Ar-0-S(0)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;

Ri9 and R20 together form either a double bond, or a benzo group D’, which is optionally substituted; R’ i₆, R’ i9 and R’20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;

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

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

Y represents either a hydroxyl group or an oxo group;

- represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that formulae (XV) and (XV’) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+ on one of the rings D or E; preferentially sodium sulfonate.

As examples of dyes of formula (XV), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XV’), mention may be made of: Acid Yellow 17;

(XVI’), in which formulae (XVI) and (XVE): R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ and R₂₇, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: alkyl; hydroxyl, mercapto; alkoxy, alkylthio; aryloxy or arylthio optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0-)-, M+ with M+ as defined previously; aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0-)-, M+ with M+ as defined previously;

(di) (alkyl) amino;

(di) (hydroxy alky 1) amino ;

(0)₂S(0-)-, M+ with M+ as defined previously;

Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from: alkyl; polyhydroxyalkyl such as hydroxyethyl; aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (0)₂S(0-)-, M+ with M+ as defined previously; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously, preferentially R° represents an alkyl group; cycloalkyl; notably cyclohexyl;

Z represents a group chosen from hydroxyl and NR’2sR’29 with R’28 and R’29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (XVI) and (XVT) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+; preferentially sodium sulfonate.

As examples of dyes of formula (XVI), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2; and, as an example of a dye of formula (XVT), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (XVII) and (XVIT):

(XVID, in which formulae (XVII) and (XVII’):

R₃₀, R₃₁ and R₃₂, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: alkyl; alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; hydroxyl, mercapto; nitro, nitroso; polyhaloalkyl;

R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously;

(0)₂S(0-)-, M+ with M+ as defined previously;

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

(di) (alkyl) amino;

(di) (hydroxy alky 1) amino ; heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R₃₀, R₃₁ and R₃₂ represent a hydrogen atom;

R_c and R_d, which may be identical or different, represent a hydrogen atom or an alkyl group;

W is as defined previously; W particularly represents an -NH- group; ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- 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; particularly nitro; when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)_m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;

M’ represents a hydrogen atom or a cationic counterion;

, which may be present or absent, represents a benzo group optionally substituted with one or more R30 groups as defined previously; it being understood that formulae (XVII) and (XVIL) comprise at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+; preferentially sodium sulfonate.

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

E) the triarylmethane dyes of formula (XVIII):

(XVIII), in which: R₃₃, R₃₄, R₃₅ and R₃₆, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted with a group (O)_mS(O-)-, M+ with M+ and m as defined previously;

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

(di) (alkyl) amino; hydroxyl, mercapto; nitro, nitroso;

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

(0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

(O)CO -, M⁺ with M⁺ as defined previously; or alternatively two contiguous groups R₄₁ with R₄₂ or R₄₂ with R₄₃ or R₄₃ with R₄₄ together form a fused benzo group: G; with G optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)₂S(0-)-, M+; iv) hydroxyl; v) mercapto; vi) (di) (alkyl) amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’- C(X)-X”-; with M+, R°, X, X’ and X” as defined previously; in particular, R₃₇ to R₄₀ represent a hydrogen atom, and R₄₁ to R₄₄, which may be identical or different, represent a hydroxyl group or (0)2S(0-)-, M+; and when R₄₃ with R₄₄ together form a benzo group, it is preferentially substituted with an (0)₂S(0-)- group; it being understood that at least one of the rings G, H, I or G comprises at least one sulfonate radical (0)₂S(0-)- or one carboxylate radical -C(0)0-; preferentially sulfonate.

As examples 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 and Acid Green 50. f) the xanthene-based dyes of formula (XIX):

which:

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

R₄₉, R₅₀, R₅₁ and R₅₂, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso; (0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

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

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

L represents an alkoxide 0-, M+; a thioalkoxide S-, M+ or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium;

L’ represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom or an optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0)_mS(0-)-, M+ groups with m and M+ as defined previously;

Q and Q’, which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q’ represent an oxygen atom;

M+ is as defined previously. As examples of dyes of formula (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) the indole-based dyes of formula (XX):

(XX), in which:

R53, R54, R55, R56, R57, R58, R59 and R60, which may be identical or different, represent a hydrogen atom or a group chosen from: alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso;

(0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

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

Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XX) comprises at least one sulfonate radical (0)₂S(0-)-, M+ or one carboxylate radical -C(0)0-, M+; preferentially sodium sulfonate.

As an example of dyes of formula (XX), mention may be made of: Acid Blue 74. h) the quinoline-based dyes of formula (XXI):

R61 represents a hydrogen or halogen atom or an alkyl group;

R62, R63 and R64, which may be identical or different, represent a hydrogen atom or a group (0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion; or alternatively R_6i with R62, or R_6i with R64, together form a benzo group optionally substituted with one or more groups (0)₂S(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion; it being understood that formula (XXI) comprises at least one sulfonate radical (0)₂S(0-)-, M+, preferentially sodium sulfonate.

As examples 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 may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts.

Preferably, the direct dye(s) 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, notably polydimethylsiloxanes (PDMS), and organomodified polysiloxanes including at least one functional group chosen from amino groups, hydroxyl groups, oxyalkylene groups, aryl groups and alkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non volatile.

The non-volatile silicones that may be used in the composition according to the invention may preferably be non-volatile polydialkylsiloxanes, polyorganosiloxanes modified with organic functional groups chosen from amine groups, aryl groups, oxyalkylene groups and alkoxy groups, and also 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 described previously.

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

Preferably, the amino silicone(s) that may be used in the context of the invention are chosen from: a) the “trimethylsilyl amodimethicone” silicones corresponding to formula (C):

in which m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10; b) the amino silicones of formula (J) below:

in which: m and n are numbers ranging from 1 to 5000, and in particular n possibly denoting a number from 10 to 2000 and notably from 100 to 1000, and in particular m possibly denoting a number from 1 to 100;

Ri and R2, which may be 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; A denotes a linear or branched alkylene radical containing 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 may denote the following divalent radicals: -CH2CH2CH2- or -CH₂CH(CH )CH₂-. Preferably, Ri and R2, which may be 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, Ri and R2 denote dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, Ri and R2, which may be 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 notably from 100 to 1000; m is a number ranging from 1 to 100;

Ri and R2, which may be identical or different, represent a saturated linear alkyl group comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and preferably 12 to 20 carbon atoms; chosen in particular from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals; preferably, Ri and R2, which may be identical or different, are chosen from hexadecyl and octadecyl radicals; and

A comprises from 3 to 6 carbon atoms, preferably 4 carbon atoms; preferably, A is branched; and more preferentially, A is chosen from the following divalent radicals: -CH2CH2CH2- and -CH₂CH(CH )CH₂-.

The amino silicones of formula (J) that are particularly preferred are those corresponding to the INCI name bis-cetearyl amodimethicone. In particular, the amino silicones of formula (J) correspond to the silicone sold by the company Momentive under the name Silsoft AX; c) the amino silicones of formula (K) below:

in which the value of n is such that the weight-average molecular weight (Mw) of the silicone ranges from 500 to 55000 g/mol.

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

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

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

Examples of organic solvents that may be mentioned include C2-C4 lower alcohols, such as ethanol and isopropanol; polyols, notably those containing from 2 to 6 carbon atoms, for instance glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; polyol ethers, for instance 2-butoxyethanol, propylene glycol monomethyl ether and diethylene glycol monomethyl ether or monoethyl ether; and mixtures thereof.

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 water is present in the composition used in the process according to the invention, ranges from 40% to 99.8% by weight relative 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/methanol mixture.

According to another embodiment, the composition is anhydrous. The term “anhydrous composition” means 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 notably water-free; where appropriate, such small amounts of water may notably be introduced by ingredients of the composition that may 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 provitamins, including panthenol, fillers, oils, opacifiers, sequestrants, film-forming polymers, thickeners, antioxidants, antifoams, moisturizers, emollients, penetrants, fragrances and preserving agents.

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

Needless to say, a person skilled in the art will take care to select this or these additives such that the advantageous properties intrinsically associated with the composition of the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

Energy supply

The process according to the invention also comprises a step b) of supplying energy to the keratin fibres, chosen from a heat treatment using a heating means and/or irradiation with artificial or natural light radiation.

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

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

The heating means that may be used according to the invention may be chosen from those commonly used in the field of hair cosmetics. Preferably, the heating means are chosen from hairdryers, irons such as straightening irons, steam irons, curling irons, crimping irons and curlers; preferentially from irons;

Several heating means may also be combined, for instance the use of a hairdryer, of a heating brush or of a hood followed by the use of an iron.

According to a particular embodiment of the invention, the heating means is chosen from hairdryers and heating hoods. According to this embodiment, the heating means may be applied to wet or dry keratin fibres.

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

Preferably, the duration of the heat treatment of the keratin fibres using a hairdryer or a heating hood is between 30 seconds and 60 minutes, more preferentially between 1 minute and 45 minutes, even more preferentially between 2 minutes and 30 minutes, and better still 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 fibres, i.e. keratin fibres that have been dried beforehand using air or a device such as a hairdryer or a heating hood whose temperature is below 80°C.

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

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

According to a particular form of the invention, the heating step with the iron is performed on dry keratin fibres, i.e. a step of drying with air or a hood or with a heating brush or with a hairdryer precedes the heat treatment step with the iron.

For the purposes of the present invention, the term “iron” means a means for heating keratin fibres by contact with said keratin fibres. As examples of irons that may be used according to the invention, mention may be made of any type of flat iron, for example those described in patents US 5 957 140 and US 5 046 516.

The iron may be applied to said keratin fibres in successive separate touches of a few seconds, or by gradual movement or sliding along the keratin fibres.

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

According to the invention, step b) may be a step of irradiating the keratin fibres 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 of natural daylight (generated by the sun).

According to another embodiment of the invention, the light radiation is artificial, and may or may not be continuous.

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

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

Preferably, the artificial light radiation has an amount of energy per unit area of greater than or equal to 1 J/cm², more preferentially strictly greater than 1 J/cm², even more preferentially from 1.001 to 100 J/cm², better still from 2 to 50 J/cm², particularly preferably from 3 to 10 J/cm².

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 halogen lamps, light-emitting diodes (LED), organic light- emitting diodes (OLED) and lasers.

Mention may be made, for example, of goLITE BLU from the company Philips, the lamp Energylight HF 3319/01 from the company Philips, the lamps Dayvia White and Messa from the company Solvital, the lamp Lumino Plus from the company Lanaform, the lamp Medibeam from the company Medibeam, the lamp M-LED 01 from the company Meimed, the lamp Lifemax Light Pod from the company Lifemax, the lamp Lite-Pad from the company Reicorp, the lamps Omnilux Clear-U and New- U from the company Omnilux, the 1000 W xenon arc lamp from the company Lot- Oriel and the lamp Camag Box 3 (4x8 W) from the company Camag. Preferably, the duration of exposure of the keratin fibres to artificial or natural light radiation is greater than or equal to 5 seconds, more preferentially from 10 seconds to 60 minutes, even more preferentially from 15 seconds to 55 minutes, and 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 performed in static mode (i.e. the lamp does not move relative to the hair, such as a lamp placed in a fixed position above the head, for example). Preferably, the duration of exposure of the keratin materials to artificial light radiation is greater than or equal to 5 seconds, more preferentially from 10 seconds to 60 minutes, even more preferentially from 15 seconds to 55 minutes, and better still from 20 seconds to 45 minutes.

According to a preferred embodiment, when the process according to the invention comprises step a) followed by step b), i.e. when step b) is performed after step a), the duration of exposure of the keratin fibres to artificial light radiation ranges from 5 seconds to 45 minutes; optionally, a step of leaving the composition according to the invention on said keratin fibres ranging from 1 second to 3 hours is performed between step a) and step b); optionally, a step of rinsing said keratin fibres is performed after step b).

According to yet another preferred embodiment of the invention, the step of irradiation with artificial light radiation is performed in dynamic mode (i.e. the lamp moves relative to the hair, for example). Preferably, the duration of exposure of the keratin fibres 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 preferentially from 1 second to 30 seconds, even more preferentially from 3 seconds to 20 seconds and better still from 4 seconds to 10 seconds. This step may be repeated as many times as necessary so that each exposed hair strand or group of hair strands undergoes cumulative exposure of 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 with artificial or natural light radiation, preferably a heat treatment using a heating means followed by irradiation with artificial or natural light radiation, more preferentially a heat treatment using a heating means and irradiation with artificial light radiation, or even irradiation with an irradiation device with heating light radiation. Advantageously, the process according to the invention comprises step a) followed by step b), i.e. step b) is performed after step a).

Preferably, the composition applied in step a) is left on for a time of between 1 second and 3 hours before performing the treatment step b).

On conclusion of the treatment step b), the keratin fibres are optionally rinsed with water or washed with a shampoo. The keratin fibres may then be dried or left to dry.

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

Compound comprising at least two tetrazole groups

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

Preferably, these compounds are those of formula WW(TET)_ni defined previously, in particular the compounds of formula (I), and those of formula POL(TET)_n4, and mixtures thereof. More preferentially, they are chosen from the compounds of formula (V), the 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 process according to the invention described previously.

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 colouring agent chosen from pigments, direct dyes and mixtures thereof.

The composition according to the invention may comprise one or more compounds of structure WW(TET)_ni, as defined previously, one or more compounds of structure POL(TET)_n4, as defined previously, a mixture comprising at least one compound of structure WW(TET)_ni and at least one compound of structure POL(TET)„4.

The composition according to the invention has the same preferences and the same embodiments as the composition applied in step a) of the process according to the invention described previously. The composition according to the invention may be in any presentation form 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 caring for and/or repairing keratin fibres, preferably repairing keratin fibres, more preferentially repairing the split ends of the hair.

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

Another subject 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 colouring agent chosen from pigments, direct dyes and mixtures thereof, for dyeing keratin fibres.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

Examples For the purposes of the present invention, in the text that follows, the term

“alkaline solubility (AS)” means the loss of mass of a sample of 100 mg of keratin fibres under the action of a decinormal sodium hydroxide solution for 30 minutes 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: [Table 2]

PTC A: 2-phenyl-2H-tetrazole-5-carboxylic acid; DCC: N,N'-dicyclohexylcarbodiimide;

TTD : 4,7 , 10-trioxa- 1 , 13 -tridecanediamine The PTCA dissolved in the dichloromethane was placed in a 50 mL three necked flask, with magnetic stirring. Once dissolved, the DCC was added to the medium. The mixture was refluxed for 40 minutes. Monitoring by TLC was performed to monitor the reaction: ethyl acetate. Rf PTCA = 0; Rf solvent front compound = 0.83.

The TTD was added to the reaction medium via a dropping funnel. The reaction was maintained for 50 minutes after the addition of the diamine. The contents of the flask were then evaporated on a rotary evaporator. Compound 1 was purified by column chromatography on silica using a heptane/EtOAc solvent gradient. On conclusion of the purification, 58 mg of compound were obtained. Analysis by HPLC/MS (peak at 564) and NMR 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 as weight percentages of active material (AM). [Table 31

(1) PEG- 12 dimethicone: reference Xiameter OFX-0193 Fluid from the company Dow Coming.

3. Evaluation of the keratin fibre repair A. Procedure - preparation of four locks A lock of hair was moistened (bleached hair with an alkaline solubility value of 20) by soaking it in MilliQ water. The lock was then spread out on a plastic film placed on a hotplate at 33°C. Composition 1 was applied to the lock with a bath ratio of 1:1 (1 g of composition per 1 g of lock of hair). The lock was then massaged with the fingers, making circular movements along the entire length of the lock (10 times). The lock was covered with aluminium foil and was then left for 2 minutes per side on the hotplate. The lock was then combed.

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

Shampooing was then performed with DOP shampoo according to the following protocol: the locks were moistened with tap water at 38°C for 10 seconds, the shampoo was then applied (0.4 g/g of hair), the lock was then massaged for 15 seconds and was then rinsed with water for 20 seconds.

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

This is the lock treated according to the process according to the invention. It is referred to hereinbelow as lock A.

A second lock was prepared according to a procedure which differs from the above in that, during the step of irradiation of the lock with the UV lamp, the lock was covered with aluminium foil so as to protect it against the UV radiation. This is a lock treated according to a comparative process. This lock is referred to as comparative lock

B.

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

A fourth lock was prepared. No composition was applied to this lock. The lock of hair was irradiated for 20 minutes (10 minutes per side) with a UV lamp (power: 7 to 8 mW/cm2; wavelength: 254 nm).

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

B. Study of the breakage of hair via the cyclic fatigue test The cyclic fatigue technique is known to those skilled in the art for the breakage of keratin fibres (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 cycles of extension of a single fibre before breakage of the fibres. Fibres 30 mm long were subjected to a constant tension (100 MPa) at a constant speed (40 mm/s). The studies were performed at 25°C and at 45% relative humidity. A Diastron CYC 801 machine from the company Diastron was used. A series of measurements included 50 hair strands. The results are collated in Table 4 below.

[Table 4]

The above results clearly show that the performance in terms of resistance to breakage of the hair was better for the lock treated with process A according to the invention than for the comparative locks B, C and D. Specifically, the lock treated with the process of the invention withstood more than 12 000 cycles, whereas the comparative locks broke quickly.

C. Differential scanning calorimetry study

The differential scanning calorimetry technique is known to those skilled in the art as a method for quantifying the reinforcement of proteins in the cortex of keratin fibres. The principle of the test is to measure the protein denaturing temperature. The higher the protein denaturing temperature, the better the integrity of the proteins of the cortex, which is reflected by less breakage of the fibres.

The denaturing temperature is directly linked to the bonding density of the keratin proteins present in the cortex. Thus, the lower the denaturing temperature, the lower the bonding density between the proteins. In point of fact, the disulfide bridges break and the cortex is damaged. The test was performed and the results are collated in Table 5 below: [Table 5]

A 2°C increase in the denaturing temperature of the hair was observed for lock A relative to lock C. The application of composition 1 to lock A gave rise to this increase. This means that reinforcement of the protein network of the cortex has taken place. The protein bonding density is higher, and thus bonds have formed in the cortex. On the other hand, a significant decrease in the denaturing temperature was observed for lock D. Treatment of the lock by irradiation with UV light without application of composition 1 gave rise to degradation of the fibre.

The results thus show that better performance is obtained 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 resistance to 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 m = 1 :

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

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

Compound 5 is a mixture of three 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:

[Table 61

PTCA: 2-phenyl-2H-tetrazole-5-carboxylic acid;

OC: oxalyl chloride;

PPD: polypropanediol: Sensatis H250 from the company Allessa.

The PTCA dissolved in the dichloromethane was placed in a three-necked round-bottomed flask, with magnetic stirring. The reaction mixture was placed under argon (inert atmosphere). Once dissolved, the OC was added to the medium, followed by one 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 on an external ice bath. The solution with the PTCA was added dropwise to the PPD solution via a dropping funnel. The reaction was stirred under an inert atmosphere for 20 hours and the medium was then poured into water. The aqueous phase was extracted with dichloromethane (twice). The organic phase was washed with saturated aqueous sodium bicarbonate solution and then with 2N HC1 solution. It was then dried over Na2S04, filtered and concentrated under reduced pressure. Compounds 2 to 4 were obtained by purification by means of column chromatography on silica, using a 95/5 dichloromethane/ethyl acetate and then 98/2 dichloromethane/methanol solvent gradient. An identical process was performed to obtain compound 5. Specifically, 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 shown in Table 7 below, the amounts of which are expressed as weight percentages of active material (AM).

[Table 7]

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

Momentive.

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

A. Procedure - preparation of three locks Compositions 2a, 2b and 2c were applied to three different dry locks (natural hair, 2 g/20 cm in length), at a rate of 0.5 g of composition per gram of hair, each of the locks being placed on a hotplate at 33°C during the application. The locks were then massaged with the fingers, making circular movements along the entire length of the lock (5 times) and then combed. The locks were then left to stand for 2 minutes (1 minute per side) on the hotplate. The locks were then dried with a hairdryer.

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

Hereinbelow, the locks are named lock E (treated with composition 2a according to the invention), lock F (treated with comparative composition 2b) and lock G (treated with composition 2c according to the invention).

B. Study of the persistence of silicone on the locks

Locks E and F were analysed by infrared (ATR-IR) before and after having been washed 10 times with a shampoo according to the following washing protocol: the locks were moistened five times and a DOP shampoo was then applied to the locks (0.4 g/g of hair), the locks were then massaged 10 times with the fingers, making circular motions along the entire length of the lock, and the locks were then rinsed 10 times in water, then dried with a hairdryer, and the entire sequence of steps was then repeated nine times.

The method employed makes it possible to quantify the amount of silicone present on the surface of the lock of hair. After applying the compositions, a silicone film formed on the surface of the lock. Ten shampoo washes were then performed. The thickness of the film decreased with the repetition of the shampoo washes. The signal representing the silicone in the infrared spectrum also decreased.

In this test, a ratiometric comparative, referred to as the ratio R, was performed between a signal representing the amides of the hair proteins (band at 1633 cm ¹ in the infrared spectrum) and a signal representing the Si-O-Si bond of the silicone polymers (band at 1258 cm ¹). If the ratio remains identical, this means that the amount of silicone remains constant on the surface of the hair. On the other hand, if the ratio increases, this means that the amount of silicone present has decreased. The results are collated in Table 8 below.

[Table 8]

The above results show that the process according to the invention made it possible to improve the persistence of the silicone on the lock with respect to shampoo washing. Specifically, the amount of silicone present on lock E treated with the process of the invention withstood at least 10 shampoo washes, in contrast with the silicone deposit on comparative lock F. C. Study of the ease of combing

The test consisted in combing each of the locks three times and in comparing the combing action with that performed on a lock obtained from the same batch, but which was not irradiated with a UV lamp. Thus, lock El is a lock onto which composition 2a was applied, but which was not irradiated. Similarly, lock FI is a lock onto which composition 2b was applied, but which was not irradiated. Finally, lock G1 is a lock onto which composition 2c was applied, but which was not irradiated. Locks El, FI and G1 are thus treated by means of a comparative process.

In the course of this test, six different combing cases are possible:

-2: very difficult along the entire lock; -1: difficult along the entire lock, very difficult at the ends;

0: difficult at the ends;

+0.5: easy, with slight resistance at the ends;

+1: easy;

+2: very easy. A control lock, referred to as lock T, is the reference lock onto which no composition was applied, but which was irradiated with a UV lamp. The score 0 was attributed to this lock since combing was difficult at the ends. Three evaluators gave their scores. The results are collated in the table below. [Table 9]

The results clearly show that lock E treated according to the process according to the present invention was easy to comb and the good combing properties given to lock E withstood even after 10 shampoo washes.

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

Compositions 3a to 3c were prepared from the ingredients shown in Table 10 below, the amounts of which are expressed as weight percentages of active material (AM). [Table 10]

(3) Poly(dimethylsiloxane)bis(3-aminopropyl) terminated (PDMS = 25 kDa) from the company Gelest (reference DMS-A31). 5. Evaluation of the frizziness control of the hair

A. Procedure - preparation of six 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 various compositions were applied to the dry lock (natural hair, 2 g/20 cm in length) placed on a hotplate at 33°C. The locks were then massaged with the fingers, making circular movements along the entire length of the lock (five times) and then combed. The locks were then left to stand for 2 minutes (1 minute per side) on the hotplate. The locks were then dried with a hairdryer and then combed. Three of the six locks of hair were then straightened with a straightening iron

(“Babyliss Pro EP technology 5.0 the straightener” iron) at a temperature of 190°C. The iron was passed through three times per lock at a speed of 4 seconds per 10 cm of locks.

The three locks concerned were the first, the third and the fifth lock. Hereinbelow, the locks straightened with the straightening iron are named lock H (treated with composition 3a according to the invention and straightened with the straightening iron), lock I (treated with composition 3b according to the invention and straightened with the straightening iron) and lock J (treated with comparative composition 3c and straightened with the straightening iron). The locks not straightened with the straightening iron are the second, the fourth and the sixth lock. Hereinbelow, these locks not straightened with the straightening iron are named lock HI (treated with composition 3a according to the invention and not straightened with the straightening iron), lock II (treated with composition 3b according to the invention and not straightened with the straightening iron) and lock J1 (treated with comparative composition 3c and not straightened with the straightening iron).

B. Study of the frizziness control of the hair All the locks were placed in a glovebox (closed box) with a relative humidity regulated at 80%. Measurements were taken at time TO and after 1 hour (Tl).

The frizziness was evaluated by measuring the mid-height width of the locks. The smaller the difference (D) between the mid-height width of the lock measured at time Tl and the mid-height width at time TO, the better the frizziness control. The results are collated in Table 11 below.

[Table 11]

The results show that the locks treated by means of the process according to the invention (using a compound according to the invention and the heat of a straightening iron) (locks H and I) were less frizzy than the locks which did not undergo any heat treatment (locks HI and II) and less frizzy than the locks onto which compositions not containing any compound according to the invention were applied (locks J and Jl). 6. Preparation of compositions 4a, 4b, 4c and 4d

Compositions 4a to 4d were prepared from the ingredients indicated in Table 12 below, the amounts of which are expressed as weight percentages of active material (AM).

[Table 121

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

(4) Pigment from the company Daito Kasei Kogyo (reference ISD-CB2). 7. Evaluation of the colouring

A. Procedure - preparation of four 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, the various compositions being applied to the dry lock (natural hair, 1 g/20 cm in length). The locks were then massaged with the fingers, making circular movements along the entire length of the lock (5 times) and then combed. The locks were then left to stand for 15 minutes. The locks were then dried with a hairdryer.

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

B. Colouring study

The colour 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 dyeing and before washing with shampoo and then after five shampoo washes, according to the following washing protocol: the locks were moistened five times and a DOP shampoo was then applied to the locks (0.4 g/g of hair), the locks were then massaged 10 times with the fingers, making circular motions along the entire length of the lock, and the locks were then rinsed 15 times in water, then dried with a hairdryer, and the entire sequence of steps was then repeated four times.

In this L*a*b* system, L* represents the lightness of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis. The smaller the value of L*, the darker and more powerful the colouring. The smaller the value of a*, the greener the colour and the higher the value of a*, the redder the colour. The smaller the value of b*, the bluer the colour and the higher the value of b*, the yellower the colour.

The resistance of the colour to repeated shampoo washing, corresponding to the variation in colouring between the locks of hair before and after the repeated shampoo washing, is defined by (DE**) according to the following equation:

DE** = V[(L1*-L*)² + (al*-a*)² + (bl*-b*)²].

In this equation, L*, a* and b* represent the values measured on locks of hair after dyeing and LI*, al* and bl* represent the values measured on the respective locks of hair washed with the shampoo. The lower the value of DE**, the greater the resistance of the colourings with respect to shampoo washing.

The results are collated in Table 13 below:

[Table 13]

The results show that the locks treated with a composition according to the invention (compositions 4a and 4c) showed significantly improved resistance of the colourings with respect to shampooing, relative to the locks onto which compositions not containing any 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 has a value from 7 to 45:

Compound 6 was prepared with the following ingredients, indicated in Table 14 and according to the following protocol: [Table 14]

PTCA: 2-phenyl-2H-tetrazole-5-carboxylic acid;

OC: oxalyl chloride;

PPD-2: Velvetol: polypropanediol from the company Allessa (molecular weight 500- 2700 g/mol; CAS No. 345260-48-2).

The PTCA dissolved in the dichloromethane was placed in a three-necked round-bottomed flask, with magnetic stirring. The reaction mixture was placed under argon (inert atmosphere). Once dissolved, the OC was added to the medium, followed by one 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 on an external ice bath. The solution with the PTCA was added dropwise to the PPD solution via a dropping funnel. The reaction was stirred under an inert atmosphere for 20 hours and the medium was then poured into water. The aqueous phase was extracted with dichloromethane (twice). The organic phase was washed with saturated aqueous sodium bicarbonate solution and then with 2N HC1 solution. It was then dried over Na2S04, filtered and concentrated under reduced pressure. Compound 6 was obtained by purification by means of column chromatography on silica, using a 95/5 dichloromethane/ethyl acetate and 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 as weight percentages of active material (AM).

[Table l5]

3. Evaluation of the repair of split ends

A. Procedure Each of the natural fibres used was first split longitudinally in two at the end.

The fibres used are fibres sold by the company IHIP (Glendale, NY 11385, United States - Reference: Split End Hair, length 15 cm).

The fibres were then soaked in composition 5a or in composition 5b, for 30 seconds. The fibres were then suspended and left to dry naturally. The fibres were then straightened with a straightening iron (“Babyliss Pro EP technology 5.0 the straightener” iron) at a temperature of 190°C. The iron was passed through three times per fibre at a speed of 4 seconds per 10 cm of fibre.

Hereinbelow, the fibres soaked in composition 5a and straightened are referred to as the fibres according to the invention, and the fibres soaked in composition 5b and straightened are referred to as the comparative fibres.

B. Study of the repair of split ends

The observations were made using a magnifying optical microscope (Model 175 X optical “MightyScope 1.3M Digital Microscope” sold by the company Aven Inc., USA).

Observations by microscope of the fibres before soaking were performed. Observations by microscope of the fibres according to the invention and of the comparative fibres were also performed. The change in the fibres was then evaluated by means of the microscope. More particularly, the repair of the fibre was evaluated. If the two parts of the end of a fibre have been united, then the fibre is repaired. If not, the fibre is not repaired. It was found that three out of five fibres were repaired as regards the fibres according to the invention, whereas no fibres were repaired as regards the comparative fibres.

The results thus show that the process according to the invention using a particular compound of formula (V) made it possible to repair the damaged split ends.

Claims

1. Process for treating keratin fibres, notably the hair, comprising: a) a step of applying to the keratin fibres a composition comprising one or more compounds comprising at least two tetrazole groups, and optionally at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; b) a step of supplying energy to the keratin fibres, chosen from a heat treatment using a heating means and/or irradiation with artificial or natural light radiation.

2. Process according to Claim 1, characterized in that said compound comprising at least two tetrazole groups is of formula (Al) below: WW(TET)_ni (Al), in which:

WW denotes a linear or branched or (hetero)cyclic, saturated C₂ to C₃₀ multivalent radical, an aromatic radical, or a heteroaromatic cyclic radical, WW also possibly containing one or more heteroatoms such as O and N and/or one or more functions chosen from ester, ketone, amide and urea functions, preferably ester and amide functions, and/or possibly being substituted with one or more linear or branched Ci to C₁₀ alkyl groups, or linear or branched Ci to C₁₀ alkoxy groups, it being understood that when the radical WW is substituted, the tetrazole groups may be borne by the substituent(s);

TET denotes a tetrazole group; m denotes an integer greater than or equal to 2, preferably between 2 and 10, preferably between 2 and 5, in particular 2.

3. Process according to Claim 1 or 2, characterized in that said compound comprising at least two tetrazole groups is of formula (I) below:

(I), in which:

A represents a linear or branched, saturated or unsaturated C₂ to C₃₀ hydrocarbon-based chain, optionally containing one or more groups or heteroatoms chosen from O, S, N, CO, or combinations thereof such as -CO-O, -O-CO-,

-CO-NH-, -NH-CO-; Ri and R2, which may be identical or different, represent a Ci to Ce alkyl group or an aromatic group.

4. Process according to Claim 3, characterized in that A is of formula (IIA) below: -C(0)-Xi-B-X₂-C(0)- (IIA), in which:

Xi and X₂, which may be identical or different, represent an oxygen atom or a group NR with R denoting a hydrogen atom or a Ci to C4 alkyl radical such as methyl;

B represents a linear or branched, saturated or unsaturated C₂ to C₂s hydrocarbon-based chain, optionally interrupted with one or more heteroatoms chosen from O, S and N.

5. Process according to Claim 4, characterized in that B is interrupted with one or more oxygen atoms, preferably with several non-adjacent oxygen atoms.

6. Process according to any one of Claims 3 to 5, characterized in that A is of formula (IIIA) below: -C(0)-0-CH₂-CH₂-CH_2-[0-CH₂-CH₂-CH₂]„₂-0-C(0)- (IIIA), in which n₂ is an integer ranging from 1 to 8, preferably from 1 to 7; or of formula (IV A) below: -C(0)-NH-CH₂-CH₂-CH₂-[0-CH₂-CH₂]„₃-CH₂-NH-C(0)- (IV A), in which n3 is an integer ranging from 1 to 8, preferably from 1 to 7 and more preferentially from 1 to 3.

7. Process according to any one of Claims 3 to 6, characterized in that Ri and R₂ represent an aromatic group, preferably a phenyl group.

8. Process according to Claim 1, characterized in that said compound comprising at least two tetrazole groups is of formula (A2) below: POL(TET)_n4 (A2), in which:

POL denotes a multivalent polymeric radical which is carbon-based or silicon-based or comprising carbon and silicon atoms, POL also possibly comprising one or more heteroatoms such as O, N or S, and/or one or more functions chosen from ester, ketone and amide functions, and/or possibly being substituted with one or more linear or branched Ci to C10 alkyl groups, or linear or branched Ci to C10 alkoxy groups, it being understood that when POL is substituted, the tetrazole groups may be borne by the substituent(s);

TET denotes a tetrazole group; denotes an integer greater than or equal to 2, preferably between 2 and 1000, preferably between 2 and 500.

9. Process according to Claim 8, characterized in that POL is of formula (IIB) below: -C(0)-X’I-BI-X’₂-C(0)- (IIB), in which: X’_I and X’2, which may be identical or different, represent an oxygen atom or a group NR’ with R’ denoting a hydrogen atom or a Ci to C4 alkyl radical such as methyl, preferably a hydrogen atom;

Bi represents a linear or branched, saturated or unsaturated C31 to C3000 hydrocarbon-based chain, interrupted with one or more heteroatoms chosen from O, and optionally S and N.

10. Process according to Claim 9, characterized in that Bi is interrupted with one or more oxygen atoms, preferably with several non-adjacent oxygen atoms.

11. Process according to Claim 9 or 10, characterized in that Bi is of formula (IIIB) below: -C(0)-0-CH₂-CH₂-CH_2-[0-CH₂-CH₂-CH₂]_n5-0-C(0)- (IIIB), in which ns is an integer ranging from 9 to 990, preferably from 9 to 500; or of formula (IVB) below: -C(0)-NH-CH₂-CH₂-CH₂-[0-CH₂-CH₂]_n6-CH₂-NH-C(0)- (IVB), in which P₆ is an integer ranging from 9 to 1000, preferably from 9 to 500.

12. Process according to any one of the preceding claims, characterized in that said compound comprising at least two tetrazole groups is chosen from the compounds of formula (V) below, and mixtures thereof:

(V), in which is an integer ranging from 1 to 990, preferably from 1 to 100 and more preferentially from 1 to 45; and the compounds of formula (VI) below, and mixtures thereof:

in which ns is an integer ranging from 1 to 1000, preferably from 1 to 100 and more preferentially from 1 to 3.

13. Process according to any one of the preceding claims, characterized in that said compound(s) comprising at least two tetrazole groups are present in a content ranging from 0.01% to 15% by weight and preferably from 0.2% to 10% by weight relative to the total weight of the composition.

14. Process according to any one of the preceding claims, characterized in that the composition also comprises one or more silicones, preferably chosen from amino silicones, silicones containing oxyalkylene groups, and mixtures thereof.

15. Process 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 preferentially from 120 to 230°C.

16. Process 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.

17. Process 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 lamps such as halogen lamps, light-emitting diodes, organic light-emitting diodes and lasers.

18. Compound comprising at least two tetrazole groups, characterized in that it is chosen from WW(TET)_ni as defined in any one of Claims 3 to 7, POL(TET)_n4 as defined in any one of Claims 9 to 11, and mixtures thereof.

19. Compound according to Claim 18, 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.

20. Composition comprising one or more compounds as defined in either of Claims 18 and 19.

21. Composition according to the preceding claim, characterized in that it comprises at least one colouring agent chosen from pigments, direct dyes, and mixtures thereof.

22. Use of at least one compound as defined in either of Claims 18 and 19 or of at least one composition as defined in Claim 20, for caring for and/or repairing keratin fibres, preferably for repairing keratin fibres, more preferentially for repairing the split ends of the hair.

23. Process for dyeing keratin fibres, comprising the application of at least one composition as defined in Claim 21, and a step of supplying energy to the keratin fibres by heat treatment and/or by irradiation using artificial or natural radiation.

24. Use of the composition as defined in Claim 21, for dyeing keratin fibres.