FR3104969A1 - Process for treating keratin fibers using a composition comprising a salt of carnitine or of a carnitine derivative comprising an aromatic organic anion - Google Patents

Abstract

The present invention relates to a process for treating keratin fibers comprising the application of a composition comprising at least one salt of carnitine or of a carnitine derivative comprising an aromatic organic anion for the care and / or repair of keratin fibers.

Description

Process for treating keratin fibers using a composition comprising a salt of carnitine or of a carnitine derivative comprising an aromatic organic anion

Technical field of the invention

The present invention relates to a method for treating keratin fibers comprising the application of a composition comprising at least one salt of carnitine or of a carnitine derivative comprising an aromatic organic anion for the care and/or repair of keratin fibres.

Background of the invention

External atmospheric agents such as pollution and bad weather, as well as mechanical or chemical treatments, or certain routines, such as brushing, combing, dyeing, bleaching, perms, straightening, repeated washing, can damage and weaken the hair. Hair can be damaged and over time become dry, rough, brittle, dull, split ends and/or limp.

In order to remedy this, it is usual to have recourse to hair compositions intended to condition the hair by providing it with satisfactory cosmetic properties, in particular smoothing, shine, softness to the touch, suppleness, lightness, good detangling properties leading to ease of combing, good discipline of the hair which is thus easier to comb and keeps its shape. However, the conditioning effect obtained by these hair care products fades quickly over time, and does not show satisfactory remanence to shampoos.

It is known that carnitine or one of its salts such as carnitine tartrate or carnitine lactate can be used in hair compositions (see in particular DE 195 39859, EP 1800654 and EP 2111852). Likewise, it is known that certain organic acids can be used in hair compositions (see in particular EP 0978272). However, these compounds do not always give complete satisfaction as regards in particular the prevention of hair breakage, for example during combing.

There is therefore still a real need to develop a process for treating keratin fibers, in particular human keratin fibers such as the hair, making it possible to preserve or even improve the quality of the fiber, in particular by improving the density of bonds between proteins present in the cortex of the fibre, in order to repair it or reduce its breakage, for example during combing or disentangling and this in a durable manner, that is to say which has a satisfactory remanence to shampoos.

The applicant has surprisingly discovered that these problems can be solved by the process according to the present invention involving the application to keratin fibres, in particular human keratin fibers such as the hair, of a composition comprising salts of carnitine or carnitine derivative having one or more aromatic organic anions.

According to a first aspect, the subject of the present invention is a method for treating keratin fibers comprising:
i) a step of applying to the keratin fibers a composition (A) comprising at least one compound of formula (I):

;
in which:
▪R ¹ ,R ² AndR ³ , identical or different, represent a group (hydroxy)(C₁-VS₄)alkyl;
▪R ⁴ represents a hydrogen atom, a group (C₁-VS₄)alkyl or a –C(O) groupR, in whichRis a group (C₁-VS₃)alkyl;
▪R ⁵ represents a hydrogen atom, a group (C₁-VS₄) alkyl, an alkali metal or an alkaline earth metal;
▪Year ^- represents an aromatic organic anion chosen from the compounds of formulas(II),(III)Or(IV)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f designate independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R'’ is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To AndR ^b can form together and with the carbon atom which carries them a saturated or unsaturated (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members and more particularly a carbocycle of 5 or 6 members;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- represents a single bond or an ethylenic double bond, provided that whenrepresents an ethylenic double bondR ^b AndR ^vs are absent;
- pis an integer equal to 0 or 1;
- ris an integer equal to 0 or 1;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge;
▪xis a stoichiometric coefficient chosen so as to guarantee the electroneutrality of the compound of formula(I).

According to a second aspect, the subject of the present invention is a composition (A) as defined above, it being understood that the composition does not comprise the following compounds of formulas 1 to 4 :

According to a third aspect, the subject of the present invention is the following compounds of formulas 5 to 29 and their mixtures:

According to a fourth aspect, a subject of the present invention is the cosmetic use of at least one compound of formula (I) , as defined above, for the care and/or repair of keratin fibres.

According to a final aspect, a subject of the present invention is the cosmetic use of at least one composition (A) as defined above for the care and/or repair of keratin fibres.

Detailed description of the invention

By "keratin fibers" is meant fibers of human or animal origin such as hair, body hair, eyelashes, eyebrows, wool, angora, cashmere or fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferably the hair.

By "alkyl group" is meant a hydrocarbon radical, linear or branched, saturated.

By "(C _x -C _y )alkyl group" is meant an alkyl group comprising from x to y carbon atoms, preferably methyl, ethyl, n -propyl, iso-propyl or butyl, more preferably methyl or n -propyl, even more preferably methyl.

By "(C _x -C _y )hydroxyalkyl group" is meant a (C _x -C _y )alkyl group in which at least one of the hydrogen atoms is replaced by a hydroxy (-OH) group.

By "alkoxyl group" is meant an alkyl group bonded to an oxygen atom.

By “(C _x -C _y )alkoxyl group” is meant an alkoxyl group comprising from x to y carbon atoms.

By "(hetero)cycle" is meant a heterocycle or a carbocycle.

By "heterocycle" is meant a cyclic group of 4 to 8 members, preferably 5 or 6 members, saturated or unsaturated or aromatic, the members of which consist of carbon atoms and at least one heteroatom chosen from: O , S, N, preferably O, N. A heterocycle designates for example morpholinyl, piperidinyl, tetrahydrofuranyl, pyrolidinyl.

By "carbocycle" we mean a cyclic group of 4 to 8 membered, 5 to 6 membered, saturated or unsaturated, the members of which consist of carbon atoms. A carbocycle designates for example a cyclopentyl or cyclohexyl ring.

By "aryl" is meant a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic. Preferably, the aryl radical is a phenyl, biphenyl, naphthyl, anthracenyl, or tetrahydronaphthyl, and more preferably a phenyl.

The "aryl" or "heterocycle" or "carbocycle" group or the aryl or heterocyclic or carbocyclic part of a group may be substituted by at least one substituent carried by a carbon atom, chosen from:
- a (C ₁ -C ₆ )alkyl group, preferably a (C ₁ -C ₄ )alkyl group, optionally substituted by one or more groups chosen from hydroxy and (C ₁ -C ₂ )alkoxyl;
- a halogen atom such as chlorine;
- a hydroxy or thiol group;
- a (C ₁ -C ₆ )alkoxy group or a (C ₁ -C ₆ )alkylthio group;
- a (C ₂ -C ₄ )(poly)hydroxyalkoxy group.

A (hetero)ring group or a non-aromatic part of an aryl group can also be substituted by one or more oxo groups.

By "protective group of phenol function", is meant a protective group such as those described in "Greene's Protective Groups in Organic Synthesis, P. G. M. Wutz,

T. Greene, ed. Wiley-Blackwell”, preferably an acyl group, in particular an acetyl group.

Unless otherwise indicated, when compounds are mentioned in the present application, it is also meant their optical isomers, their geometric isomers, their tautomers, their salts or their solvates, alone or as a mixture.

The terms "at least one" and "one or more" are synonymous and may be used interchangeably.

The expression "prevent the breakage of keratin fibres" is synonymous with the expression "increase the mechanical resistance of keratin fibres".

Treatment method

According to a first aspect, the subject of the present invention is a method for treating keratin fibers as described above. Preferably, the treatment process is a process for caring for and/or repairing keratin fibers.

The applicant has surprisingly discovered that the use of carnitine or one of its derivatives in combination with certain aromatic organic anions having a carboxylate, sulphonate or phosphonate group in the process according to the invention makes it possible to improve the resistance mechanics of keratinous fibres, in particular by improving the density of bonds between proteins present in the cortex of the fibers and thus to reduce their breakage, in particular during styling or disentangling, such as combing. Furthermore, the Applicant has also noticed that it was possible to obtain a lasting effect over time with, in particular, a satisfactory remanence to shampoos.

Membership (A)

Composition (A) comprises at least one compound of formula (I) as defined above. The compound of formula (I) is a salt of carnitine or of one of its derivatives. The cationic part of the compound of formula (I) is carnitine or one of its derivatives and the anionic part An ⁻ of the compound of formula (I) is an aromatic organic anion.

Anionic part

General formula

An ^- represents an aromatic organic anion chosen from the following compounds of formulas (II) , (III) or (IV) :

in which:

- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from:
–OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R'’ is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To AndR ^b can form together and with the carbon atom which carries them a saturated or unsaturated (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members and more particularly a carbocycle of 5 or 6 members;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- represents a single bond or an ethylenic double bond, provided that whenrepresents an ethylenic double bondR ^b AndR ^vs are absent;
- pis an integer equal to 0 or 1;
- ris an integer equal to 0 or 1;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge.

Preferably, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Preferably,R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₄)alkyl;
● a group (C₁-VS₄)hydroxyalkyl;
● a group (C₁-VS₄)alkoxyl;
● a halogen atom;
● a hydroxyl group;
● a –O-C(O)-CH group₃;
Being heard that:

▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members.

More preferentially , R ^a , R ^b , R ^c , R ^d , R ^e and R ^f represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Composition (A) may comprise a mixture of compounds of formula (I) comprising different aromatic organic anions An ⁻ chosen from the compounds of formulas (II) , (III) or (IV) as defined above.

First variant

According to a first variant,Year ^- is chosen from the compounds of formulas(IIa),(IIIa)Or(IVa)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To AndR ^b represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
▪R ^To AndR ^b can form together and with the carbon atom that carries them a C=O bond;
▪R ^To AndR ^b can form together and with the carbon atom which carries them a saturated or unsaturated (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members and more particularly a carbocycle of 5 or 6 members;
▪R ^To OrR ^b can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge.

Preferably, according to this first variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, according to this first variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Preferably, according to this first variant,R ^To AndR ^b represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₄)alkyl;
● a group (C₁-VS₄)hydroxyalkyl;
● a group (C₁-VS₄)alkoxyl;
● a halogen atom;
● a hydroxyl group;
● a –O-C(O)-CH group₃;
Being heard that:
▪R ^To AndR ^b can form together and with the carbon atom that carries them a C=O bond;
▪R ^To OrR ^b can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members.

More preferably, according to this first variant , R ^a and R ^b represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

According to this first variant,Year ^- is preferably chosen from the compounds of formulas(IIa)Or(IIIa)as defined above, more preferably from the compounds of formula(IIa).

Second variant

According to a second variant,Year ^- is chosen from the compounds of formulas(II'a),(III'a)Or(IV'a)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge.

Preferably, according to this second variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, according to this second variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

According to this second variant,Year ^- is preferably chosen from the compounds of formulas(II'a)Or(III'a)as defined above, more preferably from the compounds of formula(II'a).

Third variant

According to a third variant,Year ^- is chosen from the compounds of formulas(II''a),(III''a)Or(IV''a)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;

- R ^b represents:
● a hydrogen atom;
● a (C ₁ -C ₆ )alkyl group optionally substituted by one or more identical or different groups chosen from: –O R , –N R'R'' , –C(O)O R , –OC(O)- R , (hetero)ring, –C(O) -R , –NH-C(O) -R , –C(O)-NH- R , with R , R' and R'' as previously defined, being understood that the –N R'R'' group is different from the –NH ₂ group;
● a (C ₁ -C ₆ )alkoxyl group optionally substituted by one or more identical or different groups chosen from: –O R , –N R'R'' , –C(O)O R , –OC(O)- R , aryl and –CF ₃ and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, N R' , CO, S, SO and SO ₂ , with R , R' and R'' as defined previously , it being understood that the –N R'R' ' group is different from the –NH ₂ group;
● a halogen atom;
● a group –O- X with X as previously defined;
Being heard that:
▪ R ^b can form with R ⁶ or R ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline-earth metal, preferably a negative charge.

Preferably, according to this third variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, according to this third variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Preferably, according to this third variant, R ^b represents:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
Being heard that:
▪ R ^b can form with R ⁶ or R ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members.

More preferably, according to this third variant, R ^b represents:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

According to this third variant,Year ^- is preferably chosen from the compounds of formulas(II''a)Or(III''a)as defined above, more preferably from the compounds of formula(II''a).

Fourth variant

According to a fourth variant,Year ^- is chosen from the compounds of formulas(IIb),(IIIb)Or(IVb)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To ,R ^b ,R ^vs AndR ^d represent independently of each other:

● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R'’ is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To AndR ^b can form together and with the carbon atom which carries them a saturated or unsaturated (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members and more particularly a carbocycle of 5 or 6 members;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge;

Preferably, according to this fourth variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, according to this fourth variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Preferably, according to this fourth variant,R ^To ,R ^b ,R ^vs AndR ^d represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₄)alkyl;
● a group (C₁-VS₄)hydroxyalkyl;
● a group (C₁-VS₄)alkoxyl;
● a halogen atom;
● a hydroxyl group;
● a –O-C(O)-CH group₃;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members.

More preferably, according to this fourth variant, R ^a , R ^b , R ^c and R ^d represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

According to this fourth variant,Year ^- is preferably chosen from the compounds of formulas(IIb)Or(IIIb)as defined above, more preferably from the compounds of formula(IIb).

Fifth variant

According to a fifth variant,Year ^- is chosen from the compounds of formulas(IIc),(IIIc)Or(IVc)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To AndR ^d represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R'’ is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge.

The ethylenic double bond between –C R ^a and –C R ^c can be cis or trans.

Preferably, according to this fifth variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, according to this fifth variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Preferably, according to this fifth variant, R ^a and R ^c represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group.

More preferably, according to this fifth variant, R ^a and R ^c represent independently of each other:

● a hydrogen atom;

● a (C ₁ -C ₄ )alkyl group;

● a (C ₁ -C ₄ )alkoxyl group;

● a (C ₁ -C ₄ )hydroxyalkyl group;

● a hydroxyl group.

According to this fifth variant,Year ^- is preferably chosen from the compounds of formulas(IIc)Or(IIIc)as defined above, more preferably from the compounds of formula(IIc).

Sixth variant

According to a sixth variant,Year ^- is chosen from the compounds of formulas(IId),(IIId)Or(IVd)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R'’ is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To AndR ^b can form together and with the carbon atom which carries them a saturated or unsaturated (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members and more particularly a carbocycle of 5 or 6 members;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge.

Preferably, according to this sixth variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;

it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members.

More preferably, according to this sixth variant, R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

Preferably, according to this sixth variant,R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₄)alkyl;
● a group (C₁-VS₄)hydroxyalkyl;
● a group (C₁-VS₄)alkoxyl;
● a halogen atom;
● a hydroxyl group;
● a –O-C(O)-CH group₃;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members.

More preferably, according to this sixth variant, R ^a , R ^b , R ^c , R ^d , R ^e and R ^f represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group.

According to this sixth variant,Year ^- is preferably chosen from the compounds of formulas(IId)Or(IIId)as defined above, more preferably from the compounds of formula(IId).

Composition (A) may comprise a mixture of compounds of formula (I) comprising different An ^- aromatic organic anions chosen from the compounds of formulas (II _a ) , (III _a ) , (IV _a ), (II' _a ) , (III' _a ) , (IV' _a ), (II'' _a ) , (III'' _a ) , (IV'' _a ), (II _b ) , (III _b ) , (IV _b ), ( II _c ) , (III _c ) , (IV _c ), (II _d ) , (III _d ) or (IV _d ) as defined above.

Preferably, An ^- is chosen from the compounds of formula (II) as defined above or from the compounds of formula (IIa) as defined above or from the compounds of formula (II'a) as defined above or from the compounds of formula (II''a) as defined above or from the compounds of formula (IIb) as defined above or from the compounds of formula (IIc) as defined above before or among the compounds of formula (IId) as defined above.

According to a preferred embodiment, An ^- is chosen from the following compounds (II ₁ ) to (II ₂₉ ) :

According to a more preferred embodiment, An ⁻ is chosen from compounds (II ₁ ) to (II ₁₁ ) as defined above. According to an even more preferred embodiment, An ⁻ is chosen from compounds (II ₁ ) or (II ₂ ) as defined above.

Cationic part

In the case where R ⁵ represents an alkali metal, it may be sodium.

Preferably, the compound of formula (I) is a carnitine salt. Thus, preferably, R ¹ , R ² and R ³ represent a methyl group and R ⁴ and R ⁵ represent a hydrogen atom.

Preferably, the cationic part of the compound of formula (I) is in the form of an optical isomer of L (levorotatory) or D (dextrorotatory) configuration, more preferably of L configuration.

The compound of formula (I) can be obtained by mixing a first composition comprising the cationic part of the compound of formula (I) optionally in the form of a salt and a second composition comprising the anionic part of the compound of formula (I) optionally in the form of a salt. The mixture can be extemporaneous.

The compound of formula (I) can be chosen from the following compounds of formulas 1 to 29 and their mixtures:

Preferably, the compound of formula (I) can be chosen from the compounds of formula (I) of formulas 1 to 11 as defined above and their mixtures. More preferentially, the compound of formula (I) can be chosen from the compounds of formula 1 or 2 as defined above and their mixtures.

Composition (A) may comprise a total content of compound(s) of formula (I) ranging from 0.1% to 100%, preferably from 0.5% to 50%, more preferably from 0.5% to 20 %, even more preferably from 1% to 10% by weight relative to the total weight of composition (A) .

Other elements/ingredients

Composition (A) used in the process according to the present invention is a cosmetic composition, ie which comprises a cosmetically acceptable medium, that is to say a medium compatible with human keratin fibres.

Composition (A) may comprise a solvent chosen from water, ethanol, isopropanol, glycerin, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol , 2-butoxyethanol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether and mixtures thereof.

Composition (A) may comprise a solvent chosen from water, C ₂ -C ₄ alcohols, polyols, polyol ethers and mixtures thereof. In this case, the compound of formula (I) may be in dissociated form in composition (A) .

Preferably, composition (A) may comprise a solvent chosen from water, ethanol, isopropanol, propylene glycol and mixtures thereof.

More preferably, composition (A) may comprise a solvent chosen from water, ethanol, propylene glycol and mixtures thereof.

Composition (A) may advantageously comprise a water/ethanol mixture, preferably a water/ethanol mixture comprising at least 10%, more preferably at least 20%, even more preferably at least 30% by weight of ethanol. According to this last embodiment, the composition (A) can in particular be formulated in the form of a lotion applied to the dry keratin fibers, the use of ethanol making it possible to facilitate the wetting of the dry keratin fibers, the drying of the fibers keratin fibers thus treated as well as the diffusion of the active agents within the keratin fibres.

Composition (A) may also comprise at least one cosmetic ingredient chosen from nonionic, anionic, cationic and amphoteric surfactants, vitamins and pro-vitamins including panthenol, fillers, coloring materials, pearlescent agents, opacifying agents, sequestering agents, film-forming polymers, cationic, anionic or neutral polymers, associative polymers, plasticizing agents, silicones, thickening agents, oils, antifoaming agents, moisturizing agents, emollients, penetrating agents, perfumes, preservatives and mixtures thereof.

These usual cosmetic ingredients may be present in composition (A) in usual amounts, easily determined by those skilled in the art, and which may range, for each ingredient, from 0.01% to 20% by weight relative to the weight total of the composition (A) . A person skilled in the art will take care to choose the ingredients entering into composition (A) , as well as their quantities, so that they do not harm the properties of the composition.

Composition (A) can be in any galenic form conventionally used for hair application. In a non-limiting manner, composition (A) can be in the form of a lotion, a cream, a mousse, a gel, a spray or a lacquer.

Composition (A) can be used in rinse-out or leave-in application.

Composition (A) can be in the form of a shampoo, a mask, a conditioning composition or a pre-shampoo. Composition (A) can also be in the form of a composition to be added or mixed before application with a shampoo, a mask or a conditioning composition.

Composition (A) can be packaged in a pump-dispenser bottle or in an aerosol container, in order to ensure application of composition (A) in vaporized form (lacquer) or in the form of a mousse. In these cases, composition (A) preferably comprises at least one propellant.

Composition pH (A)

Composition (A) may have a pH ranging from 3 to 10, preferably from 4 to 7. The pH may be adjusted using an organic or mineral acid or an organic or mineral base usually used in cosmetics .

Additional process-related features

Composition (A) can be applied to dry or wet keratin fibers, preferably to dry keratin fibers.

The liquor ratio of composition (A) applied to the keratin fibers can range from 0.1 to 10. By liquor ratio is meant the ratio between the total weight of composition (A) applied and the total weight of fibers keratins to be treated.

The process according to the present invention may comprise at least one additional step following step i) chosen from the following steps ii) to iv):
ii) a step of applying composition (A) to the keratin fibers, preferably lasting at least 10 seconds, said step of applying optionally being carried out under an airtight film of the foil type or plastic film;
iii) a step of rinsing and/or washing the keratin fibres;
iv) a step of drying the keratin fibers in ambient air or using a heating device.

Preferably, the method may comprise the additional steps ii) and iv) as described above and carried out in this order. More preferably, the method may comprise all of the additional steps ii), iii) and iv) as described above and carried out in this order.

The laying step can have a duration ranging from 10 seconds to 60 minutes, preferably from 30 seconds to 30 minutes.

The washing step can for example be carried out using a shampoo.

The temperature of the heating device can range from 45°C to 230°C, preferably from 45°C to 100°C, more preferably from 50°C to 80°C. One can for example use as a heating device a hair dryer, a heating cap, an iron or a heating brush.

Step iv) of drying can also be a combination of drying in the air or with a heating device at a temperature ranging from 50° C. to 80° C. such as a hair dryer or a heated helmet, followed by an ironing stage.

In the case where the process does not comprise a step iii) of rinsing and/or washing the keratin fibres, the composition (A) can for example comprise a water/ethanol mixture which comprises at least 10%, preferably at least 20%, more preferably at least 30% by weight of ethanol. The use of such a mixture makes it possible in particular to facilitate the evaporation of the composition.

Membership (A)

According to a second aspect, the subject of the present invention is a composition (A) as defined above, it being understood that the composition does not comprise the following compounds of formulas 1 to 4 :

Compounds

According to a third aspect, the subject of the present invention is the following compounds of formulas 5 to 29 and their mixtures:





preferably, compounds of formulas 5 to 11 and mixtures thereof.

Uses

According to a fourth aspect, the subject of the present invention is the cosmetic use of at least one compound (I) as described above for the care and/or repair of keratin fibres, preferably to prevent the breakage of the fibers keratins. Any of the compounds (I) described above can be used for this purpose.

According to a final aspect, a subject of the present invention is the cosmetic use of a composition (A) as described above for the care and/or repair of keratin fibres, preferably for preventing the breakage of keratin fibres.

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

Examples

In the following text, "alkaline solubility (AS)" means the loss of mass of a sample of 100 mg of keratin fibers under the action of a decinormal sodium hydroxide solution for 30 min at 65°C.

Preparation of the carnitine salts used in the examples:

L-Carnitine DL-Mandelate

L-carnitine DL-Mandelate was prepared according to the following procedure:

Table of reagents and solvents:

Ingredient Quantity L-carnitine
Supplier: Sigma Aldrich, Reference C0158 20g (i.e. 124mmol) DL-mandelic acid
Supplier: Sigma Aldrich, Reference M2101 18.87g (i.e. 124mmol) Water 10mL Ethanol (EtOH) 20mL

Procedure:

In a monocol dissolve 20g of L-carnitine in 10ml of water. In a beaker weigh 18.87g of solid mandelic acid (DL) add 20ml of EtOH. Gradually pour the mandelic acid solution onto the L-carnitine using a pipette, the compounds dissolving little by little. At the end of the addition, a colorless translucent homogeneous medium is obtained. Transfer to a flask and place in a rotavapor to evaporate the solvents. A sticky white wax with a mass of 38g is obtained. The melting point of the compound obtained is 96°C.

L-Carnitine (R)-(-)-Mandelate

L-carnitine -(R)-(-)-Mandelate was prepared according to the following procedure:

Table of reagents and solvents:

Ingredient Quantity L-carnitine
Supplier: Sigma Aldrich, Reference C0158 20g, 124mmol (R)-(-)-mandelic acid
Supplier: Sigma Aldrich, Reference M2209 18.87g, 124mmol Water 10mL Ethanol 20mL

Procedure:

In a monocol dissolve 20g of L-carnitine in 10ml of water. In a beaker weigh 18.87g of solid ((R)-(-)-mandelic acid add 20ml of EtOH. Gradually pour (vol 5ml) using a pipette the mandelic acid solution onto the carnitine , The compounds gradually dissolve.At the end of the addition, a homogeneous translucent colorless medium is obtained.Transfer into a flask and place in a rotavapor to evaporate the solvents.A sticky white wax with a mass of 38g is obtained. The melting point of the compound obtained is 97°C.

Differential scanning calorimetry study and study of hair breakage by the Flexabrasion test

Compositions tested:

The following compositions were prepared and then tested according to the procedure described below:

Compositions Ingredients 1*
Invention 2*
Invention 3**
Comparative 4**
Comparative 5
Comparative 6
Placebo L-Carnitine DL-Mandelate


5g, 16mmol


-







L-Carnitine (R)-(-)-Mandelate

-


5g, 16mmol








DL-Mandelic acid
-
-
5g,
33mmol



(R)-(-)-Mandelic acid
-
-
5g,
33mmol

L-Carnitine - -
5g, 31mmol Water / ethanol (4/1 w/w) 100g 100g 100g 100g 100g 100g

* Spontaneous pH of 4.2

** pH adjusted to 4.2 using 1N NaOH or HCl

Procedure:

Six locks of damaged hair (2.7g / 27cm; alkaline solubility of 20) placed on a heating plate maintained at a temperature of 33°C and covered with cling film. Composition 1 , 2 , 3 , 4 , 5 or 6 to be tested is then applied to one of the six locks with a liquor ratio of 0.4 (0.4 g of composition per g of hair). The locks are then kneaded with the fingers by making circular movements all along the lock (5 times) then the locks are covered with cling film for 5 min. The film is removed, the locks are washed. The washing protocol consists of wetting the locks with tap water at 38°C for 10 seconds. Apply shampoo (0.4g/g hair). Massage for 15 seconds and rinse thoroughly with water for 20 seconds. Squeeze strands between two fingers, running fingers from root to tip twice to remove excess water. Comb. Dry with a helmet (60°C, 10min/g hair). These different steps are repeated to have 5 applications in total on each of the locks.

Two control locks (a lock of identical damaged hair, but untreated and a lock of untreated natural hair) are also studied.

The denaturation temperature of the proteins of the six locks to which compositions 1 , 2 , 3 , 5 or 6 are applied as well as of two control locks (a lock of identical, but untreated damaged hair and a lock of untreated natural hair) are measured by differential scanning calorimetry. The median fall time before breakage is also measured by the Flexabrasion test for the locks treated with compositions 1 , 2, 3 , 5, 6 and the two control locks.

Differential scanning calorimetry study

The differential scanning calorimetry technique is known to those skilled in the art as a method which makes it possible to quantify the reinforcement of proteins in the cortex of keratin fibers. The principle of the test is to measure the denaturation temperature of proteins. The higher the temperature of protein denaturation, the better the integrity of the proteins of the cortex, which reflects a greater resistance of the fibers to breakage (F.-J. Wortmann and H. Deutz, J. Appl. Polym Sci ., 48, 137 (1993).

The denaturation temperature is directly related to the binding density of the keratin proteins present in the cortex. Thus, the lower the denaturation temperature, the lower the bond density of proteins between them, the disulfide bridges break, the cortex is damaged. A difference of 2°C is recognized by those skilled in the art as a significant difference. The device used to perform the measurements is a Mettler Toledo DSC 3+ Star system reference device (temperature range: 30°C - 250°C; heating ramp of 10°C/min). The measurement is carried out on 6 fibers of the roving.

Study of hair breakage by the Flexabrasion test

The flexabrasion technique is known to those skilled in the art for breaking keratinous fibers (references: Flexabrasion: A Method for Evaluating Hair Strength, Cosmetics & Toiletries Journal, June 26, 2009 and Hair Breakage in Normal and Weathered Hair: Focus on the Black Patient, Journal of Investigative Dermatology Symposium Proceedings, Volume 12, Issue 2, December 2007, Pages 6-9). The principle of the test is to measure the breakage time of hair fibers subjected to mechanical stress (bending and abrasion). A Flexabrasion device (fibrestress model from the company Textechno) is used. A hair is fixed to a mass of 20 g at one end and the other end is fixed to a stationary bar. The hair moves back and forth on a 300 μm stainless steel wire. The movement has an amplitude of 10mm and a frequency of 0.5Hz. Breakage detection is carried out by an optical sensor which records the lifespan (falling time before breakage) in seconds, i.e. the time it takes for the hair to break. A measurement series comprises 75 hairs. A difference of 100 s in fall time is recognized by those skilled in the art as a significant difference.

Results:

Differential Scanning Calorimetry Study:

Examples Wick Description Average denaturation temperature (°C) 1
(Invention) Wick treated with composition 1
(L-Carnitine DL-Mandelate) 156.8 2
(Invention) Wick treated with composition 2
(R)-(-)-L-Carnitine Mandelate) 157.2 3
(Comparative) Wick treated with composition 3
(DL-Mandelic Acid) 152.5 5
(Comparative) Wick treated with composition 5
(L-Carnitine) 143.3 6
(Comparative) Wick treated with composition 6
(Placebo) 144.8 7
(Comparative) Strand of damaged hair
(Witness) 137.7 8
(Comparative) Strand of natural hair
(Witness) 152.9

A higher protein denaturation temperature is observed for the locks treated using a method according to the invention (Examples 1 and 2) than for the comparatives (Examples 3, 5, 6, 7, 8). This means that there has been a strengthening of the protein network of the cortex and that the protein binding density is higher. The quality of the hair fiber of the locks treated using the method according to the invention is therefore improved.

Hair breakage study by the Flexabrasion test:

Examples Wick Description Median drop to break time (s) 1
(Invention) Wick treated with composition 1
(L-Carnitine DL-Mandelate) 1098 3
(Comparative) Wick treated with composition 3
(DL-Mandelic Acid) 884 5
(Comparative) Wick treated with composition 5
(L-Carnitine) 874 7
(Comparative) Strand of damaged hair
(Witness) 584 8
(Comparative) Strand of natural hair
(Witness) 982

A better performance in terms of anti-breakage is observed for the lock treated using a process according to the invention (Example 1) than for the comparative locks (Examples 3, 5, 7 and 8).

Claims (25)

Process for the treatment of keratinous fibers comprising:
i) a step of applying to the keratin fibers a composition(AT)comprising at least one compound of formula(I):
;
in which:
▪R ¹ ,R ² AndR ³ , identical or different, represent a group (C₁-VS₄)alkyl or a group (C₁-VS₄)hydroxyalkyl;
▪R ⁴ represents a hydrogen atom, a group (C₁-VS₄)alkyl or a –C(O) groupR, in whichRis a group (C₁-VS₃)alkyl;
▪R ⁵ represents a hydrogen atom, a group (C₁-VS₄) alkyl, an alkali metal or an alkaline earth metal;
▪Year ^- represents an aromatic organic anion chosen from the compounds of formulas(II),(III)Or(IV)following:

in which:
- R ⁶ ToR ¹⁰ represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl, the group (C₁-VS₆)alkyl or (C₁-VS₆)alkoxyl being optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂;Rrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl,R'AndR'’ independently representing a hydrogen atom, a group (C₁-VS₄)alkyl or a group (C₁-VS₄)alkylcarbonyl such as acetyl, provided that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-X, in whichXrepresents a hydrogen atom or a phenol-protecting group such as an acyl group, in particular an acetyl group;
it being understood that two groupsR ⁶ ToR ¹⁰ adjacent can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 members, saturated or unsaturated or aromatic;
- R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₆)alkyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, (hetero)cycle, –C(O)-R, –NH-C(O)-R, –C(O)-NH-R, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a group (C₁-VS₆)alkoxyl optionally substituted by one or more identical or different groups chosen from: –OR, -NOTR'R'', –C(O)OR, –O-C(O)-R, aryl and –CF₃and/or optionally interrupted by one or more groups or heteroatoms chosen from: O, NR', CO, S, SO and SO₂, withR,R'AndR''as previously defined, it being understood that the group –NR'R''is different from the –NH group₂;
● a halogen atom;
● a group –O-XwithXas previously defined;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To AndR ^b can form together and with the carbon atom which carries them a saturated or unsaturated (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members and more particularly a carbocycle of 5 or 6 members;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members;
- represents a single bond or an ethylenic double bond, provided that whenrepresents an ethylenic double bond,R ^b AndR ^vs are absent;
- pis an integer equal to 0 or 1;
- ris an integer equal to 0 or 1;
- R ¹¹ represents a hydrogen atom, a negative charge, an alkali metal or an alkaline earth metal, preferably a negative charge;
▪xis a stoichiometric coefficient chosen so as to guarantee the electroneutrality of the compound of formula(I). Process according to the preceding claim, in which:
▪R ¹ ,R ² AndR ³ represent a methyl group;
▪R ⁴ AndR ⁵ represent a hydrogen atom. Process according to Claim 1 or 2, in which R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a halogen atom;
● a hydroxyl group;
● a –OC(O)-CH ₃ group;
it being understood that two adjacent R ⁶ to R ¹⁰ groups can also form together and with the carbon atoms which carry them a (hetero)cycle of 5 or 6 saturated members. Process according to any one of the preceding claims, in which R ⁶ to R ¹⁰ represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )alkoxyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group. A method according to any preceding claim, whereinR ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f represent independently of each other:
● a hydrogen atom;
● a group (C₁-VS₄)alkyl;
● a group (C₁-VS₄)hydroxyalkyl;
● a group (C₁-VS₄)alkoxyl;
● a halogen atom;
● a hydroxyl group;
● a –O-C(O)-CH group₃;
Being heard that:
▪ (R ^To AndR ^b ) and or (R ^vs AndR ^d ) can form together and with the carbon atom that carries them a C=O bond;
▪R ^To OrR ^b OrR ^vs OrR ^d can train withR ⁶ OrR ¹⁰ and the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, more particularly a carbocycle of 5 to 6 members. Process according to any one of the preceding claims, in which R ^a , R ^b , R ^c , R ^d , R ^e and R ^f represent independently of each other:
● a hydrogen atom;
● a (C ₁ -C ₄ )alkyl group;
● a (C ₁ -C ₄ )hydroxyalkyl group;
● a hydroxyl group. A method according to any preceding claim, whereinYear ^- is chosen from the compounds of formulas(IIa),(IIIa)Or(IVa)following:

in which:
- R ⁶ ToR ¹⁰ are as defined in any one of claims 1, 3 or 4;
- R ^To AndR ^b are as defined in any one of claims 1, 5 or 6;
- R ¹¹ is as defined in claim 1;
preferably, from the compounds of formulas(IIa)Or(IIIa), more preferably from the compounds of formula(IIa). A method according to any of claims 1 to 6, whereinYear ^- is chosen from the compounds of formulas(II'a),(III'a)Or(IV'a)following:


in which:
-R ⁶ ToR ¹⁰ are as defined in any one of claims 1, 3 or 4;
-R ¹¹ is as defined in claim 1, 5 or 6;
preferably, from the compounds of formulas(II'a)Or(III'a)as defined above, more preferably from the compounds of formula(II'a)as defined above. A method according to any of claims 1 to 6, whereinYear ^- is chosen from the compounds of formulas(II''a),(III''a)Or(IV''a)following:

in which:
-R ⁶ ToR ¹⁰ are as defined in any one of claims 1, 3 or 4;
-R ^b is as defined in any one of claims 1, 5 or 6;
-R ¹¹ is as defined in claim 1;
preferably, from the compounds of formulas(II''a)Or(III''a)as defined above, more preferably from the compounds of formula(II''a)as defined above. A method according to any of claims 1 to 6, whereinYear ^- is chosen from the compounds of formulas(IIb),(IIIb)Or(IVb)following:

in which:
-R ⁶ ToR ¹⁰ are as defined in any one of claims 1 to 3 or 4;
-R ^To ,R ^b ,R ^vs AndR ^d are as defined in any one of claims 1, 5 or 6;
-R ¹¹ is as defined in claim 1;
preferably, from the compounds of formulas(IIb)Or(IIIb)as defined above, more preferably from the compounds of formula(IIb)as defined above. A method according to any of claims 1 to 6, whereinYear ^- is chosen from the compounds of formulas(IIc),(IIIc)Or(IVc)following:

in which:
-R ⁶ ToR ¹⁰ are as defined in any one of claims 1, 3 or 4;
-R ^To AndR ^d are as defined in any one of claims 1, 5 or 6;
-R ¹¹ is as defined in claim 1;
preferably, from the compounds of formulas(IIc)Or(IIIc)as defined above, more preferably from the compounds of formula(IIc)as defined above. A method according to any of claims 1 to 6, whereinYear ^- is chosen from the compounds of formulas(IId),(IIId)Or(IVd)following:

in which:
-R ⁶ ToR ¹⁰ are as defined in any one of claims 1, 3 or 4;
-R ^To ,R ^b ,R ^vs ,R ^d ,R ^e AndR ^f are as defined in any one of claims 1, 5 or 6;
-R ¹¹ is as defined in claim 1;
preferably, from the compounds of formulas(IId)Or(IIId)as defined above, more preferably from the compounds of formula(IId)as defined above. Process according to any one of the preceding claims, in which An ^- is chosen from the compounds of formula (II) as defined in any one of Claims 1, or 3 to 6 or from the compounds of formula (IIa) such as defined in claim 7 or from the compounds of formula (II'a) as defined in claim 8 or from the compounds of formula (II''a) as defined in claim 9 or from the compounds of formula ( IIb) as defined in claim 10 or from the compounds of formula (IIc) as defined in claim 11 or from the compounds of formula (IId) as defined in claim 12. Process according to any one of the preceding claims, in which An ^- is chosen from the following compounds (II ₁ ) to (II ₂₉ ) :






preferably from compounds (II ₁ ) to (II ₁₁ ) , even more preferably from compounds (II ₁ ) or (II ₂ ) . Process according to any one of the preceding claims, in which the compound of formula (I) is chosen from the following compounds of formulas 1 to 29 and their mixtures:





preferably from the compounds of formulas 1 to 11 and their mixtures, more preferably from the compounds of formulas 1 or 2 and their mixtures. Process according to any one of the preceding claims, in which the cationic part of the compound of formula (I) is in the form of an optical isomer of L or D configuration, preferably of L configuration. Process according to any one of the preceding claims, in which composition (A) comprises a total content of compound(s) of formula (I) ranging from 0.1% to 100%, preferably from 0.5% to 50% , more preferably from 0.5% to 20%, even more preferably from 1% to 10% by weight relative to the total weight of composition (A) . Process according to any one of the preceding claims, in which composition (A) comprises a solvent chosen from water, C2-C4 alcohols, polyols, polyol ethers and mixtures thereof, preferably from water, ethanol, isopropanol, propylene glycol and mixtures thereof, more preferably from water, ethanol, propylene glycol and mixtures thereof. Process according to any one of the preceding claims, in which the composition (A) comprises a water/ethanol mixture, preferably a water/ethanol mixture comprising at least 10%, more preferably at least 20%, even more preferably at least 30% by weight of ethanol. Process according to any one of the preceding claims, in which the composition (A) is applied to the dry or wet keratin fibres, preferably to the dry keratin fibres. Process according to any one of the preceding claims, comprising at least one additional step following step i) chosen from the following steps ii) to iv):
ii) a step of applying composition (A) to the keratin fibers, preferably for a duration of at least 10 seconds;
iii) a step of rinsing and/or washing the keratin fibres;
iv) a step of drying the keratin fibers in ambient air or using a heating device. Composition (A) as defined in any one of Claims 1 to 19, it being understood that the composition does not comprise the following compounds of formulas 1 to 4 :
Compounds of formulas 5 to 29 following and their mixtures:






preferably, compounds of formulas 5 to 11 and mixtures thereof. Cosmetic use of at least one compound of formula (I) as defined in any one of Claims 1 to 16 for the care and/or repair of keratin fibres, preferably for preventing the breakage of keratin fibres. Cosmetic use of at least one composition (A) as defined in any one of Claims 1 to 19 and 22 for caring for and/or repairing keratin fibres, preferably for preventing the breakage of keratin fibres.