EP1680077A2

EP1680077A2 - Use of dithiols in a hair-perming composition

Info

Publication number: EP1680077A2
Application number: EP04742633A
Authority: EP
Inventors: Henri Samain; Gilles Genain; Aude Livoreil; Gabin Vic
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2003-05-06
Filing date: 2004-05-04
Publication date: 2006-07-19
Also published as: WO2004098488A3; WO2004098488A2; FR2854568B1; FR2854568A1; US20070134185A1

Abstract

The invention relates to the use of particular dithiols in a hair-perming composition. The invention also relates to a hair-perming method employing the aforementioned dithiols as well as cosmetic compositions containing at least one of said dithiols and at least one compound selected from among surface-active agents and non-ionic, anionic, cationic, amphoteric or zwitterionic polymers or cosmetic compositions containing specific dithiols.

Description

USE OF DITHIOLS IN UWE PERMANENT HAIR DEFOR ATION COMPOSITION

The subject of the invention is the use of particular dithiols in a composition for permanent deformation of the hair. It also relates to a process for permanent deformation of the hair using these dithiols, as well as cosmetic compositions containing at least one of these dithiols and at least one compound chosen from surfactants and nonionic, anionic, cationic, amphoteric polymers or zwitterionic or cosmetic compositions containing specific dithiols.

The technique for carrying out permanent deformation of the hair consists, firstly, in opening the disulfide bonds of keratin (cystine) using a composition containing a reducing agent (reduction step), then after preferably having rinsed the hair, to reconstitute in a second time said disulfide bonds by applying an oxidizing composition (oxidation step, also called fixing) so as to give the hair the desired shape. This technique makes it possible indifferently to carry out either the waving of the hair, or their straightening or their straightening, the hair possibly being, as the case may be, tensioned during all or part of the deformation process.

The compositions for carrying out the first stage of a perming operation are generally in the form of lotions, creams, gels, powders to be diluted in a liquid support, and contain a reducing agent, preferably a thiol. Among the latter, those commonly used are cysteine and thioglycolic acid as well as its esters, in particular glycerol monothioglycolate. Thioglycolic acid is particularly effective in reducing the disulfide bonds of keratin and can be considered at alkaline pH, in particular in the form of ammonium thioglycolate, as the reference compound permanently. However, it has the disadvantage of revealing an unpleasant smell. In order to remedy this, a perfume is generally used to mask odors.

Cysteine produces a much weaker odor than that of thioglycolic acid, but the degree of crimp obtained is much lower and far from satisfactory. In addition, cysteine requires the use of a very alkaline pH.

Glycerol monothioglycolate is also very smelly. It is, on the other hand, used at a pH close to neutrality, but its performance is notably lower than that of thioglycolic acid.

Various studies have been carried out with a view to remedying the drawbacks of these reducing agents, and to this end, the use of new reducing compounds or systems has been proposed. Thus, in patents US 2,719,813 and US 2,719,814, it has already been proposed to use a mercaptan and its disulfide, as a hair reduction system, by more particularly recommending adjusting the pH of the reducing composition between 8.5 and 9.5. US Patent 2,719,813 specifically relates to a reducing composition for perm formed by dithiodiglycerol and thioglycerol and US Patent 2,719,814, a reducing composition containing, in particular thiohydracrylic acid and dithiohydracrylic.

Furthermore, US Pat. No. 5,460,806 discloses the use of bis (2-mercaptoethyl) sulfone (BMS), as a reducing agent in a hair straightening or crimping hair process, without specifying the setting pH. work of reducing solutions containing such reducing agents. This compound is very slightly soluble in water and therefore of implementation practically impossible under the usual conditions of permanent deformation.

Finally, it is already known, in cosmetics, the use of certain dithiols. In particular, the French patent application, filed by the Applicant under the number

0204 352 and, not yet published, discloses a method of metal cladding conferring, with keratin fibers, residual cosmetic properties to shampoos. According to this process, a composition containing at least one metal salt is applied to the keratin fibers, then a composition containing at least one reducing agent is applied. Among the latter are cited the following dithiols: BMS (bismercaptoethylsulfone), DTT (dithiothreitol), DH (N, N'dimethyl-N, N'-bis (mercaptoacetyl) hydrazine).

In this French patent application, it is indicated that the keratin fibers can be reduced, prior to the application of the composition containing at least one metal salt. It is intended that this reduction can be carried out with one of the reducing agents described in the text of this application, such as the dithiols previously mentioned.

However, the reducing compositions for perms known to date are not yet entirely satisfactory, since the degradations of the hair fiber are too great.

In addition, when a perm is applied to hair having undergone coloring, a very strong pickling of the color is observed and the surface of the hair is greatly degraded. Conversely, if a color is applied to permanent hair, the color obtained is very different from the color normally obtained on natural non-permanent hair.

The problem posed by the invention is to provide a reducing composition, for the permanent deformation of the hair, more effective than those which already exist, in particular in terms of degree, nervousness or quality of curl, while reducing the degradation of the hair. , this reducing composition must also be practically without effect on an artificial coloring of keratin fibers.

To solve this problem, the invention proposes the use, in order to reduce the disulfide bonds of keratin, in a composition reducing the deformation of the fiber. keratin, at a pH between 5 and 8.5, of dithiols of formula I, having a solubility in water greater than 0.1 M:

HS-A-SH

G)

A is a C3 to C10 hydrocarbon chain, linear or cyclic, saturated or unsaturated, this chain possibly carrying one or more ramifications in C1 to C4 and which can be interrupted by one or more hetero atoms such as sulfur , oxygen, nitrogen, silicon or phosphorus and may also include one or more substituents, such as hydroxyl, amino, carbamate, carbonate, hydrazine, ethers, acids, esters, amide, cyano, ureido groups.

The choice of pH in the range between 5 and 8.5 leads to the following advantages: less degradation of the fiber and better cosmetic result compared to the use of the same dithiols at a more alkaline pH.

The solubility in water of the dithiols of formula I is measured at pH = 7 and at a temperature of 30 ° C.

The term “permanent deformation” is understood to mean permanent (permanent) curling, straightening or straightening of the hair.

Preferably, A is a hydrocarbon chain comprising from 3 to 8 carbon atoms, and more preferably from 4 to 6 carbon atoms.

Advantageously, the pH of the reducing composition comprising the dithiols of formula I is between 5.5 and 8.5, and more preferably between 6 and 8.

Preferably, the pKa, at 25 ° C., of the dithiol of formula I is less than 9. Another subject of the invention relates to a process for permanent deformation of the hair using a reducing composition comprising at least one compound of formula (I).

The compounds of formula (I) are generally prepared according to the procedures described in the following references:

- J. Org. Chem 91, vol 56, p2332;

- J. Org. Chem 91, vol 56, p7328;

- Methods in Enzymology, 1995, vol 251, p167.

Among the preferred compounds of general formula (I), mention may in particular be made of the compounds indicated below:

With R1, R2, R3, R4, R5 and R6 representing independently of each other: H, OH, COOH, NH ₂ , a linear or branched C1 to C10 alkyl radical, a linear C2 to C10 alkenyl radical or branched, a linear or branched C2 to C10 alkynyl radical, these radicals being capable of being interrupted by one or more hetero atoms such as sulfur, oxygen, nitrogen, silicon or phosphorus and also being able to comprise one or more several substituents such as hydroxyl, amino, carbamate, carbonate, hydrazine, ether, acid, ester, amide, cyano, ureido groups;

X = O, S or NRl

Particularly preferred are the compounds of formula I below and the corresponding optical isomers, where appropriate:

(Gl) (Hl)

(Kl)

SH o = s SH

(Ll)

Particular preference is given to the following compounds of formula I: A1, D1 and K1 and the corresponding optical isomers.

The process according to the invention for permanent deformation of the hair comprises the application of a reducing composition comprising, as agent reducing agent, a compound of formula (I). The hair is shaped using, for example, mechanical means well known to those skilled in the art, such as curlers, the reducing composition being applied before or after any means of shaping the hair, and a fixing composition being applied after the reducing composition, with or without an intermediate or subsequent rinsing step or application of an intermediate composition.

According to the present invention, the permanent deformation of the hair preferably consists, in a first step, in reducing the disulfide bonds of the keratin by application, for approximately 5 to 60 min, of a reducing composition as defined above, then , in a second step, to reform said bonds by applying an oxidizing composition or, optionally, by allowing the oxygen in the air to act.

Preferably, in the case of the perm, a reducing composition is applied as defined above to wet hair previously wound on rollers having from 4 to 20 mm in diameter, the composition possibly being able to be applied as and as the hair is rolled up; the reducing composition is then left to act for a time from 5 to 60 minutes, preferably from 5 to 30 minutes, then rinsing thoroughly; after which an oxidizing composition is applied to the coiled hair, making it possible to reform the disulphide bonds of the keratin for an exposure time of 2 to 10 minutes. After removing the rollers, rinse

^' abundantly the hair.

The laying of the reducing composition can be done under heat.

The oxidation or oxidizing composition is of the type commonly used and contains, for example, as an oxidizing agent for hydrogen peroxide, an alkali bromate, a persalt, a polythionate or a mixture of alkali bromate and persal. The concentration of hydrogen peroxide can vary from 1 to 20 volumes and preferably from 1 to 10, the concentration of alkali bromate from 2 to 12% and that of parsley from 0.1 to 15% by weight relative to the total weight of the oxidizing composition. The pH of the oxidizing composition is generally between 2 and 10. This oxidation can be carried out immediately or be delayed. The deformation of the hair according to the invention may also consist of a process for straightening or straightening the hair, in which a reducing composition according to the invention is applied to the hair, then the hair is subjected to mechanical deformation allowing fix them in their new form, by smoothing the hair with a wide-tooth comb, with the back of a comb or by hand. After an exposure time of 5 to 60 minutes, in particular, from 5 to 30 minutes, we then proceed to a new smoothing, then rinse thoroughly and apply an oxidizing or fixing composition as defined above, which leave on for about 2 to 10 minutes, then rinse the hair thoroughly.

In the perming compositions according to the invention, the reducing agent of general formula (I) is especially present at a concentration of between 0.05 and 30% and, preferably, between 0.1 and 20% by weight relative to the total weight of the reducing composition.

The pH is obtained using an alkaline agent such as, for example, ammonia, monoethanolamine, diethanolamine, triethanolamine, 1,3-propane diamine, an alkali or ammonium carbonate or bicarbonate, a organic carbonate such as guanidine carbonate, an alkali hydroxide or using an acidifying agent such as for example hydrochloric acid, acetic acid, lactic acid, oxalic acid or boric acid .

The reducing composition may also contain, in combination, another known reducing agent, such as for example thioglycolic acid, glycerol or glycol monothioglycolate, cysteamine and its acylated C1-C4 derivatives such as N-acetyl cysteamine. or N-propionyl cysteamine, cysteine, N-acetylcysteine, N-mercaptoalkylamides of sugars such as N- (mercapto-2-ethyl) gluconamide, beta-mercaptopropionic acid and its derivatives, thiolactic acid and its esters such as glycerol monothiolactate, thiomalic acid, panthetein, thioglycerol, sulfites or bisulfites of an alkali or alkaline earth metal, N- (mercaptoalkyl) o- hydroxyalkylamidβs described in patent application EP 354 835 and the N-mono- or N, N-dialkylmercapto 4-butyramides described in patent application EP 368763, the aminomercaptoalkylamides described in patent application EP 403 267 and the alkylaminomercaptoalkylamides described in patent application EP 432,000.

According to a preferred embodiment, the reducing composition also contains a surfactant of non-ionic, anionic, cationic or amphoteric type and among these, mention may be made of alkylsulphates, alkylbenzenesulphates, alkylethersulphates, alkylsulphonates, salts of quaternary ammonium, alkyl betaines, oxyethylenated alkylphenols, alkanolamides of fatty acids, esters of oxyethylenated fatty acids and other nonionic surfactants of the hydroxypropylether type.

When the reducing composition contains at least one surfactant, this is generally present at a maximum concentration of 30% by weight, and preferably between 0.5 and 10% by weight relative to the total weight of the reducing composition .

In order to improve the cosmetic properties of the hair or to attenuate or avoid its degradation, the reducing composition may also contain a treating agent of cationic, anionic, nonionic or amphoteric nature.

Among the particularly preferred treating agents, mention may in particular be made of those described in French patents No. 2,598,613 and No. 2,470,596. It is also possible to use, as treating agents, volatile or non-linear or cyclic silicones and their mixtures, polydimethylsiloxanes, quaternized polyorganosiloxanes such as those described in French patent application No. 2,535,730, polyorganosiloxanes with aminoalkyl groups modified by alkoxycarbonyalkyl groups such as those described in US Pat. polyalkylbetaine polydimethyl-siloxane described in British patent n ° 2,197,352, organo polysiloxanes modified by mercapto or mercaptoalkyl groups such as those described in French patent n ° 1,530,369 and in European patent application n ° 295,780, as well than silanes such as stearoxytrimethylsilane.

The reducing composition may also contain other treating ingredients such as cationic polymers such as those used in the compositions of French patents No. 79.32078 (2,472,382) and 80,26421 (2,495,931), or also cationic polymers of the ionene type. such as those used in the compositions of Luxembourg patent no. 83703, basic amino acids (such as lysine, arginine) or acids (such as glutamic acid, aspartic acid), peptides and their derivatives, protein hydrolysates, waxes, bulking and penetrating agents or making it possible to reinforce the effectiveness of the reducing agent such as the mixture Si02 / PDMS (polydimethylsiloxane), dimethylisosorbitol, urea and its derivatives, pyrrolidone, N- alkyl-pyrrolidones, thiamorpholinone, alkylene glycol or dialkylene glycol alkyl ethers such as for example propylene glycol monomethyl ether, dipropylene glycol monomethyl ether , ethylene glycol monoethyl ether and diethylene glycol monoethyl ether, C 3 -C 6 alkanediols such as, for example, propanediol-1,2 and butanediol-1,2, imidazolidinone-2 as well as other compounds such as fatty alcohols, lanolin derivatives, active ingredients such as panthothenic acid, fall arrest agents, dandruff agents, thickeners, suspending agents, sequestering agents, clouding agents, dyes, sunscreens as well as perfumes and preservatives.

The reducing composition according to the invention is essentially in aqueous form, in particular in the form of a thickened lotion or not, a cream or a gel.

The reducing composition according to the invention can also be of the exothermic type, that is to say causing a certain heating during application to the hair, which brings pleasure to the person who undergoes the first time of the perm. or straightening. The reducing composition according to the invention can also contain a solvent such as for example ethanol, propanol or isopropanol or also glycerol, at a maximum concentration of 20% relative to the total weight of the composition.

The vehicle for the compositions according to the invention is preferably water or an aqueous-alcoholic solution of a lower alcohol, such as ethanol, isopropanol or butanol.

When the compositions are intended for a hair straightening or straightening operation, the reducing composition is preferably in the form of a thickened cream so as to keep the hair as straight as possible. These creams are produced in the form of "heavy" emulsions, for example based on glyceryl stearate, glycol stearate, self-emulsifying waxes or fatty alcohols.

It is also possible to use liquids or gels containing thickening agents such as carboxyvinyl polymers or copolymers which "stick" the hair and keep it in the smooth position during the setting time.

The invention also relates to cosmetic compositions comprising, in a cosmetically acceptable medium, at least one dithiol of formula I chosen from the compounds of formulas (B), (C), (E), (F), (G), ( H), (I), (J), (L), (M) and (N).

(M) and (N) have the following formulas:

in which m denotes 0 or 1.

R1 and R2 represent, independently of each other, H, OH, COOH, NH2, a linear or branched C2 to C10 alkyl radical, a linear C2 to C10 alkenyl radical, a C2 to C10 alkyl radical , linear or branched, these radicals which can be interrupted by one or more heteroatoms such as sulfur, oxygen, nitrogen, silicon or phosphorus, and which can comprise one or more substituents, such as hydroxyl or amino groups, carbamate, carbonate, hydrazine, ether, ester, amide, cyano, ureido; with the restriction that,

If m = 1, R1 and R2 independently of one another represent a methyl radical or an R1 radical as indicated above,

Z represents a bond belonging to a C6 carbocycle substituted by one or more Ri groups, identical or different, Ri denoting a methyl radical or an R1 radical, as indicated above other than hydrogen or a bond belonging to a unsubstituted C6 carbocycle if at least one of R1 or R2 is different from a hydrogen atom,

R3, R4, R5, R6 have, independently of one another, the same meanings as R1 and R2 as indicated above, and can also denote a methyl radical, if R1 and R2 do not denote all two a hydrogen atom or if one of them is at least different from a methyl radical.

The invention finally relates to cosmetic compositions containing at least one compound of formula I as defined above and at least one compound, chosen from surfactants and nonionic, anionic, cationic, amphoteric or zwitterionic polymers. All these compositions can also contain the additives mentioned above.

The invention also relates to a kit, in particular, for the permanent deformation of the hair comprising, in a first compartment, as a reducing composition, a composition according to the invention comprising a compound of formula (I), and in a second compartment , an oxidizing composition.

The invention can be better understood using the nonlimiting example which follows and which constitutes a preferred embodiment of the compositions according to the invention.

Examples

We make a reducing lotion: Compound A1 20.83g

Ammonia qs pH = 7

Water qs 100g

The above lotion is applied to locks of gray hair containing 90% white hair.

We form curls, using curlers. The lotion is left to act on the coiled hair for 15 minutes. The hair is rinsed with water. A conventional fixing composition is applied, based on hydrogen peroxide (hydrogen peroxide at 8 volumes, pH = 3). We rinse again. We remove the curlers.

There is good curling. If a 7.44 CRESCENDO ® oxidation dye is applied to permanent hair with a compound A1 as indicated above, a dye closer to that obtained on non-permanent hair is observed, than in the case where a permanent treatment identical to the previous one, replacing A1 with thioglycolic acid, under conditions of obtaining allowing obtaining equivalent crimps.

Claims

1. Use, for reducing the disulfide bonds of keratin, in a composition reducing deformation of the keratin fiber, at a pH between 5 and 8.5, of dithiols of formula I, having a solubility in water greater than 0.1 M:

HS-A-SH

(I)

2. Use according to claim 1, characterized in that the pH of the reducing composition comprising the dithiols of formula I is between 5.5 and 8.5, and more preferably between 6 and 8.

3. Use according to claim 1 or 2, characterized in that A is a hydrocarbon chain comprising from 3 to 8 carbon atoms, and more preferably from 4 to 6 carbon atoms.

4. Use according to any one of the preceding claims, characterized in that the pKa, at 25 ° C, of the dithiol of formula I is less than 9.

5. Use according to any one of the preceding claims, characterized in that the dithiol of formula (I) corresponds to one of the following formulas:

X = O, S or NRL

6. Use according to any one of the preceding claims, characterized in that the dithiol of formula I corresponds to one of the following formulas, the corresponding optical isomers, where appropriate:

(Gl) (Hl)

(II) (Jl)

(Kl)

SH

O = S .SH

(Ll)

7. Use according to claim 6, characterized in that the compounds of formula I are the following: A1, D1 and K1 and the corresponding optical isomers.

8. Use according to any one of the preceding claims, characterized in that the reducing agent of general formula (I) is present at a concentration between 0.05 and 30% and preferably between 0.1 and 20% by weight relative to the total weight of the reducing composition.

9. Use according to any one of the preceding claims, characterized in that the composition also contains an additive chosen from another known reducing agent, a surfactant of non-ionic, anionic, cationic or amphoteric type, a treatment agent of a cationic, anionic, nonionic or amphoteric nature, fatty alcohols, lanolin derivatives, active ingredients such as panthothenic acid, fall arrest agents, dandruff agents, thickeners, suspending agents, sequestering agents, clouding agents, dyes, sunscreens, perfumes and preservatives.

10. A method of permanent deformation of the hair, characterized in that it comprises the application of a reducing composition defined in any one of claims 1 to 8 containing, as reducing agent, a compound of formula ( I), the hair being shaped by appropriate means; a fixing composition being, in addition, applied after the reducing composition, after optional rinsing.

11. Cosmetic composition comprising, in a cosmetically acceptable medium, at least one dithiol of formula (I) chosen from the compounds of formulas (B),

(C), (E), (F), (G), (H), (I), (J) and (L) according to claim 4 and the following compounds of formula (M) and (N):

in which m denotes 0 or 1.

12. Cosmetic compositions containing at least one compound of formula I and at least one compound, chosen from surfactants and nonionic, anionic, cationic, amphoteric or zwitterionic polymers,

HS-A-SH

(I)

A is a C3 to C10 hydrocarbon chain, linear or cyclic, saturated or unsaturated, this chain possibly carrying one or more branches in

C1 to C4 and which can be interrupted by one or more hetero atoms such as sulfur, oxygen, nitrogen, silicon or phosphorus and which can also include one or more substituents, such as hydroxyl, amino, carbamate, carbonate, hydrazine, ethers, acids, esters, amide, cyano, ureido groups.