FR2939672A1 - Use of heterocyclic disulfide compound as an agent for treating keratin fibers, such as hair, where the disulfide compound is associated with reducing agent - Google Patents

Abstract

Use of one or more heterocyclic disulfide compound (I) and their salts with an acid or base, stereoisomers, solvates or hydrates as an agent for treating keratin fibers, such as hair, is claimed, where (I) is associated with: (ii) one or more reducing agent, in the presence of heat generated by heating to a temperature of 50-250[deg] C, under an alkaline pH, provided that when (I) is lipoic acid and is associated with one or more reducing agent, then the lipoic acid is not located together in the same composition with the reducing agent. Use of one or more heterocyclic disulfide compound of formula (I) and their salts with an acid or base, stereoisomers, solvates or hydrates as an agent for treating keratin fibers, such as hair, is claimed, where (I) is associated with: (ii) one or more reducing agent, in the presence of heat generated by heating to a temperature of 50-250[deg] C, under an alkaline pH, provided that when (I) is lipoic acid and is associated with one or more reducing agent, then the lipoic acid is not located together in the same composition with the reducing agent. Z 1>, Z 2>carbonyl group or divalent group of formula (CR 1>R 2>) or (CR 5>R 6>); either R 1>-R 6>H, (1-8C)alkyl, aryl, hydroxy, (di)(1-8C)(alkyl)amino, (1-8C)alkoxy, (poly)hydroxy(1-8C) alkyl, (di)(1-8C)(alkyl)amino(1-8C)alkyl, carboxy, carboxy(1-8C)alkyl, (di)(1-8C)(alkyl) aminocarbonyl(1-8C)alkyl, amino, aminocarbonyl(1-8C)alkyl or (1-8C)(alkyl)carbonyl (1-8C)(alkyl)amino(1-8C)alkyl; or R 1>R3, CR 3>R 3>(when n is 2 or 3) : cycloalkyl, heterocycloalkyl, aryl such as phenyl (preferred), or heteroaryl; and n : 1-3, preferably 1 or 2. Independent claims are included for: (1) treating keratin fibers, by application on the human keratin fibers a composition; (2) a cosmetic composition at alkaline pH comprising: (I); and (3) cosmetic composition comprising: (I) and one or more reducing agents. [Image].

Description

The subject of the present invention is a cosmetic composition comprising a particular heterocyclic disulfide compound and a reducing agent and its use in a process for the permanent deformation of fibers. BACKGROUND OF THE INVENTION The present invention relates to a cosmetic composition comprising a heterocyclic disulfide compound and a reducing agent and its use in a permanent fiber deformation process. keratinic agents, in particular human keratinous fibers. It is known that the most usual technique for obtaining a permanent deformation of the hair consists, in a first step, in opening the disulfide bonds -SS- of the keratin (cystine) by applying to the hair previously put under tension (curlers and others) a composition containing a reducing agent (reduction step) then, after rinsing the hair thus treated, to reconstitute in a second time said disulfide bonds by applying to the hair still under tension an oxidizing composition (oxidation step, also called fixation) so as to finally give the hair the desired shape called artificial form. This technique thus makes it possible to achieve either the waving of the hair, or their straightening or their curing. The holding of the artificial form and the degradation of keratinous fibers are two major problems in the development of transformation products of said fibers, in particular for those using reducing treatments in perms or smoothings. Indeed, the two reduction and oxidation steps used in conventional permanent deformation processes, can generate, when they are repeated, degradations of keratinous fibers. In addition, the results of artificial form resistance obtained after the implementation of these methods are often insufficient for the user. Moreover, certain methods aim to overcome the problem of the odor of the perm using disulfide compounds EP 1 129 687. On the other hand, this document is not intended to improve the shape retention of the locks. Another document mentions a method for perming hair using a composition comprising lipoic acid and a reducing agent (WO 2008/110223). However permeants obtained with this process are not satisfactory in terms of efficiency especially in terms of strength and / or in terms of fiber degradation.

There is therefore a need to provide cosmetic compositions for the artificial shaping of keratinous fibers, easy to implement, durable, not having the disadvantages of increased degradation of keratin fibers by repeated application, the poor performance in the time and lack of cosmetic keratin fibers after treatment.

This object has been achieved by the present invention which relates to a process for treating keratinous fibers, in particular the hair, so as to obtain a permanent deformation of the latter, in particular in the form of permed hair, by successive application. on the keratinous fibers to be treated: i) in a first step of one or more reducing agent (s); then ii) in a second step of one or more heterocyclic compound (s) disulfide (s) of formula (I): ## STR1 ## their salts with an acid or a base, their stereoisomers, and their solvates such as hydrates, formula (I) in which: Z, and Z2, identical or different, represent a carbonyl group or a divalent group CRI R2 or CR5R6; R, R6, identical or different, represent a hydrogen atom, or a group chosen from: i) (C, -C8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C, -C8 ) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C, -C 8) alkyl, viii) carboxy, ix) carboxy (C 1 -C 8) alkyl, x) (di) (C 1 -C 8) (alkyl) aminocarbonyl (C 1 -C 8) alkyl, xii) amino, xiii) aminocarbonyl (C) -C8) alkyl and xiv) (C 1 -C 8) (alkyl) carbonyl (C 1 -C 8) (alkyl) amino (C 1 -C 8) alkyl; or when R 1 and R 3, or when n is 2 or 3, two radicals R 3 carried by adjacent carbon atoms, together with the carbon atoms carrying them, form a cycloalkyl, heterocycloalkyl, aryl group such as phenyl, or heteroaryl; especially phenyl; n represents an integer of 1, 2 or 3, especially 1 or 2; it being understood that when n is 2 or 3 then the groups R 3 and R 4 may be the same or different from each other.

Another subject of the invention is a composition in a cosmetic support comprising: i) one or more reducing agent (s) and ii) one or more heterocyclic compound (s) disulfide (s) of formula (I) I ') their salts with an acid or base, their stereoisomers, and their solvates such as hydrates, formula (I') wherein: Z, and Z2, identical or different, represent a carbonyl group or a divalent group CRI R2 or CR5R6; R1, R2, R5 and R6, which may be identical or different, represent a hydrogen atom, or a group chosen from: i) (C 1 -C 8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C) C8 -C8) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino ( C, -C 8) alkyl, viii) carboxy, ix) carboxy (C 1 -C 3) alkyl, x) (di) (C 1 -C 8) (alkyl) aminocarbonyl (C 1 -C 8) alkyl, and xii) (C -C8) (alkyl) carbonyl (C1-C8) (alkyl) amino (C1-C8) alkyl; R3 and R4, which may be identical or different, represent a hydrogen atom, or a group chosen from: i) (C 1 -C 8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C 1 -C 8) ) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C, -C 8) ) alkyl, viii) carboxy, ix) carboxy (C 1 -C 8) alkyl, x) (di) (C 1 -C 8) (alkyl) aminocarbonyl (C 1 -C 8) alkyl, and xii) (C, -C 8) (alkyl) carbonyl (C1-C8) (alkyl) amino (C1-C8) alkyl; or when R1 and R3, or when n is 2 or 3, two R3 radicals carried by adjacent carbon atoms, together with the carbon atoms carrying them, form a cycloalkyl, heterocycloalkyl, aryl group such as phenyl, or heteroaryl; especially phenyl; n represents an integer of 1, 2 or 3, especially 1 or 2; it being understood that when n is 2 or 3 then the groups R 3 and R 4 may be identical or different from one another. Another subject of the invention relates to the use of the composition according to the invention for the permanent deformation of keratinous fibers. , more particularly hair and a process of permanent deformation of keratin fibers using this composition. These methods are particularly simple and fast. They also have the advantage of transforming keratin fibers such as the hair in an aesthetic and durable manner against the various external aggressions while keeping a very suitable fiber cosmetic. In particular, the methods according to the invention make it possible to obtain crimps and behavior of loops that are more efficient than those of conventional methods that do not use disulfide compounds. Other characteristics, aspects and advantages of the invention will emerge even more clearly on reading the detailed description which will follow, as well as the various concrete, but in no way limiting, examples intended to illustrate it.

Although the following discussion is essentially based on the particular case of hair treatment, it will be noted here that the method according to the invention is applicable to all keratin fibers. The compounds of formula (I) and (I ') according to the invention are preferably used on human keratin fibers such as the hair.

The heterocyclic disulfide compounds of formula (1) and (I '):

The processes according to the invention use one or more heterocyclic compound (s) of formula (I) as defined above. According to one particular embodiment of the invention, the compounds of formula (I) are such that n is 1 or 2. One variant relates to the compounds of formula (I) or (I ') of which n is 1. According to another variant, the compounds are of formula (I) or (I ') with n being 2. Particularly at least one of the radicals R 1 to R 6 is different from a hydrogen atom. According to a particular embodiment of the invention, the compounds of formula (I) or (I ') are such that Z, represents CRI R2 and Z2 represents CR5R6 with radicals R, to R6, which are identical or different, representing an atom of hydrogen, or a group selected from: i) (C 1 -C 8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C 1 -C 8) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C 1 -C 8) alkyl, viii) carboxy, ix) amino, and x) (C, -C8) (alkyl) carbonyl (C, -C8) (alkyl) amino (C, -C8) alkyl.

In particular, the compounds of formula (I) are such that R 1 to R 6 are chosen from hydrogen and hydroxy, carboxy or (C 1 -C 3) alkylaminocarbonyl groups.

According to another preferred embodiment of the invention, the compounds of formula (I ') are such that R 1 to R 6 are chosen from hydrogen, and hydroxy, carboxy groups. Another particular variant of the invention relates to compounds of formula (I) or (I ') in which Z, and / or Z2 denote a carbonyl group, and / or R, and R3 or two radicals R3 carried by carbon atoms. adjacent carbon form together with the carbon atoms that carry them a benzene ring.

It being understood that in the definition of the radicals R 1 to R 6 of the formula (I) or (I '): the alkyl radicals are hydrocarbon radicals, saturated, linear or branched, generally C 1 -C 8, especially C 1 -C 6, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. - The alkoxy radicals are alkyl-oxy radicals with (C 1 -C 8) alkyl preferably C 1 -C 6 such as methoxy, ethoxy, propoxy and butoxy. The (poly) hydroxyalkyl radicals comprise on the (C 1 -C 8) alkyl group as defined above, one or more substituted hydroxyl groups, in particular it is a hydroxy (C 1 -C 8) alkyl (C 1 -C 8) radical; such as hydroxymethyl, hydroxyethyl and hydroxypropyl. The cycloalkyl radicals are C4-C8 cycloalkyl radicals, which may contain an unsaturation, preferably the cyclopentyl and cyclohexyl radicals. The cycloalkyl radicals may be further substituted, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups. - The herocycloalkyl radicals are radicals comprising from 4 to 8 members, containing from 1 to 3 identical or different heteroatoms, selected from the nitrogen atom, oxygen and sulfur and optionally containing from 1 to 3 carbon atoms. The heterocycloalkyl radicals may be further substituted in particular by the same groups as those defined for cycloalkyls. The aryl radicals are mono- or polycyclic carbon-based cyclic radicals comprising from 6 to 14 carbon atoms and at least one aromatic ring of which is phenyl, anthracenyl or xanthenyl, more particularly phenyl. The heteroaryl radicals are cyclic radicals, mono- or polycyclic, comprising from 6 to 14 chain members, containing from 1 to 3 identical or different heteroatoms, chosen from nitrogen, oxygen and sulfur and possibly containing from 1 to at 3 carbon atoms. The heteroaryl radicals are particularly chosen from the following groups: pyridyl, indolyl and furyl. The heteroaryl and aryl radicals may also be substituted in particular by the same groups as those defined for cycloalkyls.

As examples of heterocyclic disulfide compounds used in the process according to the invention which involves the heterocyclic compounds of formula (I), mention may be made of compounds (1) to (6), their stereoisomers and their addition salts with acid or base or their hydrates: Name CAS No. Chemical formula O OH Lipoic acid 62-46-4 sis (1) O NH2 Lipoamide 940-69-2 sis (2) OH s Asparagus acid 2224-02-4 O (3) OH HO v 4,5-dihydroxy-1,2-dithiane 14193-38-5 1 s, s (4) 3H-1,2-benzodithiol-3-one ss (5) 1,2-Dithiolane acid 4-methyl-4-carboxylic acid OH (6) By way of example of heterocyclic disulfide compounds of the composition according to the invention comprising at least one reducing agent and at least one heterocyclic compound of formula (I ') such that defined above include compounds (3) to (6) as defined above, their stereoisomers, their addition salts with an acid or a base or their hydrates.

The acid involved in the salts may be inorganic or organic. As usable acids include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, tartaric acid, methanesulfonic acid. The base involved in the salts may be mineral or organic. As bases that may be used, mention may be made of sodium, potassium or ammonium hydroxides, sodium or potassium or ammonium carbonates or bicarbonates, basic amino acids such as arginine or lysine or organic amines. non-carboxylic and especially aminoalcohols such as monoethanolamine or triethanolamine.

The heterocyclic disulfide compounds of formula (I) mentioned above are present in a cosmetic composition at a concentration which may be between 1 and 20%, preferably between 5 and 15%, by weight relative to the total weight of the composition. containing them.

Reducing agents

The process according to the invention also uses one or more reducing agent (s). By reducing agents is meant an agent capable of reducing the disulfide functions of keratin of keratinous fibers. To do this, the thiols are preferably used. More particularly, the thiols are chosen from thioglycolic acid and its salts, glycerol or glycol monothioglycolate, cysteamine and its acylated C1-C4 derivatives such as N-acetylcysteamine or N-propionylcysteamine, cysteine, N-acetylcysteine, cysteine esters, such as glycerol cystenate, N-mercaptoalkylamides of sugars such as N- (mercapto-2-ethyl) gluconamide, thiolactic acid and its esters such as glycerol monothiolactate 3-mercaptopropionic acid and its esters, such as glycerol 3-mercaptopropionate, thiomalic acid, 2-hydroxy-3-mercaptopropionic acid and its esters, such as glycerol 2-hydroxy-3-mercaptopropionate, panthétéine, thioglycerol, N- (mercaptoalkyl) hydroxyalkylamides described in the patent application EP-A-354 835 and the N-mono- or N, N-dialkylmercapto 4-butyramides described in the patent application EP-A- 368,763, the aminomercaptoalkylamides described in the patent application EP-A-432 000, the derivatives of N- (mercaptoalkyl) succinamic acids or N- (mercaptoalkyl) succiminides described in patent application EP-A-465 342, the alkylaminomercaptoalkylamides described in application EP-A-514 282, the mixture of hydroxy-2-propyl thioglycolate and hydroxy-2-methyl-1-ethyl thioglycolate described in patent application FR-A-2 679 448, the N- mercaptoalkyl alkane diamides described in patent application EP-A-653 202.

Thioglycolic acid, thiolactic acid, cysteine and its various derivatives, cysteamine and its derivatives, 3-mercaptopropionic acid and their esters or salts, in particular glycerol monothioglycolate, are preferably used.

These active agents can be used alone or as a mixture. The reducing agents above are generally present in an amount of between 0.01 and 20% by weight relative to the weight of the composition comprising them, preferably between 0.1 and 10% by weight relative to the weight of the composition. . The process of permanent deformation The keratinous fiber treatment method according to the invention first uses i) one or more reducing agent (s) and then ii) one or more heterocyclic compound (s). ) disulphide (s) of formula (I).

According to a particular embodiment of the invention the method comprises: a first step in which one or more reducing agent (s) is applied to the keratinous fibers to be treated, a second step in which said fibers are rinsed, a third step in which is applied to said fibers one or more heterocyclic compound (s) disulfide (s) of formula (I) as defined above.

Another particular embodiment of the invention consists in applying to keratin fibers a composition comprising one or more reducing agents as defined above and one or more heterocyclic disulfide compounds of formula (I '). More particularly, this process according to the invention comprises: a first step in which a composition comprising one or more reducing agent (s) and one or more heterocyclic compound (s) is applied to the keratinous fibers to be treated; ) disulphide (s) of formula (I ') as defined above; and a second step in which said fibers are rinsed.

It can be used in the method of mechanical tensioning means for keratinous fibers. These means may be used before or during the application of one or more reducing agent (s) or before or during the application of the composition comprising one or more reducing agent (s) and a or more heterocyclic compound (s) disulfide (s) of formula (I '). After the step of applying the heterocyclic compound (s) disulfide (s) of formula (I) or the combination of the reducing agent (s) and the heterocyclic compound (s) of formula (I ') the tensioning means are separated from the keratinous fibers. According to one particular embodiment of the process of the invention, the reducing agent (s) are (are) applied to wet hair. Preferably, the wet hair has previously been wound on tensioning means such as rollers, preferably having from 2 to 30 mm in diameter. The reducing agent (s) or the combination of one or more reducing agent (s) and one or more heterocyclic disulfide compound (s) of formula (I ') may also be applied as winding of the hair or impregnated in the curler when it is for example foam. It is also possible to apply, on the wound hair, the heterocyclic compound (s) disulfide (s) of formula (I) which can then react with the keratinous fibers. According to another variant, the combination of the reducing agent (s) and the heterocyclic compound (s) disulfide (s) of formula (I ') is applied to the coiled hair.

Generally, the reducing agent (s) is then allowed to act for a period of 5 to 60 minutes, preferably 15 to 45 minutes, followed by extensive rinsing.

According to a particular method of the invention, the application of the heterocyclic compound (s) disulfide (s) of formula (I) or the combination of one or more reducing agents and one or more heterocyclic compounds disulphides of formula (I ') is followed by a step of fixing the keratinous fibers using one or more oxidizing agent (s). Optionally after the step of applying the heterocyclic compound (s) disulfide (s) of formula (I) or (I ') and / or the step of application of the oxidizing agent (s) , the keratinous fibers are rinsed. The oxidizing agent (s) make it possible to reform the disulfide bonds of keratin with the compounds of formula (I) or (I ') which has reacted. The exposure time is preferably from 2 to 10 minutes. It is also possible, after application of the heterocyclic compound (s) disulfide (s) of formula (I) or (I '), to subject the hair to heat treatment by heating at a temperature between 30 and 60 ° C during all or part of the exposure time. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices.

When it is desired to carry out the straightening or the prior curing of the hair, i) one or more reducing agent (s) is applied to the hair, and then the hair is subjected to mechanical deformation by a hair removal operation. smoothing the hair with a comb with large teeth, with the back of a comb or by hand. After generally a laying time of 5 to 60 minutes, preferably 15 to 45 minutes, a new smoothing is carried out, then rinsed thoroughly and ii) is then applied to the keratin fibers under tension or not one or more compound (s) heterocyclic (s) disulfide (s) of formula (I) or (I '), then iii) the keratinous fibers are optionally treated with one or more oxidizing agent (s), which is left to act during about 2 to 10 minutes, then rinse the hair thoroughly.

The process defined above comprises a step of drying the keratinous fibers. The drying of the keratinous fibers may be partial drying or complete drying, and may be carried out for example with a domestic hair dryer or a helmet or a heating cap, or may be carried out by careful spinning. Preferably, the drying of the keratinous fibers is complete drying. Preferably, a heating system is used to dry the hair. The reducing agent (s), the heterocyclic compound (s) disulfide (s) of formula (I) and the oxidizing agent (s) may be contained in compositions separated or in a single composition. Compositions The compositions according to the invention comprise a cosmetic support which generally contains water, a mixture of water and one or more organic solvents, or a mixture of organic solvents. By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it.

Organic Solvents: As an organic solvent, there may be mentioned, for example, C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol. The organic solvents are present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dyeing composition, and even more preferably between 5 and 30% by weight approximately. Admixtures: The The compositions of the dyeing method according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, polymers anionic, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as e.g. Examples are volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents and opacifying agents. Said adjuvants are preferably chosen from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the deformation process according to the invention are not not, or not substantially, impaired by the addition or additions envisaged.

The compositions used according to the invention and in particular that comprising one or more heterocyclic disulfide compounds of formula (I) or (I ') may further comprise one or more alkalinizing agents. These alkalinizing agents contribute in particular to adjust the pH.

Basifying Agents The basifying agent used in the compositions that are useful according to the invention is an agent for increasing the pH of the composition or compositions in which it is present. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. In particular, the basifying agent is chosen from: a) ammonia, b) alkanolamines such as mono-, di- and triethanolamines and their derivatives, c) oxyethylenated and / or oxypropylenated ethylenediamines, d) mineral hydroxides or organic, e) alkali metal silicates such as sodium metasilicates, f) amino acids of basic preferences such as arginine, lysine, ornithine, citruline and hystidine, g) (bi) carbonates, especially of primary, secondary or tertiary amine (ammonium), of alkali metal or alkaline earth metal, and h) compounds of the following formula (II): ## STR2 ## wherein W is a propylene residue optionally substituted by a hydroxy group or a C1-C4 alkyl radical; Ra, Rb, R, and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The inorganic or organic hydroxides are preferably selected from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as hydroxides of sodium or potassium, c) the hydroxides of a metal of such as the hydroxides of Group III, IV, V and VI metals, d) the hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

The hydroxide may be formed in situ such as, for example, guanidine hydroxide by reaction of calcium hydroxide and guanidine carbonate.

The alkalinizing agent (s) as defined above preferably represent from 0.001% to 10% by weight of the weight of the composition containing them. More particularly from 0.005% to 8% by weight of the composition. When a composition in the invention comprises one or more reducing agents, the pH of the composition is preferably between 5 and 11.5 and even more preferably between 6 and 10. The compositions which are useful in the invention may be present under the form of a lotion, thickened or not, a cream, a gel or any other suitable form and may contain additives known for their use in reducing compositions for the permanent deformation of the hair. The compositions useful in the invention may also be of the exothermic type, that is to say causing some heating during application to the hair, which brings an amenity to the person who undergoes the permanent. This composition may also contain a solvent such as, for example, ethanol, propanol, isopropanol, glycerol, propylene glycol or even diethylene glycol at a maximum concentration of 20% relative to the total weight of the composition.

The oxidizing agent (s) may be in an oxidizing composition. The oxidizing agents are preferably chosen from hydrogen peroxide or hydrogen peroxide, alkaline bromates, persalts, polythionates and a mixture of alkaline bromate and persalt. The concentration of hydrogen peroxide can vary from 1 to 20 volumes and preferably from 1 to 10, the alkali bromate concentration from 2 to 12% and that persalt 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 and it is preferably i.e. acid of between 2 and 5.

The other common characteristics of the compositions of the invention described above apply to this oxidizing composition.

The powering up means The keratinous fibers can be put into tension by any means and for example with elastics, clips, combs, bars, tubes or with conventional cylindrical curlers or rollers, and tulip curlers. Curlers can be foam as for example those described in US-5,992,425. In this case, the foam roller may be impregnated with a hair product such that the cosmetic composition comprising at least one reducing agent or said composition further comprising at least one heterocyclic disulfide compound of formula (I ') as defined above and on wherein the wick of keratinous fibers is wound in order to coat this wick with product over its entire length of winding. Tulip hair curlers consist of an elongated shaft forming a body terminated at one end by a head having at least one perforation. The body of the curler is made of flexible and flexible material, so that its free end can be introduced into the perforation of the head and be held there by elastic clamping. A hair curler of the type defined above is for example described in the patent application FR2602650. The use of a tulip curler makes it possible to control the tension applied to the hair and thus makes it possible to give a rounded shape to the locks of hair during the treatment period. More particularly, the powering means are curlers having a diameter of 2 to 30 mm. EXAMPLES OF PERMANENT DEFORMATIONS EXAMPLES 1 and 2

1- Compositions The following compositions were prepared (contents expressed in grams of active material): Composition 1 (reducing lotion): Ingredients (MA) Thioglycolic acid 7 Ammonia (in aqueous 20% ammonia solution) 9.1 Ammonium bicarbonate 2.5 Ammonium chloride 1.7 Diethylene triamine pentaacetic acid (40% sodium salt 0.4 in water) Demineralized water qs 100 Compositions 2 and 3 (intra-permanent) comprising a heterocyclic compound disulfide of formula (I): ingredients Composition 2 Composition 3 g (MA) g (MA) Lipoic acid 0.5 - Trans-4,5-dihydroxy-1,2-dithiane - 10 monoethanolamine qsp pH 8 qs pH 6.5 Demineralized water qs 100 qs 100 Composition 4 (fixative) comprising the oxidizing agent: ingredients g (MA) 35% hydrogen peroxide in water 5.15 sodium salicylate 0.01 8-hydroxyquinoline sulphate 0, 0125 Citric acid qs pH 3 Demineralized water qs 100 Application process Step 1: one step 1 gram of hair is wound on a curler 17 mm in diameter, Step 2: the reducing composition 1 is applied in a bath ratio of 1.5 (1.5 grams of formulation for 1 gram of hair) for 15 minutes, Step 3: the wick is rinsed with clean water, Step 4: Composition 2 (or 3) is applied in a bath ratio of 1.5 for 10 minutes, Step 5: Composition 4 is applied in a bath ratio of 1.5 for 5 minutes, Step 6: the lock of hair is unwound, rinsed with clear water and then dried.

Treatment not involving step 4 is chosen as the reference test. Example 1 A strand of Caucasian natural hair (pitch of 3) and a strand of discolored hair (discoloration of 30 minutes at 35 ° C using a bleaching composition consisting of a mixture weight for weight of Platifiz Précision and hydrogen peroxide 20 volumes, commercial references L'Oréal Professionnel) were permed according to the process indicated above including the composition 2. The wicks thus treated were compared to the reference locks (treated without the step of intra -permanent) in terms of crimp performance and loop strength.

The composition and the method of the invention allow a loop result superior to the conventional method, whether on natural hair or on discolored hair. A loop holding test is performed by keeping the strands under tension for 5 hours at 40 ° C. at 100% relative humidity. At the end of the strength test, the locks treated according to the permanent method of the invention have loop yields higher than the reference locks. Example 2 A strand of Caucasian natural hair (pitch of 3) and a strand of discolored hair (see Example 1) were permed according to the process indicated above including composition 3. The strands thus treated were compared to reference locks (processed without the intra-permanent step) in terms of crimp performance and loop strength.

The composition and the method of the invention offer a loop result superior to the conventional method, whether on natural hair or on discolored hair. The locks thus permeated were subjected to the loop-holding test indicated in Example 1. The crimps obtained with the permanent treatment of the invention are more stubborn than the crimps obtained according to the reference treatment.

Claims (21)

REVENDICATIONS1. Process for treating keratinous fibers in order to obtain a permanent deformation of the latter, by successive application on the keratinous fibers to be treated: i) firstly one or more reducing agent (s) and then ii) in a second step of one or more heterocyclic compound (s) disulfide (s) of formula (I): ## STR1 ## their salts with an acid or a base, their stereoisomers, and their solvates such as that hydrates, formula (I) wherein: Z, and Z2, identical or different, represent a carbonyl group or a divalent group CR, R2 or CR5R6; R, R6, identical or different, represent a hydrogen atom, or a group chosen from: i) (C, -C8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C, -C8 ) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C, -C 8) alkyl, viii) carboxy, ix) carboxy (C 1 -C 8) alkyl, x) (di) (C 1 -C 8) (alkyl) aminocarbonyl (C 1 -C 8) alkyl, xii) amino, xiii) aminocarbonyl ( C1-C8) alkyl and xiv) (C1-C8) (alkyl) carbonyl (C1-C8) (alkyl) amino (C1-C8) alkyl; or when R1 and R3, or when n is 2 or 3, two R3 radicals carried by adjacent carbon atoms together with the carbon atoms bearing a cycloalkyl, heterocycloalkyl or aryl group; n represents an integer equal to 1, 2 or 3, it being understood that when n is 2 or 3 then the groups R 3 and R 4 may be identical or different from each other. 30 2. Method according to the preceding claim wherein the heterocyclic compound (s) (s) of formula (I) are such that n is 1 or 2. 3. Method according to any one of the preceding claims wherein the heterocyclic compound (s) of formula (I) has (s) one or more radicals R, R6 different from a hydrogen atom. 4. Process according to any one of the preceding claims, in which the heterocyclic compound (s) of formula (I) are such that R 1 to R 6 are chosen from a hydrogen atom and the hydroxyl and carboxy groups. , carboxy (C 1 -C 6) alkyl, aminocarbonyl (C 1 -C 6) alkyl. 10 5. Method according to any one of the preceding claims wherein the heterocyclic compound (s) of formula (I) are such that Z, and / or Z2 denote a carbonyl group, and / or R, and R3 or two R3 radicals carried by adjacent carbon atoms together with the carbon atoms which carry them a benzene ring 6. Process according to any one of the preceding claims, in which the heterocyclic compound (s) of formula (I) are chosen from compounds (1) to (6), their stereoisomers and their addition salts with a acid or base or their hydrates: Denomination Chemical formula Lipoic acid o OH ss (1) Lipoamide o NH2 (-c (2) Asparagusic acid OH SO (3) 4,5-dihydroxy-1,2-dithiane HO (4) ) 1 S5SH-1,2-benzodithiol-3-one (5) O ss 1,2-Dithiolane-4-methyl-4-carboxylic acid (6) 7. Process according to any one of the preceding claims, in which the heterocyclic compound (s) of formula (I) are present in a composition used in the process of the invention at a concentration of between 1 and 20. % by weight relative to the total weight of the composition containing them. 8. Process according to any one of the preceding claims, in which the reducing agent (s) is (are) chosen from thioglycolic acid and its salts, glycerol or glycol monothioglycolate, cysteamine and its C1-acyl derivatives. C4, cysteine, N-acetylcysteine, cysteine esters, N-mercaptoalkylamides of sugars, thiolactic acid and its esters, 3-mercaptopropionic acid and its esters, thiomalic acid, 2- 3-mercaptopropionic hydroxy and its esters, pantheatin, thioglycerol, N- (mercaptoalkyl) -hydroxyalkylamides and N-mono- or N, N-dialkylmercapto-4-butyramides, aminomercaptoalkylamides, N- (mercaptoalkyl) succinamic acid derivatives or N- (mercaptoalkyl) succiminides, alkylaminomercaptoalkylamides, the mixture of 2-hydroxypropyl thioglycolate and 2-hydroxy-1-methylethyl thioglycolate and the N-mercaptoalkylalkanediamides. 9. Method according to any one of the preceding claims wherein the reducing agent (s) (s) are present in an amount of between 0.01 and 20% by weight relative to the weight of the composition comprising them. 10. A method for treating keratinous fibers, according to any one of the preceding claims, which comprises: a first step in which one or more reducing agent (s) as defined in claim 1 or the reducing agent (s) are applied to the keratinous fibers to be treated; 8, a second step in which said fibers are rinsed, a third step in which is applied to said fibers one or more heterocyclic compound (s) disulfide (s) of formula (I) as defined in any one of the claims 1 to 6. 11. Method according to any one of the preceding claims, wherein means are used for mechanically tensioning the keratinous fibers before or during the application of one or more reducing agent (s), said means being separated from the fibers. keratin after the step of applying the heterocyclic compound (s) disulfide (s) of formula (I). 12. Method according to any one of the preceding claims, wherein the step of the heterocyclic compound (s) (s) disulfide (s) of formula (I) is followed by a step of fixing the keratin fibers using one or more oxidizing agent (s) and then optionally a rinsing step. 13. Process according to the preceding claim, in which the oxidizing agent (s) is (are) preferably chosen from hydrogen peroxide or hydrogen peroxide, alkaline bromates, persalts, polythionates and a mixture of bromate. alkaline and persalt. 14. Cosmetic composition comprising: i) one or more reducing agent (s) as defined in claim 1, 8 and 9; ii) one or more heterocyclic disulfide compound (s) of the formula (I ') ## STR1 ## their salts with an acid or a base, their stereoisomers, and their solvates, such as hydrates, formula (I ') wherein: Z, and Z2, identical or different, represent a carbonyl group or a divalent group CR, R2 or CR5R6; R1, R2, R5 and R6, which may be identical or different, represent a hydrogen atom, or a group chosen from: i) (C 1 -C 8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C) -C8) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C) , -C8) alkyl, viii) carboxy, ix) carboxy (C 1 -C 3) alkyl, x) (di) (C 1 -C 8) (alkyl) aminocarbonyl (C 1 -C 8) alkyl, and xii) (C, -C8) (alkyl) carbonyl (C1-C8) (alkyl) amino (C1-C8) alkyl; R3 and R4, which may be identical or different, represent a hydrogen atom or a group chosen from: i) (C 1 -C 8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C 1 -C 8) (alkyl) amino, v) (C 1 -C 8) alkoxy, vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C 1 -C 8) alkyl, viii) carboxy, ix) carboxy (C 1 -C 8) alkyl, x) (di) (C 1 -C 8) (alkyl) aminocarbonyl (C 1 -C 8) alkyl, and xii) (C 1 -C 8) ( alkyl) (C 1 -C 8) carbonyl (alkyl) amino (C 1 -C 8) alkyl; or when R 1 and R 3, or when n is 2 or 3, two radicals R 3 carried by adjacent carbon atoms, together with the carbon atoms carrying them, form a cycloalkyl, heterocycloalkyl or aryl group; n represents an integer equal to 1, 2 or 3, it being understood that when n is 2 or 3, then the groups R 3 and R 4 may be identical or different from each other. 15. Composition according to the preceding claim wherein the heterocyclic compound (s) of formula (I ') are such that n is 1 or 2. 16. Composition according to claims 14 or 15 wherein the heterocyclic compound (s) of formula (I ') has (s) one or more radicals R, R6 different from a hydrogen atom. 17. Composition according to any one of claims 14 to 16 wherein the heterocyclic compound (s) of formula (I ') are such that the radicals R, to R6, identical or different, represent a hydrogen atom. or a group selected from: i) (C 1 -C 8) alkyl, ii) aryl, iii) hydroxy, iv) (di) (C 1 -C 8) (alkyl) amino, v) (C 1 -C 8) alkoxy , vi) (poly) hydroxy (C 1 -C 8) alkyl, vii) (di) (C 1 -C 8) (alkyl) amino (C 1 -C 8) alkyl, viii) carboxy, ix) amino, and x) (C) , C8) (alkyl) carbonyl (C, -C8) (alkyl) amino (C, -C8) alkyl. 18. Composition according to the preceding claim wherein the heterocyclic compound (s) of formula (I ') are such that the radicals R, R6, R, R6 are chosen from a hydrogen atom, and hydroxy, carboxy, aminocarbonyl (C 1 -C 3) alkyl groups. 19. Composition according to any one of claims 13 to 18 wherein the heterocyclic compound (s) of formula (I ') are such that Z, and / or Z2 denote a carbonyl group, and / or R, and R3 or two radicals R3 carried by carbon atoms together form with the carbon atoms which carry them a benzene ring. 20. Composition according to any one of claims 14 to 19 wherein the heterocyclic compound (s) of formula (I ') are chosen from compounds (3) to (6), their stereoisomers and their salts. addition with an acid or a base or their hydrates: Denomination Chemical formula Asparagusic acid OH SO (3) 4,5-dihydroxy-1,2-dithiane HO (4) OH v 1 s's 3H-1,2-benzodithiol-3- one (5) ss 1,2-dithiolane-4-methyl-4-carboxylic acid OH sùs (6) 21. Use of a composition as claimed in any one of claims 14 to 20 for the permanent deformation of keratinous fibers, more particularly hair.