US20140326268A1

US20140326268A1 - Process for straightening keratin fibres with a heating means and denaturing agents

Info

Publication number: US20140326268A1
Application number: US14/295,435
Authority: US
Inventors: Michel Philippe; Gerard Malle; Philippe Barbarat
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2006-05-24
Filing date: 2014-06-04
Publication date: 2014-11-06
Also published as: EP2029095A2; WO2007135297A2; BRPI0711196A2; FR2901472B1; US11399611B2; US20120192888A1; JP2009537618A; EP2029095B1; BRPI0711196B1; FR2901472A1; US8765107B2; US20190125051A1; WO2007135297A3; US20100028280A1

Abstract

The invention relates to a process for straightening keratin fibres, comprising: (i) a step in which a straightening composition containing at least two denaturing agents is applied to the keratin fibres, (ii) a step in which the temperature of the keratin fibres is raised, using a heating means, to a temperature of between 110 and 250° C.

Description

The invention relates to a process for relaxing keratin fibres with a heating means and at least two denaturing agents.
The relaxing process according to the invention is performed without using a reducing agent or a lanthionization agent. It does not comprise any reducing or lanthionizing step.
According to the invention, the term “keratin fibres” means fibres of human or animal origin such as head hair, bodily hair, the eyelashes, wool, angora, cashmere or fur. Although the invention is not limited to particular keratin fibres, reference will nevertheless be made more particularly to head hair.
According to the invention, the term “relaxing” covers the relaxing, straightening or uncurling of Caucasian or African hair.
The term “denaturing agent” means a compound of organic or mineral origin containing both at least one electron-donating site of basic or nucleophilic nature and at least one electron-accepting site of acidic or electrophilic nature, which interacts with the weak bonds of keratin.
According to the invention, a denaturing agent is a compound capable of reducing the optical rotation of a model protein, for instance bovine serum albumin, by at least 7° and/or 5° at 579 nm, the measurements being taken after incubation for 3 hours at 37° C., using a polarimeter, as described in Biochemistry 2 (1), 47-57, 1963:

- either in TRIS 0.05 M pH 7.6 buffer
- or in a 5.45 M urea solution when the solubility of the compound is insufficient in the TRIS 0.05 M pH 7.6 buffer.

The compound is considered as being a denaturing agent according to the invention if the reduction of the optical rotation is at least 7° in TRIS 0.05 M pH 7.6 buffer and/or at least 5° in 5.45 M urea solution.
The term “weak bonds of keratin” means all the non-covalent bonds such as:

- the saline bonds resulting from coulombic interactions between the functional groups present on the side chains of amino acids
- the hydrogen bonds that become established between amino acids especially via oxygen and hydrogen atoms
- the hydrophobic bonds resulting from the tendency of the non-polar chains of amino acids to associate in order to minimize the contacts with water.

The term “heating means” means any means for heating keratin fibres to a temperature of at least 110° C., such as heating irons, for example flat or round irons, microwave generators or sources of infrared radiation.
Two techniques are used for permanently reshaping the hair. They are based on cleavage of the disulfide covalent bonds present in keratin (cystine):

- the first consists, in a first stage, in performing this opening of the disulfide bonds using a composition containing a reducing agent, and then, after having preferably rinsed the hair, in reconstituting the said disulfide bonds in a second stage, by applying to the hair, which has been placed under tension beforehand with rollers or the like or shaped or straightened out by other means, an oxidizing composition also known as a fixer, so as to give the head of hair the desired shape. This technique makes it possible either to make the hair wavy or to relax it, uncurl it or straighten it out;
- the second consists in performing a “lanthionization” operation using a composition containing a base belonging to the hydroxide family. This leads to replacement of the disulfide bonds (—CH2-S—S—CH2-) with lanthionine bonds (—CH2-S—CH2-). This lanthionization operation involves two consecutive chemical reactions:
- the first reaction consists of a beta-elimination on cystine brought about by a hydroxide ion, leading to the cleavage of this bond and to the formation of dehydroalanine:

- the second reaction is a reaction of dehydroalanine with a thiol group. Specifically, the double bond of the dehydroalanine formed is a reactive double bond. It can react with the thiol group of the cysteine residue that has been released to form a new bond referred as a lanthionine bridge or bond or residue.

Relative to the first technique using a reducing agent, this lanthionization technique does not require a fixing step, since the formation of the lanthionine bridges is irreversible. It is thus performed in a single step and makes it possible either to make the hair wavy, or to relax it, uncurl or straighten it out. However, it is mainly used for relaxing naturally curly hair.
For the first technique, the reducing compositions generally used for the first step of a permanent-waving or hair-relaxing operation contain thiols, sulfites or bisulfites as reducing agent. These agents are generally used in essentially aqueous medium at concentrations of between 0.5 and 1 M to obtain good opening of the disulfide bonds. Among the thiols, those commonly used are thioglycolic acid, cysteamine, glyceryl monothioglycolate, thiolactic acid and cysteine. Thioglycolic acid is particularly efficient at reducing the disulfide bonds of keratin at alkaline pH, especially in the form of ammonium thioglycolate, and constitutes the product most frequently used in permanent waving (“hair waving”). It has been found, however, that thioglycolic acid must be used in sufficiently basic medium (in practice at a pH of between 8.5 and 9.5) if curling of satisfactory intensity is to be obtained. Besides the drawback of releasing an unpleasant odour requiring the use of more or less efficient fragrances to mask the odours, the use of a thiol at alkaline pH also results in degradation of the fibre and most particularly in impairment of artificial colorations.
Sulfites or bisulfites are mainly used for relaxing the hair. They have drawbacks similar to those of thiols, with lower efficacy.
Thiols and sulfites (or bisulfites) also have the drawback of having poor stability in aqueous solution.
In general, the durability of the reshaping effects obtained with thiols and sulfites by reduction of disulfides following by fixing is judged to be very much lower than that which may be obtained via the lanthionization technique.
For the second technique, the compositions generally used to perform lanthionization contain as base a hydroxide such as sodium hydroxide, guanidinium hydroxide or lithium hydroxide. These lanthionization active agents, which allow opening of the disulfide bonds via a beta-elimination mechanism, are generally used as a water-oil emulsion at concentrations of between 0.4 and 0.6 M, by leaving them to act generally for 10 to 15 minutes at room temperature. Sodium hydroxide remains the agent most frequently used. Guanidinium hydroxide is now the preferred compound for many compositions. These two hydroxides, sodium hydroxide and guanidinium hydroxide, are the two main agents used for the relaxing or uncurling of naturally curly hair. They have several advantages over ammonium thioglycolate and sulfites, in particular the absence of unpleasant odour, the fact that only one operating step is required (shorter treatment time) and much greater durability and efficacy of reshaping of the hair.
However, these hydroxides have the major drawback of being caustic. This causticity affects the scalp by causing irritation, which is occasionally severe. This may be partially remedied by applying beforehand to the scalp fatty protective cream often referred to as a “base” or “base cream”, the word “base” in this case not having the meaning of a basic agent in the chemical sense. When the protective cream is combined with the hydroxide in a single composition, it is generally referred to as “no-base”, as opposed to the above name. This “no-base” technique is preferred.
The causticity of hydroxides also affects the state of the hair by firstly giving it a coarse feel and secondly making it much more brittle, this brittleness possibly going as far as crumbling or breaking or even dissolution of the hair if the treatment is prolonged. In certain cases, hydroxides also cause decoloration of the natural colour of the hair.
Formulations containing sodium hydroxide are generally referred to as “lye relaxers” and those not containing it are referred as “no-lye relaxers”.
The main relaxing formulations known as “no-lye” relaxers use guanidinium hydroxide. Since guanidinium hydroxide is unstable, it is generated at the time of use by mixing guanidinium carbonate and a source of sparingly soluble hydroxide such as calcium hydroxide. The reaction between these two compounds leads to the formation of guanidinium hydroxide and calcium carbonate, which precipitates in the composition. The presence of this precipitate makes the final rinsing of the hair much more difficult and leaves mineral particles on the hair and the scalp, which give it a coarse feel and an unaesthetic appearance resembling dandruff. The recent success of guanidinium hydroxide (“no-lye”) over sodium hydroxide (“lye”) appears to arise from better relaxing efficacy and better skin tolerance. However, these techniques using bases of the hydroxide family remain very aggressive to the hair and the scalp and require very strict control of the duration of application to avoid excessive irritation and impairment of the hair that may go as far as breakage. This aggressiveness arising from the causticity of hydroxides is justification for not using these hair lanthionization compositions for permanent waving (hair waving), but solely for hair straightening or hair relaxing.
Furthermore, hydroxides are known to be good agents for hydrolysing amide functions (cf. for example March's Advanced Organic Chemistry, 5th edition, Wiley Interscience, New York, “Hydrolysis of Amides” page 474 et seq.), which thus lead to cleavage of peptide bonds by direct nucleophilic attack. It is thus probable that the observed impairments of the hair and of keratin materials in the broad sense are largely due to partial hydrolysis of the amide bonds of keratin.
There is thus a real need for relaxing compositions that are markedly less aggressive to the hair.
Various studies have been conducted in order to overcome both the drawbacks of reducing agents (first technique) and/or those of hydroxides (second technique).
Thus, many reducing agents have been proposed to replace thioglycolic acid, but thioglycolic acid in the form of ammonium thioglycolate remains both the reference compound and the compound most widely used in cosmetic formulations, not only for shaping but also for straightening the hair.
It has also been proposed in numerous patents to combine common reducing agents (thiols, sulfites or bisulfites) with urea or alkyl ureas to reduce the irritation and damage caused to the hair, not only for shaping but also for relaxing. Mention will be made, for example, of:

- patent application CA 1315204, which describes a composition containing ammonium thioglycolate (5.5-11.5%) and urea or a monoalkyl urea (1-3%) for shaping the hair,
- U.S. Pat. No. 3,847,165, which describes a composition containing ammonium thioglycolate (1.2-1.4 M) and urea (2.0-2.7 M) for shaping the hair at an acidic pH,
- patent application NL 6410355, which describes a composition containing a sulfite (0.8-1.5 M) and urea (0.6-3.0 M) for shaping and relaxing the hair,
- patent application JP 2000/229 819, which describes a composition containing a sulfite or bisulfite (0.5-15%), urea (0.5-15%) and an alcohol (ethanol and/or isopropanol, 1-30%) for shaping and relaxing the hair.

It has also been proposed in numerous patents to combine hydroxides, serving as lanthionization active agent, with certain additives generally serving to protect the hair. Mention will be made, for example, of:

- patent application WO 2002/003 937, which describes a composition containing C3-C5 monosaccharides,
- patent application WO 2001/064 171, which describes a composition containing complexing agents,
- U.S. Pat. No. 5,641,477, which describes a composition containing a hydrogenated starch hydrolysate,
- patent application WO 02/085 317, which describes a composition containing organic nucleophiles that react during the second step with the dehydroalanine formed with hydroxides, to give new bridges.

Although all these proposals lead to more or less pronounced improvements, they are not able to sufficiently reduce the damage associated with the very causticity of hydroxides.
As indicated previously, the use of reducing agents leads to poor durability of the relaxing or straightening of the hair and the use of hydroxides, on account of their causticity, limits their use in the field of hair relaxing.
The use of resorcinol at a concentration of 40% and at a pH of 7 for relaxing the hair has been reported by M. Wong et al.: M. Wong, G. Vis-surel, and J. Epps J. Soc. Cosmet. Chem. (1994), 45, 347-352. However, the tests that we have performed under these conditions on naturally curly African hair do not relax it, but lead, at the very best, to slight uncurling.
After considerable studies, it has now been discovered, entirely surprisingly and unexpectedly, that hair can be durably relaxed by combining the action of at least two denaturing agents and of a means of heating to a temperature above 110° C. Excellent results in terms of relaxing, cosmetic properties of the hair and fibre integrity are thus obtained.
Without being bound by theory, the Applicant considers that there is a combined action, on the keratin fibres, of at least two denaturing agents and of a heating means, which allows the fibres to be efficiently and durably relaxed.
The Applicant has found that it is possible to overcome the drawbacks of the prior art and to satisfy the abovementioned objectives by performing a process for relaxing keratin fibres, comprising:

- a step of applying to the keratin fibres a hair-relaxing composition containing at least two denaturing agents,
- a step of raising the temperature of the keratin fibres, using a heating means, to a temperature of between 110 and 250° C.

Advantageously, the denaturing agents have a molar mass of greater than 18.1 g/mol and preferably between 40 and 600 g/mol.
Preferably, the hair-relaxing composition comprises an overall concentration of denaturing agents of between 1 M and 8 M and more advantageously between 2 M and 8 M of the said denaturing agents; this corresponds to a weight concentration of between about 6% and about 80% and more advantageously between about 12% and about 80%, relative to the total weight of the composition, of the said denaturing agents.
Advantageously, the temperature is raised using a heating means to a temperature of between 120° C. and 220° C. and more advantageously between 140° C. and 220° C.
According to one embodiment, the said composition is applied to wet keratin fibres.
A step intended to remove the excess composition, for example using a towel, may also be introduced between the step of applying the composition and the step of raising the temperature.
Preferably, the denaturing agents are chosen from protein-denaturing agents such as:

- ureas,
- guanidines,
- α-hydroxy acid and α-keto acid derivatives,
- mono-, di-, tri- or polyhydroxylated aromatic derivatives,
- cyclic or linear amides,
- surfactants or detergents, especially those containing sugar or choline or deoxycholine or polyethylene glycol units, such as the following compounds:
- acetobromo-α-D-glucose
- taurodeoxycholic acid sodium salt
- N-octyl-β-D-glucopyranoside
- MEGA-8
- N-hexyl-β-D-glucopyranoside
- N-heptyl-β-D-thioglucopyranoside
- N-heptyl-O-D-glucopyranoside
- glycodeoxycholic acid sodium salt
- sodium deoxycholate
- sodium cholate
- CHAPSO
- CHAPS
- octaethylene glycol mono-N-dodecyl ether
- N,N′-bis(3-D-gluconamidopropyl)cholamide
- polyoxyethylene (23) lauryl ether C12E23
- nonaethylene glycol monododecyl ether
- cetrimide
- decyl glucoside
- decyl maltoside
- N,N-bis(3-D-gluconamidopropyl)deoxycholamide
- digitonine
- dodecyl maltoside
- dioctyl sodium sulfosuccinate
- lauryldimethylamine oxide
- octaethylene glycol isotridecyl ether
- glycocholic acid, sodium salt
- sodium lauryl sulfate
- octanoyl-N-methylglucamide
- nonanoyl-N-methylglucamide
- decanoyl-N-methylglucamide
- nonyl glucoside
- nonaethylene glycol octylphenyl ether
- octyl thioglucoside
- polyethylene polypropylene glycol
- monosodium taurocholic acid
- nonaethylene glycol octylphenyl ether
- polyoxyethylene sorbitan monolaurate
- polyoxyethylene sorbitan monooleate
- N-octylsulfobetaine
- N-decylsulfobetaine
- N-dodecylsulfobetaine
- N-hexyldecylsulfobetaine,
- amidines, such as acetamidine hydrochloride,
- thioureas, urethanes, alcohols, polyols, amine oxides such as N-methylmorpholine N-oxide, metal salts, sulfamides, carboxylic acids and amino acids, nitrogenous heterocycles of the imidazole or triazole family, such as imidazole hydrochloride.

Advantageously, the said denaturing agents are chosen from the family of ureas, guanidines, α-hydroxy acid or α-keto acid derivatives, mono-, di, tri- or polyhydroxylated aromatic derivatives, and cyclic or linear amides.
The term “urea”, which may be used as hair-relaxing active agent, means any derivative comprising in its chemical formula a carbonyl group simply bonded to two nitrogen atoms. These ureas are more particularly selected from the compounds of general formulae (I) and (II) below:
in which:
R1, R2, R3 and R4 represent, independently:

(i) a hydrogen atom or
(ii) a linear or branched C1-C4 lower alkyl or alkenyl radical, optionally substituted with a radical chosen from: hydroxyl, amino, dimethylamino, carboxyl or carboxamide or N-methylcarboxamide,
when R1, R2 and R3 represent a hydrogen atom, R4 may also denote a radical chosen from: carboxamide; methoxy; ethoxy; 1,2,4-triazolyl; cyclopentyl; methoxy-carbonyl; ethoxycarbonyl; CO—CH═CH—COOH; phenyl optionally substituted with a chlorine atom or a hydroxyl radical; benzyl; or 2,5-dioxo-4-imidazolidinyl,
when R1 and R3 represent a hydrogen atom, R2 may also represent a hydrogen atom or a methyl or ethyl radical and R4 an acetyl radical,
when R1=R2=H, R3 and R4 may also form, with the nitrogen atom that bears them, a piperidine or 3-methylpyrazole or 3,5-dimethylpyrazole or maleimide ring, and finally, R1 and R2 and also R3 and R4 may also form, with the nitrogen atom that bears them, an imidazole ring.

in which:
R5 and R6 represent, independently of each other:

(i) a hydrogen atom or
(ii) a linear or branched C1-C4 lower alkyl radical, optionally substituted with a radical chosen from: hydroxyl, amino, dimethylamino, carboxyl and carboxamide, and
A represents the radicals: CH2-CH2 or CH═CH or CH2-CO or CO—NH or CH═N or CO—CO or CHOH—CHOH or (HOOC)CH—CH or CHOH—CO or CH2-CH2-CH2 or CH2-NH—CO or CH═C(CH₃)—CO or NH—CO—NH or CH2-CH2-CO or CH2-N(CH3)-CH2 or NH—CH2-NH or CO—CH(CH3)-CH2 or CO—CH2-CO or CO—NH—CO or CO—CH(COOH)—CH2 or CO—CH═C(COOH) or CO—CH═C(CH3) or CO—C(NH2)=CH or CO—C(CH3)=N or CO—CH═CH or CO—CH═N or CO—N═CH.

Among the compounds of formula (I), mention may be made especially of the following preferred compounds:

- urea
- methylurea
- ethylurea
- propylurea
- isopropylurea
- n-butylurea
- sec-butylurea
- isobutylurea
- tert-butylurea
- cyclopentylurea
- 1-ethoxyurea
- 2-hydroxyethylurea
- N-(2-hydroxypropyl)urea
- N-(3-hydroxypropyl)urea
- N-(2-dimethylaminopropyl)urea
- N-(3-dimethylaminopropyl)urea
- 1-(3-hydroxyphenyl)urea
- benzylurea
- N-carbamoylmaleimide
- biuret
- N-carbamoylmaleamic acid
- 1-piperidinecarboxamide
- 1,2,4-triazol-4-ylurea
- hydantoic acid
- methyl allophanate
- ethyl allophanate
- acetylurea
- 2-hydroxyethyleneurea
- 2-(hydroxyethyl)ethyleneurea
- N-allyl-N′-ethylurea
- diallylurea
- 2-chloroethylurea
- N,N-dimethylurea
- N,N-diethylurea
- N,N-dipropylurea
- 1-cyclopentyl-1-methylurea
- 1,3-dimethylurea
- 1,3-diethylurea
- 1,3-bis(2-hydroxethyl)urea
- 1,3,bis(2-hydroxypropyl)urea
- 1,3-bis(3-hydroxypropyl)urea
- 1,3-dipropylurea
- 1-ethyl-3-propylurea
- 1-sec-butyl-3-methylylurea
- 1-isobutyl-3-methylurea
- 1-cyclopentyl-3-methylurea
- N-acetyl-N′-methylurea
- trimethylurea
- 1-butyl-3,3-dimethylurea
- tetramethylurea
- benzylurea.

Among the compounds of formula (II), mention may be made especially of the following preferred compounds:

- parabanic acid
- 1,2-dihydro-3-H-1,2,4-triazol-2-one
- barbituric acid
- uracil
- 1-methyluracil
- 3-methyluracil
- 5-methyluracil
- 1,3-dimethyluracil
- 5-azauracil
- 6-azauracil
- 5-fluorouracil
- 6-fluorouracil
- 1,3-dimethyl-5-fluorouracil
- 5-aminouracil
- 6-aminouracil
- 6-amino-1-methyluracil
- 6-amino-1,3-dimethyluracil
- 4-chlorouracil
- 5-chlorouracil
- 5,6-dihydrouracil
- 5,6-dihydro-5-methyluracil
- 2-imidazolidone hydrate
- 1-methyl-2-imidazolidinone
- 1,3-dimethyl-2-imidazolidinone
- 4,5-dihydroxyimidazolidin-2-one
- 1-(2-hydroxyethyl)-2-imidazolidinone
- 1-(2-hydroxypropyl)-2-imidazolidinone
- 1-(3-hydroxypropyl)-2-imidazolidinone
- 4,5-dihydroxy-1,3-dimethylimidazolidin-2-one
- 1,3-bis(2-hydroxyethyl)-2-imidazolidinone
- 2-imidazolidone-4-carboxylic acid
- 1-(2-aminoethyl)-2-imidazole
- 4-methyl-1,2,4-triazoline-3,5-dione
- 2,4-dihydroxy-6-methylpyrimidine
- 1-amino-4,5-dihydro-1H-tetrazol-5-one
- hydantoin
- 1-methylhydantoin
- 5-methylhydantoin
- 5,5-dimethylhydantoin
- 5-ethylhydrantoin
- 5-n-propylhydantoin
- 5-ethyl-5-methylhydantoin
- 5-hydroxy-5-methylhydantoin
- 5-hydroxymethylhydantoin
- 1-allylhydantoin
- 1-aminohydantoin
- hydantoin 5-acetic acid
- 4-amino-1,2,4-triazolone-3,5-dione
- hexahydro-1,2,4,5-tetrazine-3,6-dione
- 5-methyl-1,3,5-triazinon-2-one
- 1-methyltetrahydropyrimidin-2-one
- 2,4-dioxohexahydro-1,3,5-triazine
- urazole
- 4-methylurazole
- orotic acid
- dihydroxyorotic acid
- 2,4,5-trihydroxypyrimidine
- 2-hydroxy-4-methylpyrimidine
- 4,5-diamino-2,6-dihydroxypyrimidine
- barbituric acid
- 1,3-dimethylbarbituric acid
- cyanuric acid
- 1-methylhexahydropyrimidine-2,4-dione
- 1,3-dimethyl-3,4,5,6-tetrahydro-2-1H-pyrimidinone
- 5-(hydroxymethyl-2,4-(1H,3H)-pyrimidinedione
- 2,4-dihydroxypyrimidine-5-carboxylic acid
- 6-azathymine
- 5-methyl-1,3,5-triazinan-2-one
- N-carbamoylmaleamic acid
- alloxan monohydrate.

Among the compounds of formula (I), mention may be made especially of the following particularly preferred compounds:

- urea
- methylurea
- ethylurea
- propylurea
- 1-ethoxyurea
- 2-hydroxyethylurea
- N-(2-hydroxypropyl)urea
- N-(3-hydroxypropyl)urea
- N-(2-dimethylaminopropyl)urea
- N-(3-dimethylaminopropyl)urea
- 1-(3-hydroxyphenyl)urea
- N-carbamoylmaleimide
- N-carbamoylmaleamic acid
- 1-piperidinecarboxamide
- 1,2,4-triazol-4-ylurea
- hydantoic acid
- acetylurea
- 2-hydroxyethyleneurea
- 2-(hydroxyethyl)ethyleneurea
- N-allyl-N′-ethylurea
- diallylurea
- 2-chloroethylurea
- N,N-dimethylurea
- 1,3-dimethylurea
- 1,3-diethylurea
- 1,3-bis(2-hydroxyethyl)urea
- 1,3-dipropylurea
- 1-ethyl-3-propylurea
- N-acetyl-N′-methylurea
- benzylurea.

Among the compounds of formula (II) mention made be made especially of the following particularly preferred compounds:

- 1,2-dihdryo-3-H-1,2,4-traizol-2-one
- uracil
- 1-methyl-2-imidazolidinone
- 1,3-dimethyl-2-imidazolidinone
- 4,5-dihydroxyimidazolidin-2-one
- 1-(2-hydroxyethyl)-2-imidazolidinone
- 4,5-dihydroxy-1,3-dimethylimidazolidin-2-one
- 1,3-bis(2-hydroxyethyl)-2-imidazolidinone
- 2-imidazolidone-4-carboxylic acid
- 1-(2-aminoethyl)-2-imidazole
- hydantoin
- 5-hydroxymethylhydantoin
- hydantoin 5-acetic acid
- urazole
- orotic acid
- dihydroxyorotic acid
- 2,4,5-trihydroxypyrimidine
- 4,5-diamino-2,6-dihydroxypyrimidine
- 2,4-dihydroxypyrimidine-5-carboxylic acid
- 5-methyl-1,3,5-triazinan-2-one
- 1,3-dimethyl-3,4,5,6-tetrahydro-2-1H-pyrimidinone
- N-carbamoylmaleamic acid
- alloxan monohydrate.

The term “guanidine”, which may be used as relaxing active agent, means any derivative comprising in its chemical formula at least one carbon atom doubly bonded to a nitrogen atom and singly bonded to two other nitrogen atoms. These guanidines are more particularly selected from the compounds of general formula (III) below:
in which
R1, R2, R3, R4 and R5 represent, independently:

(iii) a hydrogen atom or
(iv) a linear or branched C1-C4 lower alkyl or alkenyl radical, optionally substituted with one or two radicals chosen from: hydroxyl, amino, dimethylamino, methoxy, ethoxy, carboxyl, carboxamide, N-methylcarboxamide or SO₃H,
- when R1, R2 and R3 and R4 represent a hydrogen atom, R5 may also denote a radical chosen from the following: acetyl; chloroacetyl; carboxamide; methoxy; ethoxy; 1,2,4-triazolyl; cyclopentyl; methoxycarbonyl; ethoxycarbonyl; CO—CH═CH—COOH; phenyl optionally substituted with a chlorine atom or a hydroxyl radical; benzyl; thiazolidone; benzimidazole; benzoxazole; benzothiazole; or C(═NH)—NR6R7 in which R6 and R7 denote, independently of each other, a hydrogen atom or a linear or branched C1-C4 lower alkyl radical, optionally substituted with one or two radicals chosen from: hydroxyl, amino, dimethylamino, carboxyl or carboxamide; or N-methylcarboxamide; or alternatively a phenyl radical,
- when R1=R2=R3=H, R4 and R5 may also form, with the nitrogen atom that bears them, a pyrrolidine, piperidine, pyrazole or 1,2,4-triazole ring optionally substituted with one or two radicals chosen from: hydroxyl, amino or carboxyl,
- when R1=R2=H and R4=H or methyl, R3 and R5 may also together form a 5-membered ring optionally containing an oxo group,
- and the organic or mineral salts thereof.

Among the compounds of formula (III), mention may be made especially of the following preferred compounds:

- guanidine hydrochloride
- guanidine acetate
- guanidine sulfate
- guanidine carbonate
- guanidine bicarbonate
- guanidine phosphate
- guanidine sulfamate
- aminoguanidine
- aminoguanidine hydrochloride
- aminoguanidine sulfate
- aminoguanidine bicarbonate
- 1,3-diaminoguanidine hydrochloride
- 1-acetylguanidine
- chloroacetylguanidine hydrochloride
- guanylurea
- guanylurea phosphate
- phenylguanidine carbonate
- phenylguanidine bicarbonate
- 1-methylguanidine hydrochloride
- 1,1-dimethylguanidine hydrochloride
- 1-ethylguanidine hydrochloride
- 1,1-diethylguanidine hydrochloride
- creatine
- creatine monohydrate
- creatinine hydrochloride
- agmatine
- agmatine sulfate
- guanidinoacetic acid
- guanidinosuccinic acid
- 3-guanidinopropionic acid
- 4-guanidinobutyric acid
- 5-guanidinovaleric acid
- β-N-methylguanidinopropionic acid
- N-methylguanidinopropionic acid
- N-(2-hydroxyethyl)guanidine
- N-(3-hydroxypropyl)guanidine
- biguanide hydrochloride
- N-methylbiguanide hydrochloride
- N-ethylbiguanide hydrochloride
- N-propylbiguanide hydrochloride
- N-butylbiguanide hydrochloride
- N-butylbiguanide hydrochloride
- 1,1-dimethylbiguanide hydrochloride
- 1-phenylbiguanide
- 1,1,3,3-tetramethylguanidine hydrochloride
- 1-phenylbiguanide
- 1,1,3,3-tetramethylguanidine hydrochloride
- 2-tert-butyl-1,1,3,3-tetramethylguanidine hydrochloride
- L-arginine
- D-arginine
- DL-arginine
- arginic acid
- N-amidino-N-(2,3-dihydroxypropyl)glycine
- N-amidinotaurine
- 2-imino-2-imidazolidineacetic acid
- 1-(2,2-diethoxyethyl)guanidine
- 1H-pyrazole-1-carboxamidine hydrochloride
- 5-hydroxy-3-methyl-1H-pyrazole-1-carboximidamide
- 3,5-diamino-1H-1,2,4-triazole-1-carboximidamide hydrochloride
- 2-guanidone-4-thiazolidone
- 2-guanidinobenzimidazole
- 2-guanidinobenzoxazole
- 2-guanidinobenzothiazole
- pyrrolidinoformamidine hydrochloride.

Among the compounds of formula (III), mention may be made especially of the following particularly preferred compounds:

- guanidine hydrochloride
- guanidine acetate
- guanidine sulfate
- guanidine carbonate
- guanidine bicarbonate
- guanidine phosphate
- guanidine sulfamate
- aminoguanidine hydrochloride
- aminoguanidine sulfate
- aminoguanidine bicarbonate
- 1,3-diaminoguanidine hydrochloride
- guanylurea phosphate
- 1-methylguanidine hydrochloride
- 1,1-dimethylguanidine hydrochloride
- 1-ethylguanidine hydrochloride
- creatine monohydrate
- creatinine hydrochloride
- agmatine
- agmatine sulfate
- guanidinoacetic acid
- guanidinosuccinic acid
- 3-guanidinopropionic acid
- β-methylguanidinopropionic acid
- N-methylguanidinopropionic acid
- N-(2-hydroxyethyl)guanidine
- N-(3-hydroxypropyl)guanidine
- biguanide hydrochloride
- N-methylbiguanide hydrochloride
- N-ethylbiguanide hydrochloride
- 1,1-dimethylbiguanide hydrochloride
- 1,1,3,3-tetramethylguanidine hydrochloride
- 2-tert-butyl-1,1,3,3-tetramethylguanidine hydrochloride
- L-arginine
- DL-arginine
- arginic acid
- N-amidino-N-(2,3-dihydroxypropyl)glycine
- N-amidinotaurine
- 2-imino-1-imidazolidineacetic acid
- 1H-pyrazole-1-carboxamidine hydrochloride
- 3,5-diamino-1H-1,2,4-triazole-1-carboximidamide hydrochloride
- 2-guanidone-4-thiazolidone.

The term “α-hydroxy acid and α-keto acid derivatives”, which may be used as hair-relaxing active agent, means any derivative selected from the compounds of general formulae (IV) and (V) below:
R1 represents H, OH, NH2, CH2-COOH or a linear or branched C1-C4 alkyl radical,
R2 represents H, COOH, CHOH—COOH, CF3, CH═CH2, NHCONH2, a linear, branched or cyclic C1-C8 alkyl radical optionally substituted with a radical chosen from OH, Cl, NH2, COOH, CF3 and SCH3; or a phenyl or benzyl radical optionally substituted with one OH or OCH3 radical;
or alternatively the radical
R1 and R2 may also together form an oxo radical (═O) or a cyclopropyl, cyclobutyl, hydroxycyclobutyl, cyclo pentyl or cyclohexyl ring with the carbon atom that bears them, or alternatively a radical
when R1=H, R2 may also represent a (CHOH)2CH2OH or (CHOH)3CH2OH radical,
R represents OH or NR3R4 with R3, R4=H or a linear or branched C1-C4 alkyl radical optionally substituted with one or two OH radicals
and the stereoisomers, organic or mineral salts and solvates thereof.
Preferred compounds of formula (IV) that may be mentioned include:
glycolic acid
oxalic acid
lactic acid
1-hydroxy-1-cyclopropanecarboxylic acid
2-hydroxy-3-butenoic acid
2-hydroxyisobutyric acid
2-hydroxy-n-butyric acid
isoserine
glyceric acid
2-hydroxy-3-methylbutyric acid
2-hydroxy-2-methylbutyric acid
2-hydroxyvaleric acid
4-amino-2-hydroxybutyric acid
1-hydroxycyclohexanecarboxylic acid
dihydroxyfumaric acid
citramalic acid
tartaric acid
citric acid
2-hydroxy-4-(methylthio)butyric acid
mandelic acid
2-hydroxy-3-methylvaleric acid
glyoxylurea
β-imidazolelactic acid
2-trifluoromethyl-2-hydroxypropionic acid
hexahydromandelic acid
2-hydroxyoctanoic acid
arabic acid
3-phenylactic acid
hydroxyphenylglycine
3-hydroxymandelic acid
4-hydroxymandelic acid
2-hydroxynonanoic acid
L-arginic acid
3-methoxymandelic acid
4-methoxymandelic acid
3-(4-hydroxyphenyl)lactic acid
tartronic acid
tartaric acid
β-chlorolactic acid
1-cyclopentanol-1-carboxylic acid
1,2-dihydroxycyclobutanecarboxylic acid
2-ethyl-2-hydroxybutric acid
α-hydroxyisocaproic acid
α-hydroxycaproic acid
2-hydroxy-3,3-dimethylbutyric acid
malic acid
hydroxytartronic acid
gluconic acid
lactamide

N-methyllactamide

N-ethyllactamide

N,N-dimethyllactamide

N-2-hydroxyethyllactamide
and the stereoisomers, organic or mineral salts and solvates thereof.
The compounds of formula (IV) that are particularly preferred are chosen from:
glycolic acid
oxalic acid
L-lactic acid
DL-lactic acid
D-lactic acid
malic acid
tartaric acid
DL-glyceric acid
arabic acid
gluconic acid
hydroxytartronic acid
lactamide

N-methyllactamide

N-ethyllactamide

N-2-hydroxyethyllactamide
Definition of the α-keto acid derivatives of general formula (V):
R5 represents COOH, a linear or branched C1-C6 alkyl radical optionally substituted with an OH, COOH or Br radical; a phenyl or benzyl radical optionally substituted with an OH or COOH radical; or an indolyl radical or
and the stereoisomers, organic or mineral salts and solvates thereof.
The preferred compounds of formula (V) are chosen from:
pyruvic acid
2-ketobutyric acid
O-hydroxypyruvic acid
3-methyl-2-oxobutyric acid
2-oxovaleric acid
ketomalonic acid
3-methyl-2-oxovaleric acid
trimethylpyruvic acid
oxolacetic acid
2-ketoglutaric acid
benzylformic acid
2-oxooctanoic acid
2-oxoadipic acid
phenylpyruvic acid
bromopyruvic acid
2-ketopimelic acid
4-hydroxyphenylpyruvic acid
3-indoleglyoxalic acid
imidazolopyruvic acid HCl
2-keto-L-gulonic acid
2-carboxy-α-oxobenzeneacetic acid
3-indolepyruvic acid
2-ketoglutaric acid dihydrate
pyruvamide

N-methylpyruvamide

N-ethylpyruvamide

N,N-dimethylpyruvamide

N-2-hydroxyethylpyruvamide
and the stereoisomers, organic or mineral salts and solvates thereof.
The compounds of formula (V) that are particularly preferred are chosen from:
pyruvic acid
2-ketobutyric acid
β-hydroxypyruvic acid
ketomalonic acid
oxolacetic acid
2-ketoglutaric acid
2-keto-L-gulonic acid
2-ketoglutaric acid dihydrate
pyruvamide
and the stereoisomers, organic or mineral salts and solvates thereof.
The term “polyhydroxylated aromatic derivatives”, which may be used as hair-relaxing active agent, means any derivative selected from the compounds of general formula (VI) below:
in which:

- R1, R2, R3 and R4 represent, independently of each other:
- H, F, Cl, Br, OH, OCH₃, OEt, CHO, COCH₃, COOH, CH₂NH₂, CH₂CH₂NH₂, CH₂OH, CH₂CH₂OH, CH₂COCH₃, CH₂COOH, CH₂CH₂COOH, CH₂CONH₂, CHOH—CH₂OH, —CH(NH₂)COOH, NHCOCH₃, COCH₂CH₃, CONH₂
- or alternatively a linear or branched C1-C5 alkyl radical
  when the two OH radicals are in a meta position and when R1, R2 and R3 represent a hydrogen atom, R4 may also represent NH₂,
  and the stereoisomers, organic or mineral salts and solvates thereof.
- The preferred compounds of formula (VI) are chosen from:
  catechol
  resorcinol
  4-methylcatechol
  3-methylcatechol
  2-methylresorcinol
  5-methylresorcinol
  4-methylresorcinol
  pyrogallol
  1,2,4-trihydroxybenzene
  phloroglucinol
  3-fluorocatechol
  4-fluorocatechol
  4-fluororesorcinol
  2,3-dihydroxybenzaldehyde
  3,4-dihydroxybenzaldehyde
  2,4-dihydroxybenzaldehyde
  3,5-dihydroxybenzaldehyde
  4-ethylcatechol
  4-ethyl resorcinol
  2,5-dimethylresorcinol
  4,5-dimethylresorcinol
  2,4-dimethyl-1,3-benzenediol
  3,4-dihydroxybenzylamine
  3,5-dihydroxybenzylamine
  3-methoxycatechol
  5-methylpyrogallol
  3,4-dihydroxybenzyl alcohol
  5-methoxyresorcinol
  2,4,6-trihydroxytoluene
  3,5-dihydroxybenzyl alcohol
  2-methoxyresorcinol
  5-methylpyrogallol
  4-methoxyresorcinol
  3,5-dihydroxytoluene monohydrate
  4-chlorocatechol
  3-chlorocatechol
  4-chlororesorcinol
  2-chlororesorcinol
  3′,4′-dihydroxyacetophenone
  2′,3′-dihydroxyacetophenone
  2′,6′-dihydroxyacetophenone
  2′,4′-dihydroxyacetophenone
  3′,5′-dihydroxyacetophenone
  2,6-dihydroxy-4-methylbenzaldehyde
  3-isopropylcatechol
  4-isopropylcatechol
  4-propylresorcinol
  2,4-dihydroxy-1,3,5-trimethylbenzene
  3,4-dihydroxybenzamide
  3,5-dihydroxybenzamide
  2,6-dihydroxybenzamide
  2,4-dihydroxybenzamide
  3-hydroxytyramine
  2,3-dihydroxybenzoic acid
  3,4-dihydroxybenzoic acid
  2,4-dihydroxybenzoic acid
  2,6-dihydroxybenzoic acid
  3,5-dihydroxybenzoic acid
  2,3,4-trihydroxybenzaldehyde
  2,4,6-trihydroxybenzaldehyde
  3,4,5-trihydroxybenzaldehyde
  2,4,5-trihydroxybenzaldehyde
  2-(3,4-dihydroxyphenyl)ethanol
  2,4,6-trihydroxy-1,3-dimethylbenzene
  2,6-dihydroxy-4-methylbenzyl alcohol
  2-fluoro-3,4-dihydroxybenzaldehyde
  3,4-dihydroxy-6-fluorobenzaldehyde
  2-methoxyphloroglucinol
  3,5-dihydroxyanisole hydrate
  4-aminoresorcinol hydrochloride
  2-aminoresorcinol hydrochloride
  5-aminobenzene-1,3-diol hydrochloride
  phloroglucinol dihydrate
  3′,4′-dihydroxypropiophenone
  3,4-dihydroxyphenylacetone
  (2,3-dihydroxyphenyl)acetone
  2′,4′-dihydroxypropiophenone
  2′,4′-dihydroxy-3′-methylacetophenone
  (2,4-dihydroxyphenyl)acetone
  (3,5-dihydroxyphenyl)acetone
  2,6-dihydroxy-4′-methylacetophenone
  4-tert-butylcatechol

4-N-butylresorcinol

2,4-diethyl-1,3-benzenediol
3,4-dihydroxyphenylacetamide
3-hydroxyacetaminophen
2′,3′,4′-trihydroxyacetophenone
3,4-dihydroxyphenylacetic acid
2,3-dihydroxy-4-methoxybenzaldehyde
3,4-dihydroxy-5-methoxybenzaldehyde
2′,3′,4′-trihydroxyacetophenone
2′,4′,6′-trihydroxyacetophenone
3,5-dihydroxy-4-methylbenzoic acid
2,6-dihydroxy-4-methylbenzoic acid
2,4-dihydroxy-6-methylbenzoic acid
3,5-dihydroxyphenylacetic acid
2-ethyl-5-methoxybenzene-1,3-diol
3,4,5,-trihydroxybenzamide
4-amino-3,5-dihydroxybenzoic acid
2,3,4-trihydroxybenzoic acid
2,3,4-trihydroxybenzoic acid
gallic acid
2,4,6-trihydroxybenzoic acid
3,4-dihydroxyphenyl glycol
1,2-dihydroxy-4,5-dimethoxybenzene
3,5-dihydroxyacetophenone monohydrate
3,4-dihydroxybenzoic acid monohydrate
3,4,5-trihydroxybenzaldehyde
hexahydroxybenzene
3,5-dihydroxybenzylamine hydrochloride
4,6-diaminoresorcinol hydrochloride
4,5-dichlorocatechol
3,5-dichlorocatechol
4,6-dichlororesorcinol
2′,4′-dihydroxy-3′-methylpropiophenone
1-(3-ethyl-2,6-dihydroxyphenyl)ethan-1-one
3-(3,4-dihydroxyphenyl)propionic acid
(2,3,4-trihydroxyphenyl)acetone
(2,4,5-trihydroxyphenyl)acetone
(3,4,5-trihydroxyphenyl)acetone
2′,6′-dihydroxy-4′-methoxyacetophenone
1-(2,6-dihydroxy-3-methoxyphenyl)ethan-1-one
3(2,4-dihydroxyphenylpropionic acid
2,4-dihydroxy-3,6-dimethylbenzoic acid
(2,3,4-trihydroxyphenyl)acetone
(2,4,5-trihydroxyphenyl)acetone
(2,4,6-trihydroxyphenyl)acetone
(3,4,5-trihydroxyphenyl)acetone
3,4-dihydroxymandelic acid
5-hydroxyisovanillic acid
3,4,5-trihydroxybenzamide hydrate
4-bromocatechol
and the stereoisomers, organic or mineral salts and solvates thereof.
The compounds of formula (VI) that are particularly preferred are chosen from:
resorcinol
2-methylresorcinol
5-methyl resorcinol
4-methylresorcinol
pyrogallol
1,2,4-trihydroxybenzene
4-ethylresorcinol
2,5-dimethylresorcinol
4,5-dimethylresorcinol
2,4-dimethyl-1,3-benzenediol
3,4-dihydroxybenzylamine
3,5-dihydroxybenzylamine
5-methylpyrogallol
3,4-dihydroxybenzyl alcohol
5-methoxyresorcinol
2,4,6-trihydroxytoluene
3,5-dihydroxybenzyl alcohol
2-methoxyresorcinol
5-methylpyrogallol
4-methoxyresorcinol
3,5-dihydroxytoluene monohydrate
4-propylresorcinol
2,4-dihydroxy-1,3,5-trimethylbenzene
3,4-dihydroxybenzamide
3,5-dihydroxybenzamide
2,6-dihydroxybenzamide
2,4-dihydroxybenzamide
3-hydroxytyramine
2,3-dihydroxybenzoic acid
3,4-dihydroxybenzoic acid
2,6-dihydroxybenzoic acid
3,5-dihydroxybenzoic acid
2-(3,4-dihydroxyphenyl)ethanol
2,4,6-trihydroxy-1,3-dimethylbenzene
2,6-dihydroxy-4-methylbenzyl alcohol
2-methoxyphloroglucinol
3,5-dihydroxyanisole hydrate
4-aminoresorcinol hydrochloride
2-aminoresorcinol hydrochloride
5-aminobenzene-1,3-diol hydrochloride
phloroglucinol dihydrate
2,4-diethyl-1,3-benzenediol
3,4-dihydroxyphenylacetamide
3,4-dihydroxyphenylacetic acid
3,5-dihydroxy-4-methylbenzoic acid
2,6-dihydroxy-4-methylbenzoic acid
2,4-dihydroxy-6-methylbenzoic acid
3,5-dihydroxyphenylacetic acid
2-ethyl-5-methoxybenzene-1,3-diol
3,4,5-trihydroxybenzamide
4-amino-3,5-dihydroxybenzoic acid
3,4-trihydroxybenzoic acid
gallic acid
2,4,6-trihydroxybenzoic acid
DL-3,4-dihydroxyphenyl glycol
1,2-dihydroxy-4,5-dimethoxybenzene
3,4-dihydroxybenzoic acid monohydrate
hexahydroxybenzene
3,5-dihydroxybenzylamine hydrochloride
sodium γ-resorcylate
sodium β-resorcylate
4,6-diaminoresorcinol hydrochloride
3-(3,4-dihydroxyphenyl)propionic acid
2,4-dihydroxy-3,6-dimethylbenzoic acid
DL-3,4-dihydroxymandelic acid
hydroxyisovanillic acid
3,4,5-trihydroxybenzamide acid hydrate
gallic acid monohydrate
and the stereoisomers, organic or mineral salts and solvates thereof.
The term “cyclic and linear amide derivatives” which may be used as hair-relaxing active agent, means any derivative selected from the compounds of general formulae (VII) and (VIII) below:
with

X=0 to 3

R1, R2, R3, R4, R5 and R6, which may be identical or different, possibly taking the following meaning:

- H,
- F,
- linear or branched C1-C30 alkyl, possibly comprising one or more unsaturations,
  - optionally interrupted with —O—, —S—, —NR7-, —C(O)—, —OC(O)—, —C(O)O—, —C(O)NR7-, —NR7C(O)—, —OC(O)NR7-, —NR7C(O)O—, —NR7C(O)NR8-, —NR7SO₂—, —NR7SO₂NR8-, —SO2NR7-, —OSO2-, —C(S)NR7-, —NR7C(S)—,
  - optionally substituted with —OR7, —SR7, —NR7R8, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —NR7C(O)R8, —OC(O)NR7R8, —NR7C(O)OR8, —NR7C(O)NR8R9, —NR7SO₂R8, —NR7SO₂NR8R9, —SO2NR7R8, —OSO2R7, —C(S)NR7R8, —NR7C(S)R8, an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, possibly containing 3 to 10 atoms,
- —OR7, —SR7, —NR7R8, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —NR7C(O)R8, —OC(O)NR7R8, —NR7C(O)OR8, —NR7C(O)NR8R9, —NR7SO₂R8, —NR7SO2NR8R9, —SO2NR7R8, —C(S)NR7R8, —NR7C(S)R8,
- an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, possibly containing 3 to 10 carbon atoms, which is optionally substituted,
- R1, R2, R3, R4, R5 and R6 possibly forming in pairs, with the carbon atoms to which they are attached, a (hetero)cycle of 3 to 7 atoms, optionally interrupted with O, S, N, —C(O)—, —C(O)O—, —C(O)NR7-,
- R1R2, R3R4, and R5R6 possibly being combined in pairs to form an oxo function,
  R7, R8 and R9, which may be identical or different, possibly taking the following meaning:
- H, F, optionally substituted linear or branched C1-C30 alkyl, possibly containing one or more unsaturations,
- one of the 20 natural N-branched amino acids, C-protected with standard protecting groups or one of the 20 natural C-branched amino acids, N-protected with standard protecting groups,
- an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, possibly containing 3 to 10 atoms,
  and also the stereoisomers, organic or mineral salts and solvates thereof.

The preferred compounds of formula (VII) are chosen from:
2-pyrrolidone
3-methyl-2-pyrrolidone
pyroglutamic acid
5-methyl-2-pyrrolidone
succinimide
α-methyl-α-phenylsuccinimide
ethyl pyroglutamate
2-oxo-4-phenylpyrrolidine-3-carboxylic acid
pyrrolidonyl-4-butyramide
5-(hydroxymethyl)-2-pyrrolidinone
methyl pyroglutamate
ethyl 2-oxo-4-phenyl-3-pyrrolidinecarboxylate
4-(hydroxy)-4-methylpyrrolidin-2-one
4-fluoro-5-pyrrolidone-2-carboxylic acid
4,4-pentamethylene-2-pyrrolidinone
[(5-oxopyrrolidine-2-carbonyl)amino]acetic acid
2-[(5-oxopyrrolidine-2-carbonyl)amino]-3-phenylpropionic acid
5-methoxy-2-pyrrolidinone
2-azabicyclo[2.2.1]hept-5-en-3-one
butyl 2-pyrrolidone-5-carboxylate
octyl 2-pyrrolidone-5-carboxylate
4-carbamoyl-2-[(5-oxopyrrolidin-2-carbonyl)amino]-butyric acid
4-hydroxy-2-pyrrolidinone
2-dimethylamino ethyl 5-oxopyrrolidine-2-carboxylate
3-(1H-indol-3-yl)-2-[(5-oxopyrrolidin-2-carbonyl)-amino]propionic acid
5-pyridin-3-ylpyrrolidin-2-one
2-azabicyclo[2.2.1]heptan-3-one
methyl 2-[3-(methoxymethyl)-5-oxo-2-pyrrolidinyl]-acetate
4-phenyl-2-pyrrolidinone
4-spiro-[3[(2-pyrrolidinone)]piperidine
(4-[3-(cyclopentyloxy)-4-methoxyphenyl]pyrrolidin-2-one
2-amino-5-oxo-5-(5-oxopyrrolidin-2-yl)pentanoic acid
2-(2,5-dioxopyrrolidin-3-ylsulfanyl)nicotinic acid
3-hydroxynorcotinine
3-benzyl-5-hydroxymethylpyrrolin-2-one
ethyl 4-methylpyroglutamate
ethyl 4-ethylpyroglutamate
ethyl 4-isopropylpyroglutamate
ethyl 4-benzylpyroglutamate
3-ethyl-5-hydroxymethylpyrrolidin-2-one
5-hydroxymethyl-3-methylpyrrolidin-2-one
5-oxopyrrolidine-3-carboxylic acid
5-hydroxymethyl-3-isopropylpyrrolidin-2-one
5-hydroxymethylpyrrolidin-2-one
5-aminomethylpyrrolidin-2-one
ethyl 2-oxopyrrolidine-3-carboxylate
3-hydroxypyrrolidin-2-one
3-ethyl-4-methylpyrroline-2-one
3,4-(1,3-propanediyl)-2-pyrrolidinone
δ-valerolactam
3-carbethoxy-2-piperidone
glutarimide
3,3-dimethylglutarimide
3-ethyl-3-methylglutarimide
6-methyl-2-piperidone
3-methylpiperidin-2-one

D-mannono-D-lactam

N-(2-aminoethyl)-2-oxopiperidine-3-carboxamide
4-phenyl-δ-valerolactam
3-amino-4-phenyl-δ-valerolactam
4-methyl-3-phenyl-δ-valerolactam
3-methyl-5-phenyl-δ-valerolactam
3-(2-isopropoxycarbonylethyl)-6-oxopiperidine-3-carboxylic acid
3-(2-benzylcarbamoylethyl)-6-oxopioperidine-3-carboxylic acid
methyl-2-oxopiperidine-3-carboxylate
3,4,5-trihydroxy-6-oxo-2-piperidinecarboxylic acid
2-piperidinone-6-carboxylic acid
5-hydroxypiperidin-2-one
ethyl 5-methyl-2-oxo-3-piperidinecarboxylate
6-oxopiperidine-2-carboxylic acid
4-hydroxypiperidin-2-one
2-azetidinone
ε-caprolactam
and the stereoisomers, organic or mineral salts and/or solvates thereof.
The compounds of formula (VII) that are particularly preferred are chosen from:
2-pyrrolidone
pyroglutamic acid
3-methyl-2-pyrrolidone
5-methyl-2-pyrrolidone
5-(hydroxymethyl)-2-pyrrolidinone
5-oxopyrrolidine-3-carboxylic acid
5-aminomethylpyrrolidin-2-one
4-hydroxy-2-pyrrolidinone
and the stereoisomers, organic or mineral salts and/or solvates thereof.
Definition of the linear amides of general formula (VIII)
with

X=0 or 1;

if X=0

R2 possibly taking the following meaning:

- H
- F, Cl
- an optionally substituted, heterocyclic or non-heterocyclic, aromatic or non-aromatic ring, which may contain 3 to 10 atoms, —OR7, —SR7, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —OC(O)NR7R8, —SO2NR7R8, —C(S)NR7R8,
  R3 possibly taking the following meaning:
- H, except if R2 is 3-pyridine
- linear or branched C1-C30 alkyl, possibly comprising one or more unsaturations,
  - optionally interrupted with —O—, —S—, —NR7-, —C(O)—, —OC(O)—, —C(O)O—, —C(O)NR7-, —NR7C(O)—, —OC(O)NR7-, —NR7C(O)O—, —NR7C(O)NR8-, —NR7SO2-, —NR7SO₂NR8-, —SO2NR7-, —OSO2-, —C(S)NR7-, —NR7C(S)—,
  - optionally substituted with:
    - F, Cl
    - —OR7, —SR7, —NR7R8, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —NR7C(O)R8, —OC(O)NR7R8, —NR7C(O)ORB, —NR7C(O)NR8R9, —NR7SO₂R8, —NR7SO2NR8R9, —SO2NR7R8, —OSO2R7, —C(S)NR7R8, —NR7C(S)R8
    - a heterocyclic or non-heterocyclic, aromatic or non-aromatic ring, possibly containing 3 to 10 atoms,
      R7, R8 and R9, which may be identical or different, possibly taking the following meaning:
- H,
- linear or branched C1-C30 alkyl, possibly comprising one or more unsaturations,
- one of the 20 natural N-branched amino acids, C-protected with standard protecting groups, or one of the 20 natural C-branched amino acids, N-protected with standard protecting groups,
- a heterocyclic or non-heterocyclic, aromatic or non-aromatic ring, possibly containing 3 to 10 atoms,

if X=1

R1 possibly taking the following meaning:

- linear or branched C1-C30 alkylene, possibly containing one or more unsaturations,
  - optionally interrupted with —O—, —S—, —NR7-, —C(O)—, —OC(O)—, —C(O)O—, —C(O)NR7-, —NR7C(O)—, —OC(O)NR7-, —NR7C(O)O—, —NR7C(O)NR8-, —NR7SO₂—, —NR7SO2NR8-, —SO2NR7-, —OSO2-, —C(S)NR7-, —NR7C(S)—,
  - optionally substituted with:
    - F, Cl
    - —OR7, —SR7, —NR7R8, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —NR7C(O)R8, —OC(O)NR7R8, —NR7C(O)OR8, —NR7C(O)NR8R9, —NR7SO2R8, —NR7SO2NR8R9, —SO2NR7R8, —OSO2R7, —C(S)NR7R8, —NR7C(S)R8,
    - an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, possibly containing 3 to 10 atoms, with the exception of hydroxyl or oxo substituents in a position alpha to the amide function
      R2 possibly taking the following meaning:
- H
- F, Cl
- an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, which is optionally substituted, possibly containing 3 to 10 atoms,
- —OR7, —SR7, —NR7R8, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —NR7C(O)R8, —OC(O)NR7R8, —NR7C(O)OR8, —NR7C(O)NR8R9, —NR7SO₂R8, —NR7SO2NR8R9, —SO2NR7R8, —C(S)NR7R8, —NR7C(S)R8
  R3 possibly taking the following meaning:
- H
- linear or branched C1-C30 alkyl, possibly containing one or more unsaturations,
  - optionally interrupted with —O—, —S—, —NR7-, —C(O)—, —OC(O)—, —C(O)O—, —C(O)NR7-, —NR7C(O)—, —OC(O)NR7-, —NR7C(O)O—, —NR7C(O)NR8-, —NR7SO2-, —NR7SO2NR8-, —SO2NR7-, —OSO2-, —C(S)NR7-, —NR7C(S)—,
  - optionally substituted with:
    - F, Cl
    - —OR7, —SR7, —NR7R8, —C(O)R7, —OC(O)R7, —C(O)OR7, —C(O)NR7R8, —NR7C(O)R8, —OC(O)NR7R8, —NR7C(O)OR8, —NR7C(O)NR8R9, —NR7SO₂R8, —NR7SO₂NR8R9, —SO2NR7R8, —OSO2R7, —C(S)NR7R8, —NR7C(S)R8
    - an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, possibly containing 3 to 10 atoms,
      R7, R8 and R9, which may be identical or different, possibly taking the following meaning:
- H,
- linear or branched C1-C30 alkyl, possibly containing one or more unsaturations,
- one of the 20 natural N-branched amino acids, C-protected with standard protecting groups, or one of the 20 natural C-branched amino acids, N-protected with standard protecting groups,
- an aromatic or non-aromatic, heterocyclic or non-heterocyclic ring, possibly containing 3 to 10 atoms,
  if R2(R1)x represents a fatty acid-based saturated or unsaturated alkyl radical, this alkyl radical contains less than 16 carbon atoms,
  and also the stereoisomers thereof and the organic or mineral salts and solvates thereof.

Preferably, if R2(R1)x represents a fatty acid-based saturated or unsaturated alkyl radical, this alkyl radical contains fewer than 9 carbon atoms.
The preferred compounds of formula (VIII) are chosen from:
acetamide

N-methylacetamide

propionamide

N-ethylacetamide

N-methylpropionamide

N-butyramide

N-(hydroxymethyl)acetamide

methoxyacetamide
hydracrylamide
2-mercaptoacetamide
acetoacetamide

N—(N-propyl)acetamide

N— ethylpropionamide
valeramide
malonamide

N-acetylethylenediamine

2-amino-N-ethylacetamide

N-acetylethanolamine

3-chloropropionamide
glycinamide

N-(cyclopropylmethyl)acetamide

N-methylacetoacetamide

1-acetamidoacetone

N-methylvaleramide

N-butylacetamide

hexanamide

N-acetylglycinamide

succinamide
N-ethyl-2-methylaminoacetamide

N-acetylglycine

succinamic acid
methylcarbamoylacetate
N-(2-hydroxyethyl)propionamide
N1-(3-hydroxypropyl)acetamide
5-hydroxyvaleramide
3-amino-3-thioxopropanamide
O-(2-hydroxyethyl)glycolamide
3,4-dihydroxybutyramide
N-(2-chloroethyl)acetamide
N-(3-methylbutyl)acetamide
N-methylsuccinamic acid
ethyl carbamoylacetate
glycylglycine
asparagine
2-amino-N-(2-methoxyethyl)acetamide
2-(2-amino-2-oxoethoxy)acetic acid
2-phenylacetamide
pyridine-2-acetamide
pyridine-4-acetamide
methylsulfonylacetamide
4-aminobutyramide
5-acetaminomethyltetrazole
thiphene-2-acetamide
4-thiazoleacetamide
1-aminocyclopentanacetamide
2-piperazin-1-ylacetamide

N-octanamide

N,N′-diacetylethylenediamine
adipamide
2-morpholinoacetamide
ethyl acetamidoacetate
4-acetamidbutyric acid
2-(acetylamino)ethyl acetate
N-(2-hydroxyethyl)acetoacetamide
isopropyl carbamoylacetate
2-amino-N-methylsuccinamic acid
glutamine
N-(2-methoxyethyl)-2-methylaminoacetamide
N-methyl-2-phenylacetamide

N-benzylacetamide

N-propylpyrrolidine-2-carboxamide
N-(tert-butyl)-1,2,3,4-tetrahydroisoquinoline-2-carboxamide

N,N-butylpropionamide

N-1,3,3-trimethylbutanamide
N-α-acetyl-L-lysine-N-methylamide

L-proline N-octylamide

and also the stereoisomers thereof and the organic or mineral salts and solvates thereof, and also the following amino acids and derivatives:

AC-ALA-NHME

AC-β-ALA-OH

AC-β-ALA-OME

AC-GLY-NHME

AC-HIS-NHME

AC-ILE-NHME

AC-LEU-GLY-OH

AC-LEU-NHME

AC-LYS-NHME

AC-PHE-NHME

AC-SER-GLY-OH

AC-VAL-NHME

H-β-ALA-GLY-OH

H-β-ALA-NH2

H-GLY-β-ALA-OH

H-GLY-NHME

H-PRO-ALA-OH

H-PRO-O-ALA-OH

H-PRO-GLY-NH2

H-PRO-GLY-OH

H-PRO-ILE-OH

H-PRO-LEU-OH

H-PRO-NHCH3

H-PRO-NHET

H-PRO-SER-OH

H-PRO-VAL-OH

SAR-GLY-OH

SAR-NH2

and also the stereoisomers thereof and the organic or mineral salts and solvates thereof.
The compounds of formula (VIII) that are particularly preferred are chosen from:
glycinamide
acetamide

N-methylacetamide

N-ethylacetamide

propionamide

N-ethylpropionamide

and also the stereoisomers thereof and the organic or mineral salts and solvates thereof.
In the compositions according to the invention intended for a process of relaxing, uncurling or straightening the hair, the mixture in any proportion of at least two denaturing agents as defined previously is advantageously present in an overall molar concentration of between 1 M and 8 M and more advantageously in a concentration of between 2 M and 8M.
In the process according to the invention and in the kit, the pH of the compositions is preferably less than 9 and more preferentially less than 7.
The compositions according to the invention are either in the form of an aqueous solution or in the form of a thickened cream so as to keep the hair as straight as possible. These creams are prepared in the form of “heavy” emulsions.
For the purpose of improving the cosmetic properties of keratin fibres or to attenuate or avoid their degradation, the composition used according to the invention may also comprise one or more additional cosmetic active agents. Generally, the said additional cosmetic active agent(s) represent(s) from 0.01% to 30% and preferably from 0.1% to 10% by weight relative to the total weight of the cosmetic composition.
Generally, the composition applied to the keratin fibres is applied in an amount of from 0.05 to 20 g and preferably from 0.1 to 10 g of composition per gram of dry keratin fibre.
After applying the composition, and before raising the temperature of the keratin fibres using a heating means, the said composition may be left to act, generally for 30 seconds to 60 minutes and preferably 5 to 45 minutes.
The process according to the invention includes, after the step of applying the composition, a step of raising the temperature of the keratin fibres, using a heating means, to a temperature of between 110° C. and 250° C.
Advantageously, an iron is used as heating means.
For the purposes of the present invention, the term “iron” means a device for heating keratin fibres that places the said fibres and the heating device in contact, the end of the iron that comes into contact with the hair generally having two flat surfaces. These two flat surfaces may be metallic. They may be smooth or crinkled.
As examples of irons that may be used in the process according to the invention, mention may be made of flat irons of any type, and in particular, in a non-limiting manner, those described in patents U.S. Pat. No. 5,957,140 and U.S. Pat. No. 5,046,516.
The iron may be applied by successive separate touches of a few seconds, or by gradually moving or sliding it along the locks.
Preferably, in the process according to the invention, the iron is applied by continuous movement from the root to the end, in one or more passes.
The process according to the invention may also include an additional step of partial predrying of the keratin fibres before the step of raising the temperature, so as to avoid substantial evolution of steam that might burn the stylist's hands and the individual's scalp. This predrying step may take place, for example, using a hairdryer, a hood or alternatively by drying in the open air.
The invention especially concerns processes in which the composition comprises at least one of the following combinations:

- at least one denaturing agent is a guanidine corresponding to formula (III) and at least one denaturing agent corresponds to formula (V),
- at least one denaturing agent is a urea corresponding to formula (I) and at least one denaturing agent corresponds to formula (III),
- at least one denaturing agent is a urea corresponding to formula (I) and at least one denaturing agent corresponds to formula (V).

The invention also relates to a kit comprising at least:

- one heating means that affords a temperature of between 110 and 250° C.,
- one hair-relaxing composition containing at least two denaturing agents.

The invention also relates to a kit comprising at least:

- one heating means that affords a temperature of between 110 and 250° C.,
- a first hair-relaxing composition containing at least one denaturing agent,
- a second hair-relaxing composition containing at least one denaturing agent.

The invention may be understood more clearly with the aid of the non-limiting examples that follow, which constitute preferential embodiments of the compositions according to the invention.
The compositions may be applied as a mixture (see Example 1 and 2) or successively (see Example 3).

EXAMPLE 1

A simplified hair-relaxing composition is prepared, containing a mixture of guanidine hydrochloride at a concentration of 2 M and of pyruvic acid at concentration of 2 M, in water, as hair-relaxing active agent. This composition is applied to naturally curly African hair for 15 minutes at a temperature of 40° C., and the hair is then rapidly towel-dried.
Lock-by-lock straightening of the head of hair is then performed using a flat iron heated to 180° C., for 10 to 15 seconds. The hair is efficiently relaxed and feels soft.

EXAMPLE 2

A simplified hair-relaxing composition is prepared, containing a mixture of guanidine hydrochloride at a concentration of 4 M and of urea at a concentration of 4 M, in water, as hair-relaxing active agent. This composition is applied to naturally curly African hair for 15 minutes at a temperature of 40° C., and the hair is then rapidly towel-dried.
Lock-by-lock straightening of the head of hair is then performed using a flat iron heated to 180° C., for 10 to 15 seconds. The hair is efficiently relaxed and feels soft.

EXAMPLE 3

A simplified hair-relaxing composition is prepared, containing urea at a concentration of 2 M in water, as hair-relaxing active agent. This composition is applied to naturally curly African hair for 15 minutes at a temperature of 40° C., and the hair is then rapidly towel-dried. A second simplified hair-relaxing composition is prepared, containing pyruvic acid at a concentration of 2 M, in water, as hair-relaxing active agent. This composition is applied to the same hair for 15 minutes at a temperature of 40° C., and the hair is then rapidly towel-dried. Lock-by-lock straightening of the head of hair is then performed using a flat iron heated to 180° C., for 10 to 15 seconds. The hair is efficiently relaxed and feels soft.

Claims

1-33. (canceled)

34. A process for relaxing keratin fibers, comprising:

(i) applying to the keratin fibers a hair-relaxing composition comprising at least two denaturing agents, and

(ii) raising the temperature of the keratin fibers, using a heating means, to a temperature ranging from about 110 to about 250° C.

35. A process according to claim 34, wherein the pH of the composition is less than about 7.

36. A process according to claim 34, wherein the hair-relaxing composition comprises an overall concentration of denaturing agents ranging from about 2 M to about 8 M.

37. A process according to claim 34, wherein the temperature is raised to a temperature ranging from about 140° C. to about 220° C.

38. A process according to claim 34, wherein the molar mass of the denaturing agents ranges from about 40 to about 600 g/mol.

39. A process according to claim 34, wherein the denaturing agents are chosen from ureas, guanidines, α-hydroxy acid and α-keto acid derivative, mono-, di-, tri- or polyhydroxylated aromatic derivatives, cyclic or linear amides, surfactants or detergents, amidines, thioureas, urethanes, alcohols, polyols, amine oxides, metal salts, sulfamides, carboxylic acids, amino acids, and nitrogenous heterocycles of the imidazole or triazole family.

40. A process according to claim 34, wherein at least one of the denaturing agents is chosen from ureas.

41. A process according to claim 40, wherein the ureas are chosen from ureas of formula (I):

wherein:

R1, R2, R3 and R4 are independently chosen from:

(a) hydrogen; and

(b) linear or branched C1-C4 lower alkyl and alkenyl radicals, optionally substituted with a radical chosen from hydroxyl, amino, dimethylamino, carboxyl, carboxamide, and N-methylcarboxamide radicals,

when R1, R2 and R3 are hydrogen, R4 may also denote a radical chosen from carboxamide; methoxy; ethoxy; 1,2,4-triazolyl; cyclopentyl; methoxy-carbonyl; ethoxycarbonyl; CO—CH═CH—COOH; phenyl optionally substituted with a chlorine atom or a hydroxyl radical; benzyl; and 2,5-dioxo-4-imidazolidinyl radicals,

when R1 and R2 are hydrogen, R3 and R4 may also form, together with the nitrogen atom that bears them, a ring chosen from piperidine, 3-methylpyrazole, 3,5-dimethylpyrazole, and maleimide rings, and

R1 and R2 and R3 and R4 may also form, together with the nitrogen atom that bears them, an imidazole ring.

42. A process according to claim 40, wherein the ureas are chosen from ureas of formula (II):

wherein:

R5 and R6 are independently chosen from:

(a) hydrogen; and

(b) linear or branched C1-C4 lower alkyl radicals, optionally substituted with a radical chosen from hydroxyl, amino, dimethylamino, carboxyl, and carboxamide radicals, and

A is chosen from CH2-CH2, CH═CH, CH2-CO, CO—NH, CH═N, CO—CO, CHOH—CHOH, (HOOC)CH—CH, CHOH—CO, CH2-CH2-CH2, CH2-NH—CO, CH═C(CH3)-CO, NH—CO—NH, CH2-CH2-CO, CH2-N(CH3)-CH2, NH—CH2-NH, CO—CH(CH3)-CH2, CO—CH2-CO, CO—NH—CO, CO—CH(COOH)—CH2, CO—CH═C(COOH), CO—CH═C(CH3), CO—C(NH2)=CH, CO—C(CH3)=N, CO—CH═CH, CO—CH═N, and CO—N═CH radicals.

43. A process according to claim 34, wherein at least one of the denaturing agents is a guanidine of formula (III):

wherein:

R1, R2, R3, R4 and R5 are independently chosen from:

(a) hydrogen; and

(b) linear or branched C1-C4 lower alkyl and alkenyl radicals, optionally substituted with one or two radicals chosen from hydroxyl, amino, dimethylamino, methoxy, ethoxy, carboxyl, carboxamide, N-methylcarboxamide, and So₃H radicals,

when R1, R2, R3 and R4 are hydrogen, R5 may also denote a radical chosen from acetyl; chloracetyl; carboxamide; methoxy; ethoxy; 1,2,4-triazolyl; cyclopentyl; methoxycarbonyl; ethoxycarbonyl; CO—CH═CH—COOH; phenyl optionally substituted with a chlorine atom or a hydroxyl radical; benzyl; thiazolidone; benzimidazole; benzoxazole; benzothiazole; and C(═NH)—NR6R7 radicals, wherein R6 and R7 are independently chosen from hydrogen and linear or branched C1-C4 lower alkyl radicals, optionally substituted with one or two radicals chosen from hydroxyl, amino, dimethylamino, carboxyl, carboxamide, and N-methylcarboxamide radicals; or alternatively a phenyl radical,

when R1, R2 and R3 are hydrogen, R4 and R5 may also form, together with the nitrogen atom that bears them, a ring chosen from pyrrolidine, piperidine, pyrazole and 1,2,4-triazole rings optionally substituted with one or two radicals chosen from hydroxyl, amino and carboxyl radicals, and

when R1 and R2 are hydrogen and R4 is hydrogen or methyl, R3 and R5 may also together form a 5-membered ring optionally containing an oxo group

and the organic or mineral salts thereof.

44. A process according to claim 34, wherein at least one of the denaturing agents is an α-hydroxy acid derivative of formula (IV):

wherein:

R is chosen from OH and NR3R4, wherein R3 and R4 are independently chosen from hydrogen and linear or branched C1-C4 alkyl radicals optionally substituted with one or two OH radicals;

R1 is chosen from H, OH, NH2, CH2-COOH, and linear or branched C1-C4 alkyl radicals;

R2 is chosen from H, COOH, CHOH—COOH, CF3, CH═CH2, NHCONH2; linear, branched or cyclic C1-C8 alkyl radicals optionally substituted with a radical chosen from OH, Cl, NH2, COOH, CF3 and SCH3 radicals; phenyl and benzyl radicals optionally substituted with a radical chosen from OH and OCH3; or alternatively the following radical:

R1 and R2 may optionally form together an oxo radical (═O) or a cyclopropyl, cyclobutyl, hydroxycyclobutyl, cyclopentyl or cyclohexyl ring with the carbon atom that bears them, or alternatively a radical of the following formula:

and

when R1 is H, R2 may also be chosen from (CHOH)2CH2OH and (CHOH)3CH2OH radicals,

and the stereoisomers, organic and mineral salts, and solvates thereof.

45. A process according to claim 34, wherein at least one of the denaturing agents is an α-keto acid derivative of formula (V):

wherein R5 is chosen from COOH, linear or branched C1-C6 alkyl radicals optionally substituted with a radical chosen from OH, COON and Br; phenyl and benzyl radicals optionally substituted with a radical chosen from OH and COOK indolyl radicals, and a radical of the following formula:

and the stereoisomers, organic and mineral salts and solvates thereof.