FR3143342A1 - COMPOSITION COMPRISING UREA OR ONE OF ITS DERIVATIVES, A POLYCARBOXYLIC ACID AND A MULTIVALENT CATION SALT - Google Patents

Abstract

COMPOSITION COMPRISING UREA OR ONE OF ITS DERIVATIVES, A POLYCARBOXYLIC ACID AND A MULTIVALENT CATION SALT The invention relates to a cosmetic composition comprising: a) one or more compounds chosen from urea and/or urea derivatives, b) one or more carboxylic acids and/or their salts chosen from mono-hydroxylated polycarboxylic acids and non-hydroxylated polycarboxylic acids having at least one pKa less than or equal to 4.25, c) one or more inorganic salts of multivalent cations. It also relates to the use of this composition for straightening keratin fibers. Finally, it relates to a treatment process in particular for smoothing and relaxing keratin fibers.

Description

COMPOSITION COMPRISING UREA OR ONE OF ITS DERIVATIVES, A POLYCARBOXYLIC ACID AND A MULTIVALENT CATION SALT

The present invention relates to a composition comprising urea and/or its derivatives, one or more particular carboxylic acids and one or more salts of multivalent cations.

The present invention also relates to a method for treating keratin fibres, in particular human keratin fibres such as hair, comprising a step of applying to the keratin fibres a composition, in particular a cosmetic composition, comprising urea and/or its derivatives, one or more particular carboxylic acids and one or more multivalent cation salts, optionally followed by the application of a shampoo composition and a rinse.

In the hair sector, consumers want to have compositions that can make a temporary change to their hair, and this by aiming for a good hold of the effect achieved. In general, we want the change to persist after shampooing for at least 15 days, or even more depending on the nature of the change.

Heat treatments are generally used to modify the shape of the hair, in a lasting way. These treatments allow a visual modification of the appearance of the hairstyle, combining a reduction in the degree of frizz, a reduction in the overall volume of the hair, a reduction in frizz, a gain in discipline, a smoother visual appearance, a substantial gain in shine, resistance to humidity and heat for maintaining the hairstyle all day long.

These heat treatments are combined with several technologies. The first technology is based on the use of compositions based on thiolated reducers. These technologies require strict compliance with the application conditions recommended by the suppliers, particularly in terms of quantity and break time. In addition, they may be contraindicated on overly sensitized hair and may not be compatible with the application on the same day of other treatments such as coloring or bleaching. They are also malodorous.

Another technology is based on the use of compositions based on formaldehyde (or formaldehyde) and its derivatives. These treatments have the particularity of being robust, perfectly compatible with all other classic hair treatments, such as the thiol straightening mentioned above, alkaline straightening, coloring or bleaching of all types, carried out before or after. They give the hair excellent discipline, a very strong shine and ease of daily care. However, in the event of repeated applications, new damage to the hair appears which can lead to hair breakage. In addition, for toxicological reasons, the use of some of these compounds is now prohibited and/or regulated. We are therefore increasingly seeking to avoid the use of such substances, which can be aggressive for the hair and other keratin materials.

To limit the alterations of hair fibers, it has also been proposed to use compositions comprising weak acids at alkaline pH associated with a heat treatment.

There is still a need to develop a composition and a method for treating keratin fibers such as hair, which allows the smoothing/straightening and/or volume control of hair in an effective and lasting manner by limiting hair degradation while maintaining comfort at the time of application for the user and the hairdresser who applies it.

The Applicant has now discovered that the use of a composition comprising urea and/or its derivatives, one or more particular carboxylic acids and one or more multivalent cation salts makes it possible to achieve the desired properties of long-lasting smoothing without heat treatment.

• a) un ou plusieurs composés choisis parmi l’urée et/ou les dérivés d’urée,
• b) un ou plusieurs acides carboxyliques et/ou leurs sels choisis parmi :

The subject of the invention is a composition comprising:

• (a) one or more compounds selected from urea and/or urea derivatives,
• (b) one or more carboxylic acids and/or their salts chosen from:

(i) monohydroxylated polycarboxylic acids and

• c) un ou plusieurs sels inorganiques de cations multivalents.

(ii) non-hydroxylated polycarboxylic acids having at least a pKa of less than or equal to 4.25,

• (c) one or more inorganic salts of multivalent cations.

The composition according to the invention makes it possible, in particular, to discipline the hair, even to smooth the hair and to obtain hair with good relaxation of curls and better control of volume, reducing frizz.

In addition, the composition according to the invention makes it possible, in particular, to obtain a long-lasting effect which resists several shampoos.

Therefore, an object of the present invention relates to a method for treating keratin fibers, in particular human keratin fibers such as hair, comprising:

1) a step of applying to the keratin fibers a composition comprising:

(a) one or more compounds selected from urea and/or urea derivatives,

(b) one or more carboxylic acids and/or their salts chosen from:

monohydroxylated polycarboxylic acids and

non-hydroxylated polycarboxylic acids having a pKa less than or equal to 4.25,

(c) one or more inorganic salts of multivalent cations,

2) possibly followed by the application of a shampoo composition and a rinse

3) possibly followed by a drying step.

Other features and advantages of the invention will become more clearly apparent upon reading the description and examples which follow.

Preferably, the method for treating keratin fibers according to the invention is a method for smoothing keratin fibers, in particular human keratin fibers such as hair.

In the following the expression “at least one” is equivalent to the expression “one or more”.

By “multivalent cation” is meant any monatomic or polyatomic ion comprising at least two positive electrical charges and having a valence of at least 2 and preferably 2 or 3.

Preferably, the composition according to the invention does not comprise either a coloring agent or a reducing agent.

By "coloring agents" is meant according to the present invention agents for coloring keratin fibers such as direct dyes, pigments or oxidation dye precursors (bases and couplers). If they are present, their content does not exceed 0.001% by weight relative to the total weight of the composition. Indeed, at such a content, only the composition would be dyed, that is to say that no coloring effect on the keratin fibers would be observed.

It is recalled that the precursors of oxidation dyes, oxidation bases and couplers, are compounds with little or no color which, through a condensation reaction in the presence of an oxidizing agent, give a colored species. As for direct dyes, these compounds are colored and have a certain affinity for keratin fibers.

By “reducing agent” is meant according to the present invention an agent capable of reducing the disulfide bonds of the hair, such as compounds chosen from thiols, alkali sulfites, hydrides, phosphines.

By urea derivative is meant any compound other than urea CO(NH ₂ ) ₂ itself, comprising in its chemical formula a carbonyl group simply linked to two nitrogen atoms, i.e. a unit

Preferably, said compound(s) (a) are chosen from the compounds of formula (I) or (II), their salts or their hydrates:

in which:

- R1, R2, R3, R4 represent, independently:

(i) a hydrogen atom or

(ii) a linear or branched, cyclic or acyclic C ₁ -C ₅ lower alkyl or alkenyl radical, a C ₁ -C ₅ alkoxy radical, a C ₆ -C ₁₈ aryl radical, a heterocyclic radical having 5 to 8 members; these radicals being optionally substituted by a radical chosen from the radicals: hydroxyl, (di)(C ₁ -C ₄ )(alkyl)amino such as dimethylamino, carboxyl, halogen, C ₆ -C ₁₈ aryl, carboxamide and N-methylcarboxamide;

it being understood that

- when R1, R2 and R3 represent a hydrogen atom, R4 may denote a linear or branched _C1 - _C5 lower alkyl or alkenyl radical, optionally substituted by a hydroxyl radical, a carboxamide, methoxy, ethoxy, 1,2,4-triazolyl, cyclopentyl, ( _C1 - _C6 )alkylcarbonyl radical such as acetyl, ( _C1 - _C6 )alkoxycarbonyl such as methoxycarbonyl or ethoxycarbonyl,
-CO-CH=CH-COOH, phenyl optionally substituted by a chlorine atom or a hydroxyl, benzyl or 2,5-dioxo-4-imidazolidinyl radical;- when R1 and R3 represent a hydrogen atom, R2 can represent a hydrogen atom, a methyl or ethyl radical and R4 an acetyl radical;

- when R1=R2=H, R3 and R4 can form, with the nitrogen atom which carries them, a piperidine, 3-methylpyrazole, 3,5-dimethylpyrazole or maleimide cycle;

- R1 and R2 as well as R3 and R4 can form, with the nitrogen atom which carries them, an imidazole ring;

- R5 and R6 represent, independently of each other,

(iii) a hydrogen atom or

(iv) a linear or branched, cyclic or acyclic C ₁ -C ₅ alkyl, acyl or lower alkenyl radical, a C ₁ -C ₅ alkoxy radical, a C ₆ -C ₁₈ aryl radical, a heterocyclic radical having 5 to 8 members; these radicals being optionally substituted by a radical chosen from the radicals: hydroxyl, amino, dimethylamino, carboxyl, halogen, C ₆ -C ₁₈ aryl, carboxamide and N-methylcarboxamide;

- A is a radical chosen from the radicals: CH ₂ -CH ₂ , CH=CH, CH ₂ -CO, CO-NH, CH=N, CO-CO, CHOH-CHOH, (HOOC)CH-CH, CHOH- CO, CH ₂ -CH ₂ -CH ₂ , CH ₂ -NH-CO, CH=C(CH ₃ )-CO, NH-CO-NH, CH ₂ -CH ₂ -CO, CH ₂ -N(CH ₃ )-CH ₂ , NH-CH ₂ -NH, CO-CH(CH ₃ )-CH ₂ , CO-CH ₂ -CO, CO-NH-CO, CO-CH(COOH)-CH ₂ , CO-CH=C(COOH), CO-CH=C(CH ₃ ), CO-C(NH ₂ )=CH, CO-C(CH ₃ )=N, CO-CH=CH, CO-CH=N and CO-N=CH.

Among the compounds of formula (I) particularly preferred according to the invention, mention may be made of:

urea, methylurea, ethylurea, propylurea, n-butylurea, sec-butylurea, isobutylurea, tert-butylurea, cyclopentylurea, ethoxyurea, hydroxyethylurea, N-(2-hydroxypropyl)urea, N-(3-hydroxypropyl)urea, N-(2-dimethylaminopropyl)urea, N-(3-dimethylaminopropyl)urea, 1-(3-hydroxyphenyl)urea, benzylurea, N-carbamoyl maleamide, N-carbamoyl maleamic acid, piperidinecarboxamide, 1,2,4-triazol-4-ylurea, hydantoic acid, methyl allophanate, ethyl allophanate, acetylurea, hydroxyethyleneurea, 2-(hydroxyethyl)ethyleneurea, diallylurea, chloroethylurea, N,N-dimethylurea, N,N-diethylurea, N,N-dipropylurea, cyclopentyl-1-methylurea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-bis(2-hydroxyethyl)urea, 1,3-bis(2-hydroxypropyl)urea, 1,3-bis(3-hydroxypropyl)urea, 1,3-dipropylurea, ethyl-3-propylurea, sec-butyl-3-methylurea, isobutyl-3-methylurea, cyclopentyl-3-methylurea, N-acetyl-N'-methylurea, trimethylurea, butyl-3,3-dimethylurea, tetramethylurea and benzylurea.

Among the compounds of formula (II) particularly preferred according to the invention, mention may be made of:

parabanic acid, 1,2-dihydro-3H-1,2,4-triazol-2-one, barbituric acid, uracil, 1-methyl uracil, 3-methyl uracil, 5-methyl uracil, 1,3-dimethyl uracil, 5-aza uracil, 6-aza uracil, 5-fluoro uracil, 6-fluoro uracil, 1,3-dimethyl-5-fluoro uracil, 5-amino uracil, 6-amino uracil, 6-amino-1-methyl uracil, 6-amino-1,3-dimethyl uracil, 4-chloro uracil, 5-chloro uracil, 5,6-dihydro uracil, 5,6-dihydro-5-methyl uracil, 2-imidazolidone, 1-methyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 4,5-dihydroxy-imidazolidin-2-one, 1-(2-hydroxyethyl)-2-imidazolidinone, 1-(2-hydroxypropyl)-2-imidazolidinone, 1-(3-hydroxypropyl)-2-imidazolidinone, 4,5-dihydroxy-1,3-dimethyl-imidazolidin-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-ethylhydantoin, 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-methyl-tetrahydro-pyrimidin-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-methyl-hexahydropyrimidine-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 and alloxan monohydrate.

Preferably, said compound(s) (a) are chosen from urea, hydroxyethylurea, and mixtures thereof.

The said compound(s) (a) represent in total preferably from 0.1 to 30% by weight, more preferably from 1 to 20% by weight, better still from 2 to 15% by weight, relative to the total weight of the composition.

Carboxylic acids

The composition according to the invention also comprises one or more carboxylic acids and/or their salts chosen from monohydroxylated polycarboxylic acids and non-hydroxylated polycarboxylic acids having a pKa less than or equal to 4.25 and/or their salts.

Non-hydroxylated polycarboxylic acids have a pKa less than or equal to 4.25, preferably less than 4, more preferably less than 3.7.

The carboxylic acids which can be used according to the invention comprise from 3 to 10 carbon atoms .

Preferably, the carboxylic acid(s) according to the invention are chosen from the compounds of formula (I) or (II) below:

XO ₂ C−R−CO ₂ X' (I)

in which:

-R is a C ₁ -C ₈ aliphatic radical, preferably C ₁ -C ₆ , cyclic or acyclic, preferably acyclic, saturated or unsaturated, linear or branched, comprising between 0 and 7 unsaturations, (double and/or triple bonds) and/or 0 to 2 cycles, comprising a hydroxyl group and optionally substituted by one or more carboxy substituents (-COOX'');

-X and X', X'' independently represent a hydrogen atom, an ammonium salt, an alkali metal salt, such as Li, Na, K, or an alkaline earth salt such as Be, Mg, Ca or a salt derived from an organic amine such as an alkylamine.

Preferably in the above formula, and R is a C ₁ -C ₆ , better still C ₁ -C ₄ , better still C ₁ -C ₃ , acyclic, saturated or unsaturated, linear or branched aliphatic radical, comprising between 0 and 2 unsaturations, (double and/or triple bonds) comprising a hydroxyl group, optionally substituted by one or more substituents chosen from carboxy groups (-COOX'');

-X and X', X'' independently represent a hydrogen atom, an ammonium salt, an alkali metal salt, such as Li, Na, K, or an alkaline earth salt such as Be, Mg, Ca or a salt derived from an organic amine such as an alkylamine.

Even more preferably, in the above formula and R is a monohydroxylated C ₁ -C ₄ aliphatic radical, acyclic, saturated or unsaturated, linear or branched, alkyl or alkenyl comprising from 0 to 1 unsaturation, optionally substituted by one or more carboxy substituents (-COOX'').

XO ₂ C−R1−CO ₂ X' (II)

in which:

-R1 is a non-hydroxylated _C1 - _C8 , preferably _C1 - _C6 , aliphatic radical, cyclic or acyclic, preferably acyclic, saturated or unsaturated, linear or branched, comprising between 0 and 7 unsaturations, (double and/or triple bonds) and/or 0 to 2 cycles, optionally substituted by one or more carboxy substituents (-COOX'');

-X and X', X'' independently represent a hydrogen atom, an ammonium salt, an alkali metal salt, such as Li, Na, K, or an alkaline earth salt such as Be, Mg, Ca or a salt derived from an organic amine such as an alkylamine,

carboxylic acids of formula (II) having a pKa of less than 4.25, preferably less than 4.

Preferably in the above formula, R1 is a non-hydroxylated _C1 - _C6 , better still _C1 - _C4 , better still _C1 - _C3 aliphatic radical, acyclic, saturated or unsaturated, linear or branched, comprising between 0 and 2 unsaturations, (double and/or triple bonds) optionally substituted by one or more substituents chosen from carboxy groups (-COOX'');

-X and X', X'' independently represent a hydrogen atom, an ammonium salt, an alkali metal salt, such as Li, Na, K, or an alkaline earth salt such as Be, Mg, Ca or a salt derived from an organic amine such as an alkylamine.

Even more preferably, in formula (II) above and R1 is a non-hydroxylated _C1 - _C4 aliphatic radical, acyclic, saturated or unsaturated, linear or branched, alkyl or alkenyl comprising from 0 to 1 unsaturation, optionally substituted by one or more selected substituents, carboxy (-COOX'').

By “aliphatic radical” we mean a non-aromatic, saturated or unsaturated hydrocarbon radical which may be an open-chain hydrocarbon (linear or branched) or an alicyclic radical (i.e. comprising one or more non-aromatic cycles).

Preferably, the carboxylic acids according to the invention may be chosen from malonic acid, malic acid, citraconic acid, citric acid, maleic acid, succinic acid, fumaric acid, tricarballytic acid and/or their salts and their mixtures.

Preferably, the monohydroxylated polycarboxylic acids and the non-hydroxylated polycarboxylic acids having a pKa less than or equal to 4.25 are chosen from malonic acid, citric acid, malic acid, succinic acid, tricarballylic acid and mixtures thereof; preferably chosen from citric acid, malic acid, and mixtures thereof. More particularly preferably, the carboxylic acid is citric acid.

The carboxylic acid(s) (b) may be present in the composition according to the invention in a total content ranging from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, better still from 1 to 10% by weight, relative to the total weight of the composition.

The molar ratio of urea and/or urea derivative/carboxylic acid (b) can vary from 0.5 to 10, preferably from 1 to 5, better still from 1.5 to 3.

The composition according to the invention also comprises one or more inorganic salts of multivalent cation (c).

The multivalent cation salts in accordance with the invention are preferably chosen from

- salts of alkaline earth cations such as Berylium, Magnesium, Calcium, Strontium, Barium salts;

- lanthanide salts such as cerium, lanthanum, ytterbium and yttrium salts, preferably cerium.

Salts of multivalent cations can be anhydrous or hydrated.

Preferably, the multivalent cation salt(s) according to the invention are chosen from calcium halides (for example calcium iodide, calcium bromide, calcium chloride), magnesium halides, calcium carbonate, calcium sulfate, cerium halides (for example cerium chloride) and mixtures thereof.

More preferably, the multivalent cation salt(s) used in the composition according to the invention are calcium chloride, calcium carbonate, cerium chloride or their mixtures.

Even more preferably, the calcium salt used in the composition according to the invention is calcium chloride, in particular the dihydrate salt.

The inorganic salt(s) of multivalent cation c) may be present in the composition according to the invention in a total content ranging from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight relative to the total weight of the composition.

The composition according to the invention generally has a pH of 2 to 5, preferably 3 to 4.

The composition according to the invention advantageously comprises water which advantageously represents from 10 to 95%, preferably from 40 to 90%, better still from 50 to 85% by weight, relative to the total weight of the composition .

The composition according to the invention may also comprise one or more fatty substances.

By fatty substance is meant an organic compound insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mm Hg), having a solubility in water of less than 5% by weight, preferably less than 1%, and even more preferably 0.1%.

Furthermore, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, ethanol, benzene, vaseline oil or decamethylcyclopentasiloxane.

The said fatty substance(s) which can be used in the composition according to the invention are preferably chosen from hydrocarbons, fatty alcohols, fatty acid and/or fatty alcohol esters, non-salified fatty acids, silicones and mixtures thereof.

The fatty substance(s) may be liquid or non-liquid at room temperature and atmospheric pressure.

Said fatty substance(s) may represent from 0.001 to 90% by weight, better still from 0.1 to 50% by weight, preferably from 0.5 to 30% by weight, even better still from 1 to 20% by weight relative to the total weight of the composition.

The composition may further comprise one or more water-soluble organic solvents (solubility greater than or equal to 5% in water at 25°C and at atmospheric pressure).

As a water-soluble organic solvent, mention may be made, for example, of linear or branched, preferably saturated, monoalcohols or diols comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol, 3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol, propylene glycol; aromatic alcohols such as phenylethyl alcohol; polyols with more than two hydroxyl functions such as glycerol; polyol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether; as well as diethylene glycol alkyl ethers, in particular _C1 - _C4 , such as, for example, diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

The water-soluble organic solvents, when present, generally represent between 1 and 20% by weight relative to the total weight of the composition according to the invention, and preferably between 5 and 10% by weight relative to the total weight of the composition.

The composition according to the invention may also contain one or more additives different from the compounds described above chosen from the active ingredients and cosmetic adjuvants commonly used in the hair care field. These additives are chosen for example from fixing polymers, conditioning agents and in particular cationic polymers, silicones, chitosans and derivatives; UV filters, fillers such as mother-of-pearl, titanium dioxide, resins, clays; perfumes, peptizers, vitamins, preservatives, acidic agents, alkaline agents, oxidants, amino acids, oligopeptides, peptides, hydrolyzed or unhydrolyzed proteins, modified or unmodified, enzymes, organic acids, antioxidants and free radical scavengers, chelating agents, anti-dandruff agents, seborrhea regulating agents, soothing agents, plasticizers, glitter, propellant gases.

The above additives may be present in an amount varying from 0.01 to 20% by weight relative to the total weight of the composition according to the invention.

The composition according to the invention can be presented in the form of wax, paste, cream, gel, mousse, spray, lotion.

The present invention also relates to the use of the composition as defined according to the invention for smoothing/defrizzing and/or for reducing frizz in keratin fibers, preferably hair, for controlling the volume of the hair.

Finally, the invention also relates to a treatment method, in particular for smoothing keratin fibers, preferably hair, comprising:

(i) a step of applying the composition according to the invention to the keratin fibers, then;

(ii) possibly followed by the application of a shampoo composition and a rinse

(ii) possibly followed by a drying step

In a first embodiment, the composition according to the invention is applied to damp or dry hair, preferably damp, with or without application time. The bath ratio of the applied formulation can vary from 0.1 to 10, more particularly from 0.2 to 5. The keratin fibers are then wrung out or not, preferably wrung out.

The hair then undergoes, or not, one or more of the following operations: rinsing, shampooing and treatment with a rinsed conditioning agent, drying, preferably using a hood or a hair dryer.

Preferably, when a setting time is implemented, said setting time is preferably 5 minutes to 1 hour, preferably 10 to 45 minutes.

Preferably, the step of applying the composition according to the invention is followed by a rinsing step then the application of a shampoo composition and a shampoo rinse.

Preferably, the step of applying the composition according to the invention is followed by a rinsing step then drying preferably using a hood or a hair dryer.

By bath ratio we mean the ratio between the total weight of the composition applied and the total weight of keratin fibers to be treated.

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

Examples

The compositions were prepared by mixing the ingredients in the tables below. (the quantities are expressed as a percentage by weight relative to the total weight of the composition).

Example 1

A (invention) B C Citric acid 9.6 9.6 urea 6 6 CaCO3 0.026 0.026 0.026 Soda qs pH 3.5 pH 3.5 Phosphoric acid qs pH 3.5 Water qsp 100 100 100

The processing method used in these examples is as follows:

- Shampoo then dry the strands of hair studied,

- Application of one of the compositions in table 1 to damp hair (0.15g of product per g of hair)

- Exposure time: 30 minutes

- Rinsing

- shampoo

- Rinsing

- Drying with a hair dryer

Starting strands: Natural curly type IV Caucasian

The hair strands then undergo 1 and 3 shampoos in order to assess the persistence over time of the smoothing processes, volume control, reduction of frizz, etc.

Results :

The quality of curl relaxation and volume control are visually assessed after one shampoo and after three shampoos.

The process with composition A according to the invention provides better curl relaxation as well as better volume control than the process with comparative compositions B and C not comprising the combination according to the invention.

In addition, the composition according to the invention provides better cosmetics for the hair. The strands are smoother to the touch, right down to the ends.

Example 2

A1 (invention) B1 C1 Citric acid 9.6 9.6 Hydroxyethyl urea 10.4 10.4 CaCO3 0.026 0.026 0.026 Soda qs pH 3.5 pH 3.5 Phosphoric acid qs pH 3.5 Water qsp 100 100 100

The processing method used in these examples is as follows:

- Shampoo then dry the strands of hair studied,

- Application of one of the compositions in table 1 to damp hair (0.15g of product per g of hair)

- Exposure time: 30 minutes

- Rinsing

- shampoo

- Rinsing

- Drying with a hair dryer

Starting strands: Natural curly type IV Caucasian

The hair strands then undergo 1 and 3 shampoos in order to assess the persistence over time of the smoothing processes.

Results :

The quality of curl relaxation and volume control are visually assessed after one shampoo and after three shampoos.

The process with composition A1 according to the invention provides better curl relaxation as well as better volume control than the process with comparative compositions B1 and C1 not comprising the association according to the invention.

Example 3

A2 (invention) B2 (invention) C2 invention D2 Citric acid 9.6 9.6 9.6 9.6 Hydroxyethyl urea 5.2 5.2 5.2 5.2 CaCl2 dihydrate 0.3 CeCl3 0.3 MgCl2 0.3 NaCl 0.3 Soda qs pH 3.5 pH 3.5 pH 3.5 pH 3.5 Water qsp 100 100 100 100

The processing method used in these examples is as follows:

- Shampoo then dry the strands of hair studied,

- Application of one of the compositions in table 1 to damp hair (0.15g of product per g of hair)

- Exposure time: 30 minutes

- Rinsing

- shampoo

- Rinsing

- Drying with a hair dryer

Starting strands: Natural curly type IV Caucasian

The hair strands then undergo 1 and 3 shampoos in order to assess the persistence over time of the smoothing processes.

The quality of curl relaxation and volume control are visually assessed after one shampoo and after three shampoos.

Compositions A2, B2 and C2 according to the invention provide good curl relaxation as well as good volume control, whereas comparative composition D2 comprising a monovalent cation salt provides less good curl relaxation and less good volume control.

Claims (16)

Cosmetic composition comprising:
(a) one or more compounds selected from urea and/or urea derivatives,
(b) one or more carboxylic acids and/or their salts chosen from:
monohydroxylated polycarboxylic acids, and
non-hydroxylated polycarboxylic acids having at least a pKa less than or equal to 4.25,
(c) one or more inorganic salts of multivalent cations Composition according to the preceding claim, characterized in that said compound(s) (a) are chosen from the compounds of formula (I) or (II), their salts or their hydrates;

in which:

• R1, R2, R3, R4 represent, independently:
  1. a hydrogen atom or
  2. a linear or branched, cyclic or acyclic C ₁ -C ₅ lower alkyl or alkenyl radical, a C ₁ -C ₅ alkoxy radical, a C ₆ -C ₁₈ aryl radical, a heterocyclic radical having 5 to 8 members; these radicals being optionally substituted by a radical chosen from the radicals: hydroxyl, (see text) (di)(C ₁ -C ₄ )(alkyl)amino, preferably dimethylamino, carboxyl, halogen, C ₆ -C ₁₈ aryl, carboxamide and N-methylcarboxamide;

it being understood that

• when R1, R2 and R3 represent a hydrogen atom, R4 may denote a linear or branched _C1 - _C5 lower alkyl or alkenyl radical, optionally substituted by a hydroxyl, a carboxamide, methoxy, ethoxy, 1,2,4-triazolyl, cyclopentyl, ( _C1 - _C6 )alkylcarbonyl radical such as acetyl, ( _C1 - _C6 )alkoxycarbonyl such as methoxycarbonyl or ethoxycarbonyl,
  -CO-CH=CH-COOH, phenyl optionally substituted by a chlorine atom or a hydroxyl, benzyl or 2,5-dioxo-4-imidazolidinyl radical;
• when R1 and R3 represent a hydrogen atom, R2 can represent a hydrogen atom, a methyl or ethyl radical and R4 an acetyl radical;
• when R1=R2=H, R3 and R4 can form, with the nitrogen atom which carries them, a piperidine, 3-methylpyrazole, 3,5-dimethylpyrazole or maleimide ring;
• R1 and R2 as well as R3 and R4 can form, with the nitrogen atom which carries them, an imidazole ring;
• R5 and R6 represent, independently of each other,

(iii) a hydrogen atom or
(iv) a lower C alkyl, acyl, or alkenyl radical₁-C₅, linear or branched, cyclic or acyclic, a C alkoxy radical₁-C₅, a C aryl radical₆-C₁₈, a heterocyclic radical having 5 to 8 members; these radicals being optionally substituted by a radical chosen from the radicals: hydroxyl, amino, dimethylamino, carboxyl, halogen, C aryl₆-C₁₈, carboxamide and N-methylcarboxamide;

• A is a radical chosen from the radicals: CH ₂ -CH ₂ , CH=CH, CH ₂ -CO, CO-NH, CH=N, CO-CO, CHOH-CHOH, (HOOC)CH-CH, CHOH-CO , CH ₂ -CH ₂ -CH ₂ , CH ₂ -NH-CO, CH=C(CH ₃ )-CO, NH-CO-NH, CH ₂ -CH ₂ -CO, CH ₂ -N(CH ₃ )-CH ₂ , NH-CH ₂ -NH, CO-CH(CH ₃ )-CH ₂ , CO-CH ₂ -CO, CO-NH-CO, CO-CH(COOH)-CH ₂ , CO-CH=C(COOH), CO-CH=C(CH ₃ ), CO-C(NH ₂ )=CH, CO-C(CH ₃ )=N, CO-CH=CH, CO-CH=N and CO-N=CH.

Composition according to claim 1 or 2, characterized in that the said compound(s) (a) are of formula (I) and are chosen from: urea, methylurea, ethylurea, propylurea, n-butylurea, sec-butylurea, isobutylurea, tert-butylurea, cyclopentylurea, ethoxyurea, hydroxyethylurea, N-(2-hydroxypropyl)urea, N-(3-hydroxypropyl)urea, N-(2-dimethylaminopropyl)urea, N-(3-dimethylaminopropyl)urea, 1-(3-hydroxyphenyl)urea, benzylurea, N-carbamoyl maleamide, N-carbamoyl maleamic acid, piperidinecarboxamide, 1,2,4-triazol-4-yl-urea, hydantoic acid, methyl allophanate, ethyl allophanate, acetylurea, hydroxyethyleneurea, 2-(hydroxyethyl)ethyleneurea, diallylurea, chloroethylurea, N,N-dimethylurea, N,N-diethylurea, N,N-dipropylurea, cyclopentyl-1-methylurea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-bis(2-hydroxyethyl)urea, 1,3-bis(2-hydroxypropyl)urea, 1,3-bis(3-hydroxypropyl)urea, 1,3-dipropylurea, ethyl-3-propylurea, sec-butyl-3-methylurea, isobutyl-3-methylurea, cyclopentyl-3-methylurea, N-acetyl-N’-methylurea, trimethylurea, butyl-3,3-dimethylurea, tetramethylurea and benzylurea. Composition according to claim 1 or 2, characterized in that the said compound(s) (a) are of formula (II) and are chosen from: parabanic acid, 1,2-dihydro-3H-1,2,4-triazol-2-one, barbituric acid, uracil, 1-methyl uracil, 3-methyl uracil, 5-methyl uracil, 1,3-dimethyl uracil, 5-aza uracil, 6-aza uracil, 5-fluoro uracil, 6-fluoro uracil, 1,3-dimethyl-5-fluoro uracil, 5-amino uracil, 6-amino uracil, 6-amino-1-methyl uracil, 6-amino-1,3-dimethyl uracil, 4-chloro uracil, 5-chloro uracil, 5,6-dihydro uracil, 5,6-dihydro-5-methyl uracil, 2-imidazolidone, 1-methyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 4,5-dihydroxy-imidazolidin-2-one, 1-(2-hydroxyethyl)-2-imidazolidinone, 1-(2-hydroxypropyl)-2-imidazolidinone, 1-(3-hydroxypropyl)-2-imidazolidinone, 4,5-dihydroxy-1,3-dimethyl-imidazolidin-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-ethylhydantoin, 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-methyl-tetrahydro-pyrimidin-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-methyl-hexahydropyrimidine-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 and alloxan monohydrate. Composition according to any one of claims 1 to 3, characterized in that said compound(s) (a) are chosen from urea, hydroxyethylurea, and their mixtures. Composition according to any one of the preceding claims, characterized in that the said compound(s) (a) represent in total from 0.1 to 30% by weight, more preferably from 1 to 20% by weight, better still from 2 to 15% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the said compound(s) (b) carboxylic acids according to the invention are chosen from the compounds of formula (I) and/or (II) below:
XO ₂ C−R−CO ₂ X' (I)
in which:
-R is a C ₁ -C ₈ , preferably C ₁ -C ₆ , monohydroxylated aliphatic radical, cyclic or acyclic, preferably acyclic, saturated or unsaturated, linear or branched, comprising between 0 and 7 unsaturations, (double and/or triple bonds) and/or 0 to 2 cycles and optionally substituted by one or more carboxy substituents (-COOX'');
-X and X', X'' independently represent a hydrogen atom, an ammonium salt, an alkali metal salt, such as Li, Na, K, or an alkaline earth salt such as Be, Mg, Ca or a salt derived from an organic amine such as an alkylamine,
XO ₂ C−R1−CO ₂ X' (II)
in which:
-R1 is a non-hydroxylated _C1 - _C8 , preferably _C1 - _C6 , aliphatic radical, cyclic or acyclic, preferably acyclic, saturated or unsaturated, linear or branched, comprising between 0 and 7 unsaturations, (double and/or triple bonds) and/or 0 to 2 cycles, optionally substituted by one or more carboxy substituents (-COOX'');
-X and X', X'' independently represent a hydrogen atom, an ammonium salt, an alkali metal salt, such as Li, Na, K, or an alkaline earth salt such as Be, Mg, Ca or a salt derived from an organic amine such as an alkylamine,
carboxylic acids of formula (II) having a pKa of less than 4.25, preferably less than 4. Composition according to any one of the preceding claims, characterized in that said compound(s) (b) are chosen from malonic acid, citric acid, malic acid, succinic acid, tricarballylic acid and their mixtures, preferably chosen from citric acid, malic acid, more particularly citric acid. Composition according to any one of the preceding claims, characterized in that the said compound(s) (b) represent in total from 0.1 to 30% by weight, preferably from 1 to 20% by weight, better still from 2 to 15% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the multivalent cation salts in accordance with the invention are chosen from:
alkaline earth cation salts such as Berylium, Magnesium, Calcium, Strontium, Barium salts;
lanthanide salts such as cerium, lanthanum, yttrium and ytterbium salts, preferably cerium salts. Composition according to any one of the preceding claims, characterized in that the multivalent cation salts in accordance with the invention c) are chosen from calcium halides (for example calcium iodide, calcium bromide, calcium chloride), magnesium halides, calcium carbonate, calcium sulfate, cerium halides (for example cerium chloride) and mixtures thereof, preferably calcium chloride, calcium carbonate, cerium chloride and mixtures thereof. Composition according to any one of the preceding claims, characterized in that the said compound(s) (c) represent in total from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that said composition has a pH ranging from 2 to 5, preferably from 3 to 4. Composition according to any one of the preceding claims, characterized in that said composition comprises one or more fatty substances. Use of a composition as defined in any one of the preceding claims for smoothing/de-straightening and/or for reducing frizz in keratin fibres, preferably hair, for controlling the volume of the hair. Process for treating keratin fibers, preferably hair, comprising:

1. a step of applying to the keratin fibers the composition as defined in claims 1 to 14;
2. possibly a rinse,

iii) then possibly a shampoo and a rinse,
iv) drying.