FR2959124A1 - Treatment of artificially dyed keratin fibers by direct dyeing or direct oxidation dyeing, comprises applying composition comprising s-triazine compounds substituted by at least two alkylaminonbenzoate groups in medium on the fibers - Google Patents

Abstract

Method of treatment of artificially dyed keratin fibers by direct dyeing or direct oxidation dyeing, preferably human hair, comprises applying, on the keratin fibers, a composition comprising, in a medium, one or more siliceous s-triazine compounds substituted by at least two alkylaminonbenzoate groups (I) and its tautomeric forms. Method of treatment of artificially dyed keratin fibers by direct dyeing or direct oxidation dyeing, preferably human hair, comprises applying, on the keratin fibers, a composition comprising, in a medium, one or more siliceous s-tirazine compounds substituted by at least two alkylaminonbenzoate groups of formula (D-Si(R) a-O( 3-a/2)) (I) and its tautomeric forms. R : 1-2C alkyl, phenyl, 1-2C alkoxy, OH or trimethylsilyloxy; a : 1-3; D : s-triazine of formula (II) (where (C=O)OR1 group can be at ortho, meta or para to the amino group), more silane units of formula (-A-(Si)(R)(O) (3-a)/2, or organosiloxane can contain units of formula ((R) b-(Si) (O) (4-b)/2)); R1 : 1-10C alkyl (optionally unsaturated and containing 5-6C cycloalkyl); R2 : H, OH, 1-4C alkyl or methoxy; A : divalent group comprising methylene, group of formula (-Z-CHW1-CH 2-) (III), (-Z-CH(CH 3)-) (VI), (-Z-CH=CH-) (V), (-Z-C(=CH 2)-) (VI); Z : 1-3C alkylene diradical; W1 : H, OH or 1-3C alkyl; and b : 1-3. An independent claim is included for a method for dyeing keratin fibers, preferably human hair comprising: (a) direct or oxidation dyeing of the fibers; and (b) applying a composition, on the fibers, comprising one or more s-triazine compounds (I) in a medium, where the order of steps (a) and (b) being indifferent. [Image].

Description

The subject of the present invention is a process for the treatment of artificially dyed keratin fibers by direct dyeing or by oxidation dyeing, in particular by means of dyestuffs. human hair, which comprises the application on said keratinous fibers of a composition comprising in a cosmetically acceptable medium one or more compounds s-trazine silicic acid substituted with at least two alkylaminobenzoate groups of formula (I).

The present invention also relates to the use of said method for protecting artificially dyed keratin fibers by direct dyeing or oxidation dyeing, in particular human hair against the action of atmospheric agents and in particular against the action of light .

It is well known that hair is sensitized or weakened to varying degrees by the action of atmospheric agents including light. Many publications disclose that natural light destroys certain amino acids in the hair. These aggression altering the hair fiber, they reduce the mechanical properties such as tensile strength, tensile strength and elasticity, or their resistance to swelling in an aqueous medium. The hair is dull, rough and brittle.

It is also known that, in particular, light tends to attack the natural color of the hair as well as the artificial color of the dyed hair. The color of the hair weakens little by little or turns towards unsightly or undesirable shades.

The effect of light is even more visible on hair dyed by artificial coloration, in particular oxidation dyeing or direct dyeing. In this case, exposure to light leads to degradation of the dyes present both in the hair and on its surface. This results in a significant fading and / or turning of the hair color

For many years, the cosmetics industry has been seeking substances that protect hair from damage caused by atmospheric aggressions, such as light. In particular, products which protect the integrity of the keratinous fibers, that is to say their composition, their surface state, their natural or artificial color, their intrinsic mechanical properties (the tensile strength, the load on the rupture and elasticity, or their resistance to swelling in an aqueous medium) .45 In order to prevent such damage, the use of organic filters in hair compositions, whether rinsed or not rinsed, is widespread. They are generally used in various products such as: - in specific solar hair products (before prolonged exposure to the sun and products to reapply during exhibitions) - in products intended for colored and / or highlighted hair (for the maintenance the brightness of the color and the maintenance of the original shade) - in sensitized hair products (as a means of daily photo protection against the oxidations related to solar radiation).

In particular, certain substances capable of filtering light radiation, such as 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid or its salts (FR-A-2 627 085) or 4- (2- oxo-3-bornylidene methyl) benzene sulfonic acid or its salts (EP-A-329 032) or lactoferrin (FR-A-2673839).

Japanese Patent Application JP05-043437 discloses dyestuff compositions containing 2-hydroxy-4-methoxy benzophenone-5-sulphonic acid or its salts, an aromatic alcohol and a direct acid dye.

It has also been proposed to use organic UV filters in EP1688127 in the presence of an aromatic alcohol and an aromatic carboxylic acid.

EP1738739 also proposes a method for treating colored keratin fibers by direct dyeing or oxidation by applying to the fibers organic UV filters whose log P is less than or equal to 6, and a heating iron. whose temperature is greater than or equal to 60 ° C.

EP1769788 also proposes a method for treating colored keratin fibers by direct dyeing or by oxidation by applying to the fibers organic UV filters whose log P is less than or equal to 6, and a water mixture. liquid / water vapor whose temperature is between 40 ° and 75 ° C.

However, the cosmetic photoprotection compositions of keratin fibers containing organic filters do not give complete satisfaction. The sunscreens generally used often have the disadvantage of destabilizing the hair compositions or modifying their pH and viscosity. In addition, the commonly used organic filters often have significant impacts on the cosmetic performance of the hair formulas in which they are introduced: touch more present, or even fat, which can adversely affect the detergency properties in shampoos for example. In conditioners, this gives them a heavier appearance than the same formulas without filter. Furthermore, conventional organic filters also have photo instability problems in the formulas and do not always have a favorable environmental impact. Finally, the effects obtained on the protection of the color are not completely satisfactory. There remains therefore the need to find new photoprotective agents to protect artificially colored keratin fibers effectively without the aforementioned drawbacks. The Applicant has now surprisingly discovered a new process for treating artificially dyed keratin fibers by direct dyeing or oxidation dyeing, in particular human hair comprising the application on said keratin fibers of a composition comprising in a cosmetically acceptable medium one or more compounds s-trazine silicic acid substituted by at least two alkylaminobenzoate groups of formula (I) whose definition will be defined later in detail.

In particular, this treatment method provides an improvement in the light fastness of hair dyed by direct dyeing or oxidation dyeing.

All of these discoveries are the basis of the present invention. Thus, according to the present invention, it is now proposed a method for treating artificially dyed keratin fibers by direct dyeing or by oxidation dyeing, in particular human hair, characterized in that it consists in applying to said keratinous fibers a composition comprising in a physilogically acceptable medium one or more s-trazine silicon compounds substituted by at least two alkylaminobenzoate groups of formula (I), the definition of which will be defined later in detail. Another object of the invention is the use of said method for the protection of keratin fibers against the action of atmospheric agents and in particular against the action of light.

Another subject of the invention relates to a process for dyeing keratinous fibers, in particular human hair, comprising at least the following stages a), b) and c): a) direct dyeing or oxidation of said fibers b is carried out a composition comprising, in a physiologically acceptable medium and in particular a cosmetically acceptable medium, one or more compounds s-trazine silicic acid substituted with at least two alkylaminobenzoate groups of formula (I), is applied to said fibers; the order of steps a) and b) being indifferent.

The different objects of the invention will now be detailed. The set of meanings and definitions of the compounds used in the present invention given below is valid for all the objects of the invention.

By "cosmetically acceptable" is meant compatible with the integuments (hair, eyelashes, eyebrows, scalp), skin and mucous membranes.

TRIAZINE COMPOUNDS

The s-triazine silicon compounds according to the present invention have the following general formula (I) or one of its tautomeric forms: (D) ù (Si1 lo (3-a) / 2 (1) (R) a in which - R, which may be identical or different, represent a C1-C2 alkyl radical, a phenyl radical, a C1-C2 alkoxy radical, a hydroxyl radical or the trimethylsilyloxy group;

the group (D) denotes a s-triazine compound of formula (II) below: ## STR1 ## where R ', which may be identical or different, represent a C 1 -C 10 alkyl radical, linear or branched and optionally unsaturated and may contain a C5-C6 cycloalkyl group, - the group (C = O) OR1 may be in the ortho, meta or para position of the amino group, - R2, identical or different, represent hydrogen, a hydroxy radical, a linear or branched C1-C4 alkyl radical, a methoxy radical, A is a divalent radical chosen from methylene or a group corresponding to one of the formulas (III), (IV), (V) or (VI): (Z) ùCHùCH₂ù (III) W (Z) ùCH-OH (Z) ùCH = CH ù (V) OH2 ù (Z) ù c (VI) wherein: - Z is a C1-C3 alkylene diradical; W represents a hydrogen atom, a hydroxyl radical or a C1-C3 alkyl radical; In addition to the units of the formula -Au (Si) (R) a (O) (3a), 2, the organosiloxane may include units of the formula: (R) b- (Si) (O) (4b), In which R has the same meaning as in formula (I), b = 1, 2 or 3;

It should be noted that the derivatives of formula (I) may be used in their tautomeric forms and more particularly in the tautomeric form of formula (I ') below:

Embedded image in which the group (D ') denotes an s-triazine compound of the following formula (II'): ## STR2 ## In the formulas (II) and (II ') as defined above, the alkyl radicals may be linear or branched and chosen in particular from methyl, ethyl and n-propyl radicals. isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, ethyl-2 hexyl and tert-octyl.

The particularly preferred alkyl radical is the butyl radical. The preferred s-triazine derivatives are those for which in the formula (II) or (II ') at least one, and even more preferably all, the following characteristics are met: R is methyl, a = 1 or 2, R 'is a C1-C8 radical, Z = -CH2-, W = H, the (C = O) OR1 group is in the para position of the amino group. In a preferred manner, the s-triazine compounds of the invention are represented by the following formulas (Ia), (Ib) or (Ic): R 7 R R 7 R 7

(la) (B) ù Sii O-Sii O] r [Siu0] S Siu (B)

R7 R7 (D) R7 7 7 R R

R [7 (D) (Ic) (D) -Si (R8) 3 in which: - (D) corresponds to formula (XV) as defined above, - R7, which are identical or different, are chosen from among the linear or branched C1-C20 alkyl, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy radicals or the hydroxyl radical, R8, which may be identical or different, are chosen from linear and branched C1-alkyl and alkenyl radicals; -C20, the radicals hydroxy or phenyl, - (B), which are identical or different, are chosen from the radicals R7 and the radical (D), r is an integer between 0 and 200 inclusive, 35 - s is an integer ranging from from 0 to 50 and if s = 0, at least one of the two symbols (B) denotes (D), - u is an integer from 1 to 10, u - t is an integer from 0 to 10 , it being understood that t + u is equal to or greater than 3 as well as their tautomeric forms.

The linear diorganosiloxanes of formula (Ia) are particularly preferred. The linear or cyclic diorganosiloxanes of formula (Ia) or (Ib) falling within the scope of the present invention are random oligomers preferably having at least one, and even more preferably all, of the following characteristics: - R is the methyl radical, the C1-C2 alkoxy radical or the hydroxyl radical, - B is preferably methyl (in the case of linear compounds of formula (la)),

By way of examples of compounds of formula (I) which are particularly preferred, mention will be made of the compounds of formulas (1) to (26) below, as well as their tautomeric forms: HNNNH Ti NN NH (1) (7) INP 'si. o_Si INP 'si.o_Si HN N NH Y' Y (10) NH (9) (13) (14) INP 'si.o_Si Y1' HN N NH (15) (16) O (17) HN N NH YNYN Where (20) / Si-b. ~ O (21) (22) o ~ HN N 'NL NH N NH ~ O 1 Si-O-i O 1/1 HN YNYNH N N NH (23) NH NH N N N N ~ N ~ NH - Si-0 i-0 Si NH4. ## EQU1 ## where ## STR1 ## where ## STR2 ##

## STR2 ## and more particularly compounds such as ethyl 2,4-bis (4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] s-triazine of formula (2), 2,4-bis (isopropyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (4), 2,4-bis (4) n-butyl aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of the formula (5), 2,4-bis (isobutyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s- triazine of formula (6) and 2,4-bis (4'-aminobenzoate neopentyl) - 6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl ) amino] -s-triazine of the formula (10), n-butyl 2,4-bis (4-aminobenzoate) -6 - [(3- {1,3,3,3- tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s -triazine of formula (5):

If the compounds of formula (I) can be obtained according to the reaction scheme below: where R, R ', R2, A, X, n and a are as defined above and Y is a halogen especially chlorine or bromine.

The order of introduction of the reagents can be indifferently, 2 equivalents of the derivative of formula (VII) followed by one equivalent of the derivative of formula (VIII) (lane 1) or 1 equivalent of the derivative of formula (VIII) followed by 2 equivalents of the derivative of formula (VII) (Route 2).

The above reactions may be carried out optionally in the presence of a solvent (for example: THF, acetone / water for the first step of Route 2); toluene, xylene, 2-butanone or ethyl acetate for the first step of Route I), at a temperature between 0 ° C and 200 ° C, more particularly between 0 ° C and 20 ° C for the first step of Lane II and between 50 and 120 ° C for the first step of Route 1 and in the presence or absence of a scavenging base of the acid formed (for example: sodium bicarbonate, sodium carbonate, aqueous sodium hydroxide, triethylamine or pyridine). They can also be carried out in microwaves in the presence or absence of a solvent (for example: toluene, xylene or ethyl acetate) or in the presence or absence of 10% of graphite, at a temperature of 50 to 150.degree. a power of 50-150 Watts for a period of 10 to 30 minutes Whether channels 1 or 2, the steps can be chained in the same reactor without isolation of the intermediate derivatives formed.

The compounds of formula (VII), some of which are commercial, can be obtained from a number of methods from the corresponding nitrobenzoyl chloride by reaction with the corresponding amine and reduction of nitro benzoate obtained (by autoclave with 50% Raney Nickel for example ) as described in EP 0570838; or by a (preferred) method of transesterifying ethyl (commercial) para-aminobenzoate with the alcohol Y NON-R 2 YNY 2 (R) n (VII) + H 2 N 5 A -SYO (3a) I 2 (R) a (VIII) NH2 corresponding in the presence of a catalytic amount of dibutyl tin diacetate with removal of ethanol formed.

The triazine derivatives of formula (I) according to the invention are preferably present in the compositions in accordance with the invention at contents of 0.01 to 20% by weight and more preferably of 0.1 to 10% and more more preferably from 0.1 to 6% by weight relative to the total weight of the composition.

HEAT APPLICATION

According to one particular form of the invention, the treatment method of the invention may further comprise a step of applying a heating at a temperature greater than or equal to 60 ° C. Any heating system and in particular a heating iron can be used.

The heating iron useful in the context of the invention is a heating iron conventionally used in the hair field. Such an iron, for example a curling iron or a straightening iron, is well known in the field of hair treatment. For example, irons useful for practicing the present invention are flat or round irons described in US Pat. Nos. 4,103,145, 4,308,878, 5,983,903, 5,957,140 and 5,494,058.

In the context of the invention, the temperature is greater than or equal to 60 ° C. Preferably, this temperature varies from 60 ° C to 220 ° C. More preferably, this temperature varies from 60 to 120 ° C. The application of the iron can be done by successive separate keys of a few seconds, or by progressive displacement or sliding along the wicks.

It is possible between the application of the composition containing the s-triazine compound (s) of formula (I) and the application of the heating iron to the keratinous fibers to provide a pause time.

Said pause time preferably will vary from 30 seconds to 60 minutes and more preferably from 1 to 30 minutes.

It is also possible to provide a rinsing step and / or a shampoo washing step before or after the application of the composition containing the s-triazine compound (s) of formula (I) and optionally after the application of the iron .

The method according to the invention may comprise an additional step of total or partial drying of the keratin fibers stained with a dryer prior to the use of the iron, so as to avoid large releases of vapors that could burn the hands of the hairdresser.

According to another particular form of the invention, the treatment method of the invention may further comprise a step of applying a mixture of liquid water and water vapor whose temperature is between 40 ° and 75 ° C. .

The liquid water / steam mixture constitutes a mist. Said mixture may additionally contain one or more other gases such as oxygen or nitrogen, mixtures of gases such as air or else other vaporizable compounds.

The temperature of the liquid water / steam mixture is preferably greater than or equal to 40 ° C, and is more particularly between 40 ° C and 75 ° C.

Preferably, the liquid water / steam mixture is brought into contact with the fiber for a period ranging from 1 second to 1 hour, and even more preferably from 5 minutes to 15 minutes. Of course, the application of said mixture can be repeated several times on the same fiber, each operation being carried out according to a duration as indicated above.

Preferably, a composition containing the photoprotective agents is first applied to the colored keratinous fibers, then these wicks thus impregnated are subjected to the action of the liquid water / steam mixture according to the conditions mentioned above, and then Cooling the wicks thus treated, for example by sending on or through them a stream of cold air or air at room temperature.

The production of the liquid water / steam mixture used according to the invention can be carried out using any apparatus known per se and provided for this purpose. However, according to the present invention, it is preferable to use an apparatus comprising one or more steam generators directly connected to a helmet diffusing on the keratinous fibers, in particular human hair, the mixture of liquid water and water vapor. As a type of apparatus, it will be used more particularly that sold under the name ®MICROMIST by TAKARA BELMONT.

SUPPORT The physiologically and in particular cosmetically acceptable medium is preferably constituted by water or by a mixture of water and one or more cosmetically acceptable organic solvents. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and mixtures thereof.

The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 3 and 30% by weight approximately. Additives

The composition according to the invention containing the s-trazine compound (s) of formula (I) may also contain various adjuvants conventionally used in hair treatment compositions, such as additional protective agents, conditioning agents and surfactants. nonionic, amphoteric, zwitterionic anionic or mixtures thereof, nonionic, amphoteric or zwitterionic anionic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, penetrants, sequestering agents, perfumes, buffers, dispersing agents, film-forming agents, preserving agents, opacifying agents, proteins or hydrolysates of non-cationic proteins, methyl eicosanoic acid.

These additives unless there is a further precision are present in the composition according to the invention in proportions ranging from 0 to 20% by weight relative to the total weight of the composition. The precise amount of each additive is readily determined by those skilled in the art according to its nature and function.

Additional photoprotective agents

The compositions according to the invention containing the compound (s) of formula (I) may additionally contain one or more other photoprotective agents chosen from organic UV screening agents, antiradical agents and antioxidants.

By "anti-radical agent" is meant any compound capable of trapping free radicals.

The additional photoprotective agents are preferably chosen from those whose log P is less than or equal to 6.

In the context of the invention, the value of log P conventionally represents the coefficient of partition of the dye between octanol and water. The value of log P can be calculated according to the method described in the article by Meylan and Howard "Atom / Fragment contribution method for estimating octanol-water partition coefficient", J. Pharm. Sci. 84: 83-92, 1995. This value can also be calculated from many commercially available software that determines the value of IogP as a function of the structure of a molecule. As an example, mention may be made of the Epiwin software from the United States Environmental Agency and the Virtual Computational Chemistry Laboratory software.

The organic filters are especially chosen from dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; benzimidazole derivatives and mixtures thereof.

Examples of organic UV filters are those referred to below under their INCI name:

Derivatives of para-aminobenzoic acid: PABA Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 507" by ISP Glyceryl PABA, PEG-25 PABA sold under the name "UVINUL P25" by BASF, Cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular under the trade name "PARSOL MCX" by HOFFMANN LA ROCHE, Isopropyl Methoxy cinnamate, Isoamyl Methoxy cinnamate sold under the trade name "NEO HELIOPAN E 1000" by HAARMANN and REIMER, Cinoxate, DEA Methoxycinnamate, Diisopropyl Methylcinnamate, Derivatives of dibenzoylmethane: Butyl Methoxydibenzoylmethane sold in particular under the trade name "Parsol 1789" by Hoffmann La Roche, Isopropyl Dibenzoylmethane sold in particular under the trade name "Eusolex 8020" by Merck,

Salicylic derivatives: Ethylhexyl salicylate sold under the name "NEO HELIOPAN OS" by Haarmann and REIMER, 40 Dipropylene glycol salicylate sold under the name "DIPSAL" by SCHER, TEA Salicylate, sold under the name "NEO HELIOPAN TS" by Haarmann and REIMER, Derivatives of 13,13-diphenylacrylate: 45 Etocrylene, sold in particular under the trade name "Uvinul N35" by BAS F, Derivatives of benzophenone: Benzophenone-1 sold under the trade name "UVINUL 400" by BASF, Benzophenone-2 sold under the name trade name "UVINUL D50" by BASF Benzophenone-3 or Oxybenzone, sold under the trade name "UVINUL M40" by BASF, Benzophenone-4 sold under the trade name "UVINUL MS40" by BAS F, Benzophenone-5 Benzophenone-6 sold under the trade name "Helisorb 11" by Norquay Benzophenone-8 sold under the trade name "Spectra-Sorb UV-24" by American Cyanamid Benzophenone-9 sold under the trade name "UVINUL DS-49" by BASF,

Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name "MEXORYL SD" by CHIMEX, 4-Methylbenzylidene camphor sold under the name "EUSOLEX 6300" by MERCK, Benzylidene Camphor Sulfonic Acid manufactured under the name "MEXORYL SL" by CHIMEX , 20 Camphor Benzalkonium Methosulfate manufactured under the name "MEXORYL SO" by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name "MEXORYL SX" by CHIMEX,

Phenyl benzimidazole derivatives: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name "Eusolex 232" by Merck, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name "Neo Heliopan AP" by Haarmann and Reimer, As fat-soluble organic UV filters (or lipophilic) suitable for use in the present invention, there may be mentioned more particularly: Ethylhexyl Methoxycinnamate Butyl Methoxydibenzoylmethane Ethylhexyl Salicylate, Benzophenone-3,4-Methylbenzylidene camphor,

As water-soluble (or hydrophilic) organic UV-screening agents suitable for use in the present invention, the following may be mentioned more particularly: PABA, PEG-25 PABA Benzylidene Camphor Sulfonic Acid, Camphor Benzalkonium Methosulfate Terephthalylidene Dicamphor Sulfonic Acid Phenylbenzimidazole Sulfonic Acid Disodium Phenyl Dibenzimidazole Tetrasulfonate Benzophenone-4 Benzophenone-5 Benzophenone-9 or mixtures thereof

Among these filters, Benzophenone-4 will be used more particularly.

The anti-radical agents that can be used in the composition according to the invention include vitamin E derivatives such as tocopheryl acetate; bioflavonoids; certain enzymes such as catalase, superoxide dismutase and wheat germ extracts containing it, lactoperoxidase, glutathione peroxidase and quinone reductases; benzylcyclanones; substituted naphthalenones; pidolates; guanosine; lignans; and melatonin.

The antioxidant agents are especially chosen from phenols such as BHA (tert-butyl-4-hydroxyanisole), BHT (2,6-di-tert-butyl-p-cresol), TBHQ (tert-butylhydroquinone), polyphenols such as as proanthocyanidol oligomers and flavonoids, hindered amines known under the generic term HALS (Hindered Amine Light Stabilizer) such as tetraaminopiperidine, erythorbic acid, polyamines such as spermine, superoxide dismutase, lactoferrin.

According to the invention, the additional protective agent (s) for the keratinous fibers will preferably be present at concentrations ranging from 0.15% to 50% by weight, preferably from 0.35% to 30% by weight and more particularly from 0% to , 5 to 20% by weight relative to the total weight of the composition.

Aromatic acids and alcohols

According to a preferred form of the invention, the photoprotective compositions according to the invention also comprise one or more aromatic alcohols and / or one or more aromatic carboxylic acids.

By the term "aromatic alcohol" is meant any liquid compound at ambient temperature and atmospheric pressure comprising one or more benzene or naphthalenic rings and one or more alcohol (OH) functions directly linked to one or more rings or linked to one or more substituents of said one or more rings. Preferably, the alcohol function will be on a substituent of a benzene or naphthalenic ring.

Among the aromatic alcohols that can be used in the composition according to the invention, mention may be made in particular of benzyl alcohol benzoyl isopropanol benzyl glycol phenoxyethanol di-chlorobenzyl alcohol methylphenylbutanol phenoxyisopropanol phenylisohexanol - phenylpropanol - phenylethyl alcohol - their mixtures.

Benzyl alcohol will be chosen more particularly.

According to the invention, the aromatic alcohol (s) may represent from 0.01% to 50% by weight, preferably from 0.1% to 30% by weight and more particularly from 1% to 20% by weight relative to to the total weight of the composition. Preferably, they will be used at concentrations greater than 10% by weight.

According to a preferred form of the invention, the photoprotective compositions according to the invention comprise, according to the invention, one or more optionally salified aromatic carboxylic acids.

By the term "aromatic carboxylic acid" is meant any compound comprising one or more benzene or naphthalenic rings and one or more carboxylic acid (COOH) functions, in free or salified form, directly linked to the rings or linked on one or more substituents of said one or more rings. Preferably, the acid function will be directly connected to a benzene or naphthalenic ring. The salts of the aromatic carboxylic acids may be chosen in particular from alkali metal (sodium, potassium), alkaline earth metal (calcium, magnesium) salts or organic amine or ammonium salts. Among the aromatic carboxylic acids which may be used in the composition according to the invention, mention may be made in particular of benzoic acid, para-anisic acid, diphenolic acid, ferulic acid and hippuric acid. 3-hydroxybenzoic acid - 4-hydroxybenzoic acid 45- phenylthioglycolic acid - acetylsalicylic acid 20 - para, meta or ortho-phthalic acid and their salified forms and mixtures thereof.

Benzoic acid will be chosen more particularly.

According to the invention, the aromatic acid (s) or their salts may represent from 0.001% to 30% by weight, preferably from 0.01% to 20% by weight and more particularly from 0.1% to 10% by weight relative to to the total weight of the composition.

In one variant of the invention, the compositions of the invention comprise one or more aromatic alcohols and one or more aromatic acids or their salts.

15 Conditioning Aqents

The compositions according to the invention may additionally contain one or more conditioning agents.

In the context of the present invention, the term "conditioning agent" is understood to mean any agent whose function is to improve the cosmetic properties of the hair, in particular softness, disentangling, touch, smoothing and static electricity.

The conditioning agents may be in liquid, semi-solid or solid form such as, for example, oils, waxes or gums.

According to the invention, the conditioning agents may be chosen from synthetic oils such as polyolefins, vegetable oils, fluorinated or perfluorinated oils, natural or synthetic waxes, silicones, cationic polymers, ceramide type, cationic surfactants, non-salified fatty acids and their derivatives as well as mixtures of these various compounds. The synthetic oils are in particular polyolefins, in particular poly-α-olefins and more particularly polybutene type, hydrogenated or otherwise, and preferably polyisobutene, hydrogenated or otherwise.

Isobutylene oligomers with a molecular weight of less than 1000 are preferably used and their mixtures with polyisobutylenes with a molecular weight greater than 1000 and preferably between 1000 and 15000. Examples of poly-α-olefins that may be used in Within the scope of the present invention, the polyisobutenes sold as PERMETHYL 99A, 101A, 102A, 104A (n = 16) and 106A (n = 38) may be mentioned by PRESPERSE Inc. or else the products sold under the name ARLAMOL HD (n = 3) by the company ICI (n designating the degree of polymerization), of the polydecene type, hydrogenated or not. Such products are sold, for example, under the names ETHYLFLO 5 by the company ETHYL CORP., And ARLAMOL PAO by the company ICI.

The animal or vegetable oils are preferably chosen from the group consisting of sunflower, corn, soya, avocado, jojoba, squash, grape seed, sesame, hazelnut, fish oil oils. , tricaprocaprylate of glycerol, or vegetable or animal oils of formula R90O0R10 in which R9 represents the residue of a higher fatty acid having from 7 to 29 carbon atoms and R10 represents a linear or branched hydrocarbon-based chain containing from 3 to 30 atoms carbon, especially alkyl or alkenyl, for example, Purcellin oil or liquid jojoba wax;

It is also possible to use natural or synthetic essential oils such as, for example, eucalyptus, lavandin, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile and savory oils. nutmeg, cinnamon, hyssop, caraway, orange, geraniol, cade and bergamot;

Waxes are natural substances (animal or plant) or synthetic solid at room temperature (20 ° -25 ° C). They are insoluble in water, soluble in oils and are capable of forming a water-repellent film.

On the definition of waxes, for example, D.D. Dorgan, Drug and Cosmetic Industry, December 1983, pp. 30-33. The wax or the waxes are chosen in particular from Carnauba wax, Candelila wax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, wax of rice, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of blackcurrant flower sold by the company BERTIN (France), animal waxes such as beeswax, or modified beeswax ( cerabellina); other waxes or waxy raw materials that can be used according to the invention are, in particular, marine waxes, such as the one sold by SOPHIM under the reference M82, and polyethylene or polyolefin waxes in general. The preferred conditioning agents according to the invention are cationic polymers and silicones.

The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of hair treated with detergent compositions, namely in particular those described in patent application EP-A-0 337 354. and in French patent applications FR-A-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.

Even more generally, within the meaning of the present invention, the expression "cationic polymer" denotes any polymer containing cationic groups and / or ionizable groups in cationic groups.

The preferred cationic polymers are chosen from those containing units containing primary, secondary, tertiary and / or quaternary amine groups that may either be part of the main polymer chain or may be carried by a lateral substituent directly connected thereto.

The cationic polymers used generally have a number-average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6.

Among the cationic polymers, mention may be made more particularly of polyamine, polyaminoamide and quaternary polyammonium polymers. These are known products.

Polymers of the polyamine, polyamidoamide or quaternary polyammonium type which can be used in accordance with the present invention, which may be mentioned in particular, are those described in French Pat. Nos. 2,505,348 or 2,542,997. Among these polymers, mention may be made of:

(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and having one or more of the following formulas: (X) in which: R1 and R2, which may be identical or different, represent hydrogen or an alkyl group; having from 1 to 6 carbon atoms and preferably methyl or ethyl; R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4, R5, R6, which may be identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms; X denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide.

The copolymers of the family (1) may also contain one or more comonomer-derived units which may be chosen from the family of acrylamides, methacrylamides, diacetones acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls (C1-C4). ), acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, among these copolymers of the family (1), mention may be made of: the copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl hologenide such as that sold under the name HERCOFLOC by the company HERCULES copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company Ciba Geigy, the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulphate sold under the name Reten by the company Hercules, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate quaternized or otherwise, such as the products sold under the name "GAFQUAT" by the company ISP, for example "GAFQUAT 734 "or" GAFQUAT 755 "or the products referred to as" COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573, dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP, vinylpyrrolidone copolymers. / methacrylamidopropyl dimethylamine marketed in particular under the name STYLEZE CC 10 by ISP. the quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers, such as the product sold under the name "GAFQUAT HS 100" by the company ISP. and crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (C1-C4) ammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by the methyl chloride, the homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. It is more particularly possible to use a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name "SALCARE® SC 92" by the company CIBA. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names "SALCARE® SC 95" and "SALCARE® SC 96" by the company CIBA.

(2) polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization of these polymers. Such polymers are in particular described in French Patents 2,162,025 and 2,280,361; (3) water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides may be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or else with an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bisazetidinium, a bis-haloacyldiamine, an alkyl bis-halide, a epilhalohydrin, a diepoxide or bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 moles per amine group of the polymaoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary amine functional groups, quaternized. Such polymers are described in particular in French Patents 2,252,840 and 2,368,508;

(4) polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid-diacoylaminohydroxyalkyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in French Patent 1,583,363.

Among these derivatives, mention may be made more particularly of the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz. (5) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and one or more secondary amine groups with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the polyaminoamide resulting therefrom being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents US 3,227,615 and 2,961,347.

Polymers of this type are in particular sold under the name "Hercosett 57" by the company Hercules Inc. or under the name "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid copolymer / epoxypropyl / diethylenetriamine. (6) cyclopolymers of alkyl diallyl amine or of dialkyl diallyl ammonium such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (VII) or (VIII): ## STR2 ## where K and t are 0 or 1, the sum k + t being equal to 1; R12 denotes a hydrogen atom or a methyl radical; R10 and R11, independently of each other, denote an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C1 -C4) or R10 and R11 may designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; Y- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are described in particular in French Patent 2,080,759 and in its certificate of addition 2,190,406.

R10 and R11, independently of one another, preferably denote an alkyl group having 1 to 4 carbon atoms. Among the polymers defined above, mention may be made more particularly of the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company Nalco (and its counterparts of low molecular weight average) and the copolymers of sodium chloride. diallyldimethylammonium and acrylamide sold under the name "MERQUAT 550". (7) the quaternary diammonium polymer containing repeating units corresponding to the formula: ## STR1 ## in which: R 13, R 14, R 15 and R 16, which may be identical or different, , represent aliphatic, alicyclic, or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R13, R14, R15 and R16, together or separately, together with the nitrogen atoms to which they are attached, heterocycles optionally containing a (C 2) n -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 N + Y R 10 R 11 R 10 (XIV) (XV) second heteroatom other than nitrogen or else R13, R14, R15 and R16 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl or amide group or -CO-O-R17-D or -CO-NH-R17-D where R17 is an alkylene and D is a quaternary ammonium group, Al and B1 represent polymethylenic groups containing t 2 to 20 carbon atoms may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more oxygen atoms, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X- denotes an anion derived from a mineral or organic acid; Al, R13 and R15 can form with the two nitrogen atoms to which they are attached a piperazine ring; furthermore, if Al denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a (CH2) n -CO-D-OC- (CH2) n-n group is an integer ranging from 2 to 20 in which D denotes: a) a glycol residue of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH 2 -CH 2 -O) x - CH 2 -CH 2 - - [CH 2 -CH (CH 3) -O] y -CH 2 -CH (CH 3) - where x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number of 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or the divalent radical - CH 2 -CH 2 -S-S-CH 2 -CH 2 -; d) a ureylene group of formula: -NH-CO-NH-; Preferably, X- is an anion such as chloride or bromide.

These polymers have a number-average molecular weight generally of between 1,000 and 100,000. 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and US Patents 2,273,780, 2,375,853 and 2,388,614. , 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026 .945 and 4.027.020.

Polymers of this type are described in particular in French patents. More particularly, polymers which consist of repeating units having the formula: + R 3 can be used more particularly.

- N (CH2) p- N- (CH2) p u (a) R2 X 'R4

in which R'1, R'2, R'3 and R'4, identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20 and, X'- is an anion derived from a mineral or organic acid.

A compound of formula (a) which is particularly preferred is that for which R 1, R 2, R 3 and R 4 represent a methyl radical and n = 3, p = 6 and X = Cl, referred to as Hexadimethrine chloride according to the INCI nomenclature (CTFA).

(8) quaternary polyammonium polymers consisting of units of formula (XVI): ## STR2 ## In which R18, R19, R20 and R21, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, R-hydroxyethyl, R-hydroxypropyl or -CH2CH2 radical ( OCH2CH2) pOH where p is 0 or an integer from 1 to 6, with the proviso that R18, R19, R20 and R21 do not simultaneously represent a hydrogen atom, r and s, which are the same or different, are integers between 1 and 6, q is 0 or an integer of 1 to 34, X is an anion such as a halide, A 'is a radical of a dihalide or is preferably -CH2-CH2-O-CH2-CH2-.

Such compounds are described in particular in patent application EP-A-122 324. For example, the products Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1 and the like can be mentioned. "Mirapol® 175" sold by the company Miranol.

(9) The quaternary vinylpyrrolidone and vinylimidazole polymers such as, for example, the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company B.A.S.F.

(10) Cationic polysaccharides, in particular cationic celluloses and cationic galactomannan gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives containing quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

The cellulose ether derivatives containing quaternary ammonium groups described in French Patent 1,492,597. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, are described in particular in US Pat. No. 4 131 576, such as hydroxyalkyl celluloses, such as hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyltrimethylammonium, dimethyl-diallylammonium.

The cationic galactomannan gums are described more particularly in US Pat. Nos. 3,589,578 and 4,031,307, in particular guar gums containing cationic trialkylammonium groups. For example, guar gums modified with a salt (eg chloride) of 2,3-epoxypropyltrimethylammonium are used.

Other cationic polymers which can be used in the context of the invention are cationic proteins or hydrolysates of cationic proteins, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use cationic polysaccharides, cationic cyclopolymers, in particular homopolymers or copolymers of dimethyldiallylammonium chloride, sold under the names "Merquat 100". "MERQUAT 550" and "MERQUAT S" by NALCO, quaternary polymers of vinylpyrrolidone and vinylimidazole and mixtures thereof.

The silicones that may be used in accordance with the invention are in particular polyorganosiloxanes that are insoluble in the composition and may be in the form of oils, waxes, resins or gums. The organopolysiloxanes are defined in greater detail in Walter's work. NOLL "Chemistry and Technology of Silicones" (1968) Academic Press. They can be volatile or nonvolatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and more particularly between:

(i) cyclic silicones containing from 3 to 7 silicon atoms and preferably from 4 to 5. It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE" 70045 V 2 "by RHODIA CHIMIE, decamethylcyclopentasiloxane marketed under the name" VOLATILE SILICONE 7158 "by UNION CARBIDE," SILBIONE 70045 V 5 "by RHODIA CHIMIE, as well as their mixtures.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylakylsiloxane type, such as the "VOLATILE SILICONE FZ 3109" marketed by UNION CARBIDE, of chemical structure: It is also possible to mention cyclic silicone mixtures with organic compounds derived from silicon, such as that the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '(hexa-2,2,2', 2 ', 3,3'-trimethylsilyloxy) bis-neopentane;

(ii) linear volatile silicones having 2 to 9 silicon atoms and having a viscosity less than or equal to 5 × 10 -6 m 2 / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200 "by TORAY SILICONE company. Silicones included in this class are also described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS Volatile Silicone fluids for cosmetics.

Non-volatile silicones and more particularly polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organofunctional groups and mixtures thereof are preferably used.

## STR2 ## These silicones are more particularly chosen from polyalkylsiloxanes, among which, for example, polydimethylsiloxanes containing trimethylsilyl end groups having a viscosity of 5 × 10 -6 to 2.5 m 2 / s can be mentioned. 25 ° C and preferably 1.10-5 to 1 m 2 / s. The viscosity of the silicones is for example measured at 25 ° C. according to ASTM standard 445 Appendix C.

Among these polyalkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE oils of the 47 and 70 047 series or MIRASIL 10 oils marketed by RHODIA CHIMIE, such as, for example, the 70 047 V 500 000 oil; oils of the MIRASIL series marketed by RHODIA CHIMIE; oils of the 200 series of Dow Corning, such as, more particularly, DC200 with a viscosity of 60,000 Cst; - VISCASIL oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups (Dimethiconol according to the CTFA name), such as the oils of the 48 series of the company Rhodia Chimie.

In this class of polyalkylsiloxanes, mention may also be made of the products sold under the names "ABIL WAX 9800 and 9801" by GOLDSCHMIDT which are poly (C1-C20) alkylsiloxanes.

The polyalkylarylsiloxanes are particularly chosen from polydimethyl methylphenylsiloxanes and linear and / or branched polydimethyl diphenylsiloxanes with a viscosity of from 1 × 10 -5 to 5 × 10 -2 m 2 / s at 25 ° C. Among these polyalkylarylsiloxanes, mention may be made, by way of example, of the products sold under the following names: SILBIONE oils of the 70 641 series from RHODIA CHIMIE; . RHODORSIL 70 633 and 763 series oils from RHODIA CHIMIE; 35. DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING; . silicones of the PK series from BAYER, such as the product PK20; . silicones of the PN and PH series from BAYER, such as the PN1000 and PH 1000 products; . some oils from the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265.

The silicone gums which can be used in accordance with the invention are in particular polydiorganosiloxanes having high average molecular weights of between 200,000 and 1,000,000 used alone or in a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecanes or their mixtures.

Mention may more particularly be made of the following products: polydimethylsiloxane gums polydimethylsiloxane / methylvinylsiloxane gums polydimethylsiloxane / diphenylsiloxane gums polydimethylsiloxane / phenylmethylsiloxane gums polydimethylsiloxane / diphenylsiloxane / methylvinylsiloxane gums. More particularly useful products according to the invention are mixtures such as: mixtures formed from a hydroxylated polydimethylsiloxane at the end of the chain (called dimethiconol according to the CTFA dictionary nomenclature) and a cyclic poly-dimethylsiloxane (called cyclomethicone according to the CTFA dictionary nomenclature) such as the product Q2 1401 marketed by the company Dow Corning; . mixtures formed from a polydimethylsiloxane gum with a cyclic silicone such as the product SF 1214 Silicone Fluid from the company GENERAL ELECTRIC, this product is a SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500 000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; . mixtures of two PDMSs of different viscosities, and more particularly a PDMS gum and a PDMS oil, such as the product SF 1236 from the company GENERAL ELECTRIC. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 / s and an SF 96 oil with a viscosity of 5 × 10 -6 m 2 / s. This product preferably comprises 15% of SE gum and 85% of an SF 96 oil. The organopolysiloxane resins used in accordance with the invention are crosslinked siloxane systems containing the units: R 2 SiO 2 · 2, R 3 SiOl 2, RSiO 3, 2 and SiO412 wherein R represents a hydrocarbon group having 1 to 16 carbon atoms or a phenyl group. Among these products, those particularly preferred are those in which R denotes a lower alkyl radical C1-C4, more particularly methyl, or a phenyl radical.

Among these resins may be mentioned the product sold under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure.

Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu.

The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon radical.

Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: polyethyleneoxy and / or polypropyleneoxy groups optionally comprising C 6 -C 24 alkyl groups such as the products called dimethicone copolyol marketed by the company Dow Corning under the name DC 1248 or the oils SILWET L 722, L 7500, L 77, L 711 of the company UNION CARBIDE and the alkyl (C12) methicone copolyol marketed by the company Dow Corning under the name Q2 5200; substituted or unsubstituted amine groups such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company GENESEE or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning, under the name Belsil ADM LOG 1 by the company Wacker and under the name DC2-8299 by Dow Corning The substituted amino groups are in particular C1-C4 aminoalkyl groups

thiol groups such as the products sold under the names "GP 72 A" and "GP 71" from GENESEE; alkoxylated groups, such as the product marketed under the name "Silicone Copolymer F-755" by SWS Silicones and Abil Wax 2428, 2434 and 2440 by the company GOLDSCHMIDT; hydroxyl groups such as the hydroxyalkyl-functional polyorganosiloxanes described in the French patent application FR-A-85 16334 corresponding to the formula (XVII): 22 122 122 122

Wherein R22 (XVII) R22 wherein R22 is the same or different radicals are selected from methyl and phenyl radicals; at least 60 mol% of the radicals R22 denoting methyl; the R '22 radical is a C2-C18 hydrocarbon divalent alkylene chain; p is between 1 and 30 inclusive; q is from 1 to 150 inclusive; acyloxyalkyl groups, such as, for example, the polyorganosiloxanes described in US Pat. No. 4,957,732 and corresponding to formula (XVIII): ## STR1 ## where R "R"

Where R 23 denotes a methyl, phenyl, -OCOR 5, hydroxyl group, only one of the radicals R 23 per silicon atom may be OH; R'23 is methyl, phenyl; at least 60% in molar proportion of all the radicals R4 and R'4 denoting methyl; R24 is C8-C20 alkyl or alkenyl; R "denotes a linear or branched C2-C18 divalent hydrocarbon alkylene radical, r is between 1 and 120 inclusive, p is between 1 and 30, q is 0 or less than 0.5 p, p + q being between 1 and 30, the polyorganosiloxanes of formula (XII) may contain groups: 1 CH3-Si-OH OI in proportions not exceeding 15% of the sum p + q + r.

anionic groups of the carboxylic type, for example in the products described in the patent EP 186 507 of the company Chisso Corporation, or of the alkylcarboxylic type, such as those present in the product X-22-3701E from the company Shin-Etsu; 2-hydroxyalkylsulfonate; 2-hydroxyalkylthiosulphate such as the products marketed by GOLDSCHMIDT under the names "ABIL S201" and "ABIL S255".

hydroxyacylamino groups, such as the polyorganosiloxanes described in patent application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

According to the invention, it is also possible to use silicones comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said chain. main. These polymers are for example described in patent applications EP-A-412 704, EP-A-412 707, EP-A-640 105 and WO 95/00578, EP-A-582 152 and WO 93/23009 and the US Patents 4,693,935, US 4,728,571 and US 4,972,037. These polymers are preferably anionic or nonionic.

Such polymers are, for example, the copolymers that can be obtained by radical polymerization from the monomer mixture consisting of: a) 50 to 90% by weight of tert-butyl acrylate; b) 0 to 40% by weight of acrylic acid; c) 5 to 40% by weight of silicone macromer of formula (XIX): O CH3

H2C = C-C-Where (CH2) 3 SiO1 CH3 CH3CH3 SiO0 CH3 CH3

1 ù Si ù (CH 2) 3 - CH 3

CH 3 (XIX) with v being a number from 5 to 700; the percentages by weight being calculated with respect to the total weight of the monomers.

Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connection link, mixed polymeric units of the poly (meth) acrylic acid and poly type. alkyl (meth) acrylate and polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connecting link, polymeric units of the poly (meth) acrylate isobutyl type.

According to the invention, all the silicones can also be used in the form of emulsions, nanoemulsions or microemulsions.

The polyorganosiloxanes which are particularly preferred according to the invention are the non-volatile silicones chosen from the family of polyalkylsiloxanes containing trimethylsilyl end groups, such as oils having a viscosity of between 0.2 and 2.5 m 2 / s at 25 ° C. that the oils of the DC200 series of DOW CORNING in particular that of viscosity 60 000 cst, SILBIONE series 70047 and 47 and more particularly the 70 047 V 500 000 oil sold by RHODIA CHIMIE, the polyalkylsiloxanes with terminal groups dimethylsilanol such as dimethiconol or polyalkylarylsiloxanes such as the SILBIONE 70641 V 200 oil marketed by RHODIA CHIMIE; the organopolysiloxane resin sold under the name Dow Corning 593; Polysiloxanes with amino groups such as amodimethicones or trimethylsilylamodimethicone;

The cationic protein proteins or hydrolysates are, in particular, chemically modified polypeptides carrying, at the end of the chain, or grafted thereto, quaternary ammonium groups. Their molecular weight may vary for example from 1500 to 10000, and in particular from 2000 to 5000 approximately. Among these compounds, mention may in particular be made of:

collagen hydrolysates bearing triethylammonium groups, such as the products sold under the name "Quat-Pro E" by the company MAYBROOK and referred to in the CTFA dictionary "Triethonium Hydrolyzed Collagen Ethosulfate"; collagen hydrolysates bearing trimethylammonium chloride and trimethylstearylammonium groups, sold under the name "Quat-Pro S" by the company MAYBROOOK and referred to in the CTFA dictionary "Steartrimonium Hydrolyzed Collagen"; animal protein hydrolysates bearing trimethylbenzylammonium groups, such as the products sold under the name Crotein BTA by the company CRODA and referred to in the CTFA dictionary as "Benzyltrimonium hydrolyzed animal protein"; protein hydrolysates carrying on the polypeptide chain quaternary ammonium groups containing one or more alkyl radicals having from 1 to 18 carbon atoms.

Among these protein hydrolysates, mention may be made inter alia of: - "Croquat L" whose quaternary ammonium groups comprise a C12 alkyl group; "Croquat M" whose quaternary ammonium groups contain C10-C18 alkyl groups; "Croquat S" whose quaternary ammonium groups contain a C18 alkyl group; "Crotein Q" whose quaternary ammonium groups contain one or more alkyl groups having from 1 to 18 carbon atoms. These different products are sold by Croda.

Other quaternized proteins or hydrolysates are, for example, those corresponding to formula (XX): CH 3

Wherein X- is an anion of an organic or inorganic acid, A "denotes a protein residue derived from collagen protein hydrolysates, R25 denotes a lipophilic group comprising up to 30 carbon atoms, R 26 represents an alkylene group having 1 to 6 carbon atoms, for example the products sold by the company Inolex, under the name "Lexein QX 3000", called in the CTFA dictionary "Cocotrimonium" Collagen Hydrolysate ".

Mention may also be made of quaternized vegetable proteins such as wheat, corn or soya proteins: as quaternized wheat proteins, mention may be made of those marketed by the company Croda under the names "Hydrotriticum WQ or QM", referred to in the dictionary CTFA "Cocodimonium Hydrolysed wheat protein", "Hydrotriticum QL" called in the CTFA dictionary "Laurdimonium hydrolysed wheat protein", or "Hydrotriticum QS", called in the CTFA dictionary "Steardimonium hydrolysed wheat protein".

According to the present invention, the ceramide-type compounds are in particular ceramides and / or glycoceramides and / or pseudoceramides and / or neoceramides, natural or synthetic.

Ceramide-type compounds are for example described in patent applications DE4424530, DE4424533, DE4402929, DE4420736, WO95 / 23807, WO94 / 07844, EP-A-0646572, WO95 / 16665, FR-2,673,179, EP-A- 0227994 and WO 94/07844, WO94 / 24097, WO94 / 10131, the teachings of which are hereby incorporated by reference.

Particularly preferred ceramide compounds according to the invention are for example: 2-N-linoleoylamino-octadecane-1,3-diol, 2-N-oleoylamino-octadecane-1,3-diol, N-palmitoylamino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3-diol, 2-N-behenoylamino-octadecane-1,3-diol, 2-N [2-hydroxy-palmitoyl] -aminooctadecane-1,3-diol, 2-N-stearoylaminooctadecane-1,3,4-triol and in particular N-stearoyl phytosphingosine, 2-N -methyl-hexadecane-1,3-diol (bis- (N-hydroxyethyl-N-cetyl) malonamide), - N- (2-hydroxyethyl) -N- (3-cetyloxy-2-hydroxypropyl) amide cetyl acid; N-docosanoyl N-methyl-D-glucamine or mixtures thereof.

It is also possible to use cationic surfactants among which may be mentioned in particular: salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts; imidazoline derivatives; or oxides of amines with a cationic character.

The quaternary ammonium salts are, for example: those which have the following general formula (XXI): embedded image in which the radicals R 27 to R 30, which may be identical or different, , represent a linear or branched aliphatic radical containing from 1 to 30 carbon atoms, or an aromatic radical such as aryl or alkylaryl. The aliphatic radicals can comprise heteroatoms such as in particular oxygen, nitrogen, sulfur, halogens. The aliphatic radicals are, for example, chosen from alkyl, alkoxy, polyoxyalkylene (C 2 -C 6), alkylamide, (C 12 -C 22) alkylamido (C 2 -C 6) alkyl, (C 12 -C 22) alkyl acetate, hydroxyalkyl, with about 1 to 30 carbon atoms; X is an anion chosen from the group of halides, phosphates, acetates, lactates, (C 2 -C 6) alkyl sulphates, alkyl or alkylarylsulphonates,

the quaternary ammonium salts of imidazolinium, such as for example that of formula (XVI) below: ## STR2 ##

in which R 31 represents an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, for example derived from tallow fatty acids, R 32 represents a hydrogen atom, a C 1 -C 4 alkyl radical or an alkenyl or alkyl radical comprising 8 to 30 carbon atoms, R33 represents a C1-C4 alkyl radical, R34 represents a hydrogen atom, a C1-C4 alkyl radical, X is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulphates alkyl or alkylarylsulfonates. Preferably, R 31 and R 32 denote a mixture of alkenyl or alkyl radicals containing from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R 33 denotes methyl and R 32 denotes hydrogen. Such a product is for example sold under the name "REWOQUAT W 75" by the company DEGUSSA, - - di or quaternary triammonium salts, in particular of formula (XIV):

R17 R19 R16-N- (CH2) 3 -N-R21 2X-R18 R2o (XXIII) in which R16 denotes an alkyl radical containing about 16 to 30 carbon atoms, optionally hydroxylated and / or interrupted by one or more atoms oxygen, R17 is selected from hydrogen + X- or an alkyl radical having 1 to 4 carbon atoms or a group (R16a) (R17a) (R18a) N- (CH2) 3-, NB (+ to be deleted in other projects because not obligatory) R16a, R17a, R18a, R18, R19, R20 and R21, which are identical or different, are chosen from hydrogen or an alkyl radical containing from 1 to 4 carbon atoms, and X- is an anion selected from the group of halides, acetates, phosphates, nitrates and methylsulfates. Such compounds are, for example, Finquat CT-P proposed by Finetex (Quaternium 89), Finquat CT proposed by Finetex (Quaternium 75), and quaternary ammonium salts containing at least one ester function.

The quaternary ammonium salts containing at least one ester function that may be used according to the invention are, for example, those of formula (XXIV) below (CrH2rO): ## STR2 ## ## STR2 ## ) R42 R41 in which: R41 is chosen from C1-C6 alkyl radicals and C1-C6 hydroxyalkyl or dihydroxyalkyl radicals; R 42 is chosen from: ## STR5 ## R 1 -C 2 2 hydrocarbon radicals R 1 -C 2 2 which are linear or branched, saturated or unsaturated, hydrogen atom, R 4 4 is chosen from: ## STR5 ## R48 hydrocarbon C1-C6 linear or branched, saturated or unsaturated, - the hydrogen atom, - R43, R45 and R47, identical or different, are selected from hydrocarbon radicals C7-C21, linear or branched, saturated or unsaturated; n, p and r, which may be identical or different, are integers ranging from 2 to 6; Y is an integer from 1 to 10; x and z, identical or different, are integers ranging from 0 to 10; - X- is a simple or complex anion, organic or inorganic; X- (XXIV) with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R42 is R46 and that when z is 0 then R44 is R48.

The alkyl radicals R41 can be linear or branched and more particularly linear.

Preferably R41 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical and more particularly a methyl or ethyl radical.

Advantageously, the sum x + y + z is from 1 to 10.

When R 16 is a hydrocarbon radical R 20, it can be long and have 12 to 22 carbon atoms or short and have 1 to 3 carbon atoms.

When R 18 is a hydrocarbon radical R 22, it preferably has 1 to 3 carbon atoms.

Advantageously, R43, R45 and R47, which are identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon radicals, and more particularly from linear or branched, saturated or saturated C11-C21 alkyl and alkenyl radicals. or unsaturated.

Preferably, x and z, identical or different, are 0 or 1. Advantageously, y is equal to 1.

Preferably, n, p and r, identical or different, are 2 or 3 and even more particularly are equal to 2.

The anion is preferably a halide (chloride, bromide or iodide) or an alkyl sulphate more particularly methyl sulphate. However, it is possible to use methanesulphonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.

The X- anion is even more particularly chloride or methylsulfate.

Ammonium salts of formula (XVIII) are used more particularly in which: R 41 denotes a methyl or ethyl radical, x and y are equal to 1; z is 0 or 1; - n, are equal to 2; - R42 is chosen from: the radical O R45-C- - methyl, ethyl or hydrocarbon radicals C14-C22 - the hydrogen atom; - R44 is selected from: the radical O R47ùC - the hydrogen atom; R43, R45 and R47, which are identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon radicals and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl radicals.

Advantageously, the hydrocarbon radicals are linear.

There may be mentioned for example the compounds of formula (XXIV) such as the salts (especially chloride or methylsulfate) of diacyloxyethyl dimethyl ammonium, diacyloxyethyl hydroxyethyl methyl ammonium, monoacyloxyethyl dihydroxyethyl methyl ammonium, triacyloxyethyl methyl ammonium, monoacyloxyethyl hydroxyethyl dimethyl ammonium and their mixtures. The acyl radicals preferably have from 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm oil or sunflower oil. When the compound contains more than one acyl radical, the latter may be identical or different.

These products are obtained for example by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine optionally oxyalkylenated on fatty acids or mixtures of fatty acids of plant or animal origin or by transesterification of their esters methyl. This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulphate (methyl or preferably ethyl), methyl methanesulphonate, methyl paratoluenesulfonate, glycol or glycerol chlorohydrin.

Such compounds are, for example, sold under the names DEHYQUART by the company COGNIS, STEPANQUAT by the company STEPAN, NOXAMIUM by the company CECA, REWOQUAT WE 18 by the company DEGUSSA.

It is also possible to use the ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180.

Among the quaternary ammonium salts of formula (XXI), tetraalkylammonium chlorides, for example dialkyldimethylammonium or alkyltrimethylammonium chlorides, in which the alkyl radical contains approximately from 12 to 22 carbon atoms, are preferred. , in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, benzyl dimethylstearylammonium chlorides or, on the other hand, stearamidopropyldimethyl (myristylacetate) ammonium chloride sold under the name "Ceraphyl 70" by Van Dyk. The fatty acids are chosen more particularly from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.

The fatty acid derivatives are in particular the carboxylic acid esters, in particular the mono, di, tri or tetracarboxylic esters.

The monocarboxylic acid esters are in particular saturated or unsaturated, linear or branched C 1 -C 26 aliphatic acid monoesters and linear or branched C1-C26 aliphatic saturated or unsaturated aliphatic alcohols, the total carbon number of the esters. being greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabiethyl behenate; octyldodecyl behenate; isoketyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl ricinoleate acetyl; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl palmitates and isopropyl palmitate, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl and cetyl myristate; octyldodecyl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isostearyl neopentanoate, isodecyl neopentanoate.

It is also possible to use esters of C 4 -C 22 di or tricarboxylic acids and of C 1 -C 22 alcohols and esters of mono di or tricarboxylic acids and of C 2 -C 26 di, tri, tetra or pentahydroxy alcohols. .

These include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; dicaprylate propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate.

Among the esters mentioned above, it is preferred to use ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate and alkyl myristates such as isopropyl myristate. butyl, cetyl, 2-octyldodecyl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate, isostearyl neopentanoate, isodecyl neopentanoate.

The fluorinated oils are for example perfluoropolyethers described in particular in the patent application EP-A-486135 and the fluorohydrocarbon compounds described in particular in the patent application WO 93/11103. The teaching of these two applications is fully included in this application for reference.

The term fluorohydrocarbon compounds refers to compounds whose chemical structure includes a carbon skeleton some of whose hydrogen atoms have been substituted by fluorine atoms.

Fluorinated oils may also be fluorocarbons such as fluoroamines, for example perfluorotributylamine, fluorinated hydrocarbons, for example perfluorodecahydronaphthalene, fluoroesters and fluoroethers;

Perfluoropolyethers are for example sold under the trade names Fomblin by the company MONTEFLUOS and KRYTOX by the company DU PONT. Among the fluorohydrocarbon compounds, mention may also be made of fluorinated fatty acid esters such as the product sold under the name NOFABLE FO by the company Nippon Oil.

It is of course possible to use mixtures of conditioning agents.

According to the invention, the conditioning agent (s) may represent from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight and more particularly from 0.1% to 3% by weight relative to the weight. total of the final composition.

surfactants

The compositions of the invention may furthermore advantageously contain one or more surfactants other than the cationic surfactants already mentioned which are generally present in an amount of from about 0.1% to about 60% by weight, preferably from about 1% to about 1% by weight. 40% and even more preferentially between 5% and 30%, relative to the total weight of the composition.

This or these surfactants may be chosen from anionic, amphoteric, nonionic surfactants or mixtures

The surfactants that are suitable for carrying out the present invention are, in particular: (i) anionic surfactant (s): "Anionic surfactant" means a surfactant comprising as ionic or ionizable groups only anionic groups. These anionic groups are preferably selected from the groups CO2H, CO2-, SO3H, SO3-, OSO3H, OSO3-, O2PO2H, O2PO2H-, O2PO2-.

By way of examples of anionic surfactants that can be used in the composition according to the invention, mention may be made of alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkyl ketyl polyether sulphates, monoglyceride sulphates, alkyl sulphonates and alkyl amide sulphonates. alkylarylsulfonates, alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamide-sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, D-galactosideuronic acid salts, alkyl ether-carboxylic acid salts, alkyl aryl ether-carboxylic acid salts, acid salts alkyl amidoether carboxylic acids; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds having from 6 to 24 carbon atoms and the aryl group denoting a phenyl group. These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units. The salts of C 6 -C 24 alkyl monoesters and polyglycoside polycarboxylic acids may be chosen from C 6 -C 24 alkyl polyglycoside citrates, C 6 -C 24 alkyl polyglycoside tartrates and polyglycoside sulfosuccinates. C6-C24 alkyl. When the anionic surfactant (ii) is in salt form, it may be selected from alkali metal salts such as sodium or potassium salt and sodium salts, ammonium salts, amine salts and in particular aminoalcohols or salts of alkaline earth metals such as magnesium salt. As an example of aminoalcohol salts, mention may be made especially of the salts of mono-, di- and triethanolamine, the salts of mono-, di- or tri-isopropanolamine, the salts of 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, 3-propanediol and tris (hydroxymethyl) amino methane. The alkali metal or alkaline earth metal salts and in particular the sodium or magnesium salts are preferably used.

Among the anionic surfactants, it is preferred to use according to the invention the alkyl sulphate and alkyl ether sulfate salts and mixtures thereof.

(ii) Nonionic surfactant (s):

As nonionic surfactant (s) non-silicone (s) include the nonionic surfactants well known per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178). They may be chosen in particular from (non-limiting list) alcohols, alpha-diols, alkylphenols, these compounds being polyethoxylated, polypropoxylated or polyglycerolated and having a fatty chain containing for example 8 to 18 carbon atoms, the number of oxide groups ethylene or propylene oxide may range in particular from 2 to 50 and the number of glycerol groups may range from 2 to 30. Mention may also be made of copolymers of ethylene oxide and propylene oxide, the condensates of ethylene and propylene on fatty alcohols; the polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, the polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1.5 to 4; oxyethylenated sorbitan fatty acid esters having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkylglucosamine derivatives, amine oxides such as (C 10 -C 14) alkyl oxides, or N-acylaminopropylmorpholine oxides. According to one embodiment of the invention, the alkylpolyglycosides constitute nonionic surfactants useful in the context of the present invention.

(Iii) Amphoteric Surfactant (s):

The amphoteric or zwitterionic surfactant (s) that may be used in the present invention may be in particular derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms. carbon, said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may in particular be made of (C 8 -C 20) alkyls, sulphobetaines, (C 8 -C 20) alkylamido (C 3 -C 8 alkyl) betaines or (C 8 -C 20 alkyl) amido (C 8 -C 18 alkyl) alkylamines. C6-C8) Sulfobetaines With the following optionally used quaternized secondary or tertiary aliphatic amine derivatives, as defined above, there may also be mentioned the following compounds of structures (A1) and (A2):

Ra-CONHCH2CH2-N + (Rb) (Rc) (CH2OOO-) (A1) in which: Ra represents a C10-C30 alkyl or alkenyl group derived from an acid Ra -OOOH, preferably present in hydrolysed coconut oil heptyl, nonyl or undecyl, Rb is beta-hydroxyethyl, and Rc is carboxymethyl;

and Ra'-CONHCH2CH2-N (B) (B ') (A2) wherein: B represents -CH2CH2OX', B 'represents - (CH2), - Y', with z = 1 or 2, X 'represents the group -CH 2 -OOH, CH 2 -COO 2 ', -CH 2 CH 2 -OO OH, -CH 2 CH 2 -COO 2', or a hydrogen atom, Y 'represents -COOH, -COOZ', -CH 2 -CHOH-SO 3 H or -CH 2 -CH 2 CHOH-SO3Z ', Z' represents an ion derived from an alkaline or alkaline earth metal such as sodium, an ammonium ion or an ion derived from an organic amine. Ra, represents a C10-C30 alkyl or alkenyl group of an Ra, -COOH acid preferably present in coconut oil or hydrolyzed linseed oil, an alkyl group, especially C17, and its iso form an unsaturated C17 group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names cocoamphodiacetate disodium, lauroamphodiacetate disodium, caprylamphodiacetate disodium, capryloamphodiacetate disodium, cocoamphodipropionate disodium, lauroamphodipropionate disodium, caprylamphodipropionate disodium, 35 capryloamphodipropionate disodium , lauroamphodipropionic acid, cocoamphodipropionic acid. By way of example, mention may be made of cocoamphodiacetate marketed by Rhodia under the trade name MIRANOL® C2M concentrate. Among the amphoteric or zwitterionic surfactants mentioned above, C3-C20 alkyl betaines such as cocoylbetaine, (C3-C20alkyl) amido (C3-20alkyl) betaines such as cocoylamidopropylbetaine, and mixtures thereof. More preferably, the amphoteric or zwitterionic surfactants are chosen from cocoylamidopropylbetaine and cocoylbetaine.

In the compositions according to the invention, use is preferably made of surfactant mixtures and in particular mixtures of anionic surfactants and mixtures of anionic surfactants and amphoteric or nonionic surfactants. A particularly preferred mixture is a mixture of one or more anionic surfactants and one or more amphoteric surfactants.

Preferably, an anionic surfactant chosen from sodium (C12-C14) alkyl sulphates, triethanolamine or ammonium alkyls, (C2-C14) alkyl ethersulfates of sodium, triethanolamine or ammonium oxyethylenated with 2,2 moles of ethylene oxide, cocoyl isethionate sodium and alphaolefin (C14-C16) sodium sulfonate and mixtures thereof with: - either an amphoteric surfactant such as amine derivatives called disodiumcocoamphodipropionate or sodiumcocoamphopropionate sold in particular by the company RHODIA CHIMIE under the trade name "MIRANOL C2M CONC" in aqueous solution containing 38% of active ingredient or under the name MIRANOL C32; or an amphoteric surfactant of zwitterionic type, such as alkylbetaines, in particular cocobetaine sold under the name "Dehyton AB 30" in aqueous solution containing 32% of MA by Cognis.

The compositions according to the invention may be more particularly used for washing or treating keratinous fibers such as hair.

The compositions according to the invention can be shampoos. In this embodiment of the invention, the compositions comprise a washing base, which is generally aqueous. The surfactant or surfactants forming the washing base may be indifferently chosen, alone or in mixtures, from anionic, amphoteric and nonionic surfactants as defined above. The amount and quality of the washing base are those sufficient to provide the composition with satisfactory foaming and / or detergent power. Thus, according to the invention, the washing base can represent from 4% to 50% by weight, preferably from 6% to 35% by weight, and still more preferably from 8% to 25% by weight, of the total weight of the composition. Preferably, the washing base contains at least 3% by weight of anionic surfactant, more particularly from 4 to 40% by weight relative to the total weight of the composition.

PH modifying agents

The pH of the composition applied to the keratinous fibers generally varies from 1 to 11. It is preferably from 2 to 6, and may be adjusted to the desired value by means of acidifying or alkalizing agents well known to the patient. the technique of compositions applied to keratinous fibers. (1) Alkalizing agents

The alkalinizing agents are generally such that the pKb at 25 ° C. is less than 12, and preferably less than 10, more advantageously less than 6. It should be noted that it is the pKb corresponding to the basicity function. the highest.

The alkaline agent may be chosen from ammonia, mineral bases, organic amines, organic amine salts, alone or as a mixture. By way of example of an organic amine, mention may be made of organic amines comprising one or two primary, secondary or tertiary amine functions, and one or more linear or branched C 1 -C 8 alkyl groups carrying one or more radicals. hydroxyl.

In particular, the organic amines chosen from alkanolamines, such as mono-, di- or trialkanolamines, comprising one to three identical or different C 1 -C 4 hydroxyalkyl radicals are suitable in the embodiment of the invention.

Among compounds of this type, there may be mentioned monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1propanol, triisopropanolamine, 2-amino-2 methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylaminomethane.

Organic amines of the following formula are also suitable: wherein W is a C1-C6 alkylene radical optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; RX, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl radical.

Examples of such amines include 1,3-diaminopropane, 1,3-diaminopropanol, spermine and spermidine.

According to another variant of the invention, the organic amine is chosen from amino acids.

More particularly, the amino acids that can be used are of natural or synthetic origin, in their L, D, or racemic form, and comprise at least one acid function chosen more particularly from the carboxylic, sulphonic, phosphonic or phosphoric acid functions. Amino acids can be in neutral or ionic form. Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to the following formula (XXV): ## STR3 ## where R 54 denotes a group chosen from: (XXV) - (CH 2) 3 NH 2 - (CH 2) 2 NH 2 - (CH2) 2NHCONH2;

The compounds corresponding to formula (XXV) are histidine, lysine, arginine, ornithine, citrulline.

As amino acids that may be used in the present invention, there may be mentioned in particular aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

According to a preferred variant of the invention, the organic amine is chosen from basic amino acids. Particularly preferred amino acids are arginine, lysine, histidine, or mixtures thereof.

According to another variant of the invention, the organic amine is chosen from heterocyclic organic amines. In addition to the histidine already mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, 1,2,4-triazole, tetrazole and benzimidazole.

According to another variant of the invention, the organic amine is chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made in particular of carnosine, anserin and whale.

According to another variant of the invention, the organic amine is chosen from compounds comprising a guanidine function. As amino amines of this type which can be used in the present invention, mention may in addition be made of arginine already mentioned as amino acid, creatine, creatinine, 1,1-dimethylguanidine, 1,1 diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2 - ([amino (imino) methyl] amino) ethane-1 sulfonic.

Preferably, the organic amine is an alkanolamine. More preferably, the organic amine is selected from 2-amino-2-methyl-1-propanol, monoethanolamine or mixtures thereof. Even more preferentially, the organic amine is monoethanolamine.

The alkaline agent can be an organic amine in the form of salts. By organic amine salt is meant in the sense of the present invention, the organic or inorganic salts of an organic amine as described above.

Preferably, the organic salts are chosen from salts of organic acids such as citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates and tartrates.

Preferably, the inorganic salts are chosen from halohydrates (hydrochlorides for example), carbonates, hydrogenocarbonates, sulphates, hydrogen phosphates and phosphates.

By inorganic base, within the meaning of the present invention, is meant any compound having in its structure one or more elements of columns 1 to 13 of the periodic table of the elements other than hydrogen, not simultaneously comprising atom (s) of carbon and hydrogen.

According to a particular embodiment of the invention, the inorganic base contains one or more elements of columns 1 and 2 of the periodic table of elements other than hydrogen.

In a preferred variant, the inorganic base has the following structure: (Zix) m (Z 2 y +) n 40 in which Z 2 denotes a metal of columns 1 to 13 of the periodic table of the elements, preferably 1 or 2, such as sodium or potassium ; Z1X denotes an anion chosen from the ions CO32-, OH-, HCO32-, SiO32-, HPO42-, PO43-, B4O72-, preferably from the ions CO32-, OH-, SiO32-; 45 x is 1, 2 or 3; y is 1, 2, 3 or 4; m and n are independently of one another 1, 2, 3 or 4; with n.y = m.x.

Preferably, the inorganic base corresponds to the following formula (Z1X) m (Z2y +) n, in which Z2 denotes a metal of columns 1 and 2 of the periodic table of the elements; Z, X is an anion selected from CO32-, OH-, SiO32-, x is 1, y is 1 or 2, m and n are independently 1 or 2 with n.y = m.x.

As inorganic base usable according to the invention include sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, potassium metasilicate. Ammonium salts can also be used as the alkaline agent. The ammonium salts are preferably selected from the following acid salts: carbonate, bicarbonate.

(2) Acidifying agents

Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid citric acid, lactic acid, sulphonic acids.

GALENIC FORMS The compositions of the invention may be in the form of a shampoo, a conditioner to be rinsed or not; or in the form of a composition to be applied after coloring, discoloration, permanent or straightening or between the two stages of a perm or straightening.

The compositions according to the invention may also be in the form of aqueous or hydroalcoholic lotions for the care of the hair. The cosmetic compositions according to the invention may also be in the form of a gel, a milk, a cream, an emulsion or a mousse and may be used on the hair.

The compositions may be packaged in various forms, in particular in vaporizers, pump bottles or in aerosol containers in order to ensure application of the composition in vaporized form or in foam form. Such forms of packaging are indicated, for example, when it is desired to obtain a spray, a lacquer or a mousse for the treatment of the hair. 52 COLORING KERATIN FIBERS

According to a particular embodiment, the treatment method is applied to keratinous fibers, in particular hair dyed by direct dyeing or by oxidation dyeing.

Another object of the invention is the use of said method for protecting keratinous fibers against the action of atmospheric agents and in particular against the action of light. An object of the invention is the use of said method in post-treatment of oxidation dyeing or direct dyeing of keratin fibers and more particularly hair

Another subject of the invention relates to a process for dyeing keratinous fibers, in particular human hair, comprising at least the following steps a), b): a) direct dyeing or oxidation of said fibers b) applied on said fibers a composition comprising in a physiologically acceptable medium one or more s-trazine compounds of formula (I); the order of steps a) and b) being indifferent.

A particular method of staining the fibers comprises the following steps: 1) applying to said fibers a) a direct dyeing or oxidation composition (A) for a time sufficient to develop the color, 2) optionally, then performs a rinse and / or a shampoo wash and / or a partial or total drying of said fibers, 3) a composition (B) is applied comprising in a physiologically acceptable medium one or more s-trazine compounds of formula (I) 4) optionally, then rinsing and / or washing with shampoo and / or partial or total drying of said fibers is carried out. According to a first variant, a mixture of liquid water and water vapor can be additionally applied to the fibers. whose temperature is at least 35 ° C as previously described. This step can be performed after step 3 or after step 4.

According to a second variant, it is also possible to apply to the fibers a heating iron whose temperature is greater than or equal to 60 ° C. as described above. This step is carried out after the application of the dye composition (A) or the photoprotective composition (B).

A second particular method of staining the fibers comprises the following steps: (1) a composition (B) comprising, in a physiologically acceptable medium, one or more s-trazine compounds of formula (I) 2 is applied; rinsing and / or washing with shampoo and / or partial or total drying of said fibers, 4) applying to said fibers a) a direct dyeing or oxidation composition (A) for a sufficient time to develop the color, 5) optionally rinsing and / or washing with shampoo and / or partial or total drying of said fibers is carried out.

According to a first variant, it is possible to apply in addition to the fibers a mixture of liquid water and water vapor whose temperature is at least 35 ° C. This step can be performed after step 1 or after step 2.

According to a second variant, it is also possible to apply to the fibers a heating iron whose temperature is greater than or equal to 60 ° C. this step is performed after the application of the dye composition (A) or the photoprotective composition (B).

In the various modes of staining processes, the composition (B) comprising one or more s-trazine compounds of formula (I) may be applied immediately after staining or delayed. Delayed means an application that takes a few hours, a day or several days (from 1 to 60 days) after staining. Preferably, the composition (b) will be applied immediately after staining the keratinous fibers. In the case of direct lightening dyeing, the dyeing compositions (A) result from the mixing at the time of use of a dye composition containing one or more direct dyes and a composition containing one or more oxidizing agents. .

In the case of oxidation dyeings, the dyeing compositions (A) result from the mixing at the time of use of a dye composition (AI) containing one or more oxidation bases and optionally one or more couplers and / or a or more direct dyes and a composition (A2) containing one or more oxidizing agents.

The subject of the invention is also a multi-component coloring agent or kit comprising a first component comprising a direct-dyeing composition (A) and a second component comprising a composition (B) as defined above.

The subject of the invention is also a multi-component coloring agent or kit comprising a first component comprising a composition (AI) comprising one or more direct dyes, a second component comprising a composition (A2) containing one or more oxidizing agents and a third component comprising a composition (B) as defined above.

The subject of the invention is also a multi-component coloring agent or kit comprising a first component comprising a composition (AI) containing one or more oxidation dye precursors, a second component comprising a composition (A2) containing one or more oxidizing agents and a third component comprising a composition (B) as defined above.

Direct dyes

As regards the direct dyes, the latter are more particularly chosen from ionic or nonionic species, preferably cationic or nonionic species.

As examples of suitable direct dyes, mention may be made of azo direct dyes; methinic; carbonyls; azinic; nitro (hetero) aryl; tri- (hetero) aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

More particularly, the azo dyes comprise a function -N = N-whose two nitrogen atoms are not simultaneously engaged in a ring. However, it is not excluded that one of the two nitrogen atoms of the sequence -N = N- is engaged in a cycle.

The dyes of the family of methines are more particularly compounds comprising one or more sequences selected from> C = C <and -N = C <whose two atoms are not simultaneously engaged in a ring. It is however specified that one of the nitrogen or carbon atoms of the chains can be engaged in a cycle. More particularly, the dyes of this family are derived from methine, azomethine, mono- and di-arylmethane compounds, indoamines (or diphenylamines), indophenols, indoanilines, carbocyanines, azacabocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines, hemicyanines. As regards the dyes of the carbonyl family, mention may be made, for example, of the dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso) violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin.45 Concerning the dyes of the family of cyclic azines, mention may be made in particular of azine, xanthene, thioxanthene, fluorine, acridine, (di) oxazine, (di) thiazine, pyronine.

The nitro (hetero) aromatic dyes are more particularly nitrobenzene or nitro pyridinic direct dyes.

With regard to porphyrin or phthalocyanine dyes, it is possible to use cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for example alkali and alkaline earth metals, zinc and silicon.

By way of example of particularly suitable direct dyes, mention may be made of the nitro dyes of the benzene series; azo direct dyes; azomethines; methinic; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; direct azine dyes; xanthenics; triarylmethanics; indoamines; indigoids; phthalocyanines, porphyrins and natural direct dyes, alone or in mixtures.

These dyes may be monochromophoric dyes (that is to say comprising only one dye) or polychromophoric, preferably di- or tri-chromophoric dyes; the chromophores which may be identical or different, of the same chemical family or not. It should be noted that a polychromophoric dye comprises several radicals each derived from an absorbing molecule in the visible range between 400 and 800 nm. In addition, this absorbance of the dye does not require any prior oxidation thereof, or association with other (s) species (s) chemical (s).

In the case of polychromophoric dyes, the chromophores are connected to one another by means of one or more bonding arms which may or may not be cationic.

Among the benzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-R-hydroxyethylaminobenzene, 1- 2-amino-nitro-4-bis ((3-hydroxyethyl) -aminobenzene, -1,4-bis (R -hydroxyethylamino) -2-nitrobenzene, -1-R-hydroxyethylamino-2-nitro-4-bis- (R) hydroxyethylamino) -benzene, 1-R-hydroxyethylamino-2-nitro-4-aminobenzene, -1-R-hydroxyethylamino-2-nitro-4- (ethyl) (R-hydroxyethyl) -aminobenzene, -1-amino- 3-methyl-4-R-hydroxyethylamino-6-nitrobenzene, 1-amino-2-nitro-4-R-hydroxyethylamino-5-chlorobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2 R-hydroxyethylamino-5-nitrobenzene, 1,2-bis (R-hydroxyethylamino) -4-nitrobenzene, 1-amino-2-tris- (hydroxymethyl) methylamino-5-nitrobenzene, 2-amino-5-nitrobenzene, 1-hydroxy-2-amino-4-nitrobenzene, 1-hydroxy-3-nitro-4-aminobenzene, 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-13-hy droxyethyloxy-2-13-hydroxyethylamino-5-nitrobenzene, 1-methoxy-2-R-hydroxyethylamino-5-nitrobenzene, -1-3-hydroxyethyloxy-3-methylamino-4-nitrobenzene, -1-13-y-dihydroxypropyloxy 3-methylamino-4-nitrobenzene, 1-R-hydroxyethylamino-4- (3-yl) dihydroxypropyloxy-2-nitrobenzene, -1-3-y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, - 1-13 4-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene, -1-3-hydroxyethylamino-3-methyl-2-nitrobenzene, -1-3-aminoethylamino-5-methoxy-2-nitrobenzene, 1-hydroxy-2-chloro 6-ethylamino-4-nitrobenzene, 1-hydroxy-2-chloro-6-amino-4-nitrobenzene, 1-hydroxy-6-bis (R-hydroxyethyl) -amino-3-nitrobenzene, - 1-13 hydroxyethylamino-2-nitrobenzene, 1-hydroxy-4-13-hydroxyethylamino-3-nitrobenzene. Among the azo, azomethine, methine or tetraazapentamethine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851, FR-2140205, EP 1378544, EP 1674073. Among the following compounds may also be mentioned: CH 3 -CH 3 X-N = N N CH 3 N = N N-X-, N + CH 3

CH 3 N = N NH 2 X-CH 3 CH 3 N = N NH 2 X-NH H 3 C-NF 1) C = N N 'x C N N H CH 3 The following dyes, described in the COLOR INDEX, may also be mentioned among the azo direct dyes INTERNATIONAL 3rd Edition: - Disperse Red 17 - Basic Red 22 - Basic Red 76 - Basic Yellow 57 10 - Basic Brown 16 - Basic Brown 17 - Disperse Black 9. 1- (4'-Aminodiphenylazo) -2- methyl-4bis- (13-hydroxyethyl) aminobenzene. Among the quinone direct dyes, the following dyes may be mentioned: - Disperse Red 15 - Solvent Purple 13 - Disperse Violet 1 - Disperse Violet 4 20 - Disperse Blue 1 - Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Disperse Blue 7 25 - Basic Blue 22 - Disperse Violet 15 - Basic Blue 99 as well as the following compounds - 1-N-methylmorpholiniumpropylamino-4-hydroxy-anthraquinone 30 - 1-Aminopropylamino-4-methylaminoanthraquinone - 1-Aminopropylaminoanthraquinone - 5-13-hydroxyethyl-1 , 4-diaminoanthraquinone-2-aminoethylaminoanthraquinone-1,4-bis- ((3-yl-dihydroxypropylamino) -anthraquinone Among the azine dyes, the following compounds may be mentioned: - Basic Blue 17 - Basic Red 2. H3C N Among the triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds: Basic Green 1 - Basic Purple 3 - Basic Purple 14 - Basic Blue 7 - Basic Blue 26.

Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds: - 2-R-hydroxyethlyamino-5- [bis - ((3-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone - 2- R-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone-3-N (2'-chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1,4 benzoquinone imine-3-N (3'-chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine-3- [4'-N- (ethyl, carbamylmethyl) amino] phenyl-ureido-6-methyl-1,4-benzoquinone imine.

Among the tetraazapentamethine type dyes that may be used according to the invention, mention may be made of the following compounds appearing in the table below, An being defined as above: ## STR1 ## ## STR1 ## 1 N N N N N N N N N N N N N N N N N N N N N N N N N N X N N N N N N N N N N N N N N N 25 X N + 2 - N, N N is an anion preferably selected from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate.

Among the polychromophoric dyes, mention may be made more particularly of Patent Applications EP 1637566, EP 1619221, EP 1634926, EP 1619220, EP 1672033, EP 1671954, EP 1671955, EP 1679312, EP 1671951, EP167952, EP167971, WO 06 / 063866, WO 06/063867, WO 06/063868, WO 06/063869, EP 1408919, EP 1377264, EP 1377262, EP 1377261, EP 1377263, EP 1399425, EP 1399117, EP 1416909, EP 1399116, EP 1671560.

It is also possible to use the cationic direct dyes mentioned in applications EP 1006153, which describes dyes comprising two anthraquinone chromophores connected by means of a cationic linker; EP 1433472, EP 1433474, EP 1433471 and EP 1433473 which describe identical or different dichromophoric dyes, connected by a cationic or non-cationic linking arm, as well as EP 6291333 which describes in particular dyes comprising three chromophores, one of them being an anthraquinone chromophore to which are connected two azo-type chromophores or diazacarbocyanine or one of its isomers.

Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins, haematein, hematoxylin, brasiline, brasiline. It is also possible to use the extracts or decoctions containing these natural dyes, in particular poultices or extracts based on henna.

When present, the direct dye (s) more particularly represent from 0.0001 to 10% by weight, and preferably from 0.005 to 5 by weight of the total weight of composition A and / or of composition (AI).

Oxidation dyes

The oxidation dyes are generally chosen from oxidation bases optionally combined with one or more couplers.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N- bis- (R-hydroxyethyl) paraphenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (R-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N - (ethyl, R-hydroxyethyl) paraphenylenediamine, N - ((3, y-dihydroxypropyl) by aphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (R-methoxyethyl) paraphenylene diamine, 4- aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-hydroxy-3-hydroxyethyl paraphenylenediamine, 2-hydroxy-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6 ethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (R-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid are particularly preferred.

Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( R-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts.

Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-3-chlorophenol, 4-amino-3 are exemplified. -hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (3-hydroxyethyl) aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid.

Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 3,4-diamino pyridine, and their addition salts.

Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described, for example, in patent application FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 40 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2, 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, there may be mentioned the compounds described in DE 3843892, DE 4133957 and patent applications WO 94 / 08969,10 WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4 , 5-diamino-1-methylpyrazole, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5- hydrazino pyrazole, 1-benzyl 4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1- (13-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3- methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (13-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. It is also possible to use 4-5-diamino-1- (13-methoxyethyl) pyrazole.

As a heterocyclic base, mention may also be made of 2,3-diamino-6,7-dihydro-1H5H [pyrazolol, 2α] pyrazol-1-one or one of its salts. The dye compositions of the invention may optionally comprise one or more couplers advantageously chosen from those conventionally used for dyeing keratinous fibers.

Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 2,4-diamino-1- (R hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxy indole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (3-hydroxyethyl) amino -3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H 3 -methyl 40 pyrazole 5- one, 1-phenyl 3-methyl pyrazole 5-one, 2,6-dimethyl pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1,2,4-triazole, 6-methyl pyrazolo [1,5-a] benzimidazole, their addition salts with an acid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides and sulphates. citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base (s), if they are present, each advantageously represents from 0.0001 to 10% by weight, and preferably from 0.005 to 5% by weight relative to the total weight of the dye composition (A) or ( HAVE ).

The coupler (s), if present, are each preferably from 0.0001 to 10% by weight, and preferably from 0.005 to 50% by weight based on the total weight of the dye composition (A) or (HAVE).

The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preservatives, opacifying agents.

The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.

The oxidizing agent is preferably selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates, peracids and their salts. precursors and alkali metal or alkaline earth metal percarbonates. It is also possible to use one or more oxidation-reduction enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase) as oxidizing agent, if appropriate in the presence of their respective donor or cofactor.

This oxidizing agent is advantageously constituted by hydrogen peroxide and in particular in aqueous solution (hydrogen peroxide), the titre of which may vary, more particularly, from 1 to 40 volumes, and even more preferably from 5 to 40 volumes.

According to one particular embodiment of the invention, the method of the invention may be used on hair sensitized by hair treatments other than those of the invention mentioned above.

In a preferred variant of the invention, the process of the invention is carried out on keratin fibers artificially dyed by oxidation dyeing.

The invention will now be more fully illustrated by the following examples which can not be considered as limiting the described embodiments. In all that follows or the above, the percentages expressed are by weight. In the examples, MA means active ingredient.

EXAMPLES: The contents are expressed in grams of commercial product as is per 100 grams of compositions.

EXAMPLES 1- 2 - Shampooinqs: Ingredients Ex1 Ex2 (reference) (invention) Polydimethylsiloxane (BESIL DM 60000) 2.7 2.7 Carbopol 980 0.2 0.2 N-cocoylamidoethyl N-ethoxycarboxymethyl 8 8 sodium glycinate (MIRANOL C2M ) Glycol distearate (TEGIN BL 315) 2,5 2,5 2,4-bis (n-butyl 4'-aminobenzoate) -6- - 1 [(3- {1,3,3,3-tetramethyl) 1- [(trimethylsilyl) oxy] d-isiloxanyl} propyl) amino] -s-triazine Monoisopropanolamide of coconut acids 1 (EMPILAN CIS) Cetyl alcohol oxyethylenated (200E) 0.5 0.5 (PROCETYL AWS -LQ) Lauryl ether Sodium sulphate (20E) 22 22 (TEXAPON AOS 225 UP) Hydroxypoyl guar 0.2 0.2 trimethylammonium chloride (Jagaura C13-S) Preservatives 1.5 1.5 Perfume 0.5 0.5 pH agents qs qs Deionized water Qsp 100 Qsp 100 The introduction of the UV s-triazine siliconized filter of formula (I) in the composition of Example 2 of the invention has no influence on the pH and the viscosity of the shampoo and the formula obtained is stable. The cosmetic performance of Example 1 is similar to that of the filterless shampoo of Example 1.

At first, it is dyed using an oxidation dyeing process with MAJIREL 7.1 product of 90% Permanent White hair strands. Then 3 applications of Example 1 or of Example 2 are carried out.

The colored and treated wicks are then exposed to UV / visible in the visible half of their length for a period of 18H by a Xenon lamp solar simulator reproducing a reproducible light spectrum and close to that of the sun (Suntest XLS marketed by the Atlas company). The other half of the wick is obscured by card stock.

Color degradation after UV / visible exposure is visually assessed between masked and unmasked wicks. The photo-protective contribution of the treatment is evaluated with respect to an untreated colored wick having undergone the same UV / visible exposure. Spectro-colorimetric monitoring accompanies these assessments. Measurements are made using the MINOLTA CM2022 spectrocolorimeter, before and after UV / visible exposure.

The degradation caused by UV / visible radiation is expressed as AE: AE (exposed area - unexposed area) = - q (AL * 2 + Aa * 2 + Ob * 2). The results obtained are shown in the graph of FIG. 1.20. Examples 3 and 4: After-shampoo Ingredients Ex3 Ex4 (reference) (invention) Candelilla wax 0.3 0.3 Methylalkyl alkylmidoethyl 3,3-imidalinium methosulfate in solution in the propylene glycol (VARSOFT W575 PG) 2,4-bis (n-butyl 4'-aminobenzoate) -6- - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] d isiloxanyl} propyl) amino] -s-triazine oxyethylenated sorbitan monolaurate (20 0.3 0.3 0E) (TWEEN 20-LQ) C12-C15 alcohol benzoate 5 (TEGOSOFT TN) Stearyl alcohol (LANETTE 18) 2 2 Potato Starch Modified (STRUCTURE 3 3 SOLANACE) Behenyl Trimethylammonium Chloride 2 2 (GENAMIN KDMP) Isopropyl Myristate 0.8, 08 Preservatives 0.2 0.2 Perfume 0.4 0.4 pH Agents qs qs Water The introduction of the UV s-triazine siliconized filter of formula (I) in the composition of Example 4 of the invention has no influence on the pH and the viscosity of the shampoo and the fo obtained formula is stable. The cosmetic performance of Example 4 is similar to that of the filter-free reference shampoo (Example 3). Examples 5 and 6: After-shampoos Ingredients Ex5 Ex6 (reference) (invention) Polydimethylsiloxane with 2,6 2,6 groups aminoethyliminopropyl, with methoxy and / or hydroxy function and alpha, omega silanols in 60% cationic emulsion (DOW CORNING 2-8299 CATIONIC EMULSION) Myristate / Palmitate / Stearate 0.8 0.8 myristyl / cetyl / stearyl (CRODAMOL MS) -PA- (MH)) 2,4-bis (N-butyl 4'-aminobenzoate) -6- - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] d isiloxanyl} propyl) amino] -s-triazine Hydroxyethylcellulose (MW: 1,300,000) 0.3 0.3 (NATROSOL 250 HHR) Cetyl alcohol 3.7 3.7 Liquid jojoba wax 0.1 0.1 Chloride cetyl trimethylammonium 2.5 2.5 (DEHYQUART A OR) Myristic alcohol 0.4 0.4 1-hydroxypropylmethylammonium dipalmitoylethyl methosulfate / cetearyl alcohol (DEHYQUART F30) Behenyltrimethylammonium chloride ium 0.6 0.6 (GENAMIN KDMP) Preservatives 0.2 0.2 Perfume 0.4 0.4 pH agents qs qs Deionized water Qs 100 100 Qs 100 The introduction of the s-triazine UV silicic acid filter of formula I) in the composition of Example 6 of the invention has no influence on the pH and viscosity of the shampoo and the formula obtained is stable. The cosmetic performance of Example 6 is similar to that of the reference conditioner (Example 5) without filter. Examples 7 and 8: Care not rinsed Ingredients Ex7 Ex8 (reference) (invention) Shea butter 0.1 0.1 Polydimethylsiloxane with 1,5 1,5 aminoethyliminopropyl groups, with methoxy and / or hydroxy function and alpha, omega silanols 60% cationic emulsion (DOW CORNING 2-8299 CATIONIC EMULSION) Myristate / palmitate / 1 myristyl / cetyl / stearyl myristyl mixture (CRODAMOL MS-PA- (MH)) Cetearyl alcohol 5 5 2,4-bis (4) N-Butylaminobenzoate) -6- [1 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine Behenyl chloride trimethylammonium 1 1 (GENAMIN KDMP) Preservatives 0.5 0.5 Perfume 0.4 0.4 pH agents qs qs Deionized water Qs 100 Qs 100 10

The introduction of the UV s-triazine siliconized filter of formula (I) into the composition of Example 8 of the invention has no influence on the pH and the viscosity of the shampoo and the formula obtained is stable. The cosmetic performance of Example 8 is similar to that of Example 7 without a filter. 695

Claims (15)

REVENDICATIONS1. Process for the treatment of artificially dyed keratinous fibers by direct dyeing or by oxidation dyeing, in particular human hair, characterized in that it consists in applying to said keratin fibers a composition comprising in a physilogically acceptable medium one or more compounds silicon triazine substituted with at least two alkylaminobenzoate groups of the following formula (I) and its tautomeric forms: (D) - (Si1 10 (3-a) / 2 (1) (R) a in which - R, which are identical or different represent a C1-C2 alkyl radical, a phenyl radical, a C1-C2 alkoxy radical, a hydroxyl radical or the trimethylsilyloxy group; a = 1 to 3; the (D) group denotes an s-triazine compound of formula (II) wherein R ', which may be identical or different, represents a linear or branched and optionally unsaturated C 1 -C 10 alkyl radical which may contain a C 5 cycloalkyl group; -C6, - the group (C = O) OR1 which may be in the ortho, meta or para position of the amino group, R2, which may be identical or different, represent hydrogen, a hydroxyl radical, a linear or branched C1-C4 alkyl radical or a methoxy radical; A is a divalent radical selected from methylene or a group corresponding to one of the following formulas (III), (IV), (V) or (VI): ## STR2 ## Where Z is a C 1 -C 3 alkylene diradical; W represents a hydrogen atom, a hydroxyl radical or a C 1 -C 4 alkyl radical; C3; in addition to the units of the formula -Au (Si) (R) a (O) (3a), 2, the organosiloxane may comprise units of the formula: (R) b- (Si) (O) (4b), 2 in which R has the same meaning as in formula (I), b = 1, 2 or 3; 15 2. Process according to claim 1, wherein the s-triazine derivative (s) of formula (I) are chosen from those for which the following characteristics are fulfilled: R is methyl, a = 1 or 2, R 'is a radical in C1-C $, Z = -CH2-, W = H, the group (C = O) OR1 is in the para position of the amino group. 25 3. Process according to claim 1, wherein the s-triazine derivative (s) of formula (I) are chosen from those corresponding to one of the following formulas (la, (Ib) or (Ic): R7 RR 7 R7 ( (B) ù Sii O Sii O] [Sii O] Sii (B) R7 R7 (D) R7 7 7 RR] t R [7 (D) 30 u (D) -Si (R8) 3 in which: - ( D) corresponds to formula (II) as defined in claim 1; R7, which may be identical or different, are chosen from linear or branched C1-C20, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy alkyl radicals; the radical hydroxy, - R8, identical or different, are chosen from linear and branched C 1 -C 20 alkyl and alkenyl radicals, the hydroxyl or phenyl radicals, - (B), which are identical or different, are chosen from the R 7 radicals and the radical (D), r is an integer from 0 to 200 inclusive, - s is an integer from 0 to 50 and if s = 0, at least one of the two symbols (B) denotes (D), - u is an integer ranging from 1 to 10, - t is an integer from 0 to 10, with the proviso that t + u is equal to or greater than 3 and their tautomeric forms. 4. Process according to any one of claims 1 to 3, wherein the s-triazine derivative (s) of formula (I) are chosen from the following compounds or one of their tautomeric forms: ## STR2 ## (6) INP ~ si.o_si 5. Process according to any one of claims 1 to 4, wherein the s-triazine derivative of formula (I) is n-butyl 2,4-bis (4'-aminobenzoate) - [- 3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (5): ## STR2 ## 6. Method according to any one of claims 1 to 5, further comprising a step of applying to the keratin fibers a heating at a temperature greater than or equal to 60 ° C, preferably with a heating iron. 7. Method according to any one of claims 1 to 5, further comprising a step of applying to the keratinous fibers of a liquid water / steam mixture whose temperature is between 40 ° and 75 ° C. 20 8. Method according to any one of claims 1 to 7, wherein the composition comprises one or more additional photoprotective agents of keratinous fibers selected from organic UV filters, antiradical agents and antioxidants. 74 15 9. Process according to any one of claims 1 to 8, wherein the composition comprises one more one or more aromatic alcohols and / or one or more aromatic carboxylic acids. The method of any one of claims 1 to 9, wherein the composition further comprises one or more conditioning agents. 11. The method according to any one of claims 1 to 10, wherein the composition further comprises one or more surfactants chosen from anionic, amphoteric, nonionic surfactants or mixtures thereof. 12. Use of the method as defined in any one of claims 1 to 11 in post-treatment of oxidation dyeing or direct dyeing of keratinous fibers and more particularly hair 13. A process for dyeing keratinous fibers, in particular human hair, comprising at least the following steps a) and b): a) direct dyeing or oxidation of said fibers is carried out; b) a composition comprising in a physiologically acceptable medium one or more s-trazine compounds of formula (I) as defined in any one of claims 1 to 11; ; the order of steps a) and b) being indifferent. 14. A method of dyeing according to claim 13, comprising the following steps: 1) is applied to the keratin fibers a) a composition (A) direct dyeing or oxidation for a time sufficient to develop the color, 2) optionally, then performs a rinsing and / or a shampoo wash and / or a partial or total drying of said fibers, 3) a composition (B) is applied comprising in a physiologically acceptable medium one or more s-trazine compounds of formula (I) such as defined in any one of claims 1 to 11; 4) optionally, then rinsing and / or washing with shampoo and / or partial or total drying of said fibers is carried out; said method may further comprise, after step 3 or 4, the application to the fibers of a liquid water / steam mixture whose temperature is at least 35 ° C; said method may further comprise, after application of the dye composition (A) or the photoprotective composition (B), the application to the fibers of heating at a temperature greater than or equal to 60 ° C. 15. The method of dyeing according to claim 13, comprising the following steps: 1) a composition (B) is applied comprising in a physiologically acceptable medium one or more s-trazine compounds of formula (I) as defined in any one of claims 1 to 11; 2) optionally rinsing and / or washing with shampoo and / or partial or total drying of said fibers 4) applying to said fibers a) a direct dyeing or oxidation composition (A) for a time sufficient for developing the color; 5) optionally rinsing and / or washing with shampoo and / or partial or total drying of said fibers; said method may further comprise, after step 1 or 2, the application to the fibers of a liquid water / steam mixture whose temperature is at least 35 ° C; Said method may further comprise, after the application of the dye composition (A) or the photoprotective composition (B), the application to the fibers of heating at a temperature is greater than or equal to 60 ° C.