FR2959125A1 - Method for treating keratin fibers, preferably human hair, comprises applying, on the keratin fibers, an oil-in-water emulsion containing one or more water-soluble benzylidenecamphor UV filters in a medium - Google Patents

Abstract

Method for treating keratin fibers, preferably human hair, comprises applying, on the keratin fibers, an oil-in-water emulsion containing one or more water-soluble benzylidenecamphor UV filters in a medium. An independent claim is included for a method for dyeing keratin fibers, preferably human hair comprising: (a) direct dyeing or oxidation dyeing of the fibers; and (b) applying a water-in-oil emulsion, on the fibers, comprising one or more water-soluble benzylidenecamphor UV filter in a medium, the order of steps (a) and (b) being indifferent.

Description

The present invention relates to a process for the treatment of keratinous fibers, in particular human hair, which comprises the application on the skin of a keratinous fiber. said keratin fibers of a water-in-oil emulsion comprising in a cosmetically acceptable medium one or more water-soluble benzylidenecamphor filters.

The present invention also relates to the use of said method for protecting keratin fibers, in particular human hair, against the action of atmospheric agents and in particular against the action of light.

Another subject of the invention consists in the use, in post-treatment, of an oxidation dyeing or of a direct dyeing of keratin fibers and more particularly of hair of a composition as defined above.

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 process 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, as well as an iron heater whose temperature is greater than or equal to 60 ° C. EP1769788 also proposes a method for treating colored keratinous fibers by direct dyeing or by oxidation, which consists in applying to the fibers organic UV filters whose log P is less than or equal to 6, and a mixture liquid water / steam whose temperature is between 40 ° and 75 ° C.

In oil-in-water emulsion conditioners, the presence of organic filters can lead to problems in modifying the physicochemical properties of products such as pH and viscosity drops. Moreover, the addition of organic filters in these hair care products can modify the cosmetic properties on the heads conferring to them a more present coating and a weighting effect. In oil-in-water emulsions, the deposition of the organic filter is most often in competition with that of other active agents such as fats and silicones, which tends to reduce the efficacy of the photoprotective agent. There remains therefore the need to find new photoprotective formulations based on appropriate organic filters to protect artificially colored keratin fibers effectively without the disadvantages mentioned above.

The Applicant has now surprisingly discovered a novel process for treating keratinous fibers, in particular human hair, comprising the application to said keratinous fibers of a water-oil emulsion comprising in a cosmetically acceptable medium one or more water-soluble benzylidenecamphor filters.

In particular, this treatment method results in an improvement in the light resistance of the dyed hair dyed by direct dyeing or oxidation dyeing. All these discoveries are at 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 of a water-oil emulsion comprising in a cosmetically acceptable medium one or more water-soluble benzylidenecamphor UV filters.

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 steps a), b) and c): a) direct dyeing or oxidation of said fibers b is carried out a water-in-oil emulsion comprising, in a cosmetically acceptable medium, one or more water-soluble benzylidenecamphor filters 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. By "water-in-oil emulsion" is meant any composition comprising an aqueous phase dispersed in a continuous oily phase. And the term "water-soluble filter" means any UV radiation filtering agent capable of being soluble in its cosmetically acceptable salt form in an aqueous phase at greater than 5% by weight at 25 ° C. and at atmospheric pressure (760 mm). mercury).

CAMPHRE HYDROSOLUBLES BENZYLIDENE FILTERS

Among the water-soluble benzylidene camphor UV filters useful for the invention, mention may in particular be made of water-soluble ones of the following formula: Y in which Y and Y ', which may be identical or different, denote H or SO 3 H and the corresponding salts with organic bases or mineral; at least one of Y and Y 'denoting H; Z 'denotes the group -CH2R54, with R54 denoting -NR58R59R60, -SSO3Na or -COOR61; the group COOR61; R 58 and R 59, which may be identical or different, denote linear or branched C1-C20 alkyl, linear or branched C1-C18 hydroxyalkyl or they together form, with the nitrogen atom, a heterocycle, in particular morpholine, piperidine, pyrrolidine, piperazine N-methylpiperazine, N-phenylpiperazine; R60 denotes linear or branched C1-C4 alkyl or a linear or branched C1-C4 hydoxyalkyl radical; R61 denotes a hydrogen or a C1-C4 alkyl radical; the equilibrium of the molecule is ensured by either Y = Y '= SO3-, or by Y = Y' = hydrogen, or by an X- anion which can take the meanings of SO4-alkylC1-C4, -SO3aryl, -SO3alkyl or halogen .

Examples of C 1 -C 20 alkyl radicals are: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, Methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4 methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,2-dimethylbutyl, , 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, ndodecyl, n-tridecyl, n-tetradecyl , n-pentadecyl, n-hexadecyl, nheptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl.

The aryl groups are preferably chosen from phenyl, benzyl or naphthyl rings, which may comprise one or more substituents (preferably from 1 to 3) chosen, for example, from halogen such as chlorine, fluorine or bromine; cyano; nitro; amino; C1-C4-alkylamino; C1-C4 dialkylamino; C1-C4alkyl; C1-C4-alkoxy; hydroxy. Phenyl, benzyl is more particularly preferred.

These compounds are described in patent FR 2,383,904 (US 4421739).

Among these compounds, mention may be made of the following compounds: (2-oxo-2-bornylidene-methyl) -4-benzyl diethyl methyl ammonium p-toluene sulfonate; 2-oxo-2-bornborn-3-methyl-methyl benzyl diethyl methyl ammonium sulfonate; N - [(oxo-2-bornborn-3-methyl-methyl) -4-benzyl] -N-methyl morpholinium methylsulfonate; N - [(oxo-2-bornborn-3-methyl-methyl) -4-benzyl] -N-methyl morpholinium methylsulfate; N- [2- (oxo-2-bornborn-3-methyl) -4-benzyl] -N-piperidinium p-toluenesulfonate; N - [(oxo-2-bornborn-3-methyl-methyl) -4-benzyl] -N-methylpiperidinium methylsulfonate; 2- (4-oxo-2-bornylidene-methyl) -phenyltrimethylammonium methylsulphate or (4-trimethylammonio-3-benzylidene) camphoryl methyl sulphate. (4-Trimethylammonio-3-benzylidene) camphor methylsulphate of the following formula: INCI name: CAMPHOR BENZALKONIUM METHOSULFATE such as the commercial product MEXORYL SO manufactured by CHIMEX Company.

Among the water-soluble benzylidene camphor filters of the invention, mention may also be made of benzene 1,4-di (3-methylidene-10-camphosulphonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) and its various salts, described in particular in the patent applications FR-A-2528420 and FR-A-2639347. Such a UV filter is for example manufactured under the trade name MEXORYL SX by the company CHIMEX.

This filter has the following general formula (1): + F F + (1) in which F denotes a hydrogen atom, an alkali metal or an NH (R62) 3+ radical in which the radicals R62, which may be identical or different, denote a hydrogen atom, a C1-C4 alkyl or hydroxyalkyl radical or an Mn + / n group, Mn + denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn + preferably denoting a metal cation selected from Ca2 +, Zn2 +, Mg2 +, Ba2 +, Al3 + and Zr +. It is understood that the compounds of formula (1) above can give rise to the "cis-trans" isomer around one or more double bond (s) and that all the isomers fall within the scope of the present invention.

Mention may also be made of the α- (2-oxoborn-3-ylidene) toluene-4-sulphonic acid compound of the following formula: S 'and having the INCI name: Benzylidene Camphor Sulfonic Acid and manufactured under the trade name MEXORYL SL by the CHIMEX company.

The water-soluble benzylidene camphor filters in accordance with the invention are preferably present in the compositions in accordance with the invention at contents of from 0.01 to 20% by weight and more preferably from 0.1 to 10% and even more preferentially from 0.1 to 6% by weight relative to the total weight of the composition.

OIL PHASE

The emulsion of the invention contains an oily phase which comprises one or more liquid fatty bodies at a temperature of 25 ° C and at atmospheric pressure (760 mm Hg, ie 1.013 × 10 5 Pa).

For the purposes of the present invention, the term "fatty substance" means an organic compound which is insoluble in water at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa), that is, that is to say solubility of less than 4%, and preferably less than 1%, more preferably less than 0.1% by weight. They have in their structure at least one hydrocarbon chain containing at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, the fatty substances are soluble in organic solvents under the same conditions of temperature and pressure, such as chloroform, ethanol or benzene.

The fatty substances of the invention are not oxyalkylenated and preferably do not contain a carboxylic acid function COOH.

Preferably, the fatty substances of the invention are chosen from hydrocarbons, fatty alcohols, fatty esters, silicones and fatty ethers, or mixtures thereof.

The liquid fatty substances of the invention preferably have a viscosity less than or equal to 2 Pa.s, better still less than or equal to 1 Pa.s, and more preferably less than or equal to 0.1 Pa.s at the temperature of 25.degree. a shear rate of 1 s -1.

By liquid hydrocarbon is meant a hydrocarbon composed solely of carbon atoms and liquid hydrogen at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa).

More particularly, the liquid hydrocarbons are chosen from: linear or branched C6-C16 lower alkanes, which may be cyclic. By way of example, mention may be made of hexane, undecane, dodecane and tridecane, isoparaffins such as isohexadecane, isododecane and isodecane.

linear or branched hydrocarbons of animal or synthetic mineral origin of more than 16 carbon atoms, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, liquid petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane.

In a preferred variant the liquid hydrocarbon or hydrocarbons are chosen from paraffin oils, volatile or not, and their derivatives, vaseline oil. By liquid fatty alcohol is meant a non-glycerolated and non-oxyalkylenated fatty alcohol which is liquid at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa).

Preferably, the liquid fatty alcohols of the invention have from 8 to 30 carbon atoms.

The liquid fatty alcohols of the invention can be saturated or unsaturated.

Saturated liquid fatty alcohols are preferably branched. They may optionally comprise in their structure at least one aromatic cycle or not. They are preferably acyclic.

More particularly, the liquid saturated fatty alcohols of the invention are selected from octyldodecanol, isostearyl alcohol, 2-hexyldecanol. Particularly preferred are octyldodecanol. These liquid unsaturated fatty alcohols have at least one double or triple bond in their structure. Preferably, the fatty alcohols of the invention have in their structure one or more double bonds. When several double bonds are present, they are preferably 2 or 3 and may or may not be conjugated.

These unsaturated fatty alcohols can be linear or branched.

They may optionally comprise in their structure at least one aromatic ring or not. They are preferably acyclic.

More particularly, the liquid unsaturated fatty alcohols of the invention are chosen from oleic (or oleyl) alcohol, linoleic (or linoleyl) alcohol, linolenic (or linolenyl) alcohol and undecylenic alcohol. Oleyl alcohol is most preferred.

By liquid fatty esters is meant an ester derived from a fatty acid and / or a fatty alcohol and liquid at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa).

The esters are preferably the liquid esters of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono- or polyacids and linear or branched C 1 -C 26 saturated or unsaturated aliphatic or monohydric alcohols or alcohols, the total number of carbon atoms. esters being greater than or equal to 10.

Preferably for the monoalcohol esters at least one of the alcohol or the acid from which the esters of the invention are derived is branched.

Among monoesters of monoacids and monoalcohols, mention may be made of ethyl and isopropyl palmitates and alkyl myristates, such as isopropyl or ethyl myristate, isocetyl stearate or isononanoate. ethyl 2-hexyl, isodecyl neopentanoate, isostearyl neopentanoate.

It is also possible to use C 4 -C 22 di or tricarboxylic acid esters and C 1 -C 22 alcohols and esters of monocarboxylic or tricarboxylic acids and of C 4, tri, tetra or pentahydroxy unsubstituted alcohols. -C26.

These include: diethyl sebacate; diisopropyl sebacate, di (2-ethylhexyl) sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate di (2-ethylhexyl) adipate; diisostearyl adipate; di (2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate trisostearyl citrate trilactate glyceryl; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; Diethylene glycol diisononate. The composition may also comprise, as liquid fatty ester, esters and diesters of C 6 -C 30, preferably C 12 -C 22, fatty acid sugars. It is recalled that "sugar" is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Suitable sugars include, for example, sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives. especially alkylated, such as methylated derivatives such as methylglucose.

The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C 6 -C 30, preferably C 12 -C 22 fatty acids, linear or branched, saturated or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise.

The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof.

These esters may be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as in particular the mixed oleo-palmitate, oleostearate and palmito-stearate esters.

More particularly, mono- and di-esters are used, and in particular mono- or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose.

By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Finally, it is also possible to use natural or synthetic esters of mono, di or triacids with glycerol. Among these are vegetable oils.

As vegetable oils or synthetic triglycerides that can be used in the composition of the invention as liquid fatty esters, mention may be made, for example, of: triglyceride oils of vegetable or synthetic origin, such as liquid triglycerides, fatty acids containing from 6 to 30 carbon atoms, such as the triglycerides of heptanoic or octanoic acids or else, for example, sunflower, corn, soya, squash, grape seed, sesame or hazelnut oils, apricot, macadamia, arara, sunflower, castor oil, avocado, caprylic / capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the 25 35 names Miglyol® 810, 812 and 818 by Dynamit Nobel, jojoba oil, shea butter oil.

Esters according to the invention will preferably be used as liquid fatty esters derived from monoalcohols. Myristates or isopropyl palmitate are particularly preferred.

By liquid silicone is meant a liquid organopolysiloxane at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa).

Preferably, the silicone is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes comprising at least one aryl group.

These silicones can also be organomodified The organomodified silicones that can be used in accordance with the invention are liquid silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academie 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 even more particularly from: cyclic polydialkylsiloxanes containing from 3 to 7, preferably from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane sold under the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBONE ® 70045 V5 by RHODIA, the dodecamethylcyclopentasiloxane marketed under the name of SILSOFT 1217 by MOMENTIVE PERFORMANCE MATERIALS and their mixtures.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the VOLATILE® SILICONE FZ 3109 marketed by UNION CARBIDE, of the formula: ## STR1 ## The following may also be mentioned: (i) mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture octamethylcyclotetrasiloxane and oxy-1,1 '- (hexa-2,2,2', 2 ', 3,3'-trimethylsilyloxy) bis-neopentane (ii) linear volatile polydialkylsiloxanes having 2 to 9 carbon atoms; silicon 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, silicones entering this class. are also d written in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics" .. The viscosity of silicones is measured at 25 ° C according to ASTM 445 Appendix C.

Non-volatile polydialkylsiloxanes can also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBONE® oils of series 47 and 70,047 or MIRASIL® oils marketed by RHODIA, such as, for example, 70,047 V 500,000 oil; the oils of the MIRASIL® series marketed by RHODIA; the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm 2 / s; - 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 with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA. Among the silicones with aryl groups include polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes. By way of example, mention may be made of the products sold under the following names: SILBONE® oils of the 70 641 series from RHODIA; . RHODORSIL® 70 633 and 763 RHODIA series of oils; . DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING; . silicones of the PK series from BAYER, such as the product PK20; . some oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265.

Organomodified liquid silicones may in particular have polyethyleneoxy and / or polypropyleneoxy groups. The silicone KF-6017 proposed by SHIN ETSU and the oils SILWET® L 722, L 77 from UNION CARBIDE can thus be mentioned.

The liquid fatty ethers are chosen from liquid dialkyl ethers such as dicaprylyl ether.

The compositions of the invention may also comprise one or more non-liquid fatty substances at ambient temperature and at atmospheric pressure. By non-liquids is preferably meant a solid compound or a compound having a viscosity greater than 2 Pas at 25 ° C and a shear rate of 1 s -1.

More particularly, the non-liquid fatty substances are chosen from fatty alcohols, fatty acid esters and / or fatty alcohol esters, non-silicone waxes, silicones and fatty, non-liquid and preferably solid ethers.

The non-liquid fatty alcohols that are suitable for carrying out the invention are more particularly chosen from saturated or unsaturated alcohols, linear or branched, containing from 8 to 30 carbon atoms. For example, cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol) may be mentioned.

As regards the fatty acid esters and / or non-liquid fatty alcohols, mention may be made especially of solid esters derived from C 9 -C 26 fatty acids and from C 9 -C 26 fatty alcohols.

Among these esters, mention may be made of octyldodecyl behenate; isoketyl behenate; cetyl lactate; stearyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; myristyl stearate; octyl palmitate; octyl pelargonate; octyl stearate; alkyl myristates such as cetyl, mirystyl, stearyl myristate; hexyl stearate. Still in the context of this variant, 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 di, tri, alcohols. C2-C26 tetra or pentahydroxy.

These include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate; dioctyl maleate.

Of all the additional esters mentioned above, it is preferred to use myristyl, cetyl, stearyl palmitates, alkyl myristates such as cetyl myristate, myristyl stearyl myristate, etc.

The wax or waxes (non-silicone) are chosen in particular from carnauba wax, candelilla wax, and alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or the 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.

Non-liquid silicones according to the invention may be in the form of waxes, resins or gums.

Preferably, the non-liquid silicone is chosen from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly (oxyalkylene) groups, amino groups and alkoxy groups.

The silicone gums which can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes 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, tridecane or their mixtures.

Particularly useful products according to the invention are mixtures such as: - mixtures formed from an end-hydroxylated polydimethylsiloxane, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such as the product Q2 1401 marketed by Dow Corning; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from General Electric, this product is an 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 of 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 30 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 O 12, R 3 SiO 11 2, RSiO 3 12 and SiO 4 12 in which R represents an alkyl having 1 to 16 carbon atoms.

Among these products, those which are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl.

Among these resins may be mentioned the product marketed 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.

Among the additional organomodified silicones, mention may be made of polyorganosiloxanes comprising: substituted or unsubstituted amino groups, such as 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 WACKER company and under the name DC2-8299 by the company Dow Corning The substituted amino groups are in particular amino-C 1 -C 4 alkyl groups; alkoxylated groups, such as the product marketed under the name ABIL WAX® 2428, 2434 and 2440 by the company GOLDSCHMIDT.

The non-liquid fatty ethers are chosen from dialkyl ethers and in particular dicetyl ether and distearyl ether, alone or as a mixture.

Preferably, the liquid fatty substance is chosen from volatile silicones such as cyclopentasiloxane, cyclohexasiloxane, liquid modified polydimethylsiloxanes, mineral oils, organic or vegetable oils, alkanes and more particularly C5 to C10 alkanes; liquid fatty esters and more particularly liquid benzoates or salicylates of liquid fatty alcohol.

Even more preferentially, the liquid fatty substance is chosen; silicones such as volatile silicones; mineral oils; vegetable oils such as olive, castor oil, rapeseed, copra, wheat germ, sweet almond, avocado, macadamia, apricot, safflower, bancoulier nut, camellina, tamanu, lemon liquid esters of liquid C8-C20 fatty acids and C1-C20 alcohols such as isopropyl myristate, C10-C30 liquid fatty alcohols such as oleic alcohol, esters of liquid C9-C30 fatty alcohols such as C10-C30 fatty alcohol benzoates, isononyl isononanoate, isostearyl malate, tridecyl trimate and mixtures thereof; polybutene oil, liquid esters of polyols such as pentaerythrityl tetraisostearate.

According to a preferred embodiment, the organic solvent is constituted by a silicone or a mixture of silicones such as liquid polydimethylsiloxanes and liquid modified polydimethylsiloxanes, their viscosity at 25 ° C. is between 0.1 cst and 1,000,000cst and more preferably between 1 cst and 30 000cst.45 The liquid fat or fats are generally included in the emulsion in a proportion of 0.1 and 50% by weight of the emulsion; more preferably between 0.1% and 30% by weight of emulsion, especially between 5 and 25%.

SURFACE

In general, the water-in-oil emulsions according to the invention comprise one or more surfactants. The surfactant useful in the emulsion of the invention may be any surfactant known in the art to form water-in-oil emulsions. This surfactant can be amphosteric, anionic, cationic or nonionic.

(i) Non-silicone amphoteric surfactants The non-silicone amphoteric or zwitterionic surfactant or surfactants that may be used in the present invention may in particular be derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear chain or branched having from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate group, sulfonate, sulfate, phosphate or phosphonate. Mention may in particular be made of alkyl (C8-20) betaines, sulphobetaines, (C3-C20 alkyl) amido (C3-C8) alkylbenzines or (C3-C20alkyl) amido (C6-alkyl) C $) Sulfobetaines The following optionally substituted quaternized secondary or tertiary aliphatic amine derivatives, as defined above, may also be mentioned compounds of respective structures (A1) and (A2):

Ra-CONHCH2CH2-N + (Rb) (Rc) (CH2O0-) (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 -OOOH, -CH 2 CH 2 -COOZ', or a hydrogen atom, Y 'represents -COOH, -COOZ', -CH 2 -CHOH-SO 3 H or -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 an alkyl or alkenyl group in Cao-030 of an acid Ra, -COOH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, in particular C 17 and its iso form, unsaturated C17 group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names cocoamphodiacétate disodium, lauroamphodiacétate disodium, caprylamphodiacétate disodium, capryloamphodiacétate disodium, cocoamphodipropionate disodium, lauroamphodipropionate disodium, caprylamphodipropionate disodium, capryloamphodipropionate disodium, acid lauroamphodipropionic, 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, use is preferably made of (C 8 -C 20 alkyl) betaines such as cocoylbetaine, (C 8 -C 20 alkyl) amido (C 3 -C 8 alkyl) betaines such as cocoylamidopropylbetaine, and mixtures thereof. More preferably, the amphoteric or zwitterionic surfactant (s) are chosen from cocoylamidopropylbetaine and cocoylbetaine.

(ii) Non-silicone anionic surfactants

The term "anionic surfactant" is understood to mean a surfactant comprising as ionic or ionizable groups only anionic groups. These anionic groups are preferably chosen from the groups 002H, 002-, SO3H, SO3-, OSO3H, OSO3-, O2PO2H, O2PO2H-, O2PO22-.

By way of examples of non-silicone 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, alkylaryl polyether sulphates, monoglyceride sulphates, alkyl sulphonates and alkyl amide sulphonates. alkylarylsulfonates, alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, monoester salts alkyl and polyglycoside-polycarboxylic acids, acyllactylates, D-galactoside-uronic acid salts, alkyl ether-carboxylic acid salts, alkyl aryl ether carboxylic 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 of 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 can be selected from alkali metal salts such as sodium or potassium salt and preferably sodium salts, ammonium salts, amine salts and in particular aminoalcohols or alkaline earth metal salts such as magnesium salt.

By way of example of aminoalcohol salts, mention may be made in particular 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 their mixtures. (iii) Nonionic non-silicone surfactants

As surfactant (s) nonionic (s) non-silicone (s) include nonionic surfactants well known per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, editions Blackie & Son (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 comprising, 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-alkyl glucamine derivatives, amine oxides such as (C 10 -C 14) alkylamines, or N-acylaminopropylmorpholine oxides. According to one embodiment of the invention, the alkylpolyglycosides constitute nonionic surfactants useful in the context of the present invention. (Iv) Non-silicone cationic surfactants As non-silicone cationic surfactants, it is possible to use the surfactants which are well known per se, such as salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated, quaternary ammonium salts, and mixtures thereof.

The quaternary ammonium salts are, for example: those which have the following general formula (XXI): resetting numbering formulas to I? + R27. . Wherein R27 to R30 radicals, which may be the same or different, represent a linear or branched aliphatic radical having from 1 to 30 carbon atoms, or an aromatic radical such as 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, (C2-C6) alkyl sulphates, alkyl-or-alkylarylsulphonates, - quaternary ammonium salts of imidazolinium, for example that of formula ( XVI):

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 carbonyl radical, R 32 represents hydrogen atom, a C1-C4 alkyl radical or an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, R33 represents a C1-C4 alkyl radical, R34 represents a hydrogen atom or a C1-alkyl radical; -C4, X is an anion selected from the group of halides, phosphates, acetates, lactates, alkylsulfates, 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 X.- + X - 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 R16mNu (CH2) 3mN21R21 2X-R18 R2o (XXIII)

in which R 16 denotes an alkyl radical containing about 16 to 30 carbon atoms, optionally hydroxylated and / or interrupted by one or more oxygen atoms, R 17 is chosen from hydrogen or an alkyl radical containing from 1 to 4 carbon atoms or a group (R16a) (R17a) (R18a) N- (CH2) 3_, wherein R16a, R17a, R18a, R18, R19, R20 and R21, which may be identical or different, are chosen from hydrogen or an alkyl radical containing 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 one or more ester functions.

The quaternary ammonium salts containing one or more ester functional groups which can be used according to the invention are, for example, those of the following formula (XXIV) (CrH 2 R0): ## STR1 ## where R (C 2 H 2 0) x R X (XXIV) R41 wherein: - R41 is selected from C1-C6 alkyl radicals and C1-C6 hydroxyalkyl or dihydroxyalkyl radicals; - R42 is chosen from: the radical O R45ùC - R46 hydrocarbon radicals C1-022 linear or branched, saturated or unsaturated, - the hydrogen atom, - R44 is selected from the radical 0 II O R47ùC- - the radicals R48 saturated or unsaturated linear or branched C1-C6 hydrocarbon radicals, - the hydrogen atom, - R43, R45 and R47, which are identical or different, are chosen from linear or branched, saturated or branched C7-C21 hydrocarbon radicals; 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;

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 C11-C21 alkyl and alkenyl radicals, saturated 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. Anion X- 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, p and r are 2; - R42 is chosen from: the radical O R45ùC - methyl, ethyl or hydrocarbon radicals C14-C22 - the hydrogen atom; R44 is selected from: ## STR5 ## 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 one or more ester functional groups described in US-A-4874554 and US-A-4137180.

Of the quaternary ammonium salts of formula (XV), tetraalkylammonium chlorides, such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides, in which the alkyl radical has from about 12 to 22 carbon atoms, are preferred. carbon, 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.

Non-silicone surfactants are generally present in the emulsion of the present invention in proportions ranging from 0.1% to 30% by weight of active material; more preferably between 0.5% and 15% by weight of composition.

(v) Silicone Surfactants As surfactants that can be used in the present invention, mention may also be made of the silicone surfactants described in particular in the patent FR2818902. The silicone surfactants that can be used in the present invention are those that are well known to those skilled in the art. They can be water-soluble, spontaneously water-dispersible or non-water-soluble. Preferably, they are water-soluble or spontaneously water-dispersible.

The silicone surfactants are, for example, chosen from the compounds of the following general formulas: ## STR2 ## wherein R 1 is chosen from: ## STR1 ## ## STR2 ## IC H3 SiiO SiiR1 (II) CH3 n CH3

## STR5 ## wherein R 2 is CH 2 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 R 3 3 Si [O-Si (OC 2 H 4) a (OC 3 H 6) b OR 4 (IV) CH 3 CH 3 CH 3 CH 3 CH 3 SiO Si Si Si (VI) Wherein: R 1, which may be identical or different, represents a linear or branched C 1 -C 3 alkyl or phenyl group; R 2, which may be identical or different, represents -C 2 H 2 C -O- (C 2 H 4 O) a- (C 3 H 6 O) b -R 5 or -C 2 H 2 C-O- (4H 8 O) a-R 5; R 3 and R 4, which may be identical or different, each denote a linear or branched C 1 -C 12 alkyl group, and preferably a methyl group; R 5, which may be identical or different, is chosen from a hydrogen atom, a linear or branched alkyl group containing from 1 to 12 carbon atoms, and a linear or branched alkoxy group containing from 1 to 6 carbon atoms; , a linear or branched acyl group containing from 2 to 12 carbon atoms, a hydroxyl group, -SO 3 M, -OCOR 6, a C 1 -C 6 aminoalkoxy optionally substituted on the amine, a C 2 -C 6 aminoacyl optionally substituted on the amine, NHCH 2 CH 2 O00M, -N (CH 2 CH 2 O00M) 2, C 1 -C 12 aminoalkyl optionally substituted on the amine and on the alkyl chain, C 1 -C 30 carboxyacyl, a phosphono group optionally substituted with one or two C 1 -C 6 aminoalkyl groups; Substituted C12, -CO (CH2) d000M, -OCOCHR7 (CH2) d000M, -NHCO (CH2) dOH, -NH3Y25-M, identical or different, denotes a hydrogen atom, Na, K, Li, NH4 or a organic amine; R 6 denotes a linear or branched C 1 -C 30 alkyl group; R 7 denotes a hydrogen atom or an SO 3 M group; - from 1 to 10; 30 -m varies from 0 to 20; n varies from 0 to 500; p varies from 1 to 50; - from 10 to 20; - damage from 0 to 50; 35 to 50; - a + b is greater than or equal to 1; ## STR2 ## wherein R 1 is CH 3 R 5 w varies from 1 to 100; Y represents a monovalent inorganic or organic anion such as a halide (chloride, bromide), a sulfate, or a carboxylate (acetate, lactate, citrate). Silicone surfactants having the general formulas (IV) or (VII) as defined above, and more particularly those corresponding to formulas (IV) or (VII), in which at least one of the and preferably all of the following conditions are satisfied: -equal 2 or 3; - RI denotes the methyl group; - R5 represents a hydrogen atom, a methyl group or an acetyl group and preferably a hydrogen atom; a varies from 1 to 25 and more particularly from 2 to 25; B varies from 0 to 25, preferably from 10 to 20; - from 100 to 100; p varies from 1 to 20.

The most preferred silicone surfactants are, for example, those sold under the trade names FLUID DC 193 and DC 5225C by the company Dow Corning, SILWET® L 77 by the company OSI and MAZIL® 756 by the company MAZER PPG, the LAURYL PEG / PPG-18/18 METHICONE (and) POLOXAMER 407 (and) DODECENE sold by Dow Corning as DC 5200 Although any type of ionicity can be used for the emulsions of the present invention, active agents having a hydrophilic lipophilic balance (HLB) of less than 10 are preferred. In particular, the nonionic surfactants used in the compositions of the invention preferably have a HLB ranging from 1.5 to 10, and more preferably from 1.5 to 7. The HLB or hydrophilic-lipophilic balance of the surfactant (s) Nonionic compounds used according to the invention are HLB according to GRIFFIN defined in J. Soc. Cosm. Chem. 1954 (Volume 5), pages 249-256.

The surfactant or surfactants are generally present in an amount of from 0.01 to 30% by weight, preferably from 0.1 to 30% by weight, and more preferably from 0.2 to 15% by weight based on the weight. total emulsion

According to a preferred embodiment, the surfactant or surfactants present in the emulsion are chosen from silicone surfactants.

The silicone surfactants are generally present in the emulsion of the present invention in proportions ranging from 0.1% to 30% by weight of emulsion; preferably between 0.2% and 15% by weight AQUEOUS PHASE 45 The aqueous phase preferably constitutes at least 50% by weight of the total weight of the emulsion.

The aqueous phase is preferably constituted by water or a mixture of water and one or more cosmetically acceptable water-soluble organic solvents.

By water-soluble solvent is meant in the meaning of the invention, a solvent having a solubility in water of at least 4% in water and preferably at least 5% in water at ordinary temperature (25 ° C). C) and at atmospheric pressure (760 mm Hg, 1.013.105 Pa).

As water-soluble organic solvents, mention may be made, for example, of lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, glycerol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and mixtures thereof.

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

HEAT APPLICATION According to a 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 in practicing the present invention are flat or round irons disclosed in US Pat. Nos. 4,103,145, 4,308,878, 5,983,903, 5,957,140, 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 ranges from 60 to 120 ° C.

The application of iron can be done by successive separate keys of a few seconds, or by moving or sliding progressively 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 water-soluble benzylidene camphor filter (s) 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 keratinous fibers stained with a dryer before 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 liquid / water vapor mixture 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 contacted 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, and then the wicks thus impregnated are subjected to the action of the liquid water / steam mixture according to the conditions mentioned above, then the wicks 40 thus treated are cooled, for example, by sending a stream of cold air or air at ambient temperature over them or through them.

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, use is preferably made of an apparatus comprising one or more steam generators directly connected to a helmet diffusing on the keratin fibers, in particular human hair, the liquid water / steam mixture. As a type of apparatus, it will be used more particularly that sold under the name ®MICROMIST by TAKARA BELMONT.

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, surfactants and the like. nonionic, amphoteric or zwitterionic anionic active agents 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, penetrating agents, 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 in accordance with the invention containing the s-traine compound (s) of formula (I) may contain one or more other photoprotective agents chosen from organic UV screening agents, anti-radical 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 based on 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, fat-soluble camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; benzimidazole derivatives and mixtures thereof. Examples of organic UV filters include those referred to below under their INCI name:

Derivatives of para-aminobenzoic acid: 40 PABA Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 507" by ISP 45 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,

Salicylate derivatives: Ethylhexyl salicylate sold under the name "NEO HELIOPAN OS" by Haarmann and REIMER, 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: 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 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 BASF, 35 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, 40 Benzylidene camphor derivatives: 3-Benzylidene camphor manufactured under the name "MEXORYL SD" by CHIMEX, 4-Methylbenzylidene camphor sold under the name "EUSOLEX 6300" by MERCK, 45 Derivatives of phenyl benzimidazole:

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 liposoluble (or lipophilic) organic UV filters that are suitable for use in the present invention, mention may be made more particularly of: Ethylhexyl Methoxycinnamate Butyl Methoxydibenzoylmethane Ethylhexyl Salicylate, Benzophenone-3,4-Methylbenzylidene camphor, As water-soluble (or hydrophilic) organic UV filters Suitable for use in the present invention, there may be mentioned more particularly: PABA, PEG-25 PABA 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 0.5 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 further 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 several substituents of said one or more cycles. Preferably, the alcohol function will be on a substituent of a benzene or naphthalenic ring. Among the aromatic alcohols which may be used in the composition according to the invention, mention may be made in particular of benzyl alcohol, benzoyl isopropanol, benzyl glycol, phenoxyethanol, dichlorobenzyl alcohol, methylphenylbutanol, phenoxyisopropanol, phenylisohexanol and phenylpropanol. phenylethyl alcohol their mixtures.

Benzyl alcohol will be chosen more particularly.

According to the invention, the aromatic alcohol or alcohols 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 the total weight. of the composition. Preferably, they will be used at concentrations greater than 1% 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 rings or bonded to a ring. 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 salts. organic amines or ammonium.

Among the aromatic carboxylic acids that can 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, hippuric acid, 3-hydroxybenzoic acid and acid. 4-hydroxybenzoic acid phenylthioglycolic acid acetylsalicylic acid 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.

CONDITIONING AGENTS The compositions according to the invention may additionally contain one or more conditioning agents different from the fatty substances of the invention and the previously mentioned surfactants.

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 the softness, the disentangling, the touch, the smoothing, the 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 additional conditioning agents may be chosen from cationic polymers, the compounds ceramide type, non-salified fatty acids and their derivatives as well as mixtures of these various compounds. The preferred conditioning agents according to the invention are cationic polymers.

The cationic polymers which 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, 2470596 and 2519863. More generally, within the meaning of the present invention, the expression "cationic polymer" designates all polymer containing cationic groups and / or ionizable groups into cationic groups.

Preferred cationic polymers are selected from those containing units having primary, secondary, tertiary and / or quaternary amine groups that may either be part of the polymeric backbone or may be supported by a side substituent directly attached 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 the polyamine, polyaminoamide and quaternary polyammonium type polymers. These are known products.

Polymers of the polyamine, polyamidoamide or quaternary polyammonium type, usable 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 units: R 3 R 3 1 C C 0 C H 2 H 2 H 2 OH Di DI X-AA 4 1 N R1N + R6CR1R5R2 (IX), R3R1H1C1C1C1C1H2O1H2NH2NH2AAA4N R11N + R6R1R1 (R1) wherein R1 and R2 are 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 further contain one or more units derived from comonomers 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. (X) 3 (XII) 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 holognide such as that sold under the HERCOFLOC name by the company HERCULES, the copolymers of acrylamide and 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 methosulfate sold under the name RETEN by the company HERCULES, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers 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, a bis-alkyl halide, or by an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halogenide, epilhalohydrin, 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): / (CH 2) k - (CH 2) ## STR1 ## wherein 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: R13, R14, R15 and R16, which are identical or different, represent aliphatic, alicyclic, or arylaliphatic radicals containing 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, constitute heterocycles optionally containing a second heteroatom other than nitrogen, or R13, R14, R15 and R16 represent / (C \ k - ( CH2) t- - CR12 C (R12) -CH2 (X111) 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 polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more oxygen, 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;

A1, 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 alternatively 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 between 1000 and 100000.

Polymers of this type are described in French patents 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, 2,388,614 and 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.

It is more particularly possible to use polymers which consist of repeating units corresponding to the formula: R + R 3 -N (CH 2) n -N- (CH 2) p (a) R 2 X 'R 4 X'

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 ## Wherein R18, R19, R20 and R21, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, R-hydroxyethyl or R-hydroxypropyl radical, or CH 2 CH 2 (OCH 2 CH 2) pOH where p is 0 or an integer between 1 and 6, with the proviso that R 18, R 19, R 20 and R 21 are not simultaneously hydrogen, 20 r and s, which are identical or different , are integers between 1 and 6, q is 0 or an integer from 1 to 34, X- denotes an anion such as a halide, A 'denotes a radical of a dihalide or represents preferably -CH2-CH2-O-CH2-CH2-. Such compounds are described in particular in patent application EP-A-122 324. The products "Mirapol® A 15", "Mirapol® AD1", "Mirapol® AZ1" and "Mirapol® AZ1" may, for example, be mentioned among them. "Mirapol® 175" sold by the company Miranol. (9) Quaternary polymers of vinylpyrrolidone and vinylimidazole 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, especially cationic celluloses and cationic galactomannans. 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 proteins or hydrolysates of cationic proteins are in particular chemically modified polypeptides carrying at the end of the chain, or grafted onto it, 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, there may be mentioned in particular: 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 as "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: the "Croquat L" whose quaternary ammonium groups contain a C 12 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 proteins or quaternized 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 moiety. With 30 carbon atoms, R 26 represents an alkylene group having 1 to 6 carbon atoms, for example the products sold by Inolex under the name "Lexein QX 3000", referred to in the CTFA dictionary. "Cocotrimonium Collagent Hydrolysate".

Quaternized vegetable proteins such as wheat, corn or soya proteins may also be mentioned: as quaternized wheat proteins, mention may be made of those marketed by Croda under the names "Hydrotriticum WQ or QM", referred to in US Pat. CTFA dictionary "Cocodimonium Hydrolysed wheat protein", "Hydrotriticum QL" referred to 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 of these compounds.

It is of course possible to use mixtures of conditioning agents (s to be added in PR2010020).

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 total weight of the final 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 basifying agents which are well known in the art. state of the art of the 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.

As an 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 hydroxyl radicals.

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 particular for carrying out 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.

Also suitable are organic amines of the following formula: 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 origin or of synthesis, in their L, D, or racemic form, and comprise one or more acid functional groups chosen more particularly from 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): embedded image in which R 54 denotes a group chosen from: - (CH 2) 3 NH 2 - (CH 2) 2 NHCONH 2; - (CH2) 2NH2

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

As amino acids that may be used in the present invention, mention may in particular be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine and 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 be made, in particular, of pyridine, piperidine, imidazole, 1,2,4-triazole, tetrazole and benzimidazole.

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

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 organic acid salts 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 atoms (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 the elements other than hydrogen.

In a preferred variant the inorganic base has the following structure: (Z1 x-) m (Z2y +) n in which Z2 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-; x is 1, 2 or 3; 40 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; Z1x denotes 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.

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.

COLORING KERATIN FIBERS

According to one 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 water-in-oil emulsion comprising in one physiologically acceptable medium one or more water-soluble benzylidene camphor UV filters; ; 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 rinsing and / or shampooing and / or partial or total drying of said fibers, 3) applying a water-in-oil emulsion (B) comprising in a physiologically acceptable medium one or more UV filters benzylidene camphor water-soluble; 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 carried out 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) applying a water-in-oil emulsion (B) comprising in a physiologically acceptable medium one or more water-soluble benzylidene camphor UV filters; 2) optionally rinsing and / or washing with shampoo and / or partial or total drying of said fibers, 4) applying to said fibers a) a composition (A) direct dyeing or oxidation 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 carried out after the application of the dye composition (A) or the photoprotective composition (B).

In the various modes of coloring processes, the composition (B) can be applied immediately after coloring or in a delayed manner. 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.

The nature and concentration of the dyes present in the (A) coloring composition is not critical.

In the case of lightening direct dyes, the coloring compositions (A) result from the mixing at the moment of use of a dye composition (Al) containing one or more direct dyes and a composition (A2) 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 (Al) 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 (A1) 45 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 (A1) 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 With regard to direct dyes, the latter are more particularly chosen from ionic or nonionic species, preferably cationic or nonionic.

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 linking 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, 45-1-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, 1-hydroxy 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 hydroxyethyloxy-2-13-hydroxyethylamino-5-nitrobenzene, 1-methoxy-2-R-hydroxyethylamino-5-nitrobenzene, -1-3-hydroxyethyloxy-3-methylamino-4-nitrobenzene, -I-13, -y- dihydroxypropyloxy-3-methylamino-4-nitrobenzene, -1-R-hydroxyethylamino-4- (3, y-dihydroxypropyloxy-2-nitrobenzene, -1-3-yl dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, 1- 13-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, 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 N-CH 3 XH N = N N CH 3 1 N = N N 1 X-N + CH 3 CH 3 N = N NH 2 X The following dyes, described in COLOR INDEX INTERNATIONAL 3rd edition: - Disperse Red, may also be mentioned among the azo direct dyes; 17 - Basic Red 22 - Basic Red 76 - Basic Yellow 57 10 - Basic Brown 16 - Basic Brown 17 - Disperse Black 9. We can also mention 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 - Basic Blue 22 - Disperse Violet 15 - Basic Blue 99 as well as the following compounds: - 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone 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. OCH3 X- Among the triarylmethane dyes that can 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 ## 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 N N N N N N N N N N N N N N N N N N N N N N N N 2 - N, N N X 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 the composition (Al). .

Oxidation dyes The oxidation dyes are generally chosen from oxidation bases optionally combined with one or more couplers. For example, the oxidation bases are chosen from para-phenylenediamines and 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, N, N'-bis- (R-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N, may be mentioned by way of example. N, N'-bis- (R-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 the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (R) 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-diamino pyridine, 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 the 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-methoxypyrazolo [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-ylpyrazolo [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 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, , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5 diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 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-methylpyrazole, 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-meth 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-hydroxyindole, 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- (3-hydroxyethylamino) toluene, 6-hydroxy indoline, 2,6-dihydroxy-4-methyl pyridine, 1-H 3 -methyl 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, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base (s), if present, are each advantageously from 0.0001 to 10% by weight, and preferably from 0.005 to 50% by weight relative to the total weight of the dye composition (A). or (Al).

The coupler (s), if present, are each advantageously 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 (Al) .

The dyeing 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 and cationic polymers. nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickening agents, 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 nature of the oxidizing agent used in the direct lightening dyeing (direct dyeing with an oxidizing agent) or in the oxidation dyeing is not critical.

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 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 40 and in particular in aqueous solution (hydrogen peroxide) whose title 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 can be used on hair sensitized by hair treatments other than those of the invention mentioned above. In a preferred variant of the invention, the method 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 - Conditioners Ex1 Ex2 (Reference) (Invention) Camphor Benzalkonium Methosulfate - 3.3 30% aqueous solution (MEXORYL SO) Sucrose 15 PEG18 / POP18 Dimethicone (DOW CORNU, 5225C) Cyclopenta dimethylsiloxane (MIRASIL CM 5.5 5.5 BLUESTAR) Propylene glycol 5.5 5.5 Behenyl trimethylammonium chloride 3.5 3.5 Isopropyl myristate 2.1 2.1 Preservatives 0.4 0.4 Perfume 0.4 0 , 4 pH agents qs qs Deionized water qs 100 qs 100 Influence on pH and viscosity

The introduction of the water-soluble benzylidene camphor UV filter 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.

25 Filtration of the filter

The filter deposits were measured in vitro on moderately discolored strands of hair and the following values are obtained according to the filter level in the W / O emulsions: The values conventionally deposited with this filter by O / W emulsions are of the order of 1000 μg / g for a content of 1% active ingredient. Deposits are therefore increased in this type of care as indicated by the graph in Figure 1.

Photoprotective treatment after staining

At first, it is dyed using an oxidation dyeing process with MAJIREL 7.1 product of 90% Permanent White hair strands. 3 applications of Example 1 or of Example 2 are then carried out. 3 applications are also carried out with composition 3, after standard shampoo in the form of an oil-in-water emulsion. Ingredients Ex3 (reference) Amodimethicone 37 ( WACKER-BELSIL ADM LOG 1) Myristate / Palmitate / Stearate Blend 0 8 Myristyl / Cetyl / Stearyl (CRODAMOL MS-PA- (MH)) Hydroxyethyl Cellulose 0.25 (NATROSOL 250 HHR) Cetyl Alcohol 3.7 (LANETTE 16) Chloride of cetyltrimethylammonium (DEHYQUART A GOLD) Myristyl alcohol (LANETTE 14) 0.4 Dipalmitoylethylhydroxyethyl 1 methylammonium methoxy / cetearyl alcohol (DEHYQUART F3C Behenyltrimethylammonium chloride 0.6 (GENAMIN KDMP) Preservatives qs Perfume qs pH qs Water The colored and treated strands are then exposed to visible UV / visible light over half of their length for a period of 18 h by a Xenon lamp solar simulator reproducing a luminous spectrum. roductible and close to that of the sun (Suntest XLS marketed by the company Atlas). The other half of the wick is masked by card stock.

Color degradation after UV / visible exposure is visually assessed between masked and unmasked wicks. The photoprotective 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 evaluations. 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) = ~ (AL * 2 + Aa * 2 + Ob * 2). The results obtained are shown in the graph of FIG. 2. Examples 6-7: Conditioners Ingredients Ex6 Ex7 (reference) (invention) Terephthalylidene acid Dicamphre Sulfoniq - 0.5 to 33% in aqueous solution (MEXORYL SX CHIMEX) Sucrose 29 , 29.5 PEG18 / POP18 Dimethicone (DOW CORNU, 0.6 0.6 5225C) Palmityl amidoproi chloride 5.5 5.5 trimethylammonium 60% in propylene glycol (VARISOFT PATC) Dimethicone (viscosity 5 cst) 5.5 5.5 Isoparaffin (6-8 moles of 3,5 3,5 hydrogenated isobutyler (PARLEAM) Dyes 0,004 0,004 Preservatives 1,2 1,2 Perfume 0,4 0,4 pH agents qs qs Deionized water qs 100 qs 100 Influence on pH and viscosity

The introduction of the water-soluble benzylidene camphor UV filter in the composition of Example 7 of the invention has no influence on the pH and the viscosity of the shampoo and the formula obtained is stable. 10 20

Claims (17)

REVENDICATIONS1. Process for the treatment of keratinous fibers, in particular human hair, characterized in that it consists in applying to said keratin fibers an oil-in-water emulsion comprising in a physilogically acceptable medium one or more water-soluble benzylidenecamphor UV filters. 2. Process according to claim 1, wherein the water-soluble benzylidenecamphor UV filter is chosen from those corresponding to the following formula: in which Y and Y ', which may be identical or different, denote H or SO 3 H and the corresponding salts with organic or inorganic bases; at least one of Y and Y 'denoting H; Z 'denotes the group -CH2R54, with R54 denoting -NR58R59R60, -SSO3Na or -COOR61; the group COOR61; R58 and R59, which may be identical or different, denote C1-C20 linear or branched alkyl, linear or branched C1-C18 hydroxyalkyl or together they form with the nitrogen atom a heterocycle, in particular morpholine, piperidine, pyrrolidine, piperazine, N-methylpiperazine, N-phenylpiperazine; R 60 denotes linear or branched C 1 -C 4 alkyl or a linear or branched C 1 -C 4 hydoxyalkyl radical; R61 denotes a hydrogen or a C1-C4 alkyl radical; the equilibrium of the molecule is ensured by either Y = Y '= SO3-, or by Y = Y' = hydrogen, or by an X- anion which can take the meanings of SO4alkyl at C1-C4, -SO3aryl, -SO3alkyl or halogen. 3. The process as claimed in claim 2, in which the water-soluble benzylidenecamphor UV filter is (4-trimethylammonio-3-benzylidene) camphor methylsulfate of the following formula: The process according to claim 1, wherein the water-soluble benzylidenecamphor filter is selected from benzene 1,4-di (3-methylidene-10-camphosulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) - the acid α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid (INCI name: Benzylidene Camphor Sulfonic). 15 5. Method according to any one of claims 1 to 4, 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. 6. Method according to any one of claims 1 to 4, furthermore comprising a step of applying to the keratinous fibers a mixture of liquid water and water vapor whose temperature is between 40 ° and 75 ° C. . 7. Method according to any one of claims 1 to 6, wherein the composition comprises one or more photoprotective agents of additional keratin fibers chosen from organic UV screening agents other than those of the invention, anti-radical agents and agents. antioxidants. (claim to be repeated in this form in PR2010020) The process of any one of claims 1 to 7, wherein the composition comprises one or more aromatic alcohols and / or one or more aromatic carboxylic acids. 9. The method according to any one of claims 1 to 8, wherein the composition further comprises one or more conditioning agents other than the fatty substances of the emulsion, preferably selected from cationic polymers. 10. Process according to any one of claims 1 to 9, wherein the emulsion additionally comprises one or more surfactants chosen from anionic, cationic, amphoteric, nonionic surfactants or mixtures thereof. 11. Method according to any one of claims 1 to 10, the keratinous fibers being artificially dyed by direct dyeing or by oxidation dyeing, 12. Use of the method according to any one of claims 1 to 11 for the protection of keratin fibers against the action of atmospheric agents and in particular against the action of light. 13. 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 25. 14. 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) an emulsion (B) is applied to said fibers water-in-oil comprising in a physiologically acceptable medium one or more water-soluble benzylidene camphor UV filters as defined in any one of claims 1 to 10; the order of steps a) and b) being indifferent. 15. A dyeing method according to claim 14, comprising the following steps: 1) a direct dyeing or oxidation composition (A) is applied to the keratinous fibers a) for a time sufficient to develop the color, 2) optionally this is followed by rinsing and / or washing with shampoo and / or partial or total drying of said fibers, 3) applying a water-in-oil emulsion (B) comprising in a physiologically acceptable medium one or more benzylidene UV filters. water-soluble camphor as defined in any one of claims 1 to 4) optionally, followed by rinsing and / or washing with shampoo and / or partial or total drying of said fibers; said method may further comprise, after step 3 or 4, the application to the fibers of a mixture of liquid water and water vapor having a temperature of at least 35 ° C; further, after the 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. The staining method according to claim 14, comprising the steps of: 1) applying a water-in-oil emulsion (B) as defined in any one of claims 1 to 10; 2) optionally rinsing and / or washing with shampoo and / or partial or total drying of said fibers, 4) applying to said fibers a) a composition (A) direct dyeing or oxidation 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; 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 a heating at a temperature greater than or equal to 60 ° C. 17. Method or use according to any one of the preceding claims, characterized in that the coloring is an oxidation dye 25