FR2548018A1 - Composition intended for protecting the hair against ultraviolet radiation, and containing keratin derivatives possessing grafted ultraviolet-absorbing residues as active substances - Google Patents

Abstract

This composition intended for treating and protecting natural or sensitised hair against all photochemical degradation contains at least one keratin derivative which is chemically modified, where appropriate after hydrolysis, of molecular weight between 500 and 50,000 and corresponding to the general formula: Y = residue of a UV-absorbing molecule; P1, P2 = unmodified residues of the derivative; M<(+)> + H<(+)>, metal cation, N<(+))<R2)4; Q = residue of the amino acids of keratin; T = O, NH, S; Z = SO3<(-)>M<(+)>, residue obtained by N- or S-alkylation; q between 1 and 5.

Description

COMPOSITION INTENDED TO PROTECT THE HAIR AGAINST ULTRA-VIOLET RAYS AND CONTAINERS, AS SUBSTANCES
ACTIVE, CONTRIBUTING KERATINIC DERIVATIVES, IN GRAFTING,
REMAINS ABSORBERS OF ULTRA-VIOLETS.

The present invention relates to a composition for treating and protecting the hair against any photochemical degradation, and containing, for this purpose, keratin derivatives which have been chemically modified so as to exhibit ultra-radiation absorbing residues. -purple, which are grafted onto the keratin channels.

A large number of keratin hydrolysates are already known, which exhibit advantageous cosmetic properties for the treatment of the skin coating or of the hair. It is known, moreover, to graft onto synthetic polymer chains the remains of molecules having a filtering effect against ultraviolet radiation, these grafted synthetic polymers can be used to produce cosmetic compositions which filter out harmful solar radiation. the skin ; however, it has been observed that these polymers are generally not very soluble in the usual cosmetic solvents, that they form films whose texture is too rigid and that they often have a relatively low absorbing power for UV radiation, which means that they must be included. in high concentration in the compositions which contain them.

The applicant company has already proposed, in French patent application No. 82 14 480 filed on August 23, 1982, a chemically treated keratin hydrolyzate which can be used, simultaneously as a treatment product and as a skin protection product, against adverse effects of ultraviolet radiation. This product uses a natural polymetric channel as a support for the grafting of molecules filtering UV radiation Its use on the skin therefore leads to benefit both from the treatment effect due to the presence of keratin channels and from the protective effect à to the presence of the grafted molecules. In addition, the protective films which are formed on the skin have satisfactory flexibility, so that the use of compositions containing these products is more pleasant than that of sun protection compositions comprising synthetic polymers with filter grafts.

The applicant company has discovered that the keratin hydrolysates belonging to the general family of derivatives described in its aforementioned patent application as well as in its patent application filed on the same day as the present application and having the title "Protein derivative comprising, in grafting , ultraviolet absorbing residues, preparation process and composition containing it ", as well as your chemically modified keratins, even without having previously undergone hydrolysis, can be used to produce compositions applicable to natural or sensitized hair , in order to filter the solar radiation harmful to the latter, the filtering effect of these keratins being greater than that of the synthetic polymers which are already known for this application. The term "sensitized hair" is understood to mean hair which has undergone a perm treatment , staining or discoloration.

formule dans laquelle - Y est un reste d'une molécule absorbant le rayonnement ultra-violet;; - P1 et P2 sont des restes du dérivé kératinique non acylés et non modifiés chimiquement par addition ou substitution nucléophile 0représente H#. un cation dérivant d'un métal alcalin ou du magnésium ou N# (R2)4, formule dans laquelle les radicaux R2 sont identiques ou différents et représentent un atome d'hydrogène, un radical alkyle ou un radical hydroxyalkyle ayant au plus 4 atomes de carbone ; - Q est un reste alkyle, aryle ou aralkyle des amino-acides constitutifs de la kératine ; - T représente 0, NH ou S ; - Z est . un reste SO3#M#, le cation M# ayant la même signifi- cation que ci-dessus ;
. ou SR3, formule dans laquelle R3 représente ::

formules dans lesquelles p est un entier compris entre 0 et 5 (bornes incluses) ; R4 est un atome d'hydrogène ou un radical alkyle ayant au plus 4 atomes de carbone et R5 représente :

formules dans lesquelles D est un groupement alkylène linéaire ou ramifié comportant au total de 2 à 10 atomes de carbone, le cation M ayant la méme signification que cidessus, les radicaux R6 étant identiques ou différents et représentant un atome d'hydrogène, un radical alkyle ou hydroxyalkyle ayant au plus 4 atomes de carbone, E étant un ion halogénure, ou un ion carboxylate, sulfonate ou sulfate, dont le squelette carboné comporte jusqu'd 10 atomes de carbone
ou encore un reste aminé provenant d'un amanoac basique de la kératite mono- ou di- substitué par un reste R3, R3 ayant la même signification que ci-dessus - q est un nombre entier compris entre 1 et 5 (bornes incluses), sauf que, lorsque Z représente un reste So3#M#ou SR3, q est nécessairement égal à 1 - les motifs A représentant de 1 à 70 Z en poids du dérivé kératinique - les motifs B représentant de O à 15 % en poids du dérivé kératinique.The present invention therefore relates to a composition intended to treat and protect, vis-à-vis any photochemical degradation, natural or sensitized hair, characterized in that it continents in the presence of an appropriate support , an effective amount of at least one chemically modified keratin derivative having a molecular weight of between approximately 500 and 50,000 and corresponding to the following general formula

formula in which - Y is a residue of a molecule absorbing ultraviolet radiation ;; - P1 and P2 are residues of the keratin derivative which are not acylated and not chemically modified by addition or nucleophilic substitution O represents H #. a cation derived from an alkali metal or from magnesium or N # (R2) 4, formula in which the radicals R2 are identical or different and represent a hydrogen atom, an alkyl radical or a hydroxyalkyl radical having at most 4 atoms of carbon; - Q is an alkyl, aryl or aralkyl residue of the constituent amino acids of keratin; - T represents 0, NH or S; - Z is. a residue SO3 # M #, the cation M # having the same meaning as above;
. or SR3, formula where R3 is ::

formulas in which p is an integer between 0 and 5 (limits included); R4 is a hydrogen atom or an alkyl radical having at most 4 carbon atoms and R5 represents:

formulas in which D is a linear or branched alkylene group comprising in total from 2 to 10 carbon atoms, the cation M having the same meaning as above, the radicals R6 being identical or different and representing a hydrogen atom, an alkyl radical or hydroxyalkyl having at most 4 carbon atoms, E being a halide ion, or a carboxylate, sulfonate or sulfate ion, the carbon skeleton of which contains up to 10 carbon atoms
or an amino residue originating from a basic amanoac of keratitis mono- or di- substituted by a residue R3, R3 having the same meaning as above - q is an integer between 1 and 5 (limits included), except that, when Z represents a residue So3 # M # or SR3, q is necessarily equal to 1 - the A units representing from 1 to 70 Z by weight of the keratin derivative - the B units representing from 0 to 15% by weight of the derivative keratin.

The keratin from which the keratin derivative of formula (I) is prepared can come from different sources. Thus, the basic keratin can come from a material of animal origin taken from the group formed by hair, wool, horn, hair or bristles and feathers.

Furthermore, the keratin derivative can be a keratin hydrolyzate, which has been chemically modified by the grafting of the ultraviolet absorbing residues, after the hydrolysis which gave rise to it.

Preferably, the residue Y of the chemically modified keratin derivative of formula (I) belongs to the group consisting of the following radicals - a cinnamoyl residue optionally substituted by one or more lower alkoxy groups - a para-dialkylamino benzoyl residue - a salicyloyl residue - an acyl or sulfonyl residue originating from a carboxylic or sulfonic acid derived from benzylidene-camphor optionally substituted on the aromatic nucleus by one or more alkyl, lower alkoxy, sulfonic or by an alkenyl radical bearing one or more alkoxy radicals -carbonyl and / or optionally substituted on the carbon atom in position 10 of camphor by a sulfonic group - a sulfonyl residue originating from an optionally substituted iso- or t8rephthalylidene-camphor radical - an acyl or sulfonyl residue originating from a carboxylic or sulfonic acid, derivative of heterocyclic absorber belonging to the group formed by 2-arylbenzimidazoles, 2-aryl benzofurans, aryl-2benzoxazoles, aryl-2benzotriazoles and aryl-2 indoles - an acyl or sulphonyl residue originating from a carboxylic or sulphonated acid, derivative of an absorber belonging to the family of hydroxpbenzophenones; ; - an acyl residue derived from an absorber of coumarinic carboxylic structure optionally substituted by one or more lower alkyl or alkoxy radicals - an acyl residue derived from an absorber of mono or di-phenyl-cyano-acrylic structure, optionally substituted on the ( or the) aromatic nucleus (s) - an acyl or sulfonyl residue derived from an absorber of dbenzoylmethane structure optionally substituted by one or more hydroxyl, alkoxy or lower alkyl radicals.

It is especially preferred that the Y- group of the chemically modified keratin derivative belongs to the group consisting of the following radicals

It is also preferred for the chemically modified keratin derivative to have a molecular weight of between 5,000 and 30,000.

Likewise, when Z represents SR3, it is preferred that p is equal to O and that R4 is a hydrogen atom in formulas (II) and gV).

To prepare the chemically modified keratin derivatives of formula (I), the following procedure is carried out: - optionally, first, the starting keratin is subjected to an acid or enzymatic hydrolysis, so that the molecular weight of the hydrolyzate obtained or between approximately 500 and 50,000 - secondly, the grafting on the keratin molecule, optionally hydrolyzed, of absorbing residues of ultraviolet radiation is carried out, by reacting with all or part of the amino and alcohol groups or optionally hydrolyzed keratin thiol, one or more compounds corresponding to the following formula YX formula in which X represents a halogen atom and Y has the same meaning as above; - optionally, in the third place, and in the case where there are still amine functions available after the chemical grafting of the absorbing residues of ultraviolet radiation, an N-akoylation phase is carried out by means of an alkylating agent corresponding to to one of the following formulas:

formules dans lesquelles X1 représente un atome d'halogène, R4, R5 et p ont les significations données précédemment, et R7 désigne un atome d'hydrogèneouunradical alkyle inférieur comportant au plus 4 atomes de carbone - éventuellement, en quatrième lieu, ou bien, on oxyde tout ou partie des ponts disulfure des groupements cystine de la kératine ayant subi le (ou les) traitement(s) prEcédent(s3, de façon à obtenir des groupements acides-S03H, cette oxydation étant suivie ou non d'une salification des groupements acides S03H précites ; ou bien on réduit tout ou partie des ponts disulfure des groupements cystine de la kératine ayant subi le (ou les) traitement(s) précédent (s), de façon à obtenir des groupements thiol, cette réduction étant suivie d'une S-alcoylation au moyen d'un agent d'alcoylation répondant à l'une des formules (IIa), (IIIa), (IVa) et (IV'a) définies ci-dessus.

formulas in which X1 represents a halogen atom, R4, R5 and p have the meanings given previously, and R7 denotes a hydrogen atom or a lower alkyl radical comprising at most 4 carbon atoms - optionally, in the fourth place, or else, we oxidizes all or part of the disulfide bridges of the cystine groups of keratin having undergone the previous treatment (s) (s3, so as to obtain acid-SO3H groups, this oxidation being followed or not by a salification of the groups S03H acids mentioned above; or else all or part of the disulfide bridges of the cystine groups of keratin having undergone the previous treatment (s) are reduced, so as to obtain thiol groups, this reduction being followed by S-alkylation by means of an alkylating agent corresponding to one of the formulas (IIa), (IIIa), (IVa) and (IV'a) defined above.

The process for preparing the keratin derivative comprises successive phases, namely optionally a first phase of hydrolysis, a second phase of chemical grafting, optionally a third phase of N-alkylation, and, optionally, a fourth phase, either of oxidation, or S-alkylation on reduced-SH groups. Stick insects 2, 3 and 4 can be swapped.

The optional first phase of the preparation process can be a conventional acid hydrolysis or an enzymatic hydrolysis by means of known proteolytic enzymes (proteinase "PSF 2019" pronase, papain trypsins, etc.).

The operating conditions of the hydrolysis differ according to the enzyme used, with regard to the pH and the enzyme / substrate ratio.

The second phase of the preparation process consists in particular of an acylation which aims to graft onto the reactive amino, alcohol or thiol sites of the optionally hydrolyzed keratin acyl or sulfonyl residues originating from one or more molecules absorbing ultraviolet radiation. . The acylation is carried out in a conventional manner using a halide, in particular an acid chloride in an alkaline medium.

The optional third phase of the preparation process can consist of an N-alkylation carried out by means of an alkylating agent corresponding to one of the formulas (IIa) @ (IIIa), (IVa) or (IV'a) indicated. above. The N-alkylating agent used advantageously corresponds to the following formula
X1-CH2-CO2 # M #, X1 and M # having the meanings indicated above. The preferred N-alkylating agent is monochloroacetic acid,
The optional fourth phase of the process can consist either of an oxidation of the disulfide bonds of the cystine groups of the keratin, or again of an
S-alkylation of -SH groups obtained by prior reduction of the sulfide bridges of keratin with a solution of a reducing agent of conventional type such as, for example, an alkali metal thioglycolate or ammonium thioglycolate.

The oxidation of the keratin having undergone the previous treatment (s) allows, after having broken the disulfide bonds of the cystine groups of the keratin, to
convert them to acid groups ................................

cysteic. The oxidation is advantageously carried out in an acidic medium by means of an oxidizing agent, such as hydrogen peroxide or a peracid. The oxidation can between, optionally, followed by a salification of the -SO3H group.

The S-alkylation is carried out by means of an alkylating agent which corresponds to one of the formulas (IIa), (IIIa), Va) or V 'a) ndicated above, the preferred agents and the agent particularly preferred being those indicated in connection with N-alkylation.

The compounds of the invention filter solar radiation in a region of wavelengths which depends on the nature of the filter grafted onto the keratin derivative.

Thus, when Y- represents a cinnamoyl residue optionally substituted by one or more alkoxy group, a p-dialkylamino benzoyl residue, a salicyloyl residue, an acyl residue originating from a carboxylic or sulfonic acid derived from benzylidene-camphor, a sulfonyl residue originating from of an isophthalylidene-camphor radical, an acyl residue originating from a carboxylic or sulfonic acid derived from 2-arylbenzimidazoles, 2-arylbenzofurans, 2-arylbenzoxazoles, 2-arylbenzotriazoles, 2-arylindoles, hydroxybenzophenones or an acyl residue derived from an absorber of carboxylic coumarin structure, the compounds generally absorb in a region of wavelengths between 280 and 320 nm.

When Y- represents a sulfonyl residue originating from a terephthalylidene-camphor radical, an acyl residue originating from a carboxylic or sulfonic acid derived from aryl-2benzotriazoles, from hydroxybenzophenones or an acyl residue derived from an absorber of structure mono or diphenyl cyanoacrylic compounds generally absorb in a region of wavelengths between 320 and 380 run.

When Y- represents an acyl residue derived from a
dibenzoylmethane structure absorber possibly subs
tituated, the compounds generally absorb in an area of
wavelengths between 300 and 380 rm.

The compound (s) of formula (I) is (are) present in the composition according to the invention, preferably in proportions by weight of between 0 5 and 15 X relative to the total weight of the composition. Moreover, it (these) is (are) solubilized; in a solvent chosen from the group consisting of water, lower monoalcohols or polyols and hydro-alcoholic solutions. The more particularly preferred mono or polyalcohols are chosen from ethanol, isopropanol, propylene glycol or glycerin.

The compositions intended to protect and treat natural hair or hair sensitized vis-à-vis ultraviolet radiation which is the subject of the present invention can contain the adjuvants usually used in this type of compositions, such as more particularly
nonionic, anionic, cationic or
amphoteric well-known from the state of tecyhnique, oils or waxes
amimal, mineral, vegetable or synthetic, silicone derivatives,
fatty alcohols, anionic, cationic, non-ionic resins
ques or amphoteric usually used in cosmetics,
emulsifiers, sun filters compatible with
compounds of formula (I), organic solvents, thick
sizers, opacifiers, preservatives, sequestrants,
antioxidants, perfumes, pearlescent agents, dyes,
pH modifiers, reducing agents, electro
lytes, oxidants, natural substances, agents
antiseborrheics, anti-fatty agents, anti-peel agents
liculars, restructuring agents, substances
active agents that can have an effect on the treatment,
hair care or protection.

These compositions can in particular be used
read as shampoos, as coloring products, as rinse-off compositions to be applied before or after shampooing, before or after coloring or bleaching, before or after perm, as styling or restructuring lotion, as treatment lotion such as antiseborrheic, anti-dandruff, as lotion for brushing, as hairspray, as styling lotion, as perming compositions.

When the compositions constitute shampoos, the latter are essentially characterized in that they contain at least one anionic, nonionic or amphoteric surfactant or a mixture thereof, and a compound of formula in aqueous medium. These compositions can also contain different adjuvants -
------------ such as cationic surfactants, colorants in the case of coloring shampoos, preservatives, thickening agents, foam stabilizers, synergists, softening agents, sequestering, anionic, cationic, amphoteric or nonionic polymers, perfumes, protein derivatives, natural substances, oils as well as any other adjuvant used in a shampoo.In these shampoos, the detergent concentration is generally between 2 and 50% by weight.

Among the nonionic detergents, there may be mentioned in particular the condensation products of a mono-alcohol, of a + (- diol, of an alkylphenol, of an amide or of a diglycolamide with glycidol, such as for example nonionic surfactants, described in French patents 2,091,516, 2,328,763, 1,477,048; as well as alcohols, alkylphenols, or polyethoxylated or polyglycerolated fatty acids with fatty channels comprising from 8 to 18 carbon atoms most often containing 2 to 30 moles methylene dioxide, copolymers of ethylene and propylene oxides, o ~ gbs condensates of ethylene and propylene with fatty alcohols, polyethoxylds fatty amides, polyethoxyldes fatty amines , ethanolamides, fatty acid esters of glycol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkylethers of glycoside.

The anionic surfactants which can optionally be used as a mixture with the nonionic surfactants are chosen in particular from alkali metal salts, ammonium salts, amine salts or amino alcohol salts, following compounds: - alkylsulphates, alkyl ether sulphates, alkylamide sulphates and alkyllamido ether sulphates, alkylarylpolyethersulphates, monoglycerides sulphates, - alkylsulphonates, alkylamides sulphonates> alkylaryl sulphonates, succoslamide sulphonates, alcoylaryl sulphonates, succoslamid sulphonates, & alpha-alkyl sulphonates; - alkylsulfosuccinamatesf - alkylsulfoacetates, alkylpolyglycerol carboxylates, - alkylphosphates, alkyletherphosphates, - alkylsarcosinates, alkylpolypeptidates, alkylpolyglycerol carboxylates, - alkylphosphates, alkyletherphosphates, - alkylsarcosinates, alkylpolypeptidates, alkylpolypeptidates, alcoyl-tideptidates, - alcoylidopolypeptidates, allcoyltidate-alkylidates, - 18-carbon atoms, alkylidates, alcoyltidates, 12-alkylidates, alcoyltidates, 18-carbon atoms, alkyption fatty acids such as oleic, ricinole Ic, palmitic, stearic, acids of coconut oil, or of hydrogenated coconut oil, carboxylic acids of polyglycolic ethers of the formula
Alk - (OCH2 -CH2) n- OCH2 C CO2H where the Alk substituent corresponds to a linear chaste having from 12 to 18 carbon atoms and where n is an integer between 5 and 15. Any other anionic detergent can also be used not mentioned above well horned in the state of the art.

Among the amphoteric surfactants which can be used, there may be mentioned more particularly alkyl
amino, mono and dipropionate of betaines such as N-alkylbetarnes, N-alkylsulfobetaines, N-alkylamido betoins, cycloimidiniums such as alkyllimidazolines, asparagine derivatives. The alkyl group in these surfactants preferably contains at most 22 carbon atoms.

When the compositions according to the invention constitute leave-in lotions (styling lotions, for brushing, etc.), they generally comprise, in aqueous, alcoholic or hydroalcoholic solution, at least one cationic, anionic, nonionic, amphoteric polymer. or their mixture in amounts generally between 0.1 and 10% and, preferably, between 0.1 and 3% by weight.

When the compositions are rinsed out lotions, they are applied before or after coloring, before or after bleaching, before or after perm before or after shampooing or between two shampoo stages, then rinsed after an exposure time.

These compositions can be aqueous or hydroalcoholic solutions optionally comprising censio-active agents, emulsions or gels. These compositions can also be pressurized as an aerosol.

dans laquelle R8 désigne un radical aliphatique, cycloaliphatique ou arylaliphatique ayant 7 à 21 atomes de carbone et leurs mélanges, les channes aliphatiques pouvant comporter des groupements éthers, thioéthers et hydroxyméthylène et r designe une valeur statistique variant de 1 à 10 inclus ; des composés de formule

dans laquelle Rg désigne un radical alcoyle, alcényle ou alcoylaryle et s désigne une valeur statistique variant de 1 à 10 inclus ; des composés de formule :

dans laquelle R1G est un radical aliphatique pouvant comporter éventuellement un ou plusieurs groupements OH ayant de 8 à 30 atomes de carbone t représente un nombre entier ou décimal compris entre 1 et 5.The surfactants which can be used in the solutions are essentially nonionic or cationic surfactants of the type of those described above for shampoo compositions and in particular condensation products of a monoalcohol or a diol; ; of an alkylphenol, of an amide or of a diglycolamide with glycidol, such as, for example, compounds of formula

in which R8 denotes an aliphatic, cycloaliphatic or arylaliphatic radical having 7 to 21 carbon atoms and their mixtures, the aliphatic channels possibly comprising ethers, thioethers and hydroxymethylene groups and r denotes a statistical value varying from 1 to 10 inclusive; compounds of formula

in which Rg denotes an alkyl, alkenyl or alkylaryl radical and s denotes a statistical value varying from 1 to 10 inclusive; compounds of formula:

in which R1G is an aliphatic radical which may optionally contain one or more OH groups having from 8 to 30 carbon atoms; t represents an integer or decimal between 1 and 5.

It is also possible to use alcohols, alkylphenols, polyethoxylated or polyglycerolated fatty acids with a fatty channel having between 8 and 18 carbon atoms and most often comprising 2 to 15 moles of ethylene dioxide.

The concentration of surfactants can vary between 0.1 and 10% and, preferably, from 0.5 to 7% by weight.

Nonionic, cationic, anionic or amphoteric polymers and optionally anionic or amphoteric surfactants can be added to these compositions.

When the compositions are in the form of an emulsion, they can: be nonionic or anionic.

Nonionic emulsions consist mainly of a mixture of oils and / or fatty alcohols and polyethoxylated fatty alcohols such as stearyl or cetylstearyl alcohols polyethoxylated in the presence of water. Cationic surfactants or cationic polymers can be added to these compositions.

Anionic emulsions are formed from soaps and contain the compound (s) of formula (I) of anionic or nonionic nature.

When the compositions are in the form of gels, they contain thickeners in the presence or absence of solvents. The thickeners which can be used can be sodium alginate or acacia or cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose. It is thus also possible to obtain a thickening of the lotions by mixing polyethylene glycol and polyethylene glycol stearate or distearate or by a mixture of phosphoric esters and amides.

The concentration of thickeners can vary from 0.5 to 30% and, preferably, from 0.5 to 15% by weight.

In order to better understand the subject of the invention, several embodiments will be described below, by way of purely illustrative and non-limiting examples.

Example 1
Preparation of a hydrolyzate of formula (I), formula in which the level of units B is zero, the weight level of units A is about 40%, M represents H and the unit A has the formula

Q representing the alkyl, aryl or aryl groups of the amino acids of keratin and T representing NH or 0.

First step: Extraction of keratin from chicken feathers.

100 g of washed chicken feathers are introduced into a 4-liter reactor, 2.1 liters of dimethyl-formamide and 860 cm3 of water. The mixture is refluxed for 8 hours then filtered hot. The filtrate is diluted with 15 liters of water and the precipitate is isolated by filtration. The keratin thus obtained contains between 6o and 80% water.

Relative amino acid analysis reveals similar rates between untreated chicken feathers and extracted keratin. In both cases, the cystine level is close to 7% (between 6.5 and 7.5 depending on the starting material).

Second step: Enzymatic hydrolysis of keratin.

As starting material, a keratin obtained as indicated in the first step described above is used. A suspension of 5 kg of keratin at 30% by weight in 3.5 liters of deionized water is produced; this suspension is brought to 400C; the pH is brought to 8.6 by adding a 30% by weight aqueous sodium hydroxide solution.

48 g of "PSF 2019" proteinase are added all at once and the mixture is stirred for 3 hours at 400C + 1 "C while maintaining the pH at 3.4-8.6 by adding a 30% aqueous sodium hydroxide solution. by weight The pII of the solution obtained is then adjusted to 7.5 by adding concentrated hydrochloric acid and the enzyme is deactivated by heating at 950 ° C. for 5 minutes The mixture is rapidly cooled to room temperature, centrifuged, filter the supernatant liquid through celite and the solution is freeze-dried.

In this way 1375 g of a water-soluble beige powder is obtained. The yield is approximately 92%.

Third step: Grafting of a filtering effect molecule.

The following products - 110 g of hydrolyzed keratin obtained in the 2nd stage - 250 cm3 of water - 250 cm3 of acetone - 10 cm3 of a 30% by weight aqueous sodium hydroxide solution (the pH is thus brought to 9).

82 g (0.24 mol) of benzylidene-3-camphosulEonic acid-4 'acid chloride are then added in small amounts over 1 hour, the pH being maintained between 8.9 and 9.2. The reaction is complete after 6 hours of stirring. the pH of the solution is then brought to 2.5 by adding 30 cm3 of concentrated hydrochloric acid. After dilution in 2 liters of water, a gum is obtained, which is decanted and then taken up in 500 cm3 of water and triturated until complete crystallization. Filtered, re-paste in 500 cm of water, washed twice in a row in 400 cm of water, finely ground and dried by lyophilization after dissolution in water at pH 7.

95 g of a beige powder are thus obtained. The efficiency is around 60%,
Example 2
Preparation of a hydrolyzate of formula (I) containing 40% by weight of units A and 2.5% by weight of units
B, M representing H #, the unit A having the same formula as in example 1, the unit B comprising a group
Z of formula -SCH2COOH.

First step: Reduction of cystine to cysteine.

The product obtained at the end of Example 1 is used as the starting product. The following products are stirred for 20 hours at room temperature and under nitrogen: - 42 g of the product obtained in Example 1 - 210 cm3 of water - 3.1 cm of 95% by weight thioglycolic acid - sodium hydroxide in an amount sufficient to bring the pH to 9-9.5.

Second step: 5-carboxymethylation.

12.3 g of monochloracetic acid (0.13 mol) are added to the solution obtained at the end of the first stage of this example; the pH-a 9-9.5 is adjusted and the mixture is stirred for 2 hours at room temperature. It is then acidified to pH 2-2.5, diluted with water, the precipitate is filtered off, washed with water to pH 6, dissolved in water at pH 7 and lyophilized.

A beige powder is thus obtained. The yield is about 88%.

Example 3:
Preparation of a hydrolyzate of formula (I), comprising 39% by weight of units A, 3% by weight of units B, M 69 representing H #, A having the same meaning as in Example 1, B comprising a radical Z having the meaning

The solution obtained at the end of the first step of Example 2 is used as the starting product. To this quantity of solution 34.5 g (0.13 mol) of 1-dimethyl-ethylammonio-acrylamido-3 bromide are added. propane and stirred for 4 hours at room temperature and pH 9-9.5.

After acidification with a dilute hydrochloric acid solution, it is filtered, several successive washings are carried out, dissolved at pH 7 and lyophilized. 31 g of a beige powder are thus obtained. The yield is approximately 74%.

où Q représente les groupes acyle, aryle ou aralkyle des amino-acides de la kératine et T représente NR ou 0, M ayant la signification H ,le taux de motifs B étant nul.Example 4
Preparation of a hydrolyzate of formula (I) comprising 30% by weight of units A corresponding to formula

where Q represents the acyl, aryl or aralkyl groups of the amino acids of keratin and T represents NR or 0, M having the meaning H, the level of units B being zero.

The hydrolysate obtained at the end of the second stage of Example 1 is used as starting raw material.

The following products - 70 g of hydrolyzed keratin obtained at the end of the second stage of Example 1 - 175 cm3 of water - 175 cm3 of water are introduced into a 2 liter reactor thermostatically controlled at 200 ° C. + 0.2 ° C. Acetone - 5 cm3 of a 30% by weight aqueous sodium hydroxide solution - 54 g of 3-benzylidene-3-camphosulfonic acid chloride (0.16 mol).

After 2 hours of stirring, a precipitate of sodium 3-benzylidene camphosulphonate-10 appears, which is removed by filtration.

Filtra t is treated as in the third step of Example 1. 36 g of a beige powder are obtained. The yield is about 34%.

Example 5
Preparation of a hydrolyzate of formula (I) comprising 33% by weight of units A having the same formula as in Example 4 and 3.5% by weight of units B, the group Z appearing in the units B having the meaning - SCH2COOH, M representing H.

The following mixture is produced - 23 g of the product obtained at the end of Example 4 - 200 cm3 of water - 2.95 cm3 of thioglycolic acid at 95% by weight - aqueous sodium hydroxide solution at 30% by weight by weight sufficient amount to bring the pH to 9-9.5.

Stirred for 20 hours at room temperature and under nitrogen. Then 11.34 g (0.12 mol) of monochloroacetic acid are added and the pH is adjusted to 9-9.5 with an aqueous sodium hydroxide solution at 30% by weight. After 4 hours of stirring, a slight insoluble material is filtered off, the filtrate is acidified to pH 2-2.5; diluted with water; the precipitate is filtered off; washed with water to pH 6; it is dissolved in water at pH 7 and then lyophilized. 20 g of beige powder are thus obtained. The yield is about 87%.

formule dans laquelle Q représente les groupes alkyle, aryle, aralkyle des amino-acides de la kératine et T représente
NH ou 0, le taux de motifs B étant nul, M 9représentant H&commat;. Example 6:
Preparation of a hydrolyzate of formula (I) containing 14.5% of units A corresponding to formula

formula in which Q represents the alkyl, aryl, aralkyl groups of the amino acids of keratin and T represents
NH or 0, the level of units B being zero, M 9 representing H &commat;.

The following products are introduced into a 2-liter reactor thermostatically controlled at 10 + 0.2 C - 53 g of product obtained at the end of the second stage of Example 1 - 125 cm3 of water - 125 cm3 of acetone - 30% by weight aqueous sodium hydroxide solution in an amount sufficient to bring the pH to 9.

29 g (0.147 mol) of p-methoxycynnamic acid acid chloride are then added over 1 hour; the stirring and the temperature are maintained for 2 hours on the one hand and the pH at a value between 8.5 and 9 on the other hand.

It is then allowed to return to room temperature over 2 hours; acidification is carried out to pH 6 with a 6 times normal hydrochloric acid solution; the precipitate of p-methoxycynnamic acid formed is filtered off, washed twice with 200 cm 3 of water and the filtrate is acidified to pH 5.5. This is then extracted with three times 300 cm of ether and then precipitated by acidification to pH 2.5 with concentrated hydrochloric acid and then by dilution in 500 cm of water.

A gum is obtained and the gum is decanted and taken up in water; the precipitate obtained is filtered off and washed with water until pH 6. After grinding, dissolution in water at pH 7 and lyophilization, 25 g of a beige powder are obtained. The yield is 33%.

formule dans laquelle Q représente les groupes alkyle aryle, aralkyle des aminoacides de la kératine, T représente NH ou O, le taux de motifs B étant nul, M représentant H#. Example 7
Preparation of a hydrolyzate of formula (I) comprising 30% of units A, units A having the formula

formula in which Q represents the alkyl, aryl, aralkyl groups of the amino acids of keratin, T represents NH or O, the level of units B being zero, M representing H #.

The following products are introduced into a 2-liter reactor thermostatically controlled at 200C + 0.20C: - 50 g of hydrolyzed keratin obtained at the end of the second stage of Example 1 - 250 cm3 of water - 250 cm3 acetone - 30% by weight aqueous sodium hydroxide solution in sufficient quantity to bring the pH to 9
Over 4 hours, 45 g (0.128 mol) of p-terbutylphenyl-2-benzoxazole sulfonic acid-6 acid chloride are added and the mixture is stirred for 48 hours at 200C while maintaining the pH at 8.5-9. A slight insoluble matter is filtered off, acidified to pH 5.5 with a dilute hydrochloric acid solution, extracted with three times 250 cm3 of ether, acidified to pH 2 with semi-normal hydrochloric acid, diluted with 1 liter of water and the gum obtained is decanted.

The gum is then taken up in water; the precipitate obtained is filtered and washed with water until pH 6. After grinding, dissolution in water at pH 7 and lyophilization, 13 g of a beige powder are obtained. The yield is about 15%.

Table 1 gives a certain number of properties of the hydrolysates obtained in Examples 1 to 7.

TABLE I

<SEP>% <SEP> filter
<tb><SEP> Solubility <SEP> fixed <SEP>% <SEP> Amino
Examples <SEP> in <SEP> H2O <SEP> UV <SEP> H2O <SEP> determined <SEP> Material <SEP> acids
<tb><SEP> to <SEP> pH <SEP> 7 <SEP>#<SEP> max <SEP> * <SEP>% <SEP> filter <SEP> by free <SEP> protein <SEP>
<tb><SEP> (in <SEP> weight) <SEP> (nm) <SEP> E (1%) <SEP> fixed <SEP> hydrolysis
<tb><SEP> 1 <SEP>#<SEP> 20 <SEP>% <SEP> 300 <SEP> 225 <SEP> 30 <SEP>% <SEP> 40 <SEP>% <SEP> 41 <SEP> % <SEP> NO
<tb><SEP> 2 <SEP>#<SEP> 20 <SEP>% <SEP> 297 <SEP> 302 <SEP> 40 <SEP>% <SEP> 40 <SEP>% <SEP> 43 <SEP> % <SEP> NO
<tb><SEP> 3 <SEP>#<SEP> 20 <SEP>% <SEP> 300 <SEP> 308 <SEP> 41 <SEP>% <SEP> 39 <SEP>% <SEP> 38.5 <SEP>%<SEP> NO
<tb><SEP> 4 <SEP>#<SEP> 20 <SEP>% <SEP> 300 <SEP> 207 <SEP> 31 <SEP>% <SEP> 30 <SEP>% <SEP> 48.5 <SEP>%<SEP> 0.4 <SEP>%
<tb><SEP> 5 <SEP>#<SEP> 20 <SEP>% <SEP> 297 <SEP> 286 <SEP> 41 <SEP>% <SEP> 33 <SEP>% <SEP> 58.3 <SEP>%<SEP> NO
<tb><SEP> 6 <SEP>#<SEP> 20 <SEP>% <SEP> 310 <SEP> 215 <SEP> 15 <SEP>% <SEP> 14.5 <SEP>% <SEP> 76 <SEP>%<SEP> NO
<tb><SEP> 7 <SEP>#<SEP> 20 <SEP>% <SEP> 302 <SEP> 375 <SEP> 27 <SEP>% <SEP> 30 <SEP>% <SEP> 40.4 <SEP>%<SEP> NO
<tb> * E (1%) represents optical density, measured at wavelength
maximum absorption, for an aqueous solution containing 1% by
weight of filter material.

Example 8
A shampoo is prepared having the following formulation - Compound of Example 1 ........................ 1.2 g - Alkoyl (C12-C14) triethanolamine sulfate ..... 8.0 g - Cycloimidazolinic derivative of coconut oil,
sold under the name "MIRANOL C2M" by
The company "MIRANOL" ................................ 4.0 g - pH adjusted by HCl to 7.5
Water qsp 100 g
Applied to natural hair, this shampoo brings softness and shine to the hair.

Applied to dyed hair, it protects them from external atmospheric agents.

Example 9
A shampoo is prepared having the following formulation - Compound of Example 3 .................... 1.5 g - Nonionic surfactant of formula
R-CHOH-CH2-O- (CH2-CHOH-CH2-O) nH where R represents a mixture of C9-C12 alkyl radicals
and n represents an average statistical value
3.5 ......................................... 8 g - Lauryl diethanolamide ...................... 1.5 g - NaCl ...................... ................... 3.5 g - pH adjusted to 7.3 - Water ... qsp .............. ................. 100 g
Applied to dyed hair, this shampoo brings softness and disentangling and protects them from external atmospheric agents.

Example 10
A conditioner (rinse) is prepared having the following formulation - Compound of Example 5 .............................. . 1 g - Mixture of cetylstearyl alcohol and alcohol
oxyethylenated cetylstearyl with 1.5 moles of oxide
of ethylene sold under the name "SINNOWAX
AO. "By the company" HNKEL "................. 3 g - Mixture of fatty alcohols and oxyethylenated products
sold under the name "POLAWAX GP 200" by
the Company $ 'CRODA "............................ 1.5 g - Hydroxyethylcellulose sold under the name
"CELLOSIZE QP 4400" by the company "UNION CARBIDE" 0.5 g - pH adjusted to 7 - Demineralized water qsq ........................ 100 g
This composition is applied on
clean, damp hair for 5-10 minutes 2 la
hair is then rinsed. and dried. your hair
are brilliant.

Example 11
A styling lotion is prepared having the following formulation - Compound of Example 4 ..................... 0.8 g - Vinyipyrrolidone / acetate copolymer vinyl
(60/40) ........................................... 0, 5 g - Trimethyl cetyl ammonium eromide ............. 0.2 g - Water qsq ........................ ............... 100 g
This lotion is applied to clean hair. Dried hair is easily disentangled and
are protected from external atmospheric agents.

Claims (17)

1. Composition intended to treat and protect natural or sensitized hair, vis-à-vis any photo-chemical degradation, characterized in that it contains, in the presence of an appropriate support, an effective amount of least one chemically modified keratin derivative having a molecular weight of between approximately 500 and 50,000 and corresponding to the following formula:

formula in which - Y is a residue of a molecule absorbing ultraviolet radiation; - P1 and P2 are residues of the keratin derivative which are not acylated and not chemically modified by addition or nucleophilic substitution; - M # represents H # a cation derived from an alkali metal or magnesium or N # (R2) 4, formula in which the radicals R2 are identical or different and represent a hydrogen atom, an alkyl radical or a hydroxyalkyl radical having at plus 4 carbon atoms - Q is an alkyl, aryl or araikyl residue of the constituent amino acids of keratin; - T represents 0, NH or S; - Z is: . a residue SO3 # M #, the cation M # having the same meaning as above; or SR3, formula in which R3 represents:

formulas in which p is an integer between O and 5 (terminals included); R4 is a hydrogen atom or an alkyl radical having at most 4 carbon atoms and R5 represents:

keratin. - the units B representing from 0 to 15 7. by weight of the derivative keratin; - the units A representing from 1 to 70% by weight of the derivative SR3> q is necessarily equal to 1; having the same meaning as above - q is an integer between I and 5 (limits included), except that, when Z represents a remainder SO3 # M # or as mono- or di- keratin substituted with a residue R3, R3 or an amino residue from two basic audroacids has up to 10 carbon atoms ;; xylate, sulphonate or sulphate, of which the carbon skeleton of carbon, being a halide ion, or a carbon ion alkyl or hydroxyalkyl radical having at most 4 atoms or different and representing a hydrogen atom, a tion as above, the radicals R6 being identical linear or branched comprising a total of 2 to 10 carbon atoms, the cation M # having the same significance formulas in which D is an alkylene group 2. Composition according to Claim 1, characterized in that the keratin from which the keratin derivative of formula (I) is prepared is a keratin. from a material of animal origin taken from the group formed by hair, wool, horn, hair or silks and feathers. 3. Composition according to one of Claims 1 and 2, characterized in that the keratin derivative of formula (I) is a keratin hydrolyzate which has been modified. chemically after the hydrolysis that gave rise to it. 4. Composition .......... according to one of the returns dications 1 to 3, characterized by the fact that the remainder Y of the chemically modified keratin derivative of formula (I) belongs to the group consisting of the following radicals: - a cinnamoyl residue optionally substituted by one or more lower alkoxy groups - a paradialkylamino benzoyl residue - a salicyloyl residue - an acyl or sulfonyl residue originating from a carboxylic or sulfonic acid derived from benzylidene-camphor optionally substituted on the aromatic nucleus by one or more alkyl, lower alkoxy, sulfonic or by an alkenyl radical bearing one or more alkoxy-carbonyl residues and / or optionally substituted on the carbon atom in position 10 of camphor by a sulfonic group ;; - a sulfonyl residue originating from an optionally substituted iso- or tér8phthalyliddne-camphor radical - an acyl or sulfonyl residue originating from a carboxylic or sulfonic acid derived from a heterocyclic absorber belonging to the group formed by 2-arylbenzimidazoles, aryl -2 benzofurans, aryl-2 benzoxazoles, aryl benzotriazoles and aryl-2 indoles; an acyl or sulfonyl residue originating from a carboxylic or sulfonic acid derived from an absorber belonging to the family of hydroxybenzophenones; an acyl residue derived from an absorber of carboxylic coumarinic structure optionally substituted by one or more alkyl or lower alkoxy radicals; - an acyl residue derived from an absorber of mono or di-phenyl-cyano-acrylic structure, optionally substituted on the aromatic ring (s); - an acyl or sulfonyla drive residue of an absorber of dibenzoylmethane structure optionally substituted by one or more hydroxyl, alkoxy or lower alkyl radicals. 5. Composition according to Claim 4, characterized in that the Y- group of the chemically modified keratin derivative of formula (I) belongs to the group consisting of the following radicals

(with R = H, CH3, Cl or OCH3)

6. Composition according to one of claims 1 to 5, characterized in that the keratin derivative of formula (I) has a moldular weight of between S,000 and 30,000. 7. Composition according to one of claims 1 to 6, characterized in that, when the substituent Z of the chemically modified keratin derivative of formula (I) represents SR3, R3 corresponds to one of formulas (II) or (IV ), R4 is a hydrogen atom and p is 0. 8, Composition according to one of claims I to 7, characterized in that the keratin derivative (s) of formula (I) are present in proportions by weight of between 0.5 and 15% relative to the total weight of the composition. 9. Composition according to one of Claims 1 to 8, characterized in that the keratin derivative (s) of formula (I) is (or are) dissolved in a solvent chosen from the group constituted by water, monoalcohols or lower polyols and hydro-alcoholic solutions. 10. Composition according to one of claims 1 to 9, characterized in that it contains at least one adjuvant chosen from nonionic, am @@@ - ques, cationic or amphoteric surfactants, minimum luiles or cares , mineral, vegetal or synthetic, atltconé derivatives, fatty alcohols, anionic, cationic, nonionic or amphoteric resins, emulsifiers, sun filters compatible with the compounds of formula (I), organic solvents, thickeners , opacifiers, preservatives, sequestering agents, antioxidants, perfumes, pearlescent agents, colorants, pH modifying agents, reducing agents, electrolytes, oxidants, natural substances antiseborrheic agents, anti-fatty agents , anti-dandruff agents, restructuring agents. 11. Composition according to one of claims 1 to 10, characterized in that it is provided in solution in the form of a lotion, in an emulsion in the form of a cream, or of milk, in the form of a gel, or else is packaged in aerosol. 12. Composition according to one of claims 1 to 11, characterized in that it constitutes a shampoo and that it contains, in addition to the compound of formula (I), an anionic, nonionic or amphoteric surfactant in proportions of between 2 and 50% by weight. 13. Composition according to one of claims 1 to 11, characterized in that it constitutes a leave-in lotion and that it contains, in addition to the compound of formula (I) an anionic, nonionic, cationic or amphoteric polymer in proportions of between 0.1 and 10% and preferably between 0.1 and 3% by weight. 14. Composition according to one of claims 1 to 11> characterized in that it constitutes a rinse-off lotion and that it contains, in aqueous, alcoholic or hydroalcoholic solution, at least one compound of formula (I) and optionally from 0.1 to 10% by weight of nonionic or cationic surfactant. 15. Composition according to one of claims 1 to 11, characterized in that it constitutes a nonionic emulsion to be rinsed off and that it contains at least one compound of formula (I) in the presence of oils and / or d fatty alcohols and polyethoxylated fatty alcohols and water. 16. Composition according to one of claims 1 to 11, characterized in that it constitutes an anionic emulsion to be rinsed off and that it contains at least one compound of formula (I) and soaps. 17. Composition according to one of claims 1 to 11, characterized in that it constitutes a gel and that it contains at least one compound of formula (I) and 0.5 to 30% by weight of a thickening.