LU85047A1 - PROTEIN DERIVATIVE INCLUDING, IN GRAFTING, REMAINS OF COLORED MOLECULES, PREPARATION METHOD THEREOF AND COMPOSITIONS CONTAINING THE SAME - Google Patents

Description

* * 28.030 2.4781

Patent application \ no ^. ... - y ·. · 'De .i.4 .... octobF-e .-. L.-9- & 3 / Designation of the Inventor (1) The undersigned .... Maitr.e .... Alain ... BU .KAV! INA l .. lawyer., .... lla., ..... bo.ulev.ar.d .................

..J.as.eph ... XI ...................'................... .................................................. .................................................. .............................................

acting as depositor - agent of the depositor - (2) L.LQ.REAL .... S .-. A «.., .... 14., r.ue ... fio.ya.le , ..... 7.5QQ.8 P.ar.is, —irance ...............................

(3) of the invention concerning: "MrlY.é.s ... pr.o..t.é.i" lqu.e ..... QQ! Iap.Qx.t.axit. ".. ... ea .... gr.e £ lag.ö4 ..... des..xestes ..... de ..... $ .......

..molecules..coloured., ..... itsproceded ... preparation.at-ion ... and..cQmposit.ions ..le., .. c.Qnt.e.nan.t.!. '................................................. .................................................. ...................................-.............. ....................

designates as ifwestettRÎiÔx; fourth inventor: 1. Name and first names ..J.UNINO .... AXex ................................ .................................................. .............................................

Address 21 ·, —Fue ..du .Moulin .de -la .Vile -93600. .Aulnay, France -.................

2. Surname and first names ............................................. .................................................. .................................................. .......................

Address ................................................. .................................................. .................................................. .....................................

3. Surname and first names ............................................. .................................................. .................................................. .......................

Address ................................................. .................................................. .................................................. ........................................

He affirms the sincerity of the above indications and declares to assume full responsibility for them.

Luxembourg .............................—, on .... 2.6 .. QctQbr.e ...... ............................. 19 .... 83 .. · ............ ...................................

jy j (signature) A 68026 _! _ l_ Γ7: (1) Last name, first names, company, address.

(2) Last name, first names and address of the depositor.

'28.030 - 2.4781

‘’ ΪΓ7ΓΤ- GRAND-DUCHY OF LUXEMBOURG

Patent N · ß g QL 7 of _____14 nfttnhrii 1 QHj Dear Minister for the Economy and the Middle Classes

Title issued., Intellectual Property Service

““ LUXEMBOURG

Invention patent application 'Mcpmto ^ âMii'quahcàia mwriÂa ^ MàtwtAitudJ ^ {/ l .L * ..... company ..... anonymous ..... say ...... L'OREAL, ...... l ^ rue-Royale, ...... 75008 - (1) in Luxembourg, lia, boulevard Joseph II, acting as quality (2) ........... ..... .....................-, - λ., ·. ,, .____________________.___________ depositor) ce QiiAtQrKe ioctPbra 19QQqwatrx-yiijtt-tröi «__________ (3) at ........ lg e QQ heures, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent of invention concerning: .... .................................................. .................................................. .................................................. .................................................. ..... (4) "Protein derivative comprising, engraving, of" axBÂtaa ... de_ ........ molecule "colored with its process 4a preparation at compositions —the ..... content ± the. ^ ---------------------------------------------- ~ ---------------- 1 .1 ------------------------------ -------------------------- 2. the delegation of power, dated_________Parla________________________________ on ..... 10 ..... QCtPbr. a..JL9B 3 3. description in language_________fraPCaiM __________________ of the invention in two x copies; V * 4 ........... DD ............. drawing boards, in two copies; .

5. the receipt of the taxes paid to the Luxembourg Registration Office; on ..... 1.4 ..... octohr.e ..... 198.3 ............................ .................................................. .................................................. .................................................. ...

will declare) assuming responsibility for this declaration, that the inventor (s) are (are): ... MonsieurGérardLANG ....... 4.4 .. avanuaLacour, ...... 95210 Saint-Gratien ^ ) ... MonaleurSer.ge ..... FORESTIER ....... 14 + ..... Hameau ..... desLaur ± erat.7.74lQ..Glay.e- .. Souiily * Monsieur ..... GérardHALLE ....... 5 2, ...... avenue duParc, ....... 932.90 ______ th, j Tremblay ^ lee-Gonease ...... To. ua ..... the three ..... "nFrance ................................... .............: .------------ 1/7 & i / fJW7wC4 / vu claims (nt) for the above patent application the priority of one ( des) request (s) from Ût7yyi4ülÀ) .......................... DD .............. ............................................... filed (s) ) in (7) //, .......................................... .................................................. ....................

do ............................ U .................... .................................................. .................................................. .....................: ............................ .................................................. .......... (8) in nomrde ... .............. U ................. .................................................. ..........-....................................... .................................................. ............................................. (9) elects ( elect) for him (her) and, if appointed, for his representative, in Luxembourg_______________________________ "JUrlU ..... boulevard Joseph II ...................... .................................................. .................................................. ....................................... (io) request) the grant of a patent of invention for the object described and represented in. above-mentioned annexes, - with postponement of this issue to ................ eighteen ........... months. (11): The ..... agent ......... 0 ....................

w ff H. Deposit Report

The above patent application has been filed with the Ministry of the Economy and the Middle Classes, Intellectual Property Service in Luxembourg, on:

14 octobjTa lQflT

.

/ Pr. The Minister at 3 p.m. {Êf '·· tr \ de l'Economie et fles Moyen Classes, fil} p "'%! ^! W“ · / A /

2.478I

I _ r Λ.

’^ Ί DESCRIPTIVE MEMORY filed in support of an INVENTION PATENT application in the Grand Duchy of LUXEMBOURG in the name of L'OREAL S.A.

for: "Protein derivative comprising, in grafting, remains of colored molecules, its preparation process - and compositions containing it".

m _ U / fS / ir PROTEIN DERIVATIVE COMPRISING, IN GRAFTING, REMAINS OF COLORED MOLECULES, PREPARATION METHOD THEREOF AND COMPOSITIONS CONTAINING THE SAME.

4 "

The present invention relates to a protein derivative which has been chemically modified so as to present residues of colored molecules, which are grafted? on the protein chain. The invention also relates to a process for the preparation of this protein derivative and to coloring compositions which contain this protein derivative only as active substance and which are intended either for coloring keratinous supports, such as keratin fibers and especially human hair, or to be applied to the skin covering.

The term "colored molecules" is understood here to mean molecules carrying chromophoric or chromogenic groups.

A large number of protein hydrolysates are already known, which have advantageous properties in cosmetics for the treatment of the skin covering or the hair. We also know how to graft on chains this synthetic polymers the remains of colored molecules; these grafted synthetic polymers can be used to make coloring compositions; however, it has been found that these polymers are generally sparingly soluble in conventional cosmetic solvents and that they form films whose texture is too rigid.

The present invention aims to provide a protein derivative chemically treated and usable simultaneously as a treatment product and coloring product. The product according to the invention uses a natural polymer chain as a support for the grafting of rearing relecuks; its use on the skin and the hair therefore leads to benefit both from the treatment effect due to the presence of the protein chains and from the coloring effect due to the presence of the grafted molecules. In addition, it is found that the 2 ί ί satisfactory, so that the use of the compositions containing the products of the invention is more pleasant than that of the compositions comprising synthetic polymers with color grafts.

Furthermore, it has been found that, compared with colored synthetic polymers, the protein derivatives according to the invention are more soluble in the usual cosmetic solvents, and, in particular, in water. Furthermore, it is estimated that in the non-aqueous medium where the colored proteins are dispersed, these, after application to the skin, form a protective film having a satisfactory and better flexibility than that provided by known synthetic polymers.

The subject of the present invention is therefore a chemically modified protein derivative, characterized in that it has a molecular weight of between approximately 500 and 50,000 and that it corresponds to the following general formula: 0 0

Il - r ~ li —j P) @ 20 I 1 I J. ^ 2 f P Wq

I T-X-Y Z

25 A B

formula in which î - Y is a residue of a colored molecule; - X is a group ensuring the chemical bond between the colored molecule and the protein derivative, or else represents a direct covalent bond; ^ and P2 are non-acylated protein residues which are not chemically modified by nucleophilic addition or substitution; 35 - M® represents H®, a cation derived from an λ ix 3 alkali metal or magnesium, or else N® formula in which the radicals are identical or different and represent a hydrogen atom or else an * alkyl radical or hydroxyalkyl having at most 4 carbon atoms; 5 - Q is an alkyl, aryl or aralkyl residue of the amino acids constituting the protein; - T represents 0, NH or, when the protein con-V holds cysteine, S; m - Z is: © © © iü. an SO 3 M residue, the cation H having the same meaning as above; . or SR3, formula in which R3 represents: - (CH2) —ÇH-C02 © M® (II);

- R

4 Θ 0 - (CH2> —ÇH-SO3 M (Iix); .20 R4 or - (Œ2) —Œ-C0-R5 (IV); R4 25 ® formulas in which the cation M has the same meaning as above above; p is an integer between 0 and 5 (limits included); R ^ is a hydrogen atom or an * alkyl radical having at most 4 carbon atoms; and 30 represents: J * h '- N — D - J — Rfi E ® (V); 35 R6 / // I ί i 4 or -H — D — SO, ® Μ® (VI); I 3 * ^ 5 formulas in which D is a linear alkylene group-- '' area or branched comforting in total from 2 to 10 carbon atoms, the cation M® having the same meaning as above, the radicals R ^ being identical or different and representing a hydrogen atom, an alkyl or hydroxyalkyl radical 10 having at most 4 carbon atones, E® being a halogen- (r) r) re, or RC00, RSO ^ or RSO ^ -7, with R representing a hydrocarbon radical containing from 1 to 10 carbon atoms; "Or else an amino residue originating from a basic amino acid of the protein mono- or di-substituted by a residue R 1, R 6 having the same meaning as above; Z don't. possibly representing SQ ^ îà and SR ^ only when the protein contains cystine; - q is an integer between 1 and 5 20 (limits included), except that when Z represents a residue so3® ^ or SR ^, q is necessarily equal to 1 and the protein contains cystine; - The units A representing from 1 to 70% by weight of the protein derivative; - the units B representing from 0 to 15% by weight of the protein derivative.

The protein from which the protein derivative of formula (I) is prepared can come from different

V

sources. Thus, the basic protein can be derived from a T 30 material of animal origin and taken from the group formed by * keratin, gelatin, egg white albumin, blood albumin. , casein and lactalbumin. Keratin can come from a material taken from the group formed by hair, wool, horn, hair or bristles and feathers.

35 Likewise, the basic protein can come from an if material? 1 5 of vegetable origin taken from the group formed by soybeans, peanuts and cotton seeds.

Furthermore, the protein derivative may be a protein hydrolyzate, which has been chemically modified for grafting the remains of the colored molecules, after the hydrolysis which gave rise to it.

The radical Y of the chemically% modified protein derivative of formula (X) may be a residue of an azo dye, an anthraquinone dye, a phthalocyanine derivative or a nitro derivative of the benzene series.

In particular, Y can belong to the group consisting of the residues of Azo dyes, anthraquinone dyes or phthalocyanine derivatives corresponding to the formulas indicated in the "Color Index" 15 (3rd edition, volume 3, pages 3391 to 3560 (1971 ) and 3rd ^ revised edition, volume 6, pages 6265 to 6345 (1975)) under the names "reactivated", the remainder -X- then being taken from the group consisting of: 2o s ° 3Na I II with R - Q; Ύ N / • 25 ““ - SO ^ * CH / dd ”CH2 * ï 30 *** ^

J V

6 - so2 “NH-ch2-ch2 -; j - NH - C —CH2— CH2 -; and 5 8 w - NH - C - - CH2 -.

H

'h-

In particular, Y can belong to the group consisting of the remains of the dyes corresponding to the formulas indicated in the "Color Index" under the references: CI 13 245 ("Reactive Yellow 3") CI 14 824 ("Reactive Red 22") 15 CI 16 202 ("Reactive Red 23") v CI 17 865 ("Reactive Orange 2") CI 17 756 ("Reactive Orange 7"), CI 17 757 ("Reactive Orange 16") CI 17 910 ("Reactive Red 9" ) 20 CI 18 096 ("Reactive Violet 4") CI 18 097 ("Reactive Violet 5") CI 18 105 ("Reactive Red 4") CI 18 156 ("Reactive Red 12") CI 18 157 ("Reactive Violet 2 ") 25 CI 18 159 (" Reactive Red 3 "); CI 18 852 ("Reactive Yellow 17") CI 18 972 ("Reactive Yellow 2") CI 18 990 ("Reactive Yellow 13") CI 19 036 ("Reactive Yellow 14") 30 CI 61 200 ("Reactive Elue 19" ) * CI 61 210 ("Reactive Blue 5") CI 61 211 ("Reactive Blue 2") CI 74 460 ("Reactive Blue 7") CI 74 459 ("Reactive Blue 15").

Among the residues Y, mention may also be made of those 7 which come from dyes having a carboxylic acid function or a sulfonic acid function, the residue —X— associated with one or the other of these two residues Y being 2 respectively - * or —S—, and the rest —T— associated ”representing NH. ^

Mention will be made in particular of the residues Y which are represented by the following two formulas: v

V

_ / _ CH3 (OV- - <0> -k (ch,; and - {oy * - * - <ôVn Ç3 and which come respectively from the following dyes:

COOH

20 / CI 13 020 ('CI Acid Red 2 "); and 25 i **** - (ο) -» - {ô) - (* 30 CI 13 025 ("CI Acid Orange 52") * where the grafting onto the protein chain is therefore carried out by the formation of an amide or a sulfonamide respectively.

We. will also cite the case where Y is represented by the formula: /// i i 8 Λ / N02

: 3 pT

no2 10 originating either from 2,4-dinitro-chlorobenzene or from 2,4-dio-2,4-fluorobenzene, these compounds being able to react on the amino functions of the protein with elimination of hydrochloric acid or hydrofluoric acid respectively. Under these conditions, the associated -X- residue is represented by a direct bond and the -T- associated residue by -NH-.

It is also preferred that the chemically modified protein derivative has a molecular weight of between 5,000 and 30,000.

Similarly, when Z represents SR ^, it is preferred that p is equal to 0 and that R ^ is a hydrogen atom in formulas (II) and (IV).

The present invention also relates to a process for the preparation of the chemically modified protein derivative of formula (I), characterized in that - optionally, firstly, the starting protein is subjected to acid or enzymatic hydrolysis, so that the molecular weight of the hydrolyzate obtained is between approximately 500 and 50,000; - secondly, grafting onto the protein molecule, optionally hydrolyzed, of * residues of colored molecules, by reacting on all or part of the amino, alcohol or thiol groups of the optionally hydrolyzed protein, a or more compounds corresponding to the following formula: 35 Y-X '/ ii 9% \ \ \

V

formula in which Y has the same meaning as above, and X 'represents a reactive group containing one or more nucleofuges or one or more activated double bonds; -.5 - possibly, thirdly, and in the case where there are amine functions available after the chemical grafting of the colored molecules, ..................... ..

........ an N-alkylation phase is carried out using an alkylating agent corresponding to one of the following formulas t 10: 0 J® fil> · Χχ- (CH2) _Œ- C02 3 15 w / N Λ X - "... '(CH0) - * -" CH-SOo Μ (XIX) j J · L p IJ "*' P'4 20 (CH2) —Oi-CO-Rs (IV.); R4 25 or Ry— <Hc = Ç —— 00 — Rj (IV 'a); E4 formulas in which X ^ represents a halogen atom, R ^, R ^ and p have the meanings given above, and * "Ry denotes a hydrogen atom or an alkyl radical having at most 4 carbon atoms; - optionally, fourthly, and in the case where the protein used contains cystine, or else, all or part of the disulphide bridges are oxidized from the ί 10 ri cystine groups of the protein which has undergone the treatment (s) ( s) above, so as to obtain acid groups -SQ ^ K, this oxidation being followed or not by salification of the acid groups -SO ^ H mentioned above; or else all or part of the disulfide bridges of the cystine groups of the protein having undergone the previous treatment (s), so as to obtain thiol groups, this reduction being followed by an S-alkylation using an alkylating agent corresponding to one of the 10 formulas (IIa), (XIIa), dVQ) and ÇLV '^) defined above.

The reactive groups which constitute X1 can be chosen from those described in "The Chemistry of Synthetic dyes", Vol. VI, pages 1 to 209 (Ed. K. VSNKAT & BAMÄN, Academie Press, New York 1972).

15 When Y belongs to the group consisting of the residues of azole dyes, anthraquinone dyes or phthalocyanine derivatives corresponding to the formulas indicated in the "Color Index" (3rd edition, volume 3, pages 3391 to 3560 (1971 ) and 3rd revised edition, 20 volume 6, pages 6265 to 6345 (1975)) under the names "reactivated", X 'represents a group taken from the group consisting of: -HN CI S03Na; 25 with R «1 1 N |

γ V

NHR

30 - S02-CH2-CH2-0S03 Na rfy ”\ X, / é ί> 11 - S02-NH-CH2-CH2-0S03Na;

(J

- NH- G - CH = Œ2; 9

5 hrs

- NH - C - CH ~ CH9 - Br; and |

Br 0

, Λ H

10 - NH - C - Cs = CH2

Br

In the case where the residue Y is a residue of a dye having a carboxylic acid function or an α-sulfonic function, such as for example the rest of a dye corresponding to the formulas:

K

. C00H

20, - / y-- J ch3 (^) y— N * N -y y—- N \; and CI 13 020 ("CI Acid Red 2'1) 3 25

QJ

Na ° 3s - = n n \ CI 13 025 (”CI Acid Orange 52”) 30 0 0 *! it X1 represents respectively - C - Cl or - S - Cl 5 â ί ι 12

In the case where Y-X- is represented by: 5

Oj

T

10 NO,

Ab »\ \‘ 1v \ _ fi

ί I

13 we have seen that Y-X * is: X * 5 1 () I with X * "Cl or F.

: 'v ®) 2 ^ The process for the preparation of the protein derivative comprises successive phases, viz. evexi tuelleises ^ first phase, of hydrolysis, a second phase of chemical graft & ^ g, possibly a third phase of K-aXcoyla-tion , and, optionally a fourth phase, either of osydation, or of S-alkylation on reduced -SH groups. Phases 2, 3 and 4 can be reversed.

The first possible phase of the preparation process can be conventional acid hydrolysis or enzymatic hydrolysis by means of known proteolytic enzymes (proteinase "PSF 2019", pronase, trypsin, etc.). The operating conditions for 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 in grafting on the amino, alcohol or rhiol sites that the protein optionally hydrolyzed, these compounds carrying chromophoric or chromogenic groups. These compounds have a reactive group containing one or more nucleo-fugues or else a or several activated double bonds allowing the grafting by addition or substitution nucleo-v *> phile * The grafting is carried out in conventional manner under conditions of variable pH depending on the nature of the reactive group and of the protein.

The third possible phase of the pre-paraticn process can consist of an X-alkylation operated at r.::yen i k

U

alkylating agent ion corresponding to one of the formulas (II,), (IIIJ. (IV,) or (IV *) indicated above. The N-aleoylating agent used advantageously corresponds to the following roriruie X * -CH0-CO ^ $ 4, X, and H® having the meanings 5 indicated above The N-alkylating agent preererates mono cb.Io racic acid.

The fourth possible phase of the process can consist either of a 0x3-dati.cn of the aisuliurs links. uw cystine protein groups, or still *. -i ;.

10 S-alkylation of the -SH groups obtained by prior re-octron of the disulfide bridges of the protein by tr.a seo-tion of a reducing agent of conventional type such as eue, for example, an alkali metal thioglyeolate or the. thioglyco-late ammonium, 15 The oxidation of the protein having undergone the previous treatment (s) makes it possible to transform the cystine groups of the protein * - ™ into cysteic acid groups. The r / dation is advantageously carried out in an acid medium by means of an oxidizing agent, such as hydrogen peroxide or a peracid "The oxidation can be, optionally, followed by salification of the group" SO ^ K.

S-alkylation is carried out by means of an alkylating agent which corresponds to one of the formulas (II.,) R (Zi ,.), 25 (IVa) or (IV *,) indicated above. , the preferred agents% A Ck and the particularly preferred agent being those indicated in connection with K-alkylation.

The compounds according to the present invention have a color which depends on the nature of the grafted colored molecule.

The present invention also relates to a coloring composition containing, in an appropriate carrier, an effective amount of at least one compound of formula (X) and which can be used for coloring the keratinous carriers, such as hair and the like. nails, iû i 15 The invention relates equally to a coloring composition intended to be applied to the coating of the skin and containing, in a suitable carrier, an effective amount of at least one compound of formula (I), 5 On therefore sees that the colored protein derivatives ο 'according to the invention find use in two; dentures in the cosmetic industry, namely in hair cosmetics,; and in the processing products and / c-r. of makeup artist: ··. lu skin coating- In the latter case, the? prie'te - ·· <£ .î.sr.

10 the invention has the function of coloring the eempeticien itself cü the skin covering and they can confer siradtanemant on the latter the treatment and protection effect due to the presence of protein chains,

The proportions of the compound (s) of formula 15 (I) in the compositions according to the invention vary according to the nature of the colored molecule grafted onto the protein and according to the intensity of the coloration sought for the composition. Furthermore, it (s) is (are) sclubilised (s) in a solvent chosen from the group consisting of water, the 20 lower monoalcohols or polyols and iss hydro-alcoholic solutions. The more particularly preferred mono- or polyalcohols are chosen from ethanol, isopropanol, propylene glycol or glycerin. The compounds of formula (I) 'can also be dispersed in these carriers? not aqueous.

In the case of those known for the cooration of keratin fibers and, in particular, their human hair, in general, the proteins eoi.?tc'-s according to the invention are present in a proportion eon- 30 taken between 0.003% and 10% and, preferably? ent y, 02 Λ ** and 8% by weight, relative to the total weight of the composition.

The pH of the composition is between 5 and 11 and, preferably, between 6 and 10. The compositions according to 1'.w / enfion, used for dyeing iceratin fibers and.

35 in particular, hair is applied ;; · inclination 1 to / i i.

16 45 minutes and preferably 5 to 30 minutes, it being understood that for the lotions applied in hair rinsing: *, there is no exposure time, said lotions being applied, then dried.

5 The compositions according to the invention can be used in the form of colored, conditioned, lacquers? possibly ‘icus form of aerosol in the presence of propellants q commonly used.

The compositions according to the invention can also be used in direct dyeing and contain, in addition to the colored proteins of the invention, other dyes, in particular direct dyes such as Azo dyes, anthraquinone dyes, and celers. are nitrates of the benzene series, 2,5-diaminoquinones, 15 indophenols, las indoanilines, inda ,, iint \ ?,

The compositions according to the invention can also be used in oxidation dyeing and contain, in addition to colored proteins, oxidation dye precursors chosen from precursors of the "para" type such as diamines or aminophenols. whose functional groups are in para relative to each other, "crtho * type precursors whose groups are ortho to each other, as well as couplers, chosen from m- diamines, m.-aininophén.ol *, 25 m-diphéiols and phenols,

The compositions according to the invention not in the form of aqueous solutions, optionally added with alkalinizing or acidifying agents and / or solvents and / or polymers and / or treatment products with a cationic content. and / or amides and / or thickeners and / or surfactants and / or additives usually used in hair cosmetics such as sun filters, optical brighteners, antioxidants, sequestrasus, perfumes .

The alkalizing agents which are present without the compositions according to the invention can be sono or tri-ethanolamine, ammonia, phosphate or sodium carbonate. The acidifying agents which are present in the composition according to the invention may be pnosphoric, hydrochloric, lactic, tartaric, acetic or citric acids. These alkalinizing or acidifying agents are intended to regulate the composition; dye with the values indicated above ·

The solvents contained in the cc-mp citions “e.-.cn 10 the invention may be low molecular weight alcohols having 2 to 4 carbon atoms, such as ethyl alcohol or isopropyl alcohol or glycols ccace l ethylene glycol, propylene glycol, or outylene glycol or alternatively glycol ethers such as methyl ether, ethyl ether or butyl ether of ethylene glycol. The abovementioned solvents are present in amounts of between 0.5 and 50% by weight and, preferably, between 1 and - 15% by weight relative to the total weight of the composition.

The polymers contained in the composition are cosmetically acceptable polymers known to those skilled in the art,

These polymers are introduced at concentrations "of between 0.1 and 4% by weight and preferably between 0.3 and 2% by weight relative to the octal weight of the composition.

The amides contained in the compositions according to the invention can be mono or diethanolarides of fatty acids optionally oxyethylenated.

The thickeners can be cyclic derivatives such as carboxymethylcellulose, hydroxypropyl -% =. methylceliulese, hydroxyétliylcellulose.

The surfactants can be anioni-? cations, cationics, nonionics or amglionates such as sulfates, ethers sulfates, fatty alcohol sulfates, acids or oxyethylenated fatty alcohols, 18 ii oxyethylenated alkylphenols, amines and salts quaternary ammonium.

When the compositions constitute oxidation dyes, they additionally contain an oxidizing agent which can be hydrogen peroxide, urea peroxide or persalts such as ammonium persulfate. The oxidizing agent is added to the composition just before use.

; The compositions according to the invention can be present in the form of gel, cream, foaming liquid, milky liquid, packaged in bottles, tubes or aerosols.

The compositions according to the invention intended to be applied to the skin contain the compound (s) of formula (X) in proportions by weight of between 0.01 and 10% relative to the total weight of the composition.

The cosmetic makeup compositions according to the invention can be in the form of sticks, pastes, emulsions, suspensions, dispersions, powders or solutions and constitute lipsticks, mascaras, lip glosses. , blushes, eyeshadows, foundations, eyeliners or powders,

According to the invention, the colored protein can be combined with mineral or organic pigments and in particular with lacquers such as those commonly used.

The mineral pigments are generally oxides of iron (red, brown, black and yellow), of chromium, outremers 30 \ i * \ \ - i X Ί 19 (polysulfides of aminosilicates), titanium di-oxide, manganese pyrophosphate and prussian blue (ferric ferrocyanide). These different compounds alone or in. mixtures are generally used at concentrations of between 0.1 and 40% by weight relative to the total weight of the cosmetic composition.

Furthermore, these compositions may also contain pearlescent agents such as bismuth oxychloride, mica titanium and guanine crystals.

When the compositions are in the form of sticks and in particular lipsticks, eyeshadows or blushes and foundations, a significant part of these compositions is constituted by the fatty substance which may consist of one or more several waxes, and, in this case, this may be, for example: ozokerita, lanolin, lanolin alcohol, hydrogenated lanolin, acetylated lanolin, lanolin wax, wax bee, Candellila wax, microcrystalline wax, Carnauba wax, cetyl alcohol, stearyl alcohol, cocoa butter, lanolin fatty acids, petrolatum, petrolatum, mono, di and concrete triglycerides at 25 ° C, concrete fatty esters at 25 ° C, silicone waxes such as methyloctacecane-oxypolysiloxane and poly (dimethylsiloxy) stearyloxysiloxone, moncetha olamide stearic, rosin and its derivatives such as glycol and glycerol abietates, hydrogenated oils which are concrete 25 ° C, sucroglycerides and oleates, myristates, lanolates, stearates and dihydroxystea-spleens of calcium, magnesium, zirconium and aluminum.

The fatty substance can also consist of a mixture of at least one wax and at least one oil and in this case the oil can be for example: paraffin oil, Pu rcellin oil, perhydrosqualene, sweet almond oil *, avocado oil, calophylium oil, castor oil, sesame oil, jojoba oil, mineral oils having a point boiling range between 310 and

1 X

2010 ° C., silicone oils such as dimethylpolysiloxanes, linoleic alcohol, linolenic alcohol, oleal alcohol, cereal seed oil such as wheat germ oil, isopropyl lanolate, isopropyl palmitate, isopropyl myristate, butyl myristate, cetyl myristate, hexadecyl stearate, butyl stearate, decyl oleate, acetyl -glycerides, * octanoates and decanoates of alcohols and polyalcohols such as those of glycol and glycerol, ricinoieates g'alcohols and polyalcohols such as that of cetyl, isostearyl alcohol, isocetyl lanolate , isopropyl adipate, hexyl laurate and octyidodecanol.

Generally, the fatty substance in these stick form compositions can represent up to 99.9% by weight of the total weight of the composition.

These compositions may also contain other ingredients such as, for example, glycols, polyethylene thylene glycols, polypropylene glycols, monoalkanolamides, uncoloured polymers, mineral or organic fillers, preservatives, filters. Ü.V. or other usual additives in cosmetics.

These compositions, in the form of a stick, can contain a certain amount of water generally not exceeding 40% relative to the total weight of the cosmetic composition.

When the cosmetic compositions according to the invention are in semi-solid form, that is to say in the form of pastes or creams, they constitute mascaras, eyeliners, foundations, blushes , 30 eyeshadows, lipsticks, concealers, ^ etc ...

These pastes or creams are emulsions of the water-in-oil or oil-in-water type whose fatty phase represents from 1 to 98.8% by weight, the water phase from 1 to 35 98.8%. by weight and the emulsifying agent from 0.1 to 30% by weight.

I fc 21

These compositions can also contain other conventional ingredients such as perfumes, antioxidants, preservatives, gelling agents, UV filters, dyes, pigments, pearlescent agents, uncoloured polymers and mineral fillers. or organic.

When the compositions are in the form of a powder, they essentially consist of an inorganic or organic filler such as talc, kaolin, starches, polyethylene powders or polyamide powders as well as additives such as binders, dyes, etc ...

Such compositions may also contain various additives customary in cosmetics such as perfumes, antioxidants, preservatives.

* - \ "s \! (/ I * 22

To better understand the object of the invention, several modes of implementation will be described below, by way of purely illustrative and nonlimiting examples.

5 EXAMPLE 1

Preparation of a colored protein derivative of formula (I), formula in which the rate of units δ is ✓7 ^ ΐ zero, the weight rate of units A is approximately 61%, represents H ^ and the unit A has for formula: “I si --NH-CH-CJ- 0 - IJ Na03yA ^ Y ^ s 15 II> NH 0 ch2-ch2-so2-j ^ γ 20 Q representing the alkyl, aryl or aralkyl groups of the 2 ^ amino acids of the protein and T representing urî or C or S.

The protein derivative on which the grafting is carried out is a keratin hydrolyzate.

First step: Hydrolysis of keratin î a) A suspension of 2q 100 g of chicken feathers in 2 liters of dimethylfomamide and 0.8 liters of water is brought to reflux in 1 hour. It is filtered hot, washed with 2 liters of water and the treated feathers are air dried.

b) 100 g of treated feathers are suspended in 2 liters of water. The pH is adjusted to 8.6-9.0 and the temperature is brought to 40 ° C. 3.5 g of PSF 2019 enzyme are added.

t *.

23

The pH is maintained between 8.5 and 8.8 by adding sodium hydroxide at 3 After adding 1 liter of sodium hydroxide at 3%, the pH is allowed to drop to 8.45, then it is adjusted to pH 7 with 1 * acid dilute hydrochloric acid. The mixture is heated for 5 minutes at 95 ° C. to inactivate the enzyme, then it is allowed to return to room temperature. A slight insoluble material is filtered, then the filtrate is lyophilized. 50 to 60 g of keratin hydro-lysate are obtained in the form of a beige powder.

The content of free amines is 2 meq / g.

10 Second step: Grafting of the dye:

The following are heated to 40 ° C.: - 5 g of the keratin hydrolyzate obtained above, - 20 cm of water.

„15 - 20 cm ^ of acetone.

- IN soda, in sufficient quantity to bring the pH to 9. ^

10 g of REMAZOL BLEU BRILLANT R (CI n ° 61200) 50% with the following structure are added over 2 hours:

Wy ο S02-CH2-CH2-0-S03Na i 30 I * 24

The pH is maintained between 8, S and 9.2 by adding IN sodium hydroxide.

The mixture is stirred for 2 hours after the end of the addition of dye, then diluted with 150 cm of water. The pH is adjusted to 3 by addition of concentrated hydrochloric acid. The colored protein precipitates. It is filtered, washed with 8 times 150 cnr * of water and dried in air, s 5 g of colored keratin are obtained in the form of a blue powder.

10 EXAMPLE 2

Preparation of a colored protein derivative of formula (I), formula in which the proportion of units B nvt ^ »tau ^ by weight of units A is approximately 68%, represents P and the unit A has the formula: 15 —- -HH-CH-1--

2 ° L. J

. 25 __o Na ° 3 ^ Λ> ^ vso3Ha / \ <Lnh oh I Ί j j 30

Na ° 3S

/

V

i ".

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

The protein derivative on which the grafting is carried out is a casein hydrolyzate.

'' First step: Hydrolysis of casein:

100 g of food casein are suspended in 1 liter of water. The pH is adjusted between 1.8 and 2.0 by adding 35% hydrochloric acid. 0.2 g of pepsin 1: 60000 SIGMA® is added after stabilizing the temperature at 38-1 ° C., stirring is continued for 8 hours at this temperature, then the enzyme is inactivated at pH 8- 8.5 for 10 hours. The solution is ultrafiltered so as to remove the mineral salts and the fraction of 15 molecular weights less than 1000. After lyophilization, 85 g of hydrolyzate is obtained having an amine content of 2.54 meq / g.

Second step: Grafting of the dye:

Heated to 40 ° C: 20 - 5 g of the casein hydrolyzate obtained above.

- 25 cm ^ of water.

- 25 cm ^ of acetone.

- 1N sodium hydroxide, in sufficient quantity to bring the pH to 9.

-We add, in 1 hour 30 minutes, 11.8 g of CIBACROIT ^ ROUGE BRILLANT 3 ΒΔ (CI n ° 18105) having the following structure; 4 * 26 5 Na03V% S03Na

x X I i I

fYvw ”10

Na ° 3S

The pH is maintained between 8.8 and 9.2 by addition of IN sodium hydroxide.

The mixture is stirred for 4 hours after the addition of the dye. It is adjusted to pH 2.2 by addition of 2N hydrochloric acid. The colored protein precipitates. Filter, wash thoroughly with water and air dry.

4.5 g of colored casein are obtained in the form of 2o of a red powder.

EXAMPLE 3

Preparation of a colored protein derivative of formula (X), formula in which the proportion of units B is zero, the proportion by weight of units A is approximately 34%, represented by Na® and unit A a for formula î 30 _ S'SSS ^^ 35 A * 27 ---- NH-CH-P "-— '

- Q * J

5 * - m

Ma ° 3syi ^ N tr ^ N

10 nh '^ nx'nhν ^ == HV / ^ * h l C1 N ΥΧ H0 ^ - “\> λν 15 ^

Cl 20 Q representing the alkyl, aryl or aralkyl groups of the amino acids of the protein and T represents NH or 0 or S.

The protein derivative on which the grafting is carried out is a keratin hydrolyzate.

25

The following are heated to 45 ° C.: - 10 g of 1 * keratin hydrolyzate obtained in the first step of Example 1.

- 50 cm ^ of water.

30 - 50 cm ^ of acetone, - Soda at 30%, in sufficient quantity to bring the pH between 8.5 and 9.5.

10.3 g of CIBACRON ® YELLOW GLOSS 3 G-P (CI n® 18972) having the following structure are added in 2 hours: a 4 t 28 C1 5 d / Sj

V

CH

; J *

THIS

10 _N l

HO S

N ^ S03Na 15. . Cl

The pH is maintained between 8.5 and 9.5 by adding 30% sodium hydroxide.

Stirred for 1 hour at 45 ° G after 1 * addition of the dye, then left in contact overnight at room temperature.

The reaction mixture is adjusted to pH 3 by addition of concentrated hydrochloric acid. It is filtered, washed thoroughly with water, then the precipitate is redissolved at pH

7.5 by addition of soda.

After lyophilization, 3 g of colored keratin are obtained in the form of a yellow powder.

EXAMPLE 4

Preparation of a colored protein derivative of formula (I), formula in which the level of units B is zero, the level by weight of units A is approximately 10%, K

30 represents H® and the motif A has the formula.

- 0 ~ 29 4 t --NH —- CH - C —-- NH2 0

5 DD

10 0¾ ch2 S02 0 15 Q representing the alkyl, aralkyl or aryl groups of the amino acids of the protein and T representing NH or 0.

The protein derivative on which the grafting is carried out is a gelatin hydrolyzate.

This protein derivative is obtained according to the procedure described in Example 1 in which the keratin hydrolyzate is replaced by ASF ROUSSELOT gelatin having an amine content of 1.7 meq / g.

Table 1 gives a number of characteristics of the colored protein derivatives obtained in Examples 1 to 4.

TABLE 1 SU ** 2 °

Example N® / Λ max% Dye grafted 30 1,594 nm 61% 2,517 nm 68% 3,403 nm 34%

4,596 nm 62 Z

. I— il II I —— III .......... 11,. L .—— - IM I · ”. ···· - M——” I.

// i * 30, EXAMPLE 5

A styling lotion having the following formulation is prepared: - Compound of Example 1 ..................... 0.1 g 5 - Copolymer vinyl acetate / crotonic acid (90/10) .................................. 1.8 g - Vinylpyrrolidone / vinyl acetate copolymer (60/40) ................................. 0.4 g - Alcohol ethyl ........................... qs 50 ° alcoholixpe • * 0 "Triethanolamine ............" ·. *. · »··. ······ qs pH 7 - Demineralized water .......................... qs 100 g

This styling lotion is applied to brown hair. After drying and shaping, this hair has an ashy reflection.

13 EXAMPLE 6

A lotion having the following formulation is prepared; - Composed of 1 * example 2 ..................... 0.05 g 2o ot Colorant "CI 62045" sold under the name of "Bleu dimacide A 2 BL "by the company" PCUK "0.04 g - N-jl-hydroxyethylamino-2-hydroxy-5-nitro-benzene ......................... ........... 0.02 g - Dye "CI 13065" sold under the name of 25 "Acetacid yellow 4 R extra" by the company "PCUK" .......... ........................... 0.02 g - Vinyl acetate / vinylpyrrolidone copolymer (30/70) ..... ............................ 0.6 g - Ethyl alcohol .............. 10 g 30 - Propylene glycol ......... 1 g - Nonylphenol oxyethylenated with 9 moles of ethylene oxide ....................... .......... 2 g - Sorted thano laminated ............................ qs pH 7 - Demineralized water .......................... qs 100 g 35 This liquid is applied to brown hair it 31 dark. The hair is dried which then presents a copper mahogany reflection.

EXAMPLE 7

A styling lotion having the following formulation is prepared; c L - Compound of 11 example 3 ............ 0.05 g "Np" -hydroxyethylamino-2 (di-NV ^ -ß-hydroxyethyl-- amino ”41) anilino-5 benzoquinone -1.4. 0.016 g "N-Cchloro-Z1 hydroxypnenyl-4!) - acetylamino-3-methoxy-6 benzoquinoneimine-lj4 ................ 0.024 g = N- (chloro- 3 * methylamino-4 ') phenyl-ureido-3 methyl-6 benzoquinoneiraine-1,4 ................. 0.009 g - Copolymer of vinyl acetate / crotonic acid ( 90/10) ....................................... 2.7 g 15 - Copolymer vinylpyrrolidone / vinyl acetate (60/40) ....................................... 0 , 5 g - Ethyl alcohol .............................. qs 50 ° alcoholic - Triethanolamine ........ .................. a .. ,, qs pK 7 »Demineralized water ..................... ........ qs 100 g 20 This styling lotion is applied to light brown hair. After drying, a mahogany brown hair is obtained.

25 .i * i t 32 EXAMPLE 8

A temporary coloring product is prepared having the following formulation 2 - Compound of 1 * example 2 ............., ............ 0.05 g 5 - Dye "CI 20170" sold under the name "Brun r clair sella acid RF" by the company "CIBA GEIGY" 0.015 g - Dye "CI 62045" sold under the name "Bleu ~ dimacide A 2 BL" by the Company "PCUK" 0.02 g - Copolymer of vinyl acetate / vinylpyrrolidone 10 (30/70) .............................. ........... 0.6 g - Ethyl alcohol ............................ ···· 10 g "Propylene glycol ................................ 1 g - Nonylphenol oxyethylenated with 9 moles of oxide ethylene ............................................ 2 g 15 »Sorted thanolamine ................................. qs pH 7 - Demineralized water ........ ....................... qsplOO g

This temporary coloring product is applied to light blond hair. After drying, the hair has a pearly beige reflection.

20 EXAMPLE 9

A shaping lotion is prepared having the following formulation: - Compound of 1 * example 1 ................... 0.1 g - Compound of example 2 ......................... 0s05g 25 »Devinyl acetate / crotonic acid copolymer (90/10) ........... ............................. 2.7 g - Vinylpyrrolidone / vinyl acetate copolymer (60/40) ..... ................................... 0.5 g

- Ethyl alcohol .............................. qs 50 ° alcodliqLB

30 - Sorted thano laminate ............................... qs pH 7 - Demineralized water ........ ..................... qsplOO g

This shaping lotion is applied to light brown hair. After drying, an ashy purple reflection is obtained.

35 ”- * 1 33 EXAMPLE 10

A styling lotion having the following composition is prepared:. - Compound of example 2 ..,., ................ 0.1 g 5 - Vinyl acetate / crotonic acid copolymer (90/10) .... ................................ 1.8 g - Vinylpyrrolidone / vinyl acetate copolymer (60/40) .. ............................... 0.4 g “Ethyl alcohol> ···“ · (·· ΐ) ( ΐιιι ·· ι ····· <····· qs 50 alcoholic 10 ~ Sorted thano laminated ........................ .qs pH 7 - Demineralized water .......................... qs 100 g

This composition is a styling lotion which is applied to brown hair. After drying and shaping, the hair is nuanced in a mahogany reflection.

15 EXAMPLE 11

A liquid composition is prepared having the following formulation: - Compound from Example 1 .......... 0.03g - Compound from Example 2 ............. ........ 0.02g 2o ”Dye" CI 62045 "sold under the name" Blue dimacideA2BL "by the company" PCUK "......... 0.01g" N-hydroxyethylamino- 2 5-hydroxy-nitro-benzene ..................... 0.01g - Dye "CI 13065" sold under the name "Yellow acetacide4R extra" by "PCUK" company .... 0.02 g - Vinyl acetate / vinylpyrraiidone (3C / 70) copolymer 0.6 g - Ethyl alcohol ................... ......... 10 g - Propylene glycol ........................ 1 g - Nonylphenol oxyethylenated to 9 moles dfaxyde of ethylene 2 g 30 - Sorted thano laminated .......... ·. ··· .... ····. · Qs pH 7 - Demineralized water ............ ............... qs 100 g

This liquid composition is applied to natural or colored dark blonde hair. After drying, this hair is dyed in a copper-beige reflection.

/ * λ 34 EXAMPLE 12

The oxidation tincture is prepared having the following formulation: - Compound of 1 * example 4 ....................... 0.2 g 5 - Compound of 1 * example 1 ....................... 0.1 g “Paratoluylenediamine” · »·. ·· ....... 0.35 g w Paraammophenol ...... 0 ....................... 0.09g * - Resorcin ............ 0, 25g - Me t aamx nopheno1 .................. 0.1 g 10 - Nonyl phenol oxyethylenated to 4 moles of ethylene oxide sold under the name of "REMCOPAL 334" by the company "GERLAND" ...... 22 g - Nonyl phenol oxyethylenated to 9 moles of ethyl oxide * sold under the name of 15 "REMCOPAL 349" by the company "GERLAND" ..... 22 g - Butylcellosolve. .......... 8 g * Propylene glycol 8 g ° »Ethylenediamine tetracetic acid ........... 0.2 g

O

- Ammonia at 22 ° Bé .......................... 4 cnr 20 - Sodium bisulphite at 35 ° Bé ........ .......... 1 cm ^ - Water ..... qs ............................. .. 100 g

This liquid is mixed with an equal weight of 6% hydrogen peroxide just before dyeing.

Applied to light brown hair, it gives it, at room temperature, after 30 minutes of laying, rinsing and drying, a dark ash blonde color.

/ (fM

* * 35 EXAMPLE 13

The lipstick having the following composition is prepared î 5 - Compound of 1 Example 2 ... ,,, ...., ............. 2 g - Castor oil .. .............................. 65 g - Lanolin 10 g - isopropyl fristete ......... ............... 5 g - Beeswax ................ 5 g 10 - Carnauba wax ..... ......................... 3 g - C'andellila wax ................. .......... 3 g - Ozokerite .................................... 3 g

The oils and fatty substances are heated to 60-65 ° C. and at this temperature the colored protein dispersed with vigorous stirring. After cooling, a magenta-colored stick is obtained.

EXAMPLE 14

The foundation having the following composition is prepared: - Compound of example 3 ....................... 1.5 g - Compound of 'example 2 ....................... 0.1 g - Oxyethylenated lanolin fatty alcohols containing 20 moles of ethylene oxide ..... ............. 7 g 25 - Triglycerides of coconut fatty acids ....,.,. 30 g - Glycerol monostearate, .................... 2 g - Silicone oil ................. ........... 1.5 g - Cetyl alcohol ............................. 1.5 g - Water ..... qs ............................... 100 g 30 The colored proteins are dissolved r " . in the water containing the emulsifiers (oxyethylenated lanolin fatty alcohols and glycerol nxmostearate).

* The aqueous phase is heated to around 80 ° C; the fatty phase previously heated to 80 ° C. is added with vigorous stirring. Allow to return to room temperature 36 te · with moderate stirring ,,

A foundation is obtained which is applied easily and evenly to the skin.

9; “Ît V 'M- * il“ 1

Claims (40)

1. Chemically modified protein derivative, characterized in that it has a molecular weight between t 500 and 50,000 and that it corresponds to the following general formula: 'Τ' -0- ^ 0- - MH— PJ —----- NH-ÇH-C - * “--- NH-CH-C— - .. P2-CO20 M ® XQ (ÇHOa m 10 | {Y _ T — XJ v ZK“ = - V · - AB formula in which: - Y is a residue of a colored molecule; 15. X is a group ensuring the chemical bond between r the colored molecule and the protein derivative bu, well represents a direct covalent bond; - P 1 and P 2 are protein residues which are not acylated and are not chemically modified by addition or substitution with nucleophary; - M ^ represents H®, a cation derived from an alkali metal or magnesium, or else N® (R2) ^, formula in which the radicals R2 are identical or different and represent a hydrogen atom or else an alkyl or hydroxy radical - 25 alkyl having at most 4 carbon atoms; - Q is an alkyl, aryl or arallcyl residue of the amino acids constitutive of the protein; - T represents 0, M or, when the protein contains cysteine, S *, 30. Z is: _ ^. one remains the cation H ^ having the same meaning as above; *. or SR3, formula in which represents: - (CH,) - CH-CO, 0! ·! ® (XI); 35 i R4 tï "38" (CH2) p — ÇH-SO ^ M® (III); R4 5 or - (CH2) p-pî-CO-R5 (IV); R, 5Γ 4 formulas in which the cation M® has the same meaning as above; p is an integer between 0 and 5 (limits included); R ^ is a hydrogen atom or an alkyl radical having at most 4 carbon atoms; and R ^ represents: R * 1¾ (Z) - N — D-N ^ - RÄ E ^ (V); | | 6, 15 R6 R6 Λ or - | T — D- S03 © Μ® (VI); L 20 6 formulas in which D is a linear or branched alkylene group comprising in total from 2 to 10 h} carbon atoms, the cation M '"-' having the same meaning as above, the i * adicals Rg being identical or different and representing a hydrogen atom, an alkyl or hydroxyalkyl radical having at most 4 carbon atoms, E® being a halide ion, or RCOO ^, RSO ^ or RS0®9 R representing a hydrocarbon radical containing 1 to 10 carbon atoms ^ 30. being able to represent S0 ^ ®M® and SR ^ only when the protein contains cystine; -. Or also an amino residue coming from a basic amino acid of the protein mono- or di- substituted by a residue R ^ s R ^ having the same meaning as above; // / 39 <·, - q is an integer between 1 and 5 (bounds included (ses), except that when Z represents a residue SO ^ M or SRgj q is necessarily equal to 1, and the protein contains cystine; 5. the units A representing from 1 to 70 % by weight of the protein é derivative; - * = the units B representing from 0 to 15% by weight of the protein derivative v, 2. Protein derivative according to claim 1, characterized in that the protein from which it is prepared is a protein derived from a material of animal origin and is taken from the group formed by keratin, gelatin, 1 * egg white albumin, 1 * blood albumin, casein and lactalbumin 15 3, Protein derivative according to claim 1, - characterized in that the protein from which it * is prepared is a protein from a material of ~ plant origin taken from the group formed by soybeans, peanuts and cotton seeds. 20 4c Protein derivative according to one of Claims 1 to 3, characterized in that it consists of a protein hydrolyzate which has been chemically modified after the hydrolysis which gave rise to it. 5. Protein derivative according to one of claims 1 to 4, characterized in that the radical Y is a residue of an azoi dye * an anthraquinone dye, a nitro derivative of the benzene series or a phthalocyanine derivative. 6. Protein derivative according to claim 5, characterized in that the radical Y belongs to the group- pe consisting of the remains of azoi'ques dyes, anthraquinone dyes or phthalocyanine derivatives - corresponding to the formulas indicated in the ”Color Index” (3rd edition, volume 3, pages 3391 to 3560 (1971) and 3rd 35 revised edition, volume 6, pages 6265 to 6345 (1975)) under the fl i L. 40 denominations “reactive" * the remainder -X ”then being taken from the group consisting of z 'ΎΤ (Cy8031.3 I j | with R“ Γ) ”: Y ^ OR 10 - S02-CH2 ~ CH2”; 15 - - y “so2-nh-ch2-ch2 - 5 20 8 - NH - G - Œ9 - CH9“; and -'r · .- · 25 7. Protein derivative according to claim 6, characterized in that the radical Y belongs to the group consisting of the remains of the dyes corresponding to the formulas indicated in the "Color Index" under the references-30 ces: CI 13 245 ("Reactive Yellow 3 ") CI 14 824 (" Reactive Red 22 ") -> CI 16 202 (" Reactive Red 23 ") CI 17 865 (" Reactive Orange 2 ") 35 CI 17 756 ("Reactive Orange 7") / 41 ", CI 17 757 (" Reactive Orange 16 ") CI 17 910 (" Reactive Red 9 ") CI 18 096 (" Reactive Violet 4 ") CI 18 097 ( "Reactive Violet 5") 5 CI 18 105 ("Reactive Red 4") P CI 18 156 ("Reactive Red 12") CI 18 157 ("Reactive Violet 2") * CI 18 159 ("Reactive Red 3") CI 18 852 ("Reactive Yellow 17 ") 10 CI 18 972 ("Reactive Yellow 2") CI 18 990 ("Reactive Yellow 13") CI 19 036 ("Reactive Yellow 14") CI 61 200 ("Reactive Blue 19") CI 61 210 ("Reactive Blue 5" ) 15 CI 61 211 ("Reactive Blue 2") CI 74 460 ("Reactive Blue 7") CI 74 459 ("Reactive Blue 15") » 8. Protein derivative according to one of claims 1 to 5, characterized in that the remainder Y comes from a dye having a carboxylic acid function or a sulfonic acid function, the rest -X- associated with one or the other of these two residues Y being respectively »Ü - or - 1 -, and the associated -T- residue representing NH. 25 () 9. Protein derivative according to claim 8, characterized in that the residue Y is a residue represented by the formula ï <ô $ - = - (S) - <1; · / 35 42 or a remainder represented by the formula: 5 ^ ö> a = .- <ö> {*. iT v and comes respectively from the dyes% V 10 COOH Œ3 15 CI 13 020 ("CI Acid Red 2") V M I; · 20 _ <j, H3 Na03S "- \ C3 25 CI 13 025 ("CI Acid Orange 52"). 10. Protein derivative according to one of claims 1 to 5, characterized in that Y is represented by the formula j / \ ^ N02 6Γ no2 - the associated -X- residue being represented by a direct bond 9 and the rest -T- associated, by NH. 11. Protein derivative according to one of the claims //% t, 43 tions 1 to 1Q, characterized in that it has a molecular weight of between 5,000 and 30,000. 12. Protein derivative according to one of claims 1 to 11, characterized in that, when the substituent Z represents SR ^, Rg corresponds to one of the ^ formula (II) or (IV), R ^ is a hydrogen atom and p is 0. 13. Process for the preparation of the protein derivative as defined in one of claims 1 to 12, character-ized by 1e, makes that; - Optionally in the first place, the starting protein is subjected to acidic or enzymatic hydrolysis, so that the molecular weight of the hydrolyzate obtained is between approximately 500 and 50,000; 15. secondly Er, chemically grafting it onto the tH ï \ j / A 44 protein molecule possibly hydrolyzed from the remains of colored molecules, by reacting on all or part of the amino, alcohol or thiol groups of the optionally hydrolyzed protein, one or more compounds 5 corresponding to the following formula: "Y - X1 (VII), formula in which Y has the same meaning as in claim 1, and X * represents a reactive group containing a or more nucleofuges or one or more activated double bonds; - Thirdly, possibly, and in the case where there are amine functions available after the chemical grafting of the colored molecules, an N-alkylation phase is carried out by means of an alkylating agent corresponding to 15 l8one of the formulas following; V X1 ~ (CH2) p — CH-C02® M © (Ha); R4 20 X1 ~ '(CH2> p' ~ CH-SO® (Ilia); R4 Xl ~ (CH2) p — Oî-œ-îls (IVa);. 25 k or R, - CH = »C — CO — R - (IV'a), 'I 5 R4 30 "w formulas in which X ^ represents a halogen atom, R ^, R ^ and p have the meanings given in claim 1, and Ry denotes a atom * hydrogen or an alkyl radical having at most 4 carbon atoms; - fourthly, optionally, and in the case where the protein used contains cystine, or else there are ί 45 oxide all or part of the disulfide bridges of the groups cystine of the protein having undergone the previous treatment (s), so as to obtain acid groups -SOgH, this oxidation being followed or not with a salification of the acid groups-SO ^ H or all or part of the disulphide bridges of the cystine groups of the protein having undergone the previous treatment (s), so as to obtain thiol -SH groups, this reduction being followed of an S-alkylation by means of a alkylating agent corresponding to one of the formulas (IIa), (IIIa), CLVa) and (IV'a) defined above. 14. The method of claim 13, characterized in that the residue Y is a residue of an azo dye, an anthraquinone dye, a nitro derivative of the benzene series, or a phthalocyanine derivative. 15. Method according to claim 14, characterized in that the residue Y belongs to the group consisting of the residues of the azo dyes, anthraquinone dyes or phthalocyanine derivatives corresponding to the formulas indicated in the "Color Index "(3rd edition, volume 3, pages 3391 to 3560 (1971) and 3rd revised edition, volume 6, pages 6265 to 6345 (1975)) under the names" reactivated ", the remainder X 'then being taken from the group consisting by: 25 cl SOÿïa | with R ~ N ^ N Is ^ J NHR -S02-CH2-CH2-0S03Na; 46 J r! . i ^ VV 5. Cl; : vks / iy - S02-NH-CH ^ CH2-0S03Na; 10 0 - NH - 8 - CH = CH2 5 15 -NH - ^ - (jM-CH2-Br; and <Br w -NH-1-C = CH2 20 Br 16. The method of claim 13, for 1 Obtaining a compound of formula (I) in which the residues Y and X are as defined in one of claims S or 9, characterized in that the residue X ' respectively represent: - Ü-Cl or - U Ie grafting of the rest of the colored molecule 8 3q leading to the formation respectively of one. amide or a Sulfonamide. 17. The method of claim 13, for 'obtaining a compound of formula (I) in which the residues Y and X are as defined in claim 10, characterized in that the residue X' represents Cl or F, i 47 I t grafting of the rest of the colored molecule taking place on the amino functions of the protein chain. 18. Method according to one of claims 13 to 17, characterized in that the agent of S- or N-5 alkylation used corresponds to the following formula: © © 'xx - ch2 - CO ^ M "ς formula in which X ^ and M® have the meanings indicated in claim 13. 19. Method according to one of claims 13 to 18, characterized in that the oxidation of the optional fourth step is carried out in an acid medium with hydrogen peroxide or a peracid. \ l * · \ \ à 48 9 »20o Coloring composition intended for coloring keratinous supports such as hair and nails, characterized in that it contains, in the presence of a cosmetically acceptable support, an effective amount 5 at least one protein derivative as defined in one of claims 1 to 12. "21. Coloring composition intended to be applied to the skin covering, characterized in that it contains, in the presence of a support cosmetically acceptable, an effective amount of at least one protein derivative as defined in one of claims 1 to 12. 22. Coloring composition according to either of Claims 20 and 21, characterized in that the protein derivative (s) of formula (I) is (or are) dissolved in a solvent chosen from the group consisting of water, monoalcohols or lower plyols and hydroalcoholic solutions, or is (or are) dispersed in a non-aqueous support, 23. Composition according to one of claims 20 20 and 22, characterized in that it contains from 0.005% to 10% by weight relative to the total weight of the composition, of the compound (s) of formula (I). 24. Composition according to Claim 23, characterized in that it contains from 0.02% to 8% by weight 25 relative to the total weight of the composition, of the compound (s) of formula (I) . 25. Composition according to one of claims 20 and 22 to 24, characterized in that its pH is between 5 and 11. 26. Composition according to Claim 25, characterized in that its pH is between 6 and 10 n 27. Composition according to one of claims 20 and 22 to 26, used in direct coloring, characterized in that it contains, in addition to the compound (s) of formula (1), direct dyes chosen among the 499 azoi'ques dyes, anthraquinone dyes, nitro dyes of the benzene series, 2,5 - diamino-quinones, indophenols, indoanilines and inda-mines. 28. Composition according to one of claims 20 5 and 22 to 26, used in oxidation dyeing, characterized in that it contains, in addition to (or the) ^ compound (s) of formula (I ), oxidation dye precursors chosen from "para" type precursors, "ortho" type precursors and couplers chosen from m-diamines, m-aminophenols, m-diphenols and phenols. 29. Composition according to one of claims 20 and 22 to 28, characterized in that it contains alkalizing or acidifying agents and / or T ** oxidizing agents and / or solvents and / or polymers and / or treatment products of a cationic nature and / or amides and / or thickeners and / or surfactants and / or additives usually used in hair cosmetics such as sun filters, optical brighteners, antioxidants, sequestrants, perfumes. 30. Composition according to one of claims 21 and 22, characterized in that the protein derivative (s) of formula (I) are present in proportions by weight of between 0, 01 and 10% relative to the total weight of the composition. 31. Composition according to one of claims 21, 22 and 30, characterized in that it contains at least one adjuvant chosen from mineral or organic pigments, fatty substances such as waxes and mineral oils, vegetable ^ or organic, glycols, polyethylene glycols, ~ propylene glycols, monoalkalnolamides, uncolored polymers, UV filters, perfumes, antioxidants, preservatives, mineral or organic fillers. ύ r v 50 32. Composition according to one of claims 20 to 31, characterized in that it is in solution in the form of lotion, lacquer, in emulsion in the form of cream or milk, in the form of gel, in the form stick, dispersion or powder, or it is packaged as an aerosol. S Drawings: ..... plates ____ £ .3L. Pages of which ...... JL ...... cover page description pages ..... AH ... claim pages * -. ........ A ..... descriptive abstract Luxembourg, OCT 14. 1983 The representative: Me AlaimRjul ^ viiâ JpW ^ V