GB2147807A

GB2147807A - Cosmetic colouring compositions containing protein derivatives

Info

Publication number: GB2147807A
Application number: GB08425868A
Authority: GB
Inventors: Serge Forestier; Gerard Malle; Alex Junino; Gerard Lang
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1983-10-14
Filing date: 1984-10-12
Publication date: 1985-05-22
Also published as: GB8425868D0; GB2147807B; DE3437360C2; FR2553285B1; DE3437360A1; FR2553285A1; LU85047A1

Abstract

A cosmetic colouring composition is disclosed which comprises a cosmetically acceptable support and at least one chemically modified protein derivative which has a molecular weight of from 500 to 50,000 of formula (I): <IMAGE> in which essentially: - Y is a residue of a coloured molecule; - X is any group which joins the coloured molecule residue and the protein residue or is a direct covalent bond; - P1 and P2 are non-acylated protein residues which are not modified chemically by addition or nucleophilic substitution.

Description

SPECIFICATION Cosmetic colouring compositions containing protein derivatives The present invention relates to cosmetic colouring compositions which contain, as an active substance, at least one protein derivative which contains residues of coloured molecules grafted onto the protein chain.

By "coloured molecules" are meant molecules which contain chromophoric or chromogenic groups. The colouring compositions according to the invention may be used to colour keratinous supports, such as keratin fibres, and, in particular, human hair, or may be applied to the skin surface.

Coloured protein derivatives have already been described in the literature, but they have never been proposed as active substances in cosmetic colouring compositions. French Patent No. 1,310,583 describes substances obtained by grafting coloured molecules onto proteins, especially onto casein, these substances being used for colouring viscose masses, as pigments or for dyeing synthetic resins.

Many protein hydrolysates are known which have useful properties for treating the skin surface or hair. It is known, furthermore, how to graft residues of coloured molecules onto chains of synthetic polymers; these grafted synthetic polymers can be used to produce colouring compositions; however, these polymers are generally only sparingly soluble in common cosmetic solvents, and they form films which are excessively rigid.

We have found that protein derivatives which incorporate residues of coloured molecules possess better properties than could have been expected. Due to the presence of the protein polymer chains and the colouring effect of the grafted molecules, the following useful cosmetic properties are observed: The protein derivatives used in the present invention are more soluble in the common cosmetic solvents, particularly in water, than many coloured synthetic polymers.

The coloured proteins form, particularly in non-aqueous media, after application to the skin, a flexible protective film which is better than that provided by known synthetic polymers.

As a result, the use of the cosmetic colouring compositions according to the invention, in which the active substance consists of natural polymer chains onto which coloured molecules are grafted, is preferred to the use of compositions which incorporate synthetic polymers having grafts of colouring materials.

The present invention provides a cosmetic colouring composition which comprises a cosmetically acceptable support and at least one chemically modified protein derivative which has a molecular weight of from 500 to 50,000, preferably from 5,000 to 30,000, of formula (I):

in which: Y is a residue of a coloured molecule; Xis any group which joins the coloured molecule residue and the protein residue, or is a direct covalent bond; P1 and P2 are non-acylated protein residues which are not modified chemically by addition or nucleophilic substitution; M+ is H+, a cation derived from an alkali metal or magnesium, or N+ (R2)4, wherein the R2 groups, which may be identical or different, are a hydrogen atom or an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms; Q is an alkyl, aryl or aralkyl residue of the constituent amino acids of the protein;; T is O, NH or, when the protein contains cysteine, S; Zits: a a SO3 - M + residue, M + having the same meaning as above; SR3, wherein R3 is:

wherein M + has the same meaning as above, p is 0 or an integer from 1 to 5, R4isa hydrogen atom or an alkyl group of 1 to 4 carbon atoms and R5 is::

wherein D is a linear or branched alkylene group of to 10 carbon atoms, M+ has the same meaning as above, the groups R6, which may be identical or different, are a hydrogen atom or an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms, E- is a halide, RCOO-, RSO3 or RSO4- ion, wherein R is a hydrocarbon group of 1 to 10 carbon atoms; or an amino residue from a basic amino acid of the protein which may be mono- or di-substituted with an R3 group as defined above; with the proviso that Z is only SO3 - M + or SR3 when the protein contains cysteine; q is an integer from 1 to 5 with the proviso that, when Z is SO3 -M+ or SR3, q is 1 and the protein contains cysteine; the units A make up 1 to 70% by weight of the protein derivative; and the units B make up 0to 15% by weight of the protein derivative.

The protein from which the protein derivative of formula (I) is prepared may originate from many sources.

Thus, the parent protein may be of animal origin and can originate from, for example, keratin, gelatin, egg albumin, blQod serum albumin, casein or lactalbumin. The keratin can originate from, for example, hair, wool, hpm, animal hairs, bristles or feathers. The parent protein may also be of vegetable origin, for example originating from soya, groundnut or cotton seed.

The protein derivative can be a protein hydrolysate, which has been chemically modified for grafting the residues of the coloured molecules after the hydrolysis from which it has arisen.

The group Y of the chemically modified protein derivative of formula (I) may be an azo dye residue, an anthraquinone dye residue, a naphthoquinone dye residue, a residue of a phthalocyanin derivative or a residue of a nitrated derivative of the benzene series.

More particularly, Y may be a residue of the azo dyes, anthraquinone dyes or phthalocyanin derivatives which are defined in "Colour Index" (3rd edition, volume 3, pages 3391 to 3560 [1971] and reversed 3rd edition, volume 6, pages 6265 to 6345 [175]) under the designation "reactive", the residue -X- then being;

where R =

-SO2-CH2-CH2-;

Most particularly, Y may be a residue of the dyes defined in "Colour Index" under the references:: Cl 13245 ("Reactive Yellow 3") CI 14824 ("Reactive Red 22") Cl 16202 ("Reactive Red 23") Cl 17865 ("Reactive Orange 2") CI 17756 ("Reactive Orange 7") Cl 17757 ("Reactive Orange 16") CI 17910 ("Reactive Red 9") Cl 18096 ("Reactive Violet 4") Cl 18097 ("Reactive Violet 5") Cl 18 105 ("Reactive Red 4") Cl 18156 ("Reactive Red 12") Cli 8 157 ("Reactive Violet 2") Cli 18159 ("Reactive Red 3") CI 18852 ("Reactive Yellow 17") CI 18972 ("Reactive Yellow 2") Cl 18990 ("Reactive Yellow 13") Cl 19036 ("Reactive Yellow 14") Cl 61 200 ("Reactive Blue 19") Cl 61 210 ("Reactive Blue 5") Cl 61 211 ("Reactive Blue 2") Cl 74460 ("Reactive Blue 7") Cl 74459 ("Reactive Blue 15") Y may also originate from dyes possessing a carboxylic acid or sulphonic acid group, the residue -Xassociated with these two Y residues being respectively

and the associated residue -T- being NH.

Y may also be of the formulae:

which may originate, respectively, from the following dyes:

Cl 13020 ("Cl Acid Red 2"); and

Cl 13,025 ("Cl Acid Orange 52") If Y is either of these two groups, the grafting onto the protein chain is accomplished by the formation, respectively, of an amide or sulphonamide.

Y can also originate from dyes possessing a 2,3-epoxy-1-propyloxy function, in which case -X- is -CH2-CHOH-CH2-O- and -T- is -NH- or-O-.

Y may also be:

which may originate from the following dye:

which originates, for (C1), from 2,4-dinitro-1 -chlorobenzene or from 2,4-dinitro-1 -fluorobenzene, which can react with the amino functions of the protein with elimination of hydrochloric acid or hydrofluoric acid, respectively, and, for (C2), from 2,3-dichloro-1 ,4-naphthoquinone, which can react with the amino functions of the protein with elimination of hydrochloric acid and hydrolysis of the second chlorine atom. Under these conditions, -X- is a direct bond and -T- is -NH-.

When Z denotes SR3, it is preferred that p is 0 and R4 is a hydrogen atom in the formulae (II) and (IV).

Chemically modified protein derivatives of formula (I) may be prepared as follows: The starting protein may optionally be subjected to acid hydrolysis or enzymatic hydrolysis, so that the molecular weight of the hydrolysate obtained is from about 500 to 50,000; The grafting of the residues of coloured molecules onto the protein molecule is carried out by reacting all or part of the amino, alcohol or thiol groups of the protein with one or more compounds of formula: Y-X' wherein Y has the same meaning as above and Xis a reactive group containing one or more nucleofuges or one or more activated double bonds; Then, optionally, if any available amine groups remain after the chemical grafting of the coloured molecules, an N-alkylation phase is carried out using an alkylating agent of the formulae::

wherein X1 is a halogen atom, R4, R5 and p have the same meaning given above and R7 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms; After this, if the protein used contains cysteine, either all or part of the disulphide bridges of the cysteine groups may be oxidised in the protein so as to obtain acid -SO3H groups, this oxidation optionally being followed by salification of the abovementioned acid -SO3H groups; or alternatively all or part of the disulphide bridges of the cysteine groups are reduced in the protein so as to obtain thiol groups, this reduction being followed by S-alkylation using an alkylating agent of the formulae (ilk), (lily), (IVa) and (lV'a) defined above.

X' may be chosen from those described in "The Chemistry of Synthetic Dyes", Vol. VI, pages 1 to 209 (Ed.

K. VENKATARAMAN, Academic Press, New York 1972).

If Y is a residue of an azo dye, an anthraquinone dye or a phthalocyanine derivative of the formulae given in "Colour Index" (3rd edition, volume 3, pages 3391 to 3560 [1971] and revised 3rd edition, volume 6, pages 6265 to 6345 [1975]) underthe designation "reactive", X' may be:

where R =

-SO2-CH2-CH2-OSO3Na;

-SO2-NH-CHrCH2-OSO3Na;

If Y is a residue of a dye possessing a carboxylic acid function or sulphonic acid function, such as, for example, the residue of a dye of the formulae:

Cl 13 025 ("Cl Acid Red 2")

Cl 13 025 ("Cl Acid Orange 52") X' is, respectively,

If Y is a residue of a dye possessing a 2,3-epoxy-1 -propyloxy function, for example the residue of a dye of the formula:

X' is

If Y-X- is represented by::

it is seen that Y-X' is respectively or

where X' = Cl or F, which is converted in alkaline medium at the time of grafting onto the protein, to

The process for the preparation of the protein derivative incorporates successive phases, nameiy an optional first hydrolysis phase, a second chemical grafting phase, optionally a third phase of N-alkylation, and optionally a fourth phase, either of oxidation or of S-alkylation on reduced -SH groups. The order of the phases 2,3 and 4 can be transposed.

The optional first phase of the preparation process can be a conventional acid hydrolysis or an enzymatic hydrolysis using proteolytic enzymes, for example proteinase "PSF 2019", pronase, trypsin and papain. The working conditions, for example the pH and enzyme/substrate ratio for the hydrolysis vary according to the enzyme used.

The second phase of the preparation process consists in particular in grafting compounds bearing chromophoric or chromogenic groups onto the amino, alcohol orthiol sites of the protein. These compounds possess a reactive group containing one or more nucleofuges or alternatively one or more activated double bonds which permit grafting by addition or nucleophilic substitution. The grafting may be performed in a conventional manner under variable pH conditions, according to the nature of the reactive group and of the protein.

The third optional phase of the preparation process may consist in an N-alkylation using an alkylating agent of formulae (lea), (lily), (IVa) or (lV'a) given above. The N-alkylating agent used advantageously may have the formula: X-CH2-CO2-M+, Xr and Ms having the meaning given above. The preferred N-alkylating agent is monochloroacetic acid.

The optional fourth phase of the process can consist either of oxidation of the disulphide bonds of the cysteine groups of the protein, or else of S-alkylation of the -SH groups obtained by prior reduction of the disulphide bridges of the protein by a solution of a reducing agent, an alkali metal thiogylcolate or ammonium thioglycolate.

Oxidation of the protein which has undergone above treatment or treatments converts cysteine groups of the protein to cysteic acid groups. This oxidation is advantageously carried out in acid medium using an oxidising agent such as hydrogen peroxide or a peracid. The oxidation can optionally be followed by a salification ofthe-SO3H group.

S-alkylation is carried out using an alkylating agent, preferably of formulae (ilk), (lily), (IVa) or (lV'a) given above, the preferred agents and the especially preferred agent being those given in relation to the N-alkylation.

The colour of the keratin derivatives of formula (I) depends on the nature of the coloured molecule grafted.

The proportions of the compound or compounds of formula (I) in the compositions according to the invention vary according to the nature of the coloured molecule grafted onto the protein and to the intensity of the coloration sought for the composition. In the composition according to the invention, the compound or compounds of formula (I) may be dissolved in a solvent, for example water, a lower monoalcohol or polyol or an aqueous-alcoholic mixture. The preferred mono- or polyalcohols are ethanol, isopropanol, propylene glycol or glycerin. The compounds offormula (I) can also be dispersed in non-aqueous supports.

If the compositions according to the invention are intended for colouring keratin fibres such as human hair and nails, especially human hair, the coloured proteins are generally present in a proportion of from 0.005% to 10%, and preferably of from 0.02% to 8%, by weight relative to the total weight of the composition. The pH of the composition is preferably from 5 to 11, and more preferably from 6 to 10. The compositions according to the invention used in this manner are preferably applied for 1 to 45 minutes, more preferably 5 to 30 minutes, although for lotions applied as a hair rinse, there is no treatment time, the said lotions being applied and then dried.

The compositions according to the invention can also be used in the form of coloured lacquers, optionally in aerosol form using a propellent.

The compositions according to the invention can be used in direct dyeing and can contain, in addition to the coloured proteins, other colorants, in particular direct dyes such as azo dyes, anthraquinone dyes, nitrated dyes of the benzene series, 2,5-diaminoquinones, indophenols, indoanilines and indamines.

The compositions according to the invention can also be used in oxidation dyeing and can contain, in addition to the coloured proteins, precursors of oxidation dyes, for example precursors of the "para" type, such as diamines or aminophenols in which the functional groups are in the para-position with respect to one another, and precursors of the "ortho" type, in which the groups are in the ortho-position with respect to one another, and also couplers such as m-diamines, m-aminophenols, m-diphenols and phenols.

The compositions according to the invention can also contain alkalisation or acidification agents and/or solvents and/or polymers and/or treatment products of cationic character and/or amides and/or thickeners and/or surfactants and/or additives commonly used in capillary cosmetics, such as sun filters, optical blues, antioxidants, sequestering agents and perfumes.

The alkalisation agents which may be present in the compositions according to the invention can be, for example, mono- ortriethanolamine, ammonia, sodium phosphate or sodium carbonate. The acidification agents which may be present in the composition according to the invention can be, for example, phosphoric, hydrochloric, lactic, tartaric, acetic or citric acid. These alkalisation or acidification agents are intended for adjusting the pH of the tinctorial composition to the desired value.

The solvents present in the compositions according to the invention may be alcohols of 2 to 4 carbon atoms, such as ethyl or isopropyl alcohol or gylcols such as ethylene gylcol, propylene glycol, or butylene glycol, or glycol ethers such as the methyl, ethyl or butyl ether of ethylene glycol. The solvent is preferably present in an amount of from 0.5 to 50% by weight, preferably from 1 to 15% by weight, relative to the total weight of the composition.

The polymers which may be present in the composition are cosmetically acceptable polymers known to the specialist.

These polymers may be used at concentrations of from 0.1 to 4% by weight, preferably from 0.3 to 2% by weight, relative to the total weight of the composition.

The amides which may be present in the compositions according to the invention can be mono- or diethanolamides of fatty acids, optionally oxyethyleneated.

The thickeners may be cellulose derivatives such as carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

The surfactants may be anionic, cationic, non-ionic or amphoteric surfactants, such as sulphates, ether sulphates, fatty alcohol sulphonates, oxyethyleneated fatty acids or alcohols, oxyethyleneated alkyphenols, amines and quaternary ammonium salts.

When the compositions constitute oxidation dyes, they may also contain an oxidising agent which can be hydrogen perioxide, urea peroxide or a peroxy-salt such as ammonium persulphate. The oxidising agent is preferably added to the composition immediately before use.

The compositions according to the invention may be in many forms, for example in the form of a gel, cream, foaming liquid or milky liquid, and can be packaged in, for example, bottles, tubes or aerosols.

If compositions according to the invention are treatment and/or make-up products for the skin surface, the coloured protein derivatives have the function of colouring the composition itself or the skin surface, and they can simultaneously confer on the latter the treatment effect and protection effect due to the presence of the protein chains.

The compositions according to the invention intended for application to the skin preferably contain the compound or compounds of formula (I) in an amount of from 0.01to 10% by weight, relative to the total weight of the composition.

The cosmetic make-up compositions according to the invention may, for example, take the form of sticks, pastes, emulsions, suspensions, dispersions, powders or solutions, and may form lipsticks, mascaras, lip glosses, blushers, eye shadows, make-up foundations, eyeliners or powders.

The coloured protein can be associated with inorganic or organic pigments, and especially with lacquers such as those commonly used.

The inorganic pigments are in general iron oxides (red, brown, black and yellow), chromium oxides, the ultramarines (aminosilicate polysulphides), titanium dioxide, manganese pyrophosphate and Prussian Blue (ferric ferrocyanide). These various compounds alone or mixed together are generally employed at concentrations of from 0.1 to 40% by weight with respect to the total weight of the cosmetic composition.

These compositions can also contain agents imparting pearlescence such as bismuth oxychloride, titanium mica and guanine crystals.

When the compositions take the form of sticks, especially lipstick, eye shadow, blusher and make-up foundation, a significant part of the compositions may consist of a fatty substance which can comprise one or more waxes, for example ozokerite, lanolin, lanolin alcohol, hydrogenated lanolin, acetylated lanolin, lanolin wax, beeswax, candellila wax, microcrystalline wax, carnauba wax, cetyl alcohol, stearyl alcohol, cocoa butter, lanolin fatty acids, petrolatum, vaselines, mono, di- and triglycerides solid at 25"C, fatty esters solid at 25"C, silicone waxes such as methyloctadecane-oxypolysiloxane and poly(dimethylsiloxy)stearoxysiloxane, stearic acid monoethanolamide, colophony and its derivatives such as glycol abietate and glycerol abietate, hydrogenated oils solid at 25at, sucroglycerides, and calcium, magnesium, zirconium and aluminium oleates, myristates, lanolates, stearates or dihydroxystearates.

The fatty substance may also consist of a mixture of at least one wax and at least one oil, for example: paraffin oil, purcellin oil, perhydrosqualene, sweet-almond oil, avocado oil, oil of calophyllum, castor oil, sesame oil, jojoba oil, mineral oils having a boiling point between 310 and 410"C, silicone oils such as dimethylpolysiloxanes, linoleyl alcohol, linolenyl alcohol, oleyl alcohol, the oil of cereal seeds such as wheatgerm oil, isopropyl lanolate, isopropyl palmitate, isopropyl myristate, butyl myristate, cetyl myristate, hexadecyl stearate, butyl stearate, decyl oleate, acetylglycerides, octanoates and decanoates of such alcohols and polyalcohols as glycol and glycerol, the ricinoleates of alcohols and polyalcohols such as cetyl ricinoleate, isostearyl alcohol, isocetyl lanolate, isopropyl adipate, hexyl laurate or octyldodecanol.

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

The compositions may also contain other ingredients such as glycols, polyethylene glycols, polypropylene glycols, monoalkanolamides, uncoloured polymers, inorganic or organic fillers, preservatives, UV filters or other additives common in cosmetics, The compositions in stick form may contain a quantity of water, generally not exceeding 40% relative to the total weight of the cosmetic composition.

When the cosmetic compositions according to the invention are semi-solid in form, that is in the form of pastes or creams, they may be used as a mascara, an eyeliner, a make-up foundation, a blusher, an eye shadow, a lipstick, or a concealer.

These pastes or creams may be emulsions of the water-in-oil or oil-in-water type, in which the fatty phase preferably represents from 1 to 98.8% by weight and the water phase preferably represents from 1 to 98.8% by weight and the emu Isifier preferably represents from 0.1 to 30% by weight.

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

When the compositions take the form of a powder, they may consist essentially of an inorganic or organic filler such as talc, kaolin, starches, polyethylene powders or polyamide powders, as well as additives such as binders, colourings and the like.

Such compositions can also contain various additives commonly used in cosmetics such as perfumes, antioxidants and preservatives.

The invention is further described with the aid of the following Examples.

Example 1 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of unit A is approximately 61% by weight, M+ denotes H and the unit A has the formula:

Q denoting alkyl, aryl or aralkyl groups of the amino acids of the protein, and T denoting NH or O or S.

The protein derivative on which the grafting is performed is a keratin hydrolysate.

Firststage: Hydrolysis of the keratin: a) A suspension of 100 g of chicken feathers is brought to reflux in the course of 1 hour in 2 litres of dimethylformamide and 0.8 litre of water. The mixture is filtered hot and the treated feathers are washed with 2 litres of water and dried in the air.

b) 100 g of treated feathers are suspended in 2 litres of water. The pH is adjusted to 8.6-9.0, and the temperature is adjusted to 40"C. 3.5 g of enzyme PSF-2019 are added. The pH is maintained between 8.5 and 8.8 by adding 3% strength caustic soda. After addition of 1 litre of 3% strength caustic soda, the pH is allowed to fall to 8.45 and is then adjusted to pH 7 with dilute hydrochloric acid. The mixture is heated at 950C for 5 minutes to inactivate the enzyme, and is then allowed to return to room temperature. A little insoluble material is filtered off and the filtrate is lyophilised. 50 to 60 g of keratin hydrolysate is obtained in the form of a beige powder.

The content of free amines is 2 meq/g.

Second stage: Grafting of the dye: The following are heated to 40 C; - 5 g of keratin hydrolysate obtained as above - 20 cm3 of water - 20 cm3 of acetone - 1 N caustic soda, in sufficient quantity to bring the pH to 9.

There are added, in the course of 2 hours, 9 of REMAZOL R BRILLIANT BLUE R (Cl No.61 200) at 50% strength, which possesses the following structure:

The pH is maintained between 8.8 and 9.2 by adding 1N caustic soda.

The mixture is stirred for 2 hours after the end of the addition of dye, and is then diluted with 150 cm3 of water. The pH is adjusted to 3 by adding concentrated hydrochloric acid. The coloured protein precipitates. It is filtered off, washed with 8 times 150 cm3 of water and dried in the air.

5 g of coloured keratin are obtained in the form of a blue powder possessing the following characteristics: Xmax = 594 nm (measured in an aqueous solution containing 1% coloured protein) percentage of grafted dye = 61% Example 2 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of units A is approximately 68% by weight, Mt denotes Hw+ and the unit A has the formula:

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

The protein derivative on which the grafting is performed is a casein hydrolysate. Firststage: Hydrolysis of the casein: 100 g of nutrient casein is suspended in 1 litre of water. The pH is adjusted to between 1.8 and 2.0 by adding 35% strength hydrochloric acid. After the temperature has stabilised at 38 t 1"C, 0.2 g of SIGMAB pepsin 1 :60,000 is added. Stirring is maintained for 8 hours at this temperature, and the enzyme is then inactivated at pH 8-8.5 for 10 hours. The solution is ultrafiltered so as to remove inorganic salts and the fraction of molecular mass below 1000. After lyophilisation, there are obtained 85 g of hydrolysate possessing an amine content of 2.54 meq/g.

Second stage: Grafting ofthe dye: The following are heated to 40at: - 5 g of casein hydrolysate obtained as above - 25 cm3 of water - 25 cm3 of acetone - 1 N caustic soda in sufficient quantity to bring the pH to 9.

There are added, in the course of 1 hour 30 minutes, 11.8 g of CIBACRON BRILLIANT RED 3 BA (Cl No.

18,105), which possesses the following structure:

The pH is maintained between 8.8 and 9.2 by addition of-1 N caustic soda.

The mixture is stirred for 4 hours after the end of the addition of the dye. The pH is adjusted to 2.2 by adding 2N hydrochloric acid. The coloured protein precipitates. The product is filtered, washed copiously with water and dried in the air.

There are obtained 4.5 g of coloured casein in the form of a red powder possessing the following characteristics: Xmax = 517 nm (measured in an aqueous solution containing 1% colour protein) Percentage of grafted dye = 68%.

Example 3 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of unit A is approximately 34% by weight, M'3 denotes Na and the unit A has the formula:

Q denoting alkyl, aryl or aralkyl groups of the amino acids of the protein and T denoting NH or O or S.

The following are heated to 45"C: - 10 g of the keratin hydrolysate obtained in the first stage of Example 1 - 50 cm3 of water - 50 cm3 of acetone - 30% strength caustic soda in sufficient quantity to bring the pH to between 8.5 and 9.5.

There are added, in the course of 2 hours, 10.3 g of CIBACRONB BRILLIANT YELLOW 3 G-P (Cl No. 18,972) which possesses the following structure:

The pH is maintained between 8.5 and 9.5 by addition of 30% strength caustic soda.

The mixture is stirred for 1 hour at 45"C after adding the dye, and the reactants are then left in contact overnight at room temperature.

The reaction mixture is adjusted to pH3 by adding concentrated hydrochloric acid. It is filtered and the precipitate is washed copiously with water and then redissolved at pH 7.5 by adding caustic soda.

After lyophilisation, there are obtained 3 g of coloured keratinin the form of a yellow powder possessing the following characteristics: Xmax = 403 nm (measured in aqueous solution containing 1% of coloured protein) Percentage of grafted dye = 34%.

Example 4 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of the unit A is approximately 10% by weight, M t and H + and the unit A has the formula:

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

The protein derivative on which the grafting is performed is a gelatin hydrolysate.

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

The blue powder obtained possesses the following characteristics: Xmax = 596 m, (measured in aqueous solution containing 1% coloured protein) Percentage of grafted dye = 62%.

Example 5 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of the unit A is approximately 16% by weight, M + denotes Na + and the unit A has the formula:

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

9.03 g of gelatin ASF ROUSSELOT are dissolved in 35 cm3 of water and 35 cm3 of acetone. The pH of the solution is adjusted to 9.5 by means of 4N caustic soda. 4.8 g of 4-chlorosulphonyl-4' (dimethylamino)azobenzene are introduced slowly while maintaining the pH of the reaction medium between 9 and 9.5 by adding 4N caustic soda. The reaction is allowed to continue for 15 hours at room temperature, and the acetone is then distilled off under reduced pressure. The aqueous solution thus obtained is dialysed and then lyophilised. There are obtained 5.2 g of coloured gelatin in the form of an orange powder which possesses the following characteristics: Xmax = 445 nm (measurement made in N/10 solution of NaOH containing 1% coloured protein) Percentage of grafted dye = 16%.

Example 6 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of the unit A is approximately 12% by weight, M + denotes (CH3CH2)3N + H and the unit A has the formula:

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

A solution containing 20 g of gelatin ASF ROUSSELOT,6.16 g of 2,4-dinitro-1 -fluorobenzene and 5.32 cm3 oftriethylamine in 80 cm3 of water and 80 cm3 of acetone is heated under reflux for 2 hours 30 minutes. After being cooled, the reaction mixture is poured into 500 cm3 of acetone. The gummy precipitate is washed with acetone, then ground and dried. There are obtained 17.5 g of coloured gelatin in the form of a yellow powder which possesses the following characteristics: Xmax = 340 nm (measurement made in a N/10 solution of NaOH containing 1% coloured protein).

percentage of grafted dye = 12% Example 7 preparation of a coloured protein derivative of formula (i) in which formula the proportion of units B is nil, the proportion of the unit A is approximately 5% by weight, M + denotes H + and the unit A has the formula:

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

A suspension of 8.16 g of gelatin ASF ROUSSELOT and 2.75 g of 1 -epoxypropyloxy-3-methylamino-4- nitrobenzene in 130 cm3 of ethanol containing 1.9cam3 of triethylamine is heated for 8 hours at 80"C. At the end of the reaction, the ethanol is distilled off under reduced pressure. The residue is redissolved in 50 cm3 of water. The pH of the solution is adjusted to 2 by means of dilute hydrochloric acid. The solution is poured into 200 cm3 of acetone. The gummy precipitate is washed with acetone, and then ground and dried under vacuum. There are obtained 7 g of coloured gelatin in the form of a yellow powder which possesses the following characteristics: wax = 428 nm (measurement made in a N/10 solution of NaOH containing 1% coloured protein).

Percentage of grafted dye = 5% Example 8 Preparation of a coloured protein derivative of formula (I), in which formula the proportion of units B is nil, the proportion of the unit A is approximately 14% by weight, M + denotes H + and the unit A has the formula:

6.02 g of gelatin ASF ROUSSELOT, 1.14 g of 2,3-dichloro-1 ,4-naphthoquinone in 30 cm3 of ethanol and 5 cm3 of water containing 1.01 g of triethylamine are heated for 5 hours at 80 C. The reaction mixture is concentrated under reduced pressure. The residue is taken up in 150 cm3 of water and the solution is adjusted to pH 4.2 with dilute hydrochloric acid. The gummy precipitate is washed with water and then acetone, ground and dried. There are obtained 3.03 g of coloured gelatin in the form of a brown powder possessing the following characteristics: Xmax = 465 nm (measurement made in a N/10 solution of NaOH containing 1% coloured protein) Percentage of grafted dye = 14%.

Example 9 A setting lotion having the following formulation is prepared: - Compound of Example 1 ......................................................................... 0.1 g - Vinyl acetate/crotonic acid (90:10) copolymer ................................................. 1.8 g - Vinylpyrrolidone/vinyl acetate (60:40) copolymer ............................ 0.4 g - Ethyl alcohol ............................... qs 50 alcoholic strength -Triethanolamine qs pH 7 qspH7 -Demineralised water ........................................................................................... qs 100 g This setting lotion is applied to brown hair. After drying and shaping, the hair possesses an ash-grey tone.

Example 10 A lotion having the following formulation is prepared: -Compound of Example2 ......................... 0.05g - Dye "Cl 62 045" sold under the name "Bleu dimacide A 2 BL" by the Société "PCUK" ........................... 0.04 g -2-(,-Hydroxyethyl )amino-5-hydroxy-1 -nitrobenzene ......................... 0.02 g - Dye "Cl 13 065" sold under the name "Jaune acétacide 4 R extra" by the Société "PCUK" ............... 0.02 g -Vinyl acetate/vinylpyrrolidone (30::70) copolymer ......................... 0.6 g - Ethyl alcohol ............................................................................... 10 g - Propylene glycol .............................................................................. 1 g - Nonylphenol oxyethyleneated with 9 mol of ethylene oxide ............................. 2 g - Triethanolamine ......................................................................... qs pH 7 - Demineralised water ................................................................... qs 100 g This liquid is applied to dark chestnut-coloured hair. The hair is dried and then possesses a copper-coloured dark auburn tone.

Example 11 A setting lotion having the following formulation is prepared: -Compound of Example3 ................................ 0.05g - 2-(ss-Hydroxyethyl)amino-4'-(N,N-bis-[ss-hydroxyethyl]amino)-5-anilino-1,4-benzoquinone 0.016 9 - 3-(N-[2-Chloro-4-hydroxyphenyl]-N-acetylamino)-6-methoxy-1,4-benzoquinoneimine 0.024 g - 3-(N-[3-Chloro-4-methylaminophenyl]ureido)-6-methyl-1,4-benzoquinoneimine 0.009 9 -Vinyl acetate/crotonic acid (90:10) copolymer ........................................ 2.7 g - Vinylpyrrolidone/vinyl acetate (60::40) copolymer ............................................................ 0.5 g - Ethyl alcohol ......................... qs 50 alcoholic strength - Triethanolamine ........................................................................... qs pH 7 - Demineralised water ............................... qs 100 g This setting lotion is applied to light chestnut-coloured hair. After drying, there is obtained hair with a dark auburn-brown tone.

Example 12 A temporary colouring product having the following formulation is prepared: - Compound of Example 2 .................................................................................. 0.05 g - Dye "Cl 20 170" sold under the name "Brun clair sella acide RF" by the Société "CIBA GEIGY" ........... 0.015 g - Dys "Cl 62 045" sold underthe name "Bleu dimacide A 2 BL" by the Société "PCUK" ........................ 0.02 g - Vinyl acetate/vinylpyrrolidone (30::70) copolymer ................................................................ 0.6 g - Ethyl alcohol .................................................................................................... 10 g - Propylene glycol ............................ 1 9 - Nonylphenol oxyethyleneated with 9 mpl of ethylene oxide ................................... 2 9 - Triethanolamine ............................................................................................... qs pH 7 - Demineralised water : qs 100 g This temporary colouring product is applied to light blond hair. After drying, the hair possesses a pearly beige tone.

Example 13 A styling lotion having the following formulation is prepared: - Compound of Example 1 .............................................................................................. 0.1 g - Compound of Example 2 ............................................................................................. 0.05 g - Vinyl acetate/crotonic acid (90:10) copolymer : 2.7 g - Vinylpyrrolidone acetate (60::40) copolymer ........................................................................ 0.5 g - Ethyl alcohol ................................................................................... qs 50 alcoholic strength - Triethanolamine .................................................................................................. qs pH 7 - Demineralised water .............................. qs 100 g This styling lotion is applied to light chestnut-coloured hair. After drying, an ash-mauve tone is obtained.

Example 14 A setting lotion having the following composition is prepared: - Compound of Example 2 ..................................................................................................... 0.1 g - Vinyl acetate/crotonic acid (90:10) copolymer .................... 1.8 g - Vinylpyrrolidone/vinyl acetate (60:40) copolymer ................................... 0.4 g - Ethyl alcohol .............................. qs 50 alcoholic strength - Triethanolamine .......................................................................................................... qs pH 7 - Demineralised water ............................... qs 100 g This composition is a setting lotion which is applied to chestnut-coloured hair. After drying and styling, the hair is shaded in a dark auburn tone.

Example 15 A liquid composition having the following formulation is prepared: - Compound of Example 1 ........................................................................................................ 0.03 g - Compound of Example 2 ........................................................................................................ 0.02 g - Dye "Cl 62 045" sold under the name "Bleu dimacide A 2 BL" by the Société "PCUK" .................. 0.01 g -2-(ss-Hydroxyethyl)amino-5-hydroxy-1-nitrobenzene ............................................................................. 0.01 g - Dye "Cl 13 065" sold under the name "Jaune acétacide 4 R extra" by the société "PCUK" 0.02 9 - Vinyl acetate/vinylpyrrolidone (30: :70) copolymer ............................................................................ 0.6 g - Ethyl alcohol ................................................................................................................ 10 g - Propylene glycol ............................. 1 9 - Nonylphenol oxyethyleneated with 9 mol of ethylene oxide ................................ 2 9 - Triethanolamine ............................................................................................................ qs pH 7 - Demineralised water ............................ qs 100 g This liquid composition is applied to natural or dyed dark blond hair. After drying, the hair is tinted with a beige copper-coloured tone.

Example 16 The oxidation dye having the following formulation is prepared: - Compound of Example 4 ...................................................................................................... 0.2 g - Compound of Example 1 ...................................................................................................... 0.1 g - para-Toluenediamine ....................................................................................................... 0.35 g - para-Aminophenol ........................................................................................................... 0.09 g - Resorcinol ........................................................................................................................ 0.25 g -meta-Aminophenol 0.1 g - Nonylphenol oxyethyleneated with 4 mol of ethylene oxide, sold under the name "REMCOPAL 334" bytheSoci6t6"GERLAND" 22 9 - Nonylphenol oxyethyleneated with 9 mol of ethylene oxide, sold under the name "REMCOPAL 349" by the Société "GERLAND" ........................................................................................................... 22 g - Butyl cellosolve ............................................................................................................ 8 g - Propylene glycol ........................................................................................................... 8 g - Ethylenediaminetetraacetic acid ................................. 0.2 g - Ammonia at 22 Be ........................................................................................................ 4 cm -Sodiumbisulphiteat350Be 1cm3 - Water ................................................................................................................... qs 100 g This liquid is mixed with an equal weight of 6% strength hydrogen peroxide immediately before dyeing.

Applied to light chestnut-coloured hair, it imparts, after 30 minutes of exposure at room temperature, rinsing and drying, a dark ash-blond colour.

Example 17 The lipstick having the following composition is prepared: - Compound of Exampl2 2 ........................................................................................................ 2 g - Castor oil .................................................................................................................. 65 g - Lanolin ..................................................................................................................... 10 g - Isopropyl myristate X 5 g - Beeswax ..................................................................................................................... 6 g -Carnaubawax wax - Candellila wax ................................................................................................................. 3 g - Ozokerite ...................................................................................................................... 3 g The oils and fatty substances are heated to about 60-65 C, and at this temperature the coloured protein is dispersed with vigorous stirring. After cooling, a magenta-coloured stick is obtained.

Example 18 The make-up foundation having the following composition is prepared: -Compound of Example3 ................................ 1.5g - Compound of Example 2 ............................................ 0.1 g - Lanolin fatty alcohols oxyethyleneated with 20 mol of ethylene oxide ........................ 7 g -Triglycerides of coconut fatty acids .............................. 30 g - Glycerol monostearate .............................. 2 9 -Silicone oil 1.5 9 - Cetyl alcohol ................................................................................................................. 1.5 g - Water ..................................................................................................................... qs 100 g The coloured proteins are dissolved in water containing the emulsifiers (oxyethyleneated lanolin fatty alcohols and glycerol monostearate).

The aqueous phase is heated to about 80 C; the fatty phase, previously heated to 800C, is added with vigorous stirring. The mixture is allowed to return to room temperature with moderate stirring.

A make-up foundation is obtained which can be applied readily and uniformly to the skin.

Example 19 The setting lotion having the following composition is prepared: - Compound of Example 6 ....................................................................................................... 0.14 g - Compound of Example 1 ........................... 0.06 g - Compound of Example .................................................................................................. 0.08 g - Vinyl acetate/vinylpyrrolidone copolymer ........................... 1.2 g -Ethyl alcohol ...................................... 15g - Propylene glycol ................................................................................................ 1g - Triethanolamine ......................................................................................... qs pH 7.5 - Demineralised water qs qs 100 9 Applied to light chestnut-coloured hair, this setting lotion imparts, after drying, a dark chestnut colour with dark auburn tones.

Example 20 The make-up foundation having the following composition is prepared: - Compound of Example ..................................................................................................... 0.15 g - Compound of Example 7 ....................................................................................... 1.1 g - Compound of Example 8 ....................................................................................... 0.4 g - Lanolin fatty alcohols oxyethyleneated with 20 mol of ethylene oxide .......................... 7 g - Triglycerides of coconut fatty acids ................................ 30 g - Glycerol monostearate ......................................................................................... 2 g -Silicone oil 1.5 9 - Cetyl alcohol .............................................................................................. 1.5 g water qs 100 9 qslOOg The procedure is as described in Example 18. A make-up foundation which can be readily and uniformly applied to the skin is likewise obtained.

Example 21 The hair dye having the following composition is prepared: - Compound of Example 3 ....................................................................................... 0.3 g - Compound of Example 5 ...................................................................................... 0.45 g - Compound of Example 8 ...................................................................................... 0.51 g - N-methyl-N4,N4-bis-(ss-hydroxyethyl)-2-nitro-para-phenylenediamine .......................................... 0.1 g - (N-Nitro-3-methylaminophenoxy)ethanol ...................................................................... 0.06 g - Lauric acid amide ............................................................................................ 1.5 g - Lauric acid ................................................................................................... 1 g - Butylglycol ................................................................................................... 6 g - Hydroxyethylcellulose ......................................................................................... 5 g - Monoethanolamine qs qs pH 9 - Water ..................................................................................................... qs 100 g This composition is applied to blond hair for 20 minutes at room temperature. After rinsing, the hair is dyed a light chestnut colour.

Claims

1. A cosmetic colouring composition which comprises a cosmetically acceptable support and at least one chemically modified protein derivative which has a molecular weight of from 500 to 50,000 of formula (I):

in which -Y is a residue of a coloured molecule; -X is any group which joins the coloured molecule residue and the protein residue or is a direct covalent bond; -P1 and P2 are non-acylated protein residues which are not modified chemically by addition or nucleophilic substitution; -M+ is H+, a cation derived from an alkali metal or magnesium, or N+(R2)4, wherein the R2 groups, which may be identical or different, are a hydrogen atom or an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms; -Q is an alkyl, aryl or aralkyl residue of the constituent amino acids of the protein; -T is O, NH or, when the protein contains cysteine, S; -Z is:: a # SO3 -M+ residue, M+ having the same meaning as above; SR3, wherein R3 is:

wherein M+ has the same meaning as above, p isO or an integer from 1 to 5; R4 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms and R5 is::

wherein D is a linear or branched alkylene group of 2 to 10 carbon atoms, M t has the same meaning as above, the groups R6, which may be identical or different, are a hydrogen atom or an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms, E- is a halide, RCOO-, RSO3- or RSO4- ion, wherein R is a hydrocarbon group of 1 to 10 carbon atoms; or an amino residue from a basic amino acid of the protein which may be mono- or di-substituted with an R3 group as defined above, with the proviso that Z is only SO3 - M+ or SR3 when the protein contains cysteine; - q is an integer from 1 to 5 with the proviso that, when Z is SO3 M + or SR3, q is 1 and the protein contains cysteine; -the units A make up 1 to 70% by weight of the protein derivative; and - the units B make up 0 to 15% by weight of the protein derivative.

2. A composition according to claim 1, in which the protein is of animal origin.

3. A composition according to claim 2 in which the protein of animal origin is derived from keratin, gelatin, egg albumin, blood serum albumin, casein or lactalbumin.

4. A composition according to claim 1 in which the protein is of vegetable origin.

5. A composition according to claim 4 in which the protein of vegetable origin is derived from soya, groundnut or cotton seed.

6. A composition according to any one of the preceding claims, where the protein derivative consists of a protein hydrolysate which has been chemically modified after the hydrolysis from which it has arisen.

7. A composition according to any one of the preceding claims wherein Yin the protein derivative is an azo dye residue, an anthraquinone dye residue, a residue of a nitrated derivative of the benzene series or a residue of a phthalocyanin derivative.

8. A composition according to claim 7, wherein Y is an azo dye residue, an anthraquinone dye residue, or a residue of a derivative which corresponds to the formulae given in the "Colour Index" (3rd edition, volume 3, pages 3391 to 3560 [1971] and revised third edition, volume 6, pages 6265 to 6345 [1975]) under the designation "reactive" and residue -X- is

where R

-SO2-CH2-CH2-;

-SO2-NH-CH2-CH2-;

9.A composition according to claim 8, wherein Y is a residue of a dye as defined in "Colour Index" under the references: Cl 13 245 ("Reactive Yellow 3") Cl 14824 ("Reactive Red 22") Cli 16 202 ("Reactive Red 23") Cl 17 865 ("Reactive Orange 2") Cl 17 756 ("Reactive Orange 7") Cl 17 757 ("Reactive Orange 16") Cl 17 910 ("Reactive Red 9") Cl 18 096 ("Reactive Violet 4") Cl 18 097 ("Reactive Violet 5") Cl 18 105 ("Reactive Red 4") Cl 18156 ("Reactive Red 12") Cli 18 157 ("Reactive Violet 2") Cli 8 159 ("Reactive Red 3") Cl 18 852 ("Reactive Yellow 17") Cl 18 972 ("Reactive Yellow 2") Cl 18 990 ("Reactive Yellow 13") Cl 19 036 ("Reactive Yellow 14") Cl 61 200 ("Reactive Blue 19") Cl 61 210 ("Reactive Blue 5") Cl 61 211 ("Reactive Blue 2") Cl 74 460 ("Reactive Blue 7") or Cl 74 459 ("Reactive Blue 15")

10. A composition according to any one of claims 1 to 7, in which Y originates from a dye which contains a carboxylic acid or sulphonic acid group, and -X- associated with the Y residue being

respectively and -T- denotes NH.

11. A composition according to claim 10, in which Y is

which originate, respectively, from the dyes:

and Cl 13020 ("Cl Acid Red 2")

Cl 13025 ("Cl Acid Orange 52")

12. A composition according to any one of claims 1 to 8, in which Y originates from a dye which contains a 2,3-epoxy-1-propyloxy group, the associated residue -X- is -CH2-CHOH-CH2-O- and the associated residue -T- is -NH- or-O-.

13. A composition according to claim 12, in which Y is:

and originates from the dye:

14. A composition according to any one of claims 1 to 8, in which Y is:

the associated residues -X- is a direct bond, and the associated residue -T- is NH.

15. A composition according to any one of the preceding claims in which the compound of formula (I) has a molecular weight of from 5,000 to 30,000.

16. A composition according to any one of the preceding claims in which the protein derivative or derivatives of formula (I) are dissolved in a solvent which is water, an alcohol of 2 to 4 carbon atoms, a polyol or an aqueous-alcoholic mixture or a glycol ether.

17. A composition according to any one of the preceding claims for colouring keratinous supports which contains from 0.005% to 10% by weight ofthe compound or compounds of formula (I), relative to the total weight of the composition.

18. A composition according to claim 17 which contains from 0.02% to 8% by weight of the compound or compounds of formula (I), relative to the total weight of the composition.

19. A composition according to claim 18 for use in direct dyeing which contains, in addition to the compound or compounds of formula (I), a direct dye which is an azo dye, an anthraquinone dye, a nitrated dye of the benzene series, 2,5-diaminoquinone, an indophenol, an indoaniline or a indamine.

20. A composition according to claim 18, for use in oxidation dyeing which contains, in addition to the compound or compounds of formula (I), a precursor of an oxidation dye which is a precursor of the "para" type or a precursor of the "ortho" type, and a coupler which is a m-diamine, a m-amino-phenol, a m-diphenol or a phenol.

21. A composition according to any one of claims 17 to 20 which contains an alkalisation or acidification agent and/or an oxidising agent and/or a solvent and/or a polymer and/or a treatment product of a cationic character and/or an amide and/or a thickener and/or a surfactant and/or an additive commonly used in capillar cosmetics.

22. A composition according to any one of claims 1 to 16 for application to the skin surface, in which the protein derivative or derivatives of formula (I) are present in a proportion of from 0.01 to 10% by weight relative to the total weight of the composition.

23. A composition according to claim 22, which contains at least one adjuvant which is an inorganic or organic pigment, a fatty substance, a glycol, a polyethylene glycol, a propylene glycol, a monoalkanolamide, an uncoloured polymer, a UV filter, a perfume, an antioxidant, a preservative or an inorganic or organic filler.

24. A composition according to any one of the preceding claims which has a pH of from 5 to 11.

25. A composition according to claim 24 in which the pH is from 6 to 10.

26. A composition according to any one of the preceding claims which is in the form of a lotion or lacquer, an emulsion in the form of a cream or milk, in gel form, in stick, dispersion or powder form, or an aerosol.

27. A composition according to claim 1 substantially as herein described in any one of Examples 9 to 21.

28. A composition according to claim 1 which contains a coloured protein derivative as described in any one of Examples 1 to 8.