LU82581A1 - HAIR DYEING PROCESS HAVING A SCALP PROTECTION STEP - Google Patents

Description

• 1>

Hair dyeing process comprising a step of protecting the scalp.

The present invention relates to a new process for dyeing human hair.

In the dyeing of keratin fibers and in particular human hair, there are essentially two types of dyeing: permanent dyeing and semi-permanent or direct dyeing.

The permanent coloring is obtained according to a process consisting in applying a dye composition which contains dye precursors known as oxidation and an oxidant added to said composition just before application, or a composition without oxidant, applied 1 * 5 directly on the hair when it contains so-called rapid oxidation dyes or certain diphenylamines, the oxygen in the air causing in the latter case the development of color.

Aromatic compounds PO are called oxidation dyes. .

of the diamme, ammophenol or phenol type which are not dyes in themselves but which are transformed into dyes by a process of oxidative condensation. Among these oxidation dyes, a distinction is generally made on the one hand, the para-oxidation dye precursors of the para type chosen from diamines or aminophenols whose functional groups are located in para relative to each other and, d on the other hand, the precursors of oxidation dyes of the ortho type, and modifier or coupler compounds which are generally so-called "meta" derivatives chosen more particularly from metadiamines, metaaminophenols, metadiphenols and also phenols.

Dye precursors of the benzene series comprising on the nucleus three substituents chosen from the group formed by groups are called rapid oxidation dyes. 55 pements hydroxy, methoxy, amino and likely to oxidize η / directly to air. / h d 2

H

In the following, the term “oxidizable dyes will be used to denote these different types of dye precursors.

In semi-permanent dyeing processes using S. .

direct dyes, a solution or dispersion of these dyes is simply applied to the hair.

The term "direct dyes" means compounds colored in themselves, and more particularly belonging to the class of> nitro derivatives of the benzene series, azo, anthraquinone, indophenols, indoanilines, indamines.

Means have long been sought for preventing or limiting the contact of the scalp with the products used in the dye compositions and in particular with direct dyes or dye precursors, as well as the intermediate products and the final products. resulting from oxidative condensation.

It is generally accepted that the quantities of products which may possibly penetrate into the stratum corneum are approximately proportional to the concentration of the products in the dye composition. Furthermore, it is recognized that some of the products present can subsequently diffuse into the body.

This possibility of diffusion in the organism, of the compounds present in the dye compositions, can not pose problems of general or specific toxicity.

In all cases, it is desired to protect the scalp from coloring substances.

The applicant has protected, in its Luxembourg patent application of December 13, 1979 (No. 81994) entitled "Hair dyeing process", the use of a composition having a viscosity suitable for its application on the head, based of a suspended mineral substance having adsorbent properties in order to avoid or at least limit contact of the scalp with the components generally used in oxidation dyes and consequently reduce penetration. Lar / / / plaintiff noted in particular that the application in uiy // Λ * 3 first time of a composition based on mineral substances in suspension having adsorbent properties nevertheless made it possible to dye the hair suitably while giving a good unison on all their length and in particular their roots.

The Applicant has now discovered what is the subject of the present invention that substances of plant or animal origin or synthetic organic substances having a viscosity suitable for application to the head and having covering properties also make it possible to avoid or at the very least to limit the contact of the scalp with the components generally used in oxidation dyeing or in direct dyeing.

It also discovered that the use of mineral substances in suspension and having the above-mentioned adsorbent properties made it possible to avoid or limit the penetration of direct dyes to the scalp.

She found that the use of these substances made it possible to dye the hair over its entire length, giving good unification.

The protective effect of the compositions based on these substances is demonstrated by the absence of spots on the scalp after dyeing according to this process.

Tests carried out on the rat show the very low penetration or non-penetration of the coloring substances into the epidermis.

This protective effect results in whole or in part from the adsorbent properties of the substances, from a chemical fixation of the coloring compounds on these substances, from a screen effect, from deactivation of the dye precursors or of the colored products before that these do not reach the scalp. It goes without saying that this explanation of the protective effect cannot be regarded as a limitation of the invention.

35 The present invention therefore relates to a hair dyeing process consisting in first applying at least one composition based on original substances / / TY <-r λ4 · 1 Λ r · Λ1 * -IW 1 m ^ 1 Λ "1 -1 Λ A m. . In ^ J. m U ~ A _ _ -A A -. _! - - _ _ _ __ _L_ Ta ίϊ i_ JH. . A Lm / / 4 in suspension or in solution in a solvent and having covering properties on the scalp. Other objects of the invention will result from reading the description and examples which follow.

The hair coloring process according to the present invention is essentially characterized in that a composition based on, substances of plant or animal origin or of synthetic organic substances in suspension or in solution in a first step is applied. a solvent and having a viscosity suitable for application on the head or in powder form and having covering properties and that, in a second step, the hair is dyed using one or more compositions, at least one of which contains a dye oxidizable and / or direct, the dyeing being followed after 1.5 hours of exposure sufficient to color the hair with a rinsing optionally followed by a shampoo.

The solvents making it possible to put the covering substances in suspension or in solution are chosen from cosmetically acceptable solvents such as more particularly water, alcohols such as ethanol or isopropanol, polyalkylene glycols such as polyethylene glycol, polyols such as glycerol or glycols and their mixtures.

The substances used according to the present invention must essentially have the following criteria when they are in suspension or in solution: (1) they must be covering so as to constitute, after application, an essentially continuous coating.

30 (2) they must have sufficient viscosity not to leak during application. Preferably suspensions or solutions of the above substances are used at a concentration sufficient to obtain a viscosity of 80 to 8000 cps at 20 ° C. /

35 (3) must be easily removed with water or / / V

shampoo.

* 5 (4) The following test must be positive, that is to say when the paper which has been protected by the composition according to the invention is practically not colored.

This test consists in applying the suspension containing the substance of vegetable or animal origin or the synthetic organic substance on white paper (Canson C with grain 180 g / m2) over 1 mm of thickness, the composition being deposited „between wedges 1 mm thick. The paper thus covered is dried at 50 ° C for 10 min. A conventional oxidation dye having the following composition is then deposited: Paraphenylenediamine dihydrochloride 2 g

2,4-diaminoanisol dihydrochloride 2.35 g and these dyes are dissolved in a support comprising:

Oleic alcohol with 2 moles EO 4.5 g ^ Oleic alcohol with 4 moles EO 4.5 g

Ethomeen C25 (polyethoxylated coconut amine with 15 moles of EO 4.5 g

Coconut fatty acid dietamides 9.0 g

Propylene glycol 3.6 g

ο O

Butoxyglycol 8.0 g

Ethanol at 96 ° 5.4 g

Sodium bisulphite at 35 ° Be 1.0 g

Ammonia at 22 ° Be 10, 0 g and water is added in sufficient quantities for 25 100 g. To 50 g of this composition is added 50 g of oxy water generated at 20 volumes. The dye composition is applied to the paper thus prepared, left to stand for 30 minutes and the excess dye is removed. We rub after this exposure time using a sponge soaked in shampoo. If the substance can be used for the purposes of the present invention the paper should hardly be colored.

It goes without saying that the substances selected must also be cosmetically acceptable and able to be brought into contact with the skin.

Among the more particularly preferred substances of vegetable origin, mention may be made of activated carbon prepared from vegetable matter such as wood, peat, lignite, kelp, which is carbonized. ; carrageenans which are essentially sulfate esters of polysaccharides extracted from red marine plants and in particular from "Chrondus Crispus". These products essentially contain lambda and Kappa carrageenate.

Among the substances of animal origin or may be cited animal black originating in particular from calcination in a closed cup of animal materials such as bone. Animal black or activated carbon is preferably used in the form of a suspension in polyethylene glycol. Animal black or activated carbon can also be used in powder form.

The synthetic organic substances are in particular cosmetically acceptable polymers having a molecular weight of between 50,000 and 500,000 and in particular salts of polystyrene sulfonic acid and in particular the sodium salts sold under the name Flexan such as more particularly the product sold under the name Flexan 130 having a molecular weight of about 100,000. Such compounds are described in French patent 2,198,729.

The mineral substances suspended in water are essentially based on alumina, alumino-silicates or aluminum phosphates and meet the four criteria above.

The products giving in this case particle results; are particularly satisfactory are based on clay such as preferably montmorillonites.

These mineral-based compositions make it possible to protect the scalp from direct dyes preferably used with thickening agents such as cellulose derivatives.

The list of preferred compounds indicated above would in no way be limiting and it goes without saying that those skilled in the art will be able to find other substances which can be used according to the invention in so far as they meet the requirements of the invention.

35 criteria defined above in particular with regard to / viscosity, covering properties and elimination with ali / or shampoo and the test on protected paper. / W

7 ♦

The amount of substances of plant or animal origin, synthetic organic substances or mineral substances having covering properties to be used in the suspensions used according to the present invention is between 1 and 60%.

In addition to the covering properties, the viscosity and the elimination properties mentioned above, the products used according to the invention must also allow the penetration of the dye into the hair so that the root thereof can be dyed. .

The composition once applied to the scalp is preferably dried by the usual means used in hairdressing salons such as under a helmet.

The dyeing methods used after this first treatment are methods well known in themselves which can take place in one or more stages and use very diverse compositions well known in the state of the art.

It is thus possible to apply, after treatment of the scalp 20 with the composition as defined above, either a composition containing at least one dye precursor of ortho or para type or their mixtures and to develop the coloring using an agent. oxidant present in the composition applied in the second stage of the process according to the invention or applied to the hair in a third stage and optionally direct dyes, ie a composition containing at least one direct dye.

Among the precursors of para type dyes, mention may be made more particularly of the compounds corresponding to the formula R1 R9 I / R6 -R3 fl 35 r5 r4% nh2 (I) “8 in which: and R2 independently denote the one on the other, hydrogen, phenyl, furfuryl, tetrahydrofurfuryl; a linear or branched alkyl group which may comprise, at the chain end, substitutions such as hydroxy, alkoxy, amine (the amine function may be primary, secondary or tertiary or may be part of a heterocycle such as piperidino, morpholino), acylamino, alkyl or arylsulfonyl-, amino, carbalkoxyamino, ureido, carboxy, carbamyl (in which the nitrogen atom can carry one or two substituents), sulfo, sulfonamido (in which the nitrogen atom can carry one or two substituents); this alkyl group can be interrupted by one or more heteroatoms such as oxygen, nitrogen and carry other alcohol or amine functions; R ^ and R2 can also form, together with the nitrogen atom to which they are attached, a heterocycle such as piperidino or morpholino; Ry R ^, Rg, Rg independently of one another, denote hydrogen, halogen, linear or branched alkyl optionally substituted by one or more OH, amino or alkoxy groups; an OZ group, Z denoting alkyl; hydroxyalkyl, alkoxyalkyl, acylaminoalkyl, carbalkoxyaminoalkyl; mesylaminoaicoyl, ureidoalkyl, aminoalkyl, mono- or di-alkylaminoalkyl, the alkyl radicals having 1 to 6 carbon atoms, provided that when R2 denotes phenyl R ^, R3, R4, R5 and Rg denote hydrogen and that when and 25 R2 are both different from hydrogen, R ^ and R ^ denote hydrogen, as well as the organic or inorganic acid salts of these bases such as hydrobromide, hydrochloride, sulfate, acetate, tarträte, etc ...

Other oxidation dye precursors of the “para” type which can be used according to the invention are chosen from paraaminophenols, heterocyclic precursors derived from pyridine, benzomorpholine, indole, bis-condensed precursors such as Ν, Ν'-diarylalkylene diamines whose aryl groups are substituted para by an OH or amino group optionally substituted by an alkyl group and which can be substituted on the nucleus by / an alkyl radical or a halogen atom, whose groupemerÆ? /

V

9 ♦ alkylene can be interrupted by a heteroatom such as 0 or N and optionally substituted by OH or an alkyl group, the nitrogen atoms of the alkylene group possibly being substituted by an alkyl, hydroxyalkyl, 5-aminoalkyl group.

Such compounds are described inter alia in French patent No. 2,016,123.

These compositions may also contain precursors of oxidation dyes of the ortho type such as orthophenylene diamines, orthoamino phenols, ortho dihydroxy benzenes or their derivatives substituted on the nitrogen atom by a alkyl or hydroxyalkyl group or substituted on the nucleus by one or more alkyl or alkoxy groups.

The compositions containing the dye precursors of ortho or para type may also contain modifiers or couplers well known in the art.

These couplers can also be applied to the hair either before the application of the composition containing the dye precursors of the para or ortho type or after the application of the composition containing the said precursors.

In this case, the oxidizing agent can be present either in the composition applied in the second step, or in a composition applied in the third step.

The couplers more particularly usable in the process according to the invention are chosen in particular from monophenolic derivatives, metadihydroxybenzenes, meta-aminophenols, metadiamines, heterocyclic compounds derived from pyridine or from morpholine, or pyrazolones. 30 ias diketonic compounds and their salts.

The diphenylamines which can be used in the process according to the invention are diphenylamines in which the two nuclei are substituted in position 4 and 4 'by two groups such as hydroxyl and / or N (R') (R ") where R 'and R" denote independently or simultaneously: hydrogen, alkyl, hydroxyalkyl * and when R "denotes carbamylalkyl, mesylaminoalkyl, / '/ acylamino alkyl, sulfoalkyl, piperidino alkyl, mor - /// ♦ * 10 t pholino alkyl, R' denotes H or alkyl The radicals R * and R "can form with the nitrogen atom to which they are attached a piperidinic or morpholinic heterocycle. The other positions of the two benzene rings can be occupied by one or more groups such as alkyl, alkoxy, the alkyl radical being able to form a heterocycle with a primary or secondary amine group in position 4 or 4 ′; a halogen atom, a ureido radical; amino optionally substituted with a hydroxyalkyl, carbamyl-10alkyl, mesylaminoalkyl, acyl or carbalkoxy group.

These diphenylamines can be used in the form of their salts such as sulfate, hydrobromide, hydrochloride, acetate, tartrate ...

These diphenylamines are described in French patents 1,222,700, 2,056,799, 2,174,473, 2,145,724, 2,262,023, 2,262,024, 2,261,750 and the applicant's patent application 75.05.503, incorporated by reference.

These diphenylamines can be used either in compositions containing the para or ortho type dye precursors, or in compositions containing the oxidizing agent or the modifiers or in both compositions.

It is also possible, in the second step, to dye the hair using compositions containing so-called "rapid" oxidation dyes which are capable of developing by simple contact with air. Such compositions may in particular contain dyes chosen from polyhydroxybenzenes and polyhydroxynaphthalenes, poly-aminobenzenes, polyaminophenols, polyamino-polyhy-droxybenzenes in which the amino groups are optionally substituted by an alkyl radical; polyhydroxy and poly-aminohydroxy indoles.

In the formulas of the abovementioned oxidizable dyes, the alkyl groups preferably denote groups having between 1 and 6 carbon atoms; alkoxy denotes a group preferably having 1 to 6 carbon atoms; acyl 1 denotes a group having 1 to 7 carbon atoms; halogen Λ 1+ 11 preferably denotes chlorine, bromine and fluorine? the substituents of the nitrogen atom are preferably alkyl groups having 1 to 6 carbon atoms.

the permanent coloring dye compositions 5 used in the process according to the invention may also contain the intermediate products or the final products resulting from the oxidative condensation and direct dyes. The Applicant has noted more particularly that the application in a first step of the composition based on ^ substances of plant or animal origin or of synthetic organic substances having covering properties according to the invention, made it possible in particular to stop the so-called bases of Bandrowski which can result from the autocondensation of paraphenylenediamines on themselves. It noted in particular that the Bandrowski base could be stopped by the compositions according to the invention in proportions of up to 90% by weight.

The semi-permanent dye compositions used in the process according to the invention contain PO

essentially direct dyes in a cosmetically acceptable medium.

The direct dyes which can be used are well known in the state of the art and belong to the classes of nitres derivatives of the benzene series, azo, anthraquinone, indophenols, indamines, or indoanilines and have the common characteristic that to communicate to the hair their own coloring.

The nitro derivatives of the benzene series used in a preferential manner can be nitrophenylenediamines, nitro-aminobenzenes, dinitroaminobenzenes, nitro-aminophenols and their derivatives as described in French patent application by the applicant 2,290,186 as well as nitrodiphenylamines .

The dye compositions for permanent coloring have a pH of between 8 and 11.5. The dye compositions.

rials for semi-permanent coloring have a pH between / 3 and 11.5. / $ 35 ► 12

The dye compositions which can be used in the process j according to the invention may also contain anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof, well known in the art. The 5 surfactants are present in the dye compositions used according to the invention in the proportions of between 0.5 and 55% by weight, and preferably between 4 and 40% by weight relative to the total weight of the composition.

These compositions can also contain organic solvents to dissolve compounds which would not be. sufficiently soluble in water. These solvents are preferably present in proportions ranging from 1 to 40% by weight and more particularly from 5 to 30% by weight relative to the total weight of the composition.

^ It is naturally possible to add to the dye compositions any other adjuvant usually used in dye compositions for hair and in particular sequestering agents, film-forming agents, buffers, thickeners, antioxidants, perfumes.

^ The presence of thickeners is particularly desired in the case of semi-permanent dye compositions insofar as the protective effect of the composition applied at first is reinforced by the presence of these substances and in particular by the presence of derivatives Cellulose such as carboxymethyl or ethyl cellulose, polyacrylic acid derivatives, bentonite, sodium al-ginate or gum arabic.

The dye compositions used can be in various forms, such as liquid, cream, gel, or any other form suitable for dyeing the hair.

They can in particular be packaged in aerosol bottles in the presence of a propellant.

When the composition contains an oxidizing agent, this is chosen from hydrogen peroxide, urea peroxide. Preferably a solution of hydrogen peroxide at 20 volumes is used. / / * 13 The application of dyes to the hair is followed by a sufficient exposure time to allow coloring. Generally this exposure time is between 10 and 40 minutes.

^ After coloring, the hair is rinsed thoroughly so as to also eliminate all the composition applied at first, and optionally it is washed with shampoo, rinsed again, then dried.

The following examples are intended to illustrate without limiting the present invention.

EXAMPLE 1

A liquid dye composition is prepared by mixing the following components:

Nonylphenol containing 9 moles of ethylene oxide 5 g 3 g

Oleic alcohol 9 g

Diethanolamide lauric 11.5 g

Oleic acid 18 g

Propylene glycol 9 g

Benzyl alcohol 11 g

Ammonia at 22 ° baby 14 ml

Monoethanolamine 6.5 g p-aminophenol 0.2 g

0.1 g m-diaminoanisole sulfate.

25 Resorcin 0.5 g m-aminophenol 0.2 g p-toluylenediamine 2 g

Ethylene diamine tetracetic acid sold under the name Trilon B 3g 30 Sodium bisulfite (d = 1.32) 1.2 g * Water q.s.p. 100g

30 g of this composition are mixed in a bowl with 30 g of hydrogen peroxide at 20 volumes.

A 35% aqueous suspension of a sodium polystyrene sulfonate sold by National Starch under the name FLF.XAN 130 is applied to white paper (Canson C grain 180 / g / m2). / jy% if 14

The paper is then dried at 50 ° C for 10 min. The oxidation dye described above is then deposited.

After the usual exposure time (30 minutes) the excess dye is removed and rubbed with a sponge soaked in shampoo.

We see that the paper has been protected.

The composition of Flexan 130, packaged in a polyethylene bottle comprising an applicator, is applied to the head by pressing on the bottle. The composition is deposited in the form of lines according to the conventional technique commonly * used by hairdressers. After drying under a helmet, the dyeing is carried out by applying the composition described above. After 30 minutes of exposure, the hair is rinsed, shampooed, rinsed and dried. The hair is colored in dark chestnut and the scalp has been well protected.

EXAMPLE 2

By proceeding as described in Example 1, the dye composition is deposited on a paper covered with a suspension of 30% animal charcoal with 15% ash, marketed by PROLAB0, in polyethylene glycol of molecular weight 400. also finds good protection of the paper and scalp by applying the method of Example 1.

55 EXAMPLE 3

A dye composition is prepared in liquid form by mixing the following ingredients: triethanolamine lauryl sulfate at 40% active ingredient 4 g 30 2-octyl dodecanol sold under the name EüTANOL G by the company HENKEL 11 g

Diethanolamide lauric 8 g

Nonyl phenol with 9 moles of ethylene oxide 3 g 35 Oleic acid 21 g

Benzyl alcohol 12 g $ 15

Ethyl alcohol at 96 ° 8g

Ammonia at 22 ° Be 19 ml p-aminophenol 0.30 g Resorcin 0.65 g 5 m-aminophenol 0.65 g p-toluylenediamine 0.15 g

Ethylene diamine tetracetic acid sold under the name Trilon B 3g

Sodium bisulphite (d = 1.32) 1.2 g

Water q.s.p. 100 g *

30 g of this composition are mixed in a bowl with 30 g of hydrogen peroxide at 20 volumes.

The procedure is as in Example 1 by depositing this dye composition on a paper covered with an aqueous gel containing 3.3% of carrageenate sold by the company SATIA under the name of SATIAGEL GS 350. After the usual exposure time ( 30 min), washing with shampoo you can see that the paper has been properly protected.

By applying this composition to the hair as indicated in Example 1, there is a light golden blonde coloring and the absence of spots on the scalp.

EXAMPLE 4

Finely ground in polyethylene glycol of molecular weight 400, the dye prepared in Example 3 is applied to a paper covered with a suspension of 30% activated vegetable charcoal marketed by PROLABO, and the paper was washed. effectively protected.

EXAMPLE 5

The following dye composition for semi-permanent coloring is prepared:

(2-nitro, 4-amino) phenoxyethanol hydrochloride 2 g

Amino-1 nitro-2 methyl-4-amino benzene 0.5 g

Carboxymethylcellulose 5 g 35 Ammonia at 22 ° Be q.s.p. pH 10

Water q.s.p. 100 g / / 'lö

This composition is applied to different Canson papers protected respectively by the compositions described in Examples 1 to 4 and dried at 50 ° C for 10 minutes and to samples of unprotected paper.

5

After 20 minutes of laying, washing with shampoo and drying, it is found that the unprotected control samples have a copper-red coloring while the papers covered with different compositions have been well protected.

By dyeing the protected hair as indicated in Example 1, there is also the absence of spots on the scalp.

EXAMPLE 6

A composition based on clay is prepared by slowly introducing 10 g of clay sold under the name IF- ° Gelwhite into 90 g of deionized water containing 0.3 g of a preservative with good stirring. The suspension is very viscous and thixotropic.

This composition is applied under the conditions described in Example 1 to the scalp.

in.

After drying under a helmet at 50 ° C. for 10 minutes, the hair is dyed according to the usual semi-permanent coloring method using the composition described in Example 5.

After application to the hair, leave on for 30 minutes, rinse, shampoo, rinse and dry.

It is found that the clay-based layer has well protected the scalp which does not have spots and the hair "/ are dyed evenly.

4

Claims (23)

1. A method of coloring the hair, characterized in that a composition based on a substance of plant or animal origin or on a synthetic organic substance in suspension or in solution in a solvent and having a viscosity suitable for application on the head or in powder form, making it possible to avoid or substantially limit the passage of dyes, and / or dye precursors to the scalp and that in a second step, dyeing the hair using one or more compositions, at least one of which contains either an oxidizable dye or a direct dye, the dyeing being followed after an exposure time sufficient to color the hair, by rinsing and optionally a sham-15 pooing. 2. Hair coloring method, characterized in that a composition is first applied with a viscosity suitable for application to the head on the base of a mineral substance in suspension in water and having adsorbent properties and that in a second step, the hair is dyed using one or more compositions, at least one of which contains a direct dye, the dyeing being followed after an exposure time sufficient to color the hair with a rinse and possibly a shampoo. 3. Method according to claim 1 or 2, characterized in that a composition is applied firstly in the form of a suspension or a solution in a cosmetically acceptable solvent of a substance 30 vegetable or animal or organic synthetic character, characterized by the fact that when applied to a thickness of 1 mm on a sheet of paper it essentially prevents the passage of dyes from a dye composition to oxidation. based on paraphenylene diamine up to 35 on paper and has a viscosity of 80 to 8000 cps. 4. Method according to claim 1 or 3, characterized in that the solvent is chosen from water, alcohols ^ y / L / ^ / T! 18 such as ethanol or isopropanol, polyalkylene glycols, polyols, or glycols or mixtures thereof. 5. Method according to any one of claims 1, 3 or 4, characterized in that the substance of plant origin 5 is chosen from activated carbon or carrageenan. 6. Method according to any one of claims 1, 3 or 4, characterized in that the substance of animal origin is animal black. 7. Method according to claim 5 or 6, characterized in that the activated carbon or the animal black is used in the form of powder, 8. Method according to claim 5 or 6, characterized in that the activated carbon or the animal black are used in suspension in polyethylene glycol. 9. Method according to any one of claims 1, 3 or 4, characterized in that the organic substance of synthetic origin is a cosmetically acceptable polymer having a molecular weight between 50,000 and 20,500,000. 10. Method according to claim 9, characterized in that the said polymer is a salt of polystyrene sulfonic acid, 11. Method according to claim 2, characterized in that the mineral substance is a clay. 12. Method according to any one of claims 1 to 11, characterized in that the amount of substance of plant or animal or synthetic organic origin, or of mineral substance present in the suspension or solution in the cosmetically acceptable solvent is between 1 and 60% by weight. 13. Method according to any one of claims 1 to 12, characterized in that one proceeds to the drying of the composition applied to the hair at first. 14. Method according to any one of claims 1 to 13, characterized in that a composition comprising at least one precursor of * 19 dye of ortho or para type or their mixtures is applied in a second step, and that the coloring is developed using an oxidizing agent present in the composition applied in the second step or applied to the hair in the third step, 15. The method of claim 14, characterized in that the composition applied in the second step further contains a coupler. 16. The method of claim 14 or 15, characterized in that a composition containing at least one coupler is applied either before the application of the composition containing the dye precursor of ortho or para type, or after application of this composition. 17. Method according to any one of claims 1 to 16, characterized in that at least one of the dye compositions applied after the preliminary treatment contains a diphenylamine. 18. Method according to any one of claims 1 to 12, characterized in that at least one of the compositions applied in the second step contains so-called "rapid" oxidation dyes capable of developing by simple air contact. 19. Method according to any one of claims 1 to 12, characterized in that one of the compositions applied in the second step contains at least one direct dye. 20. The method of claim 19, characterized in that the direct dye is chosen from nitro derivatives of the benzene series, azo dyes, anthraquinones, indophenols, indamines or indoanilines. 21. Protective composition for the scalp, characterized in that it comprises a substance chosen from 5 substances of plant or animal origin, synthetic organic substances or mineral substances having adsorbent properties in suspension or in solution in a solvent cosmetically acceptable, this composition being covering, having a viscosity sufficient not to flow when applied to the hair, being removed with water or t "in shampoo and essentially preventing the passage of dyes, of a composition oxidation dye based on paraphenylenediamine even on paper, when applied to a thickness of 1 mm on a sheet of paper. 21. Method according to any one of claims 1 to. 20, characterized in that the compositions applied after the preliminary treatment contain agents making it possible to adjust the pH to values allowing hair dyeing, anionic, cationic, nonionic, amphoteric surfactants or their mixtures, organic solvents, thickeners, antioxidants, sequestering agents, film formers, buffers, ^ / 20 1 yew? perfumes as well as any other adjuvant usually used in dye compositions for hair. 22. Composition according to claim 21, characterized in that it has a viscosity of 80 to 8000 cps. 23. Composition according to claim 21 or 22, characterized in that it contains a substance chosen from activated carbon, animal black, carrageenans, 2Φ polymers derived from polystyrene sulfonic acid, clays. Drawings: ____________planchas H .... pages of which ....... À ........ pane de parde JJ, ........ ps ü3 description A. p'csi? of claims ..... J ........ descriptive abbreviation Luxambci'T. le "JU1L 1980 Le rnatîdaiaîie \ / / / Ût · Charles München *