LU81994A1 - HAIR DYEING PROCESS - Google Patents

Description

, 1

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

It is well known to color keratin fibers and in particular human hair according to a process which consists in applying a dye composition which contains an oxidant added to said composition just before application, for oxidation dyes and diphé-nylamines or using an oxidant-free composition, applied directly to the hair when it contains Ί0 so-called rapid oxidation dyes or certain diphenyl-amines, the oxygen in the air causing in the latter case the development of color.

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Aromatic compounds such as diamine, aminophenol or phenol which are not dyes per se but which are transformed into dyes by oxidative condensation are called oxidation dyes. Among these oxidation dyes, a distinction is generally made on the one hand, the para-oxidative dye precursors of the para type chosen from diamines or aminophenols, the functional groups of which are located in para with respect to one another and , on the other hand, the ortho-type oxidation dye precursors, and modifier or coupler compounds which are generally so-called "meta" derivatives chosen more particularly, particularly from metadiamines, metaminophenols, metadiphenols as well as phenols.

Rapid oxidation dyes are called dye precursors of the benzene series comprising on the nucleus three substituents chosen from the group formed by hydroxy, methoxy, amino groups and capable of oxidizing directly in air.

The term oxidizable dyes will be used hereinafter to designate these different types of dye precursors.

We have been looking for a long time for means of em-55 fishing or limiting the contact of the scalp with the products used in the dye compositions and more / '“...... 7> 2 intermediates as well as the final products resulting 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 pose problems of general or specific toxicity.

In all cases, we want to protect the scalp> from coloring substances.

The Applicant has discovered that by using a composition having a viscosity suitable for its application on the head, based on a mineral substance in suspension having adsorbent properties makes it possible to avoid or at least limit the contact of the scalp with the components generally used in oxidation dyes and therefore to decrease penetration. The Applicant has noted in particular that the application in the first instance of a composition based on mineral substances in suspension having adsorbent properties makes it possible, however, to dye the hair properly by giving one; 25 good unison along their entire length and in particular their roots.

The protective effect of the composition based on suspended mineral substances and having adsorbent properties 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 weak penetration or non penetration of the coloring substances in the epidermis.

The subject of the present invention is therefore a process for dyeing hair consisting in first applying at least one composition based on mineral substances / in suspension in water and having adsorption properties -A / 3 bantes on leather. hairy. Other objects of the invention will result from reading the description and examples which follow.

The process for the permanent coloring of hair according to the invention is essentially characterized by the fact that a composition having a viscosity suitable for application to the head is first applied, based on mineral substances suspended in the 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 an oxidizable dye, the dyeing being followed after an exposure time sufficient to develop the color on the hair, a rinse and possibly a shampoo.

The composition having the viscosity suitable for application to the head, based on mineral substances in suspension in water and having adsorbent properties is preferably in the form of a suspension in water of a product based either of alumina, or of 20-aluminosilicates, or of aluminum phosphates.

- The more particularly preferred products consist of alumina, aluminum phosphates and clays such as kaolinites, attapulgites, monts. morillonites. The clays giving particularly remarkable results and used in the preferred embodiments of the invention are montmorillonites.

In the literature, the term montmorillonite can be used in a more general sense to designate either the family or the minerals having swelling and contraction properties of this species; it can then include the trioctahedral types and be synonymous with smectite, monmorin. (Mineralogy of clays. S. Caillère and S. Hénin. Masson.

1963).

Montmorillonites correspond to the general formula: 35 ^ si (4) / ai (2_x) rx 1 o1Q (oh) 2 cex, ηΗ ,, ο /

CE being exchangeable cations and R magnesium, iron or / manganese. / W

(f - / 4 As an example, we can cite the results of the chemical analysis of a series of montmorillonites.

112 15

SiO, 50.04 57.49 50.06 51.52 60.3 5 A1203 20.16 20.27 25.1 17.15 18.5

Fe203 0.68 2.92 0.5 5.65 0.70

FeO 0.19 0.32

CaO 1.46 0.23 4.9 1.72

MgO 0.23 3.18 7.2 2.80 3.8 K20 1.27 0.28 0.85 4.0.1

Na20 Traces 1.32 0.15 5.3 15 Ti02 0.12 0.48 0.25 (6.85 8.55 H2 ° - ((26.00 7.63 11.7 11.22 7.5 20 1 - Montmorillonite, Montmorillon (Vienne) 2 - Bentonite, üpton, Wyoning (Ü.SA) 3 - Montmorillonite, Maharitra (Madagascar) 4 - Montmorillonite, Amoy, Mississipi (Ü.SA)

’5 - Clay sold under the name Gel white ÜSP

25 by Euroclay

In addition, their large specific surfaces give them interesting properties.

The amount of mineral substances having adsorbent properties present in the aqueous suspensions 50 according to the invention is between 5 and 60%.

The product according to the invention must have, as mentioned above, a viscosity which must be sufficient so that the latter does not run during application to the head. For this purpose, products preferably used.

35 / base of mineral substances having adsorptive properties and swelling and swelling after introduction into water. In addition, it is preferable that the substances give easy-to-apply thixotropic compositions because they are fluid after stirring and highly viscous once deposited on the scalp which prevents the product from leaking, which is particularly advantageous in the case montmorillonites.

These products must also be able to be easily removed with water or shampoo by resuspension.

A preferred embodiment is to use products colored in white so that the applicator can easily determine whether the entire scalp has been adequately protected. This color of the product also makes it possible to verify that it has been completely eliminated after rinsing.

15 This product must also allow the dye to penetrate the hair so that the root can be dyed.

After applying the above-defined composition to the scalp, drying is preferably carried out by the usual 2 ^ means used in hairdressing salons such as by drying 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 with the composition as defined above, a composition containing at least one dye precursor of the ortho or para type or their mixtures and to develop the coloring using an oxidizing agent 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. ,

Among the precursors of dyes of the para type, it is possible to mention / 55 / h * 6 more particularly the compounds corresponding to the formula R1 R? K / 2 5 r _ _R, 6 \ 3 r5 R4 NH2 (I) in which: R ^ and R2 denote independently of one another, 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 which may be part of a heterocycle such as piperidino, morpholino), acylamino , alkyl or arylsulfonylamino, 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 being capable of being interrupted by one or more heteroatoms such as oxygen, nitrogen and carrying other alcohol or amine functions; and R2 can also form, together with the nitrogen atom to which they are attached, a heterocycle such as piperidino or morpholino; R ^, R4, Rg, Rg independently of each other, hydrogen, halogen, linear or branched alkyl optionally substituted by one or more OH, amino or alkoxy groups; an OZ group, Z denoting alkyl; hydroxyalkyl, alco-xyalkyl, acylaminoalkyl, carbalkoxyaminoalkyl; mesyl-aminoalkyl, ureidoalkyl, aminoalkyl, mono- or di-al-coylaminoalkyl, the alkyl radicals having 1 to 6 carbon atoms, provided that when R2 denotes phenyl R ^, R ^, R ^, Rg and Rg denote hydrogen and when R ^ and R2 are both different from hydrogen, R ^ and Rg denote hydrogen, as well as the organic or inorganic acid salts of these bases such as hydrobromide, hydrochloride, sulfate, acetate, tartrate, etc ... /

Mention may be made, among the compounds corresponding to formula (I), of / / 7 paraphenylenediamine, paratoluylene diamine, methoxy paraphenylene diamine, chloroparaphenylenediamine, 2,6-dimethyl paraphenylene diamine, 2,5-dimethyl paraphenylene diamine, 4-amino diphenylamine, 2-methyl 5-methoxy paraphenylene diamine, 2,6-dimethyl 5-methoxy 0 paraphenylene diamine, N, N- (dimethyl) paraphenylene diamine, 3-methyl 4-amino N, N - (diethyl) aniline, N-mono- and N, N-di (ß -hydroxyethyl) paraphenylene diamine, 3-methyl 4-amino N, N-di (fi -hydroxyethyl) aniline, 3-chloro 4- amino N, N-di (ß-hydroxyethyl) aniline, 4-amino N, N- (ethyl, carbamyl-methyl) aniline, 3-methyl 4-amino N, N- (ethyl, carbamyl-methyl) aniline, 4-amino N, N- (ethyl, ß -morpholinoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, ß -morpholinoethyl) aniline, 4-amino N (acetylaminoethyl) aniline, 4- amino ^ N, N (ethyl, acetylaminoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, acetylaminoethyl) a niline, 4-amino N, N (ethyl, ß-mesylaminoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, ß-mesylaminoethyl) aniline, 4-amino N, N- (ethyl, ß -sul-20 foethyl) aniline, 3-methyl 4-amino N, N- (ethyl, ß -sulfo-ethyl) aniline, N- / T (4 '-amino) phenyl morpholine, N - /' ( 4, -amino) phenyl7 piperidine, 4-amino N, N- (ethyl, pipé-ridinoethyl) aniline, 3-methyl 4-amino N-methyl aniline, * 2-chloro 4-amino N, N- ( ethyl, sulfonamidomethyl) aniline, 2-chloro 4-amino N-ethyl aniline, 2-methyl 4-amino N- (/ 3-hydroxyethyl) aniline, (2,5-diamino) phenoxyethanol, 4- (ß -methoxyethyl) amino aniline, N-methyl paraphenylenediamine, 4-amino, N, N (^ -hydroxyethyl, ß-mesylaminoethyl) aniline, 4-amino N-Γβ- {β '-hydroxyethoxy) -ethyljaniline, / Î2-N- (β -hydroxyethyl) amino, 5-aminoq7 phenoxyethanol, 4-N- (tetrahydrofurfuryl) amino aniline; 4-N- (furfuryl) amino aniline.

Other oxidation dye precursors of the "para" type which can be used according to the invention are chosen from paraaminophenols such as paraaminophenol, 2-methyl 4-amino phenol, 3-methyl 4-amino phenol, 2-chloro / 4-amino phenol, 3-chloro 4-amino phenol, 2,6-dimethyiff y.

♦ 8 4- amino phenol, 3,5-dimethyl 4-amino phenol, 2,3-di-methyl 4-amino phenol, 2,5-dimethyl 4-amino phenol, N-methylparaaminophenol; heterocyclic precursors derived from pyridine such as 2,5-diamino pyridine, 2-dimethylamino 5-amino pyridine, 2-diethylamino 5-amino-pyridine or else 2-methyl 6-amino benzomorpholine, 5-amino indole; bis-condensed precursors such as Ν, Ν'-diarylalkoylene 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, the alkylene group of which may 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 a alkyl, hydroxyalkyl, aminoalkyl group.

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

These compositions can also contain precursors of oxidation dyes of the ortho type such as or-thophénylène diamines, orthoamino phenols, ortho-diphenols or their derivatives substituted on the nitrogen atom by an alkyl group or hydroxyalkyl or substituted on the nucleus by one or more alkyl or alkoxy groups.

2 ^ 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.

55 The couplers more particularly usable in the process according to the invention are chosen in particular from / monophenolic derivatives, metadiphenols, metaamino- /] // 9 phenols, metadiamines, heterocyclic compounds derived from pyridine or from morpholine, pyrazolones or diketonic compounds and their salts.

Among the preferred couplers, mention may be made of resorcins such as resorcin, 2-methyl resorcin, 4-chloro resorcin, metaaminophenol, 2,4-diamino anisole, 2-methyl 5-ureido phenol, 2,6 -dimethyl 3-aminophenol, 2-methyl 5-acetylaminophenol, 2,6-dimethyl 5-acetylamino phenol, 3-amino 4-methoxy phenol, 2-methyl 5-N- (ß - ^ hydroxyethyl) aminophenol, metaphenylene diamine, meta-toluylene diamine, N-methyl metaaminophenol, 6-methyl „3-aminophenol, (2,4-diamino) phenoxyethanol, 3- N- (diethyl) aminophenol, 6-methyl 3 -N- (ß-mesylamino ethyl) aminophenol, 6-methyl 3-N- (carbamylmethyl) aminophenol, 3-N (carbamylmethyl) aminophenol, 2-N- (ß -hydroxyethyl) amino 4-aminophenoxyethanol , 6-hydroxy benzomorpholine, 6-amino benzomorpholine, Ck-naphthol, 2,6-diaminopyridine, or the salts of these compounds.

The diphenylamines which can be used in the process according to 2q 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') (RM) where R 'and R "denote independently or simultaneously: hydrogen, alkyl, hydroxyalkyl * and when R "denotes carbamylalkyl, mesylaminoalkyl, 0 [_ acylamino alkyl, sulfoalkyl, piperidino alkyl, moral 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 nuclei can be occupied by one or more groups such as alkyl, alkoxy, the radical alkyl which can form a heterocycle with a primary or secondary amine group in position 4 or 4 ′; a halogen atom, a ureido radical; amino optionally substituted by a hydroxyalkyl, carbamylalkyl, mesylaminoalkyl, acyl or carbalkoxy group.

These diphenylamines can be used in the form of / their salts such as sulfate, hydrobromide, · hydrochloride, acéV? / Täte, tartrate ... ju 35 ’10

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.

• | 0 Finally, it is possible to proceed with the dyeing of the hair using compositions containing oxidation dyes known as "rapid" capable of developing by simple contact with air. Such compositions may in particular contain dyes chosen from poly-hydroxybenzenes and polyhydroxynaphthalenes such as pyro-gallol, 1,2,4-trihydroxybenzene, 1,3,5-trihydroxyben-zene, 1,4, 5-trihydroxynaphthalene, 2,4,5-trihydroxyto-luene, 5- (ß -aminoethyl) 1,2,4-trihydroxybenzene; polyaminobenzenes such as 1,2,4-triaminobenzene; poly-aminophenols such as di or tri-aminophenols; poly-amino-polyhydroxybenzenes, the amino groups of which are optionally substituted by an alkyl radical; poly-hydroxy and polyaminohydroxy 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 denotes a group having 1 to 7 carbon atoms; halogen preferably denotes chlorine, bromine and fluorine; the substituents 2q of the nitrogen atom are preferably alkyl groups having 1 to 6 carbon atoms.

The dye compositions used in the process according to the invention may also contain, as mentioned above, the intermediate products or the final products resulting from oxidative condensation. The Applicant has noted more particularly that the application initially of the composition based on inorganic substances in suspension / having adsorbent properties according to the invention, perV ^ / * 11 put to stop in particular the bases known as Bandrowski gui may result from the self-condensation of the paraphenylene diamines on themselves. It noted in particular that the Bandrowski base could be stopped by virtue of the compositions here based on suspended mineral substances and having adsorbent properties according to the invention in proportions of up to 90% by weight.

These dye compositions have a pH of between 8 and 11.5.

IQ The dye compositions which can be used in the process according to the invention may also contain anionic, cationic, nonionic amphoteric surfactants or their mixtures, well known in the state of the art. The 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 are not 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 penetration agents, sequestering agents, film-forming agents, buffers, thickeners, antioxidants, perfumes.

The dye compositions used can be presented 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.

The oxidizing composition contains oxidizing agents / - - ~ -...........- ....... 1 * 12 preferably a solution of hydrogen peroxide at 20 volumes. The mixture thus obtained is applied to the hair.

The application of the dyes to the hair is followed by a sufficient exposure time to allow the development of the coloring. Generally this exposure time is between 10 and 30 minutes.

After development of the coloring, the hair is thoroughly rinsed so as to also eliminate all of the composition t 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 composition based on clay is prepared by introducing 15 g of clay sold under the name GELWHITE slowly into 90 g of deionized water in which 0.3 g of a preservative has been dissolved beforehand. agitation. The suspension thus obtained is very viscous and thixotropic.

This composition, packaged in a polyethylene bottle containing an applicator, is applied to the head by pressing on the bottle. The composition is deposited in the form of lines according to the technique commonly used by hairdressers. After drying under a helmet at 50 ° C for 10 ‘minutes, the hair is dyed according to the usual method.

A dye composition having the following composition is applied for this purpose:

Paraphenylenediamine dihydrochloride 0.67 g NP-hydroxyethyl paraphenylene diamine sulfate 0.67 g N, N-di- (/ 3-hydroxyethyl) paraphenylenediamine dihydrochloride 0.67 g Resorcin 0.67 g Metaminophenol 0.67 g 55 2,4-d .iamino anisole 0.67 g 4.02 g /

These dyes are dissolved in the following support: / ΙΑ 9 "13"

Support 1:

Remcopal 334 (nonylphenol with 4 moles of 8g thylene oxide)

Remcopal 349 (nonylphenol with 9 moles of ethyl oxide 8 g lene) çj Propylèneglycol 20 g.

The pH of the composition is adjusted to 10 with ammonia at 22 ° Bé and water is added in amounts sufficient for 100 g.

* Δ part of this composition (50 g) hydrogen peroxide is added to 20 volumes (50 g). After applying the dye composition to the hair, leave it on for 30 minutes, rinse, shampoo and rinse a second time.

We see that the protective layer based on clay,

I can be easily removed and the scalp has been effectively protected and in particular does not have spots.

EXAMPLE 2

The procedure is as described in Example 1 by first applying a viscous suspension of pre-prepared clay by suspending in 60 g of deionized water, 40 g of a superfine green clay sold by the company Argiletz, and the support having the following composition is used in place of the support 1 of the tincorial composition.

Support 2:

Oleic alcohol with 2 moles of ethylene oxide 4.5 g

Oleic alcohol with 4 moles of ethylene oxide 4.5 g

Ethomeen C25 4.5 g

Coconut fatty acid diethanolamides 9 g

Propylene glycol 3.6 g

Butylglycol 8 g

Ethanol at 96 ° 5.4 g sodium bisulfite at 35 ° Be 1 g

Ammonia at 22 ° Be 10g

and water is added in amounts sufficient for 100 g. The pH of these compositions is 10.2. As in example 1, effective protection of the scalp and /? / Absence of stains is noted. / JfJ

U

* 14 EXAMPLE 3

The procedure is as described in Example 1, using a dye composition for hair dyeing having the following composition: 5 Paraphenylene diamine diehlorhydrate 1 g

Paraaminophenol 1 g Resorcin 0.67 g £ X -naphthol 0.67 g 6-hydroxybenzomorpholine 0.67 g 10 4.01 g.

These dyes are dissolved in the support 1 mentioned above. It is observed, as in Example 1, that the scalp is effectively protected from the dyes present in the dye composition.

1 5 EXAMPLE 4

The operation is carried out under the same conditions as those described in Example 2, with the difference that the dye composition of Example 3 is used with the support No. 2 defined above. As before, there is good protection of the scalp.

EXAMPLE 5

The operation is carried out under the same conditions as those described in Example 1, by dyeing the hair with * a dye composition having the following composition: 25 N- ^ 0-hydroxyethyl paraphenylenediamine sulfate 0.67 g N, N-di - fi (-hydroxyethyl) paraphenylenediamine diehlorhydrate 0.83 g diamino-2,4 'methyl-5-hydroxy-4-diphenylamine 0.3 g 30 Resorcin 0.67 g Metaaminophenol 0.67 g 2,4-diaminoanisol 0.67 g 3.81 g

These dyes are dissolved in the support 1. After application, application, rinsing, shampooing and rinsing again, it is found, as in the preceding examples, that the scalp has been effectively protected. fV / / * 15 EXAMPLE 6

By proceeding as described in Example 2, but using the dye composition of Example 5 with the support 2, it is found that the scalp is also well protected thanks to the composition of Example 2, EXAMPLE 7

First of all, a head suspension in water containing 15% kaolinite is applied to the head according to the technique described in Example 1. After drying under the conditions described in • jO Example 1 / the dye composition described in Example 1 above is applied to the hair. After rinsing,. shampoo and rinsing again we can see that the composition based on kaolinite has limited the passage of dyes to the level of the scalp.

1 5 EXAMPLE 8

The aqueous suspension containing Gelwhite clay, prepared as described in Example 1, is applied to white paper (Canson C with a grain of 180 g / m2) 1 mm thick, leveling the deposited composition between 1 mm shims. thick. The paper covered with clay is dried at 50 ° C for 10 minutes.

An oxidation dye having the same composition as that described in Example 3 is then deposited. After the usual exposure time (30 minutes) the excess dye is removed * and it is found that the layer of clay deposited on the paper 25 is very colored in brown. We rub with a sponge soaked in shampoo, the clay layer is easily removed. It can be seen that the paper has been protected; it is practically not colored.

EXAMPLE 9 jO A 20% attapulgite suspension in water is applied to the hair according to the technique described in Example 1. After drying, the dye composition described in Example 1 is applied. After leaving to stand for 30 minutes at room temperature, it is rinsed, shampooed, rinsed a second time and dried. The protective composition /

is removed well and we see that the application of the layer / clay has limited the passage of dyes to leather chQr // hairy. / M

* 4 p.m.

EXAMPLE 10

A 20% suspension of attapulgite in water is applied to the hair according to the technique described in Example 1. After drying, the dye composition 5 used in the process described in Example 5 is applied. After washing and shampooing, it is found that the composition applied beforehand protects the scalp well.

EXAMPLE 11

A slurry is prepared containing 55% of colloidal alu-10 minium phosphate in water.

t This composition is applied to the head, it is dried and ♦ the dyeing is carried out according to the process described in Example 1 with the dye composition described in Example 1.

It can be seen that the composition applied at first limits the passage of the dyes present or formed towards the scalp.

EXAMPLE 12 A suspension in water containing 25% of alumina sold under the name Alumina metallography quality, fineness 48 hours by the company DURMAX is prepared.

By proceeding as described in Example 5, it is also observed that the composition applied to the head in the first time limits the passage towards the scalp of the dyes present in the composition and of the products formed during / during the oxidation. . / n 30 '

Claims (13)

1. Permanent hair coloring process characterized by the fact that a composition is first applied with a viscosity suitable for the application on the head, based on 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 an oxidizable dye, the dyeing being followed after a setting time sufficient to develop the color. on the . hair, a rinse and possibly a shampoo. 2. Method according to claim 1, characterized in that one applies in the first time a composition in the form of a suspension in water of a product-15 based on alumina, alumino-silicates, or aluminum phosphates. 3. Method according to claim 1 or 2, characterized in that the product based on aluminosilicates consists of a clay. 4. Method according to claim 3, characterized by the fact that a thixotropic clay is used. 5. Method according to claims 3 or 4, characterized in that the clay is chosen from montmoril- "lonites. 6. Method according to any one of claims 2 to 5, characterized in that the quantity of mineral substance having adsorbent properties present in the aqueous suspension is between 5 and 60% by weight, 7. Method according to any one of claims 1 to 50 characterized in that one proceeds to the drying of the composition applied to the hair at first. 8. Method according to any one of claims 1 to 7, characterized in that a composition is applied in a second step containing at least one precursor of 55 dye of ortho or para type or their mixtures, and that the 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. /// /. / 4-, r 18% 9. Method according to claim 8, characterized in that the composition applied in the second step also contains a coupler. 10. Method according to claim 8 or 9, 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. 11. Method according to any one of claims 1 to 10 10 ,. characterized in that at least one of the dye compositions applied after the preliminary treatment contains a diphenylamine. 12. Method according to any one of claims 1 to 5, 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 contact. to the air. 13. Method according to any one of claims 1 to 12, characterized in that the compositions applied after the preliminary treatment contain agents for adjusting the pH to values for dyeing the hair, anionic surfactants , cationic, nonionic, amphoteric or their mixtures, organic solvents. * nics, thickeners, antioxidants, penetrating agents, sequestering agents, film formers, pads, perfumes and any other adjuvants commonly used in hair dye compositions. Γ: - / ·: ·. : ...... / L ..... · ’. 1 - -JLS A - ’· - ... A 4 ·· ·. : - ......... L · ... . ..... Z ........! - J 3 xhJurmSlm