CA1298042C - Process for dying keratinic fibers with 5,6-dihydroxyindole or its derivatives and a metallic anion - Google Patents

Abstract

The invention relates to a process for dyeing keratin fibers, characterized in that a composition containing, in a medium suitable for dyeing, at a pH between 2 and 10, an anion is successively applied to these fibers (a) of a metal having a good affinity for keratin and having a redox potential greater than that of 5,6-dihydroxyindole or its derivatives, of formula (I) below, and (b) a composition containing in a medium suitable for dyeing, at a pH between 7 and 10, a dye of formula (I): <IMG> (I) in which R1 and R2 denote, independently of one another, a hydrogen atom or a methyl or ethyl group. The invention applies in particular to the dyeing of human hair and makes it possible to significantly improve the dyeing power of 5,6-dihydroxyindole or its derivatives.

Description

~ z91 ~ 2 The invention relates to a process for dyeing keratin fibers, in particular human hair, with 5,6-dihydroxyindole or its derivatives and an anion metallic.
Dyeing of human keratin fibers, and especially ~ human hair, with the help of 5,6-di-hydroxyindole, is well known and has been the subject of patents French numbers 1.133.594, 1.166.172, 2.390.158 and

2,536,993 in the name of the Claimant.
Among the hair dyeing methods described in these various documents, it was mentioned the possibility usefulness of using, as oxidation catalyst, different metal salts such as manganese salts, cobalt, iron, copper, silver. The latest patent recommends the use of cupric ions in an alca- solution line but also of metal ions such as those of iron, cobalt, manganese, silver, titanium, zirconium, tantalum, chromium, nickel, palladium, platinum, gold, mercury, cadmium, zinc, tin, an-timoine, lead and bismuth.
These different processes use metal cations used as "melano promoters"
genesis "or" oxidation catalysts ".
We have also already recommended the use, in hair dye ~ potassium permanganate or sodium dichromate but in conditions such as these derivatives could only react on the hair under their reduced form, that is to say of metal cations.

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The Applicant has discovered what is the subject of the invention, which could be improved in a way important the dye power of 5,6-dihydroxyindole or some of its derivatives by pretreating the fibers keratin with a metallic anion having good affinity for keratin and having an oxidative potential reduction greater than that of 5,6-dihydroxyindole or its derivatives.
The advantages of this pretreatment are manifested especially during repeated coloring treatments or for the dyeing of keratinous fibers such as for example hair such as "unnatural" hair, that is to say already sensitized by a cosmetic treatment such as discoloration or perm.
Without this explanation being limiting, the Applicant thinks that the anlon once fixed on the fiber keratin, acts as an oxidant against 5.6 dihydro-xyindole or its derivatives.
The present invention therefore relates to a method for dyeing keratin fibers, in particular human hair, using pretreatment with a metallic anion with good affinity for keratin, this pretreatment being followed by the application of 5,6-dihy-droxyindole or some of its derivatives.
The invention also relates to a device for several compartments, or "kit" of dye, allowing the implementation of the process according to the invention.

~ LZ ~ 80 ~ 2 The process for dyeing keratin fibers, and in particular human hair, in accordance with the invention is essentially characterized by the fact that one successively apply to these fibers:
(a) a composition containing in a medium suitable for dyeing, at a pH between 2 and 10, an anion of a meta ~ with an affinity for keratin and having a redox potential greater than that of 5,6-dihydroxyindole or its derivatives, of formula (I) below, and (b) a composition containing in a medium suitable for dyeing a dye of formula (I):

in which Rl and R2 denote, independently one of the other, a hydrogen atom or a methyl group or ethyl.
For example, the redox potential, extrapolated to pH 0, 5,6-dihydroxyindole being + 0.25 volts / H2, the anions used in accordance with llinven tion must therefore have a redox potential higher, under these conditions, than that of the dye.

38 ~ 2 The method according to the invention is applied from preference to dyeing hair and in particular living human hair. The medium suitable for kein-In this case, it is cosmetically acceptable.
The preferred dyes of formula (I) are 5,6-dihydroxyindole, 2-methyl 5,6-dihydroxyindole,

3-methyl 5,6-dihydroxyindole and 2,3-dimethyl 5,6-dihydro-xyindole.
Particularly preferred anions are killed by permanganate (MnO ~) and dichromate anions (Cr2O72) and more particularly derived from permanganate potassium and sodium dichromate.
The composition containing the metal anions to preferably an anion molality greater than l0 3 mole / l000 g, and preferably between l0 2 mole / l000 g and l0 l mole / l000 g. This corresponds for MnO4 to a concentration greater than 0.012 g% and preferably included between 0.12 and 1.18 g ~, and for Cr2O72 a concen tration greater than 0.022 g%, and preferably understood between 0.22 and 2.16 g ~.
The pH of the composition containing the anion is adjusted with acidifying or basifying agents which no reducing effect on anions.
In a particularly embodiment preferred, the composition used for the pre-treatment is acid and preferably has a pH between 2 and 5 and particular close to 3. A usable inorganic acid may be, for example, sulfuric acid.

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The pretreatment composition can also contain other inorganic adjuvants. As an example, mention may be made of silicas or clays, allowing particular to thicken or swell this composition. She does not contain adjuvants capable of reducing the anion.
This composition preferably has a viscosity sufficient for head application.
The composition containing 5,6-dihydroxyindole or one of its derivatives, of formula (I), is adjusted by prefe-rence has a pH between 7 and 10 using an agent alkalizing, inorganic or organic, known per se. AT
for this purpose, it is possible to cite as alkalizing agents ammonium niac or amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ~ a diethylamine, hydroxylamine.
Concentration of 5,6-dihydroxyindole or its derivatives, of formula (I), can vary between 0.5 and 2% in weight, and preferably between 1 and 1.5% by weight, per relative to the total weight of the composition used in the second stage of the process.
This composition may contain, in addition to water, different solvents among which mention may be made of alca-lower Cl-C4 nols such as ethanol, isopropanol, propanol, tertiary butyl alcohol, ethylene glycol, monomethyl, monoethyl or monobutyl ethers of ethylene glycol and ethylene monoethyl ether acetate ne glycol, propylene glycol, monomethyl ethers of propylene glycol or dipropylene glycol and lactate methyl. Solvents are used in proportions preferably between 1 and 30% by weight, and more particularly between 3 and 20% by weight.
This composition may also contain other adjuvants such as surfactants, electrolytes, tes, anti-oxidizing agents, tampons, perfumes, fatty amides, keratin fiber bulking agents that like urea, sequestrants, film-forming agents, preservatives, etc. These compositions can also be thickened, in particular with agents chosen from sodium alginate, gum arabic, guar gum, biopolymers such as xanthan gum or scleroglucans, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmé-thylcellulose, ca ~ boxymethylcellulose and polymers various having thickening functions such as acrylic acid derivatives. These compositions can also-be thickened with mineral thickeners such as bentonite. Thickeners are pre-preferably feeling, in proportions between 0.1 and 5 ~ by weight, and in particular between 0.5 and 3% by weight relative to the total weight of the composition.
An embodiment of the invention may also consist in storing the dye in an anhydrous medium as described in French patent number 2,390,158 of the Applicant and to mix just before use this composition with an aqueous medium suitable for dyeing. The anhydrous medium can consist of solvents defined above containing less than 1% water.

-The process according to the invention consists essentially of tial to apply J at first and during a duration of 3 to 30 minutes, preferably 5 to 20 minutes composition containing the anion defined above, at the time ambient perature of the order of 25 to 35C. It is possible possibly speed up treatment with a light heating up to around 40C
The fibers are rinsed. We apply after this treatment the dye composition for a duration of 2 at 10 minutes, rinse with water and possibly perform washing and rinsing again.
This process can be used to dye natural or already dyed hair, permed or not, or straightened or hair ~ strongly or slightly discolored and possibly permanent. It is also possible to use to dye furs or wool.
Another object of the invention is constituted by a multi-compartment device, or dye "kit", comprising in a single presentation a plurality of containers, one of which contains the coloring composition, the other the anion, and possibly a third containing the aqueous medium when the dye is kept in the form anhydrous.
The pretreatment composition can be condi-in two parts, one containing the anion in the form of aqueous solution, the other containing an aqueous solution thickened ~ It is understood that these different compartments are intended to be mixed just before employment.

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When the coloring process according to the invention applies to hair dyeing, it can possibly still be preceded or followed by other treatments cosmetics known in themselves.
The following examples are intended to illustrate the invention without, however, having a limiting character tif.
The trademarks mentioned in these examples design the following products:
C ~ RBOPOL 940: crosslinked acrylic acid homopolymer by a multifunctional agent sold by GOODRICH Company CELLOSIZE ~ P03H -: hydroxyethylcellulose sold by the UNION CARBIDE company.
GEL WHITE H / USP: Montmorillonite sold by the Company GEORGIA KAOLIN.

Stock solution of potassium permanganate stable is prepared by dissolving 1.8 g of KMnO4 in 100 ml of water (final volume) adjusted to pH 3 with H25O4. This solution is kept in a bottle protected from light mother.
To a gel prepared by kneading 7 g of silica, AEROSIL 200 (trademark); DEGUSSA with 85 grams of water brought to pH 3 with H2SO4, intimately incorporated under stirring, 9 g of the stock solution of permanganate potassium.
The hair is covered with the gel thus prepared for using a spatula or brush.

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The pose lasts 10 minutes.
The hair is rinsed with water to remove the gel.
A thick solution is prepared before use containing:
-NH4C1 5.0g -CELLOSIZE WP03H (trademark) 5.0g NH40H qs pH 9.0 -Water qs 80g It is incorporated just before use and very quick-ment, 1 g of 5,6-dihydroxyindole previously dissolved in 20 g of anhydrous ethanol.
The pretreated hair is covered with this solution.
tion.-The pose lasts 5 minutes.
The hair is abundantly rinsed with water. Sodium lauryl sulfate shampoo is applied to the head.
The initially gray hair, 90% white, is turned black.

The preprocessing is identical to that of Example 1.
Before use, a thickened solution is prepared containing:
~ Dipotassium hydrogen phosphate 5.6g - Potassium dihydrogen phosphate 2.2g -CELLOSIZE WP03H (trademark) 5.0g -HCl or NaOH qs 7.0g ~ z ~

-Water qs 80g It is incorporated just before use and very quick-ment, 1 g of 5,6-dihydroxyindole previously dissolved in 20 g of anhydrous ethanol.
The pretreated and rinsed hair is covered with this solution.
The installation lasts S minutes ~
The hair is abundantly rinsed with water. A
sodium lauryl sulfate shampoo is applied to the head.
The initially gray hair, 90% white, has taken a very intense gray tint.

The mother solution of potassium permanganate is that described in Example 1.
A gel is prepared by kneading 7 g of silica, AEROSIL 200 (trademark) DEGUSSA with 76 g of water brought to pE ~ 3 with H2SO4; we intimately incorporate under stirring 18 g of the mother solution of permanganate potassium.
The hair is covered with gel and the pose lasts S
minutes.
The hair is rinsed with water.
We use to dye this hair the same composition dyeing and the same process as that described in Example 1.
The initially gray hair, at 90 ~ white, is turned black.

The mother solution of potassium permanganate is that described in Example 1.
A thickened solution is prepared by mixing 15 g of clay, GEL WHITE H / USP (trademark) to 70 g of water. The pH is adjusted to 3 with a minimum of sulfuric acid.
risk. 11.5 g of permanent mother solution are then incorporated.
potassium ganate.
I, e final weight is adjusted to 100 g with a little water pH 3 (H2SO4).
The hair is covered with this thick solution.
sie.
The pose lasts 5 minutes.
The hair is rinsed with water.
Before use, a thickened solution is prepared containing:
-NH4C1 5.0g -CARBOPOL 940 (trademark) 0.7g -NH40H qS H 9.0 -Water qs at 0g It is incorporated just before use and very quickly 1.2 g of 5,6-dihydroxyindole previously dissolved read in 20 g of ethanol.
The pretreated hair is covered with this solution.
The pose lasts 5 minutes.
The hair is abundantly rinsed with water. A
sodium lauryl sulfate shampoo is applied to the head.

The hair initially ~ ris, 90% white, is turned black.

A potassium dichromate solution is prepared by dissolving 2.94 g of K2Cr207 in 100 ml of water (final volume), adjusted to pH 3 with H2SO4. This solution is kept in a bottle protected from light.
A thickened solution is prepared by mixing 15 g of clay, GEL WHITE H / USP (trademark) to 50 g of water. The pH 3 is adjusted with sulfuric acid. We then incorporate 30 g of bichromate mother solution potassium.
The final weight is adjusted to 100 g with a little of water at pH 3 with H2SO4.
The hair is covered with this thick solution-sie.
The pose lasts 10 minutes.
The che ~ eu is rinsed with water.
Before use, a thickened solution is prepared of 5,6-dihydroxyindole, as in Example 4.
The pretreated hair is covered with this solution.
tion.
The pose lasts 5 minutes.
The hair is abundantly rinsed with water. A
sodium lauryl sulfate shampoo is applied.
The initially gray hair, 90% white, is turned black.

~ z ~ o ~ z A permanganate gel is prepared as described in example l.
We treat a lock of hair discolored with gel mentioned above, for 10 minutes at room temperature then the hair is rinsed with water to remove the gel We incorporate, ~ uste before emplol, l, 2 g of 5.6 dihydroxyindole in a thickened solution containing:
-Alkylether of glycoside TRITON CG 110 (trademark) 5g MA
-Gar Guar JAGUAR HP 60 t mark trade) lg -Ammonium chloride 5g - Ammonia qs ~ pH 9 -Water qs 80g This thickened solution is applied for 10 min.
on this wick, rinse with water, wash and dry.
The hair is dyed in raven black.

We prepare the same solutions as in the example 6 but by replacing the 5.6 dihydroxyindole:
either with 1.3 g of 2-methyl 5,6-dihydroxyindole, -or by 1.4 g of 2,3-dimethyl 5,6-dihydroxyin-dole, either with 1.2 g of 3-methyl 5,6-dihydroxyindole, and also replacing the lock of discolored hair with a lock of natural gray hair containing 90% white hair.

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The following colors are obtained respectively.
your:
- dark brown gray, - dark green gray, - dark blue gray.

We use Example 1 and replace the hair natural by permed hair and we get a intense black coloring.

We prepare a solution of potassium permanganate-sium by dissolving 1.58 g of KMnO4 in 1000 ml of water (final volume) adjusted to pH 3 at ~ ec sulfuric acid.
A woven ribbon of 1 g of wool is immersed in 30 ml of KMnO4 solution for 10 min at 30C, the ribbon is then rinsed with water.
A solution is also prepared by dissolving 1.2 g of 5,6-dihydroxyindole in 20 ml of anhydrous ethanol. We add 80 ml of a pH 9 buffer solution comprising 62.5 g NH4Cl in 1000 ml of water adjusted to pH 9 with ammonia niac.
The 1 g woven ribbon of pretreated wool with permanganate solution is brushed with 10 ml of this composition then placed 10 min at 30C in a parailm. The ribbon is then rinsed with water, washed with sodium lauryl sulfate 10% and dried.
The woolen fabric is dyed in raven black.

Claims (32)

1. Process for dyeing keratin fibers, characterized by the fact that one successively applies to said fibers:
(a) a composition containing in a medium suitable for dyeing, at a pH between 2 and 10, a metal anion with good affinity for kera-tine and having a redox potential greater than that of 5,6-dihydroxyindole or its derivatives, of formula (I) below, and (b) a composition containing in a medium suitable for dyeing a dye of formula (I):

(I) in which R1 and R2 independently denote one of the other, a hydrogen atom or methyl group or ethyl. 2. Method according to claim 1, characterized by the fact that the dye of formula (I) is chosen from the group consisting of 5,6-dihydroxyindole, 2-methyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxyindole and 2,3-dimethyl 5,6-dihydroxyindole. 3. Method according to claim 1, characterized by whether the anion is a permanganate or a dichromate. 4. Method according to claim 3, characterized by the fact that the anion is derived from potassium permanganate or sodium dichromate. 5. Method according to claims 1, 3 or 4, characterized by the fact that the anion is present at a molality greater than 10-3 mole / 1000 g. 6. Method according to claims 1, 3 or 4, characterized by the fact that the anion is present at a molality between 10-2 mole / 1000 g and 10-1 mole / 1000 g. 7. Method according to claim 1, characterized by the fact that the pH of the composition containing the anion is acid and that it is adjusted with inorganic acids. 8. Method according to claim 7, characterized by the fact that the pH of the composition containing the anion is between 2 and 5. 9. Method according to claim 8, characterized by the fact that the pH of the composition containing the anion is close to 3. 10. Method according to claims 1, 3 or 4, characterized in that the composition containing the anion is in the form of an aqueous composition containing at least one inorganic adjuvant capable of imparting it a viscosity allowing application on the head. 11. Method according to claims 1 or 2, character-laughed at by the fact that a composition (b) is used in which the dye of formula (I) is present in a proportion between 0.5 and 2% by weight, relative to total weight of the composition (b). 12. Method according to claims 1 or 2, character-laughed at by the fact that a composition (b) is used in which the compound of formula (I) is present in a proportion between 1 and 1.5% by weight, relative to the total weight of the composition (b). 13. Method according to claims 1 or 2, character-laughed at by the fact that the pH of the composition containing the dye of formula (I) is between 7 and 10. 14. Method according to claim 1, characterized by the fact that the composition containing the dye of formula (I) is aqueous and also contains at least one solvent chosen from the group consisting of lower alkanols in C1-C4, ethylene glycol, monomethyl ethers, monoethyl and monobutyl ethylene glycol or ethylene glycol monoethyl ether acetate, propylene neglycol, the monomethyl ethers of propylene glycol or dipropylene glycol and methyl lactate. 15. Method according to claim 14, characterized by the fact that the solvent is present in the composition containing the dye of formula (I) in a proportion between 1 and 30% by weight, relative to the total weight of the composition. 16. Method according to claim 15, characterized by the fact that the proportion of solvent is between 3 and 20% by weight. 17. Method according to claim 1, characterized by the fact that the composition containing the dye of formula (I) also contains at least one cosmetic adjuvant acceptable chosen from the group of agents antioxidants, buffers, fragrances, surfactants active, fatty amides, bulking agents keratin fiber, sequestrants, film-forming agents, preservatives and thickening agents. 18. The method of claim 17, characterized by the fact that the composition containing the dye of formula (I) additionally contains at least one thickening agent in a proportion of between 0.1 and 5% by weight, per relative to the total weight of the composition. 19. The method of claim 18, characterized by the fact that the proportion of thickening agent is understood between 0.5 and 3% by weight. 20. Method according to claim 1, characterized by the fact that an anhydrous solution is prepared beforehand 5,6-dihydroxyindole or one of its derivatives, of formula (I), in an organic solvent and at the time of application tion, a suitable aqueous medium is mixed with said solution.
prayed for tincture. 21. Method according to claim 1, characterized by the fact that the composition containing the anion is maintained in contact with the fibers for a period of 3 to 30 minutes, its application being followed by rinsing with water, and by fact that the composition, containing the dye of formula (I) is kept in contact with the fibers for a period of 2 to 10 minutes followed by rinsing with water, and possibly-washing and rinsing again. 22. Method according to claim 21, characterized by the fact that the composition containing the anion is maintained in contact with the fibers for a period of 5 to 20 minutes. 23. Method according to claims 21 or 22, ca-characterized by the fact that the composition containing the anion is applied at room temperature in the range of 25 to 35 ° C. 24. Method according to claim l, characterized by the fact that the keratin fibers treated are human hair. 25. Multi-compartment device for tincture of keratin fibers characterized in that one of the compartments has at least one composition container in a medium suitable for dyeing, at a pH
between 2 and 10, an anion of a metal having good affinity for keratin and having an oxidore-higher than that of 5,6-dihydroxyindole or its derivatives, of formula (I) below, and that another com-partiment contains a composition containing in a medium suitable for dyeing a dye of formula (I):

(I) in which R1 and R2 independently denote one of the other, a hydrogen atom or a methyl group or ethyl, the contents of said compartments being intended for be applied successively to said keratin fibers ques. 26. device with several compartments according to the claim 25, characterized in that a first compartment contains the composition containing the anion, a second compartment contains 5,6-dihydroxyindole or one of its derivatives of formula (I) in a solvent medium anhydrous and a third compartment contains a medium the contents of the second and third compartments being intended to be mixed just before use. 27. Multi-compartment device according to the claim 25, characterized in that a first compartment contains the composition containing the anion, a second compartment contains an aqueous solution thickened acid, that a third compartment contains the 5,6-dihydroxyindole or one of its derivatives, of formula (I), in an anhydrous solvent medium, and that a fourth compartment contains an aqueous medium, the contents of the first and second compartments and the contents of the third and fourth compartments being intended to be mixed just before use. 28. Device with several compartments according to the claims 25,26 or 27, characterized in that the anion is derived from potassium permanganate or dichromate sodium. 29. Device with several compartments according to the claim 25, characterized in that the dye of formula (I) is chosen from the group consisting of 5,6-dihydroxyindole, 2-methyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxyindole and 2,3-dimethyl 5,6-dihy-droxyindole. 30. Multi-compartment device according to the claim 25, characterized in that the pH of the composition containing the dye of formula (I) is included between 7 and 10. 31. Device with several compartments according to the claim 25, characterized in that the composition containing the dye of formula (I) is aqueous and contains in addition at least one solvent chosen from the group consisting by C1-C4 lower alkanols, ethylene glycol, monomethyl, monoethyl and monobutyl ethers of ethylene glycol or ethylene monoethyl ether acetate neglycol, propylene glycol, monomethyl ethers of propylene glycol or dipropylene glycol and lactate methyl. 32. Device with several compartments according to the claim 25, characterized in that the composition containing the dye of formula (I) further contains at minus a cosmetically acceptable adjuvant selected from the group consisting of antioxidants, buffers, perfumes, surfactants, fatty amides, keratin fiber swelling agents, sequestering agents, film-forming agents, preservatives and thickening agents.