FR2994082A1 - Coloring human keratin fibers e.g. hair, involves applying pretreatment composition, comprising alkaline metal carbonates and/or bicarbonates and aromatic alcohols, on keratin fibers and applying dye composition with natural dyes on fibers - Google Patents

Abstract

Coloring human keratin fibers such as hair, comprises applying a pretreatment composition, comprising alkaline metal carbonates and/or alkaline metal bicarbonates and aromatic alcohols, on the keratin fibers, where the pretreatment composition has a pH value of less than 10, and applying a dye composition containing natural dyes on the keratin fibers. An independent claim is included for a multi-compartment device or kit for coloring comprising a first compartment comprising containing a pretreatment composition, a second compartment containing the dye composition, and optionally a third compartment containing a composition with metal salts.

Description

The invention relates to a process for dyeing keratinous fibers, comprising the application of a pretreatment composition comprising one or more alkali metal (bi) carbonates and one or more aromatic alcohols, and then the application of a coloring composition containing one or more natural dyes. It is known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho or para-aminophenols. and heterocyclic compounds. These oxidation bases are generally associated with couplers. These bases and couplers are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation.

This type of oxidation coloring makes it possible to obtain colorings with a very good level of visibility, coverage of white hair and in a wide variety of shades. But it causes degradation of keratin fibers by the use of oxidizing agents (in particular by repeated application or in combination with other treatments). In addition, there is still progress to be made in terms of color retention over time. It is also known to dye keratinous fibers and in particular human hair, with dyeing compositions containing direct dyes. The standard dyes that are used are in particular nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane or natural dyes.

These dyes may be nonionic, anionic, cationic or amphoteric. These dyes are colored molecules or dyes having an affinity for keratinous fibers. Most of the direct dyes used have sufficient aqueous solubility and there are now many coloring media adapted to receive them. These compositions containing one or more direct dyes are applied to the keratinous fibers for a time necessary to obtain the desired coloration, and then rinsed.

However, the resulting colorations are particularly chromatic but temporary or semi-permanent colorations because the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to washes. Nowadays, hair dyeing processes using natural products are more and more appreciated by users. It is known from FR 2 549 721 to use natural dyes for hair dyeing. However, the method described still needs to be improved in terms of efficiency. There is therefore a real need to develop hair coloring processes leading to powerful colorations, allowing a good level of coverage of white hair, little dependent on the nature of the hair (natural, sensitized, Caucasian, Chinese, Indian), resistant to hair. external agents (light, bad weather, shampoos), respecting the nature of the hair, from compositions containing natural dyes. The object of the present invention is therefore to propose a dyeing process based on natural dye (s) offering powerful, homogeneous coloring from one hair to the other, that is to say seldom or not very sensitive. the nature of the hair (Caucasian, Chinese, Indian), resistant and which degrade the hair fiber. This object is achieved by the present invention which relates to a method for dyeing keratinous fibers, such as human keratinous fibers, and in particular the hair, comprising the following steps: - application to the keratinous fibers of a pre-treatment composition comprising one or more alkali metal carbonates and / or alkali metal bicarbonates, and one or more aromatic alcohols, the pH of said pretreatment composition being less than 10, then - application on the keratinous fibers of a dye composition containing one or more several natural dyes.

The alkali metal carbonates and / or bicarbonates of alkali metals present in the pretreatment composition used in the process according to the invention may be chosen from sodium carbonate, potassium carbonate, sodium bicarbonate and sodium bicarbonate. potassium.

The alkali metal carbonates and / or alkali metal bicarbonates generally represent from 0.01 to 30%, preferably from 0.1 to 10% by weight, of the total weight of the pretreatment composition. The aromatic alcohol (s) present in the pretreatment composition may be chosen from benzyl alcohol, phenyl ethanol and phenyl propanol. The aromatic alcohol or alcohols generally represent from 0.1 to 30%, preferably from 1 to 20% by weight, of the total weight of the pretreatment composition.

As explained above, the pH of the pretreatment composition is less than 10. This pH can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibers or else using buffer systems classics.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

In addition to the alkali metal carbonates or bicarbonates present in the pretreatment composition, the alkaline agents optionally present to adjust the pH of the pretreatment composition may be selected from ammonia, alkanolamines such as mono-, di- and triethanolamines and their derivatives, oxyethylenated and / or oxypropylenated ethylenediamines, inorganic or organic hydroxides, alkali metal silicates such as sodium metasilicates, amino acids, preferably basic such as arginine, lysine, ornithine , citruline and hystidine, and the compounds of formula (I) below: wherein W is a (C1-C8) alkylene residue, preferably propylene optionally substituted by a hydroxy group or a C1-C4 alkyl radical; Ra, Rb, R, and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. Preferably, the pretreatment composition is applied for a pause time of at least 30 seconds, preferably ranging from 3 to 120 minutes, more preferably from 10 to 60 minutes. The pretreatment composition may be applied under heat. Thus, after application of the pretreatment composition and before its removal, the keratinous fibers can be subjected to heat treatment by heating at a temperature higher than that of the application, and in particular between 25 and 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. It is also possible to use keratinous fibers, a heating iron, at a temperature of between 60 and 220 ° C. and preferably between 120 and 200 ° C.

Then, preferably, the keratinous fibers are rinsed and / or washed. The keratinous fibers can then be dried. As explained above, the dye composition used in the process according to the invention contains one or more natural dyes. By natural dyes is meant any dye or dye precursor having a natural occurrence and produced either by extraction (and optionally purification) from a plant or animal matrix, or by chemical synthesis.

The suitable natural dye (s) may be chosen from curcumin, chlorophylline, hematoxylin, haematein, braziline, brazilin, sorghum, laccaic acid, indigo, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, isatin, spinulosin, apigenidine, orceins. Preferably, the natural dye (s) are chosen from curcumin, chlorophylline, hematoxylin, haematein, braziline, braziline, sorghum, laccaic acid and indigo. The formulas of certain natural dyes are given in Table 1 below. Table 1 ## STR1 ## Oleo (Oxidized Form) O HO Hemein (Oxidized Form) OH OH HO HO HO * HO HOO 0 0 HO HO Hematoxylin (Natural Black 1 - Braziline (Natural Red 24 - CAS 517-28-2) CAS 474-07-7) Among the hematoxylin / haematein and brazilin / braziline compounds, there may be mentioned, for example, hematoxylin (Natural Black 1 according to the INCI name). ) and braziline (Natural Red 24 according to the INCI name), composed of the family of indochromanes, which are commercially available. These can exist in an oxidized form and can be obtained by synthesis or by extraction of plants or plants known to be rich in these compounds. Preferably, the natural dye (s) present in the dye composition used according to the invention have a log (P) greater than 1.

The natural dye (s) generally represent from 0.01 to 30%, preferably from 0.1 to 15% by weight, of the total weight of the dye composition.

The dye composition may further comprise one or more aromatic alcohols. The aromatic alcohol or alcohols present in the dye composition used according to the invention may be chosen from benzyl alcohol, phenyl ethanol and phenyl propanol. Preferably, the aromatic alcohol is benzyl alcohol. The aromatic alcohol or alcohols generally represent from 0.1 to 30%, preferably from 1 to 20% by weight, of the total weight of the dye composition.

The dye composition used according to the invention may further comprise one or more direct dyes different from the natural dye or dyes described above. These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of current use such as neutral, benzene neutral, acidic or cationic direct dyes, direct dyes neutral, acidic or cationic azo, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azine, triarylmethane, indoamine, methines, styrils, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and fluorescent dyes. Preferably, the pH of the dye composition ranges from 2.7 to 11, preferably from 2.7 to 9.

This pH can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. As acidifying or alkalinizing agents, mention may be made of the agents already mentioned for adjusting the pH of the pretreatment composition. Whatever the mode of application, the application temperature of the dye composition is generally between room temperature (15 to 25 ° C) and 220 ° C and more particularly between 15 and 45 ° C.

Advantageously, the coloring composition is applied under heat. Thus, after application of the dye composition and before its removal, the keratinous fibers can be subjected to heat treatment by heating to a temperature greater than that of the application, and in particular of between 25 and 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. It is also possible to use, as a means for heating the keratinous fibers, a heating iron at a temperature of between 60 and 220 ° C. and preferably between 120 and 200 ° C. The coloring composition is generally applied during a pause time ranging from 3 to 120 minutes, preferably from 10 to 60 minutes. The keratinous fibers can then be washed and / or rinsed and then dried. According to a first particular embodiment, the method according to the invention comprises, between the application of the pretreatment composition and the application of the dye composition or after the application of the dye composition, a step of application of a composition comprising one or more metal salts, such as salts of zinc, manganese, aluminum or iron. According to a second particular embodiment, the dye composition used in the process according to the invention contains one or more metal salts, such as salts of zinc, manganese, aluminum or iron. The metal salt (s) may be chosen from organic and inorganic salts. For the purposes of the present invention, the term "inorganic salts" means inorganic salts, that is to say not having in their structure a carbon atom bonded to at least one hydrogen atom. The metal mineral salt or salts are advantageously chosen from halides, sulphates, phosphates, nitrates, carbonates and perchlorates.

The metal salts, and in particular of zinc, can be introduced in solid form in the compositions, or can come from natural, mineral or thermal water, rich in these ions or even seawater (dead sea in particular) . They may also come from mineral compounds such as earths, rocks, ochres such as clays (eg green clay) or even plant extract containing them, as described for example in document FR 2 814 943. As a mineral rock containing zinc salts, mention may be made of the following rocks: Boyleite (ZnMg) SO4-4H20 Changoite Na2Zn (SO4) 2-4H20 Clinohedrite CaZn [SiO4] -H2O Gaultite Na4Zn2Si7018-5H20 Goslarite ZnSO4-7H2O Hardystonite Ca2Zn [Si2O7] Hopeite Zn3 (PO4) 2-4H20 Hydrozincite Zn5 [(OH) 31 CO3] 1MA2008-048 Zn6 (PO4) 4-7H20 Minrecordite CaZn (CO3) 2 Osakaite Zn4 (SO4XOH) 6-5H20 Parahopeite Zn3 (PO4) 2-4H20 Parascholzite CaZn2 (PO4) 2-2H2O Scholzite CaZn2 (PO4) 2-2H2O Simonkolleite Zn5 [(OH) gCl2-H2O Skorpionite Ca3Znz [(OH) 2 CO31 (PO4) 2] -H2O Smithsonite ZnCO3 Spencerite Zn4 [01-11PO4] 2- 3H20 Tarbuttite Zn2 [0F111304] Basic Zinc Sulfate Hydrate Zn4SO4 (OH) 6-4H2O Willemite Zn2 [SiO4] Zincsilite Zn3Si4010 (OH) 2-4H20 Zinkosite ZnSO4 Among the organic salts of zinc, it is possible to mention zinc glycinate and zinc gluconate. The metal salt or salts generally represent from 0.01 to 20%, preferably from 0.4 to 10% by weight, of the total weight of the composition containing them. According to one variant of the invention, between the step of applying the pre-treatment composition and that of applying the dyeing composition, it is possible to proceed with a step of rinsing the keratinous fibers with water and / or in a washing step with a shampoo followed by rinsing with water, optionally followed by drying or dewatering of the fibers. Similarly, at the end of the pause time of the dye composition, it is optionally possible to rinse and / or wash with a shampoo and then rinse with water the fibers, the latter being subsequently dried or left to dry. The process according to the invention may also comprise an oxidation step. The pretreatment composition and / or the dye composition and / or the composition comprising optional metal salts may be independently of one another in various galenic forms, such as a lotion, a mousse, a cream, a gel or in any other form suitable for dyeing keratinous fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. The compositions used in the process according to the invention comprise a medium suitable for dyeing, also called coloring support, which may contain water, a mixture of water and one or more organic solvents or a mixture of solvents. organic.

According to one particular embodiment of the invention, the composition or compositions used according to the invention contain water. As an organic solvent, there may be mentioned, for example, C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol. The organic solvents are present in proportions, preferably between 1 and 40% by weight approximately relative to the total weight of the composition. The pretreatment composition, the dye composition and the composition comprising optional metal salts used in the dyeing process according to the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as surfactants. anionic, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickening agents, and in particular anionic, cationic polymeric associative thickeners nonionic and amphoteric agents, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preservatives, opacifying agents. The adjuvants are generally present in an amount for each of them of between 0.01% and 40% by weight relative to the weight of each composition, preferably between 0.1% and 20% by weight relative to the weight of each composition used. implemented. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition (s) useful in the dyeing process according to the invention are not, or substantially not, altered by the addition or additions envisaged. The invention also relates to a multi-compartment device or "kit" for staining comprising: - a first compartment comprising a pretreatment composition as defined above comprising one or more alkali metal carbonates and / or alkali metal bicarbonates, and one or more aromatic alcohols, the pH of said pretreatment composition being less than 10, as defined above, and - a second compartment comprising a dye composition containing one or more natural dyes, as defined above.

According to a variant, the device according to the invention further comprises a third compartment comprising a composition containing one or more metal salts, preferably chosen from zinc, manganese, iron or aluminum salts. The compositions of the kit are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges. The kit mentioned above can also be equipped with means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2,586,913. The present invention is illustrated by the following examples. Examples Example 1 An alkaline pre-treatment composition and a coloring composition are prepared. Their formulations are given in Tables 2 and 3 respectively. The quantities are expressed in grams of active ingredient. Table 2 Benzyl alcohol 5g Ethanol 15g Sodium bicarbonate 2g Water Qsp 100 pH 9,8 Table 3 Benzyl alcohol 4,8g Ethanol 14,4g Bentonite 3,8g HAEMATOXYLON CAMPECHIANUM oxidized 4g Water Qsp 100 Strands of Caucasian natural hair with 90% of White hair and strands of natural Chinese hair with 100% white hair are treated for 15 minutes at 27 ° C by the alkaline pre-treatment composition. Other locks of hair of the two preceding types are treated for 60 minutes at 40 ° C. with the alkaline pre-treatment composition. Other hair check locks of the two preceding types are not treated with the alkaline pre-treatment composition. The locks are then rinsed and wrung out.

The locks are then stained for 45 minutes at 40 ° C. by the coloring composition. They are then rinsed, shampooed and dried.

More intense and stubborn stains are obtained in the case of the locks treated according to the invention. It is also noted that for wicks colored according to the process of the invention, that is to say having undergone alkaline pretreatment, we obtain the same mahogany reflection regardless of the nature of the hair 90% Caucasian natural white hair and Chinese. On the other hand, for the control wicks not treated with the alkaline pre-treatment of the process of the invention, it is found that the coloration is more variable: a mahogany reflection is obtained on the Caucasian locks and a coppery reflection on the Chinese locks. EXAMPLE 2 Strands of permed hair are stained by means of the coloring process according to the invention. Strands of hair with 90% of Caucasian white hair permed are treated for 30 minutes at 27 ° C. with the alkaline pretreatment composition of Example 1. Other hair locks of the same type are not treated with the composition. alkaline pre-treatment. The locks are then rinsed and wrung out. The locks are then stained for 45 minutes at 40 ° C. with the coloring composition of Example 2. They are then rinsed, shampooed and dried.

The mahogany coloring is intense and stubborn in the case of the locks treated according to the invention. It is also noted that the locks stained according to the process of the invention, that is to say having undergone alkaline pretreatment, have a more intense reflection than the control locks on which it has not been carried out pretreatment.

Claims (16)

REVENDICATIONS1. Process for dyeing keratinous fibers, such as human keratinous fibers, and in particular the hair, characterized in that it comprises the following steps: - application to the keratinous fibers of a pretreatment composition comprising one or more metal carbonates alkalines and / or bicarbonates of alkali metals, and one or more aromatic alcohols, the pH of said pretreatment composition being less than 10, and then - application on the keratinous fibers of a dye composition containing one or more natural dyes. 2. Coloring process according to claim 1, characterized in that the alkali metal carbonates and alkali metal bicarbonates are chosen from sodium carbonate, potassium carbonate, sodium bicarbonate and sodium bicarbonate. potassium. 3. The method of dyeing according to claim 1 or 2, characterized in that the aromatic alcohol or alcohols are selected from benzyl alcohol, phenyl ethanol and phenyl propanol. 4. Staining process according to any one of the preceding claims, characterized in that the natural dye (s) are chosen from curcumin, chlorophylline, hematoxylin, haematein, braziléine, braziline, sorghum, laccaic acid, indigo, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, isatin, spinulosin, apigenidine, orceins . 5. The method of dyeing according to claim 4, characterized in that the natural dye or dyes are selected from curcumin, chlorophylline, hematoxylin, haematein, braziléine, braziline, sorghum, laccaïque acid, indigo. 6. dyeing process according to any one of the preceding claims, characterized in that the natural dye or dyes have a log (P) greater than 1. 7. Coloring process according to any one of the preceding claims, characterized in that the dye composition comprises one or more aromatic alcohols. 8. The method of dyeing according to claim 7, characterized in that the aromatic alcohol or alcohols are selected from benzyl alcohol, phenyl ethanol and phenyl propanol. 9. Coloring process according to any one of the preceding claims, characterized in that the aromatic alcohol is benzyl alcohol. 10. Coloring method according to any one of the preceding claims, characterized in that the pH of the dye composition varies from 2.7 to 11, preferably from 2.7 to 9. 11. The method of dyeing according to any one of the preceding claims, characterized in that the dye composition comprises one or more metal salts. 12. Coloring process according to any one of the preceding claims, characterized in that the coloring composition is applied under heat. 13. The method of dyeing according to any one of claims 1 to 10 and 12, characterized in that it comprises, between the application of the pretreatment composition and the application of the dye composition or after the application of the coloring composition, a step of applying a composition comprising one or more metal salts. 14. The method of coloring according to claim 11 or 13, characterized in that the metal salt or salts are chosen from organic and inorganic salts of zinc, manganese, iron and aluminum. 15. The method of dyeing according to claim 13, characterized in that the metal salt or salts are selected from halides, sulphates, phosphates, nitrates, carbonates and perchlorates. 16. Multi-compartment device or "kit" for coloring, characterized in that it comprises - a first compartment comprising a pretreatment composition comprising one or more alkali metal carbonates and / or alkali metal bicarbonates, and one or more alcohols aromatic, the pH of said pretreatment composition being less than 10, as defined in any one of claims 1 to 3 and - a second compartment comprising a coloring composition containing one or more natural dyes as defined in any one of Claims 1 and 4 to 11, - optionally a third compartment comprising a composition containing one or more metal salts, preferably selected from zinc, manganese, iron or aluminum salts.