LU86947A1 - PROCESS FOR DYEING KERATINIC FIBERS, ESPECIALLY HUMAN, WITH 5- (HYDROXY OR-METHOXY) 6-HYDROXYINDOLE - Google Patents

Description

* ί * # L '/.- i-EAL £' i δ 2.5538. - * - ·. ·· * ’l

---. . 7 ~ / GRAND-DUCHY OF LUXEMBOURG

Brevet N "V ... V ..., .V_ .... t w (Jul 17 July 1987 $ ÊSÊLJî Minister for the Economy and the Middle Classes

Title issued: ........................................ Intellectual Property Service

; - LUXEMBOURG

Patent Application I. Application

The society. ... anonymous ..... âitgj ...... L 'OREAL ..... S, A, ..., ...... 1.4 ..... ru.e ... . Royal., .............................................. ...... (1) F-75008 Paris, represented by Alain RUKAVINA, attorney-at-law, '' resident "in Luxembourg, ÏÔA bd de la Foire, acting in court ±" té ..... of ..... mandate area .......................................... .................................................. .................................................. .................... ('............................ ................................. seventeen t "j ü'ill e t ..... I '900' '' 'qU'atrë- ^ n2t sept .......................

at .....?:. ^ ...: .. 9.9 ...... hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent of invention concerning:, \ ProÇ..é..dé ..... de ..... tincture ...... des ..... f, ib.r..es. ... k.éxat.ini.q.ues., ...... in ..... p.ar..tic.ul.ier _______ (4) human, with 5- (hydroxy or - methoxy) 6-hydroxvindole.11 .......................

2. the delegation of power, dated ......................................... ............................... the .................. ............................................

3. description in language ^> ran ^ a ^ se ............................... of the invention in two copies; 4 .......... he .............. drawing boards, in two copies; 5. the receipt of the taxes paid to the Luxembourg Registration Office on ...... 17 ..... July ..... 1.9.87 ............ .................................................. .................................................. .................................................. ....................................

declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): ------------------------- ---------------------------------------------------------- ---------------------------------------------------------- ---------------------------------------------------------- --------------------------------------............ ............................- (5) MQnsieur ..... J..e..an .-. Fr an.ç..Q.is ..... GROLLIER., ..... i, jg_i> 4 ^ - ^ 0u ~ 3rev-az: <d ~ "Morl ~ af) â ...... .......................— F-75004 PARIS ____________________________________________________________________________________________________________________________________________________________...................... ................... 1____________________ claim) for the above patent application the priority of one (or more) application (s) of (6) ...... ......................... LJ ........................ .................................. filed in (7) __________________________________________________________________________________________________________________ ___________________ the ................................................ .................................................. ............. (8) on behalf of ............................... .................................................. ............................ (9) elect (elect) for him / her and, if appointed, for his / her proxy, to Luxembourg______________________ lQA .... bd .... de .... la ... Foir.e ______________________________________________________________________________________________________________________________________ (10) requests (s) the grant of a patent for the invention for the subject described and represented in the appendices above, - with postponement of this issue to ............ month. (11)

The man ^ iij.iref .............

/ EL Procès-verbal de Dépôt / The above application for a patent for invention has been filed with the Ministry of the Economy and the Middle Classes, Intellectual Property Service in Luxembourg, dated: I7.j0 ^ gag7v_

Av * ^ V \ / i Pr. Minister 1 b nn / * * at ‘hours I £ = ï of Economy and the Middle Classes, \ S:% if P-d-

fa K

A 6S007, 1987-07-17 11:58 D.R CRSRLÜNGFI JOSSE PARIS 33 1 45632696 -P.02 • 3 * * *

1081/87 GD / DD

LU 415

Public limited company called: L'OREAL

Process for dyeing ceratinous fibers, in particular human fibers / with 5- (hydroxy or -methoxy) 6-hydroxyindole.

Invention of Jean-François GROLLIER

1987-07-17 11 = 58 D.fl CASRLGNGA JOSSE PARIS 33 1 4563269S P.03 * î * · '

Process for dyeing keratin fibers, in particular human fibers “with 5- (hydroxy or -methoxy) 6-hydroxyindole.

5 The subject of the invention is a new process for dyeing keratin fibers, in particular human keratin fibers such as the hair, the hair (beard, mustache, eyelashes, eyebrows), with a view to imparting them a natural coloring by putting in place work 10 5- (hydroxy or -methoxy) 6-hydroxyindole.

Dyeing human hair with 5,6-dihydroxyindole or its derivatives is well known. It is also known that the hair color comes mainly from the melanin pigments secreted by the melanocytes and that these pigments of natural origin include eumelanins whose natural biosynthesis takes place in several stages by polymerization of the oxidation product of an acid. amine: tyrosine, one of the oxidation products of tyrosine being 5,6-dihydroxyindole.

The Applicant has described in its unpublished French patent application No. 87 00527, a process for 2 V "dyeing keratin fibers with 5.6 ~ dihydroxyindole comprising the application to these fibers of at least one composition (A) containing, in a medium suitable for dyeing, 5.6 "5-dihydroxy-indole in combination with iodide ions, the application of composition (A) being preceded or followed by the application of a composition (B) which contains, in a suitable medium, for the dyeing of hydrogen peroxide.

The Applicant has just found that it was possible to surprisingly improve the coloring power obtained by this process by following the application of the composition (a) by a step of drying or evaporation of the liquid medium. .

Among the dyeing or bleaching techniques commonly used in the hair field, one of these consists in partially treating the hair in order to obtain a so-called "wicking" effect.

This effect is generally obtained by applying the coloring or bleaching product to isolated wicks, either that the wicks have been pulled through a plastic cap placed on the scalp or that they have been isolated by another method. such as cotton, aluminum foil, etc., or also by the technique called "sweeping" with a comb.

In view of the advantage of 5,6-dihydroxy-indole, it has also been envisaged to apply this dyeing process using iodide ions and hydrogen peroxide in order to obtain the so-called "effect". wicks ".

The Applicant has however noted that by implementing this process in several steps to partially dye the hair in order to obtain 1987-07-17 12 = 00 D.fl CASALONGA JOSSE PARIS 33 1 45632G96 P.04 3 l effect called "wicks", we got an imperfect and unattractive dye "

Indeed, the Applicant has found that this process often results in staining of the hair near the strands to which the composition was applied due to the significant diffusion of the dye on the neighboring fibers during development with hydrogen peroxide.

This drawback manifests itself especially when it is desired to dye short white or gray hair and more particularly hair at the level of the male temples. In fact, in this case, it is practically impossible to dye using a cap, the hair being too short. Furthermore, the fact of not using a cap also saves time.

The Applicant has found that, surprisingly, it was possible to remedy the staining or aesthetic problems caused by. this two-step dyeing process described above and that it was also possible, as indicated above, to obtain colorations with improved potency.

This process involves the application of 5 "- (hydroxy or -methoxy) 6-hydroxyindole with iodide ions followed by the application of hydrogen peroxide, characterized by an intermediate stage of drying or evaporation of the medium. dye.

The object of the invention is therefore constituted by a new process for dyeing keratin fibers, and in particular human fibers.

Other objects of the invention will appear on reading the description and the examples which follow.

The dyeing process for keratin fibers and in particular human fibers is 1987-07-17 12:01 DA DA CASALONGA JOSSE PARIS 33 1 45632696 P.05 4 essentially characterized by the fact that a first step is applied to these fibers. liquid composition (A) suitable for dyeing containing S-hydroxy or (methoxy) 6-hydroxyindole in combination with iodide ions, in a second step, the fibers are brought to the dry state by drying or evaporation of the liquid medium , and thirdly, the application of a composition (B) containing, in a suitable liquid medium, for the dyeing of hydrogen peroxide is carried out.

The iodide ion used in the process according to the invention is preferably an iodide of alkali or aloalino-earth metal or of ammonium, and more particularly potassium iodide.

During the process according to the invention, it is possible after drying to remove the dried product on the surface of the fibers by brushing so as to leave only the dye which has penetrated.

This method is preferably used for partially dyeing hair which has turned white or gray by loss of natural pigmentation, in order to obtain a so-called "wicking" effect.

This method is particularly advantageous for dyeing the hair of the male temples or the hair of the beard, mustaches, eyelashes or eyebrows.

In the compositions used in the process according to the invention, 5- (hydroxy or -methoxy) 6-hydroxyindole is generally present in proportions of between 0.01 and 5% by weight, and preferably between 0.03 and 3% by weight, relative to the weight of the composition (A). The proportion of iodide in composition (A), applied during the process according to the invention, is between 0.007 and 4% by weight expressed as I ions ”and preferably between 0.08 1987-07-17 12: 02 DA CASALONGA JOSSE PARIS 33 1 45632696 P.06 t 5 and 2.5% relative to the total weight of the composition (A).

The ratio 5- (hydroxy or -methoxy) 6-hydroxy-indole / l- is preferably between 0.05 and 10 and 5 more particularly between 0.5 and 2.

The pH of the composition (A) is preferably between 2 and 7.

The hydrogen peroxide is present in composition (B) in proportions generally of between 1 and 40 volumes and preferably between 2 and 20 volumes and more particularly between 3 and 15 volumes * This composition has a pH of between 2 and 11,

The process according to the invention is carried out by providing exposure times for the composition (A) containing the 5r (hydroxy or -methoxy) 6-hydroxyindole in combination with the iodide ions, between 10 seconds and 45 minutes and preferably of the order of 2 to 25 minutes and more particularly around 2 to 15 minutes, and for the composition (B) containing hydrogen peroxide, exposure times between lo seconds and 45 minutes and preferably between 1 minute and 30 minutes.

The drying or evaporation time is preferably between 2 minutes and 50 minutes and is carried out at a temperature of 20 ° C. to 50 ° C.

The Applicant has found that the process used makes it possible to obtain "wicking" effects having powerful colors, penetrating well into fibers, in particular human keratin fibers such as the hair, in relatively short times. in the range of 2 to 15 minutes.

The process according to the invention also makes it possible to obtain clear shades, either by using low concentrations of 5- (hydroxy or 1987-07-17 12:03 D.fl CASALONGA JOSSE PARIS 33 1 45632696 P.07 6 -methoxy) 6-hydroxyindole and iodide within the limit of the ratio 5- (hydroxy or -methoxy) 6-hydroxyindole / I “indicated above and very short exposure times for the application of the peroxide composition hydrogen 5 (B) f either by lightening dark shades already obtained by leaving the composition of hydrogen peroxide (B) in a prolonged manner.

The compositions used for carrying out the process according to the invention may be in various forms, such as more or less thickened or gelled liquids, creams, emulsions, foams or other forms suitable for make a dye.

The dye compositions intended for use in the process according to the invention and containing either 5- (hydroxy or -methoxy) 6-hydroxyindole in combination with iodide ions, or hydrogen peroxide, generally include an aqueous medium consisting little. dw water OR a water-20 solvanl (s) mixture, the solvent (s) being preferably chosen from organic solvents such as ethyl alcohol, propyl or isopropyl alcohol, l tertiary butyl alcohol, ethylene glycol, monomethyl, ronoethyl or monobutyl ethers of ethylene glycol, ethylene glycol monoethyl acetate, propylene glycol, monomethyl ether of propylene glycol and dipropylene glycol and lactate.

The preferred solvents are ethyl alcohol and propylene glycol.

It is also possible to store 5- (hydroxy or -methoxy) 6-hydroxyindole and / or iodide in a medium consisting of essentially anhydrous solvents and to mix this or these solvent (s) with an aqueous medium, time of employment.

1987-07-17 14:06 D.fi CßSALGNGA JOSSE PARIS 33 1 45632696 P.01 7

The solvents are chosen from those mentioned above,

An solvent comprising less than 1% water is called anhydrous solvent.

When the medium consists of a water-solvent mixture, the solvents are present in concentrations of between 0.5 and 75%, in particular between 2 and 50% by weight relative to the total weight of the composition, and more particularly between 10 2 and 20%,

Composition (A) may contain other dyes, either oxidation or direct, which make it possible to obtain a coloration or shade in the presence of the iodide ion and hydrogen peroxide.

The compositions used, in accordance with the invention, can contain fatty amides such as mono- or diethanolamides of acids derived from coconut, lauric acid, oleic acid, in concentrations of between 0.05 and 10% by weight.

They may also contain surfactants, anionic, cationic, nonionic, amphoteric or mixtures thereof.

These surfactants are preferably used in proportions of between 0.1 and 50% by weight relative to the total weight of the composition, and advantageously between 1 and 20% by weight.

The compositions defined above and used in the process according to the invention can be thickened with thickening agents such as sodium alginate, gum arabic, guar gum, biopolymers such as xanthan gum or scleroglucans, cellulose derivatives such as methylcellulose, hydroxyethylcelluloae, hydroxypropylmethylcellulose, sodium salt of carboxymethylcellulose and acid polymers 1987-07-17 14 ·· 07 D.fi CASALONGA JOSSE PARIS 33 1 45632696 P.02 8 acrylic crosslinked or not. It is also possible to use mineral thickening agents such as bentonite. These thickeners are used alone or as a mixture and are preferably present in proportions of between 0.1 and 5% by weight relative to the total weight of the composition and advantageously between 0.5 and 3%.

The alkalizing agents which can be used in these compositions may in particular be amines such as alkanolamines, alkylamines, hydroxides or alkali or ammonium carbonates. The acidifying agents which can be used can be chosen from lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid and citric acid, but it is of course possible to use other alkalinizing or acidifying agents suitable for dyeing.

It is optionally possible to add to each of the compositions a keratin fiber swelling agent such as, for example, urea.

When the composition containing 5 ~ (hydroxy or -methoxy) 6-hydroxyindole is used in the form of foam, it can be conditioned under pressure in an aerosol device in the presence of a propellant 25 and a foam generator. The foaming agents can be anionic, cationic, nonionic, amphoteric foaming polymers or surfactants as indicated above.

The compositions used in the process according to the invention may also contain various adjuvants such as perfumes, sequestering agents, film-forming agents, fiber treatment agents, dispersing agents, conditioning agents. , preservatives, opacifiers.

9

With a view to carrying out the process in accordance with the invention, the compositions can be added to the list. several compartments also called "kits" or dye kits comprising all the components intended to be applied for the same dye on keratin fibers in successive applications with or without premix.

Such devices are known per se 10 and may comprise a first compartment containing the composition of 5,6-dihydroxyindole or its methoxylated derivative in the presence of iodide ions in a liquid medium suitable for dyeing, in a second compartment a solution of hydrogen peroxide, optionally a third compartment containing an alkalizing agent in a medium suitable for dyeing. It is also possible to provide a fourth compartment containing one or more oxidation or direct dyes, in a medium 20 suitable for dyeing, the contents of the third and second compartments being mixed just before use and that of the fourth compartment. being intended to be mixed with the contents of the first compartment ♦ 25 If the medium containing 5- (hydroxy or -methoxy) 6-hydroxyindole consists of an anhydrous solvent, a mixture is used before use with an aqueous medium suitable for dyeing , possibly present in a fifth compartment.

The 5- (hydroxy or -methoxy) 6-hydroxyindole in an anhydrous medium can also be applied directly to the wet keratin fibers.

According to another embodiment, the “kit” or the dyeing kit comprises a first compartment containing a composition containing, in 1987-07-17 14--08 D.fi CASALONGA JOSSE PARIS 33 1 45632696 P. 03 10 a medium suitable for dyeing, iodide ions, a second compartment containing a composition containing, in a liquid medium suitable for dyeing, 5- (hyroxy or -methoxy) 6-hydroxyindole, a third compartment containing a solution of peroxide of hydrogen, optionally a fourth compartment containing an alkalizing agent * The composition contained in the second compartment is intended to be mixed, at the time of use, with the contents of the first compartment and that contained in the fourth is intended to be mixed extemporaneously with that of the third.

These devices can be equipped with mixing means known in themselves and be packaged under an inert atmosphere.

The methods according to the invention and the corresponding compositions can be used for dyeing natural or already dyed hair, permed or not or straightened or strongly or slightly discolored and optionally permed hair.

As indicated above, they are preferably applied to partial dyeing in order to obtain a so-called "wicking" effect, in particular on short hair which has partially lost its natural pigmentation, but also on hairs such as beard, mustache, eyelashes, eyebrows, which do not allow the use of a cap.

The process of the invention can be preceded or followed by other cosmetic treatments known in themselves.

It is also possible to use it to dye furs or wool.

The following examples are intended to illustrate the invention without, however, being limiting in nature.

11 EXAMPLE 1

In a hair comprising 80% of white hair, the composition (A) is applied with a small brush on a part of the hair, from the root to the tip, so that only half of the white hair is covered with composition (A).

Dry under helmet for lo minutes.

Composition (B) is applied for 10 minutes,

Rinse and dry the hair. After drying, part of the hair is black, the rest of the hair remains white, reducing the entire head of hair to around 40% white hair.

15

Composition A x - 5,6-dihydroxyindole 2.5 g - Potassium iodide 2.0 g 20 - Ethyl alcohol 10.0 g * Guar gum sold under the name "jaguar HP 60" by the

CELANESE 1.0 g - Alcoholether glycoside sold at a concentration of 60% MA under the name "TRITON CG 110" by the

SEPPÏC 5.0 g MA

- spontaneous pH “6.5 - Water qs 100.0 g 1987-07-17 12:04 D.fl CASALONGA JOSSE PARIS 33 1 45632696 P.08 12

Composition B ï - Hydrogen peroxide 3.75 g * - Ammonium lauryl sulfate 6.7 g 5 ~ CARBOPOL 940 (crosslinked acrylic polymer) sold by the company GOODRICH 1.0 g - Stabilizer O, 03 g - Perfume qs 10 - Amino -2 2-methyl-propanol-1 qs pH “4 - Water qs 100.0 g EXAMPLE 2 15 Example 1 is repeated using, as composition (A), the following composition:“ 5,6-dihydroxyindole 2 , 0 g - Potassium iodide 1.0 g 20 - Ethyl alcohol 10, O g * "Guar gum sold under the name" JAGUAR HP 60 ”by the Company CELANESE 1.0 g mvifl fiihnn do gly ···! * "Uiu.Au i. the 25 onnrentrnt · i on of 60¾ MA under the name "TRITON CG 110” by the

SEPPIC 5.0 g MA

- Triéthnnolamine qop pH = C

- Water qs 100.0 g 30

Composition B is identical to that of Example 1 ·

We get a brown color on the part of the dyed hair "* · * 1987-07-1? 12:05 D.A CASALONGA JOSSE PARIS 33 1 45632696 p.09 13 EXAMPLE 3

Example 1 is repeated using # as composition (A), the following composition i 5 - 5-methoxy 6-hydroxyindole 2.0 g - potassium lodide 2.0 g - Ethyl alcohol 10.0 g - Gum of guar sold under the name "JAGUAR HP 60" by the company CELMESE 1.0 g - Glycoside alkylether sold at a concentration of 60% MA under the name "TRITON CG 110" by the

SEPPIC 5.0 g MA

15 - spontaneous pH - 6.2 - Water qs 100.0 g

Composition (B) has the following composition: s 20 - Hydrogen peroxide 3.75 g - Ammonium lauryl sulfate 6.7 g - CARBOPOL 1345 (crosslinked acrylic polymer) sold by the company GOODRICH 0.7 g 25 - Stabilizer 0.03 g - Perfume qg "Amino-2 methyl" * 2 propanol-1 qs pH = 3.8 - Water qgp 100.0 g 30 A harmful color is obtained on the part of the hair dyed.

Claims (16)

1987-07-17 12:06 D.A CASALONGA JOSSE PARIS 33 1 45632696 P.10 14 1. A process for dyeing keratin fibers, in particular human fibers, characterized in that at least one composition (A) is applied to these fibers, containing, in a liquid medium suitable for dyeing, 5- (hydroxy or -methoxy) 6-hydroxyindole in combination with iodide ions, that in a second step, the dye composition applied is brought to the dry state 10 On the fibers, by drying or evaporation of the liquid medium, that in a third step, a composition (B) is applied which contains, in a liquid medium suitable for dyeing, hydrogen peroxide. 2. Method according to claim 1, characterized in that the liquid medium is dried or evaporated for a period of 2 minutes to 50 minutes at a temperature between 20 and 50oC, 3. Method according to any one of claims 1 to 2, characterized in that the iodide ion is chosen from iodides of alkali metal, alkaline-earth or ammonium. 4. Method according to any one of claims 1 to 3, characterized in that the 5,6-dihydroxyindole or its 5-methoxy derivative is present in the composition (A) in proportions of between 0.01 and 5 % by weight and preferably between 0.03 and 3% by weight relative to the total weight of the composition (A). 5. Method according to any one of claims 1 to 4, characterized in that the iodide ion is present in the composition (A) in proportions of between 0.007 and 4% by weight expressed in ion I ", and of preferably between 0.08 and 15 I Λ * 4 1 * 2/5% relative to the total weight of the composition (A) * 6. Method according to any one of claims 1 to 5, characterized in that the ratio of 5 ~ (hydroxy or -methoxy) 6-hydroxyindo.le to 5 the iodide ion is between 0.05 and 10 and preferably between 0.5 and 2 ♦ 7. Method according to any one of claims 1 to 6 / characterized in that the content of hydrogen peroxide in composition (B) is between 1 and 40 volumes, and preferably between 2 and 20 volumes and more particularly between 3 and 15 volumes. 8 * process according to any one of claims 1 to 7, characterized in that the composition (A) contains an oxidation dye or a direct dye making it possible to obtain a coloration or a shade in the presence of the ion iodide and hydrogen peroxide. 9 * Process according to any one of Claims 20 to 8, characterized in that the composition (A) containing the iodide ions in the form of alkali metal, alkali metal iodide is applied in the first step earthy or ammonium and 5- (hydroxy or -methoxy) 6-hydroxyindole, then composition (B) containing hydrogen peroxide at a pH between 2 and 11, 10. Method according to any one of claims 1 to 9, characterized in that the method is implemented by providing exposure times 30 for the composition (A) containing 5- (hydroxy or -methoxy) 6- hydroxyindole in combination with iodide ions, between 10 seconds and 45 minutes / preferably between 2 and 25 minutes and more particularly between 2 and 15 minutes, and that the composition containing the hydrogen peroxide (b) is 1987 -07-17 14:09 D.ft CflSflLONGA JOSSE PARIS 33 1 45632696 P.04 t · * 4 "* I" 16 applied during exposure times between 10 seconds and 45 minutes and preferably between 1 minute and 30 minutes , according to the desired colors. 11 * Method according to any one of claims 5 to 10, characterized in that the compositions used are in the form of more or less thickened or gelled liquids, creams, emulsions, foams. 12. Belon method any one of claims 10 to 11, characterized in that the composition (A.) containing 5- (hydroxy or -methoxy) 6-hydroxyindole in combination with the iodide ions, comprises an aqueous medium consisting of water or a water-solvent mixture (s) and that it has a pH between 15 2 and 7. 13. Method according to any one of claims 1 to 11, characterized in that the composition (A) is in the form of an anhydrous solution ♦ 14. Method according to any one of claims 1 to 13, characterized in that the solvents are chosen from ethyl, propyl, isopropyl, tert-butyl, 11-ethylene glycol, monomethyl, monoethyl or monobutyl ethers of ethylene glycol, acetate monoethyl ether of ethylene glycol, propylene glycol, monomethyl ether of propylene glycol or dipropylene glycol and methyl lactate. 15. Method according to any one of claims 1 to 14, characterized in that compositions containing one or more adjuvant (s) chosen from fatty amides are used in proportions of 0, 05 to 10%, anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof, present in proportions included _ 'V 1987-07-17 12:08 DA CASALONGA JOSSE PARIS 33 1 45632696 R.11 l ^ * 17 between 0.1 and 50% by weight, deg thickening agents in deg proportions between 0.1 and 5% by weight, perfumes, sequestering agents, film-forming agents, treatment agents, dispersing agents, conditioning agents, preserving agents, opacifying agents, keratin fiber swelling agents. 16. Method according to any one of claims 1 to 15, characterized in that one proceeds to the partial dyeing of human keratin fibers by applying the dye composition (A) to locks of hair having lost completely or partially their natural pigmentation or beard, mustache, eyelash or eyebrow hair. Drawings: .......... plates \% .pages of which ...... J \ ...... cover page ______ I3-- description pages _________ H ... claim pages .. ..... descriptive abbreviation Luxembourg, la The representative: Me Alain Rukavina