LU84122A1 - COMPOSITION BASED ON QUINON DYES FOR USE IN HAIR DYEING, PROCESS FOR PRESERVING QUINONIC DYES AND USE IN DYEING HAIR - Google Patents

Description

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1- ·., Composition based on quinone dyes intended to be used for hair dyeing, process for preserving quinone dyes and use for dyeing! hair,

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The present invention relates to a process allowing! i both the conservation of quinone dyes belonging to the! class of benzoquinones and naphthoquinones, to compositions allowing the conservation of these dyes and to the use; Use of these compositions for the preparation of composites. dyeing for hair.

"2-hydroxynaphthoquinones as well as benzoquinones I are dyes known in themselves and which for the most part I I of them have not been used until now for the dyeing of hair. The use for dyeing the hair was the subject of two Luxembourg patent applications filed on December 2, 1981 under the titles: - "Use of • benzoquinones for the direct dyeing of keratin fibers", under the number 83.807 , and i - Use of hydroxynaphthoguinones for dyeing keratin fibers i, dyeing process using them and dye composition used ", under No. 83.808.

# 2-hydroxy S 1,4-naphthoquinone, also known as Lawsone, which is one of the dyes responsible for henna dye, has also been known for a long time.

{| The 2-hydroxynaphthoquinones which are the subject of the Luxembourg patent application n ° 83808 previously filed | by the plaintiff respond to the following formula: I r5 o

R4_ — pH

; I I

R3 -; r2 0 in which R ^ denotes hydrogen, hydroxyl, alkoxy, nitro, I halogen, alkyl, acyl, R2, R3, R4, R ^ denote independently ^ 2. # amment each of hydrogen, hydroxyl, alkoxy, alkyl or acyl at least one of the substituents R ^ to being different from hydrogen. In this formula R_ and R cannot simultaneously denote hydroxyl if R ^, R3 and R4 denote hydrogen. The alkoxy or alkyl groups preferably denote groups having between 1 and 4 carbon atoms and acyl denotes a group having from 2 to 4 carbon atoms.

The benzoquinones which are the subject of the Luxembourg patent application No. 83807 of the applicant respond to a. the formula: 0 1 * 4 --R1 R3 R2 0 - i in laguelle R ^ and R3 independently of one another denote hydrogen, hydroxyl, alkoxy, optionally hydroxylated alkyl, I R2 and R ^ independently of one the other denote hydrogen,! hydroxyl, alkoxy, alkyl having 1 to 3 carbon atoms,

Iphenyl optionally substituted by OH, these compounds having at most two alkyl or alkoxy groups on the quinone nucleus.

These compounds have a good dyeing power vis-à-vis the hair when used as direct dyes. However, they present certain problems insofar as they are sparingly soluble in particular in water and, on the other hand, they are unstable in aqueous solution during storage.

A first solution which made it possible to use them was to use them in powder form with other pulverulent products serving as a support. By dilution, we obtain; thus holds a coloring poultice.

1 'I This mode of implementation, if it is very interesting, however has the defect of requiring dissolution of the dye at the time of use, that is to say at the time of r the pasting of the powder with water. We are limited by oe, J i 3 ψ done in dye power by the speed of solubilization! and the limit of solubilization of the abovementioned dyes.

The Applicant has discovered that if these dyes lose their dyeing capacity during storage in aqueous compositions usually used for dyeing | hair, certain benzoquinones or naphthoquinones stored i | surprisingly see this tinctorial power during the | storage in certain anhydrous solvents.

j. The present invention therefore relates to solutions of | certain quinone dyes in a solvent or mixture of anhydrous solvents.

Another object of the invention consists of a process for preserving these dyes in the anhydrous solvent (s).

'! A subject of the invention is also a process for the preparation of: the immediately applicable dye compositions 1 on the hair, consisting in introducing the solutions mentioned above into a * or agous cosmetic supports usually used in dyeing the hair. r:. Other objects of the invention will appear on reading the description and the examples which follow.

The solutions of stable dyes in accordance with the invention are essentially characterized in that they contain at least one quinone dye corresponding to the formulas; i r5 0 0 I R4 ^^ X ^ ^ »^ X._OH ^^ X oh! Kl L -i i- R3 \ jAy ~ Rl R6 X ^ CH3 i R2 0 0 i (I ') (II ·) / i' r Î Γ r in which R ^, R2, R3, R ^, R ^ , Rg and R ^ have the meanings below> î

Compound R ^ r2 r3 - r4 r5 Rg r? 1 HH HH H - - 2 OH H HH H - - 3 HH H OH H - - 4 HH HH OCH3 5 OCH3 H HH H -

6 H OH HH H

7 HH OCH3 H H - -

! 8 H OH HH OH

9 - - - OH OCH3 io - - - - - och3 och3

11 - - - OH H

! __J_____ in an anhydrous solvent or mixture of solvents.

The term "anhydrous" means solvents or mixtures of; solvents containing not more than 1% water. These solvents are cosmetically acceptable and are chosen in particular from lower saturated monoalcohols such as ethanol, isopropanol, long chain saturated monoalcohols such as cetyl alcohol? polyols such as alkylene glycols such as ethylene glycol, propylene glycol, glycerol, diethylene glycol; glycol ethers such as mono, di and triethylene glycolmonoalkyl ethers, such as for example ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether; esters such as, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; esters of saturated fatty acids and saturated lower alcohols such as myristate or isopropyl palmitate. The preferred compositions contain in particular ethanol, cetyl alcohol, propylene glycol, ethylene glycol monoethylethet or ethylene glycol monobutyl ether.

ί! ί I 5 ϋηβ * λ7ΐϊ®Ι? ι ^ β preferred of the invention consists in using an anhydrous medium constituted by one or more anhydrous solvents mentioned above and by one or more anhydrous surfactants so that these compositions contain at least 15% solvent (s) and at least 20% surfactant (s).

j Surfactants usable in this form of realization! sation of the invention belong to the different classes of anionic, nonionic, cationic, anhydrous amphoteric surfactants, or their mixture. Mention may in particular be made of polyoxyethylenated fatty alcohols, alkylphenols or naphthols! polyoxyethylenated, amine alkylsulfates, halides) of monoalkyl trimethylammonium, dialkyldimethylammonium halides, soaps, polyglycerolated fatty alcohols.

Non-ionic surfactants are particularly preferred.

I The dyes used in accordance with the invention are present, in these compositions, alone or in combination in proportions ranging from 0.001 to 5% by weight and preferably between 0.005 and 2% by weight relative to the total weight of the anhydrous composition.

The compositions according to the invention may contain an anhydrous alkaline or acidifying agent. For this purpose, for example, citric acid, ascorbic acid, acetic acid, lactic acid and alkanolamines such as those which are completely substituted on the amino moiety such as dimethylaminoethanol are used. .

i S In the case where an acidifying agent is used j; Particularly preferred dyes are dyes 1 to 6 and 9 to 11 in the above table and in the case where an alkalizing agent is used, particularly preferred dyes are dyes 2 to 8 in the above table.

Preferred embodiments of the invention therefore consist of these two types of composition on the one hand compositions having an acidic pH after dilution with water and containing the dyes 1 to 6 and 9 to 11 and on the other hand the / n fi / d.

j 6 "'-" Μ ** ·· I compositions having an alkaline pH after dilution with water and containing the dyes 2 to 8.

Apart from the compounds described above, the anhydrous compositions in accordance with the invention may contain | many additives only if they contain | less than 1% water.

IA this effect, one can quote among the other additives, the perfumes, the sequestering agents, the thickening agents, | . agents treating the hair, antioxidants, vegetable or mineral oils, preservatives and organic salts.

These compositions may also contain other dyes intended for use in hair dyeing, belonging to the class of direct dyes. We can in particular- | use natural direct dyes which are not very stable in an aqueous solution, which are thus enhanced. Among these types of dyestuffs, mention may be made of hematoxil line, which is the dye present in logwood, brasiline, which is the dye present in Brazilian wood, and also henna extract. Like other coloring extracts! obtained from the coloring plants, i can cite, for example, extracts of madder, matrix, turmeric, l; annatto.

î I The direct dyes other than those corresponding to the formulas (I *) and (II *), which can be used in accordance with the invention are well known in themselves and are chosen in particular from> anthraquinone, azo, triarylmethane dyes,? azines, nitro derivatives of benzene, such as nitro-phenylenediamines, nitroaminophenols, dinitroaminophen-

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nols, nitroaminobenzenes, nitrodiphenylamines. Anthraquinone dyes and in particular the hydroxyanthraquinones described in the French patent application of the applicant No. 82 03 294 will preferably be used.

The dyes other than those of formula (I ') or (II') are present in the anhydrous dye compositions j according to the invention in proportions ranging from 0.01 a. j I 3% preferably 0.05 to 2% by weight relative to the total weight ·, f of the anhydrous composition. L / y! I> es compositions according to the invention can be stored for long periods without degradation of the dye power of the dyes corresponding to formulas (I ') and (ΓΙ').

These compositions can be applied as such to wet hair, or be diluted just before; employment. In the latter case, at the time of dyeing, the compositions according to the invention are diluted with a solution ti | - aqueous so that the ratio between the composition | according to the invention and the aqueous solution is between 0.25 and 2 by weight. The aqueous solution can consist of pure water but also of any other complex aqueous liquid *, more or less thickened, such as for example a Ü! support usually used in dye compositions for hair.

In this case, the components of the cosmetic medium can | S be any type of cosmetically acceptable ingredient, 1 anhydrous or not, usually used in this type of 1 composition.

dd The mixture thus produced is applied to the hair | for a variable duration of between 1 minute and 1 hour 1 and preferably between 5 minutes and 30 minutes. The hair * is then rinsed, possibly washed with shampoo and dried.

The following examples are intended to illustrate the invention without, however, being limiting in nature. / i s, l / 7! * 7 p! / ’K k; y; %: s l! -! [* i; : 8 EXAMPLE 1 12-hydroxy 3-methyl 5,6-dimethoxy 1,4-benzoquinone 0.5 g 2,3-dihydroxy 1,4-naphthoquinone 0.4 g 2-hydroxy 3-methoxy 1,4-naphtoquinone 0 , 3 g

Citric acid anhydrous 1 g

Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100g

This liquid is mixed at the time of use with 1.5 times its weight of cold water. The gel obtained is applied for 30 l \ minutes to light brown hair. The hair being rinsed and dried, the hair then has a mahogany reflection it is purple.

| The conservation of tinctorial power during storage | of the initial composition is much better than that obtained I with the storage of the final gel.

I EXAMPLE 2 I 2-hydroxy 1,4-naphthoquinone 0.6 g 12-hydroxy 8-methoxy 1,4-naphtoguinone 0.25 g

Citric acid anhydrous 1 g

Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g i SINNOPAL NP 4 q.s.p. 100 g I 'This composition can be applied directly to wet hair; it can also be mixed when | of employment, with 1.5 times its weight of cold water. The gel | obtained is applied for 30 minutes to light brown S hair. After the hair is rinsed, it is dried. The hair then has an intense golden reflection.

In the liquid composition, the dyes keep r? i much better in storage than in the final gel applied on * head.

\ EXAMPLE 3 | · '- I 2,3-dihydroxy 1,4-naphthoquinone 0.5 g s 2,5-dihydroxy 1,4-naphthoquinone 0.3 g [| 8-methoxy 2-hydroxy 1,4-naphthoguinone 0.15 g / P /; /! F Lr r & i 9

Citric acid anhydrous 1 g

Cetyl alcohol 24 g MERGITAL CS 15 E 23 g EÜTANOL G q.s.p. 100g

This cream is mixed at the time of use with an equal weight of lukewarm water. The creamy mixture obtained is applied to light brown hair. After 30 minutes of application, rinse and dry. The hair then has a beige copper reflection.

The three dyes in the starting composition keep

Ivent better in it than in the composition applied to the head.

EXAMPLE 4 2-hydroxy 3-methoxy 1,4-naphthoquinone 0.7 g 2,5,8-trihydroxy 1,4-naphtoquinone 0f05 g N, N-dimethylaminoethanol 0.7 g

Anhydrous ethyl alcohol 21.5 g SINNOPAL NP 9 31 g SINNOPAL NP 4 q.s.p. 100 g; This liquid is diluted with 1.5 times its weight in cold water to give a gel which is applied for 10 minutes to a hair; dark blond lure. The hair is rinsed and dried. They *! then have an auburn reflection.

The dyes keep much better in the liquid composition than in the final gel.

! EXAMPLE 5 2,5-dihydroxy 3-methyl 6-methoxy 1,4-benzoquinone 0.7 g 2,7-dihydroxy 1,4-naphthoquinone 0.3 g

Citric acid anhydrous 1 g

Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g, SINNOPAL NP 4 q.s.p. 100 g! At the time of use, 1.5 times its weight of water is added to the above liquid. The gel obtained is applied for 30; minutes on light brown hair. The hair is then rinsed and dried. A purple coloration is obtained. ^ "/‘ L / • * Λ ίο t In the liquid composition, the dyes are preserved better than in the final gel applied to the head.

EXAMPLE 6 2,3-dihydroxy 1,4-naphthoquinone O, 8 g 2-N- / à-hydroxyethylamino 5-hydroxynitrobenzene 0.15 g Hematoxylin 0.15 g Ν, Ν-dimethylaminoethanol 1 gi Anhydrous ethyl alcohol 24 g SINNOPAL NP 9 28.5 g | SINNOPAL NP 4 q.s.p. 100 g '1 d · This liquid composition is mixed at the time of use; with 1.5 times its weight of water. The gel obtained is applied to i dark brown hair for 30 minutes, after which it is rinsed and dried. The hair then has a pearly ashy I reflection.

i The dyeing power is preserved much better during the storage of the liquid composition than if the gel is stored; final.

; EXAMPLE 7 ij 1 ..... ... '- 2,5-dihydroxy 3-methyl 6-methoxy 1,4-benzoquinone 1.1 gj 2-hydroxy 3-methoxy 1,4-naphthoquinone 0.35 g I 3-carboxy 1,2,4-trihydroxy 9,10-anthraquinone 0.1 g! Anhydrous citric acid 1 g Cetyl alcohol 24 g MERGITAL CS 15 E 23 g EÜTAN0L G q.s.p. 100 g j This composition which constitutes a cream is diluted with! when using with its own weight of lukewarm water. The cream obtained is applied 30 minutes to brown hair | dark. After rinsing and drying the hair has a purple reflection.

The initial anhydrous composition leads to a much better conservation of the dyes on storage than the final composition applied to the head. f / / ·

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'11 «EXAMPLE 8 2-hydroxy 1,4-naphthoquinone 0.20 g 2,5-dihydroxy 1,4-naphtoguinone 0.15 g 2-hydroxy 9,10-anthraquinone 3-sodium sulfonate, monohydrate 0.40 g

Citric acid anhydrous 1 g

Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100g

This composition is in the form of a liquid which IJ ’can be directly applied to damp hair or that! it is mixed at the time of use with 1.5 times its weight J of cold water. The gel obtained is applied to light brown hair. After 40 minutes of application, rinse and dry.

The hair is dyed with a coppery beige reflection.

The storage stability of the dyes is much better in the liquid composition than in the final gel.

EXAMPLE 9 2-hydroxy 3-methoxy 1,4-naphthoquinone 0.7 g 2-hydroxy 1,4-naphtoguinone 0.25 g

Citric acid anhydrous 1 g | Cetyl alcohol 24 g îj MERGITAL CS 15 E 23 g I EÜTANOL G q.S.p. 100 g || * At the time of use, this cream is diluted with an * equal weight of lukewarm water. The mixture obtained is a cream which 1 is applied for 30 minutes to brown hair. After rinsing and drying the hair is adorned with an intense red copper tint.

The dyes having much better stability in the starting composition than in the composition applied to the head.

ï EXAMPLE 10 2,3-dihydroxy 1,4-naphthoquinone 0.45 g 2,5-dihydroxy 1,4-naphtoquinone 0.35 g 2,7-dihydroxy 1,4-naphtoquinone 0.1 gj Ν, Ν-dimethylaminoethanol 1 g /; />; ί [ί! 12!

Anhydrous ethyl alcohol 24 g SINNOPAL NP 9 28.5 g SINNOPAL NP 4 q.s.p. 100g

This liquid is diluted at the time of use with 1.5 times its weight of water. The gel obtained is applied 30 minutes to brown hair. The hair is rinsed and then dried. The hair then has an ashy reflection.

The dyes are more stable when stored in the. anhydrous liquid support as they would be in the gel which is applied to the head.

EXAMPLE 11

COMPOSITION A

2-hydroxy 3-methoxy 1,4-naphthoquinone 0.25 g 2.5- dihydroxy 1,4-naphthoquinone 0.25 g j Anhydrous ethyl alcohol q.s.p. 100 g f | At the time of use, 25 g of this composition are diluted | A with 75-g of composition B.

| COMPOSITION B

p Tetradecyl trimethylammonium bromide 1.5 g UKANIL 25 3g j UKANIL 43 2g j Citric acid q.s.p. pH 3 | Distilled water q.s.p. 100g

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j The whole constitutes a foaming lotion which we learn | * pligue 15 minutes on dark blond hair. We get | after rinsing and drying the dyed hair with a red copper reflection.

If all A + B were kept in storage in the dj proportions indicated, much degradation would be observed

! more nuance than storing composition A

and diluting it at the time of use with composition B.

EXAMPLE 12

COMPOSITION A

2.5- dihydroxy 3-methyl 6-methoxy 1,4-benzoquinone 0.8 g

Monoethyl ether of ethylene glycol q.s.p. 100 g / /

At the time of use, 25 g of this composition A are diluted with 75 g of the composition B. / h ü I 13

COMPOSITION B

I Tetradecyltrimethylammonium bromide 1.5 g OKANIL 25 3g ÜKANIL 43 2g

Citric acid q.s.p. pH 3

Distilled water q.s.p. 100 g The set is applied for 30 minutes to dark blond hair. The hair is then rinsed and dried. They have | . then an ashy reflection. If the complete aqueous solution containing the benzoquinine dye were stored during storage, the latter would degrade very quickly and quickly if it did not degrade in composition A.

| EXAMPLE 13

! COMPOSITION A

2,5-dihydroxy 3-methyl benzoquinone 0.3 g i! 2,5-dihydroxy 1,4-naphtoguinone 0.2 g t j Anhydrous ethyl alcohol qs 100 g I At the time of use, dilute 25 g of this composition i A with 75 g of composition B.

COMPOSITION B

Tetradecyltrimethylammonium bromide 1.5 g ÜKANIL 25 3g i ÜKANIL 43 2g; '' Citric acid qs pH 3

Distilled water qs 100 g

The resulting foaming lotion is applied for 20 minutes to dark blond hair.

The hair is then rinsed and dried. They have a mahogany reflection.

; If the final foaming lotion were stored, the conservation of the two dyes would be much worse than in the / composition A. fj j \ '; 14 1 In the examples above, the trade names used correspond to the following products: I SINNOPAL NP 9 Nonylphenol oxyethylenated to 9 moles

of ethylene oxide sold by the company HENKEL

I SINNOPAL NP 4 4 mole oxyethylenated nonylphenol

of ethylene oxide sold by the company HENKEL

, MERGITAL CS 15 E 15 mole cetylstearyl alcohol

of ethylene oxide sold by the company HENKEL

EDTANOL G Octyldodecanol sold by the Company

HENKEL

UKANIL 25 Synthetic linear fatty alcohol in

C13C15 at 2.8 moles of ethylene oxide sold by the company PCÜK

UKANIL 43 Synthetic linear fatty alcohol in ·· Cg-C ^ to 6 moles of ethylene oxide sold by the company PCUK. / s

Claims (16)

115 1. H H H H - 1. Composition based on guinonic dye, stable in storage, characterized in that it contains in an anhydrous solvent or a mixture of solvent (s) / at least one guinonic dye of formula: R5 0 O R4 _ OH r3 - Ri r2 0 0 (I1) (II ') in laguelle R ^, R2 # R3, R4, Rg / Rg and Rj have the meanings indicated below: Compound R1 I R2 R3 R4 R ^ Rg R- ^ 2. Composition according to claim 1, characterized in that the dyes are present in the proportions of 0.001 to 5% by weight relative to the total weight of the composition. 2 OH H H H H - 3. Composition according to claim 1 or 2, character-; laughed at by the fact that the solvent (s) are chosen from 1 saturated alcohols, polyols, alkylene glycols, 'r' // '/ -v 16! glycol ethers, monoalkylethylene glycol esters, saturated fatty acid esters of saturated lower alcohols or a mixture thereof. 3. H H OH H - 4. Composition according to any one of claims 1 to 3, characterized in that it also contains at least one anhydrous surfactant. 4. H HH OCH3 5. Composition according to claim 4, characterized in that it contains at least 15% of solvent (s) and au. minus 20% surfactant (s). 5 OCH3 H H H H - 6. Composition according to claim 4 or 5, characterized in that the surfactants are chosen from anionic, cationic, nonionic, amphoteric anhydrous surfactants or their mixtures. 6. OH H H H - 7. Composition according to claim 6, characterized in that the surfactant is a nonionic surfactant. 7. H OCH3 HH - 8. Composition according to claim 6, characterized by i | the fact that the surfactants are chosen from alcohols! polyoxyethylenated fatty acids, -alkylphenols or polyoxy- [ethylene naphthols, alkylaminesulphates, halides of | monoalkyltrimethylammonium or dialkyldimethylammonium, the | soaps, polyglycerolated fatty alcohols. 8. OH H H OH - 9 - - - OH OCH3 10 - - - och3 och3 11 - - - OH H [_ ^^ _ 1 _ ^ __ 9. Composition according to any one of claims J 1 to 8, characterized in that it additionally contains I other anhydrous additives chosen from perfumes, sequestering agents, thickening agents, agents! treating the hair, antioxidants, oils: mineral or vegetable, preservatives and organic salts. 10. Composition according to any one of claims 1 to 9, characterized in that it contains an acidifying agent chosen such that the composition after dilution with water has an acidic pH and that the dyes are chosen from dyes corresponding to the formulas (! ') or (II') of claim 1 in which R ^, R2, R3, R ^ f / R5, Rg and R ^ have the following meanings:, / if i * 117 R1 R2 R3 R4 R5 R6 R7 HHHHH - OH HHHH - HHH OH H - HHHH OCH3 OCH3 HHHH - H OH HHH - * ----- OH OCH3 ----- och3 och3 OH H ' 11. Composition according to any one of claims 1 to 9 / characterized in that it contains an alkalizing agent chosen in such a way that the composition after dilution with water has an alkaline pH and that the dyes are chosen from dyes of formula (I ') in which Rir R2i R3 * and Rg denote R1 R2 R3 R4 R5 - | OH H H H H | H H H OH H H H H H OCH3 OCH3 H H H H H OH H HH ÎH H OCH3 H H H OH H H OH 12. Composition according to any one of claims! 1 to 11, characterized in that it also contains other direct dyes. 13. A method of preserving dyes as defined in claim lf, characterized in that the I introduced into a composition as defined in any one of the claims 1 to 12. / L 18 * · 14. A method of dyeing hair, characterized in that at least one composition as defined in any one of claims 1 to 12 is applied to hair wet with water. 15. Process for the preparation of a dye composition for hair intended to be immediately applied to them, characterized in that a composition as defined in any one of the claims is diluted in a cosmetically acceptable aqueous solution 1 to 12 or who! results from the process as defined in claim 13. * 16. Method according to claim 15, characterized by | fact that the weight ratio between the composition according to one j. any of claims 1 to 12 and the aqueous solution! is between 0.25 and 2. i! Drawings: plates | ..... pages of which ...... Λ ......... breed of guard; yfif ....... p «these description | ......... r-sr-.s of claims l ....... ^ c _; "descriptive ge! Luxembourg, îe 19 f.g -gg? I Charles München"! "r *;