DE2032340A1 - Process for coloring keratin fibers, in particular human hair, and coloring agents for carrying out this process - Google Patents

Description

Munich, the 3o. June 197o M / 11159

L ¹ ORBAL
14, rue Royale, Paris 8e (France)

Process for dyeing keratin fibers, especially human hair, and colorants for doing this Procedure

Tone the process that can last the longest to dye keratinous fibers, especially hair one of the most important to be mentioned is the one based on the use of so-called oxidizing dyes is based. This method is commonly used as "bases" designated compounds that are actually not dyes are, however, a coloration under certain conditions develop due to an oxidation process a. These bases are essentially aromatic o- or p-diamines, o- or p-aminophenols or their derivatives.

109808/2068

The oxidation of these compounds usually takes place in. The time of their application to all fibers to be dyed. Addition of an oxidizing agent, which is generally water " substance peroxide is.

On the other hand, in order to change the red tones obtained by this process, it has been proposed to add color modifiers or "couplers" to said bases. The couplers used are generally aromatiscne Metadiamine, W Metaaminophenole or Metadiphenole or derivatives thereof.

This process is carried out in such a way that one Gxyaationsmittei at the time of use (in practice hydrogen peroxide) the mixture of the base and of the selected coupler clogs. This implementation is very difficult and the preservation of reproducible color tones very proolematic.

The applicant has now found that it is possible in easy way to get easily reproducible color tones, if one does not use an Oxyj ^ in connection with a coupler dationsbase but uses its Cninon-Imine derivative.

The invention therefore relates to a new method for Dyeing of keratin fibers, especially human Hair, which consists in applying a solution to the hair to be dyed simultaneously or one after the other with at least one coupler and on the other hand a solution with at least one quinone imine which is derived from an oxidation base, the ratio between the molar amounts of the coupler used and of the quinone imine used, preferably greater than or equal to 1 is.

109803/2068

20323A0

The couplers used in the process of the present invention can be any known coupler. For example, aromatic metadiamines, ketaaminophenols, metaiphenols or their derivatives, arylpyrazolones or pyridine derivatives can be used. In particular, the following are mentioned: lüeta toluenediamine, resorcinol, 2,6-dianiinopyridine, 6-I>'. Ethyl-3 (N-earoaiuylinetnylamino) -piienol, S-garbamyliiiethylamtno ^ - hydroxy-toluene, 1-phenyl-3-methyl-5 -pyrazolone, 2,5-dimethylphenol, 2-methyl-5-acetaminophenol.

The quinone imines used in the method according to the invention are the quinone mono- or quinonediimines, those of conventional Oxidation bases are derived, which means compounds whose molecule is aromatic or heterosyclic Has core, which is formed by two amino groups or an airdno group and a kyaroxyl group, which are in the position or p-position to one another, is substituted. These bases can also be aromatic o- or p-diandes or o- or p-aminoptienols or their derivatives as well functional than also by substitution, as described, for example, in French patent 1 403 633.

The quinone imines used in the process according to the invention can, if they are sufficiently stable, from the appropriate bases by oxidation in an anhydrous Solvent with the help of a mild oxidizing agent such as silver oxide or lead oxide, according to the applicant in two earlier patent applications can be prepared.

In a first embodiment of the method according to the invention, which is applicable when the quinone imines used

109808/2068

are sufficiently stable, these quinone imines are separated into Shape used. They are then available as a powder, which is brought into solution at the time of use and the application to the lasers to be colored takes place at one neutral pH without the need to use an oxidizing agent.

In a first variation of this Durchführungsfprm of the process of the invention carrying in a first stage ψ to be dyed parsers are the solution of the or couplers, these are allowed for a period of 5 to act to 20 minutes, and then transmits in a second stage, preferably after Rinse the fibers on the solution of the quinone imine (s), which is allowed to act on the fibers for a period of 5 to 30 minutes.

According to a second modification of the same implementation of the process according to the invention, the solution of the coupler (s) is / are mixed with it at the time of application the solution of the ghinon imine or imines and impregnated the pastes to be dyed with this mixture, which one during a ^ Let it act for 5 to 30 minutes.

The advantage of this first embodiment of the invention The process consists in that the dyeings are carried out at neutral pH and in the absence of hydrogen peroxide can lead to particularly advantageous conditions are, if the hair is loose, an alkaline treatment and the action of hydrogen peroxide poorly tolerated or if you want to avoid a possible allergic effect to hydrogen peroxide.

1 night 3 8 0 S / "2 0 6 8

If you want to decolorize the fibers underneath at the same time as the dyeing, e3 is possible, however, before using the hydrogen peroxide solution Couplers or the quinone imines or the mixture of these Add solutions. Bs is also possible, an alkaline agent such as ammonia, the solution of or the To add couplers when the presence of such an agent is desirable, for example to improve solubility of the coupler or couplers used.

In a second embodiment of the invention Procedure that is particularly applicable if the used Quinone imines are not sufficiently stable to be isolated, these quinone imines are im Time of their application by oxidizing a solution of the corresponding base (s) with the help of an oxidizing agent that can convert these bases very quickly, produced, this oxidizing agent in excess is used in relation to the base. The oxidizing agents suitable for rapid oxidation of the bases are for Example potassium persulfate and ferricyanide and the oxidation takes place in a conventional manner in an alkaline medium, this alkaline medium is preferably obtained by adding ammonia to the solution of the base (s).

In this second embodiment of the process according to the invention, one contributes to the in a first stage coloring fibers the solution of the coupler or couplers on and lets it take effect for a period of 5 to 20 minutes. Then you rinse the fibers and wear in in a second stage the solution of the quinone imines was made immediately prior to its application.

109808/2068

The invention also relates to a coloring agent with which the method described above can be carried out. This colorant contains at the time of use a solution with at least one coupler and a solution with at least one GhInOn = ImIn ₉ which is derived from an oxidation base, the latter solution at the time of use either by dissolving the ghinon imine or by rapid oxidation of a solution of the corresponding base (s) with the aid of an oxidizing agent such as potassium ferricyanide or potassium persulfate.

In the agents according to the invention, the ratio between the molar consentration of the Ghinon-Xmine and that of the couplers vary within very wide limits; however, it is preferred to work in the presence of an over-3cnut the coupler »

The pH of the two compositions forming the agent according to the invention Solutions can be neutral or alkaline. It is preferably 7 to 10.

The agents according to the invention can Nets, dispersion, Swelling agents, penetrants or other components commonly used for coloring hair, as well as direct dyes j, used for dyeing keratin fibers are ^ sum example azo or anthraquinone dyes, contain » They can still be available as aqueous solutions or as a cream or jelly »

The following examples explain the invention without restricting it.

1038ÖS / 2QSI

20323A0

_ 7 -

Jeispi el / 1

Kan s-produces the following solution:

7-hydroxy-phenomorpholine 0.18 g

Anx.ur.iak to 22 B 8 crn ^

filled up with water to 100 cm

90> —l, r gray hair is impregnated with this solution, After an effective time of 20 minutes, the hair becomes rinsed and with the following solution that is in: Seitpunkt the Application Manufactured wirci, impregnated:

2-l. ". EtiiOxy-5-methylbenzenin-ondiimine 0.18 g

r.filled with water to 100 cm

Hacu one. SinwiTkunrszeit of 20 minutes you rinse the ilaart:, wash it with an oaiupco and dry it. Kan 'takes on a dark green color.

Example 2

Kan manufactures the following solution :

2,4-siamino-anisole 0.34 g

Ammonia at 22 ° B 8 em

filled up with water to 100 cm

100 7a-ig white hairs are impregnated with this solution. Subject an exposure time of 10 minutes, the hair is rinsed and with the following solution, which is at the time of Application is made, impregnated ':

2-methoxy-5-methyl-i »4-benzoquinonediimine 0.36 g filled up with water to 100 cm ^

After an exposure time of 10 minutes, the

10 9808/206

Hair, washes them with a shampoo and dries them. A dark blue color is obtained.

Example 3

Prepare the following solution A 5

2-methyl ~ 5-carbamylmethylaminophenol 0.54 g Sodium lauryl ether sulfate with 20 # oxyethylene alcohol 20 g

Ammonia at 22 ° B 10 cm ⁵

filled up with water to 100 cnr

On the other hand, at the time of application, the following is provided Solution B:

2-methoxy-5-methyl-benzoquinonediimine 0.45 g

ITodium lauryl ether sulfate at $ 20> 20 g

oxyethylene alcohol

filled up with waeeer to 100 cm ⁵

The two solutions A and B are mixed, 20 cm of 6 # items are used Hydrogen peroxide and then impregnated 100 # - gray hair with this mixture. After an exposure time of 30 minutes, the hair is rinsed with a shampoo washed and dried. A strong purple color is obtained.

Example 4 Make the following solution:

2,6-diethyl-3-aminophenol 0.30 g

Ammonia at 22 ° B 8 cdt

filled up with water to 100 cm '

100% white hair is impregnated with this solution. After an application time of 15 minutes, the hair will become

109808/2068

rinsed and with the following solution, which at the time of Application is made, impregnated:.

0.32 g made up to 100 g with water

After an exposure time of 15 minutes, the hair will be rinsed, washed with a shampoo and dried. Man takes on a strong purple color.

At game 5

Make the following solution:

2,4-Diamiηo-anisole 0.20g

Ammonia at 22 ° B 8 cm

made up to 100 cm ^{3 with water}

Gray hair is impregnated with this solution, left to act for 10 minutes, the hair is rinsed and then the following solution, which is prepared at the time of use, is applied :

2,6-Limethyl-5-methoxy-benzoquinonediimine 0.20 g filled up with water to 100 cm ^

After an exposure time of 20 minutes, the hair will be rinsed, washed with a shampoo and dried. A night blue color is obtained.

Example 6

The following solution is prepared

7-hydroxy-phenomorpholine 0.15 g

Ammonia at 22 ° B 5 cm

made up to 100 cm ^{5 with water}

1098087208g

ORIGINAL INSPECTED

7032340

- ίο -

White hair is impregnated with this solution. After 20 minutes the hair is rinsed and then treated with the following solution, which is prepared at the time of application :

2,6-dimethyl-5-methoxy-benzoquinone diifflin 0.10 g

filled up with water to 100 cnr

After an exposure time of 20 minutes, the hair is rinsed, washed with a shampoo and dried. Man

takes on a blue-green color.

Example 7

Make the following solution:

2,4-diamino-anisole 0.13 g

Ammonia at 22 ° B 5 ciir

made up to 100 cm ^{5 with water}

White hair is impregnated with this solution. After a Exposure time of 15 minutes, the hair is rinsed p and then the following solution, which is at the time of

Application is made, applied:

Durοchiηondiimiη "0.16 g

■ χ made up to 100 cnr with water

After a contact time of 25 minutes, the hair is rinsed, washed with a shampoo and dried. Man acquires an ash-gray color. . ·

Example 8

Make the following solution ί

2,6-dimethyl-3-aminophenol 0.13 g

ORIGINAL INSPECTED

Ammonia at 22 ° B 8 cm ⁵

made up to 100 cm ^{5 with water}

White hair is impregnated with this solution. Hach one Exposure time of 15 minutes, the hair is rinsed and then with the following solution, which was available at the time of Application is established, see p

Duroquinone diimine 0.16 g

filled up with water to 100 cnr

After a touch of 25 minutes, the hair will be rinsed, washed with a shampoo and dried. A pink-beige color is obtained.

Example 9

Make the following solution:

Resorcinol. 0.22 g

Ammonia at 22 ° B 8 cm

made up to 100 cm ^{5 with water}

White hair is impregnated with this solution. After a contact time of 15 minutes, the hair is rinsed and then treated with the following solution prepared at the time of application:

2,6-Dimethyl-5-methQxy-benzoquinonediimine 0.32 g made up to 100 cm ^{5 with water}

After a contact time of 25 minutes, the hair is rinsed, washed with a * shampoo and dried. Man acquires an ash-brown color.

109808/206 «ORIGINAL INSPECTBB

Example 10

A solution A is prepared with the following composition:

Metatoluylenediamine ammonia solution made up to 22 ° B with water

1 , 22 G (0 , 01 Mole). 10 cm 100 cm

This solution is applied to white hair for 15 minutes Apply room temperature and the hair is then rinsed with warm water.

Then solution B _1, which consists of the mixture of the following solutions C and D prepared at the time of application, is applied to the hair:

Solution C

Potassium persulfate 5.4 g (0.02 mol)

Ammonia solution at 22 ° B 10 cm '

made up to 100 cm of solution D with water

Chloroparaphenylenediamine sulfate 2.4 g (0.01 mol) Sodium alkyl ether sulfate condensed with 2 moles of ethylene oxide 20 g filled up with water to 100 cnr

After an exposure time of 15 minutes, the hair will become rinsed, washed with a shampoo and dried. Man acquires a strong midnight blue color.

109808/2068

Example 11

Make the following solution:

Resorcinol 0.24 g

Ammonia at 22 ° B 8 cnr

made up to 100 cm ^{5 with water}

White hair is impregnated with this solution. After a Contact time of 15 minutes, the hair is rinsed and treated with the following solution prepared at the time of use:

2,6-dimethyl-5-methoxy-benzoquinonediimine 0.32 g

made up to 100 cm ^{5 with water}

Subject to a contact time of 25 minutes, the hair is rinsed, washed with a shampoo and dried. Man acquires a purple-brown color.

Example 12

Prepare solution E with the following composition:

Resorcinol 1.10 g (0.01 mol)

Fa ₂ HPO ₄ 10 g

made up to 100 cm ^{5 with water}

This solution is applied to gray hair for 15 minutes at room temperature and the hair is then rinsed with warm water. Then the solution F, which consists of the mixture of the following solutions C and Q prepared at the time of use, is applied:

10 9808/2068

-H-

Solution C

Potassium Persulfate 5.4 g (0.02 KoI)

Ammonia solution at 22 ° B. 10 cnr

made up to 100 cm ^{5 with water}

Solution G

Paratoluylenediamine 1.22 g (0.01 mol)

condensed with 2 moles of ethylene oxide

Sodium alkyl ether sulfate 20 g

made up to 100 cm ^{5 with water}

After an exposure time of 15 minutes, the hair will become rinsed, washed with a shampoo and dried. Man

acquires a brown color with dale reflections.

Example 13

The solution H is prepared with the following composition:

Metatolylenediamine 0.122 g (0.001 mol)

Resorcinol 0.99 g (0.009 KoI)

Ammonia solution at 22 ° B 10 cm

made up to 100 cm ^{5 with water}

This solution is applied to discolored hair during a period of time Applied for 15 minutes at room temperature. The hair is then rinsed with warm water. ,

Solution B from Example 10 is then applied. After an exposure time of 15 minutes, the hair is rinsed, washed with a shampoo and dried. An ash-brown color is obtained.

1 o 9 8 o a / 2 o s a

ⁱ hi j

7032340

Example 14

Kan represents the solution H of the composition given above and applies it to white hair for 10 to 15 minutes at room temperature, after which the hair is removed with rinses with warm water. <

Then a solution Q is applied which consists of the mixture produced at the time of use of the aforementioned solution G and the solution K, each of which has the following composition t

Solution G

Paratoluylenediamine. 1.22 g (0.01 idol)

with 2 Kci ethylene oxide condensed
Tratrium Alkjlitaersulfat 20 g

filled up with water to 100 cm ^,

Solution K

Potassium ferricyanide 13.2 g (0.04 KoI)

Ammonia solution at 22 ° ή - 10 cm

filled with water to 100 cm ''

After an exposure time of 15 minutes, the hair will be rinsed, washed with a shampoo and dried. A green-blonde coloration is obtained.

Example 15

Prepare solution R with the following composition:

o-Hethyl-S-N-earbamylmethylamino-

phenol 1.78 g (0.01 mol)

Ammonia solution at 22 ° B 10 em

filled with water to 100 cm ⁵

109808/2068

BATH ORIGINAL.

This solution is applied to bleached hair for 10 minutes at room temperature and the hair is then rinsed with it warm water.

then a solution T is made from the at the time of use prepared mixture of the following solutions C and TJ is applied:

Solution C

Potassium persulfate 5.5 g (0.02 mol)

Ammonia solution at 22 ° B 10 cm

made up to 100 cm ^{5 with water}

Solution U

Chloroparaphenylenediamine sulfate 1.2 g (0.005 mol) paratoluenediamine 0.61 g (0.005 mol)

condensed with 2 moles of ethylene oxide
Sodium alkyl ether sulfate 20 g

made up to 100 cm ^{5 with water}

After an exposure time of 20 minutes, the hair becomes rinsed, washed with a shampoo and dried. A green-blonde coloration is obtained.

Example 16

Make the following solution:

2,4-diamino-anieol 0.22 g

Ammonia at 22 ° B 8 cur

filled up with water to 100 cm ^

White hair is impregnated with this solution, left to act for 10 minutes, then the hair is rinsed and worn

109808/2068

following solution made at the time of use will be on :

2,6-I) imethyl benzoquinone imine 0.17 g

topped up with water to 100 gh?

After a contact time of 20 minutes, the hair will rinsed, washed with a shampoo and dried. Man acquires an intense purple color.

Example 17

Make the following solution

2,4-Diamino-anise oil 1.38 g

Ammonia at 22 B 10 cnr

filled up with water to 100 cnr

This solution is applied to white hair for 10 minutes at room temperature and then rinse the hair.

The hair is then treated with a solution M, consisting of the example 10 and the following solution U from the produced at the time of using the mixture solution C 1A, im- pregnated * ί

2,6-dimethyl-4-aminophenol hydrobromide 2.18 g

Sodium Lauryl Ether Sulphate at $ 20 oxyethylene alcohol - 20 g

filled up with water 100 cm ^y

After an exposure time of 20 minutes, the hair will be rinsed, washed with a shampoo and dried. Man takes on a very dark brown-purple color "

109808/2068

70.3 2 34 G.

Example 18

Prepare the following solution;

2,4-diamino-anisole O ₉ 23 g

made up to 100 cm ^{5 with water}

Gray hair is impregnated with this solution, left to act for 15 minutes, then the hair is rinsed and worn following solution made at the time of use will be on ·.

2,6-dimethyl-benzoquinone imine 0.17 g

filled up with water to 100 cnr

After 20 minutes, the hair is rinsed, washed with a shampoo and dried "One ernält a violet-light-brown färb ton.

Example 19

One creates the following solution:

2-methyl-5-earbamylmetn.ylamino-ph.enol 1 _s 80 g ammonia at 22 ° B 10 em ⁵

topped up with water. 100 cm ⁵

This solution is applied to white hair for 15 minutes, then the hair is rinsed and impregnated with it a solution P obtained from the mixture of solution G of Example 10 and the mixture prepared at the time of use the following solution S exists:

2-methoxy-4- aminophenol 1j> 39 g

1 09000/20

7032340

Sodium lauryl ether sulfate with 20 io
uxyated alcohol 20 g

filled up with water to 100 cm

The hair will become in contact with the skin for 20 minutes Washed, washed with a shampoo and dried. Man em old a niaJiagonif aroen tone.

Example 20

Make the following solution:

2, 4-Id ami π o- anisole 1.40 g

Ammonia at 22 ° fl 10 cm ⁵

filled up with water to 100 cm ^>

Ideal solution is applied to white hair for 10 minutes and the hair was then rinsed. They are then impregnated with the solution P of example iy. After an application time of 20 minutes, the hair will be rinsed, washed with a snampoo and dried. Man acquires a dark brown color with light purple reflections.

Example 21-

Make the following solution:

2,4-i) iamino-anisole. 0.30 g

filled up with water to 100 cm ^

This solution is applied to white hair for 15 minutes and then the hair is rinsed. Then they will be provided with the following solution which was made at the time of the Use is made, impregnated:

_ _IMil 109808/2068 BAD ORIGINAL

203234Q

2,6-dimethyl-5-ynethoxy-benzoquinonediimine 0.14 g

2,6-dimethyl-benzoquinone imine 0.17 g

made up with water to 100 cur

After an application time of 20 minutes, turn the hair rinsed, washed with a shampoo and dried. A dark, slightly violet navy blue is obtained.

109808/2068

Claims (15)

Claims 1. Dyes for dyeing keratin fibers, in particular of hair ι characterized in that it is at the time the application of aaeita a solution at least one ohinone imines derived from an oxidation base and on the other hand contains a solution of at least one coupler. 2. Means according to claim 1, characterized in that the Coupler is selected from compounds whose molecule is at least one aromatic or heterocyclic Has nucleus that has two amino groups, two hydroxyl groups or one amino group and one hydroxyl group in Contains meta-position to one another. 3. Means according to claim 1, characterized in that the Quinone imines are quinone mono- or quinonediimines which have been obtained by oxidation of compounds, whose molecule has at least one aromatic or heterocyclic nucleus with two amino groups or one amino group and has a hydroxyl group in o- or p-position to one another. 4 · Agent according to claim 1, characterized in that the ratio between the molar concentration of the bases and the molar concentration of the couplers is less than or equal to 1. - 5. Means according to claim 1, characterized in that the Quinone imine solution contains an oxidizing agent. 6. Means according to claim 5, characterized in that the Oxidizing agents hydrogen peroxide, potassium persulfate or potassium ferricyanide. 10 980872068 20323A0 7. Means according to claim 1, characterized in that the pH of the two solutions is neutral. 8. Means according to claim 1, characterized in that the pH of the two solutions is alkaline and preferably 8 to 11 is. 9. Means according to claim 1, characterized in that the Quinone imines exist as a powder that is in time the application is brought into solution on the fibers to be dyed. 10. Composition according to claim 1 and 9 *, characterized in that the pH of the quinone-imine solution is neutral. 11. Means according to claim 1, characterized in that the Solution of the quinone imine (s) at the time of application on the fibers to be dyed by adding an oxidizing agent such as potassium persulphate or potassium ferricyanide, to an alkaline solution of the corresponding Baee (s) is prepared, wherein the oxidizing agent is used in excess with respect to the base. 12. Composition according to claim 11, characterized in that the pH of the quinone-imine solution is 8 to 11. 13. A process for dyeing keratin fibers, in particular hair, characterized in that a dye as defined in claims 1 to 12 is applied to the fibers to be dyed in one stage or in two stages, the application being neutral or alkaline pH, optionally in the presence of an oxidizing agent. : ^v 109808/2068 7032340 14. The method according to claim 13 »characterized in that first of all, on the fibers to be dyed - the solution of the or the coupler applies this solution in contact with the fibers for a time of 5 to 20 minutes left, then impregnated the fibers with the quinone-imine solution, if necessary after rinsing, this solution in contact with the fibers during a Leave tent for 5 to 30 minutes; then the Rinses fibers and, if necessary, washes and dries them with a shampoo. 15. The method according to claim 13, characterized in that the solution ctes or the at the time of application Coupler mixed with the solution of the quinone imine (s), the harvested drawer on the ones to be colored Fibers are applied to them for a period of time 5. Leaves in contact for up to 30 minutes, then the Rinses fibers and, if necessary, washes and dries with a shampoo. th, - ■ ORIGINAL INSPECTED 109808/2068