US3730677A - Dyeing keratinous fibers with a quinoneimine and a coupler - Google Patents

Abstract

A COMPOSITION FOR DYEING DERATINOUS FIBERS COMPRISED AN AQUEOUS SOLUTION OF AT LEAST ONE QUINONEIMINE AND AN AQUEOUS SOLUTION OF AT LEAST ONE COUPLER.

Description

United States Patent Int. Cl. A61k 9/12 US. Cl. 8-10.2 8 Claims ABSTRACT OF THE DISCLOSURE A composition for dyeing keratinous fibers comprises an aqueous solution of at least one quinoneimine and an aqueous solution of at least one coupler.

This invention relates to a process and composition for dyeing keratinous fibers, particularly human hair. More specifically, this invention relates to dyeing human hair with a dyeing composition containing a quinone imine and a coupler.

Heretofore, keratinous fibers and, in particular, human hair, have been dyed by employing oxidation dyes. In such a process, compounds commonly referred to as bases have been employed. These bases are, properly speaking, not dyes, but under certain conditions they are capable of dyeing the hair as the result of an oxidation process. These bases are essentially aromatic orthoor paradiamines, orthoor paraaminophenols, or their derivatives.

The oxidation of these compounds usually takes place at the moment of their application to the fibers to be dyed by the addition thereto of an oxidizing agent such as hydrogen peroxide.

It has also been proposed, in order to vary the shade of dyeing obtained by this process, to add to these bases, dye modifiers or couplers. The couplers generally used are aromatic metadiamines, metaaminophenols, or metadiphenols, or their derivatives.

Such a process consists in adding at the moment of use an oxidizing agent such as hydrogen peroxide to a mixture of the base and the coupler. This process, however, is rather delicate and the attainment of reproducible shades is often very speculative.

The applicants have now found that it is possible to obtain in a simple way easily reproducible shades, if, in combination with a conventional coupler, a quinoneimine is employed, rather than the conventionally employed base material.

It is therefore a principal object of the present invention to provide a novel composition and process for dyeing keratinous fibers, in particular human hair, which comprises applying to the hair, simultaneously or successively, a solution of at least one coupler and, a solution of at least one quinoneimine derived from a conventional oxidation base. The molar ratio of couplerto quinoneimine employed is generally greater than or equal to 1.

Couplers used in the process according to this invention can be any of those couplers known in the prior art. Thus, it is possible to use an aromatic metadiamine, a metaaminophenol, a metadiphenol, or their derivatives, as well as an arylpyrazolone or a pyridine derivative. Representative couplers useful in the practice of the present invention include resorcinol,

2,6-diarninop-yridine,

6-methyl-3- (N-carbamylmethyl amino phenol, 2-carbamylmethylamino-4-hydroxy-toluene, 1-phenyl-3-methyl-5-pyrazolone,

3,730,677 Patented May 1, 1973 ICC 2,5-dimethylphenol,

! Z-methyI-S-acetamino phenol,

7-hydroxy-phenomorpholine, 2,4-diaminoanisole and 2,6-dimethyl-3-amino phenol.

The quinoneimines used in the process according to this invention are quinone monoor diimines derived from conventional oxidation bases, i.e., compounds whose molecule comprises an aromatic or heterocyclic nucleus alternatively substituted by (1) two amino groups or (2) an amino group and a hydroxyl group which are.

located in ortho or para position relative to one another. These oxidation bases can be aromatic orthoor paradiamlnes or orthoor paraaminophenols or their derivatives, both functional and with substitution, such as those described, for example, in US. Pat. 3,506,389 and incorporated herein by reference.

As disclosed in US. Pat. No. 3,506,389, the oxidation base can have the formula NHz wherein R is selected from the group consisting of hydrogen and lower alkyl having 1-3 carbon, atoms and X is selected from the group consisting of (1) wherein R is lower alkyl having 1-3 carbon atoms and R is selected from the group consisting of -CH CONH CH COOH, --CH CH NHSO CH and and the other entitled, Process for Preparing Indophenols and Their Use in Dyes for Coloring Keratin Fibers, S.N. 49,905, filed June 25, 1970, now abandoned, both being incorporated herein by reference.

A typical example of the procedure involved in oxidizing the base to a quinoneimine comprises heating the base at a temperature ranging between 30 and C. in an anhydrous solvent such as ethyl ether or isopropyl ether and in the presence of an oxidizing agent such as those listed above. Generally, the oxidizing agent is present in amounts ranging between 1 to 2 times the stoichiometric quantity for oxidizing the base, and preferably. 1.5 times this stoichiometric quantity.

The resulting quinoneimine obtained in said reaction can be isolated from the reaction mass by any convenient separation technique, such as by filtration. Thereafter,

the filtrate containing the quinoneimine can be evaporated ciently stable are used in isolated form. Conveniently, these quinoneimines are in the'form of a powder which is put into an aqueous solution at the time of use. These quinoneimines are applied to the fibers to be dyed in the said solution which has generally a neutral pH. With such a solution no extraneous oxidizing agent is required.

As a first variant of this embodiment of the present invention, an aqueous solution of at least one coupler is applied in a first stage operation to the fibers to be dyed. This coupler-containing solution is left in contact with the hair for to 20 minutes. Thereafter, there is applied, in a second stage operation, preferably after rinsing the fibers, an aqueous solution of at least one quinoneimine, which is left in contact with the fibers for about 5 to 30 minutes.

As a second variant of this first embodiment of the present invention, a solution of at least one coupler is mixed with a solution of at least one quinoneimine just before application to the hair, and the fibers to be dyed are impregnated with this mixture which is left in contact with the hair for 5 to 30 minutes.

A principal advantage of this first embodiment of the process of this invention resides in the fact that it is possible to perform the dyeing operation at a neutral pH and in the absence of an extraneous oxidizing agent such as hydrogen peroxide. Such a process is highly desirable, especially in the case of porous hairs which poorly support an alkaline treatment and the action of hydrogen peroxide, or in the situation when it is desirable to avoid a possible allergy reaction to hydrogen peroxide on the part of the person whose hair is being dyed.

It is obvious, however, thatin a case where it is desired to perform, at the same time as the dyeing, an underlying bleaching operation of the fibers, an oxidizing agent such as hydrogen peroxide can be incorporated into the aqueous solution of the coupler or quinoneimine or their mixtures. An alkaline agent such as ammonia can also be added, if desired, to the solution containing the coupler to improve, for instance, the solubility of the coupler in said solution.

In a second embodiment of the process of this invention, especially in those instances where the quinoneimine employed is not sufficiently stable to permit its isolation, the quinoneimine can be formed at the time of its application to the hair, by oxidizing an aqueous solution of a corresponding oxidation base with an oxidizing agent which effects the oxidation rapidly. Generally, the oxidizing agent, which is employed in a molar excess relative to the base, can be, for example, potassium persulfate or ferricyanide. The oxidation is performed in accordance with conventional techniques such as in an alkaline medium having a pH ranging generally from about to '12, at ambient temperature and pressure. The aqueous solution can be made alkaline preferably by adding thereto suflicient amounts of ammonia to achieve the desired pH.

In this second embodiment of the process of the present invention, the coupler containing aqueous solution is applied, in a first stage, to the fibers to be dyed and left in contact therewith for about 5 to 20 minutes. The fibers are then rinsed and, thereafter, in a second stage, the quinoneimine containing aqueous solution, which is prepared just immediately before its application to the hair, is applied to the hair. The quinoneimine containing solution is permitted to remain in contact with the hair for a period of about 5-30 minutes, after which the hair is rinsed and, if desired, shampooed. In this fashion, the desired color is imparted to the hair.

In the dyeing composition of the present invention, the ratio between the molar concentration of quinoneimine and that of the coupler can vary within rather Wide limits, although preferably a molar excess of coupler is employed.

The pH of the two solutions forming the composition of this invention can be neutral or alkaline and is, prefstably, tween. ab ut 7-10.

The composition according to this invention can obviously contain such conventional additives as wetting agents, dispersing agents, swelling agents, penetrating agents or other ingredients usually employed in hair dyeing compositions. Additionally, dyes conventionally employed to color keratinous fibers, for example, azo or anthraquinone dyes, can also be used.

The dye composition of this invention can be in the form of aqueous solutions or in the form of a cream or gel.

For a better understanding of the present invention, the following examples are provided.

EXAMPLE 1 The following solution is prepared:

7-hydroxy-phenomorpholine g 0.18 Ammonia at 22 B cm. 8 Water, q.s.p. d cm. 100

gray hair is impregnated with this solution in a first stage operation. After a wait of about 20 minutes, the hair is rinsed and impregnated with the following solution, prepared just before its application to the hair:

2-methoxy-S-methyl-benzoquinonediimine g 0.18 Water, q.s.p. crn.

This quinoneimine containing solution is allowed to contact for 20 minutes. Thereafter the hair is rinsed, shampooed and dried. A dark green dyeing is obtained.

EXAMPLE 2 The following solution is prepared:

2,4-diamino-anisole g 0.34 Ammonia at 22 B cm. 8 Water, q.s.p. cm. 100

100% white hair is impregnated with this solution. After a 10-minute wait, the hair is rinsed and impregnated with the following solution, prepared just before use:

2-methoxy-5-methyl-1,4-benzoquinonediimine g 0.36 Water, q.s.p. cm. 100

This quinoneimine solution is left in contact with the hair for 10 minutes after which the hair is rinsed, shampooed and dried. A deep blue dyeing is obtained.

EXAMPLE 3 The following solution, designated as A, is prepared:

Z-methyl 5-carbamylmethylamino-phenol g 0.54 Sodium lauryl ether sulfate with 20% oxyethylened alcohol g 20 Ammonia at 22 B. cm. 10 Water, q.s.p cm. 100

A second solution, designated as B, is prepared just before use:

2-methoxy 5-methyl-1,4-benzoquinonediimine g 0.45 Sodium lauryl ether sulfate at 20% oxyethylened alcohol g Water, q.s.p cm.

EXAMPLE 4 The following solution is prepared:

2,4-diamino-anisole g 0.20 Ammonia at 22 B. cm. 8 Water, q.s.p. =u=.-"cm. lQQ

Gray hair is impregnated with this solution which is left in contact therewith for 10 minutes. The hair is then rinsed and the following solution, prepared at the moment of use, is applied:

2,6-dimethyl-S-methoxy-benzoquinonediimine g 0.20 Water, q.s.p cm. 100

The above solution is allowed to act for 20 minutes. The hair is then rinsed, shampooed and dried. A night blue dyeing is obtained.

EXAMPLE 6 The following solution is prepared:

7-hydroxy-phenomorpholine g 0.15 Ammonia at 22 B. cm. Water, q.s.p cm. 100

White hair is impregnated with this solution and after a 20-minute contact therewith the hair is rinsed and treated with the following solution which is prepared just before use:

2,6-dimethyl-5-methoxy-benzoquinonediimine g 0.10 Water, q.s.p. cm. 100

The above solution is permitted to remain in contact with the hair for about 20 minutes. Thereafter the hair is rinsed, shampooed and dried. A blue green dyeing is obtained.

EXAMPLE 7 The following solution is prepared:

' 2,4-diamino-anisole g 0.13 Ammonia at 22 B cm. 5 Water, q.s.p cm. 100

White hair is impregnated with this solution and, after 15 minutes, the hair is rinsed. The following solution, prepared at the moment of use, is then applied to the hair:

Duroquinonediimine g- 0.16 Water, q.s.p cm. 100

After 25 minutes of contact, the hair is rinsed, shampooed and dried. An ash gray is obtained.

EXAMPLE 8 The following solution is prepared:

2,6-dimethyl-3-amino-phenol g 0.13 Ammonia at 22 B cm. 8 Water, q.s.p cm. 100

White hair is impregnated with this solution and after 15 minutes of contact, the hair is rinsed. Thereafter the hair is treated with the following solution, prepared just before use:

Duroquinonediimine g 0.16 Water, q.s.p. cm. 100

After 25 minutes of contact,the hair is rinsed, shampooed and dried. A pink beige dyeing is obtained.

EXAMPLE 9 The following solution is prepared:

Resorcinol g 0.22 Ammonia at 22 B. cm. 8 Water, q.s.p cm. 100

White hair is impregnated with this solution and after a 15-minute contact period, the hair is rinsed and then treated with the following solution which is prepared just before use:

2,6-dimethyl-S-methoxy-benzoquinonediimine g 0.32 Water, q.s.p cm. 100

After a 25-minute contact period the hair is rinsed, shampooed and dried. An ash brown is obtained.

6 EXAMPLE 10 A solution, designated as C, having the following composition is prepared:

Meta'toluylene diamine g. (0.01 m.) 1.22 Ammonia solution at 22 B. cm. 10 Water, q.s.p cm.

This solution is applied to White hair for 15 minutes at ambient temperature. The hair is then rinsed in lukewarm water.

Thereafter a solution designated as D is prepared by admixing, just before use, the following solutions, designated as E and F:

Solution E Potassium persulfate g. (0.02 m.) 5.4 Ammonia solution at 22 B. cm. 10 Water, q.s.p crn. 100

Solution F Chloroparaphenylene diamine sulfate g. (0.01 m.) 2.4 Sodium lauryl ether sulfate condensed with 2 moles of ethylene oxide g 20 Water, q.s.p cm. 100

Solution D is permitted to remain in contact with the hair for about 15 minutes after which the hair is rinsed, shampooed and dried. A strong night blue is obtained.

EXAMPLE 11 The following solution is prepared:

Resorcinol -1 g 0.24 Ammonia at 22 B. cm. 8 Water, q.s.p. cm. 100

White hair is impregnated with this solution and after a 15-minute contact period, the hair is rinsed and then treated with the following solution, prepared just before application to the hair:

2,6-dimethyl-S-methoxy-benzoquinonediimine g 0.32 Water, q.s.p cm. 100

After a 25-minute contact period the hair is rinsed, shampooed and dried and a violet brown color is imparted thereto.

EXAMPLE 12 A solution designated as G and havin the following composition is prepared:

Resorcinol g. (0.01 m.) 1.10 Na2HPO4 g Water, q.s.p cm. 100

This solution is applied to gray hair for 15 minutes at ambient temperature. Thereafter the hair is rinsed in lukewarm water.

Then solution, designated as H, is prepared by admixing, just before use, the following solutions, designated as E (see Example 10) and J:

Solution H is allowed to remain on the hair for 15 minutes after which the hair is rinsed, shampooed and dried. A brown coloration with blue glints is imparted to the hair.

'Chloroparaphenylene diamine sulfate 7 EXAMPLE 13 A solution, designated as K, having the following composition, is prepared:

Metatoluylene diamine g. (0.001 m.) 0.122 Resorcinol -g. (0.009 m.) 0.99 Ammonia solution at 22 B. cm. Water, q.s.p cm. 100

This solution is applied to bleached hair for minutes at ambient temperature. The hair is rinsed in lukewarm water.

Then solution D prepared as set forth in Example 10 is applied to the hair and after it has been allowed to remain in contact with the hair for 15 minutes, the hair is rinsed, shampoosed and dried. An ash brown is obtained.

EXAMPLE 14 A solution K made in the manner disclosed in Example 13 is applied to white hair for 10 to 15 minutes at ambient temperature. Thereafter the hair is rinsed in lukewarm water.

Then a solution designated as L is prepared by admixing, just before use, solution I, disclosed in Example 12 and solution M, having respectively the following compositions:

15 minutes, the hair is rinsed, shampooed and dried. A green blond is obtained.

EXAMPLE 15 Solution N having the following composition is prepared:

6-methyl-3-N-carbamylmethylamino-phenol.

g. (0.01 m.) 1.78 Ammonia solution at 22' B. cm. 10 Water, q.s.p -cm. 100

This solution is applied to bleached hair for 10 minutes at ambient temperature. The hair is then rinsed in lukewarm water.

Then a solution designated as O is prepared by admixing just before use the following solutions, designated as E (essentially the same as disclosed in Example 10) and a solution designated as P ha ving, respectively, the following compositions:

Solution E Potassium persulfate g. (0.02 m.) 5.5 Ammonia solution at 22 B. cm. 10 Water, q.s.p cm. 100

Solution P Paratoluylenediamine g. (0.005 m.) 0.61

Sodium lauryl ether sulfate condensed with 2 moles of ethylene oxide g Water, q.s.p cm. 100

Solution E is allowed to remain in contact with the hair for 20 minutes, after which the hair is rinsed, shampoo d and dried. A gree b end is obtained.

8 EXAMPLE 16 The following solution is prepared:

2,4-diamino-anisole g 0.22 Ammonia at 22 B. cm. 8 Water, q.s.p cm.

White hair is impregnated with this solution which is left in contact therewith for 10 minutes. The hair is then rinsed, and the following solution, prepared just before use, is applied to the hair:

2,6-dimethyl-benzoquinoneimine g 0.17 Water, q.s.p cm. 100

After 20 minutes of contact, the hair is rinsed, shampooed and dried. An intense purple dyeing is obtained.

EXAMPLE 17 The following solution is prepared:

2,4-diamino-anisole g 1.38 Ammonia at 22 B. cm. 10 Water, q.s.p. cm. 100

This solution is applied to white hair for 10 minutes at ambient temperature. The hair is then rinsed followed by impregnation with a solution Q which is prepared at the moment of use by mixing a solution, designated as E as disclosed in Example 10, and the following solution R:

2,6-dimethyl-4-amino-phenol hydrobromide g 2.18

Sodium lauryl ether sulfate at 20% oxyethylened alcohol g- 20 Water, q.s.p cm. 100

After contact of Solution Q with the hair for a 20- minute period, the hair is rinsed, shampooed and dried. A very dark brown violet dyeing is obtained.

EXAMPLE 18 The following solution is prepared:

2,4-diamino-anisole g 0.23 Water, q.s.p. cm. 100

Gray hair is impregnated with this solution which is allowed to remain in contact therewith for 15 minutes. The hair is then rinsed and the following solution, prepared at the moment of use, is applied to the hair:

2,6-dimethyl-benzoquinoneimine g 0.17 Water, q.s.p cm. 100

After a 20-minute contact period, the hair is rinsed, shampooed and dried. A clear purplish blue brown shade is obtained.

EXAMPLE 19 The following solution is prepared: 2-methyl-5-carbamylmethylamino-phenol g 1.80 Ammonia at 22 B. cm. 10 Water, q.s.p cm. 100

This solution is applied to white hair for 15 minutes. The hair is then rinsed and impregnated with a solution S which is prepared by mixing, at the moment of use, solution E of Example 10 and the following solution T:

2-m6th0xy-4-amino-phenol g 1.3 9

Sodium lauryl ether sulfate at 20% oxyethylened alcohol g 20 Water, q.s.p cm. 100

After contact of about 20' minutes, the hair is rinsed, shampooed and dried. A dark auburn shade is obtained.

EXAMPLE 20 The following solution is prepared:

2,4-diamino-anisole g 1.40 Ammonia at 22 B. cm. 10 Water, q.s.p cm. 100

This solution is applied to white hair for 10 minutes, after which th hair s rins d. The air s. hen impregnated with solution S of Example 19. After 20 minutes of contact, the hair is rinsed, shampooed and dried. A dark brown with light violet glints is obtained.

. EXAMPLE 21 The following solution is prepared:

2,4-diamino-anisole g 0.30 Water, q.s.p cm 100 This solution is applied to white hair for 15 minutes. The hair is then rinsed and impregnated with the following solution, prepared at the moment of use;

2,6-dimethyl--methoxy-benzoquinonediimine g 0.14 2,6-dimethyl-benzoquinoneimine g 0.17 Water, q.s.p cm 100 After a 20-minute contact period with the above quinoneimine solution, the hair is rinsed, shampooed and dried. A deep, slightly purplish, navy blue coloration is imparted to the hair.

What is claimed is:

1. A composition for dyeing 'keratinous fibers comprising an aqueous solution of a quinone-imine selected from the group consisting of Z-methoxy-5-methyl-benzoquinonediimine, 2,6 dimethyl S-methoxy-benzoquinonediimine, duroquinonediimine and 2,6-dimethyl-benzoquinoneimine, and a coupler selected from the group consisting of an aromatic metadiamine, a metaaminophenol, a metadiphenol, an arylpyrazolone and a pyridine derivative, said quinoneimine and coupler being present in amounts effective to dye said fibers and the ratio of the molar concentration of said coupler being less than or equal to one, the pH of said composition ranging between 7-10.

2. The composition of claim 1 which also contains an oxidizing agent.

3. The composition of claim 2 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, potassium persulrfate and potassium ferricyanide.

4. The composition of claim 1 wherein the pH is essentially neutral. 7

5. The composition of claim 1 wherein the pH is alkaline.

6. A composition for dyeing keratinous fibers comprising an aqueous solution of a quinone-irnine selected from the group consisting of 2-methoxy-5-methyl benzoquinonediimine, 2,6 dimethyl-5-methoxy-benzoquinone-di imine, duroquinonediimine and 2,6-dimethyl-benzoquinoneimine, and a coupler selected from the group consisting of resorcinol, 2,6-diaminopyridine, 6-rnethyl-3-(N- carbarnylrnethylamino) phenol, 2 carbamylmethylamino- 4-hydroxy-toluene, 1 phenyl 3 methyl 5 pyrazolone, 2,5 dimethyl-phenol, Z-methyl S-acetamino-phenol, 7- hydroxy-phenomorpholine, 2,4-diaminoanisole and 2,6-dimethyl-B-amino-phenol, said quinoneimine and coupler being present in amounts eifective to dye said fibers and the ratio of the molar concentration of said quinoneimine to 10 the molar concentration of said coupler being less than or equal to one, the pH of said composition ranging between 7-10.

7. A process for dyeing keratinous fibers comprising aplying to said fibers in a first stage an aqueous solution of a coupler selected from the group consisting of an aromatic metadiamine, a metaminophnol, a metadiphenol, an arylpyrazolone and a pyridine derivative, permitting said aqueous solution of said coupler to remain in contact with said fibers for a period of about 5-20 minutes and,

in a second stage, impregnating said fibers with an aqueous solution of a quinoneimine selected from the group consisting of 2-methoxy-5-methylbenzoqninonediimine, 2, 6 dimethyl 5 methoxy benzoquinonediimine, duroquinonediimine and 2,6-dimethyl-benzoquinoneimine, permitting said aqueous solution of said quinoneimine to remain in contact with said fibers for a period of about 5- 30 minutes and rinsing and drying said fibers, the aqueous solutions of said coupler and said quinoneimine being applied in amounts effective to dye said fibers, each of said solutions having a pH of 7-10 with the molar concentration of said quinoneirnine to the molar concentration of said coupler being less than or equal to l.

8. A process for dyeing keratinous fibers comprising applying to said fibers an effective amount of an aqueous solution of a mixture of a quinoneimine selected from the group consisting of Z-methoxy-S-methyl-benzoquinonediimine, 2,6 dimethyl-5-methoxy-benzoquinonediimine,

duroquinonediimine, and 2,'6-dimethyl-benzoquinone, di-

imine, and a coupler selected from the group consisting of an aromatic metadiamine, a metaaminophenol, a metadiphenol, an arylpyrazolone and a pyridine derivative, to dye said fibers, permitting said aqueous solution to remain in contact with said fibers for a period of about 5-30 minutes, and rinsing and drying said fibers, said aqueous solution having a pH ott 7-10 and the ratio of the molar concentration of said quinoneimine to the molar concentration of said coupler being less than or equal to 1.

References Cited UNITED STATES PATENTS 2,170,191 8/1939 Fisher 260-396 NX 2,555,973 6/1951 Kartaschoif et a1. 260396 N 3,041,244 6/1962 Feit et a1 810.2 3,516,778 6/1970 Brunner 8-10.2 3,561,912 2/1971 Boosen et a1. 810.2

FOREIGN PATENTS 464,464 1/1914 France 260 396 N 1,553,212 12/1968 France 260-396 N 118,078 4/ 1899 Germany 260-396 N ALBERT T. IMEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner U.S. Cl. X.R. 81l; 200-396 N