US3088877A - Method of dyeing keratinaceous materials with p-phenylene diamine compositions - Google Patents

Description

United States Patent METHOD OF DYEING KERATINACEOUS MATE- RIALS WITH p-PHENYLENE DIAMINE COMPO- SITIONS Walter H. Brunner, Easton, Pa., and Alexander Halasz, Stamford, Conn. No Drawing. Filed Oct. 13, 1960, Ser. No. 62,321

. 11 Claims. (Cl. 16788) This invention relates to novel dyeing compositions and methods for dyeing keratinaceous materials by the use of the novel compositions. This application is a continuation-in-part of our (to-pending application Ser. No. 55,136, which was filed on September 12, 1960.

The novel dyeing compositions of this invention contain as the color forming agent or dyeing compound a p-phenylene diamine having the following generic formula:

H-I I-H wherein R is a member selected from the group consisting of an alkyl radical having from 1 to 4 carbon atoms, and the phenyl radical. Illustrative of a. specific compound represented by the above illustrated generic formula there can be mentioned:

HNH

(l) 2-nitro 4-amino N-methyl aniline In addition to the above illustrated compound there can also be mentioned: Z-nitro 4-amino N-ethyl aniline; Z-nitro 4-amino N-propyl aniline; 2-nitro 4-arnino N- isopropyl aniline; Z-nitro 4-amino N-butyl aniline; 2-nitro 4-amino N-phenyl aniline.

The p-phenylene diamines employed in this invention wherein the secondary amino group is ortho to the nitro radical can be produced by first hydrogenating a 2,4- dinitrophenylamine wherein the amino group carries the phenyl or an alkyl radical e.g. N-methyl 2,4-dinitroaniline, by introducing hydrogen into a mixture of (a) a solution of the 2,4-dinitrophenylarnine in an organic polar solvent such as ethanol; (b) a catalytically effective quantity of a platinum group metal hydrogenation catalyst such as platinum; and (c) a sutficient quantity of an aqueous solution of an acid to give the mixture a pH of less than about 4 wherein the said acid employed has a dissociation constant greater than 1X10, such as sulfuric acid. About 3 moles of hydrogen are reacted per mole of the dinitro compound at a temperature of about 60 C. and a pressure of about 2 atmospheres. The hydrogenation produces the acid addition salt of the product 2-nitro 4- amino phenylamine. To recover the 2-nitro 4-amino phenylamine free of the acid addition salt the conventional techniques of neutralizing the acid to recover the free base can be employed.

The p-phenylene diamines employed in the dyeing compositions of this invention are advantageously employed for dyeing keratinaoeous fibers and particularly human hair, e.g., living human hair, Without the use of the conventional peroxide additives, e.g. hydrogen peroxide, for color formation or fixation to keratinaceous materials. There are known nitro derivatives of phenylene 3,088,877 Patented May 7, 1963 diamines which the prior art describes as agents for dyeing keratinaceous material. The prior art teaches that various side chains or radicals such as hydroxyl radicals are a necessary part of such phenylene diamines particularly when used without the aid of conventional peroxide oxidizing agents, e.g., hydrogen peroxide. However, it has now been discovered that the hydroxyl-free phenylene diamine derivatives of this invention have excellent dyeing properties when applied to keratinaceous material such as human hair and that the excellent dyeing properties can be obtained even without the use of conventional peroxide oxidizing agents. The nitro derivatives of the phenylene diamines employed in this invention possess many advantageous properties over other nitro derivatives of phenylene diamines described by the prior art for dyeing keratinaceous material, either with or without the use of conventional peroxide additives. Such advantageous properties include a pronounced afiinity for the hair and an actual penetration of the hair shaft; 21 good dyeing union with both normal and permanently waved hair, particularly gray hair; an improved dyetake which is deep and uniform; good rubfastness; an improved washfastness, e.g. upon sh'arnpooing; production of bright and lustrous shades over a wide color range; freedom from staining the scalp; or good stability and dyetake over a wide pH range, including the pH range of about 7.5 to about 9.5 whereas many prior art compounds require pH values above 9.5, such as a pH of 10 or higher for satisfactory stability and dyetake.

The novel dyeing compositions of this invention comprise an aqueous alkaline solution of the specified phenylene diamines. In adition to the water, alkalizing agent and phenylene diamine compound, the compositions can also contain the conventional ingredients found in dyeing compositions such as organic solvents for the dye, thickeners, detergents, gums, and the like. The compositions can be applied to keratinaceous materials by the conventional techniques used in the art. Illustratively, when applied to living hair on the human head the compositions can be applied to the hair with a brush, sponge, or other means of contact, such as dipping until the hair is properly saturated With the composition. The reaction time or time of contact of the dyeing composition with the keratinaceous material is not critical and can vary over the wide range used in the dyeing art such as periods of about 5 minutes to about 2 hours and preferably from about minutes to about 60 minutes. The dyeing temperature can vary over wide limits as is conventional in the art. Thus, the dyeing temperatures can vary from about room temperature, e.g., about C. to above about 60 C. and preferably from about 20 C. to about C.

The dyeing compositions of this invention can be prepared by the conventional methods used in the dyeing art. Thus, they can be prepared by dissolving or dispersing the dye in water of the desired concentration. Water miscible organic solvents can be employed to facilitate solution of the dye; in this event, the dye can be dissolved first in the solvent and then diluted with water. Illustrative of the organic solvents which can be used, there can be mentioned: alkyl monohydric alcohols such as those having from 1 to 6 carbon atoms, e.g., ethanol, isopropanol, ctc.; alkyl dihydric alcohols such as those having from 2 to 6 carbon atoms e.g. propyleneglycol', and various polyhydric alcohols, ketones or esters. The dispersion of the various ingredients can also be facilitated by addition of a detergent or dispersing agent such as lauryl or myristyl sulfate or sulfonate.

Any water-soluble alkalizing agent that will not interfere (i.e., is compatible) with the dye employed, and will not precipitate the dye or introduce any possibility of toxicity under the conditions of use, or injure the scalp or hide of the pelt, at its ultimate concentration in the composition to be applied to the keratinaceous material, can be used. A preliminary test of some selected alkalizing agent can be made to note its compatibility with the dye or to introduce possibility of toxicity or injury.

Ammonium hydroxide, because of its freedom from toxicity over a wide concentration range and its economy is an acceptable alkalizing agent. However, there can be used in place of, or together with the ammonia, any other compatible ammonia derivative alkalizing agent such as a lower alkylolamine such as mono-, di-, or triethanolamine, or a heterocyclic amine as morpholine, or a lower alkyl monoor diamine such as monomethylamine, dimethylamine, monoethylamine, or diethylamine or amines such as tetraethylenepentamine, propylenediamine, dipropylenetriamine, etc. Any of these ammonia derivative alkalizing agents as well as ammonium hydroxide may be broadly referred to as an ammonium alkalizant.

Also, as alkalizing agent, any alkaline earth hydroxide, for example, calcium hydroxide or magnesium hydroxide, can be used up to the limit of its water-solubility and at any concentration that fails to produce a precipitate with any of the components of the composition. The dissolved alkaline earth hydroxide is preferred over the alkali metal hydroxides, such as sodium hydroxide, or potassium hydroxide, or carbonates, such as sodium carbonate and bicarbonate, and of which can also be used so long as its ultimate concentration in the final dyeing solution is below that which might possibly irritate the scalp, or injure the hide of the fur pelt.

The quantity of the various ingredients in the dyeing compositions of this invention can vary over a wide range. The phenylene diamine colorants of this invention can be employed in the conventional concentrations used in the dyeing of the various keratinaceous materials. Illustratively, tinctorially effective quantities of the phenylene diamine compound can vary from less than about .01% to greater than about 10% by weight of the aqueous solution. In the dyeing of living human hair the concentration of the dye will preferably vary from about 0.05% to about 5% by weight of the aqueous solution and particularly from about 0.1% to about 3%. Any selected compatible alkalizing agent should be used to give a pH greater than 7, such as about 7.5 to about 12 and preferably from about 8 or 8.5 to 11. The quantity of the alkalizing agent employed can vary over a wide range depending on the dye and particular alkalizing agent employed. Thus, the alkalizing agent can vary from about 0.1% to about 5% and preferably from about 0.5% to about 2% by weight of the aqueous solution. The water content of the composition is ordinarily the major constituent and can vary over a wide range dependent in large measure on the quantity of other additives such as solvents.

The phenylene diamines employed in this invention are water dispersable in the usual generic sense as embracing true solutions of the dyes in water or any aqueous medium within the bounds of the invention as well as stable homogeneous colloidal solutions of them in such aqueous medium. Thus, the aqueous medium includes the aqueous alkaline medium. It includes also any aqueous medium containing, for example, a sufficient amount of a compound, e.g., ethanol, employed as a common solvent to enhance the solution of the dye or some other organic material. The composition can be formulated as solutions, gels, emulsions, dispersions, and the like.

The following examples are illustrative of the invention:

EXAMPLE 1 Reduction of N-Methyl 2,4-Dinirraniline to Z-Nitro 4-Amino N-Methyl Aniline In a hydrogenation apparatus there were charged 0.5 gram of platinum on charcoal, a mixture of 9.9 grams of pulverized N-methyl-Z,4-dinitroaniline in 200 ml. of

ethanol (95% ethanol content) and 20 ml. of concentrated (38%) hydrochloric acid. The reaction mixture was heated to 60 C. and held at this temperature while there was introduced into the reaction chamber, with constant shaking, 0.303 gram (0.15 mole) of hydrogen at a pressure of to 40 p.s.i. (over a period of about 30 minutes). After cooling the reaction mixture to room temperature, a mixture of the catalyst and the hydrochloride of the nitroamine separated as yellow crystals. These crystals were filtered off, dissolved in 50 ml. of hot water and the undissolved catalyst filtered off. The filtrate was cooled and the resulting acid addition salt of 2-nitro 4-amino N-methyl aniline which precipitated out of solution was recovered by filtration. This acid addition salt was subsequently neutralized with ammonia to obtain the basic form of the 2-nitro 4-amino N-methyl aniline which had a dark red color.

EXAMPLE 2 Reduction of N-Ethyl 2,4-Dinitroaniline to Z-Nitro 4-Amino N-Ethyl Aniline By following the process described in Example 1 there was hydrogenated 22.0 grams (0.1 mole) of N-ethyl 2,4- dinitroaniline by hydrogenating with 0.605 gram of hydrogen (0.3 mole). From the resulting hydrochloride salt of Z-nitro 4-amino Nethyl aniline the free base was prepared by neutralization with sodium carbonate. The free base form of the 2-nitro 4-amino N-ethyl aniline had a red color.

EXAMPLE 3 Reduction of N-Phenyl-2,4-Dinitr0aniline to Z-Nitro 4-Amin0 N-Phenyl Aniline Into a hydrogenation apparatus there was charged 0.2 gram of platinum on charcoal (5%), 2 ml. of water, 20 ml. of isopropanol, 13.2 g. ,5 mole) N-phenyl 2,4-dinitroaniline, an additional 80 ml. of isopropanol and 20 grams of a 50% aqueous solution of H 50 The temperature of the reaction mixture was brought up to about 65 C. and then there was introduced into the reactor at a pressure of 50 to 40 p.s.i. about .303 gram (0.15 mole) of hydrogen over a period of 17 minutes. The temperature of the reaction mixture at the end of the 17 minute period was 52 C. The reaction mixture was permitted to cool, the autoclave was opened and the sulfate salt of 2-nitro 4-amir1o N-phenyl aniline which was produced by the hydrogenation was filtered off as a precipitate. This sulfate salt was subsequently alkalized and separated to obtain the 2-nitro 4-amino N-phenyl aniline as red crystals.

EXAMPLE 4 Reduction of N-Phenyl 2,4-Dinilr0aniline to Z-Nitro 4-Amino N-Phenyl Aniline Into a hydrogenation apparatus there was charged 0.5 gram of a 5% platinum on charcoal catalyst, 10 ml. of concentrated hydrochloric acid (38% HO] content), 13 grams mole) of N-phenyl 2,4-dinitroaniline in 200 ml. of ethanol. The reaction mixture was heated to a temperature of C. to C. and hydrogenated at 50 to 40 p.s.i. After the reaction mixture had absorbed 0.15 mole of hydrogen, the reaction mixture was cooled to room temperature and the reaction mixture was filtered from the catalyst. To the filtrate was added 200 ml. of water and a large excess of sodium bicarbonate. The mixture was permitted to stand for several hours whereupon the reaction product 2-nitro 4-amino N-phenyl aniline crystallized out of solution and was subsequently isolated by filtration.

EXAMPLE 5 A dyeing composition was prepared by dissolving 5 grams of 2-nitro 4-amin0 N-methyl aniline in 50 grams of ethanol at 50 C. The ethanolic solution of the aniline compound was then added, with stirring, to a mixture containing 500 grams of water, grams of diethanolamine and 1 gram of agar agar as a thickener. The mixture was then heated to a temperature of about to 37 C. and applied to the hair by simply pouring the mixture over the hair. The dyeing mixture was left on the hair for 20 minutes and then it was rinsed out with water. The hair was dyed a beautiful dark red color without scalp staining.

EXAMPLE 6 There was substituted in the composition and process of Example 5, Z-nitro 4-amino N-ethyl aniline instead of the Z-nitro 4-amino N-methyl aniline. The hair was dyed a bluish-red shade.

EXAMPLE 7 The following dyeing composition was prepared. Ingredient: iiiiii c lil iifs fiiin (a) Carbopol 934 (a polycarboxylated vinyl resin manufactured by the B. F. Goodrich Co.) 1.00 (1)) Sodium dodecyl benzene sulfonate 1.2 (c) Triethanolamine 0.5 (d) Water 91.2 (e) Dispersed Yellow No. 5 (Color Index designation) 0.25 (f) Z-nitro 4-amino N-ethyl aniline 0.10 (g) Isopropanol 5.75

The composition of Example 7 was prepared by first forming a mixture of ingredients (a) to (d), inclusive, and finally adding to this mixture a solution of ingredients (e) to (g), inclusive. The dyeing composition was poured on human heads having gray hair and was permitted to remain on the hair for 20 minutes at room temperature before the hair was rinsed with water. A blonde shade was obtained on the hair.

EXAMPLE 8 The following dyeing composition was prepared.

Percent by weight of composltlol (a) Acrylic acid Ingredient The dyeing composition of Example 8 was produced by first preparing a solution of ingredients (0) to (d), inclusive, and finally adding to this solution a solution of ingredients (e) to (i), inclusive. The dyeing composition was poured on to human heads having gray hair and permitted to remain on the hair for about half an hour at room temperature, after which time the hair was rinsed with water. The hair was dyed a brown shade.

What is claimed is:

l. A composition for dyeing keratinaceous material consisting essentially of an aqueous solution of from about 0.05% to about 5%, by weight, of a phenylene diamine having the following generic formula:

II-ITI-R wherein R is a member selected from the group consisting of an alkyl radical having from 1 to 4 carbon atoms and the phenyl radical; an anionic detergent; and a sufficient quantity of an alkalizing agent to give the aqueous solution a pH of about 7.5 to about 12.

2. The composition of claim 1 wherein R of the generic formula is an alkyl radical having from 1 to 4 carbon atoms.

3. A hair dyeing composition consisting essentially of an aqueous solution containing from about 0.05 to about 5%, by weight, of a phenylene diamine having the generic formula:

H-N-II wherein R is a member selected from the group consisting of an alkyl radical having from 1 to 4 carbon atoms and the phenyl radical; an anionic detergent; and a sufiicient quantity of an alkalizing agent to impart a pH of about 8 to about 11 to the said aqueous solution.

4. The composition of claim 3 wherein the phenylene diamine compound is 2-nitro 4-amino N-methyl aniline.

5. The composition of claim 3 wherein the phenylene diamine compound is 2-nitro 4-amino N-ethyl aniline.

6. A process for dyeing keratinaceous material which comprises applying thereto a tinctorially efiective quantity of an aqueous solution consisting essentially of a phenylene diamine compound having the following generic formula:

generic formula:

H-N-R H-NII wherein R is a member selected from the group consisting of an alkyl radical having from 1 to 4 carbon atoms and the phenyl radical; a sufficient quantity of an ammonium alkalizant to impart a pH of about 8 to about 11 to said aqueous solution; and wherein the said aqueous solution is at a temperature of about 20 C. to about 45 C.

8. The process of claim 7 wherein the phenylene diamine compound is 2-nitro 4-amino N-methyl aniline.

9. The process of claim 7 wherein the phenylene diamine compound is 2-nitro 4-amino N-othyl aniline.

10. A composition for dyeing keratinaceous material comprising an aqueous solution consisting essentially of about 0.05% to about 5% by weight of 2-nitro 4-amino N-phenyl aniline and a suflicient quantity of an alkalizing agent to give the aqueous solution a pH of about 7.5 to about 12.

11. A process for dyeing keratinaceous material which comprises applying thereto a tinctorially effective quantity of an aqueous solution consisting essentially of Z-nitro 4-amino N-phenyl aniline and a suflicient quantity of an 8 alkalizing agent to impart a pH of from about 8 to about OTHER REFERENCES 11 to the Sald aqueous solunon' Venkataraman: The Chemistry of Synthetic Dyes, vol.

References Cited in the file of this patent 1, Academic Press Inc., N.Y. (1952), pp. 323-324.

UNITED STATES PATENT Heilingotter: Am. Perfumer and Essential Oil Review,

S May 1954, pp. 345448. 1,900,454 Marx Mar. 7, 1933 2,692,288 Bell Oct. 19, 1954

Claims (1)

1. A COMPOSITION FOR DYEING DERATINACEOUS MATERIAL CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF FROM ABOUT 0.05% TO ABOUT 5%, BY WEIGHT, OF A PHENYLENE DIAMINE HAVING THE FOLLOWING GENERIC FORMULA: