US2875769A

US2875769A - Keratinaceous fiber dye of hydroquinone and either dihydroxyphenylalanine or dihydroxyphenylglycine and method of its use

Info

Publication number: US2875769A
Application number: US679129A
Authority: US
Inventors: Philip F Rosmarin; Pantzer Myron
Original assignee: Apod Corp
Current assignee: Apod Corp
Priority date: 1957-08-20
Filing date: 1957-08-20
Publication date: 1959-03-03
Anticipated expiration: 1976-03-03

Description

KERATINA'CEOUS FIBER DYE OF HYDROQUI- NONE AND EITHER DIHYDROXYPHENYLALA- NINE OR DIHYDROXYPHENYLGLYCINE AND METHOD OF ITS USE Philip F. Rosmarin, New York, N. Y., and Myron Pantzer, Englewood, N. J., assiguors to Apod Corporation, New York, N. Y., a corporation of New York No Drawing. Application August 20, 1957 Serial No. 679,129

19 Claims. (Cl. 132-7) This invention is that of reactant-dye compositions derived from reaction, under alkaline conditions, between hydroquinone and a dihydroxyphenylalanine, particularly 3,4-dihydroxyphenylalanine, and/or a dihydroxyphenylglycine, particularly 3,4-dihydroxyphenylglycine.

The invention also includes the preparation of these reactant-dye compositions as well as the method of dyeing keratinaceous substances such as hair (growing or shorn), wool and furs with the oxidation, especially the fresh oxidation, products of these compositions, yielding dyeings fast to light and washing.

The dye compositions of this invention are called reactant-dye. because, in dyeing the keratinaceous materials with them, the indications are that there apparently occurs some kind of reaction between the materials and the dyeing solution composition rather than a mere surface coloring.

By fresh oxidation product is meant that composition containing the reaction product between the hydroxyphenylalanine and/or the dihydroxyphenylglyc'ine and the hydroquinone promptly after adding an oxidizing agent to the product, i. e. usually within about a few or several minutes after the oxidizing agent was added and before appreciable oxidation of that reaction product occurs, or in other words, the ready dyeing solution resulting after the action of the oxidizing agent on the reactant-dye. r

In this specification 3,4-dihydroxyphenylalanine is briefly referred to as dopa, and 3,4-dihydroxyphenylglycine is briefly referred to as dopa-G.

Para-phenylenediamine and derivatives of it, and substances similar to it have been used widely in fur dyeing and to a large extent in hair dyeing, including dyeing growing human hair. However, these substances possess certain sensitizing or sensitization-provoking reactions and toxic limitations that provoke distress not only with persons handling and working with them, or dyeing hair of others with them, but especially also with many whose hair is dyed with them. Accordingly, certain states and countries prohibit their sale. Others including our country, permittheir sale only under certain restrictions, for example, that their labels bear a warning that mentions their sensitizing or sensitization-provoking reactions and toxic characteristics andrequires making a patch test to determine absence of sensitivity to them before using them.

A significant disadvantage in the use of dopa and dopa-G for dyeing hair is their usual limitation in giving only very light brown and blonde shades, and the need to re-dye to build up color even in this part of the range. Then, too, other hair dyes give only a very limited range of color.

United States Patent The reactant-dyes of this invention, are especially ap- 2,875,769 Patented Mar. 3, 1959 2 1 dark brown and even to very dark blackish-brown In addition, they leave the hair permanently dyed against repeated washing and ordinary exposure to light.

The reactant-dyes of the invention, providing these advantageous dyeing features for keratinaceous fibers, especially hair and fur, are obtained, and the method of their preparation is carried out, by allowing the hydroquinone and the dihydroxyphenylalanine, as 3,4-dihydroxyphenylalanine, and/or the dihydroxyphenylglycine, as 3,4-dihydroxyphenylglycine, to react with one another in suitable proportions in aqueous media and under non acid, and advantageously alkaline, conditions, and until the reaction has become substantially inactive. By the reaction has become substantially inactive is meant that stage at which the reaction has slowed down to a rate at which the color that developed appears to have discontinued growing any darker.

Practically directly after the joint inclusion of the hydroquinone and either or both of the amino acids in the aqueous non-acid alkaline medium, color formation commences and increases in depth until the reaction becomes substantially inactive, that is to say, when there appears to be no further increase in color depth. That generally occurs in from about five to about ten or so minutes, depending on the concentration of reactants in the alkaline vehicle.

The alkalinity canvary from about pH 8 to about pH 11, and most effectively from about pH 9 to about pH 10. Below about pH 8 the resulting hair dyes are undesirable in that the appearance of hair dyed. with them is quite unnatural and rather dull and unattractive.

As to the method of dyeing keratinaceous fibers, for

example, living hair, with the reactant-dyes of the invention, the resulting aqueous reactant-dye solution (whether true or colloidal) is mixed with a suitable quantity of a compatible oxidizing agent (either in dry form or as a compatible liquid vehicle or solvent); and the resulting fresh oxidation dyeing solution, for example, is applied directly to living hair on the head in the usual manner used by beauticians or given in directions with home use hair dyes. The latter includes, for example, parting the hair and applying the fresh oxidation dyeing solution by cotton swab or dauber or other applicator to saturate the hair close to the scalp and about two inches to each side of the part line, parting the hair a short distance from the first part and repeating the saturation of the hair with the dyeing solution, and continuing in similar mandant, of the type commonly used for fur dyeing before or after they are immersed in the fresh oxidation product obtained from the mixture of reactant-dye composition and oxidizing agent.

For beneficially eifective results, particularly with, al-

though not restricted to, hair (growing or shorn), the

hydroquinone should be used to the extent of at least about ten (10%) percent by weight, or about one-sixth mole of it to one mole of the dihydroxyphenylalanine,

such as 3,4-dihydroxyphenyla1anine, and/or the dihydroxyphenylglycine as 3,4-dihydroxyphenylglycine. Much better results are obtained byusing at least about twenty (20% percent of hydroquinone by weight of the amino 3 acid or acids.

Ordinarily,- the quantity of'hydroquinone used can be from under to about the same as that of the amino acid or acids. Yet, in some cases the hydroquinone can be used in some excess over it, as when resorcinol and catechol are included with it, as explained below, and then up to twice the amount of the amino acid or acids. In general, the greater the proportion of hydroquinone to the amino acid or acids, the deeper the shade in the dyed fiber. Also, the greater the'concentration, in the aqueous medium, of the reactant-dye (i. e. the reaction product of thefhydroquinone with the dihydroxyphenylalanine and/ or the dihydroxyphenylglycine), the deeper the resulting shade in the dyeing.

By using either or both of these amino acids, such as dopa and/or dopa-G, and the hydroquinone alone in varying relative proportions to one another for preparation of the reactant-dye compositions, mixing them with the oxidizing agent, say in solution, and then applying the resulting fresh oxidation product dyeing solution, for example, to hair (growing orvshorn), colors ranging from the palest blonde to the reddest auburn or titian are produced.

For certain variations in color, the hydroquinone can be replaced in part by an approximately equivalent amount of another polyhydric phenol, such as the trihydric phenol pyrogallol (i. e. pyrogallic acid), or of a c'arboxyl-substituted polyhydric phenol as protocatechuic acid, or quite beneficially by a quantity of jointly present dihydric' phenols as catechol and resorcinol.

Some of these color variations, especially in the lighter range, can be obtained by including pyrogallol or protocatechuic acid along with the hydroquinone. The'pr'otoca'techuic acid generally tends to yield a lightening of the shade of the same color obtained without its use. -The use of pyrogallol generally produces a yellowing of the color obtained without it. Then, by including varying amounts of both resorcinol and catechol together along with the hydroquinone and the dihydroxyphenylalanine and/or the dihydroxyphenylglycine, Without or with the pyrogallol or protocatechuic acid, colors ranging from light brown to very dark blackish-brown are obtained on the hair.

The specific ultimate color produced in the dyed keratinaceous fiber, such as growing human hair, is influenced not only by the relative proportions of the various reactants to one another, but also by such factors as their respective concentration in the aqueous medium, and the length of time that the fresh oxidation product dyeing solution remains in contact with the hair or other fiber during the dyeing step or treatment. For example, thereactant-dye compositions of individual ones of the specific complete examples below can be separately progressively diluted with water even up to nineteen parts of water to one of the reactant-dye compositions, although with not so much dilution of the lighter colors, to .obtainincreasingly lighter colors such as lighter browns down to very light blondes.

Any form of the dopa, Whether the synthetic (the racemic form), natural (the laevo-rotatory form), or dextro-rotatory form, and likewise any form of the dopa-G can be used in preparing the reactant-dye compositions. Either or both of them can be dissolved independently (at atmospheric temperature) in the alkaline aqueous medium in a suitable, or the required, concentration for the formulation for the particular color to be dyed, even up to eighteen, and, if necessary, twenty, percent, or it can be added to the aqueous liquid medium in its required concentration along with the hydroquinone.

The latter can be included also in its required concentration for the particular formulation, and, depending on the color to be dyed, can be dissolved in asuitable aqueous medium in a concentration even up to thirtyfive (35%) percent, depending on the composition of the aqueous medium, or as its own aqueous solution up to its solubility limit (or with the aid of a minimum amount of an inert mutual solvent, e. g. ethanol, beyond its water solubility limit), for the preparation of the reactant-dye composition. At that concentration it represents about four moles ofit per mole of the dihydroxyphenylalanine and/or the dihydroxyphenylglycine at the highest concentration mentioned herein of either or both of these amino acids.

. Any water-soluble alkalizing agent that will not interfere (i. e. is compatible) with any necessary reactant used in the formulation, and that will aid to dissolve any necessary reactant that otherwise is insufficiently soluble in water, and that will not precipitate the resulting reactant-dye or introduce any possibility of toxicity under the conditions of use, or injure the scalp or hide or pelt, at its ultimate concentration in the oxidation dyeing solution to be applied to the living or other hair or other keratinaceous fiber, can be used. A preliminary test of some selectedalkalizing agent can be made to notev its compatibility with the reactants and inability to precipitate the resultant reactant-dye or to introduce possibility of toxicity or injury to the skin, pelt, or hide.. Ammonium hydroxide, because of its freedom from,

toxicity over a very wide concentration range and its economy, is beneficial and favored, especially in its commercially commonly available twenty-eight (28%) percent solution.

. However, there can be used in place of, or together with, the ammonia any other compatible ammonia de-.

rivative alkalizing agent such as a lower alkanolamine as mono-, di-, or triethanolamine, or a heterocyclic amine as morpholine or pyridine, or a lower alkyl monoor di-amine such as monomethylamine, dimethylamine, monoethylamine or diethylamine. Any of these am-- monia 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,v

for example, calcium hydroxide or magnesium hydroxide (included as an alkaline earth), 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 organic orother reactants. 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, any of which also can be used so long as its ultimate concentration in the final dyeing solution is below that.

which might possibly irritate the scalp or skin or injure the hide of the fur pelt.

Any selected, compatible alkalizing agent should be used to give a pH greater than seven and at least about eight and preferably higher and within about nine to eleven and most effectively between about nine and about.

ten and best at around 9.66. However, each of dopa and dopa-G is a butter and can keep the system at.

about pH ten. Even a mixture of alkalizing agents can be used to give the required pH. Whatever alkalizing agent is used, canbe added to the aqueous medium before, with, or after, the addition of the organic reactants selected for preparing the reactant-dye.

Such other polyhydric phenols, as the pyrogallol,- protocatechuic acid, or catechol with resorcinol, as are to be included in the formulations can be added to the aqueous medium at the same time as the hydroquinone and the dihydroxyphenylalanine and/or the dihydroxyphenylglycine. Although if protocatechuic acid is to beused in a relatively high concentration, it first may need .to be heated alone in water or in presence of at least some alkalizing agent to go completely into solution, and then to be added to the other reactants. when all of the reactants and reagents have been dissolved in theaqiieous medium, the pH should be above seven, effectively to keep all of the reactants in solutioh,

It is beneficial to use initially enough alkali to give a pH that may be even between about 10.5 and 11. However,

soon after the reaction has been going on for a short time, because of the buffering action of the dopa and/ or the dopa-G, the pH will become adjusted automatically to about 9.66.

Promptly after some of both of the hydroquinone and the dihydroxyphenylalanine and/ or the dihydroxyphenylglycine has dissolved in the aqueous medium, reaction between them occurs. Within a few minutes, and at least usually, within about five to ten minutes, and advantageously always with stirring, this first reaction (i. e. before adding a specific oxidizing agent) is at least substantially complete, that is to say, becomes substantially inactive. By then all of the reactants have gone into solution and reacted together into a water-soluble, or at least colloidally dispersed, reactant-dye product.

This reactant-dye solution is ready now for the subse quent reaction, for it is to be mixed with a suitable compatible oxidizing agent if dyeing of hair or other fiber is to be done promptly thereafter. In any event, this reactant-dye dispersion or product, before being mixed with the oxidizing agent, is a finished product of the invention, and can be used at any suitable time, soon or later thereafter, on addition of the oxidizing agent, to dye living hair or other keratinaceous fiber.

There can be used any water-soluble oxidizing agent that is compatible with this water-soluble, or colloidally water-dispersed, reactant-dye product and that does not introduce into the fresh oxidation product or dyeing solution any possibility of its being toxic to the scalp, or injurious to the hair or fur or hide or the pelt, at the ultimate concentration at which it is applied.

Such suitable oxidizing agent is also compatible with the reactant-dye when it does not react with the dye to form a water-insoluble precipitate. Hydrogen peroxide, in any of its commercially commonly available strengths, because of its ready availability and low cost, is favored. It can be used, for example, as twenty volume or in its twenty-five volume strength, or even eight and a quarter volume or also one hundred volume.

In place of, or together with, the hydrogen peroxide, there can be used any other compatible oxidizing agent such as any other suitable peroxide, for example, an inorganic peroxide such as an alkali metal peroxide as sodium peroxide, or an organic peroxide as urea peroxide, or other water-soluble inorganic oxidizing agent as an alkali metal chlorate, bromate, or perborate such as sodium or potassium chlorate, bromate or perborate. Any of the foregoing, or compatible mixtures of them, can be used in preparing the dyeing solutions for dyeing live hair. In wool or fur dyeing any of them, or others, can be used.

For use in dyeing living hair or other keratinaceous fiber, the reactant-dye product of the invention is mixed with a quantity of the oxidizing agent, Whether liquid or solid, suflicient to give a convenient concentration in relation to the concentration of the reactant-dye in its solution and the concentration desired in the oxidized dye solution as it is to be applied to the hair or fur or other keratinaceous fiber. For example, hydrogen peroxide (twenty volume) can be mixed with the reactantdye solution usually in an amount of from about one quarter to one-half of, or up to equal parts or even twice, the volume of the reactant-dye solution. The solid oxidizing agents can be granulated or powdered and thus added to, and dissolved in, the reactant-dye solution, although in some cases it is advantageous to dissolve such oxidizing agent separately in Water.

The selection and quantity of the oxidizing agent will depend on the condition of the fiber to be dyed and the color to be developed in the dyeing rate. In some cases, a preliminary test on a trial lock or switch of hair or skcin or swatch of wool or patch of fur may be necessary as a guide.

The reactant-dye dispersion and the oxidizing agent,

in solution or solid, are m ed together uniformly to give what can be referred to as the oxidation dye or dyeing solution, for application to the hair. There can be included a suitable compatible wetting agent or other surfactant. It is best that the oxidation dyeing solution be applied to the hair or other fiber promptly after the reactant-dye solution and the oxidizing agent have been mixed, and preferably not more than about ten minutes or so after mixing the reactant-dye dispersion and the oxidizing agent.

The oxidation dyeing solution then can be applied tow the hair or other fiber in known manner. The hair or other fiber is kept in contact with the dyeing solution for a sufficient time for the desired color and shade of it to develop from its contact of the fiber with the dye. For most cases, as so far noted, the dyeing time can be from about fifteen to about seventy-five minutes, and often from about a half hour to about an hour. The dyeing reaction between the fiber and the oxidation dyeing solution is then terminated by shampooing and/or rinsing the hair or other fiber to remove the exhausted and any excess dyeing solution.

The reactant-dye compositions and oxidation dyeing solutions, and methods, of the invention are illustrated by, but not restricted to, the following examples which include also quantities of an oxidizing agent used relative to the reactant-dye solution produced:

Example 1.Very pale blonde on wool: one gram of 3,4-dihydroxyphenylalanine and one-half gram of hydroquinone were dissolved in twenty-five milliliters of water to which was added two milliliters of twenty-eight per cent ammonium hydroxide solution. Within a few minutes there resulted a clear, light brown reactant-dye solution. To make the dyeing solution, five milliliters of twenty volume hydrogen peroxide were added to fifteen milliliters of this light brown solution. A swatch of unbleached wool was rinsed in the twenty milliliters of this oxidation dyeing solution for fifteen minutes and then was removed and washed, and appeared as a very pale blonde dyed product. This color remained permanent, without running, after repeated washings in water with shampoo. The color also remained permanent after extended exposure to sunlight.

Example 2.Very pale blonde on grey hair: two and one-half grams of 3,4-dihydroxyphenylalanine and onequarter gram each of hydroquinone and pyrogallol were dissolved in fifty milliliters of water to which was added four milliliters of twenty-eight percent ammonium hydroxide solution. Within a few minutes there resulted a clear, light brown reactiondye solution. To this solution there was added an equal volume of twenty volume hydrogen peroxide, yielding inseveral minutes a light brown dyeing solution. This dyeing solution was applied to hair in known manner and allowed to remain for forty minutes dyeing time, after which the dyeing reaction was stopped by thorough shampoo and water rinse. About one and one-half ounces of dyeing solution was needed. The color did not change on repeated washings in water with shampoo. The same results were obtained on applying this fresh oxidation dyeing solution to living hair' by the method described in the paragraph beginning on line 32, column 2, above.

Example 3.-Champagne color on grey hair: two grams of 3,4-dihydroxyphenylalanine, one-half gram of hydroquinone, two grams of resorcinol and one gram of catechol were dissolved in fifty milliliters. of water to which five milliliters of twenty-eight percent ammonium hydroxide were added. After five minutes, there was added to this reactant-dyesolution one-half of its volume of twenty volume hydrogen peroxide. The resulting oxidation dye solution was applied to grey hair in known manner for thirty-five minutes dyeing time and then removed by a thorough shampoo and water rinse, leaving a good uniform, fast champagne color which was not removed by repeated washings.

estates Example 4; Blondeon grey hair: two grams each of 3,4wdihydroxyphenylalanine and hydroquinone were dissolved in thirty milliliters of water to which three and one-'half'milliliters of twenty-eight percent ammonium hydroxide were added. After five minutes, there was added to this reactant-dye solution an equal volume of twenty. volume hydrogen peroxide. The resulting oxidation dyeing solution was applied to grey hair in known manner for forty minutes dyeing time. Then the dyeing reaction was stopped by a thorough shampoo and water rinse. .The hair was dyed a good, uniform blonde which Was not changed by repeated washings.

Example 5 .Red maize on grey hair: two grams of 3,4- dihydroxyphenylalanine and three grams of hydroquinone were dissolved with vigorous stirring in twenty-five milliliters of water, to which four milliliters of twenty-eight percent ammonium hydroxide were added. After ten minutes, an equal volume of twenty volume hydrogen peroxide was added. The resulting oxidation dye solution was applied to grey hair in known manner for forty minutes dyeing time and then removed by a thorough shampoo and water rinse. The hair was dyed a uniform red maize color which withstood repeated Water washings.

Example 6.-Pale henna on grey hair: two grams of 3,4-dihydroxyphenylalanine, four grams of hydroquinone and five one-hundredths of a gram of pyrogallol were dissolved with vigorous stirring in twenty-five milliliters of,

water to which four milliliters of twenty-eight percent ammonium hydroxide had been added. After ten minutes,

- an equal volume of twenty volume hydrogen peroxide was added. The resulting oxidation dye solution was applied to grey hair in known manner and maintained for a forty minute dyeing time and then removed by a thorough shampoo and water rinse. The hair was dyed a uniform pale henna and showed no loss in color on repeated water washings.

Example 7.-Reddish brown on grey hair: four grams of 3,4-dihydroxyphenylalanine and three grams of hydroquinone were dissolved in sixty milliliters of water to which five milliliters of twenty-eight percent ammonium hydroxide had been added, and with vigorous stirring until solution was complete. Then there was added onequarter the volume of twenty volume hydrogen peroxide and the solution uniformly mixed. The resulting oxidation dye solution was then applied to grey hair in known manner and maintained for a forty minute dyeingtime and then removed by a thorough shampoo and water rinse. The rinsed hair was dyed a uniform, beautiful reddish brown and showed no loss in color during repeated water washings.

Example 8.Medium brown on grey hair: six grams of 3,4-dihydroxyphenylalanine, three and one-half grams of hydroquinone, six grams of resorcinol and one gram of catechol were vigorously stirred in forty milliliters of water to which was added fourteen milliliters of twentyeight percent ammonium hydroxide, until solution was complete. Then for every twenty milliliters of the solution there was added five milliliters of twenty volume hydrogen peroxide. The resulting oxidation dye solution was then applied to grey hair in known manner and allowed to remain in contact with the hair for fiftyfive minutes dyeing time, after which the unconsumed dyeing solution was removed by thoroughly washing with water and shampoo. The rinsed hair was dyed a beautiful medium brown.

Example 9.Rusty auburn on grey hair: four grams of 3,4-dihydroxyphenylalanine and three grams of hydroquinone were vigorously stirred in forty milliliters of water to which had been added five milliliters of twentyeight percent ammonium hydroxide, until solution was complete. Then there was uniformly stirred in one-half th e volume of twenty volume hydrogen peroxide. The resulting oxidation dye solution was then applied to grey hair in known manner and allowed to remain in contact with it for a arra -five minutedyeing time. Then the added twelve and one-half milliliters of twenty volume hydrogen peroxide to give a uniform oxidation dyeing solution. The latter was then applied to grey hair in known manner and allowed to remain in contact with it for a seventy-five minute dyeing time. solution was then removed by thorough shampoo and rinsing with water, leaving the hair dyed a dark brown.

In each ofthe foregoing Examples 1 through 10, replacement of the dopa by respectively the same quantity of dopa-G gives the same dyeing results on the specific fiber and human hair (shown or living) used in the individual examples. Accordingly, without unduly extending this specification by repeating each such separate dopa-G example in full, Examples 1 through 10 with their separate amounts of dopa replaced respectively by the same amount of dopa-G are incorporated herein by this reference as if each of them as so modified were recited in full herein.

. The various respective fiber (i. e. hair) dyeings obtaiued separately in each of the foregoing Examples 2 through 10, and also in their duplicates with the dopa replaced by dopa-G, were obtained on growing living hair by the method of application of the fresh oxidation dyeing solution described in the paragraph beginning on line 32, column 2, above.

The invention thus includes the method of dyeing growing hair with significant fastness to light and water which-comprises subjecting such hair, for a time sufficient for the desired color and shade to develop on it,

to the action of an oxidation dyeing solution prepared by mixing together uniformly an aqueous alkaline, reactant-dye colored composition and an oxidizing agent compatible with the compositions constituents and the hair under the dyeing conditions, for example, hydrogen peroxide, and in a quantity sufficient to yield a suitable oxidizer concentration in relation to the reactant-dye concentration in its solution and the concentration in the fresh oxidation dyeing solution for the desired color and.

shade to be developed on the hair. After the desired color and shade of it is developed on the hair, the spent and any excess dyeing solution is removed from the hair, for example, by shampooing.

In Examples 1 through 10, the dopa can be replaced by respectively the same quantity .of a suitable isomer of it. Likewise, the proportions of the various ingredients can be varied to give desired variations in color and their intensities, in the manner as above indicated to be possible. Then also it is possible to replace any polyhydroxy phenol used singly to replace a minor part of the hydroquinone by some other phenol having, say, at least three hydroxyl groups, such as tetrahydroxyquinone.

Thus, for instance, by including in Example 1 also one one-hundredth gram of tetrahydroxyquinone, the fiber is dyeda light brown. The pyrogallol can be used in an amount as small as about one-tenth percent, and at times less, of the hydroquinone up to about equal to it and even greater than it, say two, three, and four times as much. The tetrahydroxyquinone likewise can be used within the limit of its solubility in the aqueous alkaline medium. There can be used similarly 1,2,4-trihydroxybenzene (i. e. hydroxyquinol).

Likewise, protocatechuic acid can replace the hydroquinone in part. Thus, by the procedure used in the various examples, but. with 1 gram, of 3,4-dihydroxyphenylalanine, one-half gram of hydroquino'ne, and 2 grams of ,protocatechuic acid, and three millilitersiof The dyeing of water, after solution was complete, a suitablereaction: dye resulted. An oxidation dyeing solution of fifteen parts of this reaction'dye solution with two parts of twenty volume hydrogen peroxide produced on grey hair from a good medium brown blonde to a good pale brown blonde dye. Using two grams of 3,4-dihydroxyphenylalanlne, five grams of hydroquinone, six grams of protocatechuic acid, six milliliters of the ammonium hydroxide solution with one hundred milliliters of water, and two parts of the color solution to one of the twenty volume hydrogen peroxide, grey hair was dyed a good medium brown.

Reacting one gram of dopa and one gram of protocatechuic acid in fifty milliliters of water and three milliliters of 28% ammonium hydroxide, and using one part of the resulting reactant-dye solution to one-half part of the twenty volume hydrogen peroxide, grey hair was dyed a pale straw with good tone.

Instead of using either thedopa and/or the dopa-G or the protocatechuic acid in its respective free acid form, the equivalent quantity of a water-soluble salt of it can be used, for example, an alkali metal salt such as the sodium or potassium salt, or the ammonium salt, or a lower alkanolamine salt of it such as a mono-, dior triethanolamine'salt. On solution in water, such salt can produce a pH above seven and even around eight, and then require addition of only a smaller amount of the alkalizing agent to give the desired alkaline conditions for the reaction to produce the reactant-dye. Accordingly, the reference to a dihydroxyphenylalanine and specifically to 3,4-dihydroxyphenylalanine, or a dihydroxyphenylglycine and specifically to 3,4-dihydroxyphenylglycine or to 3,5-dihydroxyphenylglycine, or to protocatechuic acid, in the appended claims is to be construed as involving any of these salts as equivalents of the respectively corresponding free acid.

Either a suitable wetting agent or suspending agent can be included in the compositions of any of the examples, but neither of these is essential to the preparation of the reactant-dye. A compatible wetting agent serves ordinarily to facilitate penetration of the reactant-dye. A compatible suspending agent serves to reduce flow or drainage from the hair. Either or both can be any'compatible wetting agent or suspending agent respectively, that is innocuous in its final concentration in the fresh oxidation product dyeing solution. Either of them can be included after the reactant-dye has been produced.

The specific resulting color produced in the dyed hair or other fiber is influenced by the relative proportions of the various reactants to one another, their respective concentrations in the aqueous media, and the time that the fresh oxidation product dyeing solution remains in contact with the hair or other fibers.

The ammonium hydroxide can be replaced in whole or in part by any other compatible ammonium alkalizant or other alkalizing agent innocuous to the scalp or fur or pelt at its final concentration in the ultimate fresh oxidation product dyeing solution. So also while hydrogen peroxide is advantageous as the oxidizing agent, it can be replaced in whole or part by any other compatible oxidizing agent that is innocuous at its final concentration in the ultimate fresh oxidation dyeing solution.

Instead of using distilled water in preparing the reactant-dye products, de-ionized water can be used. Either distilled or deionized water is preferred in preparing the reactant-dye compositions in market packages to stand up under shelf life. Ordinarily, average good quality city water can be suitable where the reactant-dye compositions are to be used in preparing a dye-bath for fur, wool, or other loose keratinaceous fibers.

The reactant-dyes of the invention are water-dispersable in the usual generic sense as embracing true stable homogeneous colloidal solutions of them in such aqueous medium. Thus, the aqueous-medium includes the aqueous alkaline medium resulting from the alkalizing agent used either merely to provide the alkalinity or to enhance the dissolution of some organic reactant in the water. It includes also any aqueous medium containing, for example, a sufficient amount of any oxygenated lower aliphatic mono or dihydric alcohol employed as a common solvent to enhance the solution of some organic reactant, for example, any lower aliphatic alcohol as ethanol, methanol, propanol or iso-propanol, or lower aliphatic glycol such as propylene glycol and the like.

The reactant-dye of any of the various illustrative examples, as well as any other produced according to the invention, can be obtained in the dry state by removing the aqueous vehicle by a procedure that avoids oxidation or decomposition of, or any other deleterious effect on, it. Thus, for example, the reactant-dye can be removed from the aqueous vehicle in which it is dispersed (either in true solution-or colloidal dispersion) by lyophilization. Accordingly, the aqueous dispersion of the reactant-dye can be frozen and in the frozen state subjected to high vacuum to sublime away the frozen vehicle and leave behind the dry reactant-dye.

Alternatively, the dispersion of reactant-dye can be spray dried under conditions to avoid deleterious change.

in it, for example, by spraying it into an inert atmosphere, for example, carbon dioxide or nitrogen, or air mixed with either of them sufficiently to reduce its oxygen content to a harmless point, with or without using a spraying medium inert to the reactant-dye. Such medium can be a gas or mixture of gases as just mentioned for the inert atmosphere.

Such dried reactant-dye then can be put up either as a free running powder in bottles or powder papers (such as used for pharmaceuticals) or even can be tabletted. For tablets, it can be helpful and desirable in some cases to incorporate a suitable inert binder to give added physical.

strength to the tablets, or ingredients to enhance their disintegration when placed in Water. In packaging the reactant-dye in any of these dry forms, it is beneficial to have the container filled sufiiciently to leave in it as little air as possible and to close it tightly to avoid, while not in use, replacement of the air already in the package.

Advantageously, such powder paper or tablet can contain enough reactant-dye for a complete single dye treatment, for example, when prepared for dyeing hair on the head. When to be used, the reactant-dye either can be dissolved or otherwise dispersed in a separate suitable quantity of water and then mixed with the required amount of oxidizing agent solution, or it can be added directly to, and dissolved in, water already containing the required amount of the oxidizing agent.

The dry reactant-dye powder can be used for permanent dyeing by stirring a given quantity into a stated volume of water having dissolved in it sufficient of any of the alkalizing agents described above to give the resulting solution a pH above about eight and in the range already stated for the reactant-dye solution before it is mixed with the oxidizing agent. Alternatively, the dry reactant-dye powder can be mixed with a powdered, water-soluble, preferably non-hygroscopic, solid alkali, for example, ammonium carbonate, innocuous in its final concentration in the final dyeing solution, and in such ratio that when a given quantity of the dry mixture is stirred into a prescribed volume of Water, the pH of the resulting solution is within the range shown hereinabove.

In general, the various oxidation dyeing solutions containing any.of the various reactantdyes described can be applied with good results to hair whether or not it had been previously washed and are fast to washing and sunlight.

While the invention has been explained in detail in relation to certain specific embodiments of it, various seas-as substitutions and modifications can be made in any of them within the scope of the appended-claims which are intended also to cover equivalents of any of the various specific examples.

.This application is a continuation-in-part of our copending application Serial No. 350,756 filed April 23, 1953, and now abandoned.

What is claimed is:

l. A colored composition of matter comprising a waterdispersable reactant-dye useful in the dyeing of keratinaceous fibres with significant fastness to light and water, which dye results from the, reaction, in an aqueous medium under alkaline conditions produced by a compatible water-soluble alkalizing agent that dissolves any of the reactants insufficiently soluble under the conditions and avoids formation of a precipitate with any of the reaction products under the reaction conditions, between hydroquinone and at least one amino acid member of the class consisting of a dihydroxyphenylalanine having a formula (HO) C H CH CH(NH )COOH and a dihydroxyphenyh glycine having the formula .(HO) C H CH(NH )COOH, until the reaction is substantially complete, and wherein the hydroquinone is from about ten to about two hundred percent by weight of the amino acid used.

, 2. Acomposition comprising a reactant-dye as claimed in claim 1, wherein the hydroquinone is replaced in part by at least one polyhydric phenol member of the class consisting of pyrogallol and protocatechuic acid, and in the proportions of from a minor part of the hydroquinone to several times the remaining quantity of it.

3. A composition comprising a reactant-dye as claimed in claim 2, wherein the hydroquinone is replaced in a minor part by pyrogallol.

4. A composition comprising a reactant-dye as claimed in claim 1, wherein the hydroquinone is accompanied by at least one other polyhydric phenol substance from the class consisting of (a) tetrahydroxyquinone, (b) hydroxyquinol, and (c) resorcinol and catechol jointly, and in the proportions of from a minor part of the hydroquinone to several times the remaining quantity of it.

5. A composition comprising a reactant-dye as claimed in claim 4, wherein the hydroquinone is accompanied by resorcinol and catechol.

6. A composition comprising a reactant-dye as claimed in claim 5, wherein the weight of the dihydrophenylalanine is exceeded by the joint weight of the hydroquinone and resorcinol and catechol.

7. A composition comprising a reactant-dye as claimed in claim 6, wherein the resorcinol and catechol jointly exceed the weight of the hydroquinone, and the catechol weight is under, and at least about ten percent of, that of the resorcinol.

8. .An aqueous alkaline colored composition comprising a water-dispersable reactant-dye useful in the dyeing of keratinaceous fibers with significant fastness to light and water, which dye results from the reaction, in an aqueous medium under alkaline conditions produced by a compatible water-soluble alkalizing agent that dissolves any of the reactants insufiiciently soluble under the conditions and avoids formation of a precipitate with any of the reaction products under the reaction conditions, between 3,4-dihydroxyphenylalanine and hydroquinone until the reaction is substantially complete, and wherein the hydroquinone was from about ten to about two hundred percent by weight of the dihydroxyphenylalanine; and having a pH of from about eight to under about eleven.

9. An aqueous alkaline colored composition comprising a water-dispersable reactant-dye useful in the dyeing of keratinaceous fibers with significant fastness to light and water, which dye results from'the reaction, in an aqueous medium under alkaline conditions produced by a compatible water-soluble alkalizing agent that dissolves any of the reactants insufficiently soluble under the conditions and avoids formation of a precipitate with any of aceousfibers under the dyeing conditions, and

the reaction products under the reaction conditions, between 3,4-dihydroxyphenylglycine and hydroquinone until the reaction is substantially complete, and wherein the hydroquinone was from about ten to about two hundred percent by weight of the dihydroxyphenylglycine and havlng a pH of from about eight to under about eleven.

10. An aqueous alkaline composition as claimed in claim 9, wherein the hydroquinone is replaced in a minor part by a member of the class consisting of pyrogallol and protocatechuic acid.

ll. An aqueous alkaline composition as claimed'in claim 9, wherein the hydroquinone is accompanied by at least one other polyhydric substance from the class conslstmg of (a) tetrahydroxyquinone, (b) hydroxyquinol, and (0) resorcinol and catechol jointly, and in the proportion of from a minor part of the hydroquinone to several times the remaining quantity of it.

1 2. An aqueous alkaline composition as claimed in claim 11, wherein the weight of the dihydroxyphenylglycine is exceeded by the joint weight of the hydroquinone and the resorcinol and catechol, and the resorcinol and catechol jointly exceed the weight of the hydroquinone, and the catechol weight is under, and at least about ten percent of, that of the resorcinol.

l3 The method of preparing a colored, aqueous composition as claimed in claim 11, which comprises dissolv ing in water 3,4-dihydroxyphenylglycine to a concentratron of from about a few to about twenty percent, hydro- .quinone in an amount from about ten to about two hundred percent by weight of the dihydroxyphenylglycine,

and, to an extent to leave the resulting composition alkaline and at a pH under about eleven, a water-soluble alkalizing agent that dissolves any of the reactants instilliclently soluble under the conditions and avoids formation of a precipitate with any of the reaction products under the reaction conditions; and agitating the water until all of the reactants have gone into solution.

l4. The method of preparing a colored composition as claimed in claim 13, wherein a minor part of the hydro qu none is replaced by a polyhydric phenol from the class consisting of pyrogallol and protocatechuic acid.

15. The method of preparing a colored composition as claimed in claim 13, wherein the hydroquinone'is acconi:

panied by resorcinol and catechol and their joint weight exceeds that of the hydroquinone and the resorcinol exceeds the weight of catechol.

16. The method of dyeing keratinaceous fibers, which comprises subjecting them, for a time sufiicient for the desired color and shade to develop on them, to the actron of an oxidation dyeing solution prepared by mixing together uniformly an aqueous alkaline. reactant-dye colored composition and an oxidizing agent compatible with the constituentsof said composition and the keratinin a quantity suificient to yield a suitable concentration of it in relation to the reactant-dye concentration in its solution and the concentration in the oxidation dyeing solution for the color and shade to be developed on the keratinaceons fiber; the aqueous colored composition comprising a reactant-dye for dyeing the keratinaceous fibers with significant fastness to light and water, which dye results from the reaction, in an aqueous medium under alkaline conditions, produced by a compatible watersoluble alkalizing agent that dissolves any of the reactants insufficiently soluble under the conditions and avoids formation of a precipitate with any of the reaction products under the reaction conditions, between hydro-- quinone and at least one amino acid member of the class consisting of a dihydroxyphenylalanine have the formula (HO) C H CH CH(NH )COOH and a dihydroxyphenylglycine have the formula (HO) C H CH(NH )COOH; withe the hydroquinone being from about ten to about two hundred percent :of the weight of the .amino acid content; and removing the spent and any excess dyeing solution from the fibers when the desired color and shade has been developed on them.

17. The method of dyeing keratinaceous fibers as claimed in claim 16, wherein the keratinaceous fiber is growing hair, and the oxidizing agent is hydrogen peroxide, and ammonium hydroxide is the agent for providing the alkaline conditions for the preparation of the reaction-dye, and a minor part of the hydroquinone is replaced by pyrogallol.

18. The method of dyeing keratinaceous fibers as claimed in claim 16, wherein the keratinaceous fiber is growing hair, and the oxidizing agent is hydrogen peroxide, and ammonium hydroxide is the agent for providing the alkaline conditions for the preparation of the reaction-dye, and the hydroquinone is accompanied by resorcinol and catechol, and the joint weight of the hydroquinone, resorcinol and catechol exceeds that of the dihydroxyphenylalanine, and the catechol weight isunder, and at least ten percent of, the weight of the resorcinol.

19. The method of dyeing keratinaceous fibers as claimed in claim 16, wherein the keratinaceous fiber is growing hair, and the oxidizing agent is hydrogen peroxide, and ammonium hydroxide is the agent for providing the alkaline conditions for the preparation of the reaction-dye, and the hydroquinone is accompanied by resorcinol and catechol, and the joint weight of the hydroquinone, resorcinol and catechol exceeds that of the amino acid content, and the catechol weight is under, and at least ten percent of, the Weight of the resorcinol.

References Cited in the file of this patent UNITED STATES PATENTS 2,001,992 Wagner May 21, 1935 2,042,698 Basch June 2, 1936 2,162,458 Lehmann June 13, 1939 2,539,202 Peck Jan. 23, 1951 FOREIGN PATENTS 10,856 France Sept. 4, 1909 (Addition to No. 391,465) 17,982 Great Britain 1913 1,024 Great Britain 1915 20,793 Great Britain 1913 487,279 Great Britain June 16, 1938

Claims

1. A COLOURED COMPOSITION OF MATTER COMPRISING A WATERDISPERSABLE RACTAN-DYE USEFUL IN THE DYEING OF KERTINACEOUS FIBRES WITH SINGNIFICANT FASTNESS TO LIGHT AND WATER, WHICH DYE RESULTS FROM THE REACTION. IN AN AQUEOUS MEDIUN UNDER ALKALINE CONDITIONS PRODUCTED BY A COMPATIBLE WATER-SOLUBLE ALKALIZING AGENT THAT DISSOLVES ANY OF THE REACTANTS INSUFFICIENTLY SOLUBLE UNDER THE CONDITIONS AND AVOIDS FORMATION OF A PRECIPITATE WITH ANY OF THE REACTION QUINONE AND AT LEAST ONE AMINO ACID MEMBER OF THE CLASS QUINONE AND AT LEAST ONE AMINO ACID MEMBER OF THE CLASS CONSISTING OF A DIHYDROXYPHENYLALANINE HAVING A FORMULA (HO)2C6H3CH2CH(NH2)COOH AND A DIHYDROXYPHENYLGLYCINE HAVING THE FORMULA (HO)2C6H3CH(NH2)COOH, UNTIL THE REACTION IS SUBSTANTIALLY COMPLETE, AND WHEREIN THE HYDROQUINONE IS FROM ABOUT TWO HUNDRED PERCENT BY WEIGHT OF THE AMINO USED.