EP0678012A4

EP0678012A4 -

Info

Publication number: EP0678012A4
Application number: EP94901569A
Authority: EP
Priority date: 1992-11-19
Filing date: 1993-11-17
Publication date: 1995-11-29
Also published as: EP0678012A1; AU5611694A; CA2154750A1; WO1994010968A1

Abstract

Compositions comprising solubilized melanin and at least one water soluble or water dispersible cationic material, which composition is suitable for user as a temporary and a process for temporarily coloring hair using such compositions.

Description

COMPOSITIONS AND METHODS FOR TEMPORARILY COLORING HAIR USING SOLUBILIZED MELANIN

This application is a continuation-in-part to U. S . S . N . 07/978 , 611 filed November 19 , 1992 .

BACKGROUND OP THE INVENTION

This invention relates to compositions and methods for temporarily coloring hair using a melanin derivative that is obtained by chemically modifying melanin to impart water solubility, which melanin derivative is characterized by anionic substituent groups when solubilized.

Melanin is the naturally occurring pigment that gives hair its color. A general discussion of the properties and chemistry of melanins may be found in Prota, Progress In The Chemistry Of Melanins And Related Metabolites. Med. Res. Reviews, 8:525-56 (1988) and Moncrieff, Manufacturing Chemist, XXI, 8:330-34 (August 1950) . The gradual loss of melanin, with age, causes hair to turn gray. Although gray hair can be colored using chemical dyes, most people prefer to dye their hair with natural pigments, such as melanin-based dyes.

In the past, one of the best natural pigment methods for permanently coloring gray hair involved the use of melanin precursors (such as 5,6 dihydroxyindole (DHI) ) that when combined with an oxidant or a metal salt, form melanin pigments within the hair shaft. See, for example, U.S. Patent 3,194,734 (Seemuller et al.), U.S. Patent 4,808,190 (Grollier et al.), and U.S. Patent 4,888,027 (Grollier et al.). However, the use of these melanin precursors has many disadvantages.

The primary disadvantage is that the hair colors initially produced with melanin precursors are undesirable achromatic colors (cold grays and blacks) . Melanin precursor-dyed hair must undergo a second treatment step with an oxidant such as hydrogen peroxide to achieve natural chromatic colors (warm yellows, reds, and browns). See, for example, U.S. Patent 3,194,734 (Seemuller et al.). In addition, melanin precursors are expensive and, because they are highly reactive, are difficult to work with. The use of melanin precursors also results in undesirable scalp and skin staining.

Furthermore, because melanin precursors penetrate into the hair shaft, the hair colors produced using melanin precursors are permanent hair colors. That is, hair color must grow out with the hair. Often, consumers prefer to use a temporary hair color that will wash out after one or two shampoos. However, temporary hair colors are unacceptable to consumers unless they resist fading in sunlight, do not rub off, and do not bleed when in contact with perspiration, rain, or swimming pool water.

Melanin pigment itself is unacceptable for use in a temporary hair dye composition because it merely coats the hair shaft without appreciable affinity for the hair shaft. Consequently, the melanin is easily rubbed off the hair and leaves hair feeling rough.

Therefore, there exists a need in the art for a composition that produces, in a single treatment step, temporary natural-looking hair color that will not fade substantially in sunlight, will not rub off, and will not bleed when in contact with water; is inexpensive; will not stain skin; and is simple to work with. Applicants have surprisingly found that an aqueous composition. comprising a water soluble melanin (as hereinafter described) and at least one water soluble or water dispersible cationic material provides a hair coloring composition suitable to impart a temporary color to hair that achieves these characteristics.

U.S. Patent 5,006,331 (Gaskin) discloses the use of melanin that has been solubilized by triethanolamine and oxidized by ferric chloride. The resultant suspension mixture of melanin, triethanolamine and ferric chloride is used to obtain compositions for skin protection, for wound healing and for strengthening hair. In an alternate method, the melanin is rendered water soluble by mildly hydrolyzing the melanin using Trypsin in an alkaline medium for several days at room temperature. Melanin is present in the skin protectant compositions of Gaskin in an amount of from about 0.001 to about 0.09%, along with from about 0.0001% to about 0.27% ferric chloride, both being on a weight basis. The skin protectant composition further contains up to about 5% by weight triethanolamine. While not providing a range of concentration for the amount of melanin hydrolysate for the hair protectant compositions according to her invention, Gaskin states at column 6, line 30 that it is present therein in an amount of only about 0.0015% by weight of the total composition. However, this level of Gaskin's melanin hydrolysate is wholly insufficient to impart a color to hair. Moreover, neither of Gaskin's methods provide a melanin material of an anionic character.

Wolfram, et al. The Mechanism of Hair Bleaching. J. Soc. Cosmet. Chem. , 21:875-900 (1970), discloses extraction of melanin from hair by acid hydrolysis, and considers the reaction of melanin pigment with hydrogen peroxide. Wolfram isolates the peroxide reacted melanin by destroying the peroxide with platinum black after a reaction period of sixty minutes.

PCT Application WO 91/17738 discloses the use of soluble melanin derivatives in a process for producing lightly colored melanins that are aesthetically suitable for use in cosmetic compositions.

SϋMKARY OF THE INVENTION

It is an object of this invention to provide an aqueous composition for temporarily coloring hair using water soluble melanin derivatives.

It is also an object of this invention to provide a composition that will produce a temporary natural-looking hair color that resists fading in sunlight, will not rub off, and will not bleed when in contact with water.

It is further an object of this invention to provide an inexpensive composition for temporarily coloring hair using water soluble melanin derivatives.

It is also an object of this invention to provide a composition for temporarily coloring hair comprising soluble melanin derivatives that do not stain skin.

It is also an object of this invention to provide a composition that is simple to work with for temporarily coloring hair using water soluble melanin derivatives.

It is also an object of this invention to provide a one-step process for temporarily coloring hair.

In accordance with this invention, an aqueous composition is provided for temporarily coloring hair comprising water soluble melanin derivatives and at least one water soluble or water dispersible cationic material. Processes for temporarily coloring hair using that composition are also provided. DETAILED PB8CRIPTIQW Of THE IWYSBHΩH

The present invention provides aqueous compositions comprising water soluble melanin and at least one water soluble or water dispersible cationic material, which compositions are suitable for use as temporary hair colors.

The water soluble melanin derivatives suitable in the compositions and methods of the present invention are hereinafter referred to as "solubilized melanins," which terminology is believed to be consistent with the nomenclature used in the Wolfram article and used generally in the melanin chemistry art. The solubilized melanins useful in the compositions of the present invention are obtained by chemically modifying melanin in such manner as to impart water solubility. An essential aspect of the present invention is that the solubilized melanin in combination with a water soluble or water dispersible cationic material provides a hair dye composition which promotes affinity of the solubilized melanin for the hair. Thus, the solubilized melanin useful in the present invention is believed to form a complex with the cationic material that has such affinity for the hair. It is further believed that the solubilized melanin contains one or more anionic substituent group that not only aid in its solubilization but also permit complexation with the cationic material. Such solubilized melanin is hereinafter referred to as anionic solubilized melanin. Melaninic materials that are dissoluble in water but which do not complex with a cationic material, for example, the melanin materials described in U.S. 5,006,331 to Gaskin, are not suitable in the compositions of the present invention. Typically, the solubilized melanins used herein have a water solubility of at least 0.1%. While not limiting, the solubilized melanins generally do not have a water solubility in excess of about 10%. Generally, the water solubility ranges from about 0.1 to about 5%. As used herein the term "melanin" refers to the insoluble pigment.

Preferably, the solublized melanin of the present invention is made, as taught by the above-mentioned Wolfram reference, by reacting melanin with hydrogen peroxide in dilute aqueous alkaline solution, generally at room temperature. The Wolfram article is incorporated herein by reference thereto. The reaction proceeds typically for 30 minutes to several hours, preferably for 30 to 120 minutes, depending on the source the melanin and the concentrations of the reactants. The reaction is terminated well before the peroxide begins to bleach the melanin species present in the reaction mixture.

It is believed, based upon the observations of the hair dyeing properties of the compositions of the present invention, that the peroxide reacts with the melanin in such manner as to provide carboxylate groups to the structure of the melanin, which groups are anionic in aqueous media having a pH above 4, preferably approximately neutral, and most preferably alkaline. While solubilized melanin as obtained above may be isolated by acidification of the aqueous reaction medium, it is not preferred to do so as there is some evidence to suggest that solublized melanin in solid form ages and is less suitable in the preparation of the compositions of the present invention. Accordingly, the soluble melanin is preferably used in the form of dilute aqueous solution having a pH above 4, preferably from about 6 to about 10, most preferably from about 7 to about 8. Freshly prepared solubilized melanin in solid form may also be used with good success.

The solubilized melanin that is useful in this invention may be obtained from naturally-occurring, chemically synthesized, or biosynthetic melanin. Thus, melanins may be isolated from a variety of natural sources, including human, primate, bovine and other animals. In particular, squid melanin (sepia melanin) is commercially available. As well known in the art biosynthetic melanin can be made by reaction of dopa and tyrosinase. Similarly, various synthetic routes for making melanin are known, in particular, by the oxidation of dopa under controlled conditions. The source of the melanin is not critical. As used herein, the term "melanin" refers to the insoluble pigment. The solubilized melanin that is suitable for use with this invention may be obtained by any method that imparts an anionic character to the melanin molecule, i.e., solubilized melanin capable of forming a complex with the water soluble or water dispersible cationic material.

The amount of solubilized melanin required in the composition of this invention will vary according to factors such as the carrier used, the initial hair color of the consumer prior to dyeing, and the desired end hair color. Based on applicant's theory of the invention, the amount of solubilized melanin present in the composition would also depend upon the degree to which it complexes with the cationic material, i.e., the extent of anionic charges present on the melanin molecule. In this regard, the anionic character of the solubilized melanin obtained in accordance with the Wolfram article can be varied depending upon the severity and extent of the reaction between melanin and hydrogen peroxide. Thus, a more soluble material will be obtained with increasingly severe reaction conditions or longer duration of contact with peroxide. A tinctorially effective amount of solubilized melanin should be used. In general, however, the amount of solubilized melanin required is at least about 0.1%, typically from about 0.1% up to its solubility limit in the composition, but generally less than about 5.0%, and preferably from about 0.2 to about 3.0%, all concentrations being on a weight basis.

A water soluble or water dispersible cationic material is the second essential constituent of the hair dye composition, along with the solubilized melanin. While not wishing to be bound by any particular theory, it is believed that the cationic material complexes with the solubilized melanin molecule, especially anionic solubilized melanin, which complex has an affinity for hair. Accordingly, the complex imparts a temporary color to the hair that, in view of its affinity for the hair, does not bleed when in contact with water. The color is also resistant to fading by sunlight, does not stain skin when properly applied to hair, and is easy to use. The hair color is easily removed by shampooing, which appears to negate the affinity of the complex for the hair. By "water soluble" or "water dispersible" is meant that an amount of cationic material sufficient to complex with the soluble melanin is either dissolved or suspended in the aqueous hair dye composition. Generally, the solubility of the cationic material is at least 0.1 g/100 g of composition, preferably from about 0.5 to 10 g/100 g of composition.

As hereinafter used, "cationic material" means a water soluble or water dispersible cationic material. The cationic materials that may be used in the present invention must, when combined with the solubilized melanin, be capable of forming a composition that is suitable for use as a temporary hair color. That is, the mixture of cationic material and solubilized melanin must be either water soluble or water dispersible under the conditions at which they will be used. Preferably, the cationic material and solubilized melanin will form a stable homogeneous solution or emulsion.

Such cationic materials include cationic surface active agents, cationic surfactants, cationic polymers, and salts thereof. Compounds that assume a cationic character at a certain pH are also cationic materials in accordance with this invention. Suitable cationic materials that may be used are set forth, generally, in the CTFA Cosmetic Ingredient Handbook (1st Ed., 1988) at pages 40-42 (quaternary ammonium compounds) and in McCutcheon's Emulsifiers and Detergents (North Amer. Ed. 1987) at page 318 (identifying cationic and amphoteric surface active materials) . Suitability may be determined by one of ordinary skill in the hair dye art by simple experimentation. Suitable cationic materials are positively charged tetra-substitutednitrogenderivatives having at least one counterion which is an anionic moiety, e.g., a halide or methosulfate. Using the nomenclature of the CTFA Handbook, which is widely used and accepted by chemists in the cosmetics art, illustra¬ tive cationic materials are alkyl trimonium halides, alkylalkonium halides and the dialkyldimonium halides, wherein the alkyl groups have about 10 to about 22 carbons and the halide is Cl or Br, for example, cetrimonium chloride, dicetyldimonium chloride, myristrimonium chloride, stearalkonium chloride, etc.; quaternium compounds, for example, quaternium-16. quaternium-26, quaternium 60 etc.; polymeric quaternium compounds, for example, polyquaternium l, polyquaternium- 6, polyquaternium-7, polyquaternium-11, etc.; cationic resins such as guar hydroxypropyltri onium chloride and chitosan; and amphoteric surface active agents such as sodium cocoamphopropionate. The cationic material should be water soluble or water dispersible within the concentration ranges contemplated herein, in order to effect complexation with the solubilized melanin.

Preferred are the alkyltrimonium and dialkyldimonium chlorides, especially stearatrimonium chloride and dicetyldimonium chloride; polyquaternium-6 which is a polymer of dimethyldiallyl ammonium chloride sold under the trade name Merquat 100; polyquaternium-39 which is a terpolymer of acrylic acid, dimethyldiallyl ammonium chloride and acrylamide sold under the trade name Merquat 3330 and polyquaternium-11 which is a polymer obtained by reaction of dimethyl sulfate and a copolymer of vinyl pyrrolidone and dimethylaminomethacrylate sold under the trade names Gafquat 734 and 755.

The cationic material is present in an amount sufficient to form the aforementioned complex in the composition in sufficient concentration to effect the temporary color to hair. Preferably, substantially all of the cationic material and the solubilized melanin are complexed. Thus, the amount of cationic material present in the composition will depend on the number of cationic charges borne by the cationic material, as well as the number of anionic charges to be neutralized on the solubilized melanin. While some degree of experimentation may be required to precisely determine the amount of cationic material, in general, the com- position should contain from about 0.1 to about 20%, preferably from about 0.1 to about 10%, most prefereably from 0.2 to 5% cationic material by weight of the total composition. The weight ratio of solubilized melanin to cationic material varies widely. In general, this weight ratio will be from about 1:4 to about 10:1, preferably from about 1:1 to about 5:1.

The compositions of this invention are stable for a period of time, as demonstrated in Example 9. That is, hair can be temporarily dyed immediately after the solubilized melanin is combined with the cationic material, or application of the composition can be delayed.

Although the pH of the composition may not be so low or high as to damage hair, the composition is useful at a wide range of pH values. The correct pH for a particular composition is a function of the type of cationic material used and the amount: of solubilized melanin. In general, however, the pH of the composition will be about 3 to about 10, preferably 4 to 8.

In addition to the solubilized melanin and the cationic material, it may be desirable to include cosmetically acceptable carriers in the compositions of this invention. Acceptable carriers vary from simple solutions or dispersions with aqueous or alcoholic solvents, to complex mixtures that contain thickening agents. The carriers that may be used in accordance with this invention must be compatible with solubilized melanin.

It may also be desirable to include in the compositions of this invention adjuvants or additives that are commonly found in hair color compositions, in amounts effective to provide their intended function. Such adjuvants or additives include solvents, solubilizing agents, thickening agents, alkalizing agents, chelating agents, preservatives and fragrances.

The solvents that may be used include organic solvents or solvent systems that are compatible with solubilized melanin. A number of organic solvents are known in the art that are useful for such purposes. These organic solvents include alcohols, particularly alkyl alcohols of 1-6 carbons, especially ethanol and propanol; and glycols of up to about 10 carbons, especially diethyleneglycol, monobutyl ether, carbitols, and benzyl alcohol.

The thickening agents that may be used in the compositions of this invention include: polyvinylpyrrolidone, gum arabic, cellulose derivatives such as methylcellulose or hydroxyethylcellulose, and inorganic thickeners such as bentonite. The additional solubilizing agents that may be used in the compositions of this invention include ethoxylated fatty alcohols.

The preservatives that may be used in the compositions of this invention include: methyl- and propyl paraben, 2-phenoxyethanol, DMDMH, and Kathon CG.

The hair color compositions of this invention may be prepared by methods known in the art generally by simple admixture of the various constituents. However, it is generally preferred, especially when the final product pH will be acidic, to use an aqueous solution of the solubilized melanin. It is further preferred to form a premix of the solubilized melanin and the cationic material to which the remaining constituents are added.

This invention also provides a process for temporarily coloring hair, which comprises applying to the hair an aqueous composition comprising solubilized melanin and at least one cationic material. The compositions may be applied to the hair by conventional techniques known in the art. For example, they can be poured over the hair or applied with an applicator. The amount of time for which the dye composition must be in contact with the hair is not critical. It may vary from about 2 minutes to about 50 minutes, but is usually from about 5 minutes to about 30 minutes.

In another embodiment of the invention, the hair may be dyed by forming the hair dye complex obtained from the interaction of the solubilized melanin and the cationic material directly on the hair. Thus, the process may be practiced by applying to the hair two aqueous compositions sequentially and without intermediate rinsing, one of said two aqueous compositions containing the solubilized melanin and the other containing the cationic material. The hair dyeing complex is formed on the hair in situ and is evenly distributed by gentle massage of the scalp. In this embodiment the amounts of the solubilized melanin and cationic material are the same as when a single aqueous composition is employed. Accordingly, the concentrations of both essential constituents are seen to be based on the total weight of the two separately applied compositions. Preferably, the composition containing the cationic material is first applied to the hair, followed by application of the solubilized melanin-containing composition. The following examples are illustrative of the present invention and should not be construed as limiting the scope of this invention in any manner. In each of the following examples, sepia melanin was isolated from cuttlefish ink sacs and was used to prepare solubilized melanin according to the method described in Wolfram, et al., J. Soc. Cosmetic Chemist, 21:875-900 (1970).

The Hunter tristimulus values used below are measures of reflected light and describe color using three parameters: L, a, and b. When L = 0, the color is black, and when L = 100, the color is white. The more positive "a" is, the redder the color; the more negative "a" is, the greener the color. The more positive "b" is, the yellower the color; the more negative "b" is, the bluer the color. The Hunter colorimetry device and system is used widely in evaluating the color of hair.

EXAMPLE 1

40 mg of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml of water (Solution 1) . 40 mg dicetyldimonium chloride was added to 5 ml of water and stirred until homogeneous (Solution 2) .

Solution 1 was stirred into Solution 2 (Solution 3) . The pH of the 10 ml of combined solutions was 7.1.

A tress of Piedmont hair was treated for 2 minutes with Solution 3. The tress was then blotted dry with paper and dried with a hair dryer. The tress was several shades darker than its original color. The results are set forth in Table 1. No. Treatment Conditions Hunter Color Values Visual Color L a

1.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonde

1.2 Dyed Piedmont tress 45.4 2.6 14.5 dark blonde

The dyed tress retained its color after it was rinsed with water, but was restored to its original color after it was shampooed.

EXAMPLE 2

The procedure described in Example 1 was repeated, except, prior to being applied to the hair, the pH of Solution 3 was adjusted to 4.4 using 0.1 M HC1. The results are set forth in Table 2.

NOj. Treatment Conditions

2.1 Undyed Piedmont tress

2.2 Dyed Piedmont tress

The procedure described in Example 1 was repeated except, prior to being applied to the hair, the pH of Solution 3 was adjusted to 9.0 using dilute ammonia. The results are set forth in Table 3 .

Tftfrl ?

USJ. Treatment Conditions Hunter Color Values VjgwH CPlPf

I_t & b

3.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonde

3.2 Dyed Piedmont tress 45.8 2.8 14.7 dark blonde

BSMffLB 4

40 g of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml of water (Solution 10) . 60 mg of Polyquaternium-ll (Gafquat 755 N) was in 5 ml of water (Solution 20) . Solution 10 was stirred into solution 20 (Solution 30) . The pH of the 10 ml of combined solutions was 7.0.

A tress of Piedmont hair was treated for 2 minutes with Solution 30. The tress was then blotted dry with paper and dried with a hair dryer. The results are set forth in Table 4.

_±. Treatment Conditions

4.1 Undyed Piedmont tress

4.2 Dyed Piedmont tress The procedure described in Example 4 was repeated, except, prior to being applied to the hair, the pH of Solution 30 was adjusted to 4.4 using 0.1 M HC1. The results are set forth in Table 5.

τablβ s

No. Treatment Conditions Hunter Color Values Visual Color L

5.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonde

5.2 Dyed Piedmont tress 52.7 0.9 15.8 medium blonde

WEMPEB β

20 g of freshly prepared solubilized melanin in powder form was dissolved in 3 ml of water (Solution 100) . 160 mg of Polyquaternium-ll (Gafquat 755 N) was dissolved in 3 ml of water (Solution 200) . Solution 100 was stirred into solution 200 (Solution 300). The pH of the 6 ml of combined solutions was 6.8.

A tress of Piedmont hair was treated for 2 minutes with Solution 300. The tress was then blotted dry with paper and dried with a hair dryer. The results are set forth in Table 6. C

No. Treatment Conditions

6.1 Undyed Piedmont tress

6.2 Dyed Piedmont tress

The procedure described in Example 6 was repeated except, prior to being applied to the hair, the pH of Solution 300 was adjusted to 4.5 using 0.1 M HC1. The results are set forth in Table 7.

Εi≥X Treatment Conditions

7.1 Undyed Piedmont tress

7.2 Dyed Piedmont tress

BSMffftB ^β

40 mg of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml of water (Solution 1) . 40 mg of cationic material was added to 5 ml of water and stirred until homogeneous (Solution 2). Solution: 1 was stirred into Solution 2 (Solution 3). The pH of the 10 ml of combined solution was about 7.2 to 7.3. A tress of Piedmont hair and a tress of gray hair were treated for 10 minutes with a Solution 3. Each tress was then blotted dry with paper and dried with a hair dryer. The results are set forth in Table 8.

Formulation No. 9.1 was prepared by dissolving 40 mg of Polyquat 11 in 5 ml of water (Solution 1) . 40 mg of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml water (Solution 2) . Solutions 1 and 2 were combined (Solution 3).

Formulation No. 9.2 was prepared by dissolving 80 mg of Polyquat 11 in 5 ml of water (Solution 1) . 80 mg of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml of water (Solution 2) . Solutions 1 and 2 were combined (Solution 3). Each Formulation was applied to a tress of Piedmont hair and a tress of gray hair for 10 minutes, both immediately and 24 hours after the Formulation was prepared. The appearance of the solutions did not change during this time. The difference in hair color between the immediate and the 24 hour application is insignificant. The results are set forth in Table 9.

Table 9

Application Time After Formulation Piedmont Hair Gray Hair

Ha_*, wag Prwar Hunter Color Values Hunter Color Values a & It a h

9.1 Immediate 24 hours

9.2 Immediate 24 hours

Control Tress 68.3 -0.8 21.2 33.9 0.3 7.6

It will be apparent to those skilled in the art that the invention described herein can be practiced by other than the embodiments disclosed herein, which are presented for the purposes of illustration and not of limitation, and the present invention is limited only by the claims that follow.

Claims

WE CLAIM :

1. An aqueous hair dye composition comprising from o.l to 10% solubilized melanin in combination with 0.1 to 20% water soluble or water dispersible cationic material and water, said combination promoting affinity of the solubilized melanin for the hair, whereby application of the hair dye composition to the hair imparts thereto a temporary hair color.

2. The composition of Claim 1 wherein the cationic material is selected from the group consisting of cationic surface active agents, cationic surfactants, cationic polymers.

3. The composition of Claim 2 wherein the cationic material is a cationic surfactant selected from the group consisting of alkyltrimonium, alkylalkonium and dialkyldimonium halides wherein the alkyl group has from about 10 to about 22 carbons, and quaternium compounds.

4. The composition of Claim 3 wherein the cationic material is selected from the group consisting of cetrimonium chloride, dicetyldimonium chloride, myristrimonium chloride and steartrimonium chloride. 5. The composition of Claim 2 wherein the cationic material is a cationic polymer.

6. The composition of Claim 5 wherein the cationic polymer is selected from the group consisting of polyquaternium-1, polyguaternium-6, polyquaternium-7, polyquaternium-ll and polyquaternium-39.

7. The composition of Claim 2 wherein the cationic material is a cationic resin selected from the group consisting of guar hydroxypropyl trimonium chloride and chitosan.

8. The composition of Claim 2 wherein the cationic material is an amphoteric surface active agent.

9. The composition of Claim 8 wherein the amphoteric surface active agent is sodium cocoamphopropionate.

10. The composition of Claims 1, 3, 4, 6 or 7 wherein the solubilized melanin is anionic solubilized melanin that forms a complex with the cationic material.

11. The composition of Claims l, 3, 4, 6 or 7 wherein the solubilized melanin is obtained by the reaction of melanin with hydrogen peroxide.

12. The composition of Claim 11 wherein the solubilized melanin is present in an amount of from about 0.1 to about 5%, wherein the cationic material is present in an amount of from about 0.1 to 5%, and wherein the pH of the composition is from about 3 to about 10.

13. A method of temporarily dyeing hair comprising contacting the hair with a hair dyeing amount of a complex having an affinity for hair, said complex being obtained by the interaction between a solubilized melanin and a water soluble or water dispersible cationic material in an aqueous medium.

14. The method of Claim 12 wherein the solubilized melanin is obtained by reaction of melanin with hydrogen peroxide.

15. A method of temporarily dyeing hair comprising applying to the hair an aqueous composition containing from about 0.1 to 10% anionic solubilized melanin and 0.1 to 20% water soluble or water dispersible cationic material, said composition having a pH of from about 3 to about 10. 16. The method of Claim 14 wherein the solubilized melanin is obtained by reaction of melanin with hydrogen peroxide.

17. A method of temporarily dyeing hair comprising contacting the hair with a first aqueous composition and thereafter contacting the hair with a second aqueous composition, one of said first or second compositions containing an anionic solubilized melanin and the other of said first or second compositions containing a water soluble or water dispersible cationic material.

18. The method of Claim 16 wherein the anionic solubilized melanin is obtained by reaction between melanin and hydrogen peroxide.

19. The method of Claim 16 wherein the cationic material is present in said first aqueous composition.