CA2154750A1 - Compositions and methods for temporarily coloring hair using solubilized melanin - Google Patents
Compositions and methods for temporarily coloring hair using solubilized melaninInfo
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- CA2154750A1 CA2154750A1 CA002154750A CA2154750A CA2154750A1 CA 2154750 A1 CA2154750 A1 CA 2154750A1 CA 002154750 A CA002154750 A CA 002154750A CA 2154750 A CA2154750 A CA 2154750A CA 2154750 A1 CA2154750 A1 CA 2154750A1
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- melanin
- cationic
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
- A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
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- Cosmetics (AREA)
Abstract
Compositions comprising using 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
~ W 0 94/10968 ~ 1 ~ 4 7 ~ ~ PCT/US93/11174 .
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.
BAC~GRO~ND OF T~ 1~,V~. ~U..
This invention relates to compositions and methods for temporarily coloring hair using a melAnin derivative that is obt~i n~l by chemi~A lly modifying melanin to impart water solubility, which mel An in derivative is characterized by anionic substituent groups when solubilized.
Melanin is the naturally G~11 ing pigment that gives hair its color. A general ~isctlccion of the properties and chemistry Of mel:~n;r~c may be found in Prota, P~G~e38 Tn The Che~ictry 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 mel~r~in~ with age, causes hair to turn gray. Altho~gh gray hair can be colored using chemical dyes, most people prefer to dye their hair with natural pigments, such as melAni~-hA~^~ dyes.
In the past, one of the be~t 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 oY;~t 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 ~is~vantages.
The primary disadvantage is that the hair colors W094/10968 , PCT/US93/11 2~ 5475~
initially producQd with mel~nin precursors are undesirable achromatic colors (cold grays and blacks).
Melanin precursor-dyed hair must undergo a ~~on~
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 precur&ors are expensive and, becau~e 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 muct 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 mel A~i n is easily rubbed off the hair and leaves hair feeling rough.
Therefore, there exists a need in the art for a cnmrocition ~hat pro~ e~, 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 contac~ with water; is inexpensive; will not stain skin; and is simple to wor~ with. Applicants have surprisingly found that an aqueous composition, ~ W094/10968 2 1 5 4 7 ~ O PCT/US93/11174 comprising a water soluble me~ni n (as hereinafter r 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 (~ in) discloses the use of melanin that has been solubilized by triethanolamine and oxidized by ferric chloride. The re~ultant suspension mixture of melanin, triethanolamine and ferric chloride is used to obtain compositions for skin protection, for wound hP~ q and for streng~hPning hair. In an alternatc method, the melanin is rendered water soluble by mildly hydrolyzing the mel~n; ~ using Trypsin in an alkaline medium for several days at room temperature.
Melanin i~ present in the skin protectant compositions of ki~ in an amount of from about O.OOl to about 0.09~, along with from about O.OOOl~ to about 0.27% ferric chloride, both being on a weight basis. The skin protectant composition ~urther contains up to about 5~ by weight triethanolamine. While not providing a range of concentration for the amount of mel Ani n hydrolysate for the hair protectant compositions according to her invention, r,~c~i~ 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 's melA~in hydrolysate is wholly insufficient to impart a color to hair. Moreover, neither of ~7A Cki n ~ s methods provide a mel~ material of an anionic character.
Wolfram, et al, The Me~h~nicm of Hair Bleaching, J.
Soc. Cosmet. Chem., 2l:875-sO0 (1970), discloses extraction of melanin from hair by acid hydrolysis, and considers the reaction of m~l Ani ~ pigment with hydrogen peroxide. Wolfram isolates the peroxide reacted ~PlAnin by destroying the peroxide with platinum black after a WO94/10968 PCT/US93/11 ~
2 ~ 5 ~ 4 -reaction period of sixty minutes.
PCT Application Wo 91/17738 discloses the use of soluble mel~nin derivatives in a process for producing lightly colored mel~n;n~ that are aesthetically suitable for USQ in cosmetic composition ~ W094/10968 2 1 ~ 4 7 ~ O PCT/US93/11174 8n~Y OF ~ TNVRUTTO~
It i8 an object of this invention to provide an aqueous composition for temporarily coloring hair using water soluble melanin derivative~.
It is also an objec~ of this invention to provide a composition that will produce a temporary natural-loo~ing 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 thi~ invention to provide an inD~p~n~ive composition for temporarily coloring hair using water soluble melanin derivatives.
It is also an object of this invention to provide a compo~ition 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.
W094/10968 PCT/US93/1 ~
21547~ 6 -D~Tr~n n~TPT~ON QF TR~ l~v~
The pre~ent invention provides aqueous compositions comprising water soluble ma- An; n and at least one water soluble or water ~i-c~rsible cationic material, which compositions are suitable for use as temporary hair colors.
The water soluble r-l Ani n derivatives suitable in the compositions and methods of the present invention are hereinafter referred to as ~solubilized mel~ni~ which terminology is believed ~o be consistent with the nomenclature used in the Wolfram article and used generally in the melanin chemigtry art. The solubilized melanins usaful in the compositions of the present invention are obtained by chemically modifying melanin in such manner a~ to impart water golubility. 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 contain~ one or more anionic substituent group that not only aid in its solubilization but also permit complexation with the cationic material.
Such solubilized melanin i~ hereinafter referred to as anionic solubilized mel A~i n . Mel An; ni C 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 GA~;n, are not suitable in the compositions of the present invention. Typically, the solubilized melA~in~ used herein have a water ~ W~94/10968 2 1 5 4 7 ~ O PCT/US93/11174 v - 7 -solubility of at least 0.1%. While not limiting, the solubilized mel~ni nC generally do not have a water solubility in ~Yc~c of about lO~. Generally, the water solubility ranges from about O.l to about 5%. As used herein the term '~m~l~ni~ refers to the insolu~le pigment.
Preferably, the solublized mel~;n of the present invention is made, 8~ taught by the above-mentioned Wolfram reference, by reacting melanin with hydrogen peroxide in dilute aqueous alk~ 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, dep~n~in1 on the source the melanin and the rQn~q~trations of the reactants. The reaction is terminated well before the peroYi~ begins to bleach the melanin species present in the reaction mixture.
It i8 believed, based upon the observations of the hair dyeinq 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 ~1Anin 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 ~ugge~t that solublized melAni~ in solid form ages and is less suitable in the preparation of the compositions of the present invention. Accordingly, the soluble melanin i8 preferably used in the form of dilute aqueous solution having a pH above 4, preferably from about 6 to about lO, most preferably from about 7 to about 8. Freshly -W094/1~68 PCT/US93/11 ~
2i~4~ 8 -prepared solubilized melanin in solid form may also be used with good sl~r~e~.
The solubilized melanin that is useful in this invention may be ob~ e~ from naturally o~ ing, chemically synthesized, or ~iosynthetic mel~ni~. Thus, melAnin~ may be isolated from a variety of natural sources, including human, pri~te~ 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 rout~s 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" refars 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 me~ required in the composition of this invention will vary according to factors such as the carrier used, the initial hair color of the cQn~mer prior to dyeing, and the desired end hair color. Bafied 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 n~ i nq upon the severity and extent of the reaction between melanin and hydrogen peroxide. Thus, a more W094/10968 ~1 5 4 7 S ~ PCT/US93/11174 soluble material will be obt~i n~ with increasingly SQVere reaction conditions or longer duration of contact with peroxide. A tinctorially effective amount of solubi~ A melanin should be used. In general, however, the amount of solubilized mel~ni n required is at leaQt 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 a~out 3.0~, all concentrations being on a weight basis.
A water soluble or water dispersible cationic material is the second essQntial constituent of the hair dye composition, along with the solubilized melanin.
While not wishing to be bound by any particular theory, it i8 belisved 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 appear~
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 susr~n~ in the a~ueous hair dye composition. Generally, the solubility of the cationic material is at least 0.1 g/100 g of compo~ition, 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.
2 15 D~ r~
The cationic materials that may be used in the pre~ent in~ention 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 501ubilized melAnin will form a stable homogen~o~lc 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 thi~ invention. Suitable cationic materials that may be used are ~et forth, genQrally, in the CTFA Cosmetic Ingredient ~nAhook (lst Ed., 1988) at pages 40-42 (quaternary ~onium 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 chargedtetra-substituted nitrogenderivatives having at least one counterion which is an anionic moiety, e.g., a halide or methosulfate. Using the nomenclature of the CTFA ~nAhook~ 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 group~ have about 10 to about 22 carbons and the halide is Cl or Br, for example, cetrimonium chloride, dicetyldimonium chloride, myristrimonium chloride, ~tear~l ko~ i um chloride, etc.;
quaternium compounds, for example, quaternium-16, W094/10968 2 1 ~ 4 7 5 0 PCT/US93/ill74 quaternium-26, quaternium 60 etc.; polymeric quaternium compounds, for example, polyquaternium 1, polyquaternium-6, polyquaternium-7, polyquaternium-11, etc.; cationic resin3 such as guar hydroxypropyltrimonium chloride and chitosan; and amphoteric surface active agents such as sodium coco~mphopropionate. The cationic material should be water soluble or water dispersible within the conc~ntration ranges contemplated herein, in order to effect complexation with the solubilized mel A~i n .
Preferred are the alkyltrimonium and dialkyldimonium chlorides, especially stearatrimonium chloride and dicetyldimonium chloride; polyquaternium-6 which is a polymer of dimethyldiallyl a lonium chloride sold under the trade name Merquat 100; polyquaternium-39 which i~ a terpolymer of acrylic acid, dimethyldiallyl ammonium chloride and acrylamide sold under the trade name Merquat 3330 and polyquaternium-ll which is a polymer obt~in~ 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 aforementio~ complex in the composition in sufficient cQ~c6~tration to effect the temporary color to hair. PrQferably, sub~tantially all of the cationic material and the solubilized me~ are complexed. Thus, the amount of cationic material presQnt in the composition will dep~nd 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-WO94/10968 PCT/US93/11 ~
2i5 ~
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 ~l An i~ to cationic m2t~rial varie~ 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 composition 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 mel Ani ~ 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 abou~ 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 thicken; ng 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 WO94/10968 21~ 4 7 5 0 PCT/US93/11174 that are commonly found in hair color compositions, in amounts effectivQ to provide their int~ 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 system~ that are compatible with solubilizQd m~lanin. A numbsr of ~rganic solvQnts 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 lO 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 thirkPners 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 W094/10968 PCT/US93/11 ~
2i~
premix of the solubilized mel~ni~ and the cationic material to which the rema; n; nq 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 t~r~n;ques known in the art. For example, they can be poured over the hair or applied with an applicator. ~he 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 abou~ 30 minutes.
In another embodiment of the invention, the hair may be dyed by forming the hair dye complex obt~;n~ from the interaction of ~he solubilized melanin and the cationic material directly on the hair. Thus, the proces~ 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 masgage of the scalp. In this emhoAiment the amounts of the solubilized melanin and cationic material are the same as when a single aqueous composition i8 employed. Accordingly, the concentration5 of both essential constituents are seen to be based on the total weight of the two separately applied compositions. Prefe~ably, the composition containing the cationic material is first applied to the hair, followed by application of the solubilized melanin-contA;~;ng composition.
W094/10968 2 1 ~ 4 7 5 0 PCT/US93/11174 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 mel~in was isolated from cuttlefish ink sac~ and wa~ used to prepare solubilized mela~in 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 5 0~ the color is black, and when L 5 100 ~ 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.
~Mpr~ ~
40 mg of freshly prepared solubilized mel Ani n in particulate form wa~ dissolved in 5 ml of water (Solution l). 40 mg dicetyldimonium chloride was A~ to 5 ml of water and stirred until homogen-~ ~ (Solution 2).
Solution l wa~ stirred into Solution 2 (Solution 3).
The pH of the lO ml of combined solutions was 7.l.
A tress of Piedmont hair was treated for 2 minute~
with Solution 3. The tress was then blotted dry with paper and dried with a hair dryer. The tress was several ch~e~ darker than its original color. The results are set forth in Table l.
21547~ - 16 -T~bl~ 1 No. Tr~at~nt co~ttions ~unter Color Values Vt 8ual Color ~ ~ b.
1.1 Undyed Piedmont tress64.3 -0.8 19.3 light blonde 1.2 Dyed Piedmont tress45.4 2.6 14.5 dark blonde The dyed tress ret~;n~ its color after it was rinsed wi~h water, but wag restored to its original color after it was shampooed.
~MPr.R 2 The proce~t~re 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 ~C1. The results are set forth in Table 2.
T~hl- 2 No. Treatmont Con~it~on~ ~nter Color Values Vi~ual Col~r ~2 2.1 Undyed Piedmont tress64.3 -0.8 19.3 light blonde 2.2 Dyed Piedmont tress37.5 3.1 11.5 light brown ~aMP~-~ 3 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 ~ W094/10968 2 1 5 ~ 7 S O PCT/US93/11174 Table 3.
T~hl- 3 No. Tr~at~^nt Con~ttion~ ~nnt~r Color V~lu~8 Vi8~ Col~
~ a b 3.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blond~
3.2 Dyed Piedmont tress 45.8 2.8 14.7 dark blonde 40 mg of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml of water (Solution 10). 60 mg of Polyquaterniu~-11 (Gafquat 755 N) was in 5 ml of water (Solution 20). Solution lo was stirred into solution 20 (solution 30). The pH of the 10 ml of combined solutions was 7Ø
A tress of Piedmont hair was treated for 2 minutes with Solution 30. The tress wa~ then blotted dry with paper and dried with a hair dryer. The rQsults are sQt forth in Table 4.
T~ o 4 Treat~^nt Con~ition~ ~unter Color Values Visual Color ~ a b 4.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonde 4.2 Dyed Piedmont tress 52.0 1.1 15.1 medium blonde WO94/10968 PCT/US93/11 ~
2 lS 4r~' S ~ -- 18 ~AMPT.~ 5 The ~o~e~ule described in Example 4 was~repeated, except, prior to being applied to the hair, the pH of Solution 30 was adjusted to 4.4 u~ing 0.1 M HCl. The results are set forth in Table 5.
Table 5 NQ. Treatmont Con~ition~ ~unter Color Values Visual Color ~ a b 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 ~londe ~Mpr~ 6 20 mg 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 regults are set forth in Table 6.
~ W094/10g68 21~ ~ 7 ~ ~ PCT/US93/11174 ~I~hl O 6 No. Tre4t~ent Con~tion~ Eunter Color Valuos Visual Color ; ~ ~ b 6.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonds 6.2 Dyed Piedmont tres~ 51.9 1.0 14.9 medium blonde ~a~r-~ 7 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 HCl. The results are set forth in Table 7.
~ 7 No. --~nt Con~t~on~~nt ~ Colo~ V~luc8 V'~8~ t COl~--b 7.1 Undyed Piedmont tre~s 64.3 -0.8 19.3 light blonde 7.2 Dyed Piedmont tres~49.8 1.9 15.3 medium blondl7 ~MP~ 8 40 mg of freshly prepared solubilized mel~ni n 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:l was stirred into Solution 2 tSolution 3). The pH of the 10 ml of combined solution was about 7.2 to 7.3.
W094/10968 PCT/US93/11 ~
2 15 ~ 20 -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 dri~d ~ith a hair dryer. The results are set forth in Table 8.
~'-t~ Piod~t~nt ~a~r Gr~Y ~a~r ~. ~at~riAl ~l-nt~r Color V~lue~ ~nnter color valuo~
~ ~ b ~ ~ k 8.1 Dicetyldimonium 52.6 2.1 16.9 29.9 1.4 6.8 chloride 8.2 Merquat 3330 54.7 1.2 17.0 32.3 0.5 7.3 8.3 Polyquat 11 54.4 1.4 17.5 29.3 0.8 6.1 F~X AMPT.F! 9 Formulation No. 9.1 wa~ prepared by dissolving 40 mg of Polyquat 11 in 5 ml of watQr (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 wa~ prepared by dissolving 80 mg of Polyquat 11 in 5 ml of water (Solution 1). 80 mg of freshly prepared solubilized melAn;n in particulate form was dissolved in S ml of water (Solution 2). Solutions 1 and 2 were combined (Solution 3). Each Formulation was applied to a tress of Piedmont W094/10968 2 1 ~ ~ 7 5 0 PCT/US93/11174 hair and a tre~s of gray hair for lO minutes, both immediately and 24 hours after the Formulation wa~ prepared. The appearance of the solution~ did not change during this time. The diffeL. _e in hair color b~tween the imm~diate and the 24 hour application is insignificant. The regults are set forth in Table 9.
T~ Q 9 Applic~tio~ Ti -Aft~r ~or~ulation El~gmont ~t r ~y ~ t No. ~ p-o~r~ nt~r Color V~luos Rnnt~r Color Va1u-~
g.l Immediate 52.01.7 16.3 31.5 0.7 6.6 24 hours 54.01.3 17.7 31.4 l.0 6.8 9.2 Immediate 50.82.0 l5.9 28.4 1.4 6.5 24 hours 48.72.1 l5.0 29.5 1.3 6.7 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 ~mbodimQnts disclosQd herQin, which are presented for the pUl~ -e~
of illustration and not of limitation, and the present invention is limited only by the claims that follow.
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.
BAC~GRO~ND OF T~ 1~,V~. ~U..
This invention relates to compositions and methods for temporarily coloring hair using a melAnin derivative that is obt~i n~l by chemi~A lly modifying melanin to impart water solubility, which mel An in derivative is characterized by anionic substituent groups when solubilized.
Melanin is the naturally G~11 ing pigment that gives hair its color. A general ~isctlccion of the properties and chemistry Of mel:~n;r~c may be found in Prota, P~G~e38 Tn The Che~ictry 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 mel~r~in~ with age, causes hair to turn gray. Altho~gh gray hair can be colored using chemical dyes, most people prefer to dye their hair with natural pigments, such as melAni~-hA~^~ dyes.
In the past, one of the be~t 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 oY;~t 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 ~is~vantages.
The primary disadvantage is that the hair colors W094/10968 , PCT/US93/11 2~ 5475~
initially producQd with mel~nin precursors are undesirable achromatic colors (cold grays and blacks).
Melanin precursor-dyed hair must undergo a ~~on~
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 precur&ors are expensive and, becau~e 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 muct 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 mel A~i n is easily rubbed off the hair and leaves hair feeling rough.
Therefore, there exists a need in the art for a cnmrocition ~hat pro~ e~, 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 contac~ with water; is inexpensive; will not stain skin; and is simple to wor~ with. Applicants have surprisingly found that an aqueous composition, ~ W094/10968 2 1 5 4 7 ~ O PCT/US93/11174 comprising a water soluble me~ni n (as hereinafter r 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 (~ in) discloses the use of melanin that has been solubilized by triethanolamine and oxidized by ferric chloride. The re~ultant suspension mixture of melanin, triethanolamine and ferric chloride is used to obtain compositions for skin protection, for wound hP~ q and for streng~hPning hair. In an alternatc method, the melanin is rendered water soluble by mildly hydrolyzing the mel~n; ~ using Trypsin in an alkaline medium for several days at room temperature.
Melanin i~ present in the skin protectant compositions of ki~ in an amount of from about O.OOl to about 0.09~, along with from about O.OOOl~ to about 0.27% ferric chloride, both being on a weight basis. The skin protectant composition ~urther contains up to about 5~ by weight triethanolamine. While not providing a range of concentration for the amount of mel Ani n hydrolysate for the hair protectant compositions according to her invention, r,~c~i~ 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 's melA~in hydrolysate is wholly insufficient to impart a color to hair. Moreover, neither of ~7A Cki n ~ s methods provide a mel~ material of an anionic character.
Wolfram, et al, The Me~h~nicm of Hair Bleaching, J.
Soc. Cosmet. Chem., 2l:875-sO0 (1970), discloses extraction of melanin from hair by acid hydrolysis, and considers the reaction of m~l Ani ~ pigment with hydrogen peroxide. Wolfram isolates the peroxide reacted ~PlAnin by destroying the peroxide with platinum black after a WO94/10968 PCT/US93/11 ~
2 ~ 5 ~ 4 -reaction period of sixty minutes.
PCT Application Wo 91/17738 discloses the use of soluble mel~nin derivatives in a process for producing lightly colored mel~n;n~ that are aesthetically suitable for USQ in cosmetic composition ~ W094/10968 2 1 ~ 4 7 ~ O PCT/US93/11174 8n~Y OF ~ TNVRUTTO~
It i8 an object of this invention to provide an aqueous composition for temporarily coloring hair using water soluble melanin derivative~.
It is also an objec~ of this invention to provide a composition that will produce a temporary natural-loo~ing 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 thi~ invention to provide an inD~p~n~ive composition for temporarily coloring hair using water soluble melanin derivatives.
It is also an object of this invention to provide a compo~ition 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.
W094/10968 PCT/US93/1 ~
21547~ 6 -D~Tr~n n~TPT~ON QF TR~ l~v~
The pre~ent invention provides aqueous compositions comprising water soluble ma- An; n and at least one water soluble or water ~i-c~rsible cationic material, which compositions are suitable for use as temporary hair colors.
The water soluble r-l Ani n derivatives suitable in the compositions and methods of the present invention are hereinafter referred to as ~solubilized mel~ni~ which terminology is believed ~o be consistent with the nomenclature used in the Wolfram article and used generally in the melanin chemigtry art. The solubilized melanins usaful in the compositions of the present invention are obtained by chemically modifying melanin in such manner a~ to impart water golubility. 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 contain~ one or more anionic substituent group that not only aid in its solubilization but also permit complexation with the cationic material.
Such solubilized melanin i~ hereinafter referred to as anionic solubilized mel A~i n . Mel An; ni C 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 GA~;n, are not suitable in the compositions of the present invention. Typically, the solubilized melA~in~ used herein have a water ~ W~94/10968 2 1 5 4 7 ~ O PCT/US93/11174 v - 7 -solubility of at least 0.1%. While not limiting, the solubilized mel~ni nC generally do not have a water solubility in ~Yc~c of about lO~. Generally, the water solubility ranges from about O.l to about 5%. As used herein the term '~m~l~ni~ refers to the insolu~le pigment.
Preferably, the solublized mel~;n of the present invention is made, 8~ taught by the above-mentioned Wolfram reference, by reacting melanin with hydrogen peroxide in dilute aqueous alk~ 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, dep~n~in1 on the source the melanin and the rQn~q~trations of the reactants. The reaction is terminated well before the peroYi~ begins to bleach the melanin species present in the reaction mixture.
It i8 believed, based upon the observations of the hair dyeinq 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 ~1Anin 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 ~ugge~t that solublized melAni~ in solid form ages and is less suitable in the preparation of the compositions of the present invention. Accordingly, the soluble melanin i8 preferably used in the form of dilute aqueous solution having a pH above 4, preferably from about 6 to about lO, most preferably from about 7 to about 8. Freshly -W094/1~68 PCT/US93/11 ~
2i~4~ 8 -prepared solubilized melanin in solid form may also be used with good sl~r~e~.
The solubilized melanin that is useful in this invention may be ob~ e~ from naturally o~ ing, chemically synthesized, or ~iosynthetic mel~ni~. Thus, melAnin~ may be isolated from a variety of natural sources, including human, pri~te~ 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 rout~s 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" refars 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 me~ required in the composition of this invention will vary according to factors such as the carrier used, the initial hair color of the cQn~mer prior to dyeing, and the desired end hair color. Bafied 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 n~ i nq upon the severity and extent of the reaction between melanin and hydrogen peroxide. Thus, a more W094/10968 ~1 5 4 7 S ~ PCT/US93/11174 soluble material will be obt~i n~ with increasingly SQVere reaction conditions or longer duration of contact with peroxide. A tinctorially effective amount of solubi~ A melanin should be used. In general, however, the amount of solubilized mel~ni n required is at leaQt 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 a~out 3.0~, all concentrations being on a weight basis.
A water soluble or water dispersible cationic material is the second essQntial constituent of the hair dye composition, along with the solubilized melanin.
While not wishing to be bound by any particular theory, it i8 belisved 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 appear~
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 susr~n~ in the a~ueous hair dye composition. Generally, the solubility of the cationic material is at least 0.1 g/100 g of compo~ition, 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.
2 15 D~ r~
The cationic materials that may be used in the pre~ent in~ention 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 501ubilized melAnin will form a stable homogen~o~lc 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 thi~ invention. Suitable cationic materials that may be used are ~et forth, genQrally, in the CTFA Cosmetic Ingredient ~nAhook (lst Ed., 1988) at pages 40-42 (quaternary ~onium 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 chargedtetra-substituted nitrogenderivatives having at least one counterion which is an anionic moiety, e.g., a halide or methosulfate. Using the nomenclature of the CTFA ~nAhook~ 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 group~ have about 10 to about 22 carbons and the halide is Cl or Br, for example, cetrimonium chloride, dicetyldimonium chloride, myristrimonium chloride, ~tear~l ko~ i um chloride, etc.;
quaternium compounds, for example, quaternium-16, W094/10968 2 1 ~ 4 7 5 0 PCT/US93/ill74 quaternium-26, quaternium 60 etc.; polymeric quaternium compounds, for example, polyquaternium 1, polyquaternium-6, polyquaternium-7, polyquaternium-11, etc.; cationic resin3 such as guar hydroxypropyltrimonium chloride and chitosan; and amphoteric surface active agents such as sodium coco~mphopropionate. The cationic material should be water soluble or water dispersible within the conc~ntration ranges contemplated herein, in order to effect complexation with the solubilized mel A~i n .
Preferred are the alkyltrimonium and dialkyldimonium chlorides, especially stearatrimonium chloride and dicetyldimonium chloride; polyquaternium-6 which is a polymer of dimethyldiallyl a lonium chloride sold under the trade name Merquat 100; polyquaternium-39 which i~ a terpolymer of acrylic acid, dimethyldiallyl ammonium chloride and acrylamide sold under the trade name Merquat 3330 and polyquaternium-ll which is a polymer obt~in~ 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 aforementio~ complex in the composition in sufficient cQ~c6~tration to effect the temporary color to hair. PrQferably, sub~tantially all of the cationic material and the solubilized me~ are complexed. Thus, the amount of cationic material presQnt in the composition will dep~nd 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-WO94/10968 PCT/US93/11 ~
2i5 ~
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 ~l An i~ to cationic m2t~rial varie~ 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 composition 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 mel Ani ~ 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 abou~ 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 thicken; ng 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 WO94/10968 21~ 4 7 5 0 PCT/US93/11174 that are commonly found in hair color compositions, in amounts effectivQ to provide their int~ 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 system~ that are compatible with solubilizQd m~lanin. A numbsr of ~rganic solvQnts 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 lO 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 thirkPners 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 W094/10968 PCT/US93/11 ~
2i~
premix of the solubilized mel~ni~ and the cationic material to which the rema; n; nq 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 t~r~n;ques known in the art. For example, they can be poured over the hair or applied with an applicator. ~he 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 abou~ 30 minutes.
In another embodiment of the invention, the hair may be dyed by forming the hair dye complex obt~;n~ from the interaction of ~he solubilized melanin and the cationic material directly on the hair. Thus, the proces~ 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 masgage of the scalp. In this emhoAiment the amounts of the solubilized melanin and cationic material are the same as when a single aqueous composition i8 employed. Accordingly, the concentration5 of both essential constituents are seen to be based on the total weight of the two separately applied compositions. Prefe~ably, the composition containing the cationic material is first applied to the hair, followed by application of the solubilized melanin-contA;~;ng composition.
W094/10968 2 1 ~ 4 7 5 0 PCT/US93/11174 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 mel~in was isolated from cuttlefish ink sac~ and wa~ used to prepare solubilized mela~in 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 5 0~ the color is black, and when L 5 100 ~ 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.
~Mpr~ ~
40 mg of freshly prepared solubilized mel Ani n in particulate form wa~ dissolved in 5 ml of water (Solution l). 40 mg dicetyldimonium chloride was A~ to 5 ml of water and stirred until homogen-~ ~ (Solution 2).
Solution l wa~ stirred into Solution 2 (Solution 3).
The pH of the lO ml of combined solutions was 7.l.
A tress of Piedmont hair was treated for 2 minute~
with Solution 3. The tress was then blotted dry with paper and dried with a hair dryer. The tress was several ch~e~ darker than its original color. The results are set forth in Table l.
21547~ - 16 -T~bl~ 1 No. Tr~at~nt co~ttions ~unter Color Values Vt 8ual Color ~ ~ b.
1.1 Undyed Piedmont tress64.3 -0.8 19.3 light blonde 1.2 Dyed Piedmont tress45.4 2.6 14.5 dark blonde The dyed tress ret~;n~ its color after it was rinsed wi~h water, but wag restored to its original color after it was shampooed.
~MPr.R 2 The proce~t~re 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 ~C1. The results are set forth in Table 2.
T~hl- 2 No. Treatmont Con~it~on~ ~nter Color Values Vi~ual Col~r ~2 2.1 Undyed Piedmont tress64.3 -0.8 19.3 light blonde 2.2 Dyed Piedmont tress37.5 3.1 11.5 light brown ~aMP~-~ 3 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 ~ W094/10968 2 1 5 ~ 7 S O PCT/US93/11174 Table 3.
T~hl- 3 No. Tr~at~^nt Con~ttion~ ~nnt~r Color V~lu~8 Vi8~ Col~
~ a b 3.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blond~
3.2 Dyed Piedmont tress 45.8 2.8 14.7 dark blonde 40 mg of freshly prepared solubilized melanin in particulate form was dissolved in 5 ml of water (Solution 10). 60 mg of Polyquaterniu~-11 (Gafquat 755 N) was in 5 ml of water (Solution 20). Solution lo was stirred into solution 20 (solution 30). The pH of the 10 ml of combined solutions was 7Ø
A tress of Piedmont hair was treated for 2 minutes with Solution 30. The tress wa~ then blotted dry with paper and dried with a hair dryer. The rQsults are sQt forth in Table 4.
T~ o 4 Treat~^nt Con~ition~ ~unter Color Values Visual Color ~ a b 4.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonde 4.2 Dyed Piedmont tress 52.0 1.1 15.1 medium blonde WO94/10968 PCT/US93/11 ~
2 lS 4r~' S ~ -- 18 ~AMPT.~ 5 The ~o~e~ule described in Example 4 was~repeated, except, prior to being applied to the hair, the pH of Solution 30 was adjusted to 4.4 u~ing 0.1 M HCl. The results are set forth in Table 5.
Table 5 NQ. Treatmont Con~ition~ ~unter Color Values Visual Color ~ a b 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 ~londe ~Mpr~ 6 20 mg 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 regults are set forth in Table 6.
~ W094/10g68 21~ ~ 7 ~ ~ PCT/US93/11174 ~I~hl O 6 No. Tre4t~ent Con~tion~ Eunter Color Valuos Visual Color ; ~ ~ b 6.1 Undyed Piedmont tress 64.3 -0.8 19.3 light blonds 6.2 Dyed Piedmont tres~ 51.9 1.0 14.9 medium blonde ~a~r-~ 7 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 HCl. The results are set forth in Table 7.
~ 7 No. --~nt Con~t~on~~nt ~ Colo~ V~luc8 V'~8~ t COl~--b 7.1 Undyed Piedmont tre~s 64.3 -0.8 19.3 light blonde 7.2 Dyed Piedmont tres~49.8 1.9 15.3 medium blondl7 ~MP~ 8 40 mg of freshly prepared solubilized mel~ni n 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:l was stirred into Solution 2 tSolution 3). The pH of the 10 ml of combined solution was about 7.2 to 7.3.
W094/10968 PCT/US93/11 ~
2 15 ~ 20 -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 dri~d ~ith a hair dryer. The results are set forth in Table 8.
~'-t~ Piod~t~nt ~a~r Gr~Y ~a~r ~. ~at~riAl ~l-nt~r Color V~lue~ ~nnter color valuo~
~ ~ b ~ ~ k 8.1 Dicetyldimonium 52.6 2.1 16.9 29.9 1.4 6.8 chloride 8.2 Merquat 3330 54.7 1.2 17.0 32.3 0.5 7.3 8.3 Polyquat 11 54.4 1.4 17.5 29.3 0.8 6.1 F~X AMPT.F! 9 Formulation No. 9.1 wa~ prepared by dissolving 40 mg of Polyquat 11 in 5 ml of watQr (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 wa~ prepared by dissolving 80 mg of Polyquat 11 in 5 ml of water (Solution 1). 80 mg of freshly prepared solubilized melAn;n in particulate form was dissolved in S ml of water (Solution 2). Solutions 1 and 2 were combined (Solution 3). Each Formulation was applied to a tress of Piedmont W094/10968 2 1 ~ ~ 7 5 0 PCT/US93/11174 hair and a tre~s of gray hair for lO minutes, both immediately and 24 hours after the Formulation wa~ prepared. The appearance of the solution~ did not change during this time. The diffeL. _e in hair color b~tween the imm~diate and the 24 hour application is insignificant. The regults are set forth in Table 9.
T~ Q 9 Applic~tio~ Ti -Aft~r ~or~ulation El~gmont ~t r ~y ~ t No. ~ p-o~r~ nt~r Color V~luos Rnnt~r Color Va1u-~
g.l Immediate 52.01.7 16.3 31.5 0.7 6.6 24 hours 54.01.3 17.7 31.4 l.0 6.8 9.2 Immediate 50.82.0 l5.9 28.4 1.4 6.5 24 hours 48.72.1 l5.0 29.5 1.3 6.7 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 ~mbodimQnts disclosQd herQin, which are presented for the pUl~ -e~
of illustration and not of limitation, and the present invention is limited only by the claims that follow.
Claims (19)
1. An aqueous hair dye composition comprising from 0.1 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, polyquaternium-6, polyquaternium-7, polyquaternium-11 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 1, 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.
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97861192A | 1992-11-19 | 1992-11-19 | |
| US978,611 | 1992-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2154750A1 true CA2154750A1 (en) | 1994-05-26 |
Family
ID=25526265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002154750A Abandoned CA2154750A1 (en) | 1992-11-19 | 1993-11-17 | Compositions and methods for temporarily coloring hair using solubilized melanin |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0678012A1 (en) |
| AU (1) | AU5611694A (en) |
| CA (1) | CA2154750A1 (en) |
| WO (1) | WO1994010968A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA937753B (en) * | 1992-11-19 | 1994-04-19 | Bristol Myers Squibb Co | Compositions and methods for temporarily coloring hair using chemically synthesized or biosynthetic water-soluble melanin |
| US5702712A (en) * | 1995-12-06 | 1997-12-30 | Clairol, Incorporated | Melanoquaternary compounds and their use as hair dyes and for skin treatment |
| US5686084A (en) * | 1995-12-06 | 1997-11-11 | Clairol Incorporated | Synthesis of quaternary melanin compounds and their use as hair dyes or for skin treatment |
| FR2783520B1 (en) * | 1998-09-21 | 2000-11-10 | Oreal | NEW CATIONIC 4-HYDROXYINDOLES, THEIR USE FOR THE OXIDIZING DYE OF KERATINIC FIBERS, TINCTORIAL COMPOSITIONS AND DYING PROCESS |
| FR2817467B1 (en) * | 2000-12-04 | 2003-01-10 | Oreal | DYE COMPOSITION FOR KERATINIC FIBERS COMPRISING AN ASSOCIATIVE POLYMER AND A POLYMER WITH ACRYLAMIDE PATTERNS, DIALKYLDIALLYLAMMONIUM HALIDE AND VINYL CARBOXYLIC ACID |
| US7837742B2 (en) | 2003-05-19 | 2010-11-23 | The Procter & Gamble Company | Cosmetic compositions comprising a polymer and a colorant |
| US10646552B2 (en) | 2012-01-17 | 2020-05-12 | Tyme, Inc. | Pharmaceutical compositions and methods |
| US10272068B2 (en) | 2012-01-17 | 2019-04-30 | Tyme, Inc. | Pharmaceutical compositions and methods |
| US20130183263A1 (en) | 2012-01-17 | 2013-07-18 | Steven Hoffman | Pharmaceutical compositions and methods |
| US9585841B2 (en) | 2013-10-22 | 2017-03-07 | Tyme, Inc. | Tyrosine derivatives and compositions comprising them |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806344A (en) * | 1987-01-05 | 1989-02-21 | Gaskin Frances C | Sun protectant composition and method |
| US5157075A (en) * | 1990-05-02 | 1992-10-20 | Taenaka Mining Co., Ltd. | Modified melanin |
| WO1992016189A1 (en) * | 1990-10-25 | 1992-10-01 | Yale University | Soluble melanin |
| FR2695033B1 (en) * | 1992-08-25 | 1994-11-25 | Oreal | Water-soluble melanin coloring polymer, process for obtaining it and its use in cosmetic coloring compositions. |
| ZA937753B (en) * | 1992-11-19 | 1994-04-19 | Bristol Myers Squibb Co | Compositions and methods for temporarily coloring hair using chemically synthesized or biosynthetic water-soluble melanin |
-
1993
- 1993-11-17 CA CA002154750A patent/CA2154750A1/en not_active Abandoned
- 1993-11-17 WO PCT/US1993/011174 patent/WO1994010968A1/en not_active Application Discontinuation
- 1993-11-17 EP EP94901569A patent/EP0678012A1/en not_active Withdrawn
- 1993-11-17 AU AU56116/94A patent/AU5611694A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0678012A4 (en) | 1995-11-29 |
| AU5611694A (en) | 1994-06-08 |
| WO1994010968A1 (en) | 1994-05-26 |
| EP0678012A1 (en) | 1995-10-25 |
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