US 2007025 1024A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2007/0251024 A1 Greaves et al. (43) Pub. Date: Nov. 1, 2007

(54) COMPOSITION FOR DYEING KERATIN Publication Classification FIBERS AND AMETHOD OF DYEING HAIR USING SAME (51) Int. Cl. A6IR 8/00 (2006.01) (76) Inventors: Erjeana Greaves, New York, NY (US); (52) U.S. Cl...... 8/405 Jeffrey T. Greaves, New York, NY (US) (57) ABSTRACT Correspondence Address: GREENBERG TRAURIG, LLP A composition for dyeing keratin fibers that contains 0.1 to MET LIFE BUILDING 30 percent of at least one substantially pure plant dye 2OO PARKAVENUE material obtained using solvent or Supercritical CO2 extrac NEW YORK, NY 10166 (US) tion combined with 0.01 to 5 percent of a metal or mineral salt capable of acting as a mordant as a two part hair color (21) Appl. No.: 11/381,061 system. The addition of the encapsulation of one or both components allows the use of the plant dye in combination (22) Filed: May 1, 2006 with the metal or mineral salt in a one part hair color system. US 2007/025 1024 A1 Nov. 1, 2007

COMPOSITION FOR DYEING KERATIN FIBERS of cancer (David Steinman & Samuel Epstein, The Safe AND A METHOD OF DYEING HAIR USING SAME Shopper's Bible, Macmillan, 1995, p. 241). 0006) The main problems with using natural dyes (as FIELD OF THE INVENTION opposed to synthetic hair color formulations) to color hair 0001) This invention relates to hair dyes, specifically to have always been that natural hair dyes produce dull shades the use of substantially pure plant dye substances obtained of color and have poor wash fastness to shampoo. Natural by solvent or supercritical CO2 extraction, with or without sources of dyes, such as plants, contain low concentrations metallic or mineral salts, to make intense, fast-acting, long of colorants, and the dyes that are recovered from those lasting hair dyes. natural sources are often impure and have poor solubility (H. S. Freeman & A. T. Peters, Colorants for Non-Textile BACKGROUND OF THE INVENTION Applications, Elsevier, 2000, pp. 382–453). These problems result in products with long and inconvenient application 0002) Synthetic hair color formulations currently on the times for natural hair color technology. Moreover, most market typically fall into one of two categories: permanent natural hair dyes are offered in powder form, which is and semi-permanent. inconvenient for the user. 0003) Permanent hair color formulations consist prima 0007) There are a number of different natural plant dyes rily of oxidative dye systems based on the dual action of two available. Those plant dyes include, but are not limited to, types of precursors bases (primary intermediates) and indigo, indigo carmine, alizarine, rubiethyric acid, pur modifiers (couplers). Bases are typically aromatic diamines, puroxanthin, rubiadin, morindanigrin, munjistin, morinda diaminophenoles, aminophenols, while couplers are typi diol, carotene, crocetin, bixin, canthaxanthin, lycopene, cap cally m-diamines, m-aminophenols and polyphenols santhin, apocarotenal, Xanthophyll, curcumin, morin, (Charles Zviak, The Science of Hair Care, Marcel Dekker malclurin, luteolin, apigenin, fukugetin, datiscetin, Inc., New York, 1986, pp. 265-268; Joseph Rivlin, The kaempferol, rhamnocitrin, rhamnethin, Zanthorhamnin, Dyeing of Textile Fibers, PCT&S, Philadelphia, 1992, pp. Isorhamnetin, Rhamnazin, Quercetin, Rutin, Gossypetin, 30-52). The wash fastness of permanent dyes is about 30-40 Butin/Butein, Rottlerin, Chlorophyll A/B, Catechin, Fisetin, shampoo cycles. There are, however, a number of issues Lapachol, Juglone, Alkannin, Alkannan, Deoxysantalin, with permanent dyes. The primary amine used in these Atromentin, Awobamin, Carajuirin, Dracorhodin, Ber oxidative dye systems is generally paraphenilene-diamine berine, Betanin, Orcein, Xanthone, Naphthalene, Riboflavin, (PPD), for which there is growing evidence of and concern Anthocyanin, Lawsone, emblica extract, alfalfa extract, over its carcinogenicity and mutagenicity (The Use of black tea extract, green tea extract, white tea extract, and red Permanent Hair Dyes and Bladder Cancer Risk, SCCNFP/ sandalwood. At present, henna (Lawsonia intermis) is the 484/01, 2001). Other oxidative dye system precursors, such most commonly used natural plant dye for hair. However, as the coupler resorcinol, also show toxicity (David Steiman due to the poor solubility and low concentration of Lawsone. & Samuel Epstein, The Safe Shopper's Bible, Macmillan, the pigment in henna, a long application time (as much as 1995, pp. 240-243). The oxidative action of these types of several hours) is required to produce a weak, dull shade of dye systems is provided by hydrogen peroxide at a high pH, color. Moreover, Lawsone “has been examined by SCCNFP which is known to damage hair and irritate the scalp and ... (and). . . its latest opinion on Lawsone . . . (is) Lawsone skin. Most patented developments in the permanent dye area has genotoxicity/mutagenicity potential in vitro and in vivo are aimed at decreasing toxicity, hair damage and irritation and that therefore no safe threshold for Lawsone can be (J. F. Corbett, Hair Coloring, Clinics in Dermatology, Vol. 6, established” (SCCNFP/0798/04, 2004). no. 3, 1988, pp. 96-101). 0008 Furthermore, natural plant dyes generally lack the 0004 Semi-permanent hair color formulations are those color fastness and light fastness of synthetic hair color based on the use of coal tar dyes. Coal tar dyes fall into formulations. Problems with the substantivity of plant-based direct, acid, and basic color index categories. The wash dyes, which is the affinity that a dye has for a particular fiber, fastness of these dyes is about 2-10 shampoo cycles (Charles have existed for centuries. Mordanting has long been used as Zviak, The Science of Hair Care, Marcel Dekker Inc., New a way to increase substantivity of plant dyes. The mordants York, 1986, pp. 242-261). Recent studies in toxicology and function is to form a complex between a polyvalent metal ecology have identified most coal tar dyes, especially direct salt and a dye. The application of a mordant traditionally (as defined by color index) and mono-azo/di-azo (as defined requires at least two steps, and often includes a pre- or post by structure) dyes (the most red and red-orange shades), as treatment as well. That is because the reaction between carcinogens, teratogens and mutagens (David Steinman & mordants and dyes is virtually instantaneous, making it Samuel Epstein, The Safe Shopper's Bible, Macmillan, necessary to apply them separately. 1995, pp. 240-243). Acid dyes in particular are known to stain the scalp and skin. Most patented technologies in this 0009. The use of mordants has been limited in recent area are aimed at decreasing toxicity and irritation, as well years, however, because of their generally high toxicity. The as regulating fastness and leveling. Leveling refers to the most common mordants still in use, although rarely, are process of spreading the color from the dye evenly over the chromium salts used in the leather industry. Other mordants hair. include salts of aluminum and copper (Joseph Rivlin, The Dyeing of Textile Fibers, PCT&S, Philadelphia, 1992, p. 0005) The toxicity of current permanent and semi-per 30-52; H. S. Freeman & A. T. Peters, Colorants for Non manent synthetic hair color formulations is such that many Textile Applications, Elsevier, 2000, pp. 439-448). There U.S. physicians do not recommend hair coloring during are, however, a number of mineral or metal salts that are pregnancy, for people with cancer, or for people at high risk capable of acting as a mordant, yet lack the toxicity of US 2007/025 1024 A1 Nov. 1, 2007

chromium salts or other typical mordants. Those mineral or light and wash fast properties (stable for more than 40 metal salts include, but are not limited to, ferrous gluconate, standard shampoo cycles)—comparable or Superior to per ferrous aspartate, calcium chloride, calcium gluconate, cal manent hair dye formulations—by mixing the Substantially cium aspartate, magnesium gluconate, magnesium aspartate, pure plant dyes with mineral or metallic salts (e.g., Zinc magnesium citrate, magnesium palmitate, Zinc gluconate, gluconate, Zinc aspartate, calcium gluconate, or ferrous Zinc aspartate, and manganese gluconate. gluconate among others) in a two-part or two-step system. 0010. There remains a need for a fast-acting, light fast, These mineral or metallic salts are non-toxic salts that wash fast, color fast, natural hair dye formulation which function as mordants when mixed with the substantially pure avoids the use of potentially harmful ingredients, and in plant dyes isolated as described above. particular provides bright, intense colors without the use of 0014. In a preferred embodiment of the invention, the toxic mordanting agents. two-part system described just above comprises 2-20% (w/w) of a Substantially pure natural plant dye or combina SUMMARY OF THE INVENTION tion of dyes, depending on the color desired, isolated by solvent or supercritical CO2 extraction. The balance of the 0011. The present invention addresses the above-de formulation of the first part of the two-part system are scribed need by providing a composition for dyeing keratin diluents, which can include but are not limited to Surfactants, fibers, comprising approximately 0.1 to 30 percent of at least emulsifiers, solvents, fragrances, thickeners, humectants, one substantially pure plant dye obtained using at least one polymers, plasticizers, conditioners, and preservatives. The of a solvent or Supercritical CO2 extraction process, and first part is an aqueous solution. The second part of the approximately 0.01 to 5 percent of a mineral or metallic salt two-part system is 1.75% (w/w) of a zinc salt with the capable of acting as a mordanting agent. The plant dye can balance diluents in an aqueous Solution. Typically, the be selected from the group consisting of indigo, indigo second part of the two-part solution is rubbed into the hair carmine, alizarine, rubiethyric acid, purpuroxanthin, rubia and allowed to sit for 1-10 minutes, at which point the first din, morindanigrin, munistin, morindadiol, carotene, cro part of the two-part solution is added to the hair, rubbed in, cetin, bixin, canthaxanthin, lycopene, capsanthin, apocaro and allowed to sit for approximately 20 minutes. The total tenal, Xanthophyll, curcumin, morin, malclurin, luteolin, time is dependent on the color required. For example, if the apigenin, fukugetin, datiscetin, kaempferol, rhamnocitrin, color being applied was a shade of brown, the longer the rhamnethin, Zanthorhamnin, Isorhamnetin, Rhamnazin, solution is left on the hair the darker the shade of brown that Quercetin, Rutin, Gossypetin, Butin/Butein, Rottlerin, Chlo will result. rophyll A/B, Catechin, Fisetin, Lapachol, Juglone, Alkannin, Alkannan, Deoxysantalin, Atromentin, Awobamin, Carajui 0015. Another useful and unexpected result was obtained rin, Dracorhodin, Berberine, Betanin, Orcein, Xanthone, when either the substantially pure plant dye and/or the Naphthalene, Riboflavin, Anthocyanin, Lawsone, emblica mineral or metallic salt was encapsulated in a lipid, gelatin, extract, alfalfa extract, black tea extract, green tea extract, calcium alginate, polymethyl methacrylate urea (PMMU). white tea extract, and red sandalwood. The mineral or or other water impermeable shell. The encapsulation of metallic salt capable of acting as a mordanting agent can be either the plant dye, the mineral or metallic salt, or both selected from the group consisting of ferrous gluconate, allows the dye and salt to be combined together into an ferrous aspartate, calcium chloride, calcium gluconate, cal aqueous Solution that can be used in formulations including cium aspartate, magnesium gluconate, magnesium aspartate, but not limited to color gels, color creams, color shampoos, magnesium citrate, magnesium palmitate, Zinc gluconate, color conditioners, and the like. This compatibility is not Zinc aspartate, and manganese gluconate. One or both parts possible absent the encapsulation step because of the speed of the above described composition may be encapsulated in with which the mordant reacts with the dye to form an a water impermeable shell so that the composition may be insoluble complex that precipitates out of solution, and is used as a one-part hair dye system. Solvent extraction can less effective as a dye due to the insoluble complex of include hydrocarbon extraction, ultrafilration, and ion mordant and dye forming outside of the presence of keratin exchange separation. The invention also includes a method fiber. Moreover, these formulations with an encapsulated of manufacturing a composition for dying hair using the part are stable for long periods of time (more than 6 months), ingredients described above either in combination as a yet can be applied as a one-step, quick-action hair color (i.e., one-part system or separately as a two-part system. a one-part system) to color human hair in 10-20 minutes or less. DETAILED DESCRIPTION 0016. In a preferred embodiment of the invention, the 0012. In one embodiment of the invention, substantially one-part system described just above comprises the same pure natural plant dyes were obtained by Solvent extraction components, in the same percentages, as the composition for (e.g., hydrocarbon extraction, ultrafiltration, or ion exchange the two-part system described earlier. However, in the separation) or supercritical CO2 extraction. These substan one-part system, the Zinc salt is encapsulated in a shell of tially pure dyes produced hue, value and chroma results as hydrogenated castor oil and/or crosslinked with coacervated bright or brighter than those produced by synthetic dyes gelatin, calcium alginate, or PMMU. Such a coating can be when applied to keratin fiber (including human hair). This applied by spray drying, fluid bed drying, or any other bright color was produced both with and without the use of method known in the art. mordants. 0017 Another useful and unexpected result is that the 0013 In another embodiment of the invention, we have color produced is leveled without the addition of a leveling produced with substantially pure plant dyes (isolated by agent. It will be appreciated that it is often desirable to solvent or supercritical CO2 extraction) bright colors with promote Sustained release of either the mineral Supplement, US 2007/025 1024 A1 Nov. 1, 2007

the dye, or both after the core amount of both dye and What is claimed is: Supplement are released. This may be done by providing a 1. A composition for dyeing keratin fibers, comprising gradient of concentrations of both metal action and dye to approximately 0.1 to 30 percent of at least one concentrated conduct kinetics on the process as in regular dying systems plant dye extracted using at least one of a solvent extraction based on specially synthesized dyes, using techniques process and a Supercritical CO2 extraction process, and a known in the art. mineral or metallic salt with approximately 0.01 to 5 percent active metal capable of acting as a mordanting agent. 0018. By overcoming the problem of compatibility inher 2. The composition as defined in claim 1, wherein at least ent in combining Substantially pure plant dyes and mineral one of the concentrated plant dye and the mineral or metal or metal salts (acting as a mordant) through the use of salt capable of acting as a mordanting agent is encapsulated encapsulation, natural plant dyes can be used in a one-part in a water impermeable shell. system for applications such as: 3. The composition as defined in claim 1, wherein the salt capable of acting as a mordanting agent is encapsulated in a 0.019 1. 100% plant-based permanent hair color. water impermeable shell. 4. The composition as defined in claim 2, wherein said 0020 2. 100% plant-based semi-permanent hair color. composition is a one-part hair dye system. 0021 3. 100% plant-based demi-permanent hair color 5. The composition as defined in claim 4, wherein said composition is combined with bleach as a pretreatment to 0022 4. 100% plant-based liquid color gel. form a hair treatment system. 0023 5. 100% plant-based color shampoo 6. The composition as defined in claim 1, wherein at least one concentrated plant dye is selected from the group 0024 6. 100% plant-based color conditioner. consisting of indigo, indigo carmine, alizarine, rubiethyric acid, purpuroxanthin, rubiadin, morindanigrin, munistin, 0025 7. 100% plant-based hair color and fixative all in morindadiol, carotene, crocetin, bixin, canthaxanthin, lyco O pene, capsanthin, apocarotenal, Xanthophyll, curcumin, morin, malclurin, luteolin, apigenin, fukugetin, datiscetin, 0026 8. 100% pplant-based hair color and bleach all in kaempferol, rhamnocitrin, rhamnethin, Zanthorhamnin, O Isorhamnetin, Rhamnazin, Quercetin, Quercetin, Rutin, 0027 9. Any other hair color formulation implying use of Gossypetin, Butin/Butein, Rottlerin, Chlorophyll A/B, Cat natural plant based dye. echin, Fisetin, Lapachol, Juglone, Alkannin, Alkannan, Deoxysantalin, Atromentin, Awobamin, Carajuirin, Dracor 0028. The application of all these formulations is very hodin, Berberine, Betanin, Orcein, Xanthone, Naphthalene, similar to the application of the convenient hair color Riboflavin, Anthocyanin, Lawsone, emblica extract, alfalfa systems employing conventional synthetic dyes, but without extract, black tea extract, green tea extract, white tea extract, the potential risks of toxicity, irritation and hair damage and red sandalwood. inherent in those synthetic dye systems. 7. The composition as defined in claim 1, wherein the 0029. Thus, by combining the technologies of substan concentrated plant dye is extracted using a solvent extraction tially pure plant dyes obtained by solvent or supercritical process. CO2 extraction, and mordanting with mineral or metallic 8. The composition as defined in claim 7, wherein the salts in combination with or without encapsulation, we have Solvent extraction process is selected from the group con been able to create safe hair dyes that unexpectedly and sisting of hydrocarbon extraction, ultrafiltration, and ion Surprisingly produce bright and permanent or semi-perma exchange separation. nent colors similar to synthetic dyes in 10-20 minutes or 9. The composition as defined in claim 1, wherein the less, thereby improving on the safety, durability, quality and concentrated plant dye is extracted using a Supercritical CO2 application time of existing products on the market. extraction process. 10. The composition as defined in claim 7, wherein at 0030 The natural hair dyes described herein are not least one concentrated plant dye is selected from the group limited only to the embodiments described. It is contem consisting of indigo, indigo carmine, alizarine, rubiethyric plated that such embodiments will include not only those acid, purpuroxanthin, rubiadin, morindanigrin, munistin, described above but also embodiments comprising any morindadiol, carotene, crocetin, bixin, canthaxanthin, lyco number of other ingredients necessary for hair dye products pene, capsanthin, apocarotenal, Xanthophyll, curcumin, such as those described. Such ingredients would include morin, malclurin, luteolin, apigenin, fukugetin, datiscetin, anionic Surfactants, cationic Surfactants, nonionic Surfac kaempferol, rhamnocitrin, rhamnethin, Zanthorhamnin, tants and amphoteric Surfactants, as well as anionic emul Isorhamnetin, Rhamnazin, Quercetin, Quercetin, Rutin, sifiers, cationic emulsifiers, nonionic emulsifiers and Gossypetin, Butin/Butein, Rottlerin, Chlorophyll A/B, Cat amphoteric emulsifiers and any other ingredients necessary echin, Fisetin, Lapachol, Juglone, Alkannin, Alkannan, to practice the invention including but not limited to Sol Deoxysantalin, Atromentin, Awobamin, Carajuirin, Dracor vents, fragrances, thickeners, humectants, polymers, plasti hodin, Berberine, Betanin, Orcein, Xanthone, Naphthalene, cizers, conditioners, and preservatives. Numerous other Riboflavin, Anthocyanin, Lawsone, emblica extract, alfalfa alternatives, modifications and variations will be apparent to extract, black tea extract, green tea extract, white tea extract, those skilled in the art. Accordingly, the invention is and red sandalwood. intended to encompass all such other embodiments, alter 11. The composition as defined in claim 8, wherein at least natives, modifications and variations which fall within the one concentrated plant dye is selected from the group Scope and spirit of the invention and the following claims. consisting of indigo, indigo carmine, alizarine, rubiethyric US 2007/025 1024 A1 Nov. 1, 2007

acid, purpuroxanthin, rubiadin, morindanigrin, munistin, anionic emulsifiers, cationic emulsifiers, nonionic emulsifi morindadiol, carotene, crocetin, bixin, canthaxanthin, lyco ers and amphoteric emulsifiers. pene, capsanthin, apocarotenal, Xanthophyll, curcumin, 16. A method of manufacturing a composition for dyeing morin, malclurin, luteolin, apigenin, fukugetin, datiscetin, keratin fibers, comprising the steps of using at least one of kaempferol, rhamnocitrin, rhamnethin, Zanthorhamnin, a solvent extraction process or a Supercritical CO2 extrac Isorhamnetin, Rhamnazin, Quercetin, Quercetin, Rutin, Gossypetin, Butin/Butein, Rottlerin, Chlorophyll A/B, Cat tion process to extract a concentrated plant dye; and com echin, Fisetin, Lapachol, Juglone, Alkannin, Alkannan, bining said concentrated plant dye with a mineral or metallic Deoxysantalin, Atromentin, Awobamin, Carajuirin, Dracor salt capable of acting as a mordanting agent. hodin, Berberine, Betanin, Orcein, Xanthone, Naphthalene, 17. A method as defined in claim 16, further comprising Riboflavin, Anthocyanin, Lawsone, emblica extract, alfalfa the step of encapsulating at least one of said concentrated extract, black tea extract, green tea extract, white tea extract, plant dye and said mineral or metallic salt capable of acting and red sandalwood. as a mordanting agent in a water impermeable shell. 12. The composition as defined in claim 9, wherein at 18. A method as defined in claim 16, wherein the extrac least one concentrated plant dye is selected from the group tion process is a Supercritical CO2 extraction process. consisting of indigo, indigo carmine, alizarine, rubiethyric 19. A method as defined in claim 16, wherein the extrac acid, purpuroxanthin, rubiadin, morindanigrin, munistin, tion process is a solvent extraction process. morindadiol, carotene, crocetin, bixin, canthaxanthin, lyco pene, capsanthin, apocarotenal, Xanthophyll, curcumin, 20. A method as defined in claim 16, wherein at least one morin, malclurin, luteolin, apigenin, fukugetin, datiscetin, concentrated plant dye is selected from the group consisting kaempferol, rhamnocitrin, rhamnethin, Zanthorhamnin, of indigo, indigo carmine, alizarine, rubiethyric acid, pur Isorhamnetin, Rhamnazin, Quercetin, Quercetin, Rutin, puroxanthin, rubiadin, morindanigrin, munistin, morinda Gossypetin, Butin/Butein, Rottlerin, Chlorophyll A/B, Cat diol, carotene, crocetin, bixin, canthaxanthin, lycopene, cap echin, Fisetin, Lapachol, Juglone, Alkannin, Alkannan, Santhin, apocarotenal, Xanthophyll, curcumin, morin, Deoxysantalin, Atromentin, Awobamin, Carajuirin, Dracor malclurin, luteolin, apigenin, fukugetin, datiscetin, hodin, Berberine, Betanin, Orcein, Xanthone, Naphthalene, kaempferol, rhamnocitrin, rhamnethin, Zanthorhamnin, Riboflavin, Anthocyanin, Lawsone, emblica extract, alfalfa Isorhamnetin, Rhamnazin, Quercetin, Quercetin, Rutin, extract, black tea extract, green tea extract, white tea extract, Gossypetin, Butin/Butein, Rottlerin, Chlorophyll A/B, Cat and red sandalwood. echin, Fisetin, Lapachol, Juglone, Alkannin, Alkannan, 13. The composition as defined in claim 1, wherein at Deoxysantalin, Atromentin, Awobamin, Carajuirin, Dracor least one mineral or metallic salt capable of acting as a hodin, Berberine, Betanin, Orcein, Xanthone, Naphthalene, mordanting agent is selected from the group consisting of Riboflavin, Anthocyanin, Lawsone, emblica extract, alfalfa ferrous gluconate, ferrous aspartate, calcium chloride, cal extract, black tea extract, green tea extract, white tea extract, cium gluconate, calcium aspartate, magnesium gluconate, and red sandalwood. magnesium aspartate, magnesium citrate, magnesium palmi 21. A method as defined in claim 16, wherein at least one tate, Zinc gluconate, Zinc aspartate, and manganese glucon mineral or metallic salt capable of acting as a mordanting ate. agent is selected from the group consisting of ferrous 14. The composition as defined in claim 1, further com gluconate, ferrous aspartate, calcium chloride, calcium glu prising a Surfactant selected from the group consisting of conate, calcium aspartate, magnesium gluconate, magne anionic Surfactants, cationic Surfactants, nonionic Surfac sium aspartate, magnesium citrate, magnesium palmitate, tants and amphoteric Surfactants. Zinc gluconate, Zinc aspartate, and manganese gluconate. 15. The composition as defined in claim 1, further com prising an emulsifier selected from the group consisting of