COSMETIC COMPOSITIONS COMPRISING MELANOIDINS

Abstract

The present application is directed to a cosmetic composition comprising melanoidins, wherein said melanoidins are characterized by having a weight average molecular weight (Mw) of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa. The melanoidins are obtainable or are obtained by a process comprising the steps of: a) providing a particulate foodstuff which comprises melanoidins; b) treating said particulate foodstuff with an aqueous extractant solution having a pH greater than 7 to extract melanoidins as solute in the aqueous phase; c) physically separating said aqueous phase from the residual treated particulate foodstuff; d) fractionating the dispersed or dissolved components of said aqueous phase on the basis of molecular weight; and, e) dehydrating said fractionated aqueous phase to obtain at least one solid melanoidin fraction therefrom.

Claims

1. A cosmetic composition comprising melanoidins having a weight average molecular weight (Mw) of from 10 kDa to 300 kDa; and said cosmetic composition is substantially free of caffeine.

2. The cosmetic composition according to claim 1, wherein said cosmetic composition is a non-powdered solid cosmetic composition, a compact powder cosmetic composition or an aqueous liquid cosmetic composition.

3. An aqueous hair dyeing composition comprising: a) melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa; and, b) at least one auxiliary agent selected from the group consisting of: wetting agents; swelling agents; penetrants; pH regulators; surfactants; thickeners; antimicrobial agents; and, perfumes, and said hair dyeing composition is substantially free of caffeine.

4. The aqueous hair dyeing composition according to claim 3 comprising, based on a total weight of the hair dyeing composition: from 5 to 20 wt. % of said melanoidins; from 5 to 40 wt. % of said at least one auxiliary agent; and, from 40 to 90 wt. % of water.

5. An aqueous tattoo ink composition, comprising: a) at least one colorant comprising melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa; optionally b) at least one co-solvent; and, c) at least one auxiliary selected from the group consisting of: binders; thickeners; pH regulators; surfactants; humectants; antimicrobial agents; anti-inflammatory agents; anti-oxidants; antiseptics; and, local anesthetics, and wherein said tattoo ink composition is substantially free of caffeine.

6. The aqueous tattoo ink composition according to claim 5 comprising, based on a total weight of the tattoo ink composition: from 10 to 40 wt. % of water; from 30 to 60 wt. % of said at least one colorant; from 0 to 15 wt. % of said co-solvent; and, from 5 to 15 wt. % of said at least one auxiliary.

7. A solid cosmetic composition comprising: a) at least one colorant comprising melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa; b) at least one structurant; and, c) at least one thickener.

8. The solid cosmetic composition according to claim 7 comprising, based on a total weight of the solid cosmetic composition: from 2 to 30 wt. % of said at least one colorant; from 4 to 50 wt. % of said at least one structurant; from 4 to 50 wt. % of said at least one thickener; and, from 0 to 90 wt. % of at least one auxiliary selected from the group consisting of: carriers; stabilizers; surfactants; and, preservatives.

9. The solid cosmetic composition according to claim 7 that is substantially free of caffeine.

10. The cosmetic composition according to claim 1 wherein said melanoidins have a weight average molecular weight (Mw) of from 10 to 100 kDa.

11. The cosmetic composition according to claim 1, wherein said melanoidins have a weight average molecular weight (Mw) of from 10 to 30 kDa or from 50 to 100 kDa.

12. A process for obtaining at least one melanoidin fraction from a foodstuff, said process comprising steps of: a) treating a particulate foodstuff comprising melanoidins with an aqueous extractant solution having a pH greater than 7 to extract melanoidins as a solute in an aqueous phase; b) physically separating said aqueous phase from residual treated particulate foodstuff; c) fractionating dispersed or dissolved components of said aqueous phase based on molecular weight, wherein said fractionation yields aqueous retentates which are substantially fee from caffeine; and, d) dehydrating said aqueous retentates to obtain at least one solid melanoidin fraction.

13. The process according to claim 12, wherein the particulate foodstuff is selected from spent coffee grounds and Brewers Spent Grain (BSG).

14. The process according to claim 12, wherein the particulate foodstuff is micronized.

15. The process according to claim 12, wherein said treating step a) comprises treating said particulate foodstuff with an aqueous solution of sodium hydroxide.

16. The process according to claim 12, wherein said treating step a) is performed under centrifugation.

17. The process according to claim 12, wherein said fractionating step c) is performed by: ultra-filtration using molecular weight cut-off membranes; centrifugation; or, size exclusion chromatography.

18. The process according to claim 12, wherein said dehydrating step d) is performed by at least one of: freeze-drying; spray drying; convective drying; radiation drying; and, vacuum drying.

19. The cosmetic composition according to claim 1, wherein said melanoidins are obtained by the process of claim 12.

20. The cosmetic composition according to claim 1, wherein said melanoidins have a weight average molecular weight (Mw) of from 30 kDa to 50 kDa.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0060] The disclosure will make reference to the appended drawing in which:

[0061] FIG. 1 illustrates an embodiment of the preparation of a cosmetic composition comprising a melanoidin fraction.

DETAILED DESCRIPTION OF THE INVENTION

[0062] The present invention provides for the use in cosmetic compositions of a melanoidin fraction characterized by its molecular weight. Most broadly, said melanoidins are characterized by having a weight average molecular weight (Mw) of from 200 daltons (Da) to 300 kilodaltons (kDa). The melanoidins may, for instance, have a weight average molecular weight of from 1 to 300 kDa, for example from 1 to 200 kDa, from 1 to 100 kDa or desirably from 10 to 100 kDa. It may be practical to employ melanoidin fractions which possess a more narrowly defined molecular weight, such as from 10 to 30 kDa, from 30 to 50 kDa, from 50 to 100 kDa or from 100 to 200 kDa where, for example, a particular pigmentary or light absorption effect is desired. It is also envisaged that more than one melanoidin fraction may be present: for example, a first fraction based on melanoidins possessing a weight average molecular weight of from 10 to 30 kDa may be combined in the cosmetic composition with a second fraction based on melanoidins having a weight average molecular weight of from 50 to 100 kDa or from 100 to 200 kDa.

[0063] Whilst the present disclosure does not preclude other means of obtaining said melanoidin fractions, the present invention does provide a process for obtaining at least one melanoidin fraction from a foodstuff, said process comprising the steps of: [0064] a) providing a particulate foodstuff which comprises melanoidins; [0065] b) treating said particulate foodstuff with an aqueous extractant solution having a pH greater than 7 to extract melanoidins as solute in the aqueous phase; [0066] c) physically separating said aqueous phase from the residual treated particulate foodstuff; [0067] d) fractionating the dispersed or dissolved components of said aqueous phase on the basis of molecular weight; and, [0068] e) dehydrating said fractionated aqueous phase to obtain at least one solid melanoidin fraction therefrom.

[0069] Exemplary particulate foodstuff sources which may be provided to step a) include coffee, cocoa, bread, malt, barley, Brewers Spent Grain (BSG), soy, meat and honey. Said coffee may itself be constituted by roasted coffee beans, coffee grounds, spent coffee grounds (SCG), coffee silverskin (CS) and granulated coffee extract. Spent Brewers Grains (SBG) are the solid residues left after the processing of germinated and dried cereal grains for the production of beer and other malt products, such as malt extracts and malt vinegar: whilst barley is the main grain used for brewing, beers are also made from wheat, maize, rice, sorghum and millet. Spent coffee grounds (SCG) are the residual material obtained during the treatment of coffee grounds with hot water or steam for the instant coffee preparation. Coffee silverskin (CS) is a thin tegument of the outer layer of green coffee beans obtained as a by-product of the roasting process.

[0070] In the present disclosure, it is preferred that the particulate foodstuff is micronized. Independently or additionally, it is preferred that the particulate foodstuff is selected from spent coffee grounds and Brewers Spent Grain (BSG).

[0071] A particular preference for micronized spent coffee grounds might be noted. As regards this embodiment, the present method may encompass at least one pre-treatment step which precedes step b). It may be advantageous, for example, to dry the spent coffee grounds by exposure to a temperature condition above room temperature, such as from 50 to 100° C. Alternatively or additionally to this drying stage, the spent coffee grounds may be defatted. At least a portion of the lipids and/or oils present in the grounds may be extracted using a suitable solvent: mention may be made of carbon dioxide applied at a pressure and temperature condition such that it is a supercritical fluid.

[0072] Treatment step b) may be performed using any method which provides for the performance of the following stages: (1) the penetration of the aqueous extractant into the solid matrix of the provided or pre-treated particles; (2) the dissolution of the solute in the aqueous extractant; (3) the diffusion of the solute out from the solid matrix; and, (4) the collection of the extracted solutes. Suitable methods include but are not limited to: centrifugation; maceration; percolation; decoction; reflux extraction; pressurized liquid extraction; ultrasound assisted extraction; microwave assisted extraction; pulsed electric field extraction; and, hydro-distillation. For example, a suitable centrifugation method may comprise the addition of the aqueous extractant to the particulate foodstuff followed by the application of from 500 to 5000 gravity (G), for a period of from 5 to 60 minutes at a temperature of from 5 to 30° C.: the supernatants containing the melanoidins may then be collected. In a further example, the particulate foodstuff may be treated by pressurized liquid extraction at a temperature of from 100° to 200° C. for a period of from 10 to 120 minutes, for example from 20 to 60 minutes.

[0073] Factors which enhance the diffusivity and solubility of the melanoidins will facilitate their extraction. Herein, it is preferred that the aqueous treatment solution has a pH of above 7 but less than or equal to 12 or less than or equal to 10. The aqueous treatment solution may, alternatively or additionally to those preferred pH ranges, be an alkaline solution comprising at least one of: sodium hydroxide; potassium hydroxide; ammonia (NH.sub.3(aq)); and, calcium hydroxide.

[0074] The presence of a water-miscible solvent within the aqueous extractant solution is not precluded. Such a water-miscible solvent should not however constitute more than 20 wt. % of the aqueous extractant solution.

[0075] After separation of the aqueous phase from the aqueous phase from the residual treated particulate foodstuff (step c)) —by, for example, filtration, precipitation or decantation—the dispersed or dissolved components are fractionated on the basis of their molecular weight. This fractionation, which optionally may be preceded by the concentration of the aqueous solution or dispersion, may be effected by ultra-filtration using requisite molecular weight cut-off membranes, which technique yields a plurality of retentates which may then be further processed. Fractionation may also be effected by centrifugation or size exclusion chromatography. It will be recognized that the appropriate selection of the minimum molecular weight of the compounds to be fractionated can substantially eliminate caffeine (Mw 194 da) from the obtained retentates.

[0076] The fractionated products, such as the aforementioned retentates, are then subjected to a water removal step to yield the melanoidin fractions in solid form. Suitable methods of dehydration which may be mentioned include: freeze-drying; spray-drying; convective drying; radiation drying; and, vacuum drying. The obtained solid melanoidin fractions may be presented as particles having an average particle size (d50) of from 1 to 500 μm. Where necessary particle aggregates may be comminuted to attain this particle size.

[0077] As depicted in FIG. 1 appended hereto, the separated and dried melanoidins, fractionated on the basis of molecular weight, are combined with further ingredients to attain a cosmetic composition. The further ingredients have been identified as being a binder, solvent and additives in the appended FIGURE: this is not intended to be limiting as the exact nature of the added ingredients will dependent on the type and form of the cosmetic composition. Any added ingredients should result in the formation of a cosmetically acceptable composition.

[0078] The compositions of the present disclosure are formulated by simple mixing of the various components—as well as any adjunct ingredients—in pre-determined amounts. This may be performed using any of the mixing techniques known in the art. It would certainly be preferred however that the ingredients are not mixed by hand but are instead mixed by machine—a static or dynamic mixer, for example—in order to ensure a homogenous dispersion of: particulate ingredients; oleaginous ingredients, where said cosmetic composition is an oil-in-water emulsion; and, water and water-borne ingredients, where said cosmetic composition is a water-in-oil emulsion.

[0079] If necessary, the compositions may be prepared well in advance of their application. However, in an interesting alternative embodiment for aqueous cosmetic compositions, a concentrated composition may first be obtained by mixing components with only a fraction of the water that would be present in the composition as applied: the concentrated composition may then be diluted with the remaining water shortly before its application. It is considered that such concentrated compositions may be prepared and stored as either single-package concentrates—that can be converted by dilution with water only—or as multi-part concentrates, two or more of which must be combined and diluted to form a complete working composition according to the invention. Any dilution can be effected simply by the addition of water, in particular deionized and/or demineralized water, under mixing. The composition might equally be prepared within a rinse stream whereby one or more streams of the concentrate(s) is injected into a continuous stream of water.

[0080] Various features of the disclosure are described in the following exemplary embodiments, which are intended to be representative and not limiting.

Exemplary Embodiment 1: Aqueous Hair Dyeing Composition

[0081] In an important embodiment of the present disclosure there is provided an aqueous hair dyeing composition, comprising: [0082] a) melanoidins, wherein said melanoidins have a weight average molecular weight of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa; and, [0083] b) at least one auxiliary agent selected from the group consisting of: wetting agents; swelling agents; penetrants; pH regulators; surfactants; thickeners; antimicrobial agents; and, perfumes.

[0084] Component a) is preferably obtained from the extractive process as defined herein above and in the appended claims. For example, the hair dyeing composition of the present invention may comprise, based on the weight of the composition: [0085] from 5 to 20 wt. % of a) melanoidins, said melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa; [0086] from 5 to 40 wt. % of b) at least one auxiliary agent selected from the group consisting of: wetting agents; swelling agents; penetrants; pH regulators; surfactants; thickeners; antimicrobial agents; and, perfumes; and, [0087] from 40 to 90 wt. % of water.

[0088] It will be noted that component b) presents categorizations based on the benefit provided by the agent or the agent's postulated mode of action. This categorization is made for convenience: a given chemical ingredient—such as ammonia for example—might provide more than one benefit or operate via more than one mode of action.

[0089] As regards the aqueous hair dye compositions, it is preferred that said compositions contain from 40 to 90 wt. %, preferably from 40 to 80 wt. % and more preferably from 55 to 75 wt. %, based on the weight of the composition, of water. In an alternative but not mutually exclusive characterization, the aqueous hair dye composition may be defined by a viscosity of from 0.005 to 50 Pa.Math.s, as measured using a Brookfield viscometer at 25° C.

[0090] Exemplary wetting agents, which may be used alone or in combination, include but are not limited to: glycerin; propylene glycol; sorbitol; 1,3-butylene glycol; polyvinylpyrollidone (PVP); polyethylene glycols (PEG); polypropylene glycol (PPG); PEG/PPG-block copolymers; and, PEG/PPG-random copolymers. An illustrative PEG/PPG-random copolymer is PEG/PPG—8/17.

[0091] Exemplary swelling agents include ammonia and monoethanolamine (MEA). The ammonia, when included, would be present in the aqueous compositions of the present invention as an ammonia solution NH.sub.3(aq) which encompasses weakly basic solutions of ammonia in water which may referred to in the art as ammonium hydroxide, ammonia water, ammonia liquor, aqua ammonia, aqueous ammonia, or simply ammonia. While the term “ammonium hydroxide” suggests a base with the composition [NH.sub.4.sup.+][OH.sup.−], it is virtually impossible to isolate samples of NH.sub.4OH, insomuch as these ions do not comprise a significant fraction of the total amount of ammonia in an ammonia solution, except in the case of extremely dilute ammonia solutions.

[0092] Exemplary penetrants, which may be used alone or in combination include: monohydric alcohols having C.sub.1-C.sub.6 alkyl group such as ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; polyhydric alcohols having from 3 to 8 carbon atoms such as propanediol, butanediol, pentanediol, hexanediol, hexanetriol, heptanediol, heptanetriol, octanediol, octanetriol, isoprene glycol, propylene glycol, glycerin, and diethylene glycol monoethyl ether; esters of said polyhydric alcohols; N-alkypyrrolidones which are liquid at room temperature such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; C.sub.2-C.sub.6 alkylene carbonates such as ethylene carbonate and propylene carbonate; aromatic alcohols such as benzyl alcohol, benzyloxyethanol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, phenoxyisopropanol, 2-benzyl ethanol and β-phenylethyl alcohol. A preference for 2-propanol, 1,2-hexanediol and benzyl alcohol might be mentioned.

[0093] Examples of pH adjusters include: mineral acids, such as phosphoric acid; hydroxycarboxylic acids such as lactic acid, glycolic acid, citric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and the alkali metal or alkaline earth metal salts thereof; ammonia; alkali metal hydroxides; alkali metal carbonates; alkali metal bicarbonates; alkaline earth metal hydroxides; alkaline earth metal carbonates; and, alkaline earth metal bicarbonates.

[0094] The aqueous hair dye compositions of the present invention will typically comprise up to 10 wt. %, for example up to 5 wt. % or up to 3 wt. %, based on the weight of the composition, of surfactant. A wide variety of surfactants may be used herein—both for emulsification of the dispersed phase and to provide acceptable spreading of the applied composition—but desirable surfactants will be selected from the group consisting of: anionic surfactants; nonionic surfactants; amphoteric surfactants; non-lathering surfactants; emulsifiers; and, mixtures thereof. U.S. Pat. No. 6,280,757 (McAtee et al.) provides an instructive disclosure on suitable surfactants.

[0095] Anionic Surfactants: Non-limiting examples of anionic surfactants useful in the compositions of the present invention are disclosed U.S. Pat. No. 3,929,678 (Laughlin et al.) and U.S. Pat. No. 4,557,853. Mention may be made of anionic surfactants selected from the group consisting of: i) fatty acid soaps based on fatty acids having from 8 to 36 or from 8 to 24 carbon atoms; ii) monoalkyl, dialkyl, and trialkylphosphate salts; iii) sarcosinates, such as sodium lauroyl sarcosinate, sodium myristoyl sarcosinate and sodium cocoyl sarcosinate; iv) sulfates, including alkyl and alkyl ether sulfates of which mention may be made of sodium lauryl sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate, sodium trideceth sulfate, ammonium cetyl sulfate and sodium cetyl sulfate; v) isethionates such as sodium lauroyl isethionate and ammonium cocoyl isethionate; vi) taurates such as sodium lauroyl methyl taurate and sodium cocoyl methyl taurate; vii) lactylates such as sodium lauroyl lactylate, triethanolamine lauroyl lactylate and sodium caproyl lactylate; viii) glutamates such as sodium lauroyl glutamate, sodium myristoyl glutamate, and sodium cocoyl glutamate; and, mixtures thereof.

[0096] Non-Ionic Surfactants: Suitable nonionic surfactants having utility in the present disclosure include: alkyl glucosides; alkyl polyglucosides; polyhydroxy fatty acid amides; alkoxylated fatty acid esters; sucrose esters; amine oxides; and. mixtures thereof. Mention may, for example, be made of: C.sub.8-C.sub.14 glucose amides, C.sub.8-C.sub.14 alkyl polyglucosides, sucrose cocoate, sucrose laurate, lauramine oxide, cocoamine oxide and mixtures thereof.

[0097] Amphoteric Surfactants: The term “amphoteric surfactant” as used herein, is also intended to encompass zwitterionic surfactants. Useful amphoteric surfactants, which may be used alone or in combination, include but are not limited to: derivatives of aliphatic secondary and tertiary amines, preferably wherein the nitrogen is in a cationic state and wherein at least one aliphatic radical contains an ionizable water solubilizing group such as a carboxyl, sulfonate, sulfate, phosphate or phosphonate group; betaines; sultaines; hydroxysultaines; alkyliminoacetates; iminodialkanoates; and, aminoalkanoates.

[0098] Non-Lathering Surfactants: Given that the present hair dye compositions are not conventionally intended to have a cleansing functionality, they need not therefore be lathering systems and can comprise non-lathering surfactants. Exemplary non-lathering surfactants having utility herein include: polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20); Polysorbate 60; Polysorbate 80; polyoxyethylene 20 sorbitan trioleate (Polysorbate 85); Steareth-20; Ceteth-10; Ceteareth-20; cetyl phosphate; potassium cetyl phosphate; diethanolamine cetyl phosphate; glyceryl stearate; PPG-2-methyl glucose ether distearate; and, PEG-100 stearate.

[0099] Emulsifier systems: In addition to the above, the use of emulsifier(s) is not precluded in the present disclosure. Mention may be made of the following emulsifier mixtures: PROLIPID® 141 (glyceryl stearate, behenyl alcohol, palmitic acid, stearic acid, lecithin, lauryl alcohol, myristyl alcohol and cetyl alcohol) available from ISP; PROLIPID® 151 (Glyceryl stearate, cetearyl alcohol, stearic acid, 1-propanamium, 3-amino-N-(2-(hydroxyethyl)-N—N-Dimethyl,N—C(16-18) Acyl Derivatives, Chlorides), available from ISP; POLAWAX® NF (Emulsifying wax NF) available from Croda; INCROQUAT® BEHENYL TMS (behentrimonium sulfate and cetearyl alcohol) available from Croda; and EMULLIUM® DELTA (cetyl alcohol, glyceryl stearate, peg-75 stearate, ceteth-20 and steareth-20) available from Gattefosse.

[0100] The aqueous hair dye compositions of the present disclosure may comprise from 0 to 10 wt. %, for example from 0 to 5 wt. %, based on the weight of the composition, of one or more thickening agents. Said thickening agents may be selected from: i) carboxylic acid polymers, such as those members of the CARBOPOL®900 series available from B.F. Goodrich; ii) acrylates/C.sub.10-C.sub.30 alkyl acrylate crosspolymers, such as CARBOPOL®1342, CARBOPOL®1382, PEMULEN® TR-1 and PEMULEN® TR-2 available from B.F. Goodrich; iii) crosslinked polyacrylate polymers, which may be cationic or nonionic polymer; iv) polyacrylamide polymers, in particular nonionic polyacrylamide polymers; iv) multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids; v) polysaccharides including scleroglucans, cellulose and cellulose derivatives, such as carboxymethylcellulose and alkyl hydroxyalkyl cellulose ethers; vi) modified starches; vii) gums such as xantham gum, acacia gum, alginin, sodium alginate, locust bean gum and guar gum; viii) proteins such as collagen, albumen and gelatin; and, mixtures thereof.

[0101] The aqueous hair dye compositions of the present disclosure may comprise from 0 to 5 wt. %, preferably from 0 to 2 wt. %, based on the weight of the composition, of at least one antimicrobial agent. It is preferred that the or each antimicrobial agent included in the composition is a crystalline particulate that is insoluble in water. Exemplary antimicrobial agents include but are not limited to: sulfur; piroctone olamine; selenium sulfides, as described in U.S. Pat. Nos. 2,694,668, 3,152,046 and 4,089,945; and, pyridinethione salts, as described in U.S. Pat. Nos. 3,753,196, 4,345,080, 4,323,683, and 4,470,982.

[0102] Examples of perfumes which may be included in the aqueous hair dyeing composition include vanillin, cinnamic alcohol, heliotropine, coumalin, 2-methyl-3-(3,4-methylenedioxy-phenyl)-propanal, 4-(4-hydroxyphenl)-2-butanone, benzaldehyde, anisyl alcohol, 3,4-di methoxybenzaldehyde, heliotropyl acetate, phenyl acetaldehyde dimethylacetal, phenoxyethyl alcohol, phenyl acetaldehyde glycerylacetal, benzyl alcohol, phenylethyl alcohol, furaneol, sugar lactone, menthol, ethyl diglycol, benzyl acetate, linalool, camphor, terpineol, citronellol, geraniol, 2,6-nonadienol, methyloctyl carbonate, 3,7-dimethyl-2,6-octadienal and nonanal.

[0103] The hair dye of the present composition may be applied using conventional means to at least a portion of the hair shaft, including by finger touch, by hand, by brush or by another implement, optionally in concert with a means of delivering thermal energy or a suitable electromagnetic radiation. The composition(s) may be applied to wet hair or to dry hair. The amount applied will vary, dependent upon the thickness and length of the hair, and the desired effect.

[0104] The hair dye composition(s) may be applied to substantially all of the hair or alternatively to a portion of the hair. In one embodiment, the composition may be applied to a portion of the hair that is proximal to the scalp, for example, from 0 to 10 cm or from 0 to 5 cm proximal to the scalp. This may be desirable for the user modify the color of the roots of newly grown hair.

Exemplary Embodiment 2: Tattoo Ink

[0105] In an important embodiment of the present disclosure there is provided an aqueous tattoo ink composition composition, comprising: [0106] a) at least one colorant, wherein said at least one colorant comprises melanoidins, said melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa; [0107] optionally b) at least one co-solvent; and, [0108] c) at least one auxiliary selected from the group consisting of: binders; thickeners; pH regulators; surfactants; humectants; antimicrobial agents; anti-inflammatory agents; anti-oxidants; antiseptics; and, local anesthetics.

[0109] The melanoidins present in the colorant component a) are preferably obtained from the extractive process as defined herein above and in the appended claims. It is noted that the colorant component a) may comprise, consist essentially of or consist of said melanoidins depending on the color effect to be obtained.

[0110] In a preferred embodiment, the aqueous tattoo ink composition of the present invention comprises, based on the weight of the composition: [0111] from 10 to 40 wt. % of water; [0112] from 30 to 60 wt. % of a) said at least one colorant, wherein said at least one colorant comprises melanoidins, said melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa; [0113] from 0 to 15 wt. % of b) said co-solvent; and, [0114] from 5 to 15 wt. % of c) at least one auxiliary selected from the group consisting of: binders; thickeners; pH regulators; surfactants; humectants; antimicrobial agents; anti-inflammatory agents; anti-oxidants; antiseptics; and, local anesthetics.

[0115] It will be noted that component c) presents categorizations based on the benefit provided by the agent or the agent's postulated mode of action. This categorization is made for convenience: a given chemical ingredient—such as polyethylene glycol for example—might provide more than one benefit or operate via more than one mode of action. In this regard, it is repeated here that melanoidins themselves provide a pigmentary function and act as antimicrobial agents, anti-inflammatory agents and anti-oxidants and can thereby minimize the need to provide adjunct ingredients having these functionalities.

[0116] The aqueous tattoo ink composition of the present invention can include further colorants in addition to the aforementioned melanoidins. Said colorants are by necessity water-soluble or water-dispersible and may be selected from: inorganic pigments; organic pigments; natural dyes; synthetic dyes; and, combinations thereof. The use of organic, lacquered or lacquer pigments (“lake pigments”) —which are obtained by precipitating a natural or synthetic dye with a metal salt—is also envisaged. It is however preferred that the formulation is substantially free of metal particles and/or is substantially free of microencapsulated colorants.

[0117] For completeness, exemplary inorganic pigments include but are not limited to: metal oxides, such as iron oxide red, iron oxide yellow, iron oxide black, anatase, brookite, rutile, aluminum oxide, zirconium oxides, cobalt oxides, cerium oxides, nickel oxide, chromium oxide, nickel-chromium oxides, zinc oxides and composite oxides; metal hydroxides, such as calcium hydroxide, iron hydroxides, aluminum hydroxide, chromium hydroxide, magnesium hydroxide and composite metal hydroxides; Prussian blue; iron sulfide; manganese violet; carbon black; mica; and, kaolin.

[0118] The aqueous tattoo ink composition may comprise at least one water-miscible organic co-solvent. When present, the water and said at least one water-miscible organic solvent should be mixed at a ratio by weight of from 20:80 to 80:20, for example from 30:70 to 70:30. In an additional statement of preference, which is not intended to be mutually exclusive of those ratios mentioned above, it is preferred that the water-miscible organic solvent or the mixture of water-miscible organic solvents included in this part are selected and added to water in an amount sufficient to reduce the surface tension of the water/solvent combination to less than 64 dynes/cm at room temperature.

[0119] The at least one water-miscible organic solvent of the present invention may be selected from the group consisting of: C.sub.1-6 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol; cyclopentanol; cyclohexanol; diols, particularly diols having from 2 to 12 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, pentylene glycol, hexylene glycol but also including thiodiglycol and oligo- and poly-alkyleneglycols, such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol; triols such as 1,2,6-hexanetriol; ketones and ketone-alcohols, such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; tetrahydrofuran; dioxane; mono-C.sub.1-4-alkyl ethers of diols having from 2 to 12 carbon atoms, such as ethylene glycol mono-(C.sub.1-C.sub.4)-alkyl ethers, propylene glycol mono-(C.sub.1-C.sub.4)alkyl ethers and in particular ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; diethylene glycol mono-(C.sub.1-C.sub.4)alkyl ethers, such as diethylene glycol monomethyl ether and diethylene monobutyl ether; dipropylene glycol mono-(C.sub.1-C.sub.4)alkyl ethers, such as dipropylene glycol N-propyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl; propylene glycol phenyl ether; linear amides, such as N,N-dimethylformamide and N.N-dimethylacetamide; cyclic amides such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; sugar esters such as dimethyl isosorbide; cyclic esters such as caprolactone; and, sulfoxides, such as dimethyl sulfoxide and sulfolane. Said at least one water-miscible solvent is preferably selected from the acetone, diacetone alcohol, isopropyl alcohol and mixtures thereof.

[0120] The presence of water-immiscible organic solvents in this formulation is not strictly precluded but it does not represent a preferred embodiment. Rather it is preferred that the formulation is essentially free of water-immiscible organic solvents and as such presents as a single, continuous aqueous phase.

[0121] As regards component c) mentioned above, binders or binding agents do represent customary ingredients of aqueous tattoo ink compositions which may be present in an amount up to 5 wt. %, based on the weight of the composition. The binders are non-volatile ingredients which bind particulate colorants to each other and, in doing so, facilitate the intra-dermal or intra-epidermal introduction of the ink using needles and like injection means. Exemplary binders, which may be used alone or in combination, include but are not limited to: polyvinylpyrollidone (PVP), in particular polyvinylpyrollidone having a weight average molecular weight of from 1 to 3000 kDa; polyethylene glycols (PEG), in particular polyethylene glycols having a weight average molecular weight of from 0.2 to 6 kDa; polypropylene glycol (PPG) in particular polypropylene glycols having a weight average molecular weight of from 0.2 to 6 kDa; PEG/PPG-block copolymers, in particular PEG/PPG block copolymers having a weight average molecular weight of from 5 to 15 kDa; PEG/PPG-random copolymers; and, Shellac resin.

[0122] The aqueous tattoo ink compositions will typically comprise up to 5 wt. %, for example up to 3 wt. %, based on the weight of the composition, of surfactant. A wide variety of surfactants may be used herein—both for emulsification of the dispersed phase and to provide acceptable spreading of the applied composition—but desirable surfactants will be selected from the group consisting of: anionic surfactants; nonionic surfactants; amphoteric surfactants; non-lathering surfactants; emulsifiers; and, mixtures thereof. The disclosure regarding surfactants provided for Exemplary Embodiment 1 is considered applicable and is incorporated herein by reference.

[0123] Examples of pH adjusters: mineral acids such as phosphoric acid; hydroxycarboxylic acids such as lactic acid, glycolic acid, citric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and the alkali metal or alkaline earth metal salts thereof; ammonia; alkali metal hydroxides; alkali metal carbonates; alkali metal bicarbonates; alkaline earth metal hydroxides; alkaline earth metal carbonates; and, alkaline earth metal bicarbonates.

[0124] The formulation of this embodiment may comprise from 0 to 5 wt. %, for example from 0 to 3 wt. %, based on the weight of the composition, of one or more thickening agents. Said thickening agents may be selected from: i) carboxylic acid polymers, such as those members of the CARBOPOL®900 series available from B.F. Goodrich; ii) acrylates/C.sub.10-C.sub.30 alkyl acrylate crosspolymers, such as CARBOPOL®1342, CARBOPOL®1382, PEMULEN® TR-1 and PEMULEN® TR-2 available from B.F. Goodrich; iii) crosslinked polyacrylate polymers, which may be cationic or nonionic polymer; iv) polyacrylamide polymers, in particular nonionic polyacrylamide polymers; iv) multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids; v) polysaccharides including scleroglucans, cellulose and cellulose derivatives, such as carboxymethylcellulose and alkyl hydroxyalkyl cellulose ethers; vi) modified starches; vii) gums such as xantham gum, acacia gum, alginin, sodium alginate, locust bean gum and guar gum; viii) proteins such as collagen, albumen and gelatin; and, mixtures thereof.

[0125] As is known in the art, humectants, or moisturizing agents, are cosmetic ingredients with water binding properties that are capable of retaining large amounts of water relative to their weight. Humectants are usually more soluble in water than in oil. Instructive references on suitable humectants for use in the present formulation include WO98/22085, WO98/18444 and WO97/01326. And exemplary humectants for use herein include: amino acids; collagen amino acids or peptides; keratin amino acids; silk amino acids; urea; glycosaminoglycans; N-acetyl glucosamine; glycerin; polyethylene glycol ethers of glycerin; and, alkali metal salts of hyaluronic acid, acetyl hyaluronic acid, aspartic acid, glucuronic acid and glutamic acid.

[0126] The formulation of this embodiment may comprise from 0 to 5 wt. %, preferably from 0 to 2 wt. %, based on the weight of the composition, of at least one antimicrobial agent. It is preferred that the or each antimicrobial agent included in the composition is a crystalline particulate that is insoluble in water. Exemplary antimicrobial agents include but are not limited to: sulfur; piroctone olamine; selenium sulfides, as described in U.S. Pat. Nos. 2,694,668, 3,152,046 and 4,089,945; and, pyridinethione salts, as described in U.S. Pat. Nos. 3,753,196, 4,345,080, 4,323,683, and 4,470,982.

[0127] The formulation of this embodiment may comprise from 0 to 2 wt. %, based on the weight of the composition, at least one anti-inflammatory agent. Suitable anti-inflammatory agents, which may be used alone or in combination, include: vitamin F; vitamin E; unsaturated fatty acids; rutin; bioflavonoids; caffeic acid phenethyl ester; sea buckthorn oil; olive oil; jojoba oil; chamomile essential oil; chamomile extract; witch hazel (Hamamelis virginiana) extract; beetroot extract; horseradish extract; dandelion extract; Gamguk extract (Chrysanthemum indicum); Sukbagui extract; betamethasone; dexamethasone; and, mixtures thereof. The aforementioned extracts may be obtained by known methods including hot water or alcoholic extraction processes. A preference for witch hazel extract might be mentioned.

[0128] Illustrative antioxidants include vitamin E, vitamin F, vitamin C, rutin, resveratrol, carnosic acid, chitosan, flavonoids, gallates, anthocyanins and carotenoids. Illustrative antiseptics include captan, chlorhexidine, hexachlorophene, triclosan, triacetin and mixtures thereof.

[0129] In certain embodiments, the formulation of this embodiment may comprise up to 1 wt. %, based on the weight of the composition, of at least one local anesthetic. As is known in the art, local anesthetics reduce the excitability of sensitive nerve fibers, block the influx of sodium ions through interaction with a binding site on the inside of the membrane of the sodium ion channel and thus prevent the development of action potentials necessary for conduction of excitation. Herein preferred local anesthetics are selected from the group consisting of lidocaine, mepivacaine, prilocaine, articaine, bupivacaine, dibucaine, ropivacaine, etidocaine, dyclonin, procaine, benzocaine, 2-chloroprocaine, oxybuprocaine, tetracaine, fomocaine, etidocaine, pramocaine, Levobupivacaine, oxyprocain, hexylcaine, dibucaine, piperocaine, butamben, butamben picrate, dimethisoquin hydrochloride, diperodone, dyclonine, ketamine, p-butylaminobenzoic acid, pramoxine and their pharmaceutically acceptable salts and mixtures thereof. A preference for lidocaine and benzocaine may be mentioned: this preference is intended to encompass the pharmaceutically acceptable salts of these compounds.

[0130] The tattoo ink compositions of the present disclosure may be applied by any conventional technique. As will be recognized by the skilled artisan, the application of the tattoo may be preceded by preparation of the skin by cleaning to remove surface contaminants and/or the application of an anesthetic to provide local and temporary pain relief. The pre-application of a local anesthetic may compliment any anesthetic included within the ink composition itself, as described above.

[0131] An intra-epidermal tattoo may be regarded as a “semi-permanent colorant” in that the colorant is disposed within the epidermis but does not diffuse out of the skin and cannot be removed therefrom skin without either the physical disruption or the natural desquamation of the skin. The intra-epidermal tattoo may not, in particular, be washed off under the action or water, soap, alcoholic solvents or combinations thereof.

[0132] Epidermal administration of the compositions of the present disclosure may be effected by, for example: needle; microneedle; jet injection; thermal microporation; electroporation; sonoporation; or, combinations thereof. Moreover, the locus of epidermal administration may be to one or more of the stratum corneum, stratum lucidum, stratum granulosum, stratum spinosum and stratum basale.

[0133] Without intention to limit the present disclosure, it is considered that techniques for intra-dermal application should be characterized by the introduction of the ink into the dermis under capillary action using a needle which possesses at least three fine points, which points move backwards and forward axially at a frequency of from 50 to 5000 min.sup.−1. Under such a mode of introduction, macrophages are released within the dermis as a defensive reaction: given, however, that the ink particulates are much larger than the macrophages, the consequent effect of the ink particulates being surrounded by the phagocytic cells is to fix the ink particulates within the dermis. Under such a mode of introduction, it is also established that a fraction of the ink particulates will be taken up by fibroblasts and a further fraction will be retained within the extracellular matrix of collagen fibers in the dermis. Any ink deposited within the epidermis will however be lost given that epidermal cells are shed both naturally and in a healing response to the injury caused by the needle.

[0134] Exemplary tattoo needles for intra-dermal applications include but are not limited to those described in: EP 2454966 A1; US 2007/0038181 A (Melamud); US 2004/0186501 A (Kuei); U.S. Pat. No. 8,764,784 (Crockett); U.S. Design Patent No. 866950 S1 (Schubert); and, U.S. Design Patent No. 888240 S1 (Importla).

[0135] Whilst tattoos are intended to be permanent, it is recognized that persons do often seek to remove them from their bodies. The use of melanoidins as pigments is considered to present the benefit that these compounds can be degraded through the targeted action of enzymes and chemicals, such as hydrogen peroxide and ozone, introduced into the dermis or epidermis. The degradation of the melanoidins renders the pigment “removable”.

Exemplary Embodiment 3: Solid Cosmetic Compositions for Use as Eye Make-Up

[0136] In an important embodiment of the present disclosure there is provided a solid cosmetic composition, said composition comprising: [0137] a) at least one colorant, wherein said at least one colorant comprises melanoidins, said melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa; [0138] b) at least one structurant; and, [0139] c) at least one thickener.

[0140] It is proposed that solid cosmetic compositions as here defined above may have particular utility as facial make-up, for example as eye make-up. The melanoidins present in the colorant component a) are preferably obtained from the extractive process as defined herein above and in the appended claims. It is noted that the colorant component a) may comprise, consist essentially of or consist of said melanoidins depending on the color effect to be obtained.

[0141] In a preferred embodiment, the solid cosmetic composition of the present invention comprises, based on the weight of the composition: [0142] from 2 to 30 wt. % of a) at least one colorant, wherein said at least one colorant comprises melanoidins, said melanoidins having a weight average molecular weight of from 200 daltons to 300 kDa, preferably from 1 to 300 kDa and more preferably from 1 to 100 kDa, for example from 10 to 100 kDa; [0143] from 4 to 50 wt. % of b) at least one structurant; [0144] from 4 to 50 wt. % of c) at least one thickener; and, [0145] from 0 to 90 wt. % d) at least one auxiliary selected from the group consisting of: carriers; stabilizers; surfactants; and, preservatives.

[0146] It will be noted that component d) presents categorizations based on the benefit provided by the agent or the agent's postulated mode of action. This categorization is made for convenience: a given chemical ingredient might provide more than one benefit or operate via more than one mode of action.

[0147] The present solid cosmetic composition comprises from 4 to 50 wt. %, for example from 5 to 40 wt. % or from 5 to 30 wt. %, based on the weight of the composition, of one or more structurants.

[0148] Without intention to limit the present invention, said structurants having utility in the present invention should comprise or consist of waxes have a softening point of from 50 to 150° C. and may include one or more of: i) polyethylene having a number average molecular weight (Mn) from 500 to 7500; ii) petroleum waxes, such as paraffin wax, ozokerite wax, ceresin wax, ader wax, earth wax and microcrystalline wax; iii) synthetic waxes made by polymerizing carbon monoxide and hydrogen, such as Fischer-Tropsch wax; iv) polyolefin waxes; v) hydrogenated animal, fish or vegetable oils; and, vi) plant and animal derived waxes, such as beeswax, carnauba wax, candelilla wax, spermeceti wax and baysberry wax.

[0149] The solid cosmetic composition of this embodiment may comprise from 4 to 50 wt. %, for example from 5 to 40 wt. % or from 5 to 30 wt. %, based on the weight of the composition, of one or more thickening agents. Said thickening agents may be selected from: i) carboxylic acid polymers, such as those members of the CARBOPOL®900 series available from B.F. Goodrich; ii) acrylates/C.sub.10-C.sub.30 alkyl acrylate crosspolymers, such as CARBOPOL®1342, CARBOPOL®1382, PEMULEN® TR-1 and PEMULEN® TR-2 available from B.F. Goodrich; iii) crosslinked polyacrylate polymers, which may be cationic or nonionic polymer; iv) polyacrylamide polymers, in particular nonionic polyacrylamide polymers; iv) multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids; v) polysaccharides including scleroglucans, cellulose and cellulose derivatives, such as carboxymethylcellulose and alkyl hydroxyalkyl cellulose ethers; vi) modified starches; vii) gums such as xantham gum, acacia gum, alginin, sodium alginate, locust bean gum and guar gum; viii) proteins such as collagen, albumen and gelatin; and, mixtures thereof.

[0150] The solid cosmetic composition may comprise up to 50 wt. % of carriers which have the functionality of leaving behind, upon application, a film comprising the melanoidin component as the colorant. Exemplary carriers include: water; water-miscible solvents; water-immiscible solvents; volatile silicones, as described in Todd et al., “Volatile Silicone Fluids for Cosmetics”, Cosmetics and Toiletries, 91:27-32 (1976); non-volatile organic fluids; and, non-volatile silicone fluids. The term “volatile silicone” refers to those silicone materials that have measurable vapor pressure under ambient conditions: cyclomethicone is an important example.

[0151] For completeness, non-limiting examples of nonvolatile organic fluids include mineral oil, PPG-14 butyl ether, isopropyl myristate, petrolatum, butyl stearate, cetyl octanoate, butyl myristate, myristyl myristate, C12-15 alkylbenzoate (e.g., Finsolv™), dipropylene glycol dibenzoate, PPG-15 stearyl ether benzoate and blends thereof (e.g. Finsolv TPP), neopentyl glycol diheptanoate (e.g. Lexfeel 7 supplied by Inolex), octyldodecanol, isostearyl isostearate, octododecyl benzoate, isostearyl lactate, isostearyl palmitate, isononyl/isononoate, isoeicosane, octyldodecyl neopentanate, hydrogenated polyisobutane, and isobutyl stearate. U.S. Pat. No. 6,013,248 (Luebbe et al.) and U.S. Pat. No. 5,968,489 (Swaile et al) are considered to provide instructive references in this context.

[0152] The solid cosmetic compositions will typically comprise up to 5 wt. %, for example up to 3 wt. %, based on the weight of the composition, of surfactant. A wide variety of surfactants may be used herein—both for emulsification of the dispersed phase and to provide acceptable spreading of the applied composition—but desirable surfactants will be selected from the group consisting of: anionic surfactants; nonionic surfactants; amphoteric surfactants; non-lathering surfactants; emulsifiers; and, mixtures thereof. The disclosure regarding surfactants provided for Exemplary Embodiment 1 is considered applicable and is incorporated herein by reference.

[0153] A preservative may also be present in the solid composition. Examples thereof include: phenoxy ethanol; C.sub.1-C.sub.6 alkyl parabens; imidazolinyl urea; dimethydimethoyl hydantoin; N-(3-chloroallyl) hexaminium chloride; cetrimonium bromide; trisodium ethylene diamine tetraacetic acid; and, butylated hydroxyanisole (BHA). When present, the preservative will typically be added in an amount up to 0.5 wt. %, for instance from 0.01 to 0.1 wt. %, based on the weight of the composition. However, given the preservative functionality of melanoidins, it is also envisaged that said solid cosmetic compositions may be substantially free of preservatives.

[0154] The solid cosmetic compositions of the present invention can be formulated as any known or otherwise effective product form for providing topical application of the melanoidin active to the desired area of the skin. Non-limiting examples of such product forms include cakes, sticks, pencils and roll-ons, subject to the proviso that the selected form contains all the essential elements as defined herein. The solid compositions are generally stored in and dispensed from a suitable package or applicator device which should be closeable to prevent loss of any constituent volatile compounds prior to and between applications.

[0155] In view of the foregoing description and exemplary embodiments, it will be apparent to those skilled in the art that equivalent modifications thereof can be made without departing from the scope of the claims.