SYSTEMS, METHODS AND KITS FOR MODIFYING HAIR COLOR

Abstract

SYSTEMS, METHODS, AND KITS FOR MODIFYING HAIR COLOR The present disclosure relates to hair color modification systems comprising a pretreatment composition comprising at least one amine-based compound and a coloring composition comprising at least one microtube-dye composite. The disclosure also relates to methods of modifying hair color using the systems, as well as kits comprising the systems. Figure for abstract: none

Description

Title of the invention: SYSTEMS, METHODS AND KITS FOR MODIFYING HAIR COLOR Technical field

[0001] The present disclosure relates to systems, methods and kits for modifying hair color. CONTEXT

[0002] Consumers desire to use cosmetic compositions to improve the appearance of keratinous substrates such as hair, for example, by altering the color, style, and / or shape of the hair, and / or by imparting various properties to the hair, such as shine and conditioning. Many of the compositions and processes known for improving the appearance of hair involve chemical treatment of the hair. For example, the process of altering hair color may involve coloring the hair by depositing an artificial color onto the hair that imparts a different shade or color to the hair.

[0003] Traditional hair coloring processes include permanent and semi-permanent or temporary hair coloring. Permanent hair coloring compositions utilize oxidation dye precursors, which are also known as primary intermediates or couplers. These oxidation dye precursors are colorless or weakly colored compounds that, when combined with oxidizing agents, give rise through a process of oxidative condensation to colored complexes. Permanent hair coloring compositions also contain ammonia or other alkalizing agents that cause the hair shaft to swell, thereby allowing small oxidative dye molecules to penetrate the cuticle and cortex before the oxidation condensation process is complete.The larger colored complexes resulting from the oxidative reaction are then trapped inside the hair fiber, thus permanently changing the hair color. On the other hand, semi-permanent or temporary hair coloring compositions usually use pigments, fat-soluble dyes, natural dyes or direct dyes selected from acidic (anionic), basic (cationic) or neutral direct dyes that are deposited on the hair fiber to impart color to the hair.

[0004] However, it is known that traditional hair coloring compositions have drawbacks. For example, oxidative hair coloring processes generally cause damage to the hair, making it example brittle, dry, rough and / or fragile hair, and / or irritation of the scalp or skin due to the use of hydrogen peroxide and alkaline agents required to achieve permanent coloring of hair fibers.

[0005] Semi-permanent or temporary hair coloring compositions can provide a chromatic color to the hair, but the color may lack persistence due to the nature of the interactions that bind the direct dyes to the hair fiber and / or photosensitivity. Furthermore, semi-permanent or temporary hair coloring compositions can also cause irritation to the skin and / or scalp. In addition, semi-permanent or temporary hair colorants are ordinarily not capable of providing the same vibrancy or diversity of shades as permanent hair coloring compositions.

[0006] It has previously been discovered that aluminosilicate microtubes can be used as a carrier for synthetic or natural colorants, for example as described in U.S. Patent No. 10,799,439. However, although this microtube-dye composite can be used to deliver color to hair in a manner that does not damage the hair or cause irritation to the skin and / or scalp, the process can lead to unsatisfactory color deposition and hair coloring effectiveness.

[0007] The present inventors have now surprisingly discovered hair coloring methods using a microtube-dye composite that provides improved color deposition and more vibrant hair colors. ABSTRACT

[0008] It has been surprisingly and unexpectedly discovered that the systems, methods and kits for modifying hair color according to the disclosure can provide a more vibrant color to the hair, and have the advantage of causing less damage to the hair than traditional hair coloring processes.

[0009] In various embodiments, the disclosure relates to systems for modifying hair color comprising (a) a pretreatment composition comprising at least one amine-based compound and optionally at least one solvent, and (b) a coloring composition comprising at least one microtube-dye composite and optionally at least one solvent. The pretreatment composition may, in various embodiments, comprise a total amount of amine-based compound(s) ranging from about 0.001% to about 20% by weight, based on the total weight of the pretreatment composition. The coloring composition may, in various embodiments, comprise a total amount of microtube-dye composite(s) ranging from about 0.01% to about 15% by weight, based on the weight of the coloring composition. In various embodiments, the amine-based compounds may be selected from non-ten- sioactives, and the colorant can be chosen from synthetic or natural direct dyes.

[0010] In some embodiments, the amine-based compounds are selected from non-surfactant amine-based compounds having a molecular weight of less than about 10,000, for example, less than about 7,700, less than about 5,000, or less than about 2,500, such as from about 50 to about 10,000, from about 50 to about 8,000, from about 50 to about 6,000, from about 50 to about 4,000, from about 50 to about 3,000, from about 50 to about 2,000, from about 100 to about 10,000, from about 100 to about 7,500, from about 100 to about 5,000, or from about 100 to about 2,500.

[0011] In some embodiments, the amine-based compounds are selected from non-surfactant amine-based compounds having at least one nitrogen atom in the main chain and / or at least one HN=C imine group, such as, for example, amino acids such as arginine and / or lysine, polyamino acids such as polyarginine, and synthetic or natural polyamines, such as, for example, polyalkyleneimines, such as branched or unbranched C2-C8 or C2-C5 polyalkyleneimines. In some embodiments, a polyethyleneimine may be selected. For example, a polyethyleneimine having a molecular weight of from about 100 to about 5,000, from about 100 to about 3,500, from about 100 to about 2,500, or from about 100 to about 2,000 may be selected.

[0012] Preferably, the pretreatment and / or coloring compositions have an acidic pH, for example, a pH of about 7 or less, such as less than about 6, or less than about 5, for example, from about 2 to about 7, from about 2 to about 6, from about 2 to about 5, or from about 2 to about 4.

[0013] In at least one embodiment, the disclosure relates to systems comprising (a) a pretreatment composition comprising at least one non-surfactant amine-based compound having a molecular weight of from about 50 to about 5,000, and (b) a coloring composition comprising at least one halloysite-dye composite comprising at least one hair coloring agent and at least one solvent, wherein the pretreatment composition and / or the coloring composition each have a pH of from about 2 to about 7, such as from about 2 to about 6, from about 2 to about 5, or from about 2 to about 4.

[0014] The disclosure relates to methods of treating hair, for example by changing the color of hair, by applying to the hair systems according to the disclosure. In various embodiments, the methods comprise (a) applying to the hair a pretreatment composition according to the disclosure, and (b) applying to the hair a coloring composition according to the disclosure. Optionally, steps (a) and (b) may be repeated one or more times, with the same pretreatment and / or coloring composition(s) or a different pretreatment and / or coloring composition(s).

[0015] In various embodiments, the methods may further comprise allowing the pretreatment and / or coloring compositions to remain on the hair for an optional setting period, for example up to about 60 minutes, such as from about 2 minutes to about 50 minutes or from about 3 minutes to about 40 minutes. In other embodiments, the methods may comprise a step of drying the hair after the step of applying the pretreatment composition, for example after an optional setting period, but before the step of applying the coloring composition, which may comprise air drying the hair or drying the hair with a hair dryer or hood, optionally with heat.The drying step in various embodiments may comprise drying the hair after the step of applying the pretreatment composition (optionally after a setting period) without rinsing or otherwise removing the pretreatment composition from the hair before drying the hair.

[0016] Kits for modifying hair color comprising the systems according to the disclosure are also disclosed. In various embodiments, the kits comprise (a) a first container containing a pretreatment composition according to the disclosure, and (b) a second container containing a coloring composition according to the disclosure. BRIEF DESCRIPTION OF THE FIGURES

[0017] [Fig.lA], [Fig.lB], [Fig.lC], [Fig.lD] Figures 1A-1D are graphs demonstrating a change in AE (y-axis) of hair treated with exemplary systems and methods according to the disclosure using pretreatment compositions comprising non-surfactant amine-based compounds, then coloring compositions comprising microtube-dye composites (4A-4J), compared to hair treated with comparative compositions and methods without pretreatment (4A'-4G'), demonstrating that the systems and methods including pretreatment compositions according to the disclosure exhibit surprisingly improved color deposition.

[0018] [Fig.2A], [Fig.2B], [Fig.2C] Figures 2A-2C are graphs demonstrating a change in AE (y-axis) of hair treated with systems and methods of the disclosure using pretreatment compositions according to exemplary embodiments of the disclosure having varying pH values, and then coloring compositions according to exemplary embodiments of the disclosure having varying pH values. These graphs show that systems according to the disclosure having a lower pH of the pretreatment compositions and / or coloring provide surprisingly improved color deposit.

[0019] [Fig.3A], [Fig.3B] Figures 3A-3B are graphs demonstrating a Change in AE (y-axis) of hair treated with systems comprising exemplary pretreatment compositions comprising polyethyleneimine of different molecular weights and then coloring compositions according to exemplary embodiments of the disclosure, or treated with coloring compositions only. These graphs show that pretreatment compositions including non-surfactant amine-based compounds having lower molecular weights surprisingly give better color deposition.

[0020] [Fig.3C] [Fig.3C] is a graph showing the percentage change in AE (y-axis) of hair treated with systems comprising pretreatment compositions comprising polyethyleneimine of different molecular weights and then with coloring compositions comprising microtube-dye composites. This graph shows that, as the molecular weight of the non-surfactant amine-based compound in the systems and methods according to the disclosure decreases, the AE surprisingly increases.

[0021] [Fig.4A], [Fig.4B] Figures 4A-4B are graphs demonstrating a change in AE (y-axis) of hair treated with systems and methods according to the disclosure comprising exemplary pretreatment compositions according to the disclosure followed by exemplary coloring compositions according to the disclosure, compared to the change in AE of hair treated with pretreatment compositions having the same pH but including non-amine-based compounds, followed by exemplary coloring compositions according to the disclosure. These graphs show that pretreatment compositions comprising non-surfactant amine-based compounds provide surprisingly improved color deposition compared to pretreatment compositions comprising non-amine-based compounds, even when the pHs of the pretreatment compositions are the same and / or the molecular weights of the pretreatment agents are similar. DETAILED DESCRIPTION

[0022] The disclosure relates to systems, methods and kits for modifying hair color. The systems, methods and kits according to the disclosure surprisingly and unexpectedly provide improved color deposition on the hair which gives it a more vibrant and satisfying coloring. Systems

[0023] It has been surprisingly and unexpectedly discovered that when hair is treated with a system comprising a pretreatment composition comprising at least an amine-based compound and a coloring composition comprising a microtube-dye composite, better color deposition on the hair and more vibrant hair color can be achieved. Pretreatment compositions

[0024] The systems according to the disclosure comprise at least one pretreatment composition comprising at least one non-surfactant amine-based compound, and optionally at least one solvent.

[0025] The non-surfactant amine-based compounds useful in the pretreatment compositions of the disclosure have a molecular weight of less than about 10,000, such as less than about 8,000, less than about 6,000, less than about 5,000, less than about 4,000, less than about 3,000, or less than about 2,500.For example, the non-surfactant amine-based compounds may, in various embodiments, have a molecular weight ranging from about 50 to about 10,000, from about 50 to about 9,000, from about 50 to about 8,000, from about 50 to about 7,000, from about 50 to about 6,000, from about 5,000, from about 50 to about 4,000, from about 50 to about 3,000, from about 50 to about 2,000, from about 100 to about 10,000, from about 100 to about 9,000, from about 100 to about 8,000, from about 100 to about 7,000, from about 100 to about 6,000, from about 100 to about 5,000, or from about 100 to about 10,000. about 000, about 100 to about 4,000, about 100 to about 3,000 or about 100 to about 2,000.In some embodiments, the non-surfactant amine-based compounds may have a molecular weight ranging from about 50 to about 7,500, from about 50 to about 2,500, from about 50 to about 1,500, from about 100 to about 7,500, from about 100 to about 2,500, or from about 100 to about 1,500.

[0026] In various embodiments, the useful non-surfactant amine-based compounds include one or more nitrogen atoms in the main chain or backbone of the compound, namely at least one nitrogen atom other than as part of a side chain attached to the main chain or backbone of the compound. It is to be understood that such compounds may include one or more nitrogen atoms in one or more side chains, but such compounds will also include one or more nitrogen atoms in the main chain or backbone of the compound. For example, amino acids such as arginine and / or lysine may be used. In some embodiments, the non-surfactant amine-based compound may comprise, consist essentially of, or consist of arginine.

[0027] In other embodiments, the useful non-surfactant amine-based compounds contain one or more HN=C imine groups. For example, synthetic or natural polyamines may be selected. In various embodiments, polyalkyleneimines such as C2-C8 or C2-C5 polyalkyleneimines Branched or unbranched amines may be selected. For example, the amine-based compounds may be selected from polyethyleneimine, polypropyleneimine, poly(allylamine) and / or polyvinylamine. In at least one embodiment, the amine-based compound comprises a polyethyleneimine. Useful polyethyleneimines include products available from BASF under the names LUPASOL or POLYIMIN, for example, Lupasol® PS, Lupasol® PL, Lupasol® PR8515, Lupasol® G20 or Lupasol® G35. Optionally, dendrimers and derivatives of these polyalkyleneimines may also be used. In some embodiments, the non-surfactant amine-based compound may comprise, consist essentially of, or consist of a polyethyleneimine.

[0028] In other embodiments, polyamino acids may be selected such as, for example, polyarginine.

[0029] Optionally, the pretreatment compositions according to the disclosure may comprise a plurality of non-surfactant amine-based compounds. In embodiments where a plurality of non-surfactant amine-based compounds are present, preferably at least one has a molecular weight of less than about 10,000, such as less than about 8,000, less than about 6,000, less than about 5,000, less than about 3,000, or less than about 2,500.

[0030] The total amount of non-surfactant amine-based compounds may range from about 0.001% to about 25% by weight, based on the total weight of the pretreatment composition. For example, in some embodiments, the total amount of amine-based compounds may range from about 0.001% to about 20%, such as from about 0.001% to about 15%, from about 0.001% to about 10%, from about 0.001% to about 9%, from about 0.001% to about 8%, from about 0.001% to about 7%, from about 0.001% to about 6%, from about 0.001% to about 5%, from about 0.001% to about 4%, from about 0.001% to about 3%, from about 0.001% to about 2.5%, from about 0.001% to about 2%, from about 0.001% to about 1.5%, from about 0.001% to about 1%, 0.001% to about 0.5%, from about 0.01% to about 25%, from about 0.01% to about 20%, from about 0.01% to about 15%, from about 0.01% to about 10%, from about 0.01% to about 9%, from about 0,01% to about 8%, from about 0.01% to about 7%, from about 0.01% to about 6%, from about 0.01% to about 5%, from about 0.01% to about 4%, from about 0.01% to about 3%, from about 0.01% to about 2.5%, from about 0.01% to about 2%, from about 0.01% to about 1.5%, from about 0.01% to about 1%, from about 0.01% to about 0.5%, from about 0.1% to about 25%, from about 0.1% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 10%, from about 0.1% to about 9%, from about 0.1% to about 8%, from about 0.1% to about 7%, from about 0.1% to about 6%, from about 0.1% to about 5%, from about 0.1% to about 4%, , from about 0.1% to about 3%, from about 0.1% to about 2.5%, from about 0.1% to about 2%, from about 0.1% to about 1.5%, from about 0.1% to about 1% or from about 0.1% to about 0.5% by weight, based on the total weight of the pretreatment composition. In other embodiments, the total amount of non-surfactant amine-based compounds ranges from about 0.2% to about 25%, from about 0.2% to about 20%, from about 0.2% to about 15%, from about 0.2% to about 10%, from about 0.2% to about 9%, from about 0.2% to about 8%, from about 0.2% to about 7%, from about 0.2% to about 6%, from about 0.2% to about 5%, from about 0.2% to about 4%, from about 0.2% to about 3%, from about 0.2% to about 2.5%, from about 0.2% to about 2%, from about 0.2% to about 1.5%, from about 0.2% to about 1%, from about 0.5% to about 25%, from about 0.5% to about 20%, from about 0.5% to about 15%, from about 0.5% to about 10%, from about 0.5% to about 9%,from about 0.5% to about 8%, from about 0.5% to about 7%, from about 0.5% to about 6%, from about 0.5% to about 5%, from about 0.5% to about 4%, from about 0.5% to about 3%, from about 0.5% to about 2.5%, from about 0.5% to about 2%, from about 0.5% to about 1.5% or from about 0.5% to about 1% by weight, based on the total weight of the pretreatment composition.

[0031] The pretreatment composition comprises at least one solvent, for example, water, non-aqueous solvents, or a mixture thereof. In various embodiments, the solvent of the pretreatment composition comprises, consists essentially of, or consists of water.

[0032] Examples of non-aqueous solvents include, for example, glycerin, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, lamellar lipid materials, and mixtures thereof. Examples of organic solvents that may be mentioned, without limitation, are monoalcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example, monoethyl ether or monobutyl ether of diethylene glycol.Organic solvents can be volatile or non-volatile compounds.

[0033] In some embodiments, the pretreatment composition comprises from about 60% to about 99.999% of a solvent, such as water, by weight. In some embodiments, the pretreatment composition comprises from about 75% to about 99.999% by weight, of solvent by weight, such as from about 75% to about 99.99% by weight, about 75% to about 99.9% by weight, about 75% to about 99%, about 75% to about 98%, about 75% to about 97%, about 90% to about 99.9%, about 90% to about 99%, about 90% to about 98%, about 90% to about 97%, about 95% to about 99.9%, about 95% to about 99%, about 95% to about 98% or about 95% to about 97%, by weight, based on the total weight of the pretreatment composition.

[0034] In various embodiments, the systems comprise multiple pretreatment compositions, such as, for example, two or more pretreatment compositions. In such embodiments, the non-surfactant amine-based compound(s) present in the two or more pretreatment compositions may be the same or different. Optionally, in such embodiments, at least one non-surfactant amine-based compound has a molecular weight of less than about 10,000, such as less than about 8,000, less than about 6,000, less than about 5,000, less than about 3,000, or less than about 2,500.

[0035] The pretreatment composition(s) may comprise additional components. By way of example only, the pretreatment composition may comprise acidity regulators, preservatives, humectants, oils, fragrances, etc.

[0036] In various embodiments, the pretreatment composition(s) have a pH of less than or equal to about 7, such as less than or equal to about 6, less than or equal to about 5, less than or equal to about 4, or less than or equal to about 3. For example, the pretreatment composition may have a pH of from about 1 to about 7, such as from about 2 to about 6, from about 2.5 to about 5, or from about 3 to about 4.

[0037] It has been discovered that pretreatment compositions having a lower pH and / or comprising amine-based compounds having a lower molecular weight can exhibit surprising color-enhancing effectiveness. Therefore, in some embodiments, it may be preferable that the pretreatment composition(s) comprise(s) at least one non-surfactant amine-based compound having a molecular weight of less than about 10,000, such as less than about 8,000, less than about 6,000 or less than about 5,000, less than about 3,000 or less than about 2,500, for example, from about 100 to about 10,000, from about 100 to about 7,500, from about 100 to about 5,000, or from about 100 to about 2,500, and that the pretreatment composition has a pH of less than or equal to 7, such as from about 1 to about 5 or from about 2 to about 4.In other embodiments, it may be preferable that the pretreatment composition comprises at least one non-surfactant amine-based compound having a molecular weight of less than about 10,000 or less than about 5,000, for example, from about 100 to about 5,000 or from about 100 to about 2,500, and that the . pretreatment composition has a pH less than or equal to 7, such as from about 1 to about 5 or from about 2 to about 4. Coloring composition

[0038] The systems according to the disclosure comprise at least one coloring composition comprising at least one microtube-dye composite, and optionally at least one solvent. The dye of the composite may include at least one anionic, cationic, non-ionic or natural dye, as well as mixtures thereof.

[0039] The term “microtube” as used herein includes any tubular material having dimensions at or below the micron level (e.g., the tube length being below about 1 mm), including nanotubes, or may refer to tubular structures having an outer diameter that is submicron and lengths below about 100 microns, such as below about 50 microns or below about 10 microns. Various exemplary embodiments employ microtubes that are aluminosilicate in nature, such as halloysite and imogolite, or that are not aluminosilicate in nature, such as sepiolite or cylindrite.

[0040] Examples of non-limiting microtubes include, for example, halloysite (Al2Si2O5(OH)4) microtubes. Halloysite is in the form of small cylinders (nanotubes) which may, for example, have a wall thickness of from about 10 to about 15 atomic aluminosilicate sheets, an outer diameter of from about 50 to about 60 nm, an inner diameter of from about 12 to about 20 nm, and a length of from about 0.5 to about 10 μm, with an average length of about 1 μm. Their outer surface is primarily composed of -Si-O-Si- and their inner surface of -Al-OH, and as such, these surfaces are oppositely charged at about neutral pH. In various embodiments of the disclosure, the microtubes comprise, consist essentially of, or consist of halloysite.

[0041] The microtubes may be “loaded” with a hair coloring agent, meaning that the coloring agent is incorporated into the lumen of the microtube, to form the microtube-dye composite. The microtube-dye composite may be formed by known methods of loading microtubes (such as halloysite), for example as described in U.S. Pat. Nos. 8,507,056 and 10,799,439, and Abdullayev E. and Lvov Y., “Halloysite clay nanotubes as a ceramic 'skeleton' for functional biopolymer composites with sustained drug release,” J. Mater. Chem. B, 1(23):2894-2903 (2013).

[0042] For example, a hair coloring agent may be dissolved in a suitable solvent, such as water, a non-aqueous solvent, or a mixture thereof, to form a solution. The amount of colorant may be selected such that it approaches or is at the limit of solubility of the colorant in the solvent. In an exemplary embodiment, the solution may contain from about 1% to about 20%, such as from about 1% to about 15%, by weight, of the coloring agent. pill. In another embodiment, the solution may contain from about 1 to about 20 mg of dye per mL of solvent, such as from about 1 to about 15 mg of dye per mL of solvent. An appropriate amount of the microtube component may be added to the dye solution, e.g., in powder form, to form a dispersion. The amount of the microtube component may, for example, be selected to provide a microtube:dye weight ratio of from about 1:1 to about 5:1, such as from about 1:1 to about 4:1, from about 1:1 to about 3:1, or from about 1.5:1 to about 2.5:1, such as about 2:1, which may enhance the color.

[0043] The dispersion may optionally be homogenized, sonicated, agitated, placed under vacuum, washed and / or dried to provide microtubes loaded with the hair coloring agent. For example, the dispersion may be sonicated for a period of time such as about 2 to 10 minutes, e.g., about 5 minutes, and then mixed for a period of time such as about 10 to 60 minutes, e.g., about 30 minutes. The sonication and / or mixing steps may be repeated one or more times and may be carried out under ambient conditions, under vacuum and / or at an elevated temperature, or combinations thereof, until the microtubes are loaded with dye. Once the microtubes are loaded, the supernatant may be removed, for example, by centrifugation, and the microtube-dye composite may be dried, for example, in an oven at a temperature of at least 40°C, such as at least 45°C, for example, about 50°C.

[0044] In one embodiment, the solvent may comprise, consist essentially of, or consist of water. For example, the solvent may be water and may include a component for facilitating dissolution of the selected colorant, for example, sodium carbonate.

[0045] In other embodiments, the solvent may comprise, consist essentially of, or consist of a non-aqueous solvent. Non-limiting examples of non-aqueous solvents that may be used to load the hair coloring agent into the microtubes include alkanediols (polyhydric alcohols) such as glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, di-propylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, caprylyl glycol, 1,2-hexanediol, 1,2-pentanediol, and 4-methyl-1,2-pentanediol; alkyl alcohols having 1 to 4 carbon atoms such as such as ethanol, methanol, butanol, propanol and isopropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, mono-iso-propyl ether diethylene glycol, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-l-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, l,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitan, acetin, diacetin, triacetin, sulfolane, acetone, and mixtures thereof.

[0046] In some embodiments, the solvent may comprise both water and a non-aqueous solvent, for example, from about 1% to about 99% water mixed with about 1% to about 99% non-aqueous solvent. One skilled in the art has the ability to select the appropriate solvent and / or solvent combination, and amounts thereof, to dissolve the hair coloring agents useful according to the disclosure.

[0047] In various embodiments, the inner and / or outer surface of the microtube may be modified prior to loading with the hair coloring agent, which may facilitate dye loading and / or the hair coloring process. For example, the microtubes may be modified with an anionic surfactant such as sodium dodecyl sulfate, or may be made hydrophobic, which may be preferable when loading a hydrophobic dye. In one embodiment, the microtubes may be dispersed in an anionic surfactant solution (e.g., at a weight ratio of about 1:1), optionally agitated and / or centrifuged, and optionally, washed and / or dried, to produce microtubes modified with the anionic surfactant, having an increased net negative charge compared to unmodified microtubes.

[0048] In another embodiment, the microtubes may be rendered hydrophobic, for example, by coupling a silane coupling agent to hydroxyl groups present on the surface of the microtubes to increase the contact angle of the microtube, or by absorption of anionic amphiphilic molecules in positive light. In various embodiments, the contact angle may be increased to at least about 30°, such as at least about 50°, at least about 75°, at least about 100°, at least about 115°, such as at least about 120°. Examples of non-limiting silane coupling agents include (3-glycidyloxypropyl) trimethoxy silane (GTMS), 3-aminopropyltriethoxy silane (APTES), hexamethyldisilazane (HMDS), and octadecyltrimethoxy silane (ODTMS). For example, the microtubes may be sonicated with the silane coupling agent in a solvent, e.g., water, an organic solvent, or a mixture thereof, and then refluxed at an increased temperature, for example, above about 50°C or above about 75°C, such as about 85°C.

[0049] In yet another embodiment, the surface of the microtube may be selectively etched. For example, the inner surface of the halloysite lumen may be etched by treatment with acid, such as sulfuric acid, which may increase the diameter of the lumen. In one embodiment, the halloysite may be stirred in sulfuric acid (e.g., IM) at elevated temperature, e.g., greater than about 50°C or greater than about 75°C, such as about 80°C, for a period of time such as at least 2 hours, at least 4 hours, at least 6 hours, or at least 8 hours. Such treatment may increase the loading capacity of the microtubes by 2, 3, 4 times the pre-etching processing capacity, or even more.

[0050] Useful hair coloring agents according to the disclosure include direct dyes such as anionic, cationic, nonionic, and natural hair coloring agents, as well as mixtures of any two or more thereof. In some embodiments, the hair coloring agents comprise, consist essentially of, or consist of natural hair coloring agents. In various embodiments, the compositions are free or substantially free of oxidative hair coloring agents.

[0051] The term "anionic hair coloring agent" is intended to mean any hair coloring agent comprising in its structure at least one CO2R or SO3R substituent, wherein R indicates a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. For example, anionic hair coloring agents may be selected from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid tria-rylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoid dyes, acid natural dyes, and combinations thereof.

[0052] In an exemplary embodiment, the anionic hair coloring agent may be chosen from diaryl anionic azo dyes of formula (II) or (III):

[0053] (II)

[0054] (III)

[0055] in which

[0056] R7, R8, R9, Rio, R'7, R'8, R'9 and R'10, which may be the same or different, re have a hydrogen atom or a group chosen from:

[0057] - alkyl;

[0058] - alkoxy, alkylthio;

[0059] - hydroxyl, mercapto;

[0060] nitro, nitroso; [0061 ] R°—C(X)—X—, R°—X — C(X)—, R°—X—C(X)—X"— with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be the same or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

[0062] (O)2S(O )—, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0063] (O)CO—, M+ with M+ as defined previously;

[0064] R"—S(O)2—, with R" representing a hydrogen atom or an alkyl group, aryl, (di)(alkyl)amino or aryl(alkyl)amino; preferably, a phenylamino or phenyl group;

[0065] R'"—S(O)2—X'— with R'" representing an alkyl group or an aryl group even fully substituted, X' as defined above;

[0066] - (di)(alkyl)amino;

[0067] aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )—, M+ and iv) alkoxy, with M+ as defined above;

[0068] optionally substituted heteroaryl; preferably, a benzothiazolyl group;

[0069] cycloalkyl; in particular cyclohexyl;

[0070] Ar—N=N— with Ar representing an optionally substituted aryl group; preferably, a phenyl optionally substituted by one or more alkyl, (O)2S(O—)—, M+ or phenylamino groups; or

[0071] or alternatively two contiguous groups R7with R8or R8with R9or R9with Reform together with a fused benzo group A'; and R'7with R'8 or R'8with R'9or R'9 with R'10 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O)2S(O—)—, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R° —C(X)—X'—; vi) R°—X'—C(X)—; ix) R°—X'—C(X)—X"—; x) Ar—N=N— and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X" and Ar previously defined; and

[0072] W represents a sigma 6 bond, an oxygen or sulfur atom, or a divalent radical i) —NR—, with R as defined above, or ii) methylene —C(Ra)(Rb )—, with Ra and Rb, which may be the same or different, representing a hydrogen atom or an aryl group, or alternatively, Ra and Rb form, with the carbon atom which supports them, a spiro cycloalkyl; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

[0073] it being understood that formulas (II) and (III) comprise at least one sulfonate radical (O)2S(O )—, M+ or one carboxylate radical (O)CO—, M+ on one of the rings A, A', B, B' or C; preferably, sodium sulfonate.

[0074] As non-limiting examples of dyes of formula (II), mention may be made of acid red 1, acid red 4, acid red 13, acid red 14, acid red 18, acid red 27, acid red 28, acid red 32, acid red 33, acid red 35, acid red 37, acid red 40, acid red 41, acid red 42, acid red 44, pigment red 57, acid red 68, acid red 73, acid red 135, acid red 138, acid red 184, food red 1, food red 13, acid orange 6, acid orange 7, acid orange 10, acid orange 19, acid orange 20, acid orange 24, yellow 6, acid yellow 9, acid yellow 36, acid yellow 199, food yellow 3, acid violet 3, acid violet 7, acid violet 14, acid blue 113, acid blue 117, acid black 1, acid brown 4, acid brown 20, acid black 26, acid black 52, food black 1, food black 2 and food yellow 3 or orange yellow.

[0075] As non-limiting examples of dyes of formula (III), mention may be made of acid red 111, acid red 134 and acid yellow 38.

[0076] In another exemplary embodiment, the anionic hair coloring agent may be selected from pyrazolone anionic azo dyes of formulae (IV) and (V):

[0077] (IV)

[0078] (V)

[0079] in which

[0080] Ru, Ri2 and Rn, which may be the same or different, represent a hydrogen or halogen atom, an alkyl group or —(O)2S(O ), M+ with M+ as defined above;

[0081] Represents a hydrogen atom, an alkyl group or a —C(O)O— group, M+ with M as defined above;

[0082] Represents a hydrogen atom;

[0083] Represents an oxo group, in which case R'i6is absent, or alternatively Ri5with Ri6 together form a double bond;

[0084] Ri7 and Ri8, which may be identical or different, represent a hydrogen atom or a group chosen from:

[0085] (O)2S(O )—, M+ with M+ as defined previously;

[0086] Ar—O—S(O)2— with Ar representing an optionally substituted aryl group, of preferably a phenyl optionally substituted by one or more alkyl groups;

[0087] Ri9et Reform together either a double bond or a benzo group D', which is optionally substituted;

[0088] R'i6, R'i9 and R'2O, which may be the same or different, represent an atom of hydrogen or an alkyl or hydroxyl group;

[0089] R2 represents a hydrogen atom or an alkyl or alkoxy group;

[0090] Raet Rb, which may be the same or different, are as defined above, preferably, Represents a hydrogen atom and Represents an aryl group;

[0091] Y represents either a hydroxyl group or an oxo group; represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

[0092] it being understood that formulas (IV) and (V) comprise at least one sulfonate radical (O)2S(O )—, M+ or a carboxylate radical C(O)O—, M+ on one of the rings D or E; preferably, sodium sulfonate.

[0093] As non-limiting examples of dyes of formula (IV), mention may be made of acid red 195, acid yellow 23, acid yellow 27 and acid yellow 76.

[0094] As a non-limiting example of a colorant of formula (V), yellow may be mentioned. acid 17.

[0095] In another exemplary embodiment, the anionic hair coloring agent may be chosen from anthraquinone dyes of formulas (VI) and (VII):

[0097] (VII)

[0098] in which

[0099] R22, R23, R24, R25, R26, and R27, which may be the same or different, represent a hydrogen or halogen atom, or a group chosen from:

[0100] - alkyl;

[0101] - hydroxyl, mercapto;

[0102] - alkoxy, alkylthio;

[0103] optionally substituted aryloxy or arylthio, preferably substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined above;

[0104] aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O)2S(O )—, M+ with M+ as defined above;

[0105] - (di)(alkyl)amino;

[0106] - (di)(hydroxyalkyl)amino;

[0107] (O)2S(O )—, M+ with M+ as defined previously;

[0108] Z' represents a hydrogen atom or a group NR28R29 with R28 and R2g, which may be the same or different, representing a hydrogen atom or a group chosen from:

[0109] - alkyl;

[0110] - polyhydroxyalkyl such as hydroxyethyl;

[0111] aryl optionally substituted by one or more groups, more particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )—, M+ with M+ as defined previously; iii) R°—C(X)—X'—, R°—X'—C(X)—, R°—X'—C(X)—X"— with R°, X, X' and X" as defined previously, preferably, R° represents an alkyl group;

[0112] cycloalkyl; for example, cyclohexyl;

[0113] Z represents a group selected from hydroxyl and NR^sR^q, with R'28 and R'29, which may be the same or different, representing the same atoms or groups as R 28 and R29 as defined above;

[0114] it being understood that formulas (VI) and (VII) comprise at least one sulfonate radical (O)2S(O )—, M+ or one carboxylate radical C(O)O—, M+; preferably sodium sulfonate.

[0115] As non-limiting examples of dyes of formula (VI), mention may be made of acid blue 25, acid blue 43, acid blue 62, acid blue 78, acid blue 129, acid blue 138, acid blue 140, acid blue 251, acid green 25, acid green 41, acid violet 42, acid violet 43, mordant red 3 and EXT violet no. 2.

[0116] As another non-limiting example of a colorant of formula (VII), mention may be made of acid black 48.

[0117] In another exemplary embodiment, the anionic hair coloring agent may be chosen from nitro dyes of formulas (VIII) and (IX):

[0118] (VIII)

[0119] (IX)

[0120] in which

[0121] R30, RiiCt R32, which may be the same or different, represent an atom of hydrogen or halogen, or a group chosen from:

[0122] - alkyl;

[0123] alkoxy optionally substituted by one or more hydroxyl groups, alkylthio optionally substituted by one or more hydroxyl groups;

[0124] - hydroxyl, mercapto;

[0125] nitro, nitroso;

[0126] polyhaloalkyl;

[0127] R°—C(X)—X'—, R°—X'—C(X)—, R°—X'—C(X)—X'— with R°, X, X' and X" such as previously defined;

[0128] (O)2S(O )—, M+ with M+ as defined previously;

[0129] (O)CO—, M+ with M+ as defined previously;

[0130] - (di)(alkyl)amino;

[0131] - (di)(hydroxyalkyl)amino;

[0132] heterocycloalkyl such as piperidino, piperazino or morpholino;

[0133] Rcet Rd, which may be the same or different, represent a hydrogen atom or an alkyl group;

[0134] W is as defined above; for example, W may represent a group —NH—;

[0135] ALK represents a linear or branched divalent C6-alkylene group; more particularly, ALK represents a —CH2—CH2— group;

[0136] n is 1 or 2;

[0137] p represents an integer between 1 and 5 inclusive;

[0138] q represents an integer between 1 and 4 inclusive;

[0139] u is 0 or 1;

[0140] when n is 1, J represents a nitro or nitroso group;

[0141] when n is 2, J represents an oxygen or sulfur atom, or a divalent radical —S(O)m— with m representing an integer 1 or 2; for example, J represents a radical —SO2—;

[0142] M' represents a hydrogen atom or a cationic counterion; which may be present or absent, represents a benzo group even partially substituted by one or more R30 groups as defined above;

[0143] it being understood that formulas (VIII) and (IX) comprise at least one sulfonate radical (O)2S(O )—, M+ or a carboxylate radical C(O)O—, M; for example, sodium sulfonate.

[0144] As non-limiting examples of dyes of formula (VIII), mention may be made of acid brown 13 and acid orange 3.

[0145] As non-limiting examples of dyes of formula (IX), mention may be made of acid yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-[3-hydroxyethylamino-3-nitrobenzenesulfonic acid and D&C EXT Yellow 7.

[0146] In another exemplary embodiment, the hair coloring agent anionic can be chosen from triarylmethane dyes of formula (X):

[0147] (X)

[0148] in which

[0149] R33, R34, R35 and R36, which may be the same or different, represent an atom of hydrogen or a group selected from alkyl, optionally substituted aryl and optionally substituted arylalkyl; in particular, an alkyl and benzyl group substituted by a group (O)mS(O )—, M with M+ and m as defined above;

[0150] R37, R38, R39, R40, R41, R42, R43 and R44, which may be the same or different, re have a hydrogen atom or a group chosen from:

[0151] -alkyl;

[0152] - alkoxy, alkylthio;

[0153] - (di)(alkyl)amino;

[0154] - hydroxyl, mercapto;

[0155] nitro, nitroso;

[0156] R°—C(X)—X'—, R°—X'—C(X)—, R°—X'—C(X)—X"— with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be the same or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

[0157] (O)2S(O )—, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0158] (O)CO—, M+ with M+ as defined previously;

[0159] or alternatively two contiguous groups R4iwith R42or R42with R43or R43with R^ together form a fused benzo group: T; with T optionally substituted by one or more groups selected from i) nitro; ii) nitroso; iii) (O)2S(O )—, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°—C(X)—X'—; viii) R° —X'—C(X)—; ix) Ro—X'—C(X)—X"—; with M+, R°, X, X' and X" as defined above;

[0160] it being understood that at least one of the cycles G, H, I or T comprises at least one sulfonate radical (O)2S(O )— or one carboxylate radical —C(O)O—; for example sulfonate.

[0161] In a preferred embodiment of formula (X), R37 to R40 represent a hydrogen atom, and R43 to R44, which may be the same or different, represent a hydroxyl group or (O)2S(O )—, M+; and when R43 together forms a benzo group, it is preferably substituted with a (O)2S(O )— group.

[0162] As non-limiting examples of dyes of formula (X), mention may be made of acid blue 1; acid blue 3; acid blue 7, acid blue 9; acid violet 49; acid green 3; acid green 5 and acid green 50.

[0163] In another exemplary embodiment, the anionic hair coloring agent may be chosen from xanthene-based dyes of formula (XI):

[0164] (XI)

[0165] in which

[0166] R45, R46, R47 and R4x, which may be the same or different, represent an atom of hydrogen or halogen;

[0167] R41J, R50, R5i and R52, which may be the same or different, represent a hydrogen or halogen atom, or a group chosen from:

[0168] - alkyl;

[0169] - alkoxy, alkylthio;

[0170] - hydroxyl, mercapto;

[0171] nitro, nitroso;

[0172] (O)2S(O )—, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0173] (O)CO—, M+ with M+ as defined previously;

[0174] G represents an oxygen or sulfur atom or an NRe group with Retel as defined previously;

[0175] L represents an alkoxide O, M+; a thioalkoxide S, M+ or a group NRf, with Rf representing a hydrogen atom or an alkyl group and M+ as defined previously; M+ is in particular sodium or potassium;

[0176] L' represents an oxygen or sulfur atom or an ammonium group; N+RfRg, with Rfet Rg, which may be the same or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; for example L' represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O)mS(O )—, M+ with m and M+ as defined above;

[0177] Q and Q', which may be the same or different, represent an oxygen or sulfur atom; and

[0178] M+ is as defined previously.

[0179] As non-limiting examples of dyes of formula (XI), mention may be made of acid yellow 73; acid red 51; acid red 52; acid red 87; acid red 92; acid red 95 and acid violet 9.

[0180] In another exemplary embodiment, the anionic hair coloring agent may be chosen from indole-based dyes of formula (XII):

[0181] (XII)

[0182] in which

[0183] R53, R54, R55, R56, R57, R58, R59 and R60, which may be the same or different, re have a hydrogen atom or a group chosen from:

[0184] - alkyl;

[0185] - alkoxy, alkylthio;

[0186] - hydroxyl, mercapto;

[0187] nitro, nitroso;

[0188] R°—C(X)—X'—, R°—X'—C(X)—, R°—X'—C(X)—X"— with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be the same or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;

[0189] (O)2S(O )—, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0190] (O)CO—, M+ with M+ as defined previously;

[0191] G represents an oxygen or sulfur atom or an NRe group with Retel as defined previously;

[0192] R; and Rh, which may be the same or different, represent a hydrogen atom or an alkyl group;

[0193] it being understood that formula (VII) comprises at least one sulfonate radical (O)2S(O )—, M+ or a carboxylate radical C(O)O—, M+; for example, sodium sulfonate.

[0194] As a non-limiting example of a dye of formula (XII), mention may be made of acid blue 74.

[0195] In another exemplary embodiment, the anionic hair coloring agent may be chosen from quinoline-based dyes of formula (XIII):

[0196] (XIII)

[0197] in which

[0198] R6i represents a hydrogen or halogen atom or an alkyl group;

[0199] R62, Res and R64, which may be the same or different, represent an atom hydrogen or a group (O)2S(O )—, M+ with M+ representing a hydrogen atom or a cationic counterion;

[0200] or alternatively R6i with R62, or R6i with R64, together form a benzo group optionally substituted by one or more (O)2S(O )— groups, M+ with M+ representing a hydrogen atom or a cationic counterion;

[0201] it being understood that formula (VIII) comprises at least one sulfonate radical (O)2S(O )—, for example, sodium sulfonate.

[0202] As non-limiting examples of dyes of formula (XIII), mention may be made of acid yellow 2, acid yellow 3 and acid yellow 5.

[0203] Without limitation, examples of anionic hair coloring agents may be selected from (CI 45380) Acid Red 87 (Formula XI); (CI 10316) 2,4-Dinitro-1-naphthol-7-sulfonic acid sodium salt (Formula IX); (CI 10383) Acid Orange 3 (Formula VIII); (CI 13015) Acid Yellow 9 / Food Yellow 2 (Formula II); (CI 14780) Direct Red 45 / Food Red 13 (Formula II); (CI 13711) Acid Black 52 (Formula II); (CI 13065) Acid Yellow 36 (Formula II); (CI 14700) l-Hydroxy-2-(2',4'-xylyl-5-sulfonatoazo)naphthalene-4-sulfonic acid sodium salt / Food Red 1 (Formula II); (CI 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (Formula II); (CI 14805) 4-Hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid sodium salt / Acid Brown 4 (Formula II); (CI 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 4 (Formula II); (CI 15985) Food Yellow 3 / Pigment Yellow 104 (Formula II); (C.I. 16185) Acid Red 27 / Food Red 9 (Formula II); (CI 16230) Acid Orange 10 / Food Orange 4 (Formula II); (CI 16250) Acid Red 44 (Formula II); (CI 17200) Acid Red 33 / Food Red 12 (Formula II); (CI 15685) Acid Red 184 (Formula II); (CI 19125) Acid Violet 3 (Formula II); (CI 18055) l-Hydroxy-2-(4'-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid sodium salt / Acid Violet 7 / Food Red 11 (Formula II); (CI 18130) Acid Red 135 (Formula II); .

[0204] (CI 19130) Acid Yellow 27 (Formula IV); (CI 19140) Acid Yellow 23 / Food Yellow 4 (Formula IV); (CI 20170) 4'-(sulfonato-2",4"-dimethyl)bis(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24 (Formula II); (CI 20470) l-Amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid sodium salt / Acid Black 1 (Formula II); (CI 23266) (4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-hydroxy-5,8-disulfon ato)naphthylazo)biphenyl / acid red 111 (formula III); (CI 27755) Food Black 2 (Formula II) (CI 25440) l-(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-disulfonato)naphthyla zo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (Formula II), (CI 42090) Acid Blue 9 (Formula X) (CI 60730) Acid Violet 43 (Formula VI) (CI 61570) Acid Green 25 (Formula VI), (CI 62045) l-Amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid sodium salt / Acid Blue 62 (Formula VI), (CI62105) Acid Blue 78 (Formula VI), (CI 14710) 4-Hydroxy-3-((2-methoxyphenyl)azo)-l-naphthalenesulfonic acid sodium salt / Acid Red 4 (Formula II); 2-Piperidino-5-nitrobenzenesulfonic acid (Formula IX); 2-(4'-N,N-(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid (formula IX); 4-[3-hydroxyethylamino-3-nitrobenzenesulfonic acid (formula IX); (CI 42640) Acid Violet 49 (formula X); (CI 42080) Acid Blue 7 (formula X); (CI 58005) l,2-Dihydroxy-3-sulfoanthraquinone sodium salt / Mordant Red 3 (formula VI); (CI 62055) l-Amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)2-anthracenesulfonic acid sodium salt / Acid Blue 25 (formula VI); or (CI 14710) l,2-Dihydroxy-3-sulfoanthraquinone sodium salt / Mordant Red 3 (formula VI); 4-Hydroxy-3-((2-methoxyphenyl)azo)-l-naphthalenesulfonic acid / acid red 4 (formula II). Non-limiting examples of cationic dyes include hydrazono cationic dyes of formulae (Va) and (V'a), azo cationic dyes (Via) and (Vl'a) and diazo cationic dyes (Vlla) below: I (Bfe)-J (Va} 3 1 Met Ml (Rb) -J (V#aJ (Vl'a) and | - -WHü (vi xa}

[0205] in which:

[0206] - Het+ representing a cationic heteroaryl radical, preferably carrying a endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally preferentially substituted by one or more alkyl groups (C1-C8) such as methyl;

[0207] - Ar+ representing an aryl radical, such as phenyl or naphthyl, carrying a charge exocyclic cationic, preferably ammonium, in particular trialkyl(C1-C8)ammonium such as trimethylammonium;

[0208] - Ar represents an aryl group, in particular phenyl, optionally substituted, of preferably by one or more electron-donating groups such as i) optionally substituted (C1-C8)alkyl, ii) optionally substituted (C1-C8)alkoxy, iii) (di)(C1-C8)alkylamino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl (C1-C8)alkylamino, v) optionally substituted N-(C1-C8)alkyl-N-aryl (C1-C8)alkylamino or alternatively Ar represents a julolidine group;

[0209] - Ar' is an optionally substituted divalent (hetero)arylene group, such as phenylene, in particular para-phenylene, or naphthalene, which are optionally substituted, preferably by one or more (C1-C8) alkyl, hydroxyl or (C1-C8) alkoxy groups

[0210] - Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably by one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)alkylamino, (C1-C8)alkoxy or phenyl groups;

[0211] - Ra and Rb, which may be the same or different, represent an atom hydrogen or an alkyl group (C1-C8), optionally substituted, preferably by a hydroxyl group;

[0212] - or alternatively the substituent Ra with a substituent of Het+ and / or Rb with a sub substituted Ar and / or Ra with Rb form, together with the atoms which carry them, a (hetero)cycloalkyl;

[0213] - in particular, Ra and Rb represent a hydrogen atom or an alkyl group (in C1-C4), which is optionally substituted by a hydroxyl group;

[0214] - An- represents an anionic counterion such as a mesylate or a halide.

[0215] For example, useful cationic dyes may be selected from basic blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green, Basic Orange 31,1, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 76, Basic Red 51, Basic Purple 1, Basic Purple 2, Basic Purple 3, Basic Purple 10, Basic Purple 14, Basic Yellow 57 and Basic Yellow 87.

[0216] Non-limiting examples of non-ionic hydrophobic direct dyes may

[0217]

[0218] be chosen from HC blue no. 2, HC blue no. 4, HC blue no. 5, HC blue no. 6, HC blue nc 7, HC blue no. 8, HC blue no. 9, HC blue no. 10, HC blue no. 11, HC blue no. 12, HC blue no. 13, HC blue no. 15, HC blue no. 17, HC brown no. 1, HC brown no. 2, HC green no. 1, HC orange no. 1, HC orange no. 2, HC orange no. 3, HC orange no. 5, HC red BN, HC red no. 1, HC red no. 3, HC red no. 7, HC red no. 8, HC red no. 9, HC red no. 10, HC red no. 11, HC red no. 13, red HC no. 54, red HC no. 14, purple HC BS, purple HC no. 1, purple HC no. 2, yellow HC no. 2, yellow HC no. 4, yellow HC no. 5, yellow HC no. 6, yellow HC no. 7, yellow HC no. 8, yellow HC no. 9, yellow HC no. 10, yellow HC no. 11, yellow HC No. 12, HC Yellow No. 13, HC Yellow No. 14, HC Yellow No. 15. Natural hair coloring agents may also be chosen. As used herein, the term "natural" hair coloring agents includes colorants derived from natural materials (of plant, mineral, or animal origin), e.g., extracts, ground material, and decoctions, which have a higher or lower concentration of colorants. Examples of natural hair coloring agents may be selected from, but are not limited to, orceins, curcumin, indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, phthalocyanines and porphyrins optionally complexed to a metal, glycosylated or non-glycosylated iridoids, chromene dyes, anthraquinone and naphthoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chroman dyes, such as neoflavanols and neoflavanos, flavanols and anthocyanidols.Extracts containing these natural dyes may also be used, for example, plant extracts or poultices containing said dyes. In some embodiments, the dye comprises, consists essentially of, or consists of one or more natural dyes, preferably hydrophobic natural dyes. For example, the dye may comprise, consist essentially of, or consist of curcumin, indigo, or a mixture thereof. For example, in some embodiments, the microtubes may be loaded with an amount of hair coloring agent ranging from about 0.01% to about 50% by weight, based on the weight of the microtube before loading, such that of about 0.1 of about 0.1 of about 0.1 of about 0.1 of about 0.1 of about 0.1 of about 0.1 of about 0.1 of about 0.1 % to about 50 % to about 40 % to about 30 % to about 20 % to about 10 % to about 8 % to about 6 % to about 4 % to about 2 %, of about 0.1 %, of about 0.1 %, of about 0.1 %, of about 0.1 %, of about 0.1 %, of about 0.1 %, of about 0.1 %, of about 0.1 %, of about 0.1 % to about 45 % to about 35 % to about 25 % to about 15 % to about 9 % at about 7° % at about 5° % at about 3° % at about 1° ° %, ° %, ° % ° %, %, %, %, %, %, from about 0.5% to about 50%, from about 0.5% to about 45%, from about 0.5% to about 40%, from about 0.5% to about 35%, from about 0.5% to about 30%, from about 0.5% to about 25%, from about 0.5% to about 20%, from about 0.5% to about 15%, from about 0.5% to about 10%, from about 0.5% to about 9%, from about 0.5% to about 8%, from about 0.5% to about 7%, from about 0.5% to about 6%, from about 0.5% to about 5%, from about 0.5% to about 4%, from about 0.5% to about 3%, from about 0.5% to about 2%, from about 0.5% to about 1%, from about 1% to about 50%, from about 1% to about 45%, from about 1% to about 40%, from about 1% to about 35%, from about 1% to about 30%, from about 1% to about 25%, from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, from about 1% to about 9%, from about 1% to about 8%, from about 1% to about 7%, from about 1% to about 6%, from about 1% to about 5%, from about 1% to about 4%, from about 1% to about 3%, or from about 1% to about 2% by weight, based on the total weight of the microtube before loading, including all sub-ranges between these values.

[0219] For example, in some embodiments, the microtubes may be loaded with an amount of hair coloring agent ranging from about 30% to about 50% by weight, based on the weight of the microtube before loading, such as from about 35% to about 50%, from about 40% to about 50%, from about 30% to about 45%, from about 35% to about 45%, or from about 40% to about 45% by weight, based on the weight of the microtube before loading, including all sub-ranges between these values.

[0220] In other exemplary embodiments, the microtubes may be loaded with an amount of hair coloring agent ranging from about 0.01% to about 10% by weight, based on the weight of the microtube before loading, such as from about 0.01% to about 7.5%, from about 0.01% to about 5%, from about 0.01% to about 3.5%, from about 0.1% to about 10%, from about 0.1% to about 7.5%, from about 0.1% to about 5%, from about 0.1% to about 3.5%, from about 1% to about 10%, from about 1% to about 7.5%, from about 1% to about 5%, or from about 1% to about 3.5% by weight, based on the weight of the microtube before loading, including all sub-ranges between these values.

[0221] The coloring composition ordinarily comprises a solvent, in which the microtube-dye composite may be dispersed. The solvent may be selected from water, non-aqueous solvents or a mixture thereof. The solvent will advantageously be chosen so as that it does not interfere with deposition of the microtube-dye composite on the hair, and that it does not damage or irritate the hair, scalp and / or skin. In various embodiments, the solvent comprises, consists essentially of, or consists of water.

[0222] Examples of non-aqueous solvents include, for example, glycerin, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, lamellar lipid materials, and mixtures thereof. Examples of organic solvents that may be mentioned, without limitation, are monoalcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example, monoethyl ether or monobutyl ether of diethylene glycol.Organic solvents can be volatile or non-volatile compounds.

[0223] Other non-limiting examples of solvents that may be used include alkanediols (polyhydric alcohols) such as glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, caprylyl glycol, 1,2-hexanediol, 1,2-pentanediol, and 4-methyl-1,2-pentanediol; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol;glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, diethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-l-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-isopropyl ether;2-pyrrolidone, N-methyl-2-pyrrolidone, l,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitone, sorbitan, acetin, diacetin, triacetin, sulfolane, and mixtures thereof. ;

[0224] The solvent may be present in the coloring composition in an amount ranging from about 50% to about 99.99% by weight, based on the total weight of the coloring composition. For example, the total amount of solvent may range from about 80% to about 99%, from about 80% to about 98%, from about 80% to about 97%, from about 80% to about 96%, from about 80% to about 95%, from about 80% to about 94%, from about 80% to about 93%, from about 80% to about 92%, from about 80% to about 91%, or from about 80% to about 90% by weight, based on the total weight of the coloring composition.

[0225] The coloring composition may include additional components, provided that such other additional components do not substantially interfere with the deposition of the microtube-dye composite on the hair. By way of example only, the coloring composition may include acidity regulators, preservatives, humectants, oils, fragrances, etc.

[0226] In various embodiments, the coloring composition has a pH of less than or equal to about 7, such as less than or equal to about 6, less than or equal to about 5, less than or equal to about 4, or less than or equal to about 3. For example, the pretreatment composition may have a pH of from about 1 to about 7, such as from about 2 to about 6, from about 2.5 to about 5, or from about 3 to about 4.

[0227] The microtube-dye composite may be present in the coloring composition in an amount ranging from about 0.01% to about 15% by weight, based on the weight of the coloring composition, such as from about 0.1% to about 10%, from about 0.1% to about 9%, from about 0.1% to about 8%, from about 0.1% to about 7%, from about 0.1% to about 6%, from about 0.1% to about 5%, from about 0.1% to about 4%, from about 0.1% to about 3%, from about 0.1% to about 2%, from about 0.1% to about 1%, from about 0.5% to about 10%, from about 0.5% to about 9%, from about 0.5% to about 8%, from about 0.5% to about 7%, from about 0.5% to about 6%, from about 0.5% to about 5%, from about 0.5% to about 4%, from about 0.5% to about 3%, from about 0.5% to about 2%, from about 0.5% to about 1%, from about 1% to about 10%, from about 1% to about 9%, from about 1% to about 8%, from about 1% to about 7%, from about 1% to about 6%,from about 1% to about 5%, from about 1% to about 4%, from about 1% to about 3%, or from about 1% to about 2% by weight, based on the weight of the coloring composition, including all subranges of these values.

[0228] It is to be understood that the microtube-dye composite included in the coloring composition may include mixtures of different microtubes, mixtures of different dyes, or both. By way of example only, a first set of microtubes comprising halloysite may be loaded with one dye, a second set of microtubes comprising halloysite may be loaded with a second dye, and the first and second sets of microtube-dye composites may be included in the coloring composition. As another example, a first set of microtubes comprising halloysite may be loaded with a dye, a second set of microtubes comprising a structure other than halloysite may be loaded with a second dye, and the first and second sets of microtube-dye composites may be included in the coloring composition. Methods

[0229] It has been discovered that by modifying hair color using systems according to the disclosure, improved color deposition and vibrancy have been advantageously, surprisingly, and unexpectedly achieved. In particular, while it was previously discovered that microtube-dye composites could be used to impart color to hair with less damage to the hair and / or less irritation to the skin and / or scalp, the systems and methods according to the disclosure exhibit a surprisingly significant improvement in color deposition and vibrancy compared to using the microtube-dye composite alone.

[0230] Methods according to the disclosure include treating the hair with the pretreatment composition and treating the hair with the coloring composition.

[0231] In various methods according to the disclosure, the hair is first treated with the pretreatment composition, by applying the pretreatment composition to the hair and optionally massaging or combing the composition throughout the hair to ensure complete coverage. The pretreatment composition may be applied to the hair in a desired amount, for example, up to about 10 grams of pretreatment composition per gram of hair, such as up to about 5 grams per gram of hair, for example, about 4 grams per gram of hair, about 3 grams per gram of hair, about 2 grams per gram of hair, or about 1 gram per gram of hair.

[0232] The pretreatment composition may optionally be left on the hair for a period of time, for example, up to about 60 minutes or up to about 45 minutes, such as from about 30 seconds to about 60 minutes, from about 1 minute to about 50 minutes, from about 3 minutes to about 40 minutes, or from about 5 minutes to about 30 minutes. The pretreatment composition may optionally be partially, completely, or substantially removed from the hair after the leave-in period, and the hair may optionally then be partially, completely, or substantially completely dried, for example, with a hair dryer or hood or air dried. Alternatively, the hair may be partially, completely or substantially completely dried, for example with a hair dryer or hood or air dried, without removing the pretreatment composition from the hair, for example without rinsing the hair or without drying the hair with a towel. Preferably, the hair is completely or substantially completely dried after a setting period without removing the pretreatment composition from the hair, the drying step optionally including the use of heat.

[0233] The methods further include a step of applying the coloring composition to the hair after applying the pretreatment composition to the hair and optionally drying, for example by massaging or combing the composition throughout the hair to ensure complete coverage. The coloring composition, which includes a microtube-dye composite, for example a halloysite-dye composite, may be applied to the hair in a desired amount, for example up to about 10 grams of coloring composition per gram of hair, such as up to about 5 grams per gram of hair, for example, up to about 4 grams per gram of hair, up to about 3 grams per gram of hair, up to about 2 grams per gram of hair, or up to about 1 gram per gram of hair.

[0234] The coloring composition may be left on the hair for a period of time to achieve a desired coloring effect, for example, up to about 60 minutes or up to about 45 minutes, such as from about 30 seconds to about 60 minutes, from about 1 minute to about 50 minutes, from about 3 minutes to about 40 minutes, or from about 5 minutes to about 30 minutes. One skilled in the art will be able to determine an appropriate amount of time for the coloring composition to remain on the hair to achieve the desired effect.

[0235] After a desired setting period, the coloring composition may be rinsed from the hair, and the hair may optionally be washed, rinsed, dried and / or styled in any conventional manner.

[0236] In various embodiments, the steps described above of applying a pretreatment composition to the hair, optionally applying the pretreatment composition to the hair for a setting period, optionally removing the pretreatment composition from the hair, applying a coloring composition to the hair, optionally applying the coloring composition to the hair for a setting period, and optionally removing the coloring composition from the hair may be repeated one or more times, with the same pretreatment and / or coloring composition(s) or different pretreatment and / or coloring composition(s).

[0237] Thus, by way of example only, a method according to the disclosure may comprising applying a pretreatment composition (1a) to the hair, leaving the pretreatment composition (1a) on the hair for a setting period, removing the pretreatment composition (1a) from the hair, applying a coloring composition (1b) to the hair, leaving the coloring composition (1b) on the hair for a setting period, and removing the coloring composition (1b) from the hair.

[0238] Another example of a method according to the disclosure may comprise applying a pretreatment composition (la) to the hair, allowing the pretreatment composition (la) to remain on the hair for a setting period, removing the pretreatment composition (la) from the hair, applying a coloring composition (1b) to the hair, allowing the coloring composition (1b) to remain on the hair for a setting period, removing the coloring composition (1b) from the hair, applying the pretreatment composition (la) to the hair a second time, allowing the pretreatment composition (la) to remain on the hair for a setting period, removing the pretreatment composition (la) from the hair, applying the coloring composition (1b) to the hair a second time,allowing the coloring composition (1b) to remain on the hair for a setting period and removing the coloring composition (1b) from the hair, wherein the pretreatment composition (1a) in the first application is identical to the pretreatment composition (1a) in the second application, and the coloring composition (1b) in the first application is identical to the coloring composition (1b) in the second application.

[0239] Yet another example of a method according to the disclosure may comprise applying a pretreatment composition (1a) to the hair, allowing the pretreatment composition (1a) to remain on the hair for a setting period, removing the pretreatment composition (1a) from the hair, applying a coloring composition (1b) to the hair, allowing the coloring composition (1b) to remain on the hair for a setting period, removing the coloring composition (1b) from the hair, applying a pretreatment composition (2a) to the hair, allowing the pretreatment composition (2a) to remain on the hair for a setting period, removing the pretreatment composition (2a) from the hair, applying the coloring composition (2b) to the hair,leaving the coloring composition (2b) on the hair for a setting period and removing the coloring composition (2b) from the hair, wherein the pretreatment compositions (1a) and (2a) are not identical and the hair coloring compositions (1b) and (2b) are not identical.

[0240] Another example of a non-limiting method according to the disclosure may comprise applying a pretreatment composition (la) to the hair, optionally the drying the hair, applying a coloring composition (1b) to the hair without first removing the pretreatment composition (1a), optionally leaving the coloring composition (1b) on the hair for a setting period, and removing the pretreatment composition (1) and the coloring composition (1b) from the hair. Kits

[0241] In another embodiment, the disclosure relates to kits comprising the systems described herein. According to various embodiments, the kits may be multi-compartment or multi-container kits, where the compartments or containers are mutually separate. For example, the kits may comprise at least two compartments or containers, with a first compartment or container containing a pretreatment composition, and a second compartment or container containing a coloring composition according to the disclosure. In other embodiments, the kits may comprise at least three, at least four, or more compartments or containers.

[0242] The compartments or containers of the kits according to the disclosure may be in any configuration, without limitation. They may, for example, be a bottle, a tube, a sachet, an ampoule, or any other container configured to contain the pretreatment composition(s) and the coloring composition(s) in a mutually separate manner within the kit. The kits may optionally include additional compartments for additional components such as, for example, additional pretreatment compositions, additional coloring compositions, shampoo compositions, and the like.

[0243] Various exemplary embodiments of kits according to the disclosure include:

[0244] a first compartment or container that contains a pretreatment composition comprising at least one amine-based compound and optionally at least one solvent; and

[0245] a second compartment or container which contains a coloring composition comprising at least one microtube-dye composite and optionally at least one solvent, wherein, in the microtube-dye composite, the dye comprises at least one hair coloring agent.

[0246] Other exemplary embodiments of kits according to the disclosure include:

[0247] a first compartment or container which contains a pretreatment composition comprising from about 0.01% to about 15% of at least one non-surfactant amine-based compound and water,

[0248] wherein the pretreatment composition has a pH of less than or equal to about 7, such as from about 2 to about 6; and

[0249] a second compartment or container which contains a coloring composition comprising from about 0.01% to about 15% of at least one halloysite-dye composite comprising at least one hair coloring agent and water,

[0250] wherein the coloring composition has a pH of less than or equal to about 7, such as from about 2 to about 6.

[0251] In various embodiments, kits such as those described above may optionally include other compartments or containers, for example, a third compartment or container containing a pretreatment composition according to the disclosure different from that in the first compartment or container, and / or a fourth compartment or container containing a coloring composition according to the disclosure different from that in the second compartment or container.

[0252] It is to be understood that, in exemplary kits according to the invention, the pretreatment composition(s) and coloring composition(s) may be described herein for various systems, methods and examples, for example with respect to particular components and / or particular ranges thereof.

[0253] Thus, in some embodiments, the pretreatment and / or coloring composition may not be present in the kit in a solvent, or may be present in the kit in a solvent but in concentrated form. For example, the pretreatment and / or coloring composition may be present in the kit in solid or powder form, and the user may mix the solid or powder with a solvent, such as water, before use. Alternatively, the pretreatment and / or coloring composition may be present in the form of a gel or thickened liquid that must be mixed with a solvent, such as water, before use. In such embodiments, a kit with more than two compartments or containers may be contemplated.For example, a kit with three (and / or four) compartments or containers, where a third (and / or fourth) compartment or container includes a solvent, for example, to be mixed with the pretreatment composition and / or the coloring composition, may be chosen.

[0254] Kits may also include additional components or compartments, such as, for example, instructions or an apparatus or tool for applying the pretreatment and / or coloring compositions to the hair, for example, an applicator brush and / or a compartment therefor.

[0255] As used herein, the terms "comprising," "having," and "including" (or "comprise," "have," and "include") are used in their open, non-limiting sense.

[0256] The terms “a”, “an”, “the” and “the” are understood to include the plural and the singular.

[0257] The expression "and / or" should be understood to include both the conjunctive and the disjunctive. For example, "A and / or B" means "A and B" as well as "A or B", and expressly covers examples of one of the two without reference to the other. For example, "preventing and / or reducing" corrosion includes instances of both corrosion prevention and corrosion reduction, as well as instances where corrosion is reduced but not prevented, etc.

[0258] As used herein, the phrases "and mixtures thereof," "and a mixture thereof," "and a combination thereof," "or mixtures thereof," "or a mixture thereof," "or combinations thereof," and "or a combination thereof," are used interchangeably to indicate that the list of components immediately preceding the phrase, such as "A, B, C, D, or mixtures thereof," means that the component(s) may be selected from A, B, C, D, from A + B, from A + B + C, from A + D, from A + C + D, etc., without limitation on variations thereof. Thus, the components may be used individually or in any combination thereof.

[0259] Except in working examples, or unless otherwise indicated, all numbers expressing amounts of ingredients and / or reaction conditions are understood to be modified in all circumstances by the term "about," meaning to within + / - 5% of the number indicated.

[0260] All percentages, parts and ratios herein are based on the total weight of the compositions of the present invention, unless otherwise indicated.

[0261] In this document, all ranges provided are intended to include each specific range within the given ranges, as well as a combination of intermediate sub-ranges. Thus, a range of 1 to 5 specifically includes 1, 2, 3, 4, and 5, as well as sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, etc. All ranges and values ​​disclosed herein are inclusive and combinable. For example, any value or point described herein that falls within a range described herein may serve as a minimum or maximum value to infer a sub-range, etc.

[0262] As used herein, "exempt" means that the component or property is not detectable using accepted methodologies, and "substantially" or “Essentially” free means that the component or property, if detectable using accepted methodologies, is negligible.

[0263] It is to be understood that the use of the terms "treat," "treated," "treatment," and variations thereof is not intended to be limiting, but rather is intended to simply indicate that one or more compositions is / are applied to, and optionally removed from, the hair, as described herein. For example, hair that is "treated" with a pretreatment composition according to the disclosure may have had the pretreatment composition applied to it, and / or may have had the pretreatment composition applied and removed mination of the pretreatment composition, for example, by rinsing or towel drying. As another example, hair that is "treated" with a coloring composition according to the disclosure may have had the coloring composition applied, and / or may have had the coloring composition applied and rinsed. As yet another example, hair that is "treated" with a system according to the disclosure may have had the pretreatment composition applied and optionally removed, and further, may have had the coloring composition applied and optionally rinsed.

[0264] By "non-surfactant amine compounds" is meant that the amine compounds are not amine-based surfactants in the compositions in which they are present. By way of non-limiting example only, in certain embodiments, the "non-surfactant amine compounds" are not capable of reducing the surface tension of deionized water under standard conditions to a value below about 50 nM / m, when added to deionized water in a concentration by weight of 0.5 to 1%.

[0265] The following examples serve to illustrate embodiments of the present disclosure without being limiting in nature. It will be apparent to those skilled in the art that various modifications and variations may be made in the delivery system, compositions and methods of the invention without departing from the spirit and scope of the invention. EXAMPLES

[0266] Implementation of various non-limiting embodiments of the disclosure is shown by means of the following examples.

[0267] In the examples, the change in hair color is assessed with the L* a* b* system, using Colorshot MS, where the change is determined by assessing the hair color after treatment compared to the hair color before treatment. The color change (AE) is defined by: - It) 2 + H “ ®t) 2 + &î) 3

[0268] The greater the AE value, the greater the difference in color compared to the hair before treatment. Example 1 - Microtube-dye composites

[0269] The procedures of Examples IA and IB below were followed to prepare microtube-dye composites having the dye loadings shown in Table 1.

[0270] [Tables 1] Composite Color filler hc(14) Halloysite-Curcumin 1.4% hc(3) Halloysite-Curcumin 3% H-1(43) Halloysite-indigo 43% Example IA – Halloysite-curcumin composites

[0271] Curcumin was completely dissolved in acetone (10 mg dye per mL acetone) and unmodified halloysite (dye:halloysite weight ratio ~2:1) was added with stirring. The dispersion was sonicated for about five minutes and then placed under vacuum and stirred overnight. After centrifugation for about five minutes at 5000 rpm, the supernatant was discarded and the sample was dried under vacuum and crushed to a fine powder. Example IB – Halloysite-indigo composites

[0272] Indigo was completely dissolved in water (99.99% water with 0.01% sodium carbonate; 5 mg dye per mL solvent) and unmodified halloysite (dye:halloysite weight ratio ~2:1) was added with stirring. The dispersion was sonicated for about five minutes and then placed under vacuum and stirred overnight. After centrifugation for about five minutes at 5,000 rpm, the supernatant was discarded and the sample was dried under vacuum and crushed to a fine powder. Example 2 - Pretreatment compositions

[0273] The pretreatment compositions of Table 2 were prepared by dissolving the amine-based compound in water and adjusting the pH of the solution with sodium hydroxide and / or hydrochloric acid, as needed, to prepare aqueous compositions having the reported amine-based compound concentrations and pH values.

[0274] [Tables2] Pretreatment Composition Amine Compound Molecular Weight pH Concentration 2A polyethyleneimine 800 3 3.33% 2B polyethyleneimine 1300 3 0.5% 2C polyethyleneimine 1300 3 3.33% 2D polyethyleneimine 1300 3 10% 2E polyethyleneimine 1300 7 3.33% 2F polyethyleneimine 1300 11 3.33% 2G polyethyleneimine 2000 3 3.33% 2H polyethyleneimine 25000 3 3.33% 21 arginine 174.2 3 3% Example 3 - Coloring compositions

[0275] The coloring compositions of Table 3 were prepared by dispersing the specified halloysite-dye composites of Table 1 in water and adjusting the pH of the dispersion with sodium hydroxide and / or hydrochloric acid, as needed, to prepare aqueous compositions having the reported halloysite-dye composite concentrations and pH values.

[0276] [Tables3] Coloring composition Halloysite-dye composite pH Concentration 3A hc(14) 3 2.5% 3B hc(14) 7 2.5% 3C hc(14) 7 5% 3D hc(3) 7 2.5% 3E hc(3) 3 5% 3F hc(3) 7 5% 3G H-1(43) 3 2.5% 3H H-1(43) 3 5% 31 H-1(43) 7 5%

[0277] Example 4 - Demonstration of the benefit of pretreatment

[0278] The following Examples 4-1 and 4-2 show the surprising improvement in the deposition of color on hair using systems and methods according to the disclosure including pretreatment with non-surfactant amine-based compounds.

[0279] Example 4-1 - Color Provided by Systems Comprising Pretreatment Compositions and Coloring Compositions (of the Invention)

[0280] The color provided to hair with 4A-4J systems comprising combinations of pretreatment compositions prepared in Example 2 and coloring compositions prepared in Example 3 as defined in Table 4-1 was evaluated.

[0281] [Tables4] System Pretreatment composition Coloring composition AE 4A 2C 3F 27.2 4B 2C 3A 15.9 4C 2E 3B 13.2 4D 2C 3H 43.1 4E 2C 31 39.7 4F 2F 31 39.6 4G 21 3D 21.2 4H 2A 3D 19.3 41 2B 3D 20.4 4J 2D 3D 17.3

[0282] The method of treating hair with the 4A-4J systems of the invention was carried out as follows. First, 90% gray virgin hair samples were rinsed with tap water at ~37°C (five times), a commercial shampoo was applied and lathered for about 30 seconds, the sample was allowed to stand for about one minute and then rinsed with tap water for about 30 seconds. The sample was then allowed to air dry.

[0283] Once the sample was completely dry, the pretreatment composition was applied to the sample at a ratio of about 2 grams of pretreatment composition to 1 gram of hair and massaged throughout the hair for about one minute. The sample was then combed with a wide-toothed comb five times and allowed to sit at room temperature for about 30 minutes. The sample was then dried with a hot air hair dryer.

[0284] Once the sample was completely dry, the coloring composition was applied to the hair at a ratio of approximately 2 grams of coloring composition to 1 gram of hair and massaged the entire head for about a minute. After a processing period of about 30 minutes at room temperature, the hair was rinsed with tap water at ~37°C. The hair was then dried with a hot air hair dryer.

[0285] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for each of the 4A-4J systems is shown in Table 4-1 and Figures 1A-1D.

[0286] Example 4-2 - Color imparted by coloring compositions without pre-treatment (Comparative)

[0287] The color imparted to the hair with coloring compositions prepared in Example 3 and defined in Table 4-2, without a pretreatment step, was evaluated to determine the difference between the color deposited on the hair without a pretreatment composition and the color obtained with systems and methods including a pretreatment composition.

[0288] [Tables4] Composition Pretreatment composition Coloring composition AE 4A' - 3F 18.8 4B' - 3A 12.3 4C' - 3B 9.8 4D' - 3H 40.4 4E' - 31 31.7 4F' - 31 31.7 4G' - 3D 12.2

[0289] The method of treating hair with comparative compositions 4A'-4J' was as follows. First, 90% gray virgin hair samples were rinsed with tap water at ~37°C (five times), a commercial shampoo was applied and lathered for about 30 seconds, the sample was allowed to stand for about one minute, and then rinsed with tap water for about 30 seconds. The sample was then allowed to air dry.

[0290] Once the sample was completely dry, the coloring composition was applied to the hair at a ratio of about 2 grams of coloring composition to 1 gram of hair and massaged throughout the hair for about one minute. After a setting period of about 30 minutes at room temperature, The hair was rinsed with tap water at ~37°C. The hair was then dried with a hot air hair dryer.

[0291] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for each of the comparative compositions 4A"-4J' is shown in Table 4-2 and Figures 1A-1D.

[0292] As shown in Figures 1A-1D, hair treated with the inventive systems 4A-4J shows a significantly greater color change relative to the pre-treatment hair color, when compared to the color change of hair treated with the comparative compositions 4A'-4G' not using a pre-treatment composition according to the disclosure.

[0293] Example 4 thus shows that hair colored according to the disclosure, namely treated with a pretreatment composition according to the disclosure and then colored with a coloring composition according to the disclosure, surprisingly and unexpectedly exhibits better color deposition and more vibrant colors compared to hair not pretreated as described herein.

[0294] Example 5 - Demonstration of the benefit of an acidic pH

[0295] The following Examples 5-1 and 5-2 demonstrate the surprising improvement in color deposition on hair using systems and methods where the pretreatment and / or coloring composition(s) is / are acidic. The method of treating hair with Systems 5A-5F was the same as that described in Example 4-1.

[0296] Example 5-1 - Color Provided by Systems Comprising Acidic Pretreatment Compositions

[0297] The color provided to the hair with systems 5A-5D comprising combinations of pretreatment compositions prepared in Example 2 and coloring compositions prepared in Example 3 as defined in Table 5-1 was evaluated.

[0298] [Tables5] System Pretreatment composition pH pretreatment Staining composition pH staining AE 5A 2E 7 3B 7 13.2 5B 2C 3 3B 7 14.9 5C 2F 11 3G 3 40.4 5D 2C 3 3G 3 43.1

[0299] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the color of the hair before treatment. The AE for hair treated with each of the 5A-5D systems is shown in Table 5-1 and Figures 2A-2B. As can be seen, the AE for hair treated with systems 5B and 5D (pretreatment compositions with a pH below 7) is higher than the AE for hair treated with systems 5A and 5C (identical systems but with corresponding pretreatment compositions with a pH of 7 or higher).

[0300] Example 5-1 thus shows that systems according to the disclosure comprising pretreatment compositions having a lower pH surprisingly provide a greater color change than systems comprising pretreatment compositions having a higher pH.

[0301] Example 5-2 - Color provided by systems comprising compositions of acid coloring

[0302] The color provided to the hair with the 5E-5F systems comprising combinations of pretreatment compositions 2C of Example 2 and coloring compositions 31 or 3H of Example 3 as defined in Table 5-2 was evaluated.

[0303] [Tables5] System Pretreatment composition pH pretreatment Staining composition pH staining AE 5E 2C 3 31 7 39.7 5F 2C 3 3H 3 43.1

[0304] The color change for both samples was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for hair treated with systems 5E-5F is shown in Table 5-2 and in [Fig.2C]. As can be seen, the AE for hair treated with system 5F (coloring composition having a pH lower than 7) is higher than the AE for hair treated with system 5E (identical system but with a coloring composition having a pH of 7).

[0305] Example 5-2 shows that systems according to the disclosure having coloring compositions with a lower pH surprisingly provide a greater color change than systems comprising coloring compositions having a higher pH.

[0306] Example 5 therefore shows that hair colored according to the disclosure, treated with a pretreatment composition having an acidic pH and subsequently colored with a coloring composition having an acidic pH, surprisingly and unexpectedly exhibits better color deposition and more vibrant color.

[0307] Example 6 - Demonstration of the benefit of the molecular mass of the compound amine

[0308] The following Examples 6-1 and 6-2 demonstrate the surprising improvement in color deposition on hair using systems and methods according to the disclosure. The method for treating hair with systems 6A-6C and C1 was the same as that described in Example 4-1, and the method for treating hair with comparative compositions C2-C3 was the same as that described in Example 4-2.

[0309] Example 6-1 - Comparison of the color provided by systems comprising pretreatment compositions having polyethyleneimine of different molecular weights

[0310] The color provided to the hair with systems according to the disclosure comprising a combination of pretreatment composition 2C of Example 2 and coloring composition 3B of Example 3, and with a comparative system C1 comprising a combination of pretreatment composition 2H of Example 2 and coloring composition 3B of Example 3, as defined in Table 6-1, was evaluated. The color provided to the hair by comparative composition C2 was also evaluated, without a pretreatment step.

[0311] [Tableauxô] System Pretreatment Composition Amine Molecular Weight Pretreatment pH Staining Composition pH Staining AE 6A 2C 1,300 3 3B 7 14.9 Cl 2H 25,000 3 3B 7 7 C2 - - - 3B 7 9.8

[0312] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for hair treated with systems 6A and C1 and composition C2 is shown in Table 6-1 and [Fig.3A]. As can be seen, the AE for hair treated with system C1 (pretreatment composition with a polyethyleneimine having a molecular weight of 25,000) is lower than that for hair treated with either system 6A (pretreatment composition with a polyethyleneimine having a molecular weight of 1,300) or with coloring composition C2 without pretreatment.

[0313] Example 6-1 thus shows that systems according to the disclosure comprising pretreatment compositions having non-surfactant amine-based compounds with a lower molecular weight surprisingly provide a greater color change than systems comprising compositions pretreatment having amine-based compounds with higher molecular weight.

[0314] Example 6-2 - Comparison of color provided by systems comprising pretreatment compositions before polyethyleneimine of different molecular weights

[0315] The color provided to the hair with systems 6B and 6C comprising combinations of pretreatment compositions 2G and 2A of Example 2 and a coloring composition 3D of Example 3 as defined in Table 6-2 was evaluated. The color provided to the hair by comparative composition C3 was also evaluated, without a pretreatment step.

[0316] [Tableauxô] System Pretreatment Composition Amine Molecular Weight Pretreatment pH Staining Composition pH Staining AE 6B 2G 2000 3 3D 7 15.5 6C 2A 800 3 3D 7 19.3 C3 - - - 3D 7 12.2

[0317] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for hair treated with each of systems 6A-6C and composition C3 is shown in Table 6-2 and [Fig.3B]. As can be seen, the AE for hair treated with system 6B (pretreatment composition with a polyethyleneimine having a molecular weight of 2,000) is lower than that for hair treated with system 6C (pretreatment composition with a polyethyleneimine having a molecular weight of 800), but is higher than that for hair treated with coloring composition C3 without pretreatment.

[0318] Example 6-2 shows that systems according to the disclosure comprising pretreatment compositions having non-surfactant amine-based compounds with a lower molecular weight surprisingly provide a greater color change than systems comprising pretreatment compositions having amine-based compounds with a higher molecular weight.

[0319] As shown in [Fig. 3C], which shows the percentage change in AE of hair treated with systems comprising pretreatment compositions comprising non-surfactant amine-based compounds and then with coloring compositions according to the disclosure, as the molecular weight of the non-surfactant amine-based compound decreases, the AE increases in a manner consistent with the invention. Example 6 therefore shows the surprising and unexpected improvement in color deposition on hair using the systems having a pretreatment step according to the disclosure.

[0320] Example 7 - Demonstration of the benefit of amine-based pretreatment compounds

[0321] The following Examples 7-1 and 7-2 demonstrate the surprising improvement in color deposition on hair using systems and methods including a pretreatment composition comprising amine-based compounds. The method for treating hair with systems 7A-7B and C4-C5 was the same as that described in Example 4-1, and the method for treating hair with comparative compositions C6-C7 was the same as that described in Example 4-2.

[0322] Example 7-1 - Comparison of the color provided by systems comprising pretreatment compositions having amine-based compounds with the color provided by pretreatment compositions not having amine-based compounds

[0323] The color provided to the hair by the system 7A according to the disclosure comprising a combination of pretreatment composition 2C of Example 2 and coloring composition 3F of Example 3 was compared to the color provided to the hair by the comparative system C4 comprising a combination of pretreatment composition AA comprising acetic acid as a pretreatment agent and coloring composition 3F of Example 3, as defined in Table 7-1. The color provided to the hair by the comparative composition C6 was also evaluated, without a pretreatment step.

[0324] [Tables7] System Pretreatment composition Molecular weight of the agent pH pretreatment Coloring composition pH coloring AE 7A 2C 1 300 3 3F 7 27.2 C4 AA* 60.05 3 3F 7 18.2 C6 - - - 3F 7 18.8

[0325] *AA is a 1% aqueous solution of acetic acid (molecular weight 60.05) having a pH of 3

[0326] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for hair treated with each of Systems 7A and C4 and Composition C6 is shown in Table 7-1 and [Fig.4A]. As As can be seen, the AE for hair treated with system 7A (pretreatment composition with an amine-based compound having a molecular weight of 1300) is higher than that of hair treated with either system C4 (pretreatment composition with a non-amine-based compound having a molecular weight of 60.05) or with coloring composition C6 without pretreatment. Notably, the AE of hair treated with acetic acid as a pretreatment agent was lower than that of hair treated with composition C6 without pretreatment.

[0327] Example 7-1 thus shows that systems according to the disclosure comprising pretreatment compositions having amine-based compounds surprisingly provide a greater color change than systems comprising pretreatment compositions having non-amine-based compounds, even at the same pH.

[0328] Example 7-2 - Comparison of the color provided by systems comprising pretreatment compositions having amine-based compounds with the color provided by pretreatment compositions not having amine-based compounds

[0329] The color provided to the hair by the system 7B according to the disclosure comprising a combination of pretreatment composition 2C of Example 2 and coloring composition 3C of Example 3 was compared to the color provided to the hair by the comparative system C5 comprising a combination of pretreatment composition TA comprising tannic acid as a pretreatment agent and coloring composition 3C of Example 3, as defined in Table 7-2. The color provided to the hair by the comparative composition C7 was also evaluated, without a pretreatment step.

[0330] [Tables7] System Pretreatment composition Molecular weight of agent pH pretreatment Staining composition pH staining AE 7B 2C 1300 3 3C 7 16.4 C5 TA* 1701.2 3 3C 7 5.4 C7 - - - 3C 7 6.8

[0331] *TA is a 3% aqueous solution of tannic acid (molecular weight 1701.2) having a pH of 3

[0332] The color change for each sample was evaluated by determining the AE of the hair color after treatment relative to that of the hair color before treatment. The AE for hair treated with each of the 7B systems and C5 and composition C7 is shown in Table 7-2 and [Fig.4B]. As can be seen, the AE for hair treated with system 7B (pretreatment composition with an amine-based compound having a molecular weight of 1300) is higher than that of hair treated with either system C5 (pretreatment composition with a non-amine-based compound having a molecular weight of 1701.2) or coloring composition C7 without pretreatment. Notably, the AE of hair treated with tannic acid as a pretreatment agent was lower than that of hair treated with composition C7 without pretreatment.

[0333] Example 7-2 shows that systems according to the disclosure comprising pretreatment compositions having a lower pH surprisingly provide a greater color change than systems comprising pretreatment compositions having non-amine-based compounds, even when the pretreatment agents are of the same molecular weight and the pretreatment compositions have the same pH.

[0334] Example 7 therefore shows the surprising and unexpected improvement in hair color deposition using systems having a pretreatment step with a non-surfactant amine-based compound according to the disclosure.

[0335] The above examples show that the systems, methods and kits according to the disclosure surprisingly and unexpectedly provide improved color deposition on hair compared to those not according to the disclosure.

Claims

Claims

1. A method for modifying the color of hair comprising: (a) applying to the hair a pretreatment composition comprising at least one non-surfactant amine-based compound and at least one solvent, and, wherein the total amount of non-surfactant amine-based compounds is preferably from about 0.001% to about 25%, more preferably from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, most preferably from about 0.5% to about 10% by weight, based on the total weight of the pretreatment composition;and (b) applying to the hair a coloring composition comprising at least one microtube-dye composite and at least one solvent, wherein, in the microtube-dye composite, the dye comprises at least one hair coloring agent, and wherein the total amount of microtube-dye composite preferably ranges from about 0.01% to about 15%, more preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 8%, most preferably from about 1% to about 7% by weight, based on the total weight of the coloring composition.;

2. The method of claim 1, wherein at least one non-surfactant amine-based compound has a molecular weight of less than about 10,000, preferably from about 50 to about 10,000, more preferably from about 50 to about 7,500, more preferably from about 100 to about 5,000, most preferably from about 100 to about 2,500.

3. A method according to claim 1 or claim 2, wherein the at least one non-surfactant amine-based compound is selected from synthetic and / or natural polyamines, preferably polyalkyleneimines, more preferably C2-C8 polyalkyleneimines, most preferably polyethyleneimine.

4. A method according to any one of claims 1 to 3, wherein the pretreatment composition, the coloring composition, or both independently, have a pH of about 7 or less, preferably from about 2 to about 7, more preferably from about 2 to 6. approximately, even more preferably ranging from approximately 2 to approximately 5, most preferably ranging from approximately 2 to approximately 4.

5. A method according to any one of claims 1 to 4, wherein the microtube-fuel composite comprises a halloysite-dye composite comprising at least one coloring agent, preferably selected from anionic hair coloring agents, cationic hair coloring agents, non-ionic hair coloring agents and natural hair coloring agents.

6. A method according to any one of claims 1 to 5, comprising a step of drying the hair after applying the pretreatment composition to the hair and before applying the coloring composition to the hair, wherein the pretreatment composition is optionally rinsed off from the hair before drying the hair.

7. A method according to any one of claims 1 to 6, wherein steps (a) and / or (b) are repeated one or more times.

8. A system for modifying hair color comprising: (a) a pretreatment composition comprising at least one non-surfactant amine-based compound and at least one solvent, wherein the total amount of the non-surfactant amine-based compounds preferably ranges from about 0.001% to about 25%, more preferably from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, most preferably from about 0.5% to about 10% by weight, based on the total weight of the pretreatment composition; and wherein the pH of the pretreatment composition is about 7 or less, preferably from about 2 to about 7, more preferably from about 2 to about 6, even more preferably from about 2 to about 5, most preferably from about 2 to about 4;and (b) a coloring composition comprising at least one microtube-dye composite and at least one solvent, wherein in the microtube-dye composite the dye comprises at least one hair coloring agent, wherein the total amount of microtube-dye composite preferably ranges from about 0.01% to about 15%, more preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 8%, most preferably from about 1% to; about 7% by weight, based on the total weight of the coloring composition, and wherein the pH of the coloring composition is about 7 or less, preferably from about 2 to about 7, more preferably from about 2 to about 6, even more preferably from about 2 to about 5, most preferably from about 2 to about 4.

9. The system of claim 8, wherein the at least one non-surfactant amine-based compound has a molecular weight of less than about 10,000, preferably from about 50 to about 10,000, more preferably from about 50 to about 7,500, more preferably from about 100 to about 5,000, most preferably from about 100 to about 2,500, and wherein the microtube-dye composite comprises a halloysite-dye composite comprising at least one coloring agent, preferably selected from anionic hair coloring agents, cationic hair coloring agents, non-ionic hair coloring agents, and natural hair coloring agents.

10. A kit for changing hair color comprising: (a) a first container containing a pretreatment composition comprising at least one non-surfactant amine-based compound and at least one solvent, wherein the total amount of the non-surfactant amine-based compounds preferably ranges from about 0.001% to about 25%, more preferably from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, most preferably from about 0.5% to about 10% by weight, based on the total weight of the pretreatment composition; and wherein the pH of the pretreatment composition is about 7 or less, preferably from about 2 to about 7, more preferably from about 2 to about 6, even more preferably from about 2 to about 5, most preferably from about 2 to about 4; and (b) a second container containing a coloring composition comprising at least one microtube-dye composite and at least one solvent, wherein, in the microtube-dye composite, the dye comprises at least one hair coloring agent, wherein the total amount of microtube-dye composite preferably ranges from about 0.01% to about 15%, more preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 8%, most preferably from about 1% to about 7% by weight, based on the total weight of the coloring composition, and wherein the pH of the coloring composition is about 7 or less, preferably from about 2 to about 7, more preferably from about 2 to about 6, even more preferably from about 2 to about 5, most preferably from about 2 to about 4.

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